KR101328352B1 - Method and device for treating film surface and process for producing polarizer - Google Patents

Abstract

This invention arrange | positions the hard-adhesive resin film 11 which should be adhere | attached with the easily-adhesive resin film 12 in the process space 22 near atmospheric pressure. The process gas supply system 3 supplies the process gas containing the vapor of acrylic acid (polymerizable monomer) to the processing space 22. In the plasma processing unit 2, the process gas is converted into plasma to contact the hard-adhesive resin film 11. The supply flow rate of the process gas is set so that the oxygen concentration in the processing space 22 is 3000 ppm or less. This improves the adhesiveness of the hard-adhesive resin film and enables high speed processing.

Description

The surface treatment method and apparatus of a film, and the manufacturing method of a polarizing plate {METHOD AND DEVICE FOR TREATING FILM SURFACE AND PROCESS FOR PRODUCING POLARIZER}

The present invention relates to a method and an apparatus for treating the surface of a resin film, and a method for producing a polarizing plate, and in particular, a surface treatment performed on the hard-adhesive resin film when the hard-adhesive resin film and the easily-adhesive resin film are adhered. Method and the like.

The polarizing plate is inserted in the liquid crystal display device. The polarizing plate is a triacetate cellulose (hereinafter appropriately referred to as "TAC") in a polarizing film composed of a resin film (hereinafter referred to as "PVA film" suitably) containing polyvinyl alcohol (hereinafter referred to as "PVA" suitably) as a main component. The protective film which consists of a resin film (henceforth "TAC film" suitably) containing "" as a main component is adhere | attached using an adhesive agent. As the adhesive, an aqueous adhesive such as polyvinyl alcohol or polyether is used. Although PVA film has favorable adhesiveness with these adhesive agents, TAC film has poor adhesiveness. Therefore, generally, TAC film is immersed in aqueous alkali solution, such as sodium hydroxide and potassium hydroxide, and saponification prior to adhesion | attachment. Thereby, the surface of a TAC film becomes hydrophilic by hydrolysis, and an adhesive becomes easy to adhere to a TAC film.

As a surface treatment method other than a saponification process, for example, in patent document 1, after plasma-treating the surface of a to-be-processed object with the mixed gas of helium and argon under atmospheric pressure, acrylic acid is sprayed with a spray gun and acrylic acid is graft-polymerized, A method of modifying the surface of a workpiece is proposed.

In patent document 2, the method of mixing inert gas, such as nitrogen and argon, and organic thin film formation gas, plasma-discharging this mixed gas under atmospheric pressure, and supplying to a to-be-processed object, and improving the hydrophilicity of a to-be-processed object are proposed. .

Japanese Patent No. 3292924 Japanese Patent Laid-Open No. 2006-299000

The inventors have found that the adhesiveness varies depending on the concentration of oxygen in the plasma when performing a surface treatment for improving the adhesion of the hard-adhesive resin film using the plasma processing apparatus. If the oxygen concentration exceeds a certain amount, sufficient adhesive strength cannot be obtained (see Example 1 below).

The film processing method which concerns on this invention was made based on the said knowledge, As a method of processing the surface of the hard adhesive resin film which should be adhere | attached with an easily adhesive resin film,

The polymerizable monomer is activated by plasma and reacted with the hard-adhesive resin film disposed in the processing space near atmospheric pressure,

The oxygen concentration (volume concentration) in the processing space is set to be 0 or more and 3000 ppm or less.

Moreover, the plasma surface treatment apparatus which concerns on this invention is an apparatus which processes the surface of the hard adhesive resin film which should be adhere | attached with an easily adhesive resin film,

And a plasma processing portion for activating the polymerizable monomer by plasma to contact the hard-adhesive resin film disposed in the processing space near atmospheric pressure.

The oxygen concentration in the processing space is characterized by being 0 or more and 3000 ppm or less.

Activation of the polymerizable monomer includes cleavage, polymerization and decomposition of the polymerizable monomer. The activated polymerizable monomer reacts with the hard-adhesive resin film. For example, in the surface of a hard-adhesive resin film, the bond of CC, CO, CH, etc. is cut | disconnected by contact with plasma gas or irradiation of plasma light, and it is thought that the polymer of a polymerizable monomer graft-polymerizes in this bond | disconnection cutting part. . Alternatively, it is considered that the functional � Thereby, it is thought that the adhesion promoting layer is formed on the surface of the hard-adhesive resin film. By setting the oxygen concentration in the treatment space to 3000 ppm or less, it is possible to prevent the reaction such as the activation of the polymerizable monomer, the bonding with the bond break, and the like to be inhibited, and the adhesion promoting layer is reliably provided on the surface of the hard-adhesive resin film. Can be formed. Thereby, the adhesiveness of a hard-adhesive resin film can be improved reliably.

In the film processing method, a discharge is generated in the processing space, a process gas containing a vapor of the polymerizable monomer is supplied to the processing space, and a supply flow rate of the process gas is equal to or greater than zero in the processing space. It is preferable to set so that it may be 3000 ppm or less.

In the film processing apparatus, the plasma processing unit further comprises a process gas supply system having a pair of electrodes for generating a discharge in the processing space, and supplying a process gas containing the vapor of the polymerizable monomer to the processing space; It is preferable that the supply flow rate of the process gas of the said process gas supply system is set so that the oxygen concentration in the said process space may be 0 or more and 3000 ppm or less.

By supplying process gas to a process space, gas, such as air in a process space, can be expelled and replaced by process gas. By adjusting the supply flow rate of the process gas, the amount of oxygen in the processing space can be adjusted. In this embodiment, the processing space becomes a discharge space. The hard-adhesive resin film to be treated is disposed in the discharge space and directly contacts the plasma in the discharge space.

The oxygen concentration in the processing space is preferably 2000 ppm or less, more preferably 1000 ppm or less.

The supply flow rate of the process gas is preferably set such that the oxygen concentration in the processing space is preferably 2000 ppm or less, more preferably 1000 ppm or less.

Thereby, the adhesiveness of a hard-adhesive resin film can be improved more reliably.

In the film processing method, it is preferable that the hard-adhesive resin film is moved relative to the processing space, and the speed of the relative movement is set to 10 m / min or more.

In the said film processing apparatus, it is further provided with the movement means which relatively moves the said hard-adhesive resin film with respect to the said processing space, It is preferable that the speed of the said relative movement by the said movement means is 10 m / min or more.

When the hard-adhesive resin film is moved relatively, atmospheric gas, such as air, is easy to wind up in a process space with a hard-adhesive resin film. When the relative movement speed of the hard-adhesive resin film is made large, the winding flow volume of atmospheric gas increases. Thus, it leads to an increase in the oxygen concentration in the processing space. Therefore, the supply flow volume of a process gas is made large. Thereby, the wound atmospheric gas can be expelled from the processing space, and the oxygen concentration in the processing space can be made the desired size. Thereby, the relative movement speed of the hard-adhesive resin film can be enlarged, and high speed processing can be performed, ensuring the favorable adhesiveness of a hard-adhesive resin film.

The relative moving speed of the hard-adhesive resin film may be 20 m / min or more, or 30 m / min or more. By increasing the flow rate of the process gas, the oxygen concentration in the discharge space can be 3000 ppm or less, preferably 2000 ppm or less, and more preferably 1000 ppm or less by increasing the relative movement speed. The upper limit of the relative movement speed of the hard-adhesive resin film can be suitably set according to the performance of a moving means, the supply capability of a process gas, etc. For example, as for the upper limit of the relative movement speed of a hard-adhesive resin film, about 60 m / min is preferable.

It is preferable that the said process gas does not contain oxygen gas substantially.

By substituting gas, such as air in a process space, with process gas, the oxygen concentration in a process space can be reliably reduced. Substantially no oxygen gas includes a case where a small amount of oxygen is contained so as not to affect the surface treatment other than the case where the oxygen content of the process gas is zero. Specifically, the oxygen concentration (volume concentration) of the process gas that does not substantially contain oxygen gas is preferably 0 or more and 1 ppm or less, more preferably 0 or more and 0.1 ppm or less, still more preferably 0 or more and 0.01 ppm. It is as follows.

The processing space near the atmospheric pressure may be in communication with the atmosphere or may be open to the atmosphere.

Here, the vicinity of atmospheric pressure refers to the range of 1.013 × 10 ⁴ to 50.663 × 10 ⁴ Pa, and considering the ease of pressure adjustment and the simplification of device configuration, 1.333 × 10 ⁴ to 10.664 × 10 ⁴ Pa is preferable, and 9.331 × 10 ⁴ to 10.397 × 10 ⁴ Pa is more preferable.

In the plasma surface treatment apparatus according to the present invention, the pair of electrodes are arranged in a cylindrical shape with their axes directed in the axial direction, respectively, arranged in parallel to the arrangement direction orthogonal to the axial direction, and the narrowest point between these electrodes and their The periphery becomes the processing space, and is further provided on both sides of the orthogonal direction perpendicular to the axial direction and the arrangement direction with the processing space therebetween, extending in the axial direction, between the peripheral surfaces of the respective electrodes. At least one of the pair of side closure members provided between the peripheral surfaces of the pair of electrodes to form a gap allowing the winding of the hard-adhesive resin film to the respective electrodes; It is preferable that the process gas nozzle of the downstream end of the said process gas supply system is comprised.

By a pair of side closure members, almost both sides of the said orthogonal direction of a process space can be closed. Thereby, it can prevent or suppress the atmospheric gas containing external oxygen from invading a process space from the peripheral surfaces of electrodes. Therefore, the oxygen concentration in a process space can be reliably set to predetermined (3000 ppm) or less, and the adhesiveness of a hard-adhesive resin film can be improved reliably.

It is preferable that the thickness of the said gap is below the space | interval of the narrowest point between the said pair of electrodes, and it is more preferable that it is below the thickness of the said process space. Thereby, even if the supply flow volume of a process gas is made small, the oxygen concentration in a process space can be reliably set to below predetermined (3000 ppm). Here, the thickness of the processing space corresponds to a size obtained by subtracting twice the thickness of the hard-adhesive resin film from the narrowest gap between the pair of electrodes. The space | interval of the narrowest location between the said pair of electrodes is larger than at least twice the thickness of the said hard-adhesive resin film, 3 mm or less is preferable, and 1 mm or less is more preferable.

A hard-adhesive resin film can be conveyed by winding up a hard-adhesive resin film on the circumferential surface of a cylindrical electrode, and rotating a cylindrical electrode. The cylindrical electrode can also have the above moving means.

In the plasma surface treatment apparatus according to the present invention, the pair of electrodes and the pair of side blocking members are disposed between end portions of the same side in the axial direction, and are covered at the end portions of the same side in the axial direction of the processing space. It is preferable to further comprise a shaft end closure member.

By the shaft end closure member, it is possible to suppress or prevent the atmosphere gas containing external oxygen from entering the processing space from the end in the axial direction of the processing space.

Therefore, even if the supply flow rate of the process gas is made smaller, the oxygen concentration in the processing space can be reliably lower than or equal to the predetermined (3000 ppm). Furthermore, the adhesiveness of the hard-adhesive resin film can be improved reliably.

A labyrinth seal may be formed between the axial end closure member and the axial end of the cylindrical electrode. For example, a partially annular convex portion is formed on a side surface of the axial end closure member facing the electrode, and an annular concave groove is formed in an axial cross section of the electrode, and the convex portion and the concave groove are occluded. Thus, the labyrinth seal is constructed. Alternatively, as the labyrinth seal, a partially annular concave groove may be formed in the side surface of the shaft end closure member facing the electrode, and an annular convex portion may be formed in the axial direction of the electrode.

