TW201241490A - Film surface treatment method and device - Google Patents

Abstract

A film (9) to be treated is supported by a support section (10) of a film surface treatment device (1). A first gas (g1) containing a polymerizable monomer is brought into contact with the film (9) by means of a first treatment section (91). Next, a second gas (g2) containing a discharge product gas is transformed into plasma by means of a second treatment section (92) and the plasma is brought into contact with the film (9). Next, a third gas (g3) containing a polymerizable monomer is brought into contact with the film (9) by means of a third treatment section (93). Next, a fourth gas (g4) containing a discharge product gas is transformed into plasma by means of a fourth treatment section (94) and the plasma is brought into contact with the film (9). An additive component is further added to the third gas (g3) or the fourth gas (g4). The additive component is an oxygen gas, a hydrogen gas, a saturated hydrocarbon gas, an unsaturated hydrocarbon gas, or a crosslinking accelerator agent. In this manner, it becomes possible to improve the adhesion durability of a resin film.

Description

201241490 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to a method and apparatus for surface treating a resin-treated film, and relates to a bonding durability suitable for, for example, a protective film for improving a polarizing plate. A film surface treatment method and apparatus for processing or the like. [Prior Art] For example, a polarizing plate is mounted on a liquid crystal display device. The polarizing plate includes a polarizing film and a protective film. In general, the polarizing film is composed of a resin film (hereinafter referred to as "PVA film") containing polyethylene (polypropylene) as a main component. The protective film is composed of a resin film (hereinafter referred to as "TAC film") containing triacetate cellulose (TAC) as a main component. As an adhesive for the film, a water-based adhesive such as a polyvinyl alcohol-based or a squeaking system is used. The adhesion between the PVA film and the above-mentioned adhesive was good', but the adhesion of the TAC film was not good. Therefore, in the patent documents 丨, 2, before the subsequent steps, a film of a polymerizable monomer is formed on the surface of the protective film, and then the atmospheric piezoelectric slurry is irradiated. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-25604 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. Problem] In the plasma polymerization treatment of the polymerizable monomer alone, the durability is insufficient. In particular, when the plasma polymerization film is a water-soluble polymer such as polyacrylic acid, I62457.doc 201241490, the strength is likely to decrease in a high-temperature, high-humidity environment. [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 film surface treatment method for treating a surface of a resin-treated film; and includes the following steps: a first processing step The first gas containing the vaporized polymerizable monomer is brought into contact with the film to be treated; and the second treatment step is performed after the second processing step or simultaneously with the second processing step The second gas is electrocatalyzed (including excitation, activation, radicalization, ionization, etc.) and brought into contact with the film to be treated; and the third treatment step is performed after the second treatment step to contain vaporized The third gas of the polymerizable monomer is in contact with the film to be processed; and the fourth processing step is to electrically charge the fourth gas containing the discharge generating gas after the third processing step or simultaneously with the third processing step Destroying and contacting the film to be treated; and the third gas or the fourth gas further contains an additive component, wherein the additive component is oxygen, hydrogen, a saturated hydrocarbon gas, or an unsaturated component A hydrocarbon gas, or a crosslinking accelerator. By the first processing step and the second processing step, the electric correction plasma polymerization film obtained by plasma-polymerizing the polymerizable monomer in the first gas is formed on the surface II of the film to be treated, and the third processing step and the In the fourth step, the degree of polymerization of the first electropolymerized film is increased, and a second electropolymerized film layer obtained by electropolymerizing a polymerizable monomer in the third gas is formed in the above.丨电 162457.doc 201241490 on the slurry polymerization film. It is considered that by adding the above-described addition-addition component to the third gas or the fourth gas, hydrophobization or cross-linking (including polymerization) of the second plasma polymerization film can be realized, and it is considered that the component is added by adding the component. The reactivity (adhesion) of the plasma polymerization film to the adhesive can be improved. Therefore, the fueliness of the electropolymerized film can be improved. In particular, even if the plasma polymerization film is a water-soluble polymer such as polypropylene: it can surely ensure water resistance. As a result, it is possible to improve the subsequent resistance of the film to be processed. Here, the term "fourth" durability refers to the extent to which the subsequent object is exposed to a high humidity, high temperature, hot and humid environment, and then the strength is not lowered. The apparatus of the present invention is characterized in that it is a film surface treatment apparatus for treating a surface of a resin-treated film; and includes: a support portion that supports the film to be processed; and a first processing portion that performs gas-containing gas The second gas of the polymerizable monomer is brought into contact with the treated ruthenium; and the second processing portion is configured to electrically destroy the second gas containing the discharge generating gas and contact the film to be treated; a process of bringing a third gas containing a vaporized polymerizable monomer into contact with the film to be treated, and a fourth processing unit for plasma-treating and contacting the fourth gas containing the discharge generating gas And a transfer mechanism that transports the processed film in the order of the second processing unit, the second processing unit, the third processing unit, and the fourth processing unit; and the third gas or the The fourth gas further contains an additive component, and the 162457.doc -6 · 201241490 additive component is oxygen gas, a saturated hydrocarbon gas, or an unsaturated hydrocarbon gas, or a crosslinking accelerator. The film to be treated is improved. The film to be treated can be formed by forming a first condensed layer containing a polymerizable monomer in the first gas on the surface of the film to be processed by the first treatment unit. Thereafter, the film to be processed is transported to the second processing unit by the transport mechanism, and the first condensation layer is plasma-polymerized by the second treatment unit to form a plasma polymerization on the surface of the film to be treated. membrane. Then, the film to be processed is transported to the third processing unit by the transport mechanism, and the second condensed layer containing the polymerizable monomer in the third gas is formed on the surface of the film to be processed by the third processing unit. Alternatively, a second condensed layer containing a mixture of a polymerizable monomer and an additive component in the third gas may be formed. Thereafter, the film to be processed can be transported to the fourth processing unit by the transfer mechanism, and the degree of polymerization of the second plasma polymerization film can be increased by the fourth treatment unit, and the second condensation layer can be plasma-polymerized. The second plasma polymerization film is laminated on the first plasma polymerization film. It is considered that by adding the above-mentioned additive component to the third gas or the fourth gas, it is possible to achieve hydrophobization or parentalization of the second plasma polymerization film, and further, it is possible to make the plasma polymerization film pair by adding components. The reactivity (adhesiveness) of the subsequent agent is improved. Therefore, the water resistance of the electropolymerized film can be improved. Especially even if the plasma polymerization film is a water-soluble polymerization such as polyacrylic acid

The substance can also reliably ensure its water resistance. As a result, it is preferable that the support portion includes the first and second 'third rolls of metal which are arranged in parallel with each other, and the film to be processed is in the line L 〇 β .

I62457.doc 201241490 The first nozzle of the first gas is discharged. Preferably, the second #_ includes a second nozzle that ejects the second gas between the ith roller and the second roller: ^, and the second roller is formed to be adjacent to each other The discharge - the f pole. Preferably, the first processing unit includes a surface. The third surface of the red roller on the peripheral surface of the second roller is the third processing unit including the fourth gas nozzle. The fourth nozzle having a gap with the third roller, the second and third light structures, generates a pair of discharge electrodes in the vicinity of the atmosphere chamber. Thereby, the film to be processed can be fed in accordance with the first roll, the second roll, and the third report, and the (10)th from the i-th nozzle to the film to be processed can be formed on the circumferential surface of the first roll, and then In the gap between the first and second rolls, the first plasma is irradiated and irradiated to the film to be treated. Then, the body is sprayed from the third nozzle to the film to be treated, and the third surface is the third gas. After that, the formation of the first portion 1 of the first processing unit can be formed by the == fourth gasization and irradiation to the treated surface: the space. P is provided. The first roll plasmaization & electrode is formed by the second gas portion. The second roller system serves as a forming portion for providing a 12-roller and a third processing space of the first/segment portion - a pair of lightning-pole W 帛3 roller systems and a counter electrode for plasma-treating the fourth gas The surface treatment for forming the fourth processing space of the fourth processing portion and the surface treatment of the invention is preferably carried out in the second processing step and the second processing step. Here, the steps of the great deliberation of the law are in the vicinity of the atmospheric dust near the atmospheric pressure, Department & 〇 13χΐ〇4~5〇 663χΐ〇4 162457.doc 201241490

The range of Pa' is preferably Pa if it is easy to adjust or the simplicity of the device configuration, and more preferably 9 33 ΐχ 1 〇 4 to 10.397 χ 1 〇 4 pa. The film to be treated is preferably a hard-to-adhere optical resin. The present invention is suitable for improving the adhesion and adhesion durability of the difficult-to-adhere optical resin film when the difficult-to-adhere optical resin film is attached to the easily-adherent optical resin film. Examples of the main component of the above-mentioned difficult-to-adhere optical resin film include triacetyl cellulose (TAC), polypropylene (PP), polyethylene (pE, P_ethylene), and cycloolefin polymer (c〇p, Cyc丨〇〇丨· ρ〇ΐγ_), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethylmethacrylate (PMMA, polymethylmethacrylate) ), polyimide, and the like. The above treated film is more preferably a tac film. The main component of the above-mentioned easy-adhesive optical resin film may, for example, be polyvinyl alcohol (PVA) or ethylene-vinyl acetate copolymer (EVA). The polymerizable monomer of the first gas and the polymerizable monomer of the third gas are preferably the same polymerizable monomer, but may be mutually different polymerizable monomers. The polymerizable monomer of the first and third gases includes a monomer containing an unsaturated bond and a specific functional group. The specific functional group is preferably a hydroxyl group, a slow group, an ethyl fluorenyl group, a glycidyl group, an epoxy group, an ester group of a carbon number ..., ..., a valence group, an aldehyde group, and more preferably a hydrophilic group such as a carboxyl group or a hydroxyl group. . Examples of the monomer containing an unsaturated bond and a hydroxyl group include mercaptopropionic acid B 162457.doc 201241490 glycol ester 'allyl alcohol, hydroxyethyl methacrylate, and the like. Examples of the monomer containing an unsaturated bond and a carboxyl group include acrylic acid, mercaptoacrylic acid, itaconic acid, maleic acid, and 2-mercaptopropionic acid. Examples of the monomer containing an unsaturated bond and an ethyl hydrazine group include ethyl acetate vinegar and the like. Examples of the monomer containing an unsaturated bond and a glycidyl group include glycidyl acrylate and the like. Examples of the monomer containing an unsaturated bond and an ester group include acrylic acid, ethyl acrylate, and butyl acrylate. Vinegar, tributyl acrylate, 2-ethylhexyl acrylate, octyl acrylate 'methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid tert-butyl ester' Isopropyl methacrylate, 2-ethyl methacrylate, and the like. Examples of the monomer containing an unsaturated bond and an aldehyde group include acryl acid, crotonaldehyde and the like.

