CN102257045A - Method and device for treating film surface and process for producing polarizer - Google Patents

Abstract

A difficult-to-bond resin film (11) to be bonded to an easily bondable resin film (12) is disposed in a treatment space (22) having a pressure around atmospheric pressure. A process gas containing the vapor of acrylic acid (polymerizable monomer) is supplied to the treatment space (22) with a process gas supply system (3). In a plasma treatment part (2), the process gas is converted to a plasma and brought into contact with the difficult-to-bond resin film (11). The flow rate of the process gas to be supplied is set so that the treatment space (22) has an oxygen concentration of 3,000 ppm or lower. This configuration improves the bondability of the difficult-to-bond resin film and renders high-speed treatment possible.

Description

The manufacture method of the surface treatment method of film and device and polaroid

Technical field

The present invention relates to the method that the surface of resin molding is handled and the manufacture method of device and polaroid, particularly carry out surface treatment method that above-mentioned difficult adhesive resin film is carried out when bonding etc. at resin molding with the resin molding of difficult cementability and easy-adhesion.

Background technology

In liquid crystal indicator, be incorporated with polaroid.Polaroid uses caking agent that protective membrane and polarizing coating is bonding and constitute; wherein said polarizing coating by comprise as principal constituent polyvinyl alcohol (below; suitably be called " PVA ") resin molding (below; suitably be called " PVA film ") constitute; described protective membrane by comprise as principal constituent cellulose triacetate (below; suitably be called " TAC ") resin molding (below, suitably be called " TAC film ") constitute.As caking agent, use water system caking agents such as polyethenol series or polyethers system.Though the cementability between PVA film and the above-mentioned caking agent is good, the cementability between TAC film and the above-mentioned caking agent is bad.So, usually the TAC film carry out bonding before, be dipped in the alkaline aqueous solution of sodium hydroxide or potassium hydroxide etc. and be carried out saponification and handle.Thus, the surface of TAC film improves wetting ability because of adding water decomposition, thereby makes caking agent be attached to the TAC film easily.

As the surface treatment method outside the saponification processing, for example in patent documentation 1, proposition has following method: after utilizing the mixed gas of helium and argon under atmospheric pressure Cement Composite Treated by Plasma to be carried out on the surface of object being treated, by spray gun ejection vinylformic acid, make acrylic acid-grafted polymerization, thereby modification is carried out on the surface of object being treated.

In patent documentation 2, proposing has following method: rare gas elementes such as nitrogen, argon are formed with the organic system film mix with gas, under atmospheric pressure make this mixed gas carry out plasma discharge and supply to object being treated, with the wetting ability of raising object being treated.

Patent documentation 1: No. 3292924 communique of Japan's special permission

Patent documentation 2: TOHKEMY 2006-299000 communique

Contrivers etc. obtain following opinion: under the surface-treated situation of the cementability that uses plasma processing apparatus to be used to improve difficult adhesive resin film, because of the different cementabilities that cause of concentration of the intravital oxygen of plasma produce change.If it is a certain amount of that oxygen concn surpasses, then can not obtain enough bonding strengths (with reference to aftermentioned embodiment 1).

Summary of the invention

Membrane processing method of the present invention is based on above-mentioned opinion and makes, it is the method to handling with the surface of the bonding difficult adhesive resin film of easy-adhesion resin molding, described film surface treatment method is characterised in that, utilize plasma body to make polymerizable monomer activation and make it and be configured in, the oxygen concn (volumetric concentration) in the described processing space is set at below the 3000ppm near the described difficult adhesive resin film reaction of atmospheric processing spatial.

And, plasma surface processing device of the present invention is the device to handling with the surface of the bonding difficult adhesive resin film of easy-adhesion resin molding, this film surface processing device is characterised in that, has Cement Composite Treated by Plasma portion, this plasma body handling part utilizes plasma body to make the polymerizable monomer activation and it is contacted with being disposed at the difficult adhesive resin film of approaching atmospheric processing spatial, and the oxygen concn in the described processing space is below the 0 above 3000ppm.