The hard-adhesive resin film means the film whose adhesiveness with respect to an adhesive agent is comparatively lower than the film of the counterpart side adhere | attached with the said film. An easily adhesive resin film means the film whose adhesiveness with respect to an adhesive agent is relatively higher than the film of the counterpart side adhere | attached with the said film. Depending on the film of the counterpart to which the same film adhere | attaches, it may become a hard-adhesive resin film and may become an easily adhesive resin film.

As main components of the hard-adhesive resin film, for example, triacetate cellulose (TAC), polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyimide (PI), etc. are mentioned.

As a main component of the said easily-adhesive resin film, polyvinyl alcohol (PVA), an ethylene vinyl acetate copolymer (EVA), etc. are mentioned, for example.

As a polymerizable monomer, the monomer which has an unsaturated bond and a predetermined functional group is mentioned. The predetermined functional group is preferably selected from a hydroxyl group, a carboxyl group, an acetyl group, a glycidyl group, an epoxy group, an ester group having 1 to 10 carbon atoms, a sulfone group and an aldehyde group, and particularly preferably a hydrophilic group such as a carboxyl group or a hydroxyl group.

Examples of the monomer having an unsaturated bond and a hydroxyl group include ethylene glycol methacrylate, allyl alcohol, hydroxyethyl methacrylate and the like.

Acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-methacryloyl propionic acid, etc. are mentioned as a monomer which has an unsaturated bond and a carboxyl group.

Vinyl acetate etc. are mentioned as a monomer which has an unsaturated bond and an acetyl group.

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

As monomers having an unsaturated bond and an ester group, methyl acrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and methacrylic acid t-butyl, isopropyl methacrylate, 2-ethyl methacrylate, etc. are mentioned.

Acrylic monomers, crotonaldehyde, etc. are mentioned as a monomer which has an unsaturated bond and an aldehyde group.

Preferably, the polymerizable monomer is a monomer having an ethylenically unsaturated double bond and a carboxyl group. As such monomers, acrylic acid (CH ₂ = CHCOOH), methacrylic acid _{(CH 2 = C (CH 3} ) COOH). It is preferable that the said polymerizable monomer is acrylic acid or methacrylic acid. Thereby, the adhesiveness of a hard-adhesive resin film can be raised reliably. As for the said polymerizable monomer, it is more preferable that it is acrylic acid.

The said polymerizable monomer can also be conveyed by carrier gas. The carrier gas is preferably selected from inert gases such as nitrogen, argon and helium. From an economical viewpoint, it is preferable to use nitrogen as a carrier gas.

Most of the polymerizable monomers such as acrylic acid and methacrylic acid are liquid at ordinary temperature and normal pressure. Such a polymerizable monomer is vaporized in carrier gas, such as an inert gas, and the polymerizable monomer containing gas containing the mixed gas of polymeric monomer vapor and carrier gas can be obtained. As a method of vaporizing a polymerizable monomer in a carrier gas, the method of extruding saturated vapor on the liquid surface of a polymerizable monomer liquid with a carrier gas, the method of bubbling a carrier gas in a polymerizable monomer liquid, and heating a polymerizable monomer liquid The method of promoting evaporation, etc. are mentioned. Extrusion and heating or bubbling and heating can also be used together.

In the case of heating and vaporizing, in consideration of the burden on the heater, the polymerizable monomer is preferably selected to have a boiling point of 300 ° C or lower. In addition, it is preferable to select a polymerizable monomer that does not decompose (chemical change) by heating.

Moreover, in the manufacturing method of the polarizing plate which concerns on this invention, after the said easily-adhesive resin film is a transparent protective film, the said easily-adhesive resin film is a polarizing film, and after performing said film surface treatment method, the said hard-adhesive property is It is characterized by adhering the resin film to the easily adhesive resin film through a transparent adhesive agent.

By employing the surface treatment method, adhesiveness can be ensured, and further, the quality of the polarizing plate can be improved.

According to this invention, the adhesiveness of a hard-adhesive resin film can be improved reliably and a process quality can be improved.

1 is a front view schematically showing a surface treatment apparatus according to a first embodiment of the present invention.
(A) is sectional drawing of a polarizing plate, (b) is sectional drawing of the polarizing plate with a hard cord layer.
3 is a front view schematically showing a surface treatment apparatus according to a second embodiment of the present invention.
4 is a front view schematically showing a plasma processing unit of the surface treatment apparatus according to the third embodiment of the present invention.
5 is a perspective view of the plasma processing unit of the third embodiment.
FIG. 6 is a front view illustrating a modification of the third embodiment. FIG.
7 is a front view schematically showing a plasma processing unit of the surface treatment apparatus according to the fourth embodiment of the present invention.
FIG. 8 is a perspective view showing an electrode as an imaginary line, in a plasma processing unit of a fourth embodiment. FIG.
It is sectional drawing along the IX-IX line of FIG.
10 is a front view schematically showing a plasma processing unit of the surface treatment apparatus according to the fifth embodiment of the present invention.
It is sectional drawing along the XI-XI line of FIG.
It is a front view which shows the modification of 5th Embodiment.
It is sectional drawing along the XIII-XIII line of FIG.
It is a perspective view of the axial end closure member arrange | positioned at the surface depth side in FIG.
FIG. 15 is a schematic configuration diagram of a surface treatment apparatus used in Example 1. FIG.
FIG. 16 is a graph showing the results of Example 3. FIG.
FIG. 17 is a perspective view of the shaft end closure member used in Example 5. FIG.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the drawings.

2 shows a polarizing plate 10 for a liquid crystal display produced by using the surface treatment method according to the embodiment of the present invention. As shown to Fig.2 (a), the polarizing plate 10 has the polarizing film 12 and the pair of protective film 11 laminated | stacked on both surfaces of this polarizing film 12. As shown to FIG.

The protective film 11 is comprised from the TAC film which has a triacetate cellulose (TAC) as a main component. Content of the triacetate cellulose of the TAC film 11 is 90 mass% or more. The TAC film 11 may further contain about 3 to 10% by mass of a phosphate ester plasticizer such as triphenyl phosphate (TPP), or may contain an ultraviolet absorber. There is no restriction | limiting in particular in the thickness of the TAC film 11, For example, they are tens of micrometers-several hundred micrometers. The manufacturing method of the TAC film 11 is not specifically limited, For example, it is manufactured by the casting method.

The polarizing film 12 is comprised from the PVA film 12 which has polyvinyl alcohol (PVA) as a main component.

The TAC film 11 and the PVA film 12 are bonded by the adhesive agent 13. Although it does not specifically limit as the adhesive agent 13, In consideration of what is applied to the optical film 10, it is preferable to use a transparent water-based adhesive agent. As the water-based adhesive, an olefin containing a polyvinyl alcohol-based adhesive liquid mainly containing a polyvinyl alcohol aqueous solution, a polyvinyl butyral solution, etc., a vinyl-based polymer latex containing a butyl acrylate, a polyolefin-based polyol, etc. as a main component. Aqueous adhesive, a polyether adhesive, etc. are mentioned. As the adhesive 13, it is more preferable to use the polyvinyl alcohol-type adhesive agent which has a polyvinyl alcohol aqueous solution as a main component.

In the polarizing plate 10 shown in FIG.2 (b), the hard coat layer 14 is laminated | stacked as the functional layer on the front surface (surface opposite to the adhesion surface with the PVA film 12) of one TAC film 11, have. Instead of the hard coat layer 14, an AR layer and other functional layers may be laminated.

The TAC film 11 is low in adhesiveness with the adhesive 13 and constitutes a hard-adhesive resin film. The PVA film 12 has high adhesiveness with the adhesive 13 and constitutes an easily adhesive resin film. The hard-adhesive TAC film 11 is surface-treated for adhesive improvement at the time of adhesion | attachment with the easily-adhesive PVA film 12.

1 shows a surface treatment apparatus 1 used for the above-described surface treatment. The surface treatment apparatus 1 is equipped with the plasma processing part 2 and the process gas supply system 3. The plasma processing unit 2 includes a pair of electrodes 21. These electrodes 21 form the roll shape (cylindrical shape or cylindrical shape) of the same magnitude | size, mutually, and are arranged in left-right (array direction), orienting an axis line in the axial direction orthogonal to FIG. Hereinafter, when distinguishing two electrodes 21, "L" is attached | subjected to the code | symbol of the electrode 21 on the left, and "R" is attached | subjected to the code | symbol of the electrode 21 of the right side. The space around the narrowest part between these electrodes 21 is the process space 22 of atmospheric pressure. Both upper and lower ends of the processing space 22 are opened and communicate with the atmosphere. The thickness of the narrowest part between the electrodes 21 is about 0.5 to several mm, and the processing space 22 is narrow.

One of the pair of electrodes 21 is connected to the high voltage terminal of the power source 23, and the other is electrically grounded. Here, the electrode 21L on the left side is connected to the power source 23, the electrode 21R on the right side is grounded, but the power source 23 is connected to the electrode 21R, and the electrode 21L is electrically grounded. There may be. The electric field is formed between the electrodes 21 and 21 by supplying the voltage from the power supply 23, and the said processing space 22 becomes a discharge space of atmospheric pressure almost. The supply voltage from the power supply 23 and the electric field between the electrodes 21 are in the form of pulses, for example. It is preferable that the rise time and / or fall time of a pulse is 10 microseconds or less, it is preferable that an electric field intensity is 10-1000 kV / cm, and the frequency is 0.5-100 kHz. The applied voltage and the electric field are not limited to the pulse phase intermittent wave, but may be a continuous file such as a sine wave.

The roll electrode 21 has a function as a support means and a movement means of the TAC film 11 which is a to-be-processed object. The continuous sheet-like TAC film 11 spans the two roll electrodes 21 and 21, and is surrounded by, for example, an accompaniment around the upper surface of each roll electrode 21. The TAC film 11 between the roll electrodes 21 and 21 passes through the processing space 22, extends downward, and is rotated and surrounded by a pair of repeating rolls 27 and 27. By rotation of the two roll electrodes 21, the TAC film 11 is conveyed in one direction (right direction). By adjusting the rotational speed of the roll electrode 21, the moving speed of the TAC film 11 can be adjusted.

The film temperature adjusting means 28 is inserted in each roll electrode 21. The film temperature adjusting means 28 is comprised by the temperature control furnace. The temperature control medium of predetermined temperature makes the temperature control path in the roll electrode 21 flow. As the temperature control medium, for example, water is used. Thereby, the temperature of the roll electrode 21 can be adjusted and the temperature of the part which contact | connects the roll electrode 21 of the TAC film 11 can be adjusted. It is preferable that the temperature of the TAC film 11 is room temperature or more. Here, room temperature is generally 20-25 degreeC, More generally, it is 25 degreeC.

Next, the process gas supply system 3 is demonstrated.

The process gas supply system 3 is provided with the polymerizable monomer supply source 30 and the inert gas supply source 31. The polymerizable monomer source 30 is constituted by a constant temperature container (thermostat). In the constant temperature container 30, a polymerizable monomer is accumulated as a reaction component of the surface treatment. It is preferable that a polymerizable monomer has an unsaturated bond and a predetermined functional group, and it is more preferable to have hydrophilicity. As the polymerizable monomer, it is more preferable to use acrylic acid or methacrylic acid. Acrylic acid (CH ₂ = CHCOOH) is used here as the polymerizable monomer. Acrylic acid is a hydrophilic polymerizable monomer having an ethylenically unsaturated double bond and a carboxyl group. Acrylic acid AA is contained in the thermostatic container 30 in a liquid state. Saturated vapor of acrylic acid vaporized from liquid acrylic acid AA exists in the part upper side than the liquid level of liquid acrylic acid AA in the constant temperature container 30.

