TWI522400B - Membrane surface treatment method and device - Google Patents

Description

Membrane surface treatment method and device

The present invention relates to a method and apparatus for surface treatment of a resin film, and more particularly to an improvement in temperature resistance of a film laminate formed by a film which is not only suitable for improving the adhesion of the film. Membrane surface treatment method and device.

For example, a polarizing plate is mounted on a liquid crystal display device. The polarizing plate is formed as a film laminate in which a polarizing film and a protective film are laminated. In general, the polarizing film contains a resin film (hereinafter referred to as "PVA film") containing polyvinyl alcohol (PVA) as a main component. The protective film contains a resin film containing a cellulose triacetate (TAC) as a main component (hereinafter referred to as "TAC film"). A water-based adhesive such as a polyvinyl alcohol-based or polyether-based adhesive is used as an adhesive for the film. The adhesion between the PVA film and the above-mentioned adhesive is good, but the adhesion of the TAC film is not good. Therefore, in Patent Documents 1 and 2, a film (coagulation layer) of a polymerizable monomer such as acrylic is formed on the surface of the protective film before the subsequent step, and then the atmospheric piezoelectric slurry is irradiated to form a polymer film such as polyacrylic acid.

[Previous Technical Literature] [Patent Literature]

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

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-150372

The present inventors will make the TAC film and the PVA film after the above-mentioned atmospheric piezoelectric slurry is irradiated. The polarizing plate thus formed is immersed in warm water as an alternative evaluation for durability evaluation of high temperature or high humidity, resulting in color omission or delamination, resistance to warm water (temperature resistance) Lower (refer to Comparative Example 1 below). In particular, it is conceivable that when the above-mentioned polymer film is a water-soluble polymer such as polyacrylic acid, the temperature resistance of water is lowered.

The present invention has been made in view of the above-described circumstances, and it is an object of the present invention to improve not only the adhesion of the resin film but also the film formation formed by the subsequent surface treatment of the resin film constituting the film laminate such as a polarizing plate. The body's tolerance to warm water (temperature resistance) is improved.

In order to solve the above problems, the method of the present invention is characterized in that it is a film obtained by plasma-polymerizing a polymerizable monomer on the surface of a resin-treated film, and coating a film of the polymer of the polymerizable monomer on the surface. a surface treatment method comprising: a first treatment step of contacting the first gas containing the vaporized polymerizable monomer and the crosslinkable additive component capable of plasma-crosslinking the polymer; And the second processing step of plasma-dissolving the discharge generating gas (including excitation, activation, radicalization, ionization, etc.) and contacting the treated film after the first processing step or in parallel with the first processing step Further, the content of the crosslinkable additive component in the first gas with respect to the polymerizable monomer is adjusted within a specific range.

By the first treatment step and the second treatment step, a film of a plasma polymer of a polymerizable monomer can be formed on the surface of the film to be treated. Crosslinking The addition of the components allows crosslinking of the above polymers (including high degree of crosslinking). Further, the film of the polymer is an adhesion promoting layer, and the adhesion of the film to be treated can be improved, and the hydrophobicity of the adhesion promoting layer can be improved by the crosslinking, and the resistance of the film laminate after the film can be improved. Warm water. Even if the above polymer is a water-soluble polymer such as polyacrylic acid, the hydrophobicity can be sufficiently improved, and the temperature resistance can be sufficiently improved. By adjusting the content ratio of the crosslinkable additive component, the cross-linking action can be surely exhibited, and the adhesion can be ensured. If the above content ratio is too small, the crosslinking effect cannot be exhibited. If the content ratio is too large, the adhesion is lowered.

Here, the term "temperature resistance" means that a film laminate such as a polarizing plate in which the film to be processed is formed next to another film is immersed to a certain degree in temperature (for example, 50 ° C to 80 ° C) in warm water to a certain extent. For the time (for example, 1 h to 5 h), the above-mentioned film laminate is also less likely to cause fading or peeling.

The content of the crosslinkable additive component relative to the polymerizable monomer is preferably from 0.5% by weight to 10% by weight. By setting the content ratio to 0.5% by weight or more, the action of crosslinking the polymerizable monomer can be reliably exhibited. By setting the above content ratio to 10 wt% or less, the affinity for the adhesive can be maintained, and the adhesion strength can be surely obtained.

Further, the apparatus of the present invention is characterized in that it is a film surface treatment apparatus which is a plasma-polymerized monomer on a surface of a resin-treated film and which is coated with a polymer film of the above-mentioned polymerizable monomer. The present invention includes a generating unit that generates a first gas containing the polymerizable monomer and a crosslinkable additive component capable of plasma-crosslinking the polymer, and a first nozzle that sorbs the first gas To the above treated film; a pair of electrodes that generate an electric discharge in the vicinity of atmospheric pressure by applying an electric field in a gap between them; a second nozzle that supplies a discharge generating gas to the gap; and a transfer mechanism that passes the processed film to face the first The first processing space of the nozzle is transported by the gap, and the content of the crosslinkable additive component in the first gas with respect to the polymerizable monomer is adjusted within a specific range by the generating unit.

By spraying the first gas onto the film to be treated, a mixed coagulation layer of a polymerizable monomer and a crosslinkable additive component can be formed on the surface of the film to be treated. Then, by the discharge between the electrodes, the polymerizable monomer in the mixed coagulation layer is subjected to plasma polymerization to form a film of a polymer of a polymerizable monomer on the surface of the film to be treated, and by crosslinking as described above. The sexually added component can crosslink the above polymer (including high degree of crosslinking). Further, the film of the polymer is an adhesion promoting layer, and the adhesion of the film to be treated can be improved, and the hydrophobicity of the adhesion promoting layer can be improved by the crosslinking, and the resistance of the film laminate after the film can be improved. Warm water. By adjusting the content ratio of the crosslinkable additive component by the above-described production unit, the cross-linking action can be reliably expressed, and the adhesion can be ensured. The above content ratio is preferably from 0.5 wt% to 10 wt%. If the above content ratio is less than 0.5% by weight, it is difficult to express cross-linking action. When the content rate exceeds 10% by weight, for example, the affinity for the PVA-based adhesive is lowered, and then the strength is deteriorated.

As the above-mentioned adhesive, for example, a water-based adhesive is preferably used. Examples of the water-based adhesive include a polyvinyl alcohol-based adhesive and a polyurethane-based adhesive (which may be a one-component type or a two-component type), and an aqueous urethane. An ester adhesive, an acrylic adhesive, a polysulfide adhesive, a polyoxynium adhesive (which may be a one-component type or a two-component type), a modified polyfluorene-based adhesive, and an epoxy modification A polyxylene adhesive, a butyl rubber-based adhesive, or the like.

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

The film to be treated is preferably an optical resin film which is difficult to bond. The present invention is suitable for a surface treatment in which the adhesion of the optical resin film which is difficult to adhere to the optical resin film which is easy to adhere, and the adhesion and temperature resistance of the optical resin film which is difficult to bond. Examples of the main component of the above-mentioned difficult-to-adhere optical resin film include cellulose triacetate (TAC), polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), and cyclic olefin copolymer (COC). ), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyimine (PI), and the like. The above treated film is more preferably a TAC film. The main component of the above-mentioned easy-to-adhere optical resin film is, for example, polyvinyl alcohol (PVA) or ethylene-vinyl acetate copolymer (EVA).

The polymerizable monomer is preferably a monomer which is polymerized by irradiation with a plasma. The polymerizable monomer may, for example, be a monomer having an unsaturated bond and a specific functional group. The specific functional group is preferably selected from the group consisting of a hydroxyl group, a carboxyl group, an ethyl fluorenyl group, an ester group having a carbon number of 1 to 10, a mercapto group, an aldehyde group, and more preferably a carboxyl group or a hydroxyl group. A hydrophilic group such as a base.

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

Examples of the monomer having an unsaturated bond and a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and 2-methylpropenylpropylpropionic acid.

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

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

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

When the film to be treated is an olefin-based monomer polymerization film such as COP, COC, PP or PE, the polymerizable monomer may be a water-soluble monomer or an olefin-based monomer. Examples of the water-soluble monomer include acetaldehyde, vinyl alcohol, acrylic acid (AA), methacrylic acid, styrenesulfonic acid, N,N-dimethylaminopropylpropenylamine, and N,N-dimethyl group. Amidoxime and the like. As the olefin monomer, except 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-cyclopentene, 1-cyclohexene, 1-cycloheptene, 1-cyclooctene Other examples include cyclopentadiene and dicyclopentadiene (DCPD).