, 1-cyclohexene, 1_ when the film is treated as described above, -cycloheptene, 1 ·cyclooctene cyclopentadiene (DCPD, monomer. As a water-soluble monomer, can be listed (ΑΑ ,acrylic acid), mercaptopropene i-amine, methyl propyl amide, N,N-diamine decyl decylamine, etc. As a dilute hydrocarbon monomer, ene '1-octane, 1-cyclopentene Other than 1·cyclohexene, cyclopentadiene and dicyclopentadiene may be mentioned. Among the polymerizable monomers of the first, third, and third gases, the polymerizable monomer of the first gas 162457.doc •10·201241490 is more preferably an affinity with the film to be treated during plasma polymerization. The above-mentioned polymerizable monomer is a monomer having an ethylenically unsaturated double bond and a carboxyl group, and specific examples thereof include acrylic acid (CH2-CHC〇〇H) and methyl propylene g. Chu (CH2=C(CH3)C00H). The polymerizable monomer of the first emulsion and the polymerizable monomer of the third gas are more preferably acrylonitrile or methacrylic acid, and more preferably ruthenium. Thereby, the affinity with the treated crucible can be exhibited during the polymerization of the plasma. Therefore, it is possible to surely improve the adhesion of the treated crucible and even the durability. Preferably, the first gas and the second gas do not contain the additive component. Thereby, the affinity with the film to be treated can be surely exhibited when the polymerizable monomer in the above i-th gas is subjected to plasma polymerization. Even the adhesion of the two treated films and the subsequent durability can be surely obtained. The compound to which the above-mentioned additive component is different from the above-mentioned polymerizable monomer is preferably a function of hydrophobizing, cross-linking, or promoting reactivity with an adhesive agent of the plasma polymer of the above-mentioned polymerizable monomer. The fourth gas in the third and fourth gases preferably contains oxygen, hydrogen, a saturated hydrocarbon gas or an unsaturated flue gas as the above-mentioned additive component. It is considered that the additive component causes the hydrophobicization of the plasma polymer of the polymerizable precursor, the crosslinking, or the promotion of reactivity with the adhesive in the fourth treatment step, and the fourth gas contains oxygen ( 〇 2) In the case of the above-mentioned additive component, the volume rolling of oxygen in the fourth gas is preferably 5 Torr (7) to 5%. By making the oxygen concentration "swing", it is possible to ensure the desired durability. The polymerization of the monomer I62457.doc 201241490 can be prevented by blocking the oxygen concentration to 3 卯. In the case where the fourth gas contains the mouse (H2) as the additive component, the volume of the moxibustion in the fourth gas is preferably 5 〇〇 ppm to loooo PPm. By setting the hydrogen concentration to 500 ppm or more, the desired durability can be ensured. If the hydrogen concentration exceeds 8000 ppm to loooo ppm, then the increase in durability is saturated. By making the hydrogen concentration below 丨〇〇〇〇 ppm, the desired subsequent durability can be obtained and the amount of hydrogen used can be saved. Examples of the saturated hydrocarbon include methane, ethane, propane, and butane. Examples of the unsaturated smoke include ethylene and acetylene. The fourth gas may contain methane, ethylene or acetylene as the additive component. It is considered that an unsaturated hydrocarbon such as B fast contributes particularly to the crosslinking of the above plasma polymer. When the additive component is a crosslinking accelerator, the additive component (crosslinking accelerator) is a compound different from the polymerizable monomer in the first gas and the polymerizable monomer in the third gas. Examples of the crosslinking accelerator include a diallyl compound, a diamine compound, a glycidyl compound, a warp compound, and the like. (4) The compound is known as a crosslinking accelerator, and it is considered by the manufacturer to contribute particularly to the crosslinking of the above-mentioned electroporation polymer or the promotion of reactivity with a subsequent agent. The crosslinking accelerator as the additive component is preferably contained in the third gas. Examples of the diallyl compound' include diallylamine, maleic acid dipropylene vinegar, and methacrylic acid propylene glycol. The diamine compound may, for example, be ethylenediamine. Examples of the glycidol compound' include allyl glycidyl ether and methyl propylene glycol glycidol. Examples of the transbasic compound include acetoacetic acid, thioglycolic acid, and the like. 162457.doc 201241490 The first gas or the third gas may further include a transport polymerization gas. The carrier gas is preferably selected from the group consisting of nitrogen, argon, helium and the like, and is preferably a nitrogen gas as a carrier gas. Acrylic acid is a liquid phase in the presence of most polymerizable monomers such as acryl. Such a polymerizable monomer may be vaporized in a carrier gas such as an inert gas. As a method of vaporizing a polymerizable monomer in a carrier gas, an extrusion method of extruding a saturated vapor on a liquid surface of a polymerizable monomer with a carrier gas* = a polymerizable monomer liquid causes bubbling of a carrier gas The foaming method, the heating method for heating the polymerization unit = the liquid, and the heating method for promoting the evaporation thereof may be used in combination with the extrusion method, the foaming method, and the heating method. The carrier gas portion may also be introduced into the gasifier, and the remaining portion may not pass through the gasifier, so that the temperature of the above-mentioned portion of the carrier gas and the remaining portion of the combiner or the carrier gas on the downstream side of the gasifier The distribution ratio of the above-mentioned part to the remaining part, that is, the concentration of the polymerizable monomer in the first gas or the third gas. In the case of heating and vaporizing it, in consideration of the burden of the heater, it is preferable to select the Buddha point as a fan. c below. Further, it is preferred that the aggregate is selected such that it does not decompose (chemically change) by heating. In the third gas or the fourth gas, the crosslinking accelerator may be vaporized in a carrier gas such as an inert gas at a normal temperature and normal pressure phase. As a method of vaporizing a crosslinking accelerator in a carrier gas, an extrusion method of a saturated vapor on a liquid surface of a carrier gas extrusion crosslinking accelerator, and a bubbling of a carrier gas in a liquid of a crosslinking accelerator A foaming method, a heating method in which a liquid of a crosslinking accelerator is heated to promote evaporation thereof, and the like. It is also possible to use an extrusion method, a heating method, a foaming method and a heating method. One of the carrier gases (4) 162457.doc 201241490 can also be introduced into the gasifier and the remaining portion is not vaporized, so that the aforementioned portion of the carrier gas merges with the remainder on the downstream side of the gasifier. By? The temperature of the catalyst or the distribution of the above part of the carrier gas to the remainder is more ancient. The degree of inconsistency of the crosslinking accelerator in the third gas or the fourth gas. When the crosslinking agent is contained in the third gas, the mixed liquid may be vaporized by mixing the polymerizable monomer in the liquid phase with the crosslinking accelerator in the liquid phase; After the vaporization of the polymerizable monomer and the liquid phase, the gasified polymerizable monomer is mixed with the vaporized crosslinking agent. When the third gas contains the additive component, the polymerizable monomer of the third gas may be mixed with the additive component on the surface of the film to be treated. In the case where the fourth gas contains the additive component, the discharge generating gas of the fourth gas may be mixed with the additive component on the surface of the film to be treated. Examples of the discharge gas body of the second gas and the gas for forming the fourth gas include nitrogen (N2) or a rare gas (MU gas. The discharge generation gas may be a plurality of available gas: the second gas. The discharge generation gas of the gas and the discharge generation gas of the first embodiment may be the same gas and the same gas as each other. [Effects of the Invention] According to the present invention, the durability of the treated crucible can be improved. [Embodiment] 162457.doc 201241490 Hereinafter, an embodiment of the present invention will be described with reference to the drawings. Fig. 4 shows a polarizing plate pf. The polarizing plate PF includes a polarizing film 7 and a protective film. The polarizing film 7 is sandwiched between two protective films. The protective film 9 and the polarizing film 7 are bonded via the adhesive 8 . The polarizing film 7 contains a PVA film containing polyvinyl alcohol (pva) as a main component as the adhesive 8 and a PVA such as a PVA aqueous solution. The PVA-based adhesive may further contain a known additive component for improving the adhesion. The protective film 9 contains a TAC film containing the triethylene phthalocyanine (TAC) as a main component, and the thickness of the film 9 is, for example, 1 〇. 