The heater 32 is inserted into the constant temperature container 30 as a vaporization means. Liquid acrylic acid AA in the vessel 20 is heated and vaporized by the heater 32. The vaporization amount of acrylic acid can be adjusted by the heating temperature of liquid acrylic acid AA. It is preferable to make the heating temperature of acrylic acid AA into 150 degreeC or less in consideration that acrylic acid vapor is explosive, It is more preferable to set it below the flash point (54 degreeC) of acrylic acid, and the room temperature (25 degreeC)-about 80 degreeC are further more. In consideration of the flash point, room temperature (25 ° C.) to about 50 ° C. is more preferable. In the case where the vaporization amount of acrylic acid satisfies the required amount even at room temperature, the heater 32 may be omitted. In addition, the flash point of acrylic acid is 360 degreeC. The flash point of acrylic acid is 54 ° C. Incidentally, the flash point of methacrylic acid is 360 ° C. The flash point of methacrylic acid is 77 ° C.

The inert gas supply source 31 is filled with an inert gas. The inert gas plays a role as a carrier gas for conveying the polymerizable monomer vapor, and serves as a plasma generation gas for generating plasma in the processing space 22. Although nitrogen gas is used here as an inert gas, other inert gases, such as argon and helium, can also be used besides nitrogen gas.

It is preferable that a carrier gas or the gas for plasma generation does not contain oxygen substantially.

An inert gas supply passage 33 extends from the inert gas supply source 31. An inert gas supply passage 33 is branched into the plasma generation gas passage 34 and the carrier passage 35. These furnaces 34 and 35 are provided with flow rate adjusting means 34v and 35v, respectively. The flow control means 34v, 35v is constituted by a mass flow controller, a flow control valve, or the like. By these flow regulating means 34v and 35v, the fractionation ratio with respect to each furnace 34 and 35 of inert gas is adjusted.

The carrier path 35 is connected to the constant temperature container 30. The tip end of the carrier path 35 is inserted into the constant temperature container 30 and is opened, and is located in an upper portion than the liquid surface of acrylic acid AA.

The tip of the carrier 35 may be extended to the inside of the liquid of acrylic acid AA, thereby bubbling nitrogen gas in the acrylic acid AA.

The polymerizable monomer vapor 36 extends from the upper side of the constant temperature container 30. The gas for producing plasma 34 is joined to the polymerizable monomer vapor 36. From the confluence of these furnaces 34 and 36, the process gas path 37 extends to the plasma processing unit 2. The gas temperature regulating means 38 is provided in the polymerizable monomer vapor furnace 36 and the process gas furnace 37. The gas temperature regulating means 38 is comprised by the ribbon heater, for example, and covers the outer periphery of the pipe which comprises the polymerizable monomer vapor 36 and the process gas 37 over the whole length. By the gas temperature adjusting means 38, the temperature of the gas passing through the polymerizable monomer vapor furnace 36 and the process gas furnace 37 can be adjusted.

The process gas nozzle 39 is provided at the tip of the process gas passage 37. The process gas nozzle 39 is disposed at an upper portion between the pair of roll electrodes 21. The opening of the front end of the process gas nozzle 39 faces downward and toward the processing space 22. The tip end of the process gas nozzle 39 becomes thinner as it goes downward, and is fitted in a gradually narrowing portion between the roll electrodes 21.

Although the detailed illustration is abbreviate | omitted, the process gas nozzle 39 is extended substantially equal to or longer than the width | variety of the TAC film 11 in the axial direction orthogonal to the surface of FIG. Inside the process gas nozzle 39, a rectifying path for uniformly dispersing the gas from the process gas supply passage 37 in the axial direction (the orthogonal direction of the paper in FIG. 1) is formed. The rectifier includes a chamber or a slit extending in the axial direction, or a plurality of small holes arranged in the axial direction. The rectifying part having the rectifying path may be separated from the process gas nozzle 39 and interposed between the front end of the process gas path 37 and the process gas nozzle 39. The blowing port of the tip of the process gas nozzle 39 is connected to the rectifying path. The blowing port of the process gas nozzle 39 is a slit-like extending in the direction orthogonal to the surface of FIG. The blowing port of the process gas nozzle 39 may be in the form of a large number of small holes arranged at intervals in the direction orthogonal to the surface of FIG. 1.

Moreover, the temperature control furnace (not shown) is formed in the process gas nozzle 39. A temperature control medium of a predetermined temperature is passed through the temperature control furnace. As the temperature controlling medium, for example, water is used. By the temperature control medium, the structure of the process gas nozzle 39 can be maintained at a predetermined temperature, and furthermore, the temperature of the gas passing through the process gas nozzle 39 can be adjusted, and further, it is ejected from the process gas nozzle 39. The temperature of the gas can be controlled.

The method of surface-treating the TAC film 11 and manufacturing the polarizing plate 10 further using the said constituent film surface treatment apparatus 1 is demonstrated.

[Process Gas Supply Process]

Nitrogen gas from the inert gas supply source 31 is distributed from the inert gas supply passage 33 to the gas generating passage 34 and the carrier passage 35. The distribution ratio is adjusted by flow control means 34v, 35v. Nitrogen gas, which is classified as carrier 35, is introduced into the constant temperature container 30, and the acrylic acid vapor above the liquid level of the liquid acrylic acid in the constant temperature container 30 is extruded into the polymerizable monomer vapor 36. In the process gas furnace 37, the gas (nitrogen + acrylic acid vapor) from the polymerizable monomer vapor furnace 36 and the nitrogen gas from the plasma generation gas furnace 34 are mixed to generate a process gas. It is preferable that it is 2% or less in consideration of an explosion limit, and, as for the density | concentration of acrylic acid in a process gas (acrylic acid + nitrogen), about 1% is more preferable. The concentration of the process gas can be adjusted by the distribution ratio of the two furnaces 34 and 35 of nitrogen gas and the heating temperature of acrylic acid by the heater 32. This process gas is sent to the process gas nozzle 39 via the process gas 37. The process gas is uniformed in the width direction (orthogonal to the surface of FIG. 1) of the TAC film 11 at the process gas nozzle 39, and then ejected into the processing space 22.

[Plasma treatment process]

By supplying the voltage from the power source 23, atmospheric pressure discharge is formed between the electrodes 21 and 21, and the inter-electrode space 22 is used as the discharge space. As a result, nitrogen in the process gas is converted into plasma, acrylic acid vapor is activated, and cleavage of double bonds, polymerization, and the like occur. In addition, by the contact of the nitrogen plasma to the TAC film 11 or the irradiation of ultraviolet rays (337 nm) from the nitrogen plasma, the bonds of C-C, C-O, C-H and the like of the surface molecules of the TAC film 11 are cleaved. It is thought that the polymer of acrylic acid couple | bonds (graft polymerization), or the COOH group decomposed | disassembled from acrylic acid, etc. couple | bond with this bond | disconnection cutting part. As a result, an adhesion promoting layer is formed on the surface of the TAC film 11.

[Temperature Control Process]

In addition, the gas temperature adjusting means 38 adjusts the temperature of the gas passing through the polymerizable monomer vapor furnace 36 and the process gas furnace 37 to the desired value. In addition, the temperature control path in the process gas nozzle 39 adjusts the temperature of the process gas passing through the process gas nozzle 39 as desired. Thereby, the temperature (henceforth "injection temperature" hereafter) when process gas is ejected from the process gas nozzle 39 can be made into set temperature. It is preferable to set the upper limit of a jet temperature in the range which TAC film 11 does not cause thermal deformation, such as swelling. The threshold temperature at which the TAC film 11 does not cause thermal deformation such as swelling varies depending on the processing conditions and the like, but is, for example, about 80 ° C. It is preferable that the minimum of a jet temperature is room temperature or more from a viewpoint of preventing dew condensation in the gas furnace 36 and 37 and the nozzle 39. It is preferable that jet temperature is about 35 degreeC-80 degreeC, and about 40 degreeC-about 50 degreeC are more preferable.

In addition, the film temperature adjusting means 28 maintains the temperature (hereinafter referred to as "film temperature") of the portion of the TAC film 11 in contact with the roll electrode 21 at a desired temperature lower than the blowing temperature of the process gas. do. Preferably, the film temperature is made at least 5 ° C. below the ejection temperature. More preferably, the film temperature is 10 ° C. or more lower than the ejection temperature. By this temperature control, for example, acrylic acid can be reliably condensed (supported) on the surface of the TAC film 11 even under high speed conveyance of 10 m / s or more, and furthermore, an adhesion promoting layer containing a graft polymer of acrylic acid. Can be reliably formed on the surface of the TAC film 11.

[Moving process]

In parallel with the above-described process gas supply process and plasma treatment process, the roll electrode 21 is continuously rotated clockwise in FIG. 1, and the TAC film 11 is sent to the right direction. After each point (processed part) of the TAC film 11 is surrounded by the roll electrode 21 on the left side, it passes through the processing space 22 just before it falls from the roll electrode 21 on the left side, and repeats a roll After repeating (27, 27), it passes through the processing space 22 again while wrapping the roll electrode 21 on the right side. Each point (target portion) of the TAC film 11 is subjected to plasma treatment each time it passes through the processing space 22. Therefore, the TAC film 11 can be surface treated twice in one treatment space 22.

[Process Gas Flow Control Process]

Here, according to the movement of the TAC film 11 on the roll electrode 21 on the left side, the ambient gas (air) of the periphery of the said TAC film 11 is wound up in the process space 22 with the said TAC film 11. do. As the moving speed of the TAC film 11 increases, the winding amount of air tends to increase. Correspondingly, the supply flow rate of the process gas is increased. It is preferable to adjust the flow rate of the process gas by adjusting the flow rate of the plasma generation gas path 34 while keeping the flow rate of the carrier path 35 constant. Thereby, the gas in the process space 22 is replaced with process gas (mostly nitrogen, remainder acrylic acid vapor), and air and oxygen are expelled from the process space 22.

As a result, in the above-described process gas supply process, the supply flow rate of the process gas is set so that the oxygen concentration in the processing space 22 becomes less than or equal to a predetermined value. Specifically, the oxygen concentration in the processing space 22 is preferably 3000 ppm, more preferably 2000 ppm, even more preferably 1000 ppm or less. This inhibits the reactions such as cleavage and polymerization of acrylic acid in the plasma treatment step, bond cleavage of CC, CO, CH and the like of the surface molecules of the TAC film 11, bond of the polymer and functional groups of acrylic acid and the bond cleavage portion, and the like. Can be prevented. Therefore, the adhesion promoting layer can be reliably formed on the surface of the TAC film 11, and the processing quality can be stabilized. In addition, the conveyance speed of the TAC film 11 can be increased without worrying about air curling in the processing space 22. Therefore, processing time can be shortened.

[Adhesion Process]

The TAC film 11 of the hard adhesive resin surface-treated as mentioned above is adhere | attached with the PVA film 12 of an easily adhesive resin with the adhesive agent 13. Since the adhesion promoting layer is reliably formed on the surface of the TAC film 11, the TAC film 11 can be reliably adhered to the PVA film 12. Thereby, the polarizing plate 10 of favorable quality can be obtained.

Next, the surface treatment apparatus which concerns on other embodiment of this invention is demonstrated. In the following embodiment, about the structure which overlaps with 1st Embodiment, the same code | symbol is attached | subjected to drawing, and description is abbreviate | omitted.

3 shows a second embodiment of the present invention. In the second embodiment, three roll electrodes 21 are provided in the plasma generating unit 2. The three electrodes 21 form a roll shape (cylindrical shape) of the same size with each other, and are arranged on the left and right with the axes in the direction orthogonal to FIG. 3. When the three electrodes 21 are distinguished from each other, the left electrode 21 is referred to as "electrode 21L", the center electrode 21 is referred to as "electrode 21C", and the right electrode 21 is used. Is taken as the "electrode 21R".