More preferably, the above polymerizable monomer has high affinity with the film to be treated when plasma polymerization is carried out. Examples of the monomer include a monomer having an ethylenically unsaturated double bond and a carboxyl group among the polymerizable monomers, and specific examples thereof include acrylic acid (CH ₂ =CHCOOH) and methacrylic acid (CH ₂ =C(CH). ₃ ) COOH). The polymerizable monomer of the first gas and the polymerizable monomer of the third gas are more preferably acrylic acid or methacrylic acid, and further preferably acrylic acid. Thereby, affinity with the film to be treated can be exhibited when performing plasma polymerization. Therefore, the adhesion of the film to be processed and the subsequent durability can be surely improved.

The first gas may further contain a carrier gas that transports the polymerizable monomer and the crosslinkable additive component. The carrier gas is preferably an inert gas selected from the group consisting of nitrogen, argon, and helium. From the viewpoint of economy, it is preferred to use nitrogen as the above carrier gas. The component of the carrier gas may be the same as or different from the components of the discharge generating gas.

Most of the polymerizable monomers such as acrylic acid or methacrylic acid are in a liquid phase at normal temperature and normal pressure. Such a polymerizable monomer may be vaporized in a carrier gas such as an inert gas. The generating unit may further include a vaporizer of a polymerizable monomer. As a method of vaporizing a polymerizable monomer in a carrier gas, an extrusion method in which a saturated vapor on a liquid surface of a polymerizable monomer is extruded by a carrier gas; and a carrier gas in a polymerizable monomer liquid is mentioned Foaming method of foaming; heating method of heating a polymerizable monomer liquid to promote evaporation. The extrusion method and the heating method, or the foaming method and the heating method can also be used in combination. One part of the carrier gas may be introduced into the gasifier, the remainder may not pass through the gasifier, or the above part of the carrier gas may be merged with the remaining portion on the downstream side of the gasifier. The concentration of the polymerizable monomer in the first gas can be adjusted by the temperature of the gasifier or the distribution ratio of the above portion of the carrier gas to the remaining portion.

In the case of heating and gasification, in consideration of the burden of the heater, the polymerizable monomer is preferably one having a boiling point of 300 ° C or less. Moreover, it is preferable that the polymerizable monomer is selected so as not to be decomposed (chemically changed) by heating.

The crosslinkable additive component preferably has a property of causing cross-linking of the polymer by irradiation with plasma. Examples of such a crosslinkable additive component include an unsaturated hydrocarbon compound having two or more unsaturated bonds in the molecule, an unsaturated hydrocarbon compound having a triple bond, or a metal alkoxide compound such as ruthenium or titanium.

The unsaturated hydrocarbon compound having two or more unsaturated bonds may, for example, be a diallyl compound. Examples of the diallyl compound include allyl methacrylate, diallyl maleate, 1,5-hexadiene or 1,7-octadiene. The crosslinkable additive component is more preferably allyl methacrylate, whereby good cold water resistance can be obtained. The crosslinkable component is more preferably allyl methacrylate, and the content of the polymerizable monomer is from 0.5% by weight to 10% by weight. Thereby, the cross-linking action can be surely exhibited, and the adhesion can be surely obtained.

Examples of the unsaturated hydrocarbon compound having a triple bond include an alkyne compound such as 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, and acetylene.

Examples of the metal alkoxide compound include tetraethoxydecane, tetramethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, and 3-aminopropyltrimethoxydecane. - aminopropyl triethoxy decane, methyl trimethoxy decane, methyl triethoxy decane, ethyl trimethoxy decane, ethyl triethoxy decane, tert-butyl trimethoxy decane, A decane oxide compound such as a third butyl triethoxy decane or a titanium alkoxide compound such as titanium oxychloride or titanium oxychloride. Since the decane oxide compound has a low boiling point and is easily vaporized, it is preferably used as the crosslinkable additive component. The decane oxide compound constituting the crosslinkable additive component is preferably vinyltrimethoxydecane, whereby good temperature resistance can be obtained.

The crosslinkable component may be a glycidyl compound such as allyl glycidyl ether or glycidyl methacrylate, in addition to the above-exemplified compounds, and may be acrylonitrile, acrylamide or the like. Cyclopentadiene and the like.

A plurality of the crosslinkable additive components listed above may also be combined.

The crosslinkable additive component may have polymerizability similarly to the polymerizable monomer.

The above-mentioned crosslinkable additive component may have a boiling point lower than the boiling point of the polymerizable monomer, may be the same degree, or may be higher than the boiling point of the polymerizable monomer.

The crosslinkable additive component may also be a liquid at normal temperature and pressure. The generating unit may further include a vaporizer that adds a crosslinkable component. Examples of the gasification method include an extrusion method in which a saturated vapor on a liquid surface of the crosslinkable additive component is extruded by a carrier gas such as an inert gas; and a carrier gas is foamed in a solution of the crosslinkable additive component. A foaming method; a heating method in which the solution of the crosslinkable additive component is heated to promote evaporation. The extrusion method and the heating method, or the foaming method and the heating method can also be used in combination. One part of the carrier gas may be introduced into the gasifier of the crosslinkable additive component, and the remainder may not pass through the gasifier, or the carrier gas may be disposed on the downstream side of the gasifier. The above part merges with the rest. The concentration of the crosslinkable additive component in the first gas can be adjusted by the temperature of the vaporizer or the distribution ratio of the portion of the carrier gas to the remaining portion.

The first gas can be obtained by mixing a polymerizable monomer in a liquid phase with a crosslinkable component in a liquid phase to vaporize the mixture. The above content ratio can be adjusted by adjusting the mixing ratio or vaporization temperature of the above mixed liquid. Alternatively, the crosslinkable additive component of the liquid phase polymerizable monomer and the liquid phase may be separately vaporized, and then the vaporized polymerizable monomer may be mixed with the vaporized crosslinkable additive component to obtain the first 1 gas. The polymerizable monomer may be mixed with the crosslinkable additive component on the surface of the film to be treated.

The production unit may include a vaporizer that vaporizes a mixed liquid of the polymerizable monomer and the crosslinkable additive component. The generating unit may include: a first vaporizer that vaporizes the polymerizable monomer; a second vaporizer that vaporizes the crosslinkable additive component; and a mixing unit that is derived from the first gas The gas of the catalyst is mixed with the gas from the second gasifier described above.

The discharge generating gas is preferably an inert gas. As the inert gas, in addition to nitrogen (N ₂ ), a rare gas such as helium (He), argon (Ar) or helium (Ne) may be mentioned. From the viewpoint of economy, it is more preferable that the above-mentioned discharge generating gas is nitrogen. The discharge generating gas may be a mixed gas of a plurality of gases.

In the second processing step, the second gas obtained by adding oxygen to the discharge generating gas may be plasma-formed and contacted with the film to be processed. The second nozzle may be formed by supplying a second gas obtained by adding oxygen to the discharge generating gas to the gap. In this case, the second gas The oxygen content is preferably 0.5 vol% or less based on the discharge generating gas. Thereby, the temperature resistance to water can be further improved, and the decrease in the adhesion of the film to be treated can be suppressed.

According to the present invention, the adhesion of the film to be treated can be improved, and the resistance of the film laminate formed by the subsequent step to warm water (temperature resistance) can be improved.

Hereinafter, embodiments of the present invention will be described based on the drawings.

1 and 2 show a first embodiment of the present invention. The film to be processed 9 of this embodiment is a resin film which is a protective film of a polarizing plate (film laminate). The film to be treated 9 contains a TAC film containing cellulose triacetate (TAC) as a main component, and is formed into a continuous sheet shape. The thickness of the film 9 is, for example, about 100 μm.

The film surface treatment apparatus 1 includes a support portion and transport unit 3 of the film 9, a first processing unit 91, and a second processing unit 92. The support unit and the transport unit 3 include the first roller 31, the second roller 32, and the guide roller 36, and have a function as a support portion of the support film 9 and a function as a transport mechanism of the transport film 9. The rolls 31 and 32 are formed into a cylindrical body having the same diameter and the same axial length as each other. The axes of the rolls 31, 32 are oriented in a process width direction orthogonal to the plane of the paper of Fig. 1. The two rolls 31, 32 are arranged in parallel. A narrow gap 39 is formed between the rolls 31, 32. The thickness of the narrowest portion of the gap 39 is, for example, about 1 mm to several mm. Two guide rolls 36 and 36 are disposed below the gap 39.

At least the outer peripheral portion of each of the rolls 31, 32 contains a metal, and a peripheral surface of the metal portion is covered with a solid dielectric layer. These rolls 31, 32 also serve as film surfaces A pair of electrodes for plasma discharge generation of the device 1. Hereinafter, the roller 31 is appropriately referred to as a first electrode 31, and the roller 32 is referred to as a second electrode 32. The illustration is omitted, and the first electrode 31 is connected to a power source. The second electrode 32 is electrically grounded. The power source supplies high frequency power to the first electrode 31. The supplied electric power is, for example, a intermittent wave such as a pulse, but is not limited thereto, and may be a continuous wave such as a sine wave. By this power supply, a plasma discharge is generated between the electrodes 31 and 32, and the gap 39 becomes a discharge space.