〇μη1 The surface of the adhesive agent 8 on the side of the TAC film 9 is covered with an adhesion promoting 臈8〇. The next promoting film 80 is a laminated structure of two plasma polymerization films 81 and 82. • The first electron polymerization film 81 A plasma polymer containing acrylic acid (polymerizable monomer) and in contact with the TAC film 9 "the second plasma polymerization film 82 contains a plasma polymer of acrylic acid, and imparts water resistance or high reactivity with the adhesive 8 and the like. The second plasma polymerization film 82 is in contact with the adhesive agent 8. Fig. 1 shows a film surface treatment apparatus 1β film in which the adhesion promoting film 80 is formed on the TAC film 9 (hereinafter referred to as "processed film 9" as appropriate). The surface treatment apparatus 1 includes a support unit 10, a first processing unit 91, a second processing unit 92, a third processing unit 93, and a fourth processing unit 94. The TAC film 9 to be processed has a continuous film shape. The processing unit 91 is configured to perform the process of bringing the first gas gl into contact with the processed film 9 (first processing step). The second processing unit 92 is processed by the first processing unit 91. Or, simultaneously with the processing of the second processing unit 91, the second gas g2 is electrically converted (including excitation, activation, and radicalization). Ionization or the like) is brought into contact with the film to be processed 9 (the second processing step is to form the HI polymerization film 81. The third processing unit 93 is after the second processing unit 162457.doc 15 201241490 = The third gas g3 is in contact with the film to be processed in the third processing step. The fourth processing unit 94 is configured to process the fourth processing unit 93 or to simultaneously process the fourth gas g4 simultaneously with the third processing unit 93. The fourth plasma processing film is formed in contact with the substrate. The second plasma polymerization film is formed in the following. As shown in FIGS. 1 and 2, the support portion 10 includes three main rollers ", 12 , 13 and guide rollers 16, 17. The main rolls 11 to 13 are cylindrical bodies having the same diameter and the same axial length. At least the outer peripheral portion of the rolls 11 to 13 is made of a metal, and a peripheral surface of the outer periphery including the metal is covered with a solid dielectric layer. The axis of each roller ", 12, 13 is oriented with the figure! In the horizontal direction orthogonal to the paper surface (hereinafter referred to as "processing width direction", the three rollers n, 12, and 13 are arranged in this order and in parallel in FIG. 1, the i-th stick i on the left side, and the second stick 1 in the center. The gap 94a between the two gaps and the gap 94a between the center second roller 12 and the right third roller 13 are equal to each other. The thickness of the narrowest portion of the gap 92a is, for example, about mm to several mm. 11 to 13 also serve as a plasma discharge generating electrode for the plasma surface treatment apparatus. Although not shown, the power source is connected to the center roller 12, and the left and right rollers u'13 are electrically grounded. The phase & The rollers 12 and 13 are connected to the left and right rollers, respectively, and the roller 12 in the center is electrically grounded. The power source outputs, for example, a pulse wave of high-frequency power. By the power supply, the roller 11 on the left side and the roller 12 in the center are placed between A plasma discharge is generated under the pressure near the atmospheric pressure, and the gap 92a becomes a discharge space near the atmospheric pressure. Further, by the above-described power supply, the electric shock discharge is generated between the central roller 12 and the right roller 13 at a pressure near atmospheric pressure. 'The gap 94a becomes a discharge space near atmospheric pressure 162457.doc 201241490 A plurality of (two in the figure) front guide rolls 16, 16 are disposed below the rolls 11, 12. A plurality of (two in the figure) rear guide rolls are disposed below the rolls 12, 13. 17 and 17. The film-form processed film 9 is oriented such that the width direction thereof faces the processing width direction (the direction orthogonal to the paper surface in Fig. 1), and is supported by the support portion 〇. The film to be processed 9 is wound around a half cycle. The circumferential surface on the upper side of the three rolls 丨, 丨2, and 。3, and the circumferential surface including the upper side of each of the rolls 11, 12, and 13 and the half-circumferential portion of the portion where the gap ❿, 94a is formed are covered by the film to be processed 9. The film 9 to be processed between the rolls 11 and 12 is suspended downward from the gap 92a, and is wound around the guide rolls 16. Thus, the film 9 to be processed between the gaps 92a and the guide rolls 16 and 16 forms the folded-back portion 9a. The folded-back portion 9 has a triangular shape when viewed in the width direction of the processing. The film 9 to be processed between the rolls 12 and 13 hangs downward from the gap 94 & and is wound around the guide rolls 17 and 17. Thereby, the gap ... and the guide roll The film to be processed 9 between 17 and 17 forms a folded-back portion 9be folded back portion 9M when viewed in the width direction Although not shown in the drawings, each of them has a rotating mechanism, and the hard turning mechanism includes a driving unit 'such as a motor and a transmitting mechanism that transmits the driving force of the driving unit to the axis of the second two. The transmitting mechanism includes, for example, a pulley mechanism. Or a gear train. As shown by the hollow arc-shaped arrow in Fig. 1, the rollers 11, 12, 13 are respectively arranged in the same direction around their respective axes and in synchronization with each other (in Fig. 1) In the clockwise direction, the rotation is carried out. The 臈9 is transported in the right direction according to the mil, the second roller 12, and the second direction. The support unit 1G doubles as the processed HH to the large 162457.doc 201241490 ::::1 Temperature adjustment mechanisms (not shown) are provided in 12 and 13. The fishing-mechanism includes, for example, a temperature regulating path formed in the chains m, 13. Can) l = I (1) The media flows through the temperature control road and the heart, 12 temperature. Even, the film 9 to be processed on the circumferential surface of the roll u' 12 can be tempered. The rolls 11, 12, and 13 are added with a sigh of 犋9, and the degree of the dish is preferably lower than the condensing temperature of the polymerizable monomer. The first process. The crucible 91 includes a supply portion of the first gas gl. And the first nozzle 31. The first gas gl contains a polymerizable monomer and a carrier gas. Acrylic acid AA was used as the polymerizable single system. Nitrogen is used as the carrier gas system (n2:^, the detailed illustration is omitted, but the first gas supply unit 21 includes a vaporizer. The liquid acid in the vaporizer t' liquid is vaporized in the carrier gas. The foaming method may be an extrusion method. The vaporized acrylic acid is mixed with a carrier gas to form an i-th gas gl. The gas gl does not contain the following additive component. The first gas supply unit 21 passes through the gas. The first nozzle 31 is disposed above the first roller 11. The first nozzle 31 extends longer in the processing width direction and is in the circumferential direction of the second roller (Fig. The left and right sides have a certain width. The lower surface of the i-th nozzle 31 is provided with a discharge port. The discharge port is distributed over a wide range of the lower surface of the second nozzle 31 (processing width direction and pro-circumferential direction). The discharge surface (lower surface) of the first nozzle 31 faces the film to be processed 9 on the first roller 11. The first gas gl from the first gas supply unit 21 is supplied to the first gas supply line 21c via the first gas supply line 21c. The first nozzle 31' is uniformed by a rectifying portion (not shown) in the first nozzle 31, and is 'The discharge from the first nozzle 31 is ejected. The discharge gas of the first gas gl is 162457.doc -18- 201241490 is a gas flow uniformly distributed in the processing width direction. One in the gas path 2U and the i-th nozzle 31 A temperature adjustment mechanism (not shown) is provided. The temperature adjustment mechanism of the gas passage 21c includes a heating belt, etc. The temperature adjustment mechanism of the second nozzle 31 includes a temperature regulation path through which the temperature control water passes. The gas path 21 and the Kth nozzle The set temperature of 31 is higher than the condensation temperature of acrylic acid, whereby the acrylic acid can be prevented from being condensed in the gas path 21c or the nozzle 31 before being ejected from the nozzle 31. The shielding member 41 is provided at the bottom of the first nozzle 31. It is formed in a circular arc shape along the circumferential direction of the first roller 11, and has a curved plate shape extending in substantially the same length as the roller 11 in the processing width direction. The circular direction of the shielding member 41 (Fig. i Both ends of the middle and right sides of the shielding member 41 extend in the circumferential direction of the first roller 11. The circumferential direction of the arcuate direction (left and right in Fig. 1) of the shielding member 41 is, for example, 24 〇 to 3 mm. Left and right. In Fig. 1, the left end of the shielding member 41 is open. In Fig. 1, the end portion on the right side of the shielding member 4A abuts or approaches the closing member 51 to be described below. A first processing space 91a is formed between the shielding member 41 and the first roller cymbal. The first processing space 91 is provided in the forming portion of the first processing space 91a. The first processing space 91a is a space having a circular arc shape along the circumferential surface of the upper side of the first roller 11. The lower surface of the first nozzle 31 The discharge port penetrates the shielding member 41 and communicates with the first processing space 9ia. The shielding member 41 extends the first processing space 91a toward the both sides of the first roller 11 in the circumferential direction of the first nozzle 31. The end portion on the left side of the first processing space 91a in Fig. 1 is connected to the outer space on the left side (the side opposite to the side of the roller 12) of the roll. In Fig. 1, the end portion on the right side of the first processing space 91a is connected to the gap between the closing member 51 and the roller yoke described below. 162457.doc 19 201241490 * The first processing space 91a is narrow at the center of the arc direction (left and right in Fig. i)