The activation of polymerizable monomer comprises fracture, polymerization, the decomposition of polymerizable monomer.Activatory polymerizable monomer and difficult adhesive resin film react.For example, can think: the key of C-C, the C-O on difficult adhesive resin film surface, C-H etc. because of its with plasma gas contact or the irradiation of plasma light is cut off, at the polymkeric substance of this key cut-out portion graft polymerization polymerizable monomer.Perhaps, can think: in the functional group of key cut-out portion in conjunction with the decomposition of auto-polymerization monomer.Thus, can think and be formed with the cementability promoting layer on the surface of difficult adhesive resin film.Be made as below the 3000ppm by the oxygen concn that will handle in the space, can prevent to polymerizable monomer activation, produce with reaction such as combining of key cut-out portion and to hinder, can form the cementability promoting layer effectively on the surface of difficult adhesive resin film.Thus, can improve the cementability of difficult adhesive resin film effectively.

In above-mentioned membrane processing method, be preferably, in described processing space, produce discharge, the process gas that will contain the steam of described polymerizable monomer supplies in the described processing space, and the supply flow rate of described process gas is set at the oxygen concn that makes in the described processing space reaches below the 0 above 3000ppm.

In above-mentioned membrane treatment appts, be preferably, described Cement Composite Treated by Plasma portion has the pair of electrodes that produces discharge in described processing space, also has the process gas plenum system, the process gas that this process gas plenum system will contain the steam of described polymerizable monomer supplies in the described processing space, and the supply flow rate of the process gas of described process gas plenum system is set to the oxygen concn that makes in the described processing space below 0 above 3000ppm.

By in handling the space, supplying with process gas, can will handle gases such as air in the space drive out of and be replaced into process gas.By regulating the supply flow rate of process gas, can regulate the oxygen level of handling in the space.In these cases, handle the space and become discharge space.Difficult adhesive resin film as process object is configured in the discharge space, and directly contacts with plasma body in the discharge space.

Oxygen concn in the described processing space is preferably below the 2000ppm, more preferably below the 1000ppm.

Preferably, set the supply flow rate of described process gas, so that the oxygen concn in the described processing space is preferably below the 2000ppm, more preferably below the 1000ppm.

Thus, can improve the cementability of difficult adhesive resin film more effectively.

In above-mentioned membrane processing method, be preferably, described difficult adhesive resin film is relatively moved with respect to described processing space, the described speed that relatively moves is made as more than the 10m/min.

In above-mentioned membrane treatment appts, be preferably, also have the travel mechanism that described difficult adhesive resin film is relatively moved with respect to described processing space, the described speed that relatively moves of being undertaken by described travel mechanism is more than the 10m/min.

If difficult adhesive resin film is relatively moved, then environmental gas such as air is involved in difficult adhesive resin film easily and handles in the space.If the relative moving speed of difficult adhesive resin film is increased, then the flow that is involved in of environmental gas increases.Therefore, with handle the space in the rising of oxygen concn be associated.So, the supply flow rate of increase process gas.Thus, the environmental gas that is involved in can be driven out of from handling the space, thereby be made the oxygen concn of handling in the space become desirable concentration.Thus, can when guaranteeing the good cementability of difficult adhesive resin film, increase the relative moving speed of difficult adhesive resin film, thereby can carry out high speed processing.

The relative moving speed of difficult adhesive resin film both can be more than the 20m/min, also can be more than the 30m/min.According to the increase of relative moving speed, increase the supply flow rate of process gas, thereby the oxygen concn in the discharge space can be formed below the 3000ppm, be preferably formed to below the 2000ppm, more preferably form below the 1000ppm.The upper limit of the relative moving speed of difficult adhesive resin film can suitably be set according to the performance of travel mechanism etc. and the supply capacity of process gas etc.For example, the upper limit of the relative moving speed of difficult adhesive resin film is preferably about 60m/min.