The film-like processed film 9 in the continuous sheet shape has a width direction toward the processing width direction (a direction orthogonal to the paper surface of FIG. 1), and is circumferentially suspended around the circumference of the rolls 31 and 32, respectively. The peripheral surface including the upper surface of each of the rolls 31 and 32 and the portion of the half of the portion forming the gap 39 are covered by the film to be processed 9. The film to be treated 9 is vertically suspended from the gaps 39 between the rolls 31, 32, and is hung around the guide rolls 36, 36. Thereby, the processed film 9 between the gap 39 and the guide rolls 36 and 36 is formed in a triangular-shaped folded-back portion 9c as viewed from the processing width direction.

Although not shown in the drawing, a rotation mechanism is connected to each of the rollers 31 and 32. The rotation mechanism includes a drive unit such as a motor, and a transmission mechanism that transmits the driving force of the drive unit to the shafts of the rollers 31 and 32. The transmission mechanism comprises, for example, a conveyor belt, a pulley mechanism or a gear train. In Fig. 1, as indicated by a hollow arc-shaped arrow, the rollers 31, 32 are rotated about their respective axes and synchronized with each other in the same direction (clockwise in Fig. 1) by a rotating mechanism. Thereby, the film to be processed 9 is conveyed to the substantially right side in the figure in the order of the first roll 31 and the second roll 32.

A temperature control unit (not shown) is provided for each of the rollers 31 and 32. The temperature control unit includes, for example, a temperature control line formed in the rolls 31, 32. By adjusting the temperature in the pipeline The rollers 31 and 32 can be tempered by flowing a medium such as temperature-controlled water. Further, the film to be treated 9 on the circumferential surface of the rolls 31 and 32 can be tempered. The set temperatures of the rolls 31 and 32 are preferably lower than the condensation temperature of the polymerizable monomer and the crosslinkable additive component described later.

Next, the first processing unit 91 will be described. The first processing unit 91 includes a first gas supply system 10 . The first gas supply system 10 includes a first gas generating unit 11 and a first nozzle 14 . The generating unit 11 includes a gasifier. A raw material liquid is stored in the gasifier 11. The raw material liquid is obtained by mixing a specific amount of a crosslinkable additive component into a polymerizable monomer. Here, as the polymerizable monomer, acrylic acid is used. As the crosslinkable additive component, allyl methacrylate was used. A heater is attached to the gasifier 11. The temperature of the raw material liquid can be adjusted by a heater.

A carrier gas of a specific flow rate is introduced into the gasifier 11. As the carrier gas, for example, nitrogen (N ₂ ) is used. The raw material liquid component (acrylic acid + allyl methacrylate) was vaporized into the carrier gas (N ₂ ). The gasification can be a foaming method or an extrusion method. Thereby, the first gas is generated. The first gas contains acrylic acid (polymerizable monomer), allyl methacrylate (crosslinkable additive component), and nitrogen (carrier gas). The content ratio of allyl methacrylate (crosslinkable component) to acrylic acid (polymerizable monomer) in the first gas is set to be less than a specific range of acrylic acid, and is preferably set to 0.5 wt% to 10 Wt%. The above content ratio can be adjusted by the mixing ratio of the raw material liquid in the gasifier 11 or the set temperature of the gasifier 11.

Each of the first gas supply systems 10 may have a vaporizer of a polymerizable monomer and a vaporizer of a crosslinkable additive component. Can be gasified in each gasifier The gases are mixed with each other to generate a first gas.

The first gas supply line 13 extends from the gasifier 11 . A temperature control unit (not shown) including a heating belt or the like is provided in the first gas supply line 13. The set temperature of the first gas supply line 13 is higher than the condensation temperature of acrylic acid and allyl methacrylate.

The first nozzle 14 is disposed on the upper side of the first roller 31. The first gas supply line 13 is connected to the first nozzle 14 . The first nozzle 14 extends long in the processing width direction and has a certain width in the circumferential direction of the first roller 31 (left and right in FIG. 1). A shielding member 15 is provided at the bottom of the first nozzle 14. The shielding member 15 is formed in a curved plate shape having an arcuate cross section in the circumferential direction of the first roller 31 and extending substantially the same length as the first roller 31 in the processing width direction. Both end portions of the shielding member 15 in the arc direction (left and right in FIG. 1) project from the first nozzle 14 in the circumferential direction of the first roller 31.

A first processing space 93 is formed between the first nozzle 14 and the first roller 31. The lower surface of the first nozzle 14 faces the first processing space 93. The first roller 31 is provided with a first processing space forming portion as the first processing portion 91. The first processing space 93 is formed as a space having an arcuate cross section along the circumferential surface of the upper side of the first roller 31. The thickness of the first processing space 93 is, for example, about 1 mm to 10 mm. The first processing space 93 is extended toward the both sides in the circumferential direction of the first roller 31 by the shielding member 15 than the first nozzle 14 .

A discharge port 14e is provided on a lower surface of the first nozzle 14. The discharge port 14e passes through the shielding member 15 and communicates with the first processing space 93. The discharge port 14e is arranged to be distributed along the processing width direction (direction orthogonal to the paper surface of FIG. 1) of the first nozzle 14 and the roll circumferential direction (left-right direction of FIG. 1). First gas from the first gas supply pipe The path 13 is supplied to the first nozzle 14. The first gas is uniformly dispersed in the processing width direction by the rectifying portion (not shown) in the first nozzle 14, and is then ejected from the ejection port 14e. The discharge stream of the first gas is formed as a gas stream uniformly distributed in the processing width direction.

A temperature control unit (not shown) is provided in the first nozzle 14, and includes a temperature control line through which the temperature control water passes. The set temperature of the first nozzle 14 is higher than the condensation temperature of acrylic acid and allyl methacrylate.

Next, the second processing unit 92 will be described. The second processing unit 92 includes a second gas supply system 20 . The second gas supply system 20 includes a second gas supply source 21 and a second nozzle 24 . The second gas supply source 21 supplies nitrogen gas (N ₂ ) as a discharge generating gas. The second gas supply line 23 extends from the second gas supply source 21. The second gas supply line 23 is connected to the second nozzle 24 .

The second nozzle 24 is provided inside the triangular-shaped folded portion 9c of the film 9 to be processed on the lower side between the rollers 31 and 32. The second nozzle 24 extends long in the processing width direction, and the cross section orthogonal to the extending direction gradually narrows toward the upper side. The discharge port of the upper end (top end) of the second nozzle 24 faces the gap 39. The lower end of the gap 39 is blocked to some extent by the second nozzle 24. The discharge generating gas (N ₂ ) from the second gas supply source 21 passes through the supply line 23, and is uniformly dispersed in the processing width direction by the rectifying portion (not shown) in the second nozzle 24. The discharge generated gas is ejected from the discharge port at the upper end of the second nozzle 24 into the gap 39, and a plasma discharge is generated by application of an electric field in the gap 39. The discharge flow of the discharge generating gas from the nozzle 24 is formed as a gas flow uniformly distributed in the processing width direction orthogonal to the paper surface of Fig. 1 . The gap 39 constitutes a second processing space of the second processing unit 92. The rollers 31 and 32 provide a second processing space forming portion as the second processing unit 92.

A temperature control line (discharge generation gas temperature adjustment unit) (not shown) is provided in the second nozzle 24. The temperature control medium such as water passes through the temperature control line in the second nozzle 24. Thereby, the second nozzle 24 can be tempered, and the discharge temperature of the discharge generating gas can be further adjusted. The set temperature of the second nozzle 24 is lower than the set temperature of the first nozzle 14, and is preferably lower than the condensation temperature of acrylic acid (polymerizable monomer) and allyl methacrylate (crosslinking additive component).

The blocking portion 25 is disposed between the rollers 31 and 32 on the upper side of the gap 39. The blocking portion 25 faces the second nozzle 24 up and down with the gap 39 interposed therebetween. The blocking portion 25 extends long in the processing width direction, and the cross section orthogonal to the extending direction is gradually narrowed downward. The lower end (top end) of the blocking portion 25 faces the gap 39. The upper end of the gap 39 is blocked to some extent by the blocking portion 25. The blocking portion 25 may be a nozzle having the same configuration as the second nozzle 24. The nozzle 25 and the second nozzle 24 may be vertically reversed or may be configured to eject a discharge generating gas from the nozzle 25.

A method of surface-treating the film to be processed 9 by the film surface treatment apparatus 1 configured as described above and a method of manufacturing a polarizing plate will be described.

[Support steps, transfer steps]

The film to be treated 9 is hung around the rolls 31, 32 and the guide rolls 36, 36.

The rollers 31 and 32 are rotated in the clockwise direction in Fig. 1, and the film to be processed 9 is conveyed to the substantially right side.