乍 slightly widens toward both end portions in the arc direction. The thickness of the first W-space 91a is preferably about 1 mm. The thickness of the 卩 position of the first processing space is preferably, for example, about 1 melon. The second processing space is the widest. The thickness of the 卩 position is preferably, for example, about 1 〇mm. The thickness of the shield member μ may be fixed to the upstream side of the first parent 11 in the direction of rotation and the downstream side of the first nozzle 31, and the bottom surface of the second nozzle 31 is also fixed. The second processing unit 92 includes the supply unit 22 and the second nozzle 32 of the second gas g2. The second gas g2 contains a discharge generating gas, and nitrogen is used as the discharge generating gas. The second nozzle 32 is connected to the second gas supply unit 22. The second nozzle 32 is provided inside the triangular-shaped folded-back portion 9& of the processed film 9. The second nozzle u is The processing width direction extends long, and the cross section orthogonal to the extending direction faces upward and the front end is tapered. The ejection port of the upper end (front end) of the second nozzle 32 faces the inter-roll gap 92a. The lower end of the gap 92a is The second nozzle 32 is blocked to some extent. From the second The second gas g2 of the body supply unit 22 is equalized in the processing width direction by the rectifying unit (not shown) in the second nozzle 32, and then ejected from the discharge port of the second nozzle 32 to the gap 92a. The gas flow of the gas g2 is distributed in the width direction of the processing width. The gap 92a constitutes the second processing space of the second processing unit 92. The reports u and 12 serve as the second processing space of the second processing unit 92. Provided in the second nozzle 32, a temperature control path (a second gas temperature adjustment 162457.doc -20-201241490 mechanism) is provided in the second nozzle 32. The temperature control medium such as water passes through the second nozzle 32. The temperature adjustment path can be used to adjust the temperature of the second nozzle 32, and even the second gas can be adjusted. The set temperature of the second nozzle 32 is lower than the set temperature of the first nozzle 31, preferably lower. The condensing temperature of the acrylic acid (polymerizable monomer). The closing member 51 is disposed between the rolls n and 12 which are higher than the second processing space 92a. The closing member 51 is separated from the second nozzle by the second processing space 92 & The 32-way occluding member 51 extends long in the processing width direction and is orthogonal to the I extending direction The profile is tapered toward the lower front end. The occlusion member". The second processing space 92a is closed. The fourth processing space and the second processing space are connected to each other via the lower end (front end) of the blocking member 51 facing the end of the second processing space 92a by the blocking member 51 and the gap between the first roller 11 and the second processing space. . A nozzle having the same structure as that of the second nozzle 32 may be used as the closing member 51, and the second nozzle 32 may be vertically reversed, or the second gas g2 may be ejected from the nozzle 51. The third processing unit 93 includes a third gas supply unit 23 and a third nozzle 33 . The third gas supply unit 23 supplies the third gas enthalpy to the third nozzle 33. The third gas g3 contains the same gas 1 as the first gas gl, and the third gas g3 contains a polymerizable monomer and a carrier gas. As the polymerizable monomer, the olefinic acid AA is used. Nitrogen (N2) is used as a carrier gas. Although the detailed illustration is omitted, the third gas supply unit 23 of the Coix seed contains a vaporizer. In the gasifier, the liquid acrylic acid is rolled in a carrier gas. The gasification can be either a foaming method or a broadcasting method, and a third gas can be produced by mixing the vaporized acrylic acid with a carrier gas.笙^ μ 8 The first gas supply unit 21 and the third gas enthalpy supply unit 23 may also include a source of acrylic acid for the sputum >&&&& I62457.doc -21. 201241490 The third gas supply unit 23 is connected to the third nozzle 33 via the gas path 23c. The third nozzle 33 is disposed above the second roller 12 . The third nozzle 33 extends long in the processing width direction and has a certain width in the circumferential direction of the second roller 12 (left and right in Fig. 1). A discharge port is provided on the lower surface of the third nozzle 33. The discharge port is formed to be distributed over a wide range (processing width direction and roll circumferential direction) of the lower surface of the third nozzle 33. The discharge surface (lower surface) of the third nozzle 33 faces the film 9 to be processed on the second roller 12. The third gas g3 from the third gas supply unit 23 is supplied to the third nozzle 33 via the third gas supply line 23c, and is normalized by the rectifying unit (not shown) in the third nozzle 33. The discharge port of the third nozzle 33 is ejected. The discharge gas stream of the third gas g3 is a gas stream uniformly distributed in the processing width direction. The temperature control mechanism in which the gas passage 23c and the third nozzle 33 are provided with a temperature adjustment mechanism (not shown) gas passage 23c includes a heating belt or the like. The temperature adjustment mechanism of the third nozzle 33 includes a temperature adjustment path through the temperature adjustment water. The set temperature of the gas path 23c and the third nozzle 33 is higher than the condensation temperature of acrylic acid. Thereby, it is possible to prevent the acrylic acid from being condensed in the gas path 23c or the nozzle 31 before being ejected from the nozzle 33. The shielding member 43 is provided at the bottom of the third nozzle 33. The shielding member 43 has an arcuate cross section along the circumferential direction of the second roller 12, and extends in substantially the same length as the roller 12 in the processing width direction. Curved plate shape. Both ends of the arcuate direction (left and right in Fig. i) of the shielding member 43 extend toward the circumferential direction of the second roller 12 from the third nozzle. The circumferential direction of the circular arc direction (left and right in Fig. 1) of the shielding member 43 is, for example, about 240 to 300 mm. The end portion of the upstream side (left in the middle) of the rotation direction of the roller 12 of the shielding member 43 abuts or approaches the side portion of the closing member η. The downstream end of the rotation direction of the roller 12 of the shielding member 43 is 162457.doc -22-201241490 (the right side in FIG. 1) is abutted or close to the occluding member 52 described below between the shielding member 43 and the second roller 12. A third processing space 93a is formed. The second roller 12 is provided as a forming portion of the third processing space 93a of the third processing unit 93. The third processing space 93a has a space in a circular arc shape along the circumferential surface of the upper side of the second roller 12. The discharge port on the lower surface of the third nozzle 33 passes through the shielding member 43 and communicates with the third processing space 93a. The third processing space 93a is extended further to both sides in the circumferential direction of the second roller 12 than the third nozzle 33 by the shielding member 43. In Fig. 1, the end portion on the left side of the third processing space 93 & is connected to the second processing space 92a via a gap between the blocking member 51 and the parent 12. The end portion on the right side of the third processing space 93a in Fig. 1 is connected to the gap between the closing member 52 and the roller 12 described below. The third processing space 93a is slightly widened at the center portion in the arc direction (left and right in Fig. 1) as it goes toward both end portions in the arc direction. The thickness of the third processing space 93a is preferably about 1 mm to 10 mm. The thickness of the narrowest portion of the third processing space 93a is preferably, for example, about 1 μm. The thickness of the widest portion of the third processing space 93a is preferably, for example, about 丨〇 mm. The thickness of the third processing space 93a may also be fixed throughout the entire area. The shielding member 43 may be separated into a portion on the upstream side and a downstream side in the rotation direction of the second roller 12 with the third nozzle 33 interposed therebetween, and the bottom surface of the third nozzle 33 may directly face the third processing space 93a. The fourth processing unit 94 includes a supply unit 24 and a fourth nozzle 34 of the fourth gas g4. The fourth gas g4 contains a discharge generating gas and an additive component. The fourth gas supply unit 24 includes a supply unit 24a for generating a discharge gas and a supply unit 24b for adding components. 〇162457.doc • 23· 201241490 Use of nitrogen (NO as a discharge gas of the fourth gas g4) "Additional component contains oxygen (〇2 Hydrogen (H2), or a saturated hydrocarbon gas or an unsaturated hydrocarbon gas (CnH2n-2 (ng2), CnH2n (n22)). In the fourth gas supply unit 24, an additive component is mixed in the discharge generating gas. The fourth gas g4 is generated. When the additive gas is oxygen, the oxygen concentration in the fourth gas g4 is preferably 500 ppm to 3000 ppm (volume concentration). When the additive gas is hydrogen, the fourth gas g4 is used. The hydrogen concentration is preferably 500 ppm to 1 〇〇〇〇 ppm (volume concentration). Examples of the saturated hydrocarbon gas include methane (CH4), ethane (c^6), propane (c#8), and butane ( C4Hi〇), etc. Examples of the unsaturated hydrocarbon gas include ethylene (C#4) and acetylene ((: 汨2). The concentration of the saturated hydrocarbon gas or the unsaturated hydrocarbon gas in the fourth gas g4 is preferably 100 ppm. 〜1(9)(8) ppm (volume concentration) The fourth nozzle 34 is connected to the fourth gas supply unit 24. The fourth nozzle 34 is placed at the The inside of the folded portion of the triangular shape of the film 9. The fourth nozzle 34 extends long in the processing width direction, and the surface faces upward and the front end is tapered. The outlet faces the inter-roll gap 94a. The gap is somewhat occluded. Section from the 4th 'and orthogonal to the extension direction