The center roll electrode 21C is connected to the power source 23. The left and right roll electrodes 21L and 21R are electrically grounded. An electric field is formed between the adjacent electrodes 21L and 21C and between the electrodes 21C and 21R by the voltage supply from the power source 23, and the peripheral space of the narrowest portion between these electrodes is almost at atmospheric pressure. It becomes the processing space 22. When the two processing spaces 22 are distinguished from each other, the processing space 22 between the left and center electrodes 21L and 21C is referred to as "process space 22A", and the center and right electrodes 21C are used. ) And 21R are referred to as "process space 22B."

The continuous sheet-like TAC film 11 spans the three roll electrodes 21 and is surrounded by, for example, an accompaniment on the upper peripheral surface of each roll electrode 21. The TAC film 11 between adjacent roll electrodes 21 extends below the process space 22, and is surrounded by a pair of repeating rolls 27 and 27, and is repeated. By rotation of the three roll electrodes 21, the TAC film 11 is conveyed in one direction (right direction).

In the second embodiment, the first process gas supply system 3A and the second process gas supply system 4 are provided as gas supply systems. The first process gas supply system 3A has the same configuration as the process gas supply system 3 of the first embodiment. The process gas nozzle 39 is disposed between the left and center roll electrodes 21L and 21C, and faces the discharge space 22A. The first process gas supply system 3A supplies a process gas containing acrylic acid vapor to the discharge space 22A.

The second process gas supply system 4 includes a second process gas supply source 41 and a second process gas nozzle 43. The second process gas supply source 41 stores nitrogen as the second process gas. As the second process gas, other inert gas such as argon or helium may be used. The second process gas supply path 42 extends from the second process gas supply source 41 to the plasma processing unit 2. The second process gas nozzle 43 is connected to the front end of the supply passage 42. The second process gas nozzle 43 is disposed between the center and right roll electrodes 21C and 21R, and faces the discharge space 22B. Nitrogen from the second process gas supply source 41 is ejected from the nozzle 43 into the processing space 22B via the supply path 42.

When distinguishing the gases supplied to the two processing spaces 22A and 22B from each other, the gas (acrylic acid vapor + nitrogen) supplied to the processing space 22A is referred to as "first process gas", and the processing space ( The gas (nitrogen) supplied to 22B) is referred to as "second process gas".

The first and second process gas sources 31 and 41 may be composed of a common inert gas source.

In 2nd Embodiment, the 1st process gas (acrylic acid + nitrogen) is supplied and plasma-formed into the discharge space 22A between the roll electrodes 21L and 21C of the left side and center, and the surface of the TAC film 11 is made into plasma. An adhesion promoter layer containing a polymer of acrylic acid and the like is formed in the film. At this time, the flow rate of the first process gas is set so that the oxygen concentration in the discharge space 22A is preferably 1000 ppm or less, and more preferably 1000 ppm.

Next, in the discharge space 22B between the center and right roll electrodes 21C and 21R, the second process gas (nitrogen only) is converted into plasma and brought into contact with the TAC film 11. Thereby, unreacted acrylic acid of the surface of the TAC film 11 can be activated, and an adhesion promoter layer can be formed more reliably. Therefore, the adhesiveness of the TAC film 11 can be improved reliably.

Fig. 4 and Fig. 5 show a third embodiment of the present invention. The plasma surface treatment apparatus 1 according to the third embodiment is provided with a closing means 7 for the processing space 22. The blocking means 7 includes a pair of side blocking members 71 and 72. The side closure members 71 and 72 are arrange | positioned on both sides of the up-down direction (the orthogonal direction orthogonal to the axial direction and the arrangement direction of the electrode 21) with the process space 22 interposed. These blocking members 71 and 72 have a long shape extending in parallel with the axial direction of the electrode 21.

The upper side closure member 71 is disposed so as to span the peripheral surfaces above the processing space 22 in the roll electrodes 21 and 21. The cross section orthogonal to the longitudinal direction of the side closure member 71 is tapered as it goes down. The lower end of the side closure member 71 is fitted to the vicinity of the narrowest point between the pair of electrodes 21 and 21, that is, to the vicinity of the discharge space. The lower end surface of the side closure member 71 faces the processing space 22 and partitions the upper end of the processing space 22. By the side closure member 71, the upper part of the process space 22 is almost blocked.

Both left and right side surfaces of the portion tapered to the lower side of the side closure member 71 are concave curved surfaces 73 each having a partial cylindrical surface shape. The radius of curvature of the concave curved surface 73 is slightly larger than the radius of each electrode 21. The center of curvature of the concave curved surface 73 on the left side substantially coincides with the axis of the electrode 21L on the left side. The center of curvature of the concave curved surface 73 on the right side substantially coincides with the axis of the electrode 21R on the right side.

The concave curved surface 73 on the left side is along the circumferential surface of the electrode 21L on the left side. The side gap 73e is formed between the concave curved surface 73 on the left side and the peripheral surface of the electrode 21L. The gap 73e allows the winding of the electrode 21L of the film 11 to be processed. The concave curved surface 73 on the right side is along the circumferential surface of the electrode 21R on the right side. The side gap 73f is formed between the concave curved surface 73 on the right side and the peripheral surface of the electrode 21R. The gap 73f allows the winding of the electrode 11R of the film 11 to be processed.

The lower side blocking member 72 has a shape in which the upper side blocking member 71 is roughly inverted up and down. In detail, the lower side side closure member 72 is arrange | positioned so that it may span between peripheral surfaces below lower than the process space 22 in roll electrode 21,21. The cross section orthogonal to the longitudinal direction of the side closure member 72 is tapered so that it may go upward. The upper end of the side closure member 72 is fitted to the vicinity of the narrowest point between the pair of electrodes 21 and 21, that is, to the vicinity of the discharge space. An upper end face of the side closure member 72 faces the process space 22 and partitions a lower end face of the process space 22. The lower portion of the processing space 22 is almost blocked by the side closure member 72. By the side closure members 71 and 72, the processing space 22 is covered from the upper and lower sides.

Both left and right side surfaces of the portion tapered to the upper side of the side closure member 72 are concave curved surfaces 74 each having a partial cylindrical surface shape. The radius of curvature of the concave curved surface 74 is slightly larger than the radius of each electrode 21. The center of curvature of the concave curved surface 74 on the left side substantially coincides with the axis of the electrode 21L on the left side. The center of curvature of the concave curved surface 74 on the right side substantially coincides with the axis of the electrode 21R on the right side.

The concave curved surface 74 on the left side is along the circumferential surface of the electrode 21L on the left side. The side gap 74e is formed between the left concave curved surface 74 and the peripheral surface of the electrode 21L. The gap 74e allows the winding of the electrode 21L of the film 11 to be processed. The concave curved surface 74 on the right side is along the circumferential surface of the electrode 21R on the right side. The side gap 74f is formed between the concave curved surface 74 on the right side and the peripheral surface of the electrode 21R. The gap 74f allows the winding of the electrode 11R of the film to be processed 11.

The thicknesses of the gaps 73e, 73f, 74e, and 74f are thicker than the thickness of the film to be processed 11, and can sufficiently suppress the infiltration of ambient atmosphere gas into the processing space 22. It is set to a size that is enough. The thickness t of the gaps 73e, 73f, 74e, and 74f is preferably at least the distance g of the narrowest point between the electrodes 21, 21 (t≥g), and further the processing space It is preferable that it is below the thickness of (22). The thickness of the processing space 22 is the size which subtracted twice the thickness of the to-be-processed film 11 from the said space | interval g here. For example, the thickness t of the gaps 73e, 73f, 74e, and 74f is preferably about t = 0.05 mm to 0.5 mm, and more preferably about t = 0.2 to 0.3 mm. The thicknesses of the gaps 73e and 73f and the thicknesses of the gaps 74e and 74f may be the same as or different from each other.

Moreover, the space | interval g of the narrowest place between the electrodes 21 and 21 is larger than 2 times the thickness of the to-be-processed film 11, 3 mm or less is preferable and 1 mm or less is more preferable.

In addition, in FIG.4 and FIG.5, illustration of the temperature control path 28 of the inside of the electrode 21, the gas temperature control means 38 of the process gas supply system 3, the power supply 23, etc. is abbreviate | omitted. . The same is true in the following embodiments (Figs. 6 to 14).

At least one of the side closure members 71 and 72 constitutes a process gas nozzle at a downstream end of the process gas supply system 3. Here, the upper closure member 71 is provided as a process gas nozzle. The blocking member 71 corresponds to the process gas nozzle 39 of the first embodiment (FIG. 1).

The rectifying part 75 is provided above the nozzle and blocking member 71. The tip of the process gas passage 37 is connected to the rectifying portion 75. The rectifying part 75 extends in the direction orthogonal to the surface of FIG. 4 in parallel with the blocking member 71. Although the detailed illustration is abbreviate | omitted, the rectification part 75 is provided with the rectification path which equalizes the gas from the process gas path 37 to an axial direction (direction orthogonal to the surface of FIG. 4). The rectifier includes a chamber or a slit extending in the axial direction, or a plurality of small holes arranged in the axial direction.

The blowing path 76 is formed inside the nozzle and blocking member 71. The blowing path 76 is formed in a slit shape extending in the axial direction (direction perpendicular to the surface of FIG. 4). The downstream end of the jet passage 76 reaches the lower end surface of the blocking member 71 and is opened to form a jet port.

Moreover, the temperature control path 79 is formed inside the nozzle and blocking member 71. The temperature regulating furnace 79 extends in the axial direction (direction perpendicular to the surface of FIG. 4). By passing a temperature control medium, such as water, through the temperature control furnace 79, the nozzle and blocking member 71 can be temperature-controlled.

The lower blocking member 72 is a dummy nozzle and has the same outer shape as the upper nozzle and closing member 71, while the blowing passage and the temperature control furnace are not formed therein. The blocking member 72 may have a blowing path and a temperature control path similarly to the nozzle and closing member 71, and the blowing port of this blocking member 72 may be closed with a plug or the like. In addition, the side closure members 71 and 72 do not have the exhaust port or the suction port for exhausting process gas.

According to 3rd Embodiment, the process gas containing a polymerizable monomer is introduce | transduced into the rectification part 75 from the process gas path 37, and it is equalized in the longitudinal direction of the rectification part 75. FIG. After homogenization, the process gas is ejected from the jet passage 76 and introduced into the processing space 22. In the processing space 22, the process gas is plasma-formed and in contact with the film 11 to be processed. Thereby, the adhesiveness of the surface of the to-be-processed film 11 can be improved. Thereafter, the process gas flows out of the processing space 22 from the openings 22e at both ends in the longitudinal direction of the processing space 22 (axial direction orthogonal to the surface of FIG. 4). In addition, some of the process gases are externally passed through the gaps 73e, 73f, 74e, and 74f between the upper and lower closure members 71 and 72 and the peripheral surfaces of the left and right electrodes 21L and 21R. Spills.

By the upper blocking member 71, the upper part of the processing space 22 can be almost closed. By the lower blocking member 72, the lower part of the processing space 22 can be almost closed. Accordingly, even if the supply flow rate of the process gas is small, it is possible to prevent or suppress the external atmosphere gas from invading the processing space 22 from between the upper peripheral surfaces and the lower peripheral surfaces of the electrodes 21 and 21. Can be. In addition, the process gas flows out from the shaft end openings 22e and the gaps 73e, 73f, 74e, and 74f, so that external atmosphere gas flows through the shaft end openings 22e, the gaps 73e, and 73f. ), 74e, 74f can be prevented from entering the processing space 22. Thereby, the oxygen concentration in the processing space 22 can be reliably set to a predetermined size, that is, 3000 ppm or less. Therefore, the adhesiveness of the to-be-processed film 11 can be improved reliably.