Described process gas is preferably and does not contain oxygen in fact.

By the gas displacements such as air that will handle in the space is process gas, can reduce the oxygen concn of handling in the space effectively.Do not contain this situation of oxygen in fact except that the oxygen level that comprises process gas is zero situation, comprise following situation yet, promptly contain the situation that can not have influence on the oxygen of surface-treated trace.Particularly, the oxygen concn (volumetric concentration) that does not contain the process gas of oxygen in fact is preferably below the 0 above 1ppm, more preferably below the 0 above 0.1ppm, more preferably below the 0 above 0.01ppm.

Both can be communicated with near atmospheric described processing space, also can open wide towards atmosphere with atmosphere.

At this, refer to 1.013 * 10 near normal atmosphere ⁴～50.663 * 10 ⁴The scope of Pa if consider the simplification that pressure controlled facilitation and device constitute, then is preferably 1.333 * 10 ⁴～10.664 * 10 ⁴Pa, more preferably 9.331 * 10 ⁴～10.397 * 10 ⁴Pa.

In plasma surface processing device of the present invention, described pair of electrodes constitutes respectively makes axis towards axial cylindric, and along being arranged in parallel with described axial orthogonal orientation, described electrode the narrowest position and periphery thereof each other constitutes described processing space, and, also has a counter-lateral quadrents plug members, this counter-lateral quadrents plug members be arranged at across described processing space with described axially and the both sides of the orthogonal orthogonal directions of described orientation and extend axially along described, a described counter-lateral quadrents plug members across the described side face of described pair of electrodes each other, and and the side face of described each electrode between form allow described difficult adhesive resin film to described each electrode roll around the gap, at least one in the described counter-lateral quadrents plug members constitutes the process gas nozzle of the downstream end of described process gas plenum system.

Utilize a counter-lateral quadrents plug members, the both sides of handling the described orthogonal directions of spatial roughly can be stopped up.Thus, the side face that can prevent or suppress the oxygen containing environmental gas self-electrode of bag of outside is invaded in the processing space to each other.Therefore, can be effectively the oxygen concn of handling in the space be made as below the prescribed value (3000ppm), thereby can improves the cementability of difficult adhesive resin film effectively.

The thickness in described gap is preferably below the interval at described pair of electrodes the narrowest position to each other, below the more preferably described processing spatial thickness.Thus, even if reduce the supply flow rate of process gas, also can effectively the oxygen concn of handling in the space be made as below the prescribed value (3000ppm).At this, described processing spatial thickness, the size of its sizableness after the double thickness that deducts described difficult adhesive resin film from the described pair of electrodes interval at narrow position to each other.The interval at the described pair of electrodes the narrowest position each other twice than the thickness of described difficult adhesive resin film at least is big, and is preferably below the 3mm, more preferably below the 1mm.

Difficult adhesive resin film is wound on the side face of drum electrode and makes the drum electrode rotation, thereby can carry difficult adhesive resin film.Drum electrode can the above-mentioned travel mechanism of double as work.

In plasma surface processing device of the present invention, also has the axle head plug members, this axle head plug members is across between the end of the mutually the same side on an axially described pair of electrodes and a described counter-lateral quadrents plug members, described, and covers the end of described processing space in described described same side on axially.

According to the axle head plug members, can suppress or prevent the outside oxygen containing environmental gas of bag from handle spatial axes to the end enter and handle in the space.

Therefore, even if make the supply flow rate of process gas littler, also the oxygen concn of handling in the space can be made as below the prescribed value (3000ppm) effectively.And then, can improve the cementability of difficult adhesive resin film effectively.

Between the axial end portion of described axle head plug members and drum electrode, can be formed with labyrinth.For example, described axle head plug members towards the side of described electrode, be formed with part cyclic protuberance, be formed with the cyclic groove at the axial end of described electrode, by making these protuberances and engagement, constitute above-mentioned labyrinth.Perhaps,, also can constitute as above-mentioned labyrinth: described axle head plug members towards the side of described electrode, be formed with part cyclic groove, be formed with the cyclic protuberance at the axial end of described electrode.