[First Processing Step]

In the first gas supply source 11, acrylic acid (polymerizable monomer) and allyl methacrylate (crosslinkable additive component) are vaporized in a carrier gas (N ₂ ) to form a first gas. The content of allyl methacrylate in the first gas is preferably 0.5% by weight to 10% by weight based on the acrylic acid. The first gas is transported to the first nozzle 14 by the first gas supply line 13 . By adjusting the temperature of the first gas supply line 13 and the first nozzle 14, it is possible to prevent the acrylic acid and the allyl methacrylate in the first gas from being condensed in the first gas supply line 13 and the first nozzle 14.

The first gas is discharged from the discharge port 14e into the first processing space 93. This first gas is in contact with the surface of the film to be processed 9 in the first processing space 93. Then, acrylic acid and allyl methacrylate in the first gas are condensed and adhered to the film to be treated 9, and a condensation layer is formed on the surface of the film to be treated 9. By adjusting the temperature of the roller 31, the film to be processed 9 is further tempered, and the above-described condensation can be surely produced. Most of the coagulation layer is composed of an acrylic monomer in which a trace amount or a small amount of allyl methacrylate is mixed. The first gas diffusion can be suppressed by the shielding member 15, and the amount of adhesion of the condensation layer component to the film to be treated 9 can be secured.

[Second processing step]

As the rollers 31 and 32 rotate, the film 9 to be processed which has passed through the first processing step is transported to the second processing space 39. Nitrogen gas (N ₂ ) is discharged from the second nozzle 24 into the second processing space 39 as a discharge generating gas. In parallel, electric power is supplied to the first roller electrode 31, and a discharge in the vicinity of the atmospheric pressure is generated in the second processing space 39, and the nitrogen gas is plasma-formed to generate a nitrogen gas plasma. This nitrogen plasma is in contact with the surface of the film to be processed 9 in the second processing space 39. Thereby, the acrylic acid (polymerizable monomer) constituting the coagulation layer is subjected to a plasma polymerization reaction, and a plasma cross-linking reaction of allyl methacrylate (crosslinking additive component) is produced. By the above plasma polymerization reaction, a film of polyacrylic acid can be formed on the surface of the film to be treated 9. The polyacrylic acid has good affinity with TAC constituting the film to be treated 9, and sufficiently reacts with the surface molecules of TAC to be in close contact with the film to be treated 9. The polyacrylic acid film serves as an adhesion promoting layer, and the adhesion of the TAC film can be improved. Further, by the above-mentioned plasma crosslinking reaction, the polyacrylic acid film can be crosslinked, and the degree of polymerization can be improved. Thereby, the hydrophobicity of the adhesion promoting layer is improved.

The film to be processed 9 is folded back by the guide roller 36, and is reciprocated in the second processing space 39, and is subjected to secondary processing in the second processing space 39.

The surface-treated film 9 after the surface treatment was passed through a PVA-based adhesive and a PVA film to prepare a polarizing plate. Since the adhesion promoting layer containing the above plasma polymerization film is formed on the surface of the film to be processed 9, the adhesion strength between the film to be treated 9 and the PVA adhesive can be improved. Further, since the adhesion promoting layer is crosslinked to increase the degree of polymerization, the temperature resistance of the polarizing plate can be improved. That is, even if the polarizing plate is immersed in warm water for a long period of time, fading or peeling can be suppressed or prevented.

By setting the content of allyl methacrylate to acrylic acid to 0.5 wt% or more, the crosslinking action can be reliably exhibited, and the temperature resistance of the polarizing plate can be surely improved. By setting the content of allyl methacrylate to acrylic acid to 10 wt% or less, the affinity of the adhesion promoting layer to the adhesive can be ensured, and the adhesion strength can be surely improved. As a result, the quality of the polarizing plate can be improved.

Next, other embodiments of the present invention will be described. In the following embodiments, the same components as those in the above-described embodiments are denoted by the same reference numerals, and their description is omitted.

Fig. 3 is a view showing a second embodiment of the present invention. In the second embodiment, the gas composition of the second gas supply system 20 is different from that of the first embodiment. In the second gas supply source 22 of the second embodiment, the second gas obtained by adding a trace amount of oxygen (O ₂ ) to nitrogen gas (discharge generating gas) is sent to the supply line 23 . The second gas (N ₂ + O ₂ ) is supplied from the second nozzle 24 to the gap 39. The oxygen content in the second gas is preferably 0.5 vol% or less with respect to nitrogen (discharge generating gas). The second gas supply source 22 may be a storage tank storing a mixed gas of nitrogen and oxygen (N ₂ + O ₂ ), or may be a storage tank storing nitrogen gas and a storage tank storing oxygen, and storing the same. The gas of the tank is mixed in an appropriate amount.

In the second embodiment, after the formation of the condensation layer in the first processing space 93 (first processing step), the second gas (N ₂ + O ₂ ) is ejected from the second nozzle 24 to the second processing space 39. It is plasma-treated and brought into contact with the film to be treated 9 (second processing step). Thereby, the above-mentioned coagulation layer can be subjected to plasma polymerization to form an adhesion promoting layer. By including a trace amount of oxygen in the second gas, the hydrophobicity of the adhesion promoting layer can be further improved. As a result, the temperature resistance of the polarizing plate can be further improved.

4 and 5 show a third embodiment of the present invention. In the film surface treatment apparatus 1X of the third embodiment, the support unit and transport unit 3 includes three rollers 31, 32, and 33. The first processing unit 91 includes two first nozzles 14A and 14B, and the second processing unit 92 includes Two second nozzles 24A, 24B. The three rollers 31, 32, 33 are aligned in parallel with each other and sequentially in a direction orthogonal to the axis. These rolls 31 to 33 also serve as electrodes for plasma discharge generation. Hereinafter, the roller 31 is appropriately referred to as a first electrode 31, and the roller 32 is referred to as a second electrode 32. The roller 33 is referred to as a third electrode 33. Although not shown, the second electrode 32 in the center is connected to the power source, and the first electrode 31 and the third electrode 33 at both ends are electrically grounded. Alternatively, the first electrode 31 and the third electrode 33 at both ends may be connected to the power source, and the second electrode 32 at the center may be electrically grounded. A gap 39A (a second processing space in the preceding stage) is formed between the electrodes 31 and 32. A gap 39B (a second processing space in the latter stage) is formed between the electrodes 32 and 33.

The film to be treated 9 is hung around the circumferential surface on the upper side of each of the rolls 31, 32, and 33. The portion 9c between the first roller 31 and the second roller 32 in the film to be processed 9 is suspended around the guide rollers 36A and 36A to be folded back. The portion 9d between the second roller 32 and the third roller 33 in the film to be processed 9 is suspended around the guide rollers 36B and 36B to be folded back.

The first nozzle 14A is disposed on the upper side of the first roller 31. A shielding member 15A is attached to the first nozzle 14A. The shape and configuration of the first nozzle 14A and the shielding member 15A are the same as those of the first nozzle 14 and the shielding member 15 of the first embodiment. A first processing space 93A of the front stage is formed between the first nozzle 14A and the first roller 31.

The first nozzle 14B is disposed on the upper side of the second roller 32. A shielding member 15B is attached to the first nozzle 14B. The shape and configuration of the first nozzle 14B and the shielding member 15B are the same as those of the first nozzle 14 and the shielding member 15 of the first embodiment. A first processing space 93B in the subsequent stage is formed between the first nozzle 14B and the second roller 32.

The first gas supply line 13 is branched into two paths, and one of the branch passages 13a is connected to the first nozzle 14A of the preceding stage, and the other branching passage 13b is connected to the first nozzle 14B of the subsequent stage. The first gas from the supply source 11 is branched into the respective branch paths 13a and 13b, and introduced into the processing space 93A from each of the nozzles 14A and 14B. 93B. The discharge flows from the nozzles 14A, 14B may be the same or different.

Further, a first gas supply source 11 may be provided for each of the nozzles 14A and 14B. In this case, the composition, the flow rate, the content ratio of the crosslinkable additive component, and the like of the first gas of the two first gas supply sources may be the same or different from each other.

The second nozzle 24A is disposed in the folded portion 9c on the lower side of the inter-roll gap 39A. An obstruction portion 25A is disposed on the upper side of the gap 39A. The shape and structure of the second nozzle 24A and the damper portion 25A are the same as those of the nozzle 24 and the dam portion 25 of the first embodiment.

The second nozzle 24B is disposed in the folded portion 9d on the lower side of the inter-roll gap 39B in the latter stage. The blocking portion 25B is disposed on the upper side of the gap 39B. The shape and structure of the second nozzle 24B and the damper portion 25B are the same as those of the nozzle 24 and the dam portion 25 of the first embodiment.