162457.doc • 24-201241490 A temperature control path (fourth gas temperature adjustment mechanism) (not shown) is provided in the fourth nozzle 34. The temperature control medium such as water passes through the temperature regulation path in the fourth nozzle 34. Thereby, the fourth nozzle 34 can be tempered, and even the fourth gas can be adjusted to eject the temperature, and the set temperature of the fourth nozzle 34 is lower than the set temperature of the third nozzle 33, preferably lower than acrylic acid ( Condensation temperature of the polymerizable monomer). The closing members 52 are disposed between the rolls 12 and 13 which are higher than the fourth processing space 94a. The closing member 52 faces the fourth nozzle 34 via the fourth processing space 94a. The occluding member 52 extends long in the processing width direction, and the cross section orthogonal to the &quot;Hai extension direction faces downward and the front end tapers. The lower end (front end) of the blocking member 52 faces the fourth processing space 94a. The upper end portion of the fourth processing space "a is closed to some extent by the closing member 52. The third processing space 93 &amp; communicates with the fourth processing space 94a via the gap between the blocking member 52 and the second roller 12. The fourth processing space 94a is connected to the outer space on the upper side of the third roller 13 via the gap between the blocking member 52 and the third roller. A nozzle having the same configuration as that of the fourth nozzle 34 may be used as the blocking member 52, and The fourth nozzle 34 is vertically reversed, and the second gas g2 can be ejected from the nozzle 52. Hereinafter, the method for treating the surface of the film to be processed 9 by the film surface treatment device 上述 having the above configuration Further, a method of manufacturing a polarizing plate will be described. [Supporting Step, Transfer Step] The film to be processed 9 containing the TAC film is wound around the main rolls u to i3 of the support portion 1 and the guide rolls 16, 17. In the clockwise direction in FIG. 1, the film to be processed is conveyed in the order of the third roller 13 of 162457.doc -25 - 201241490 to the first roller 11 'the second roller 12 in the substantially right direction in the drawing. 1 processing step] The first processing unit 91 supplies the first gas gl from the supply unit 21 The first gas gl is ejected from the nozzle 31 to the first processing space 91ae, and the correction gas gl contacts the surface of the film 9 to be processed in the first processing space 91a. Thereby, as shown in Fig. 3 (4), the i The acrylic monomer in the gas gl is condensed and adhered to the inner film 9#; the surface of the treated film 9 forms a first condensed layer 83 containing an acrylic monomer, and more than half of the inside of the treatment space 91a. First, the gas y flows toward the second processing space 92a along the transport direction of the film to be processed 9. The shielding member 41 can suppress or prevent the first gas gl from leaking to the outside, and can secure the acrylic to the processed film 9 [Second Processing Step] As the first roller 11 rotates, the processed film 9 that has passed through the second processing step is transported to the second processing space 92a. The second processing unit 92 sets the second gas g2. The supply unit 22 is supplied to the nozzle 32. The second gas g2 is discharged from the nozzle 32 to the second processing space 92a. At the same time, electric power is supplied to the roller 12, and discharge in the vicinity of the atmospheric pressure is generated in the second processing space 92a. The gas of the discharge generating gas is plasmaized, and the nitrogen plasma is brought into contact with the second processing space 92a. The surface of the film 9 to be treated. Thereby, as shown in FIG. 3(b), the acrylic acid monomer of the first condensation layer 83 is plasma-polymerized to form a surface containing the polyacrylic acid on the surface of the film to be treated 9. (1) The plasma polymerization film 81. The polyacrylic acid has good affinity with TAC, and is sufficiently reacted with the surface molecules of TAC to be in close contact with each other. In particular, since the first gas gl and the second gas g2 do not contain the above-mentioned additive component, they can be improved. 1 162 457. doc • 26· 201241490 The purity of the polyacrylic acid of the plasma polymerization film 81 is sufficient to ensure the above affinity. The film to be processed 9 is folded back by the guide roller 16, whereby it reciprocates in the second processing space 92a, and is processed twice by the second processing unit 92. [Third processing step] The film to be processed 9 which has been reciprocated in the second processing space 92a is transported to the third processing space 93a in accordance with the second roller 12. The third processing unit 93 supplies the third gas y from the third gas supply unit 23 to the third nozzle 33 . The third gas g3 is discharged from the third nozzle 33 to the third processing space 93ae, and the third gas g3 contacts the surface of the film 9 to be processed in the third processing space 93a. As shown in Fig. 3(c), the acrylic monomer in the third gas is condensed and adhered to the film to be treated 9, and a second condensed layer 84 containing an acrylic monomer is further formed on the first plasma polymer film 81. The third gas g3 which is more than half of the third processing space 93a flows toward the fourth processing space 94a along the conveying direction of the film to be processed 9. The shielding member 43 can suppress or prevent the third gas g3 from leaking to the outside, thereby ensuring the adhesion amount of acrylic acid. [Fourth Processing Step] As the second roller 12 rotates, the film 9 to be processed which has passed through the third processing step is transported to the fourth processing space 94a. The fourth processing unit 94 supplies the fourth gas to the fourth nozzle 34 from the fourth gas supply unit 24. This fourth gas g4 is discharged from the fourth nozzle 34 to the fourth processing space 94a. In the fourth processing space "a, a discharge in the vicinity of the atmosphere is generated by the power supply. Thereby, the nitrogen of the fourth gas and the additive component are electropolymerized." The gas of the electricity is contacted with the second chamber 94a of the fourth place. The surface of the film 9 to be treated therein, whereby the degree of polymerization of the first plasma A film 81 can be increased. Further, as shown in Fig. 3 (4), the second condensation layer I62457.doc -27· 201241490 a propionate monomer The second electropolymerization film 82 containing the polyacrylic acid is laminated on the electropolymerization film to form the adhesion promoting film 80. In this case, the additive component is decomposed and bonded to the polyacrylic acid. Thereby, the degree of crosslinking of the second plasma polymer film 82 or the second plasma polymer film 82 is increased. As a result, the adhesion promoting water can be improved. The treated crucible 9 is folded back by the guide roller 17. 'There is a reciprocation in the fourth processing space 94a, and the fourth processing unit 94 performs the processing twice. The processed film 9 that has been reciprocated in the fourth processing space 94&amp; is transported along with the third roller 13 and is self-supporting. 1〇Remove. As shown in Fig. 4, the surface treatment is performed by the film surface treatment device. The treatment film 9 is adhered to the PVA film 7 via the PVA-based adhesive 8 to form the polarizing plate PF». Since the adhesion promoting film 8 is formed on the surface of the film to be processed 9, the film to be treated 9 and the pVA adhesive can be improved. In addition, since the second plasma polymerization film 82 of the adhesion promoting film 80 is hydrophobized or highly crosslinked, the water resistance is high. Therefore, the durability of the polarizing plate can be improved. (1) The plasma polymerization film 81 has a high purity due to the polyacrylic acid, so that the affinity with the TAC can be remarkably exhibited. Therefore, the adhesion between the treated crucible 9 and the adhesion promoting film 80 can be ensured. In the following embodiments, the configuration of the present invention is the same as the above-described embodiment, and the same reference numerals will be given to the drawings, and the description thereof will be omitted. Fig. 5 shows the present invention. In the film surface treatment apparatus 1A of the second embodiment, the third gas supply unit 23 of the third processing unit 93 includes the supply unit 23a of the acrylic acid and the supply unit 23b of the additive component. The fourth processing unit I62457.doc -28 · 201241490 94 Only the discharge generating gas (N2) is supplied to the fourth gas supply unit 24. The acrylic acid supply unit 23a is the same as the third gas supply unit 23 of the first embodiment (Fig. 1), and the liquid acrylic acid is supplied to the carrier gas (n2). The addition component of the component supply portion 23b contains a crosslinking accelerator. Examples of the crosslinking accelerator include a diallyl compound, a diamine compound, a glycidyl compound, a hydroxy compound, etc. As the diallyl compound, Examples of the dilutepropylamine, diisopropyl propyl maleate, and allyl methacrylate. Examples of the diamine compound include ethylenediamine. Examples of the glycidyl compound include allyl glycidyl ether and Polyacrylic acid glycidol and the like. Examples of the hydroxy compound include hydroxyethyl acrylate and methacrylic acid by ethyl ester. The additive component supply unit 23b includes a vaporizer. The above-mentioned additive component is vaporized in the carrier gas by the vaporizer. Gasification can be either extrusion or foaming. As the carrier gas, nitrogen (N2) is used. The third gas supply unit 23 mixes the vaporized additive component into the vaporized acrylic acid. Alternatively, the liquid addition component may be mixed in the liquid acrylic acid, and the mixture may be vaporized in the carrier gas. Thereby, the third gas g3 is generated. The third gas g3 contains a vapor of acrylic acid, a vapor of the above-mentioned additive component, and a carrier gas (NO. The weight of the acrylic acid