6 shows a modification of the third embodiment. In this modification, the process gas nozzle is comprised not only of the upper blocking member 71 but also of the lower blocking member 72A among the upper and lower side blocking members. The rectifying part 77 is provided in the lower part of 72 A of nozzle and blocking members. The rectifying part 77 extends in the axial direction (direction orthogonal to the surface of FIG. 6). The process gas path 37 is connected to the rectifying part 77. The rectifier 77 is provided with a rectifier for uniformizing the process gas in the axial direction similarly to the rectifier 75. The process gas 37 from the common polymerizable monomer source 30 (refer FIG. 1) may branch, and may be connected to the nozzle and blocking members 71 and 72A through the rectifying parts 75 and 77, respectively. The nozzle and blocking members 71 and 72A may be connected to different gas supply sources. One of the gas sources different from each other is the polymerizable monomer source 30, and the other of the gas sources different from each other is preferably an inert gas source 41 (see Fig. 2) such as nitrogen gas or rare gas.

The blowing path 78 and the temperature control path 79 are formed in 72 A of nozzle and blocking members. The rectifying passage of the rectifying section 77 is connected to the jet passage 78. The jet passage 78 is a slit shape extending in the axial direction (direction perpendicular to the surface of FIG. 6). The blowing path 78 reaches the upper end surface of 72 A of nozzle and blocking members, and opens, and comprises the blowing port. The ejection opening of the nozzle and blocking member 72A has the same length and width as the ejection opening of the nozzle closing member 71 on the upper side.

As a result, the process gas is not only introduced into the processing space 22 from the upper nozzle and closing member 71, but also introduced into the processing space 22 from the lower nozzle and closing member 72A. The blowing flow rates from the upper and lower nozzle and closing members 71 and 72A are preferably equal to each other. Thereby, the pressure can be applied uniformly in the processing space 22. The process gas provided for the surface treatment of the film 11 to be processed in the processing space 22 is then subjected to the axial end openings 22e and the gaps 73e, 73f, 74e, and 74 of the processing space 22 ( 74f). By the flow of the process gas, it is possible to prevent the external atmosphere gas from entering the processing space 22 from the shaft end openings 22e and the gaps 73e, 73f, 74e, and 74f. By uniformly applying pressure in the processing space 22, it is possible to prevent the concentration of external atmospheric gases from entering a portion of the gaps 73e, 73f, 74e, 74f in the processing space 22. Can be. Thereby, the oxygen concentration in the process space 22 can be reliably set to below predetermined (3000 ppm). Therefore, the adhesiveness of the to-be-processed film 11 can be improved reliably. In addition, the side closure members 71 and 72A do not have the exhaust port or the suction port for exhausting process gas.

7 to 9 show a fourth embodiment of the present invention.

In this embodiment, in addition to the side closure members 71 and 72 of 3rd Embodiment (FIGS. 4 and 5), the axial end closure member 80 is provided. As shown in FIG. 8, the axial end blocking member 80 is arrange | positioned at the both ends of the axial direction of the electrodes 21 and 21, respectively. As shown in FIG. 7, each axial end closure member 80 spans the ends of the pair of electrodes 21, 21 and the pair of side closure members 71, 72 on the same side in the axial direction. It is covered with the edge part 22e of the said same side of the axial direction of 22. As shown in FIG.

As shown in FIG. 8 and FIG. 9, the shaft end closure member 80 has a front plate 81 and a pair of side plates 82, and is U-shaped (U-shaped, U-shaped) in plan view. The front plate 81 is a flat plate extending vertically. Side plates 82 are respectively provided at left and right edges of the front plate 81. Each side plate 82 is orthogonal to the front plate 81.

The front plate 81 is separated outward in the axial direction from the cross section of the electrode 21. As shown in FIG. 7, the front plate 81 has a width dimension between the left and right electrodes 21L and 21R when viewed from the outside in the axial direction, and the top and bottom side closure members 71 when viewed from the outside in the axial direction. 72) has a vertical dimension over each other. When viewed from the outside in the axial direction, the front plate 81 is covered with the end 22e of the processing space 22.

As shown in FIG. 9, the left side plate 82 protrudes from the front plate 81 toward the cross section of the electrode 21L. The right side plate 82 protrudes from the front plate 81 toward the end face of the electrode 21R.

The side closure members 71 and 72 protrude in the axial direction from the electrode 21 and are fitted inside the axial end closure member 80. The axial end part of the side closure members 71 and 72 abuts on the inner side surface of the front plate 81, and is fixed by the bolt 89. As shown in FIG. As a result, the shaft end closure member 80 is supported by the side closure members 71 and 72. A gap is not formed between the upper side of the front plate 81 and the end surface in the axial direction of the side closure member 71. A gap is not formed between the lower side of the front plate 81 and the end surface in the axial direction of the side closure member 72.

The upper edge part of each side plate 82 of right and left touches the upper side part of the concave curved surface 73 of the side closure member 71. As shown in FIG. The gap is not formed between the upper edge of each side plate 82 and the side closure member 71. The lower edge of each side plate 82 touches the lower part of the concave curved surface 74 of the side closure member 72. A gap is not formed between the lower end edge of each side plate 82 and the side closure member 72.

In addition, a gap may be formed between the upper and lower end edges of the side plates 82 and the side closure members 71 and 72.

As shown in FIG. 9, the edge of the cross section side of the electrode 21 of each side plate 82 of left and right is separated from the electrode 21. As shown in FIG. An axial end gap 82e is formed between the side plate 82 and the end face in the axial direction of the electrode 21. Thereby, the friction of the side plate 82 and the electrode 21 at the time of rotation of the electrode 21 can be prevented. The thickness t8 of the gap 82e is preferably about t8 = 0.05 mm to about 0.5 mm, and more preferably about t8 = 0.1 mm.

In the fourth embodiment, the side closure members 71 and 72 not only prevent or prevent the external atmosphere gas from entering the processing space 22 from both the upper and lower sides of the processing space 22, but also block the shaft end. By covering the end portion 22e in the axial direction of the processing space 22 with the member 80, it is possible to suppress or prevent the external atmosphere gas from entering the processing space 22 from the end 22e. Therefore, the supply flow volume of a process gas can be made smaller. In addition, the process gas flows out of the processing space 22 through the gaps 73e, 73f, 74e, and 74f in the upper and lower portions, and also flows out of the gap 82e in the axial direction. By the flow of the process gas, it is possible to prevent the external atmosphere gas from entering the processing space 22 from the side gaps 73e, 73f, 74e, 74f and the axial end gap 82e. For example, even if an external atmospheric gas enters the interior of the shaft end closure member 80 through the shaft end gap 82e, the introduced atmosphere gas is diffused into the interior space of the shaft end closure member 80 to dilute the concentration of the atmosphere gas. can do. As a result, the oxygen concentration in the processing space 22 can be reliably set to the predetermined size or less, that is, 3000 ppm or less. Therefore, the adhesiveness of the to-be-processed film 11 can be improved reliably.

10 and 11 show a fifth embodiment of the present invention. In the fifth embodiment, a flat shaft end closure member 90 is provided in place of the U-shaped (U-shaped) shaft end closure member 80. The shaft end closure member 90 is provided in both ends of the axial direction of the electrodes 21 and 21, respectively. Each axial end closure member 90 spans the ends of the pair of electrodes 21, 21 and the pair of side closure members 71, 72 on the same side in the axial direction, and the axial direction of the processing space 22. It is covered by the end part 22e of the same side.

The cross section in the axial direction of the side closure members 71 and 72 protrudes slightly (for example, about 0.1 mm) in the axial direction than the electrode 21. The upper side portion of the shaft end closure member 90 touches the end face in the axial direction of the side closure member 71 and is connected by a bolt 99. The lower part of the shaft end closure member 90 touches the end surface of the side closure member 72 in the axial direction, and is connected by the bolt 99. Thereby, the axial end closure member 90 is supported by the upper and lower side closure members 71 and 72.

The shaft end closure member 90 is disposed slightly away from the end faces in the axial direction of the electrodes 21 and 21. A gap 91 is formed between the shaft end blocking member 90 and the electrodes 21 and 21. Thereby, the friction of the axial end blocking member 90 and the electrode 21 at the time of rotation of the electrode 21 can be prevented. The thickness of the gap 91 corresponds to the amount of protrusion of the side closure members 71 and 72 from the electrode 21. As for the thickness t9 of the clearance 91, t9 = 0.05 mm-about 0.5 mm are preferable, and about t9 = 0.1 mm is more preferable.

In this fifth embodiment, the axial end closure member 90 is covered with the end portion 22e in the axial direction of the processing space 22, thereby preventing the external atmosphere gas from entering the processing space 22 from the end 22e. Or can be prevented. Thereby, even if the supply flow volume of a process gas is small, the oxygen concentration in the process space 22 can be reliably set to below predetermined (3000 ppm). Therefore, the adhesiveness of the to-be-processed film 11 can be improved reliably.

12 and 13 show a modification of the fifth embodiment. In this modification, the labyrinth seal 93 is formed between the plate-shaped shaft end closure member 92 and the left electrode 21L. A labyrinth seal 94 is formed between the shaft end blocking member 92 and the right electrode 21R.

More specifically, as shown in FIG. 14, a plurality of arc-shaped or partially annular convex portions 95 are formed in the left portion of the surface of the inner side (side toward the electrode 21) of the shaft end closure member 90. have. These partial annular convex parts 95 are concentric circles centering on the axis line of the electrode 21 of the left side mutually. In the right part of the surface of the inner side (electrode 21 side) of the axial end blocking member 90, a plurality of circular arc-shaped or partially annular convex portions 96 are formed. These partial annular projections 96 are concentric circles centering on the axes of the electrodes 21 on the right side of each other.

As shown in FIG. 12 and FIG. 13, a plurality of annular concave grooves 97 are formed in both end surfaces in the axial direction of the left electrode 21L, respectively. These annular concave grooves 97 are concentric with each other centering on the axis line of the electrode 21L. The annular concave groove 97 corresponds one-to-one with the partial annular convex portion 95 of the shaft end closure member 90. Each partial annular convex part 95 is fitted in the corresponding annular recessed groove 97. The labyrinth seal 93 is formed by the partial annular convex portion 95 and the annular recessed groove 97.

A plurality of annular concave grooves 98 are formed in both end surfaces in the axial direction of the right electrode 21R, respectively. These annular concave grooves 98 are concentric with each other centering on the axis line of the electrode 21R. The annular concave groove 98 corresponds one-to-one with the partial annular convex part 96 of the axial end closure member 90. Each partial annular convex part 96 is fitted in the corresponding annular recessed groove 98. The labyrinth seal 94 is formed by the partial annular convex portion 96 and the annular recessed groove 98.

Although the number of the partial annular convex parts 95 and 96 and the annular recessed grooves 97 and 98 are two in a figure, respectively, it is not limited to this, It may each be three or more, and may be one. From the viewpoint of improving the sealability of the labyrinth seals 93 and 94, the number of the partial annular convex portions 95 and 96 and the annular concave grooves 97 and 98 is more preferable.

As the labyrinth seal, a partially annular concave groove may be formed in the axial end closure member 90 so that an annular convex portion that engages with the concave groove may be formed in the cross section of the electrode 21.