The second gas source 21 of the third embodiment is the same as the first embodiment, and is only for the discharge generating gas (N ₂ ). The supply line 23 of the second gas source 21 is branched into two paths, one of which is connected to the second nozzle 24A of the preceding stage, and the other branching line 23b is connected to the second nozzle 24B of the latter stage. The discharge generating gas (N ₂ ) from the supply source 21 is branched into the respective branch paths 23a and 23b, and introduced into the plasma processing spaces 39A and 39B from the respective nozzles 24A and 24B. The discharge flow rates of the discharge generating gases (N ₂ ) from the nozzles 24A and 24B may be the same or different. Further, a second gas supply source 21 may be provided for each of the nozzles 24A and 24B.

In the third embodiment, the film to be processed 9 is placed on the first roll 31 and the second roll 32, The order of the second rolls 33 is conveyed to the right in FIG. In parallel, the first gas is ejected from the first nozzle 14A, and the first condensation layer containing a mixed liquid of acrylic acid and allyl methacrylate is formed on the surface of the film 9 to be processed in the first processing space 93A in the preceding stage (previous stage) First processing step). Then, plasma discharge is performed in the second processing space 39A of the preceding stage, whereby the condensed layer component is subjected to a plasma polymerization reaction and a crosslinking reaction, and a first adhesion promoting layer is formed on the surface of the film to be processed 9 (front stage The second processing step). Further, the first gas is ejected from the first nozzle 14B, and a mixed liquid containing acrylic acid and allyl methacrylate is formed on the first adhesion promoting layer of the film 9 to be processed in the first processing space 93B in the subsequent stage. The second coagulation layer (the first treatment step of the latter stage). Then, the second condensation layer is plasma-polymerized by the plasma discharge in the second processing space 39B in the subsequent stage, and the second adhesion promoting layer is formed on the first adhesion promoting layer (the second processing in the latter stage) step). Thereby, the thickness of the adhesion promoting layer can be increased, and the degree of polymerization can be further increased, and as a result, the temperature resistance of the polarizing plate can be further improved.

Fig. 6 is a view showing a fourth embodiment of the present invention. The fourth embodiment is a modification of the second gas supply source in the film surface treatment apparatus 1X of the third embodiment. The second gas source 22 of the fourth embodiment is a second gas obtained by adding a trace amount of oxygen (O ₂ ) to nitrogen gas (N ₂ ). In the same manner as in the second embodiment, the oxygen content of the second gas is not more than 0.5 vol% with respect to nitrogen gas (discharge generating gas).

According to the fourth embodiment, the adhesion promoting layer can be hydrophobized by the treatment of nitrogen gas and oxygen plasma in the second processing space 39A in the preceding stage, and the nitrogen and oxygen in the second processing space 39B in the subsequent stage can be further Pulp processing Steps increase the hydrophobicity of the adhesion promoting layer.

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

For example, the first processing step and the second processing step may be performed in parallel at the same time. The first gas and the second gas may be directly supplied to the second processing space 39 (39A, 39B).

The main component of the film to be treated 9 is not limited to TAC, and may be polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cyclic olefin copolymer (COC), polyethylene terephthalate. Diester (PET), polymethyl methacrylate (PMMA), polyimine (PI), and the like.

As the polymerizable monomer, methacrylic acid, itaconic acid, maleic acid or the like may be used instead of acrylic acid. As the carrier gas, a rare gas such as Ar or He may be used instead of N ₂ .

As the crosslinkable additive component, other diallyl compounds such as diallyl maleate or 1,7-octadiene may be used in place of allyl methacrylate or allyl methacrylate. An alkyne compound such as 3-methyl-1-butyn-3-ol or 3-methyl-1-pentyn-3-ol can be used, and tetraethoxy decane, vinyl trimethoxy decane, or the like can be used. Further, a decyl oxide (metal alkoxide), or a glycidyl compound such as allyl glycidyl ether or glycidyl methacrylate, or acrylonitrile, acrylamide or dicyclopentadiene may be used. Wait. The first gas may also contain a plurality of crosslinkable additive components. For example, the first gas may contain allyl methacrylate and vinyl trimethoxy decane as a crosslinkable additive component.

As the carrier gas component of the first gas, a rare gas such as Ar or He may be used instead of N ₂ .

As the discharge generating gas, a rare gas such as Ar or He may be used instead of N ₂ .

The content ratio of the crosslinkable component to the polymerizable monomer in the first gas is not limited to 0.5 wt% to 10 wt%, as long as it exhibits a desired crosslinking action and then the strength does not deteriorate. Further, it may be set according to a combination of a crosslinkable additive component, a polymerizable monomer, and a component of the film to be processed 9.

In the second processing step, a so-called remote atmosphere piezoelectric slurry surface treatment apparatus may be used, in which the film to be processed 9 is disposed outside the electrodes, and the gas which is plasmad between the electrodes is directed to the outside. The treatment film 9 is ejected.

The plasma irradiation in the second treatment step is not limited to the vicinity of atmospheric pressure, and may be carried out under vacuum.

A plurality of embodiments can also be combined with each other.

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

[Example 1]

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

The film 9 was subjected to surface treatment using the film surface treatment apparatus 1 shown in Fig. 1 .

The size of the device 1 is as follows.

Axial length of the processing width direction of the rolls 31, 32: 390 mm

Diameter of rolls 31, 32: 320 mm

Spray width of the nozzles 14, 24 in the processing width direction: 300 mm

The circumference of the circular arc direction of the first processing space 93: 275 mm

Thickness of the first processing space 93: 5 mm

Thickness of the narrowest portion of the discharge gap 39: 1 mm

A TAC film was used as the film 9 to be processed. The width of the TAC film 9 is 325 mm.

The transport speed of the TAC film 9 was set to 2.5 m/min.

The temperatures of the rolls 31, 32 and the temperature of the TAC film 9 were set to 35 °C.

[First Processing Step]

In the vaporizer 11, acrylic acid (polymerizable monomer) and allyl methacrylate (crosslinkable additive component) are vaporized in a carrier gas (N ₂ ) to form a first gas. The temperature of the gasifier 11 was 130 °C. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.015 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 0.5 wt%.

The first gas is ejected from the first nozzle 14 and brought into contact with the TAC film 9 in the first processing space 93. The set temperature of the first nozzle 14 and the discharge temperature of the first gas were 75 °C.

[Second processing step]

Next, the second gas is introduced into the discharge gap 39 from the second nozzle 24, and is plasmad to contact the TAC film 9.

The composition of the second gas is only nitrogen (N ₂ ) as a discharge generating gas, and the flow rate thereof is 10 slm.

The set temperature of the second nozzle 24 and the discharge temperature of the second gas were 75 °C.

The power supply for plasma discharge is 760 W (high frequency conversion is performed at 400 V, 1.9 A DC).

The applied voltage between the electrodes 31 and 32 was 16.4 kV.

[Polarization Plate Making]

A PVA-based adhesive was applied to the surface to be treated of the surface-treated TAC film 9, and bonded to the PVA film. As the PVA-based adhesive, an aqueous solution obtained by mixing (A) a 5 wt% aqueous solution of PVA having a polymerization degree of 500 and a 2 wt% aqueous solution of (B) sodium carboxymethylcellulose was used. Mix ratio of (A) to (B) (A): (B) = 20:1. The drying conditions of the PVA-based adhesive were set to 80 ° C for 5 minutes.

The saponified TAC film was bonded to the surface on the opposite side of the PVA film by the same PVA-based adhesive as described above. Thereby, a plurality of polarized plate samples of three-layer structure were produced. The width of the polarizing plate sample was set to 1 inch.

[Follow strength evaluation]

After the agent was hardened, the adhesion strength (tensile strength) of the treated TAC film 9 and the PVA film was measured for the polarizing plate sample which was not subjected to the warm water treatment described later. The measurement method is based on the floating roll method (JIS K6854). The measurement result was 9.6 N/inch as the average of the five polarizing plate samples, and sufficient bonding strength was obtained.

[temperature resistance evaluation]

For the remaining polarizing plate samples, after the PVA-based adhesive was hardened, warm water treatment was performed. That is, the polarizing plate sample is immersed in warm water of 70 ° C In 3 hours. No peeling was observed between the treated TAC film 9 and the PVA film of the polarizing plate sample after the warm water treatment. Further, the fading width of the polarizing plate sample after the warm water treatment was measured. The measurement result was 0.91 mm based on the average of five polarizing plate samples, and sufficient temperature resistance was obtained.