and the additive component in the third gas g3 is preferably (acrylic acid): (additional component) = 99: 1~70:30. The set temperature of the gas path 23c and the third nozzle 33 is preferably higher than the condensation temperature of the acrylic acid and the added component, thereby preventing the acrylic acid and the added component at 162457.doc -29 - 201241490 Condensation in the gas path 23c or the third nozzle 33 before ejecting from the third nozzle 23. The set temperature of the rolls 11'12, 13 is preferably lower than the condensation temperature of the acrylic acid and the additive component. The film surface treatment apparatus 1A of the second embodiment is preferably formed on the surface of the film to be processed 9 in the first treatment unit 91 as shown in Fig. 6 (the magical figure). Condensation layer 83 (first processing step), and then, as shown in FIG. 6(b), the first condensation layer 83 is electropolymerized in the second treatment portion to form the second electropolymerization film 81 (second treatment) Step 3) Thereafter, in the third processing unit 93, the third gas g3 is supplied from the third nozzle 33 In the third processing space 93a (third processing step), the vaporized component (acrylic acid + additive component) in the third gas g3 is condensed as shown in Fig. 6 (4), and adheres to the film to be processed 9, The second condensation layer 86 is further formed on the first polymerization film 81. The second condensation layer 86 contains a mixed liquid of an acrylic monomer and an additive component (crosslinking accelerator). Then, in the fourth treatment portion 94, the fourth gas g4 is used. The second nozzle 3 is discharged to the fourth processing space 94a and plasmad, and the second condensed layer (9) is irradiated with nitrogen (the fourth processing step). Thereby, the first electropolymerized film is polymerized to a high height. Further, as shown in Fig. 6 (4), it is considered that the acrylic acid in the second condensation layer % is electro-destructively polymerized, so that the second electropolymerization (IV) containing the polyacrylic acid is laminated on the If-bonding film 81. ^ (4) to carry out the crosslinking of the polyacrylic acid of the second electropolymerization film 85. Further, it is considered that * the reactivity (8) of the poly(tetra) acid to the adhesive 8 is promoted by the cross-linking (4) dragon. 162457.doc -30- 201241490 By this, the formation of the adhesion promoting film 8〇β including the two-layered polymer films 81 and 85 is caused by the adhesion promoting film 80. The second plasma polymerization film 85 of the surface layer has a crosslinked structure. Therefore, the water resistance of the adhesion promoting film 80 can be improved. Further, the adhesion strength of the adhesion promoting film 80 and the adhesive 8 can be improved by the above-mentioned additive component. As a result, the durability of the polarizing plate can be improved. The present invention is not limited to the above embodiment, and various modifications can be made without departing from the scope of the invention. For example, oxygen, hydrogen, saturated hydrocarbon gas, or The saturated hydrocarbon gas is added as a component of the third gas g3. The crosslinking accelerator may be added as a component of the fourth gas g4. When the additive component is added to the third gas g3, the polymerizable monomer and the additive component of the third gas g3 may be ejected from mutually different nozzles. When the additive component is added to the fourth gas g4, the discharge generating gas and the additive component of the fourth gas g4 may be ejected from mutually different nozzles. Instead of acrylic acid, methacrylic acid 'itaconic acid, maleic acid or the like can be used as the polymerizable monomer of the i-th gas gl and the third gas g3. It is also possible to use Μ and Μ rare "generation (4) as a carrier gas. It is also possible to use a rare gas instead of N2 as a discharge generating gas. It is also possible to perform the second processing step and the third step simultaneously. The first gas may be directly introduced into the second processing space 92a from the first nozzle 31 to be plasma-formed. The planting gas in the first gas gl may also serve as the first body. The hole is recorded as the first discharge generation. Gas 162457.doc -31 - 201241490 It is also possible to simultaneously perform the processing steps 4 and 4 of the flute 3, and the third gas g3 may be directly introduced into the fourth processing space 94a and plasmad from the third. In the embodiment (Fig. 1), the first gas supply unit 21 and the third gas supply unit 23 may be combined with each other. In the second embodiment (Fig.), the first gas supply unit 21 and the acrylic acid supply unit 23a may include a common acrylic acid supply unit. In the first embodiment (Fig. U, the first gas supply unit) The carrier gas source of 21, the second gas supply unit 22, the carrier gas source of the third gas supply unit 23, and the discharge gas supply unit 24a of the fourth gas supply unit 24 may include a common nitrogen supply source. In the form (FIG. 5), the carrier gas source of the i-th gas supply unit 21, the second gas supply unit 22, and the third gas supply unit 23 The carrier gas source and the fourth gas supply unit 24 may include a common nitrogen supply source. The main component of the film to be processed 9 is not limited to TAC, and may be polypropylene (PP), polyethylene (PE), or cycloolefin. Polymer (c〇p), cyclic olefin copolymer (coc), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyimine (PI), etc. The 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] Hereinafter, examples will be described, but the present invention is not limited thereto. 162457.doc -32· 201241490 The size of the Μ 置 置 置 较 较 较 较 较 较 较 较 较 较 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 衣 12 12 12 12 12 12 '12, diameter of 丨3 · · 320 mm Spray width of nozzles 31 to 34: 300 mm circumference of circular direction of shielding members 41, 43: 275 mm Thickness of first processing space 9U: 5_(in the entire area) Fixed) Thickness of the narrowest portion of the second processing space 92a: 1 thickness of the third processing space 93a: 5 mm over the entire area (Fixed) Thickness of the narrowest portion of the fourth processing space 94a: 1 mm A TAC film was used as the film to be processed 9. The width of the TAC film 9 was 325 _. The transport speed of the TAC film 9 was set to 3 〇 m/min. The temperature of 11 to 13 and even the temperature of TAC 貘 9 is set to 4 〇 t &gt; c β power supply to the central roller electrode 12 is 30 丨 5 w (high frequency conversion of 450 V, 6.7 A DC). One half of the power (15〇7 5 W) is consumed by the plasma discharge between the roller electrodes 11, 12, and the remaining half (1507.5 W) is consumed by the plasma discharge roller electrode 11 between the roller electrodes 12, 13. The applied voltage of 12 and the applied voltage between the roller electrodes 12 and 13 were 18.1 kV. [First Processing Step] The first gas gl is brought into contact with the TAC film 9 in the first processing unit 91. Acrylic acid is used as the polymerizable monomer of the first gas gl, and nitrogen (N2) is used as the carrier gas. • 33-162457.doc 201241490 The temperature of the vaporizer of the first gas supply unit 21 is set to i4 (TC. The flow rate of the carrier gas (N2) of gl, even the flow rate of the first gas gi (acrylic acid + N〇 is set to 4 〇Slme, the flow rate of the acrylic acid in the first gas gl is 7 5 g/min. The temperature of the first nozzle 31 is even The discharge temperature of the gas gl is set to 75 ° C. [Second treatment step] Next, in the second treatment portion 92, the second gas g2 is plasma-formed and brought into contact with the TAC film 9. Nitrogen (N2) is used. The flow rate of the second gas g2 is 20 slm. The temperature of the second nozzle 32 or even the temperature of the second gas g2 is set to 4 〇. [Third processing step] Next, in the third processing unit 93, the third gas g3 is brought into contact with the TAC film 9. Acrylic acid is used as the polymerizable monomer of the third gas g3, and nitrogen (n2) is used as the carrier gas. The temperature of the vaporizer of the third gas supply unit 23 is set to i4. 〇«c. The flow rate of the carrier gas (N2) of the third gas g3, and even the flow rate of the third gas g3 (acrylic acid + N2) is set to 4 〇 sim. The acrylic acid in the third gas g3 The amount of the additive component in the third gas g3 is 〇. The temperature of the third nozzle 33 or even the discharge temperature of the third gas g3 is set to 75 〇C 〇 [fourth processing step] 162457.doc - 34-201241490 Next, 'the fourth gas g4 is plasma-formed and brought into contact with the TAC film 9 in the fourth processing unit 94. Nitrogen is used (NO is used as the discharge generating gas of the fourth gas g4, and 〇2 is used as an additive component. The flow rate of N2 in the fourth gas g4 is 20 slm. The flow rate of 〇2 in the fourth gas g4 is 20 seem. The concentration of 02 in the fourth gas g4 is 1000 ppm. The temperature of the fourth nozzle 34 is even 4 The temperature of the gas g4 is set to 40° C. The adhesive 8 is applied to the surface to be treated of the TAC film 9 after the surface treatment, and is bonded to the PVA film 7. As the adhesive 8, the (A) is used. An aqueous solution of a PVA 5 wt% aqueous solution having a polymerization degree of 5 Å and (B) a bismuth cellulose sodium 2 wt% aqueous solution. The mixing ratio of (A) and (B) is (A): (B) =2〇: ! The drying condition of the subsequent agent was set to 80 ° C for 5 minutes. On the opposite side of the PVA film 7, the TAC film which was subjected to the experience treatment was bonded by the same adhesive as described above. Thus, a plurality of polarized plate samples having a three-layer structure were prepared. The width of the polarizing plate sample was set to 25 mm. [Initial bonding strength] After the adhesive 8 was hardened, the sample was measured for the polarizing plate sample which was not subjected to the following wet heat treatment. The bonding strength of the TAC film 9 and the PVA film 7 is referred to (referred to as "initial bonding strength"). The measurement method was based on the β method of the floating roll method (JIS Κ 6854), and the average value of the five measured values was 9.6 N/25 