The labyrinth seals 93 and 94 can seal between each electrode 21 and the shaft end closure member 90, and an external atmosphere gas is processed between each electrode 21 and the shaft end closure member 90. Entering into the space 22 can be suppressed or prevented more reliably. Thereby, even if the supply flow volume of a process gas is small, the oxygen concentration in the process space 22 can be made more reliably below predetermined (300 ppm). Therefore, the adhesiveness of the to-be-processed film 11 can be improved reliably.

This invention is not limited to the said embodiment, A various change can be made within the range of the summary.

For example, in the process gas flow rate adjusting step, in addition to the flow rate control of the plasma generation gas passage 34, the flow rate of the carrier passage 35 may also be adjusted to adjust the supply flow rate of the process gas. The supply flow rate of the process gas can be adjusted by adjusting the flow rate of the carrier passage 35 while maintaining the flow rate of the plasma generation gas passage 34 constant. The supply flow rate of the process gas can be adjusted by setting the flow rate of the plasma generation gas path 34 to zero and adjusting the flow rate of the carrier path 35.

By substituting the processing space 22 and the surrounding gas with an inert gas (for example, nitrogen), the oxygen concentration in the processing space 22 is less than or equal to, that is, preferably 3000 ppm or less, more preferably 2000 ppm. Hereinafter, it can also adjust so that it may become 1000 ppm or less more preferably. By surrounding the processing space 22 and its surroundings with a chamber and replacing the gas inside the chamber with an inert gas (for example, nitrogen), the oxygen concentration of the processing space 22 can be adjusted to be below a predetermined value.

By forming a gas curtain of an inert gas (for example, nitrogen) in the peripheral portion of the processing space 22, and preventing or inhibiting atmospheric gas such as air from entering the processing space 22 by the gas curtain, the processing space ( It is also possible to adjust so that the oxygen concentration of 22) is less than or equal to the predetermined value.

Although it is preferable that oxygen is not contained in a process gas, Preferably it is 3000 ppm or less, More preferably, it may contain 1000 ppm or less.

The electrode structure of the plasma processing unit 2 is not limited to the roll electrode structure, and may be a parallel plate electrode structure (see FIG. 15) having a pair of plate-shaped electrodes, or a structure in which the plate electrode and the roll electrode are opposed to each other. The structure which opposes the electrode which has a concave curved surface, and a roll electrode may be sufficient.

As the polymerizable monomer in the process gas, methacrylic acid may be used instead of acrylic acid, or other hydrophilic polymerizable monomers may be used.

The hard-adhesive resin film 11 is not limited to a TAC film, A hard-adhesive resin film, such as COP, PP, PE, PET, can also be used.

The hard-adhesive resin film 11 may be stopped, and the processing space 22 may be moved.

Plasma treatment may be performed without relatively moving the hard-adhesive resin film 11 and the processing space 22.

Although the plasma processing unit of the embodiment was a so-called direct plasma processing apparatus in which the processing space 22 is a discharge space and the plasma is directly irradiated to the target film 11 disposed in the processing space 22, the present invention provides a processing space. The so-called remote plasma processing apparatus which opens the discharge space separately and connects the processing space to the discharge space, converts the process gas into a plasma in the discharge space and ejects the processed gas into the processing film 11 in the processing space. Applicable to Also in the so-called remote plasma processing apparatus, the oxygen concentration of the processing space can be set to be preferably 3000 ppm, more preferably 2000 ppm, and even more preferably 1000 ppm.

After supplying a gas containing a polymerizable monomer vapor to a hard-adhesive resin film and supporting (condensing, etc.) on the surface of the hard-adhesive resin film, a plasma generation gas separate from the polymerizable monomer-containing gas is plasma. It can also be made to contact the part in which the said polymerizable monomer of the hard-adhesive resin film was carried. Alternatively, the plasma generation gas may be converted into a plasma to contact the hard adhesive resin film, and then a polymerizable monomer may be brought into contact with the plasma contact portion of the hard adhesive resin film. The plasma generation gas and the carrier gas of the polymerizable monomer vapor may be composed of the same component (for example, nitrogen), and the carrier gas may also have a plasma generation gas.

After the plasma treatment step, the hard-adhesive resin film may be washed with an aqueous cleaning liquid before the bonding step.

The surface treatment method and surface treatment apparatus of a hard-adhesive resin film can also be applied to uses other than manufacture of a polarizing plate.

The side closure member 72 may be comprised with the suction nozzle which sucks the gas of the process space 22. In this case, it is noted that the external atmosphere gas is easily sucked into the suction nozzle while the inside of the processing space 22 is sucked in or the active species of the polymerizable monomer is not in contact with the film to be processed 11.

The elements of the plurality of embodiments may be combined with each other. For example, the blocking means 7 of 3rd-5th embodiment or these modified examples can also be provided also in 2nd Embodiment (FIG. 3). In this case, the blocking means 7 is provided corresponding to at least the processing space 22A among the processing spaces 22A and 22B.

The shaft end closure members 80, 90, and 92 may be provided only on one side in the axial direction.

Example 1

Although an Example is described below, this invention is not limited to these Examples.

In Example 1, the relationship between the oxygen mixing amount and the adhesiveness to the discharge space was investigated. The schematic structure of the used surface treatment apparatus is shown in FIG.

The pure nitrogen gas of the inert gas supply source 31 was introduced into the constant temperature container 30 via the inert gas 33 to obtain a process gas consisting of a mixed gas of nitrogen and acrylic acid. The flow rate of nitrogen and the flow rate of the process gas was 10 L / min. The temperature of the liquid acrylic acid AA in the thermostatic container 30 was 40 degreeC.

Process gas (acrylic acid + nitrogen) was sent from the thermostatic container 30 to the process gas supply passage 37. The oxygen mixing passage 51 was joined to the process gas supply passage 31, and oxygen from the mixing passage 51 was mixed into the process gas of the supply passage 37. The amount of oxygen mixed was adjusted in a range such that the oxygen concentration in the process gas after mixing became 0 to 2% by volume. This process gas was ejected from the nozzle 39 to the process space 22. The blowing temperature of the process gas was 32 ° C. The electrode structure of the plasma processing part 2 was set as the parallel plate electrode structure which consists of a pair of flat plate electrodes 24 and 25 opposing up and down. The process gas supply nozzle 39 is disposed on one side of the upper electrode 24, the suction nozzle 62 is provided on the other side of the electrode 24, and the processed gas in the processing space 22 is sucked. Inhalation was carried out at 62 and discharged from the exhaust means 61.

The power supply 23 was connected to the upper electrode 24, and the lower electrode 25 was grounded. The electric power supplied to the electrode 24 was 110V.

The TAC film 11 was placed on the lower electrode 25. The temperature of the electrode 25 and the film temperature were adjusted to 25 degreeC. Therefore, the temperature difference between a process gas and a TAC film was 7 degreeC.

The electrodes 24 and 25 were reciprocated relative to the other side (scanned). The moving speed was 10 m / min, and the number of round trips was 1 (2 scans).

After surface treatment, the TAC film 11 was bonded with the PVA film 12. As an adhesive, the liquid which mixed the aqueous solution of (A) 5 weight% of polyvinyl alcohols, and the aqueous solution of 2 weight% of (B) carboxymethylcellulose sodium in the volume ratio of (A) :( B) = 20: 1 was used. . The average degree of polymerization of the polyvinyl alcohol of (A) was 500.

And adhesiveness was evaluated. Adhesive evaluation was made into the hand evaluation by which a tester peels a TAC film and a PVA film by hand.

The above operation was repeated three times, and three trial data of the same conditions (oxygen mixing amount) were acquired.

The results are shown in Table 1 below. "◎" of the same Table 1 shows that adhesiveness is very favorable. "(Circle)" shows that adhesiveness is favorable. "Δ" indicates that the adhesion is slightly good. "X" represents bad adhesiveness.

When the oxygen concentration in the process gas after the oxygen incorporation was 0.5% by volume or more, the adhesion was poor. When the oxygen concentration was 0.3% by volume, a majority of the adhesive became good. When the oxygen concentration was 0.2% by volume or less, the adhesion was good. Adhesiveness became very favorable when oxygen concentration was 0.1 volume% or less. Accordingly, the oxygen concentration in the processing space 22 for obtaining good adhesion is preferably 3000 ppm or less, more preferably 2000 ppm or less, and even more preferably 1000 ppm or less.

Example 2

The apparatus of FIG. 3 was used. The width of the TAC film 11 was 33 cm. The thickness (thickness of the narrowest part between electrodes) of each process space 22A, 22B was 1 mm. The length of the upper and lower sides of each processing space 22A and 22B was about 10 cm. The volume of each processing space 22A, 22B was about 0.3L. As shown in the conditions (a) to (d) of Table 2 below, the conveyance speed of the TAC film 11 was adjusted in the range of 10 m / min to 30 m / min, and the first process gas (acrylic acid vapor + nitrogen) ) Flow rate to the processing space 22A was proportional to the conveyance speed of the TAC film (11). In addition, the flow volume of the gas furnace 34 was made into zero. Therefore, the supply flow rate of the first process gas is equal to the flow rate of the carrier passage 35. The blowing temperature of the first process gas was 40 ° C, and the temperature of the TAC film 11 was 25 ° C. The supply flow rate of nitrogen gas to the processing space 22B was 10 L / min in all about four conditions (a)-(d). The supply power to the electrode 22C and the applied voltage between the electrodes were as follows for each condition (a) to (d).

(A) Supply power: 918 W (270 V, AC to DC conversion of 3.4 A)

     Supply Voltage: Vpp = 15.3 kV

(B) Supply power: 891 W (270 V, 3.3 A DC to AC conversion)

     Supply Voltage: Vpp = 15.3 kV

(C) Supply power: 864 W (270 V, 3.2 A direct current to AC conversion)

     Supply voltage: Vpp = 15 kV

(D) Supply power: 810 W (270 V, 3 A direct current to AC conversion)

     Voltage applied: Vpp = 14.8 kV

After the plasma treatment, two pieces of sample were cut out each from one end portion, the other end portion, and the center portion in the width direction of the TAC film, and the sample pieces of the TAC film were bonded to both sides of the sample pieces of the PVA film, and the same as in Fig. 2 (a). The polarizing plate sample of the cross-sectional structure was produced. An aqueous solution having a PVA of polymerization degree 500 of 5% was used as the adhesive for evaluation. A plurality (two to three) polarizing plate samples were prepared for each condition (a) to (d). Drying conditions of the adhesive were 80 ° C. for 5 minutes. After the adhesive had cured, the adhesive strength was measured by the floating roller method (JIS K6854). As a result, as shown in Table 2, the samples under any of the conditions (a) to (d) were also broken through, and sufficient adhesive strength was obtained.

In the conditions (a) to (d), since the conveying speed of the TAC film 11 and the supply flow rate of the first process gas (acrylic acid vapor + nitrogen) are proportional, the throughput will be regarded as the same, but the conveying speed and the supply flow rate This large one confirmed the tendency for the adhesive strength to be good. Therefore, if the supply flow rate of process gas is more than a certain magnitude, it is thought that the winding amount of air can be suppressed and adhesive strength can be ensured even if a conveyance speed is large.

Comparative Example 1

As Comparative Example 1, in Fig. 3, the flow rate of the flow path 35 is set to 0, and 10 L / min of nitrogen gas flows in the order of the flow paths 33, 34, 37, and 39 in the process space. It was supplied to (22A) and the plasma was made. Therefore, acrylic acid content in the 1st process gas of the comparative example 1 is zero. The blowing temperature of the first process gas was 40 ° C, and the temperature of the TAC film 11 was 25 ° C. In addition, 10 L / min of nitrogen gas was supplied to the processing space 22B as the second process gas. The conveyance speed of the TAC film was 2 m / min. The power supply was 1107 W (AC conversion of direct current of 270 V, 4.1 A). The applied voltage between the electrodes was Vpp = 15.6 kV. After the plasma treatment, the TAC film was adhered to the PVA film in the same manner as in Example 1, but hardly adhered.