[Embodiment 2]

In the second embodiment, in the apparatus 1 of Fig. 1, the flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.3 g/min

Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 10 wt%. The processing conditions other than this are the same as those in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 8.8 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.89 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 3]

In the third embodiment, in the apparatus 1 of Fig. 1, the flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.03 g/min

Therefore, the allyl methacrylate in the first gas is relative to acrylic acid. The content rate is 1 wt%. The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 9.2 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.95 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 4]

In the fourth embodiment, in the apparatus 1 of Fig. 1, the flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.1 g/min

Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 3.3 wt%. The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 8.9 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.92 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 5]

In the fifth embodiment, in the apparatus 1 of Fig. 1, the flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.15 g/min

Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 5 wt%. The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 9.1 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.86 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Embodiment 6]

In the sixth embodiment, in the apparatus 1 of Fig. 1, the flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.2 g/min

Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 6.7 wt%. The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 8.7 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.9 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Comparative Example 1]

As a comparative example, in the apparatus 1 of Fig. 1, a crosslinkable additive component was not added to the first gas. The composition of the first gas and the flow rate of each component are as follows Said.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation was then 9.4 N/inch, and a higher adhesive strength was obtained. On the other hand, the fading width of the evaluation of the temperature resistance was 5.35 mm. Peeling between the treated TAC film 9 and the PVA film was also confirmed, and the temperature resistance and water resistance were lower than those of Examples 1 to 6.

[Comparative Example 2]

In Comparative Example 2, in the apparatus 1 of Fig. 1, the composition of the first gas and the flow rate of each component were as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.005 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 0.17 wt%.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation was then 9.5 N/inch, followed by a higher intensity. On the other hand, the fading width of the evaluation of the temperature resistance was 5.21 mm. Peeling between the treated TAC film 9 and the PVA film was also confirmed, and the temperature resistance and water resistance were lower than those of Examples 1 to 6.

[Comparative Example 3]

In Comparative Example 3, in the apparatus 1 of Fig. 1, the composition of the first gas and the flow rate of each component were as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.5 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 16.7 wt%.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The fading width of the evaluation of the temperature resistance is 0.99 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation was 2.5 N/inch, and then the intensity was low.

The processing conditions and results of Examples 1 to 6 are summarized in Table 1, and the processing conditions and results of Comparative Examples 1 to 3 are summarized in Table 2. According to the examples and the comparative examples, it was confirmed that by adding an appropriate amount of the crosslinkable additive component to the first gas, the adhesion strength of the polarizing plate can be maintained high, and the temperature resistance can be improved. The reason for this is considered to be that the plasma polymerization film of acrylic acid can be crosslinked by the crosslinkable additive component. In particular, by adding the amount of allyl methacrylate in the first gas to 0.5 wt% to 10 wt%, the adhesion strength of the polarizing plate can be maintained high, and the temperature resistance can be improved. On the other hand, it has been found that if the addition amount of the crosslinkable additive component (allyl methacrylate) is too small or too small, the desired temperature resistance water cannot be obtained, and if the addition amount is too large, the temperature resistance is higher than that of the temperature-sensitive water. High but then the strength is impaired.

[Embodiment 7]

In the seventh embodiment, the TAC film 9 was subjected to surface treatment using the film surface treatment apparatus 1 shown in FIG. The composition of the first gas and the flow rate of each component are as follows, and are the same as in the first embodiment. Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 0.5 wt%.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.015 g/min

In the second gas, oxygen (O ₂ ) is added in addition to nitrogen (N ₂ ) as a discharge generating gas. The flow rate of each component of the second gas is as follows.

N ₂ 10 slm

O ₂ 40 sccm=0.04 slm

Therefore, the oxygen content rate in the second gas is 0.4 vol% with respect to nitrogen gas (discharge generating gas).

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 8.1 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.55 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good. In particular, the temperature resistance can be greatly improved.

[Embodiment 8]

In Example 8, the flow rate of each component of the first gas in Example 7 (Fig. 3) was changed as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.3 g/min

Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 10 wt%.

The composition of the second gas and the flow rate of each component are the same as in the seventh embodiment as described below. Therefore, the oxygen content in the second gas is relative to nitrogen (discharge generation The gas) is 0.4 vol%.

N ₂ 10 slm

O ₂ 40 sccm=0.04 slm

The other processing conditions are the same as in the first embodiment and the seventh embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in Examples 1 and 7. The result of the strength evaluation is then followed by the intensity = 7.8 N/inch. As a result of the evaluation of the temperature resistance, the fading width = 0.3 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good. In particular, the temperature resistance can be greatly improved.

[Comparative Example 4]

In the comparative example 4, in the apparatus 1 of FIG. 3, the composition of the first gas and the flow rate of each component were set as follows in the same manner as in the seventh embodiment. Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 0.5 wt%.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.015 g/min

The composition of the second gas and the flow rate of each component were as follows, and the amount of oxygen added was changed with respect to Example 7.

N ₂ 10 slm

O ₂ 70 sccm=0.07 slm

Therefore, the oxygen content in the second gas is 0.7 vol% with respect to nitrogen gas (discharge generating gas).

The other processing conditions were the same as in the first and seventh embodiments. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in Examples 1 and 7. The fading width of the evaluation of the temperature resistance is 0.49 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation was 2.1 N/inch, and then the intensity was low.

[Comparative Example 5]

In the comparative example 5, in the apparatus 1 of FIG. 3, the composition of the first gas and the flow rate of each component were set to be the same as in the eighth embodiment as follows. Therefore, the content of allyl methacrylate in the first gas with respect to acrylic acid was 10 wt%.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.3 g/min

The composition of the second gas and the flow rate of each component were as follows, and the amount of oxygen added was changed with respect to Example 8.

N ₂ 10 slm

O ₂ 70 sccm=0.07 slm

Therefore, the oxygen content in the second gas is 0.7 vol% with respect to nitrogen gas (discharge generating gas).

The other processing conditions were the same as in Examples 1 and 8. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in Examples 1 and 8. The fading width of the evaluation of the temperature resistance is 0.32 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation was 1.9 N/inch, and then the intensity was low.

Table 3 summarizes the processing conditions and knots of Examples 7 and 8 and Comparative Examples 4 and 5. fruit. According to the examples and the comparative examples, it was confirmed that the temperature resistance of the polarizing plate can be further improved by adding an appropriate amount of the crosslinkable additive component to the first gas and further adding a trace amount of oxygen to the second gas. The reason for this is considered to be that the hydrophobicity of the plasma polymer film of acrylic acid is improved by the addition of oxygen. On the other hand, it has been found that if the amount of oxygen added to the second gas is too large, the adhesion strength of the polarizing plate is impaired.

[Embodiment 9]

In Example 9, the TAC film was used using the film surface treatment apparatus 1X shown in FIG. 9 surface treatment. The first gas from the first gas supply source 11 is divided into exactly two halves to the two first nozzles 14A and 14B. The flow rate of the first gas and the flow ratio of each component in the entire apparatus 1X are the same as in the first embodiment. Therefore, the composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are as follows, and the content of allyl methacrylate relative to acrylic acid is 0.5 wt%.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.0075 g/min

In addition, the discharge generated gas (N ₂ ) from the second gas supply source 21 is divided into two second nozzles 24A and 24B. The supply flow rate of the discharge generating gas to each of the second processing spaces 39A and 39B was 10 slm.

The power supplied to the center roller electrode 32 was 760 W (high frequency conversion was performed at 400 V, 1.9 A DC). One half of the power (380 W) is consumed by the plasma discharge of the discharge gap 39A of the preceding stage, and the remaining half (380 W) is discharged to the plasma discharge of the discharge gap 39B of the subsequent stage. The applied voltage between the roller electrodes 31 and 32 and the applied voltage between the roller electrodes 32 and 33 were both 16.4 kV.

The set temperatures of the rolls 31, 32, and 33 and the temperature of the film 9 were 35 °C.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by an intensity of 11.2 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.56 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance were better than those of Example 1.

[Embodiment 10]

In the tenth embodiment, the supply flow rate of the first gas component in each of the first processing spaces 93A and 93B is changed as follows in the embodiment 9 (FIG. 4).

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.15 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 10 wt%.

The processing conditions other than this were set to be the same as in the ninth embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the ninth embodiment. The result of the strength evaluation is then followed by an intensity of 10.3 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.48 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Comparative Example 6]

In the comparative example 6, in the apparatus 1X of FIG. 4, the crosslinkable additive component is not added to the first gas, and the components of the first gas are only acrylic acid (polymerizable monomer) and nitrogen gas (carrier gas). The composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are as follows.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

The processing conditions other than this were set to be the same as in the ninth embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the ninth embodiment. Then the result of the strength evaluation is 10 N/inch, then higher intensity. On the other hand, the fading width of the evaluation of the temperature resistance was 4.63 mm. Peeling between the treated TAC film 9 and the PVA film was also confirmed, and the temperature resistance was low.

[Comparative Example 7]

In the comparative example 7, in the apparatus 1X of FIG. 4, the composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are as follows.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.003 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 0.2 wt%.

The processing conditions other than this were set to be the same as in the ninth embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the ninth embodiment. The result of the strength evaluation was then 10.1 N/inch, followed by a higher intensity. On the other hand, the fading width of the evaluation of the temperature resistance was 4.56 mm, and the peeling between the treated TAC film 9 and the PVA film was confirmed, and the temperature resistance was low.