Difficult adhesive resin film refers to be compared with the film of the bonding adhering object side of this film, with respect to the relative low film of cementability of caking agent.The easy-adhesion resin molding refers to be compared with the film of the bonding adhering object side of this film, with respect to the relative high film of cementability of caking agent.Same film because of by the film difference of bonding adhering object side, both can constitute difficult adhesive resin film, also can constitute the easy-adhesion resin molding.

As the principal constituent of described difficult adhesive resin film, for example exemplify cellulose triacetate (TAC), polypropylene (PP), polyethylene (PE), cyclic olefin polymer (COP), cyclic olefine copolymer (COC), polyethylene terephthalate (PET), polymethylmethacrylate (PMMA), polyimide (PI) etc.

As the principal constituent of described easy-adhesion resin molding, for example exemplify polyvinyl alcohol (PVA), vinyl-vinyl acetate copolymer (EVA) etc.

As polymerizable monomer, exemplify the monomer of functional group with unsaturated link(age) and regulation.The functional group of regulation is preferably selected from the ester group of hydroxyl, carboxyl, ethanoyl, glycidyl, epoxy group(ing), carbonatoms 1～10, sulfo group, aldehyde radical, hydrophilic groups such as preferred especially carboxyl or hydroxyl.

As monomer with unsaturated link(age) and hydroxyl, exemplified by methyl vinylformic acid glycol ester, vinyl carbinol, hydroxyethyl methylacrylate etc.

As monomer with unsaturated link(age) and carboxyl, exemplified by acrylic, methacrylic acid, methylene-succinic acid, toxilic acid, 2-methacryloyl propionic acid etc.

Monomer as having unsaturated link(age) and ethanoyl exemplifies vinyl-acetic ester etc.

As monomer with unsaturated link(age) and glycidyl, exemplified by methyl vinylformic acid glycidyl esters etc.

As monomer with unsaturated link(age) and ester group, exemplified by acrylic methyl esters, ethyl propenoate, butyl acrylate, tert-butyl acrylate, 2-EHA, Octyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methacrylic tert-butyl acrylate, isopropyl methacrylate, 2 ethyl methacrylate etc.

As monomer, exemplify propenal, crotonaldehyde etc. with unsaturated link(age) and aldehyde radical.

Be preferably, described polymerizable monomer is the monomer with ethene unsaturated double-bond and carboxyl.As this monomer, exemplified by acrylic (CH ₂=CHCOOH), methacrylic acid (CH ₂=C (CH ₃) COOH).Described polymerizable monomer is preferably acrylic or methacrylic acid.Thus, can improve the cementability of difficult adhesive resin film effectively.Described polymerizable monomer is vinylformic acid more preferably.

Described polymerizable monomer also can be carried by carrier gas.Carrier gas is preferably selected from rare gas elementes such as nitrogen, argon, helium.From the economy aspect,, preferably use nitrogen as carrier gas.

Polymerizable monomer such as vinylformic acid and methacrylic acid mostly is liquid phase at normal temperatures and pressures greatly.Such polymerizable monomer can followingly obtain, i.e. gasification and obtain that mixed gas by polymerizable monomer steam and carrier gas constitutes contain polymerizable monomer gas in carrier gas such as rare gas element.Method as polymerizable monomer is gasified in carrier gas exemplifies: utilize the saturated vapo(u)r on the liquid level of carrier gas extruding polymerization monomer liquid method, make carrier gas in polymerizable monomer liquid blistered method, heat with the method that promotes evaporation to polymerizable monomer liquid etc.Also can use in the lump to extrude and heat or use in the lump and bubble and heating.