Example 3

In Example 3, the apparatus 1 of FIG. 3 was used. The width | variety of the TAC film 11, the thickness, and the volume of each process space 22A, 22B were made the same as Example 2. The conveyance speed V of the TAC film 11 is adjusted in the range of V = 5 m / min-30 m / min, and Q = is the supply flow rate Q of the 1st process gas (acrylic acid vapor + nitrogen) to the process space 22A. Adjusted in the range of 5 L to 33 L. In addition, the flow volume of the gas furnace 34 was made into zero. Therefore, the supply flow volume Q of the said 1st process gas is equivalent to the flow volume of the carrier path 35. The blowing temperature of the first process gas was 40 ° C, and the temperature of the TAC film 11 was 25 ° C. The supply flow rate of nitrogen gas to the processing space 22B was 10 L / min.

The probe of the oxygen concentration meter was placed under the treatment space 22A, and the oxygen concentration of the treatment space 22A was measured. As an oxygen concentration measuring instrument, the Toray Corporation make, brand name OXYGEN ANALYZER, and model number LC-850KS were used. The results are shown in Fig.

When the supply flow rate of the first process gas (horizontal axis in the graph in FIG. 16) is a constant and relatively small value, as the moving speed increases, the oxygen concentration in the processing space 22A increases. This indicates that the larger the moving speed, the larger the amount of winding of air in the processing space 22A. In addition, when the moving speed is constant, as the supply flow rate of the first process gas increases, the oxygen concentration in the processing space 22A decreases. This indicates that the gas in the processing space 22A can be replaced with the first process gas by increasing the supply flow rate of the first process gas. When the supply flow volume of the 1st process gas exceeded 20L, the oxygen concentration of process space 22A became 1000 ppm or less, and reliably became 3000 ppm or less regardless of the moving speed. Moreover, when the supply flow volume of 1st process gas exceeded 30L, the oxygen concentration of 22 A of process spaces became almost 0 ppm irrespective of the moving speed. This indicates that the gas in the processing space 22A is almost completely replaced by the first process gas.

From the above Examples 1 to 3, good adhesion is achieved by adjusting the supply flow rate of the process gas so that the oxygen concentration in the processing space 22A is preferably 3000 ppm or less, more preferably 2000 ppm, even more preferably 1000 ppm. It turned out that strength could be obtained. When the moving speed is large, it was confirmed that the supply flow rate of the process gas can be increased so that the oxygen concentration is within the above range, thereby enabling high-speed processing.

Example 4

In Example 4, using the apparatus substantially the same as the apparatus of 4th Embodiment (FIGS. 7-9), the flow volume of a process gas, the moving speed of the to-be-processed film 11, and the oxygen of the process space 22 are used. The relationship with the concentration was investigated.

The width (dimension along the axial direction of the electrode 21) of the to-be-processed film 11 was 330 mm, and the thickness of the film 11 was 0.1 mm.

The length of the axial direction of the blocking members 71 and 72 and the length of the axial direction of the electrodes 21 and 21 were 330 mm. The diameters of the electrodes 21 and 21 were 310 mm. The narrowest space | interval (thickness of the processing space 22) of the electrodes 21 and 21 was 0.7 mm.

The lower end face of the nozzle-closing member 71 was positioned at a position 21.5 mm upward with respect to the horizontal plane on which the axes of the electrodes 21, 21 were arranged. The upper end face of the closure member 72 was positioned at a position 21.5 mm below the horizontal plane. Therefore, the dimension of the up-down direction of the processing space 22 was 43 mm. The cross-sectional area of the cross section orthogonal to the axis of the processing space 22 was 72.97 mm ² . The volume of the treatment space 22 was 0.02408 L.

The thicknesses t of the side gaps 73e, 73f, 74e, and 74f were each about t = 0.5 mm.

The thickness t8 of the gap 82e between the side plate 82 and the cross section of the electrode 21 was t8 = 0.1 mm.

The length of the upper and lower sides of the shaft end closure member 80 was 134 mm, and the width (dimensions along the arrangement direction of the electrodes 21, 21) of the shaft end closure member 80 was 48 mm. The dimension of the axial direction of the axial end closure member 80 was 35 mm.

First, the atmosphere gas around the processing unit 2 and the gas in the processing space 22 were replaced with a mixed gas of 80% by volume of nitrogen (N ₂ ) and 20% by volume of oxygen (O ₂ ). Thereafter, a gas of 100% nitrogen was supplied to the processing space 22 from the upper nozzle and closing member 71 as a similar process gas. The supply flow rates of the pseudo process gas (N ₂ 100%) were as follows: four types of 10 slm, 20 slm, 30 slm and 40 slm. The feed flow rates per unit length in the axial direction were equal to four, 30 slm / m, 61 slm / m, 91 slm / m, and 121 slm / m. When the supply flow rate is 10 slm, the gas in the processing space 22 is replaced 415 times per minute. When the supply flow rate is 20 slm, the gas in the processing space 22 is replaced 830 times per minute. When the supply flow rate is 30 slm, the gas in the processing space 22 is replaced 1245 times per minute. When the supply flow rate is 40 slm, the gas in the processing space 22 is replaced by 1661 times per minute.

In parallel with the above gas supply, the electrodes 11 and 21 were rotated around the clock in FIG. 7 to convey the film 11. Or the film 11 was stopped without rotating the electrodes 21 and 21. The conveyance speeds of the film 11 were carried out like four of 0 m / min, 10 m / min, 20 m / min, and 30 m / min.

The temperature control of the electrode 21 and the nozzle and blocking member 71 was not performed.

The oxygen concentration of the processing space 22 at the time when 120 seconds passed from the start of supply of the pseudo process gas (N ₂ 100%) was measured. As the oxygen concentration meter, LC-850KS (guaranteed accuracy (repeatability) 0.05 ppm) manufactured by Toray Engineering Co., Ltd. was used. A measurement hole penetrates the bottom surface of the closure member 72 from the central portion of the upper cross section of the lower closure member 72 in the axial direction, and connects the probe of the oximeter to the opening in the bottom surface of the measurement hole. It was. With the suction pump built in the oxygen concentration meter, the gas in the processing space 22 was sucked from the measurement hole, introduced into the oxygen concentration meter, and the oxygen concentration was measured. The suction flow rate of the oxygen concentration meter was 200 ml / min.

The measurement results are shown in Table 3 below.

As the conveyance speed became larger, the oxygen concentration in the processing space 22 increased. By movement of the film 11, it is thought that the surrounding oxygen containing atmospheric gas was wound up in the process space 22.

When the feed gas flow rate was 10 slm, when the conveyance speed was 0 to 10 m / min, the oxygen concentration in the processing space 22 was a ppm concentration of 2 digits, but when the conveyance speed was 20 m / min to 30 m / min, The oxygen concentration was greatly increased to 5 ppm of ppm concentration.

When the feed gas flow rate was 20 slm, the oxygen concentration was maintained at a ppm concentration of 2 digits even when the conveyance speed was 20 m / min to 30 m / min.

When the feed gas flow rates were 30 slm to 40 slm, the oxygen concentration hardly changed even when the conveyance speed was increased.

From the above results, when the supply gas flow rate is 20 slm or more (about 60 slm / m or more per unit length in the axial direction), even if the conveyance speed of the film 11 is about 30 m / min, the winding of the atmosphere gas can be prevented. It was confirmed that it was possible to maintain the oxygen concentration sufficiently below the predetermined (3000 ppm). Therefore, by enclosing the processing space 22 with the blocking members 71, 72, and 80, the processing time can be shortened by conveying the film 11 at high speed while maintaining the oxygen concentration below a predetermined value. I can do it. Moreover, it turned out that 60 slm or more is preferable and 90 slm or more of supply gas flow volume per unit length of an axial direction is preferable. In consideration of the fact that there is a limit to the conveyance speed, and that there is a possibility of waste if gas is supplied in large quantities, the upper limit of the flow rate of the feed gas per unit length in the axial direction is preferably 180 slm.

Since it is thought that the flow volume of the atmospheric gas which enters into the process space 22 from the axial end opening 22e does not depend on the length of the axial direction of the electrode 21, the length of the axial direction of the electrode 21 and the film 11 When the width (the dimension in the axial direction) is larger than 330 mm, for example, about 1500 mm, it is inferred that the oxygen concentration in the processing space 22 can be made lower.

Example 5

In Example 5, the position of the blocking member 71 or 72 in the up-down direction was adjusted in the apparatus of Example 4. Accordingly, the thickness t of the side gaps 73e, 73f or 74e, 74f was adjusted. Specifically, the lower closure member 72 was fixed at the height in Example 4, and the upper nozzle and closure member 71 was positioned to be above the height in Example 4. The height of the nozzle and closure member 71 was made into four types of 0 mm, 0.1 mm, 0.2 mm, and 0.5 mm with respect to the height in Example 4. When the height of the blocking member 71 is 0 mm, the thicknesses t of the side gaps 73e and 73f are about t = 0.5 mm. When the height of the blocking member 71 is 0.1 mm, the thicknesses t of the side gaps 73e and 73f are about t = 0.6 mm. When the height of the blocking member 71 is 0.2 mm, the thicknesses t of the side gaps 73e and 73f are about t = 0.7 mm. When the height of the blocking member 71 is 0.5 mm, the thicknesses t of the side gaps 73e and 73f are about t = 1.0 mm.

The shaft end closure member 80 was made into a structure which can be stretched up and down in accordance with the height adjustment of the closure members 71 and 72. That is, as shown in FIG. 17, the axial end closure member 80 was made into the three stage structure of the upper end member 83, the interruption | blocking member 84, and the lower end member 85. As shown in FIG. These members 83, 84, and 85 are U-shaped (U-shaped, U-shaped) in plan view, respectively, and the upper member 83 and the lower member 85 have the same size as each other, and the stopping member ( 84 is slightly larger than the top member 83 and the bottom member 85. The upper member 83 is slidably inserted up and down on the upper side of the stopping member 84, and the upper and lower positions of the upper member 83 are fixed to the stopping member 84 by turning the bolt 86. I could do it. The lower member 85 is slidably pushed up and down to the lower side of the stopping member 84, and the upper and lower positions of the lower member 85 are fixed to the stopping member 84 of the lower member 85 by turning the bolt 87. I could do it.

Moreover, the hole 83b of the upper end member 83 is a bolt hole for connection with the edge part of the axial direction of the nozzle and closure member 71. As shown in FIG. The hole 85b of the lower member 85 is a bolt hole for connection with an end portion in the axial direction of the lower closure member 72.

The height configuration of the closure members 71 and 72 and the dimensions of the device other than the thickness t of the gaps 73e, 73f, 74e, and 74f were the same as those in the fourth embodiment.

And, in the same manner as in Example 4, followed by replacing the gas in the processing unit (2) the ambient gas around the further treatment space (22) in a nitrogen (N ₂₎ 80% by volume, oxygen (O ₂₎ gas mixture of 20% by volume. Thereafter, a gas of 100% nitrogen was supplied to the processing space 22 from the upper nozzle and closing member 71 as a similar process gas. The supply flow rates of the pseudo process gas (N ₂ 100%) were performed in three ways: 10 slm, 20 slm, and 30 slm.

In parallel with the above gas supply, the electrodes 11 and 21 were rotated around the clock in FIG. 7 to convey the film 11. The conveyance speeds of the film 11 were made into three types of 10 m / min, 20 m / min, and 30 m / min.

The temperature control of the electrode 21 and the nozzle and blocking member 71 was not performed.