mm. [Endurance bonding strength] The remaining polarizing plate samples were subjected to a damp heat treatment after the adhesive 8 was hardened. The inside of the wet heat treatment tank was set to a high temperature of 162457.doc -35 to 201241490 in a humidity environment of 60 ° C and 96% RH, and the polarizing plate sample was left in the wet heat treatment tank for 丨 hours. Thereafter, the polarizing plate sample was taken out from the wet heat treatment tank and cooled at room temperature for 15 minutes. Then, the treated butane AC film 9 was measured by the floating roll method (JIS Κ 6854) having the same initial strength as described above. The subsequent strength of the eight film 7 (referred to as "durable bonding strength") ^ was that the average of the five measured values was 91 N/25 mm. Therefore, it was confirmed that the strength was maintained even when exposed to a hot and humid environment. Further, in the fourth processing step, the concentration of ruthenium 2 in the fourth gas g4 is set to a value different from the above, and the TAC film is treated. The durability of the sample of the polarizing plate using the TAC film is measured. If the cerium concentration is less than 500 ppm, the durability and the subsequent strength are lowered, and the desired effect cannot be obtained. If the concentration of 〇2 exceeds 3000 ppm, not only the durability will not decrease, but also the initial strength will decrease. It is considered that if the concentration of 〇2 exceeds 3 〇〇〇 ppm, the polymerization reaction of acrylic acid itself is hindered. [Example 2] In the second processing step, the addition component in the fourth gas g4 was set to H2', and the flow rate thereof was 40 sccm. The concentration of η in the fourth gas g4 is 2000 ρρπ^, and the other processing conditions are the same as in the embodiment (1). The procedure for preparing the polarizing plate sample after the surface treatment, and the measurement procedure for the initial adhesion strength and the durability bonding strength were the same as in the example. In the initial stage, the strength was 9.8 N/25 mm, and the durability was 7 2 Ν/25. Therefore, it was confirmed that the strength was maintained even when exposed to a hot and humid environment. I62457.doc -36-201241490 [Embodiment 3] In the third embodiment, in the fourth step, the additive component in the fourth gas g4 is set to H2', and the flow rate is set to 丨 von 10〇. Sccm. The concentration of ruthenium 2 in the fourth gas g4 was 5000 ppm. The processing conditions of the other sounds were set to be the same as in the first embodiment. After the surface treatment, the preparation procedure of the partial sputum sample + A 箱 box nine plate sample, and the initial splicing strength and the measurement procedure for the long-term strength are the same as those of the first embodiment. The initial strength was 9.8 N/25 mrn and the durability was 8.8 N/25. This confirmed that the strength was maintained even when exposed to a hot and humid environment. [Embodiment 4] In the fourth processing step, the addition component in the fourth gas is set to h2', and the flow rate thereof is set to 16 〇 scem. The concentration of the fourth gas in § 4 is the surface. The other processing conditions (4) are the same as the implementation. The preparation of the surface-treated polarizing plate sample (4), and the initial measurement procedure of the subsequent strength and the long-lasting strength were the same as in the first embodiment. The initial strength is 9.8 N/25 mm and the durability is 93 N/25 _. Therefore, it was confirmed that the bonding strength was maintained even when exposed to a hot and humid environment. According to the examples 2 to 4, when the concentration of ruthenium in the fourth gas g4 is in the range of 2 〇〇 PPm to 8000 ppm, the endurance strength increases as the h concentration increases. Further, in the fourth processing step, the polarizing plate sample which was treated by setting the H 2 concentration in the fourth gas to a value different from that of the above Examples 2 to 3 was measured for the durability of the adhesive, and it was found that the concentration was low. At 5 〇〇 ppm, the durability is lowered and the desired effect is not obtained. When the H2 concentration is in the range of 8000 ppm or more, even if the % concentration is changed, the durability is 162457.doc •37- 201241490 and the strength is the same as that at 8000 ppm. Therefore, the effect of improving the durability is saturated. [Example 5] In the fifth processing step, the additive component in the fourth gas g4 was methane, and the flow rate was 16 〇 sccm. The concentration of decane in the fourth gas 0 was 8000. The processing conditions other than this are the same as in the first embodiment. The procedure for preparing the polarizing plate sample after the surface treatment and the measurement procedure for the initial adhesion strength and the durability bonding strength were the same as in the first embodiment. The initial bonding strength is 9·4 N/25 mm and the durable bonding strength is 9 〇 N/25 mm. Therefore, it was confirmed that the adhesion strength was maintained even when exposed to a moist heat environment. [Example 6] In the fourth processing step, the addition component in the fourth gas g4 was acetylene, and the flow rate was 16 〇 sccm. B of the fourth gas 0 has a fast wave of 80 〇〇 ppm. The processing conditions other than this are the same as those in the embodiment. The procedure for preparing the polarized plate sample after the surface treatment and the measurement procedure of the initial adhesion strength and the durability bonding strength were the same as those in the example i. The initial strength is 10.8 N/25 mm, and the strength is i〇 i Mm mm. Therefore, it was confirmed that the adhesion strength was maintained even when exposed to a moist heat environment. Table 1 shows the processing conditions and measurement results of Examples i to 6. 162457.doc -38 - 201241490 [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Apparatus Figure 1 Figure 1 Figure 1 Figure 1 Figure 1 Figure 1 Processed film TAC TAC TAC TAC TAC TAC film conveying speed m/min 30 30 30 30 30 30 Pro temperature deg 40 40 40 40 40 40 1st processing step 1st gas N2 slm 40 40 40 40 40 40 AA g/min 7.5 7.5 7.5 7.5 7.5 7.5 Gasifier Temperature deg 140 140 140 140 140 140 1st nozzle temperature deg 75 75 75 75 75 75 2nd processing step 2nd gas N2 slm 20 20 20 20 20 20 2nd nozzle temperature deg 40 40 40 40 40 40 3rd process step 3 gas N2 slm 40 40 40 40 40 40 AA g/min 7.5 7.5 7.5 7.5 7.5 7.5 Gasifier temperature deg 140 .140 140 140 140 140 3rd nozzle temperature deg 75 75 75 75 75 75 4th processing step 4th gas N2 slm 20 20 20 20 20 20 Adding component Oxygen Hydrogen Hydrogen Methane Acetylene flow seek 20 20 100 160 160 160 Concentration ppm 1000 2000 5000 8000 8000 8000 4th nozzle temperature deg 40 40 40 40 40 40 Plasma condition supply DC voltage V 450 450 450 450 450 450 Supply DC current A 6.7 6.7 6.7 6.7 6.7 6.7 Power supply W 3015 3015 3015 3015 3015 3015 Voltage applied between rolls kV 18.1 18.1 18.1 18.1 18.1 18.1 Evaluation of initial strength N/25mm 9.6 9.8 9.8 9.8 9.4 10.8 Durable strength N/25mm 9.1 7.2 8.8 9.3 9.0 10.1 [ [Example 7] In Example 7, the apparatus 1A of the second embodiment (Fig. 5) was used, and in the third processing step, an additive component was added to the third gas g3. Methyl propyl 162457.doc -39- 201241490 allyl acrylate was used as an additive component. The flow rate of the carrier gas (N2) of the third gas g3, even the flow rate of the entire third gas g3 is 40 slm, the flow rate of the acrylic acid in the third gas g3 is 7·5 g/min, and the thiol acrylic acid in the third gas g3 The flow rate of acrylonitrile was 〇.375 g/min. In the fourth processing step, the fourth gas g4 is set to be only N2 20 Slm, and the amount of the additive component in the fourth gas g4 is 〇 ^, and the other processing conditions are the same as those in the embodiment. The procedure for preparing the polarizing plate sample after the surface treatment and the measurement procedure for the initial adhesion strength and the durability bonding strength were the same as in the first embodiment. The initial adhesion strength is 10.2 N/25 mm, and the durability is then 9.8 N/25 mm. Therefore, it was confirmed that the adhesion strength was maintained even when exposed to a hot and humid environment. [Example 8] In Example 8, the apparatus 1A of the second embodiment (Fig. 5) was used, and in the third processing step, diallylamine was used as the third gas "addition of the third gas S3" The flow rate of the carrier gas (N2), even the flow rate of the entire third gas g3 is 40 Slm, the flow rate of the acrylic acid in the third gas g3 is 75 g/min, and the flow rate of the ethylenediamine in the third gas S3 is 〇· 375 g/min. Other processing conditions were the same as in Example 5. The procedure for preparing the polarizing plate sample after the surface treatment, and the measurement procedure for the initial adhesion strength and the durability bonding strength were the same as in Example 1. The strength is 10"N/25 mm, and the durable bonding strength is 9.6 N/25 mme. Therefore, it can be confirmed that the bonding strength can be maintained even when exposed to a hot and humid environment. Table 2 shows the processing conditions and measurement results of Examples 7 and 8. 