[Comparative Example 8]

In the comparative example 8, in the apparatus 1X of FIG. 4, the composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are as follows.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.25 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 16.7 wt%.

The processing conditions other than this were set to be the same as in the ninth embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the ninth embodiment. The fading width of the evaluation of the temperature resistance is 0.87 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation was 2.9 N/inch, and then the intensity was low.

The processing conditions and results of Examples 9 and 10 and Comparative Examples 6 to 8 are summarized in Table 4. It has been confirmed that by adding an appropriate amount of the crosslinkable additive component to the first gas and repeating the first treatment step and the second treatment step twice, the adhesion strength of the polarizing plate can be further improved, and the temperature resistance can be further improved. . The reason for this is considered to be that the degree of crosslinking of the plasma polymerization film of acrylic acid can be further improved by performing the two-stage treatment using the crosslinkable additive component. On the other hand, it has been found that even if the two-stage treatment is carried out, if the addition amount of the crosslinkable additive component (allyl methacrylate) is too small or too small, the desired temperature resistance water cannot be obtained, and if the above addition amount is too large, Although the temperature resistance is higher, the strength is deteriorated.

[Example 11]

In the eleventh embodiment, the TAC film 9 was subjected to surface treatment using the film surface treatment apparatus 1X shown in Fig. 6. The first gas from the first gas supply source 11 is divided into exactly two halves to the two first nozzles 14A and 14B. The composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are as follows, and are the same as in the ninth embodiment.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.0075 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 0.5 wt%.

Further, in the second gas of the second gas supply source 22, oxygen (O ₂ ) is added in addition to nitrogen (N ₂ ) as a discharge generating gas. The second gas is divided into two second nozzles 24A and 24B exactly at half. The composition of the second gas and the supply flow rate of each component in each of the second processing spaces 39A and 39B are the same as those in the seventh embodiment as described below.

N ₂ 10 slm

O ₂ 40 sccm=0.04 slm

Therefore, the oxygen content rate in the second gas is 0.4 vol% with respect to nitrogen gas (discharge generating gas).

The processing conditions other than this were set to be the same as in the ninth embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the ninth embodiment. The result of the strength evaluation is then followed by the intensity = 9.5 N/inch. Temperature resistance evaluation result, fading width = 0.51 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good. In particular, the temperature resistance can be greatly improved.

[Embodiment 12]

In the twelfth embodiment, in the eleventh embodiment (FIG. 6), the supply flow rate of the first gas component in each of the first processing spaces 93A and 93B is changed as follows.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.15 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 10 wt%.

The processing conditions other than this were the same as in the eleventh embodiment. The order of preparation of the surface-treated polarizing plate samples, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the eleventh embodiment. The result of the strength evaluation is then followed by the intensity = 9.5 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.31 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Comparative Example 9]

In the comparative example 9, in the apparatus 1 of FIG. 6, the supply flow rate of the second gas component of each of the second processing spaces 39A and 39B is changed as follows.

N ₂ 10 slm

O ₂ 70 sccm=0.07 slm

Therefore, the oxygen content rate in the second gas is 0.7 vol% with respect to nitrogen gas (discharge generating gas).

The processing conditions other than this were the same as in the eleventh embodiment. The order of preparation of the surface-treated polarizing plate samples, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the eleventh embodiment. The fading width of the evaluation of the temperature resistance is 0.56 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation was 2 N/inch, and then the intensity was low.

[Comparative Example 10]

In the comparative example 10, the composition of the first gas and the supply flow rate of each component in each of the first processing spaces 93A and 93B are the same as those in the twelfth embodiment as follows.

Carrier gas (N ₂ ) 15 slm

Acrylic 1.5 g/min

Allyl methacrylate 0.15 g/min

Therefore, the content of allyl methacrylate relative to acrylic acid was 10 wt%.

Moreover, the composition of the second gas and the supply flow rate of each component in each of the second processing spaces 39A and 39B are as follows.

N ₂ 10 slm

O ₂ 70 sccm=0.07 slm

Therefore, the oxygen content rate in the second gas is 0.7 vol% with respect to nitrogen gas (discharge generating gas).

The processing conditions other than this were the same as in the eleventh embodiment. The order of preparation of the surface-treated polarizing plate samples, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the eleventh embodiment. The fading width of the evaluation of the temperature resistance is 0.29 mm, and the temperature resistance is high. However, the result of the subsequent strength evaluation It is 1.8 N/inch and then the intensity is low.

Table 5 summarizes the processing conditions and results of Examples 11 and 12 and Comparative Examples 9 and 10. It was confirmed that the polarizing plate can be further improved by adding an appropriate amount of the crosslinkable additive component to the first gas and adding an appropriate amount of oxygen to the second gas, and further repeating the first treatment step and the second treatment step twice. The strength is then increased, and the temperature resistance can be further improved. On the other hand, it has been found that if the amount of oxygen added to the second gas is excessive, the adhesion strength of the polarizing plate is impaired.

[Example 13]

In Example 13, as the allyl methacrylate, diallyl maleate, which is also a diallyl compound, was used as the crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Diallyl maleate 0.3 g/min

Therefore, the content of diallyl maleate in the first gas with respect to acrylic acid is 10 wt%.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The result of the strength evaluation is then followed by the intensity = 8.2 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.98 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Embodiment 14]

In Example 14, as the allyl methacrylate, 1,7-octadiene which is also a diallyl compound was used as the crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

1,7-octadiene 0.3 g/min

Therefore, the content of 1,7-octadiene in the first gas with respect to acrylic acid is 10 wt%.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The strength is then 8.3 N/inch and the temperature resistance is fading width = 0.99 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 15]

In Example 15, 1,7-octadiene was used instead of allyl methacrylate as the crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

1,7-octadiene 0.15 g/min

Therefore, the content of 1,7-octadiene in the first gas with respect to acrylic acid was 5 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 8.9 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.99 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 16]

In Example 16, 3-methyl-1-butyn-3-ol as an alkyne compound was used instead of allyl methacrylate as a crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

3-methyl-1-butyn-3-ol 0.15 g/min

Therefore, the content of 3-methyl-1-butyn-3-ol in the first gas with respect to acrylic acid was 5 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 8.3 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 1.55 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 17]

In Example 17, 3-methyl-1-pentyn-3-ol as an alkyne compound was used instead of allyl methacrylate as a crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

3-methyl-1-pentyn-3-ol 0.15 g/min

Therefore, the content of 3-methyl-1-pentyn-3-ol in the first gas with respect to acrylic acid was 5 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 8.2 N/inch. The result of the evaluation of the temperature resistance water, faded Width = 1.49 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Embodiment 18]

In Example 18, tetraethoxy decane as a decane oxide was used instead of allyl methacrylate as a crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Tetraethoxy decane 0.15 g/min

Therefore, the content of tetraethoxysilane in the first gas with respect to acrylic acid is 5 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 9 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 1.22 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Embodiment 19]

In Example 19, vinyl trimethoxynonane as a decane oxide was used instead of allyl methacrylate as a crosslinkable additive component in the apparatus 1 of Fig. 1. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Vinyl trimethoxy decane 0.15 g/min

Therefore, the content of vinyltrimethoxynonane in the first gas with respect to acrylic acid is 5 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 9.6 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.9 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good.

[Example 20]

In Example 20, two kinds of allyl methacrylate and vinyltrimethoxydecane were used instead of the allyl methacrylate to obtain a crosslinkable additive component in the apparatus 1 of Fig. 1 . The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.15 g/min

Vinyl trimethoxy decane 0.15 g/min

Therefore, the total content of the crosslinkable additive component (allyl methacrylate + vinyltrimethoxydecane) relative to acrylic acid in the first gas is 10 wt%.

The processing conditions other than this were the same as those of Examples 1 and 14. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as those of Examples 1 and 14. The result of the strength evaluation is then followed by the intensity = 8.7 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.75 mm. No peeling was confirmed between the treated TAC film 9 and the PVA film. from. Therefore, both the strength and the temperature and water resistance are good.

[Example 21]

In Example 21, surface treatment was carried out using the film surface treatment 1 shown in Fig. 3 in the same manner as in Example 7. As the crosslinkable additive component, allyl methacrylate and vinyl trimethoxy decane were used. The flow rate of each component of the first gas in the first treatment step is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Allyl methacrylate 0.15 g/min

Vinyl trimethoxy decane 0.15 g/min

Therefore, the content of the crosslinkable additive component (allyl methacrylate + vinyltrimethoxydecane) in the first gas with respect to acrylic acid is 10 wt%.

The composition of the second gas and the flow rate of each component were the same as in the seventh embodiment as described below. Therefore, the oxygen content rate in the second gas is 0.4 vol% with respect to nitrogen gas (discharge generating gas).