The oxygen concentration of the processing space 22 at the time when 120 seconds passed from the start of supply of the pseudo process gas (N ₂ 100%) was measured. The used oxygen concentration meter and the measuring method were the same as in Example 4.

In addition, the upper nozzle closing member 71 was fixed at the height in Example 4, and the lower closing member 72 was positioned to be below the height in Example 4. The falling amount with respect to the height in Example 4 of the blocking member 72 was made into four of 0 mm, 0.1 mm, 0.2 mm, and 0.5 mm. When the falling amount of the blocking member 72 is 0 mm, the thicknesses t of the side gaps 74e and 74f are about t = 0.5 mm. When the falling amount of the blocking member 72 is 0.1 mm, the thicknesses t of the side gaps 74e and 74f are about t = 0.6 mm. When the falling amount of the blocking member 72 is 0.2 mm, the thicknesses t of the side gaps 74e and 74f are about t = 0.7 mm. When the falling amount of the blocking member 72 is 0.5 mm, the thicknesses t of the side gaps 74e and 74f are about t = 1.0 mm.

And the oxygen concentration of the process space 22 was measured similarly to the height adjustment of the nozzle and closure member 71 mentioned above.

The measurement results of Example 5 are shown in Table 4 below.

In Table 4, columns other than the lowest column fix the position of the lower blocking member 72, and are data when the upper blocking member 71 is raised. The lowest column is data when the position of the upper blocking member 71 is fixed and the lower blocking member 72 is lowered.

When the conveyance speed was 10 m / min and the feed gas flow rate was 10 slm, the oxygen concentration in the processing space 22 greatly increased as the position of the closure member 71 was increased. The oxygen concentration exceeded 3000 ppm only by raising the height of the blocking member 71 by 0.1 mm at the position of 0 mm.

On the other hand, if the feed rate is set at 10 m / min as above and the supply gas flow rate is 20 slm, the oxygen concentration in the processing space 22 will not change very much, regardless of the height of the blocking member 71, It could be kept below 30 ppm.

This tendency was also the same when the conveyance speed was 20 m / min. That is, when the conveyance speed is 20 m / min and the feed gas flow rate is 10 slm, the oxygen concentration in the processing space 22 is 5 ppm digit concentration, but the feed gas flow rate is 20 slm as it is at 20 m / min. The lower surface of the blocking member 71 could maintain the oxygen concentration in the processing space 22 at a substantially constant value of 30 ppm or less.

Even when the conveyance speed is 30 m / min and the feed gas flow rate is 30 slm, and the height of the closure member 71 is adjusted, the oxygen concentration in the processing space 22 is 30 regardless of the height of the closure member 71. It was possible to maintain almost constant value of below ppm.

Even when the conveyance speed is 30 m / min and the feed gas flow rate is 30 slm, and the height of the lower occlusion member 72 is adjusted, the oxygen concentration in the processing space 22 is independent of the height of the occlusion member 72. Was maintained at a two-digit ppm concentration. In this case, the oxygen concentration was slightly larger than when the upper closure member 71 was height-adjusted at the same conveyance speed and the same feed gas flow rate.

From the above results, when the supply gas flow rate is 20 slm or more (about 60 slm / m or more per unit length), even if the thickness t of the side gaps 73e, 73f, 74e, and 74f is slightly larger, Even if the conveyance speed of the film 11 was enlarged, it was confirmed that oxygen concentration can fully be kept below predetermined (3000 ppm).

1 Plasma Surface Treatment Apparatus
10 polarizer
11 TAC film (hard adhesive resin film)
12 PVA film (adhesive resin film)
13 glue
14 hard coating layer
2 plasma processing unit
21 electrode and vehicle
21L left electrode
21C center electrode
21R right electrode
22 processing space (discharge space)
22A processing space (discharge space)
22B processing space (discharge space)
22e shaft end opening
23 power
24 flat plate electrode
25 flat plate electrode
27 repeat rolls (means for movement of poorly adhesive films)
28 Film temperature control means
3 process gas supply system
03A first process gas supply system
30 Constant Temperature Containers (Polymer Monomer Source)
31 Inert Gas Source
32 burner
33 Inert Gas Supply Furnace
34 Plasma Gas Furnace
34v flow regulating means
With 35 carrier
35v flow regulating means
36 With Polymerizable Monomer Steam
37 process gas furnace
38 Gas thermostats
39, 39A process gas nozzle
4 second process gas supply system
41 Second Process Gas Source
43 Second Process Gas Nozzle
42 Second Process Gas Supply Path
51 oxygen mixing furnace
61 exhaust means
62 suction nozzle
7 means of occlusion
71 Side closure member for process gas nozzles
72 Lateral occlusion member
Side closure member with 72A process gas nozzle
73 concave surfaces
73e, 73f side clearance
74 concave surfaces
74e, 74f side clearance
75 rectifier
76 squirting furnace
77 Lower rectifier
78 Downstream
79 with temperature control
80 shaft end closure member
81 faceplate
82 shroud
82e shaft end clearance
90 shaft end closure member
91 shaft end clearance
92 shaft end closure member
93 labyrinth seal
94 Labyrinth Seal
95 partial annular convex
96 part annular convex
97 annular recess
98 annular recess

Claims (16)

As a method of treating the surface of the hard-adhesive resin film to be adhered to the easily-adhesive resin film,
The process gas containing the vapor of a polymerizable monomer is supplied to the process space near atmospheric pressure, the said polymerizable monomer is activated by a plasma, and it reacts with the said hard-adhesive resin film arrange | positioned at the process space, Pressure range from 1.013 × 10 ⁴ to 50.663 × 10 ⁴ Pa,
The process gas is made to move the hard-adhesive resin film relative to the processing space and to contain an atmosphere gas containing oxygen which is to be rolled into the process space together with the hard-adhesive resin film according to the relative movement. By expelling from the processing space, the supply flow rate of the process gas to the processing space is set in accordance with the relative movement speed of the hard-adhesive resin film so that the oxygen concentration in the processing space is 3000 ppm or less,
The easy-adhesive resin film is selected from polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA),
The hard-adhesive resin film is triacetate cellulose (TAC), polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethacryl Methyl acid (PMMA), polyimide (PI),
The polymerizable monomer is a monomer having an unsaturated bond and a predetermined functional group, wherein the predetermined functional group is selected from a hydroxyl group, a carboxyl group, an acetyl group, a glycidyl group, an epoxy group, an ester group having 1 to 10 carbon atoms, a sulfone group and an aldehyde group A film surface treatment method characterized by the above-mentioned. The method according to claim 1, wherein the processing space is formed between a pair of parallel cylindrical electrodes, a discharge is generated in the processing space, and the hard-adhesive resin film is wound around the pair of electrodes. In the electrodes, the hard-adhesive resin film is allowed to pass through the processing space while being in contact with one of the electrodes, and then returned to pass through the processing space while being in contact with the other electrode, and is rotated by the pair of electrodes. Move the hard-adhesive resin film, and supply flow rate of the process gas to the process space such that the supply flow rate of the process gas is 3000 ppm or less according to the rotational speed of the pair of electrodes. The film surface treatment method characterized by the above-mentioned. The film surface treatment method according to claim 1 or 2, wherein an oxygen concentration in the process gas is 0 or more and 1 ppm or less. The film surface treatment method according to claim 1 or 2, wherein the oxygen concentration in the treatment space is set to 2000 ppm or less. The film surface treatment method according to claim 1 or 2, wherein the oxygen concentration in the treatment space is set to 1000 ppm or less. The film surface treatment method according to claim 1 or 2, wherein the speed of the relative movement is 10 m / min or more. The film surface treatment method according to claim 1 or 2, wherein the polymerizable monomer is acrylic acid or methacrylic acid. After carrying out the film surface treatment method according to claim 1 or 2, the hard-adhesive resin film is adhered to the easy-adhesive resin film through a transparent adhesive, wherein the hard-adhesive resin film is a transparent protective film, An easily adhesive resin film is a polarizing film, The manufacturing method of the polarizing plate characterized by the above-mentioned. An apparatus for treating the surface of a hard-adhesive resin film to be bonded to an easily-adhesive resin film,
A plasma processing unit for activating the polymerizable monomer by plasma to contact the hard-adhesive resin film disposed in the processing space near atmospheric pressure;
Moving means for relatively moving said hard-adhesive resin film with respect to said processing space,
The process gas is supplied with a process gas containing the vapor of the polymerizable monomer to the processing space, and an atmosphere gas containing oxygen, which is intended to be rolled into the processing space together with the hard-adhesive resin film, in response to the relative movement. And a process gas supply system in which the supply flow rate of the process gas to the process space is set in accordance with the speed of the relative movement so that the oxygen concentration in the process space becomes 3000 ppm or less by expulsion from the process space.
The vicinity of the atmospheric pressure is a pressure range of 1.013 × 10 ⁴ to 50.663 × 10 ⁴ Pa,
The easy-adhesive resin film is selected from polyvinyl alcohol (PVA), ethylene vinyl acetate copolymer (EVA),
The hard-adhesive resin film is triacetate cellulose (TAC), polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethacryl Methyl acid (PMMA), polyimide (PI),
The polymerizable monomer is a monomer having an unsaturated bond and a predetermined functional group, wherein the predetermined functional group is selected from a hydroxyl group, a carboxyl group, an acetyl group, a glycidyl group, an epoxy group, an ester group having 1 to 10 carbon atoms, a sulfone group and an aldehyde group A film surface treatment apparatus. The said plasma processing part has a pair of electrode which generate | occur | produces a discharge in the said process space, The said pair of electrodes respectively formed the cylindrical shape which made the axis line to the axial direction, and is in the arrangement direction orthogonal to the said axial direction. It is arranged in parallel, the narrowest point between these electrodes and its periphery become the said processing space,
The hard-adhesive resin film is wound around the circumferential surface of the pair of electrodes. In the electrodes, the hard-adhesive resin film is passed through the processing space near the atmospheric pressure between the electrodes while contacting one electrode. It returns and passes through the said process space, contacting the other electrode, and the said moving means moves the said hard-adhesive resin film by rotation of the said pair of electrodes, and the process gas supply system raises the oxygen concentration in the said process space. The supply flow rate of the said process gas to the said process space is set according to the rotation speed of the said pair of electrodes so that it may be 3000 ppm or less, The film surface treatment apparatus characterized by the above-mentioned. The non-adhesive property according to claim 10, wherein the processing space is interposed between the axial direction and the orthogonal direction orthogonal to the arrangement direction, extending in the axial direction, and the poor adhesion between the peripheral surfaces of the electrodes. And a pair of side closure members spanning the peripheral surfaces of the pair of electrodes to form a gap allowing the winding of the resin film to the respective electrodes, wherein at least one of the pair of side closure members is the process gas. The film surface treatment apparatus which comprises the process gas nozzle of the downstream end of a supply system. 12. The shaft end closure according to claim 11, wherein the pair of electrodes and the pair of side closure members are disposed at ends of the same side in the axial direction and covered at the ends of the same side in the axial direction of the processing space. A film surface treatment apparatus further comprising a member. The film surface treatment apparatus according to claim 12, wherein the axial end closure member is attached to at least one of the pair of side closure members. The film surface treatment apparatus according to claim 12, wherein a labyrinth seal is formed between at least one of the pair of electrodes and the shaft end closure member. The moving means for moving the said hard-adhesive resin film relative to the said process space is further provided, The speed of the said relative movement by the said moving means is 10 m /, in any one of Claims 9-14. It is minutes or more, The film surface treatment apparatus. 15. The film surface treatment apparatus according to any one of claims 9 to 14, wherein the polymerizable monomer is acrylic acid or methacrylic acid.

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