162457.doc 201241490 [Table 2] --_ Example 7 Example 8 Apparatus Fig. 2 Fig. 2 Processed film TAC TAC Film transport speed m/min 30 30 Roller temperature deg 40 40 First gas n2 slm 40 40 First treatment Step AA g/min 7.5 7.5 Gasifier temperature deg 140 140 First nozzle temperature deg 75 75 Second processing step 2nd gas N2 slm 20 20 2nd nozzle temperature deg 40 40 n2 slm 40 40 3rd gas AA g/min 7.5 7.5 Third treatment step Addition of methacrylic acid propylene diacetate diallylamine concentration g / min 0.375 0.375 gasifier temperature deg 140 140 third nozzle temperature deg 75 75 fourth processing step fourth gas N2 slm 20 20 4th nozzle temperature deg 40 40 Supply DC voltage V 450 450 Plasma condition supply DC current A 6.7 6.7 Supply power W 3015 3015 Voltage applied between rolls kV 18.1 18.1 Evaluation initial strength N/25mm 10.2 10.1 Durable strength N/ 25 mm 9.8 9.6 [Comparative Example 1] In Comparative Example 1, no additive component was added to any of the third gas g3 in the third treatment step and the fourth gas g4 in the fourth treatment step. The processing conditions other than this are the same as in the first embodiment. Therefore, the processing conditions of the third processing 162457.doc -41 · 201241490 are the same as those of the first processing step, and the processing conditions of the fourth processing step are the same as those of the second processing step. The procedure for preparing the surface-treated polarizing plate sample and the procedure for determining the initial adhesion strength and the durability bonding strength were the same as in the first embodiment. The initial bonding strength is 10.3 N/25 mm and the durable bonding strength is 6.2 N/25 mm. Therefore, if exposed to a hot and humid environment, the adhesion deteriorates. [Comparative Example 2] In Comparative Example 2, 16 〇 3_hydrogen _ was added to the discharge generating gas (N2 20 slm) of the second gas in the second treatment step. In the third gas "and the fourth fluorine body g4, no additional components were added. The other processing conditions were the same as in the first embodiment. The preparation procedure of the polarizing plate sample after the surface treatment, and the initial bonding strength and durability were followed. The strength measurement procedure was the same as in Example 1. Initially 5.5 Ν/25. [Comparative Example 3] The subsequent strength was 10.3 Ν / 2 5 mm, and the durability was followed by a strong yield of mm. Therefore, if exposed to a hot and humid environment, Further, inferior to the third comparative example, the second gas in the second processing step is added with 16 〇 氢 hydrogen (10) to the discharge generating gas (N 2 20 slm), and is in the fourth gas g4 in the *processing step. 16 〇 读 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The same initial strength is 1 () 3 Durable strength is 5 · 9 N / 25 mme Therefore, when exposed to hot and humid environment, the adhesion deteriorates ^ "'... 162457.doc • 42- 201241490 Summary of the comparison in Table 3 Processing conditions and measurement results of Examples 1 to 3. According to the above examples and comparative examples, it was confirmed that the third gas g2 in the third processing step is not added to the first gas gl in the first processing step and the second gas g2 in the second processing step. Or, the addition component is added to the fourth gas g2 in the fourth processing step, and the adhesion durability of the TAC film 9 can be improved. [Table 3] —-~— _ Comparative Example 1 Comparative Example 2 Comparative Example 3 Film to be treated TAC TAC TAC Film transport speed m/min 30 30 30 Roll temperature deg 40 40 40 First gas n2 slm 40 40 40 First treatment Step AA g/min 7.5 7.5 7.5 Gasifier temperature deg 140 140 140 1st nozzle temperature deg 75 75 75 n2 slm 20 20 20 2nd processing step 2nd gas addition component - Hydrogen and hydrogen flow seek - 160 160 2nd nozzle temperature Deg 40 40 40 3rd gas n2 slm 40 40 40 3rd processing step AA g/min 7.5 7.5 7.5 Gasifier temperature deg 140 140 140 3rd nozzle temperature deg 75 75 75 n2 slm 20 20 20 4th processing step 4 Gas addition component - - Hydrogen flow seek - - 160 4th nozzle temperature deg 40 40 40 Supply DC voltage V 450 450 450 Plasma condition supply DC current A 6.7 6.7 6.7 Supply power W 3015 3015 3015 Voltage applied between rolls kV 18.1 18.1 18.1 Evaluation initial strength N/25 mm 10.3 10.3 10.3 Long-lasting strength N/25mm 6.2 5.5 5.9 162457.doc •43· 201241490 [Industrial Applicability] The present invention can be applied to, for example, a flat panel display (FpD, Fiat) p Disp Lay) The manufacture of polarizing plates. Ae [Simplified illustration of the drawings] Fig. 1 is a side view showing the processing apparatus of the present invention in an illustrative manner. ^(4) Film surface Fig. 2 is a perspective view of a main part of the above film surface treatment apparatus. Fig. 3 is a cross-sectional view showing the process of the surface of the surface cow 4 in the first embodiment, (4) is the first treatment = the cross-sectional view of the treatment film, (b) the treatment after the treatment, and (4) the third treatment step. FIG. 4 is a cross-sectional view showing a portion of the polarizing plate. FIG. 5 is a cross-sectional view showing a portion of the polarizing plate. FIG. 5 is a cross-sectional view showing the present invention in an illustrative manner. Side view of the second real processing apparatus. <Film surface step == surface treatment step of the second embodiment, (4) is a cross-sectional view of the first processed film, and is a photograph of the processed film after the second processing step. (4) A cross-sectional view of the film to be processed after the third processing step '(4) is a cross-sectional view of the film to be processed after the fourth processing step. [Description of main components] 1 Film surface treatment apparatus 7 PVA film 8 PVA adhesive 9 Treatment film 10 Support portion (transport mechanism) 162457.doc 201241490 11 First roller 12 Second roller 13 Third roller 16 Front guide roller. 17 Rear guide roller 21 First gas supply unit &quot; 21c First gas supply line 22 2 gas supply unit 23 third gas supply unit 23a acrylic Feeding unit (polymerizable monomer supply unit) 23b Adding component supply unit 23c Third gas supply line 24 Fourth gas supply unit 24a Discharge gas supply unit 24b Adding component supply unit 31 First nozzle 32 Second nozzle 33 Third nozzle ' 34 4th nozzle-. 41, 43 shielding member 51' 52 blocking member 80 next promoting film 81 first plasma polymerization film 82 second plasma polymerization film 162457.doc -45- 201241490 83 first condensation layer 84 second Condensation layer 85 Second plasma polymerization film 86 Second condensation layer 91 First processing unit 91a First processing space 92 Second processing unit 92a Second processing space (gap between the first and second rolls) 93 Third processing unit 93a third processing space 94 fourth processing unit 94a fourth processing space (gap between the second and third rolls) gl first gas g2 second gas g3 third gas g4 fourth gas PF polarizing plate 162457.doc · 46 ·

Claims (1)

201241490 VII. Patent application scope: h Surface treatment method, characterized in that it is processed on the surface of the resin-made film; and includes the following steps: The first processing step is to make the vaporized polymerization The second gas of the monomer is contacted with the film to be treated; and the second processing step is to electrically polymerize the second gas containing the discharge generating gas after the second processing step or simultaneously with the first step a third processing step of contacting the third gas containing the vaporized polymerizable monomer with the film to be treated after the second processing step; and a fourth processing step After the third processing step or simultaneously with the third processing step, 'the fourth gas containing the discharge generating gas is plasma-treated and brought into contact with the treated film; and the third gas or the fourth gas Further, the additive component is contained, and the additive component is oxygen, hydrogen, a saturated hydrocarbon gas, an unsaturated hydrocarbon gas, or a crosslinking accelerator. 2. The film surface treatment method according to claim 1, wherein the fourth gas contains 500 ppm to 3000 ppm of oxygen as the additive component. 3. The method of treating a surface of a film according to claim 1, wherein the first gas contains 500 ppm to 10,000 ppm of hydrogen as the additive component. 4. The film surface treatment method according to claim 1, wherein the fourth gas contains methane, ethylene or acetylene as the additive component. 5. The method of treating a surface of a film according to claim 1, wherein the third gas contains a diallyl promoter comprising a diallyl compound, a diamine compound, a glycidyl compound, and 162457.doc 201241490 as the above-mentioned addition or hydroxy compound. The gasification gas occlusion method, wherein the first polymerizable monomer is a polymerizable monomer of the film surface treatment method 1 according to any one of claims 1 to 5, and the third gas is characterized in that It is a resin-made film surface treatment apparatus that processes the surface of the crucible, and includes: a support unit that supports the film to be treated; &gt; a first treatment unit that performs gasification a process in which the first gas of the polymerizable monomer contacts the film to be processed; and a second processing unit that performs a process of slurrying the second gas 1 containing the discharge generating gas and bringing it into contact with the film to be processed; and a third processing unit; a process of bringing the gas containing the vaporized polymerizable monomer into contact with the film to be treated; and a fourth processing unit for slurrying the first gas containing the discharge generating gas and causing Contacting the treated film to be processed; Transfer the pound; and Body, or cross-linking accelerator. Detach back to rt, taste added, saturated hydrocarbon gas, or unsaturated hydrocarbon gas The first and second arranging devices arranged in parallel with each other, wherein the support portion includes phase 2 and third rolls, and the processed film is wound around I62457.doc 201241490 on the second roll, and by the rolls Rotating and transporting the first roller and the third roller in the order of the first roller and the third roller; the first processing unit includes a first nozzle of the first gas; and discharging the second processing unit toward the circumferential surface of the first newspaper includes a second nozzle in which the second gas nozzle is out of a gap between the first and the second newspaper, wherein the first and second members are configured to generate a discharge __ counter electrode in the vicinity of the atmospheric pressure; and the third processing The portion includes a third nozzle that faces the circumferential surface of the second roller and the third gas; and the fourth processing portion includes a portion that ejects the fourth gas to a gap between the second roller and the third roller In the four nozzles, the second and third rolls are formed to generate one of the discharge electrodes in the vicinity of the atmospheric pressure. 162457.doc