N ₂ 10 slm

O ₂ 40 sccm=0.04 slm

The other processing conditions are the same as in the first embodiment and the seventh embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in Examples 1 and 7. The result of the strength evaluation is then followed by the intensity = 7.7 N/inch. As a result of the evaluation of the temperature resistance, the fading width was 0.29 mm. No peeling was observed between the treated TAC film 9 and the PVA film. Therefore, both the strength and the temperature and water resistance are good. In particular, the temperature resistance can be greatly improved.

[Comparative Example 11]

As Comparative Example 11, in the apparatus 1 of Fig. 1, methyl non-crosslinkable methyl methacrylate was used as an additive component of the first gas. The flow rate of each component of the first gas is as follows.

Carrier gas (N ₂ ) 30 slm

Acrylic 3 g/min

Methyl methacrylate 0.3 g/min

Therefore, the content of methyl methacrylate relative to acrylic acid is 10 wt%.

The processing conditions other than the above were the same as in the first embodiment. The order of preparation of the polarizing plate samples after the surface treatment, and the evaluation of the subsequent strength and the evaluation of the temperature resistance and water resistance were also the same as in the first embodiment. The intensity is then 7.9 N/inch. On the other hand, the temperature resistance is fading width = 4.32 mm.

The treatment conditions and results of Examples 13 to 21 and Comparative Example 11 are summarized in Tables 6 to 8. When a diallyl compound other than allyl methacrylate such as diallyl maleate or 1,7-octadiene is used as the crosslinkable component of the first gas, the strength can be maintained. It is higher and improves the temperature resistance. In other words, by using an unsaturated hydrocarbon compound having two or more unsaturated bonds as a crosslinkable additive component, the adhesive strength can be maintained high and the temperature resistance can be improved. Further, when an alkyne compound such as 3-methyl-1-butyn-3-ol or 3-methyl-1-pentyn-3-ol, that is, an unsaturated hydrocarbon compound having a triple bond, is used as a crosslinkable additive component It is also possible to maintain the subsequent strength to be high and to improve the temperature resistance. Further, when a decane oxide compound such as tetraethoxysilane or vinyltrimethoxydecane is used as a crosslinkable component, the strength can be maintained. It is higher and improves the temperature resistance. When the crosslinkable component is mixed and used in plural amounts, the adhesive strength can be maintained high and the temperature resistance can be improved. On the other hand, in the case where the additive component of the first gas does not have crosslinkability (Comparative Example 11), the temperature resistant water resistance hardly increases.

[Industrial availability]

The present invention is applicable to the manufacture of a polarizing plate such as a flat panel display (FPD).

1‧‧‧ Film surface treatment device

1X‧‧‧ film surface treatment device

3‧‧‧Support and transport unit

9‧‧‧Processed film

9c‧‧‧return part

10‧‧‧1st gas supply system

11‧‧‧ gasifier (generating department)

13‧‧‧1st gas supply line

14‧‧‧1st nozzle

14A‧‧‧1st nozzle

14B‧‧‧1st nozzle

14e‧‧‧Spray outlet

15‧‧‧Shielding members

15A‧‧‧Shielding members

15B‧‧‧Shielding members

20‧‧‧2nd gas supply system

21‧‧‧2nd gas supply source

22‧‧‧2nd gas supply source

23‧‧‧2nd gas supply line

24‧‧‧2nd nozzle

24A‧‧‧2nd nozzle

24B‧‧‧2nd nozzle

25‧‧‧Blocking Department

31‧‧‧1st roll (electrode)

32‧‧‧2nd roller (electrode)

33‧‧‧3rd roller (electrode)

36‧‧‧guide roller

36A‧‧·guide roller

36B‧‧·guide roller

39‧‧‧ Plasma discharge gap (2nd processing space)

39A‧‧‧ Plasma discharge gap (2nd processing space)

39B‧‧‧ Plasma discharge gap (2nd processing space)

91‧‧‧First Processing Department

92‧‧‧2nd Processing Department

93‧‧‧1st processing space

Fig. 1 is a side view showing a film surface treatment apparatus according to a first embodiment of the present invention. view.

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

Fig. 3 is a side view showing a film surface treatment apparatus according to a second embodiment of the present invention.

Fig. 4 is a side view showing a film surface treatment apparatus according to a third embodiment of the present invention.

Fig. 5 is a perspective view of the film surface treatment apparatus according to the third embodiment.

Fig. 6 is a side view showing a film surface treatment apparatus according to a fourth embodiment of the present invention.

1‧‧‧ Film surface treatment device

3‧‧‧Support and transport unit

9‧‧‧Processed film

9c‧‧‧return part

10‧‧‧1st gas supply system

11‧‧‧ gasifier (generating department)

13‧‧‧1st gas supply line

14‧‧‧1st nozzle

14e‧‧‧Spray outlet

15‧‧‧Shielding members

20‧‧‧2nd gas supply system

21‧‧‧2nd gas supply source

23‧‧‧2nd gas supply line

24‧‧‧2nd nozzle

25‧‧‧Blocking Department

31‧‧‧1st roll (electrode)

32‧‧‧2nd roller (electrode)

36‧‧‧guide roller

39‧‧‧ Plasma discharge gap (2nd processing space)

91‧‧‧First Processing Department

92‧‧‧2nd Processing Department

93‧‧‧1st processing space

Claims (7)

A film surface treatment method which is characterized in that a polymerizable monomer is subjected to plasma polymerization on a surface of a resin-treated film, and a film of a polymer of the polymerizable monomer is coated on the surface, and In the first processing step, the first gas containing the vaporized monomer and the crosslinkable component capable of plasma crosslinking the polymer is brought into contact with the film to be treated; and the second treatment step After the first processing step or in parallel with the first processing step, the discharge generating gas is plasma-treated and contacts the processed film; and the polymerizable monomer is a single having an unsaturated bond and a specific functional group. The specific functional group is selected from the group consisting of a hydroxyl group, a carboxyl group, an ethyl fluorenyl group, an ester group having 1 to 10 carbon atoms, a mercapto group, and an aldehyde group; and the crosslinkable additive component is selected from the group consisting of 2 a group consisting of an unsaturated hydrocarbon compound having an unsaturated bond, an unsaturated hydrocarbon compound having a triple bond, and a metal alkoxide compound; and the crosslinkable component in the first gas is added to the polymerizable single The content ratio is adjusted to 0.5wt% ~ 10wt%. The film surface treatment method of claim 1, wherein the crosslinkable additive component is a diallyl compound, an alkyne compound, or a metal decane oxide compound. The membrane surface treatment method of claim 1, wherein the crosslinkable additive component is selected from the group consisting of allyl methacrylate, diallyl maleate, 1,7-octadiene, 3-methyl- 1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, At least one selected from the group consisting of tetraethoxy decane of a metal decane oxide compound and vinyl trimethoxy decane which is a metal decane oxide compound. The film surface treatment method according to any one of claims 1 to 3, wherein in the second processing step, the second gas obtained by adding oxygen to the discharge generating gas is plasma-treated and contacts the film to be processed. The oxygen content of the second gas is 0.5 vol% or less based on the discharge generating gas. A film surface treatment apparatus which is obtained by plasma-polymerizing a polymerizable monomer on a surface of a resin-made film to be coated, and coating a polymer of the polymerizable monomer on the surface thereof, and The production unit includes a first gas containing the polymerizable monomer and a crosslinkable additive component capable of plasma-crosslinking the polymer, and a first nozzle that sprays the first gas to the above a pair of electrodes on which a discharge in the vicinity of atmospheric pressure is generated by applying an electric field in a gap therebetween; a second nozzle that supplies a discharge generating gas to the gap; and a transfer mechanism that treats the film to be processed The first processing space facing the first nozzle is transported through the gap; and the polymerizable monomer is a monomer having an unsaturated bond and a specific functional group, and the specific functional group is selected from a hydroxyl group and a carboxyl group. a group consisting of an oxime group, an ester group having 1 to 10 carbon atoms, a mercapto group, and an aldehyde group; the crosslinkable additive component is selected from the group consisting of unsaturated hydrocarbon compounds having two or more unsaturated bonds, Unsaturated hydrocarbon compounds of the triple bond, and In the group of the metal alkoxide compounds, the content of the crosslinkable component in the first gas with respect to the polymerizable monomer is adjusted to 0.5% by weight to 10% by weight. The membrane surface treatment apparatus according to claim 5, wherein the second nozzle supplies a second gas obtained by adding oxygen to the discharge generating gas to the gap, and the oxygen content of the second gas is relative to the discharge generating gas. It is 0.5 vol% or less. The membrane surface treating apparatus according to claim 5 or 6, wherein the crosslinkable additive component is selected from the group consisting of allyl methacrylate, diallyl maleate, 1,7-octadiene, 3-methyl 1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, tetraethoxynonane as a metal decane oxide compound, vinyl trimethoxy as a metal decane oxide compound At least one of the group consisting of decane.