When carrying out heating and gasifying, consider the load of well heater, the preferred boiling point of polymerizable monomer is the material below 300 ℃.And polymerizable monomer preferably can not decompose the material of (chemical transformation) because of heating.

In addition; in the manufacture method of polaroid of the present invention; described difficult adhesive resin film is transparent protective membrane; described easy-adhesion resin molding is a polarizing coating; described manufacture method is characterised in that; after stating the film surface treatment method on the implementation, described difficult adhesive resin film and easy-adhesion resin molding is bonding via transparent caking agent.

By adopting above-mentioned surface treatment method, can guarantee cementability, and then can improve the quality of polaroid.

According to the present invention, can improve the cementability of difficult adhesive resin film effectively, thereby can improve the processing quality.

Description of drawings

Fig. 1 is the front view that the surface processing device of first embodiment of the invention represented in summary.

Fig. 2 (a) is that sectional view, (b) of polaroid is the sectional view that has the polaroid of hard coat.

Fig. 3 is the front view that the surface processing device of second embodiment of the invention represented in summary.

Fig. 4 is the front view of the Cement Composite Treated by Plasma portion of the summary surface processing device of representing third embodiment of the invention.

Fig. 5 is the stereographic map of the Cement Composite Treated by Plasma portion of the 3rd embodiment.

Fig. 6 is the front view of the variation of expression the 3rd embodiment.

Fig. 7 is the front view of the Cement Composite Treated by Plasma portion of the summary surface processing device of representing four embodiment of the invention.

Fig. 8 is shown the stereographic map that imaginary line is represented the Cement Composite Treated by Plasma portion of the 4th embodiment with electrode.

Fig. 9 is the sectional view along the IX-IX line of Fig. 7.

Figure 10 is the front view of the Cement Composite Treated by Plasma portion of the summary surface processing device of representing fifth embodiment of the invention.

Figure 11 is the sectional view along the XI-XI line of Figure 10.

Figure 12 is the front view of the variation of expression the 5th embodiment.

Figure 13 is the sectional view along the XIII-XIII line of Figure 12.

Figure 14 is the stereographic map that is disposed at the axle head plug members of paper inboard in Figure 12.

Figure 15 is the summary pie graph of embodiment 1 employed surface processing device.

Figure 16 is the result's of expression embodiment 3 a graphic representation.

Figure 17 is the stereographic map of embodiment 5 employed axle head plug members.

Embodiment

Below, with reference to the description of drawings embodiments of the present invention.

Fig. 2 is that expression utilizes the liquid-crystal display of the surface treatment method making of the embodiments of the present invention figure of polaroid 10.Shown in Fig. 2 (a), polaroid 10 has: polarizing coating 12 and a pair of protective membrane 11 that is laminated in the two sides of this polarizing coating 12.

Protective membrane 11 is made of the TAC film that with cellulose triacetate (TAC) is principal constituent.The content of the cellulose triacetate of TAC film 11 is more than the 90 quality %.In TAC film 11, can also contain the triphenylphosphate phosphate plasticizers such as (TPP) about 3～10 quality %, also can contain UV light absorber.The thickness of TAC film 11 does not limit especially, for example is tens μ m～100 μ m.The manufacture method of TAC film 11 does not limit especially, for example by the film casting method manufacturing.

Polarizing coating 12 is made of the PVA film 12 that with polyvinyl alcohol (PVA) is principal constituent.

TAC film 11 and PVA film 12 utilize caking agent 13 to bond together.As caking agent 13, be not special qualification, but consider and make it be applicable to blooming 10, preferably use transparent water system caking agent.As the water system caking agent, exemplify: be the polyethenol series caking agent liquid of principal constituent, be that the ethene base system polymerization of principal constituent is latex, is that ethylene series aqueous adhesive, the polyethers of principal constituent is caking agent etc. with polyolefin polyvalent alcohol etc. with butylacrylic acid ester etc. with polyvinyl alcohol water solution, polyvinyl butyral acetal solution etc.As caking agent 13, more preferably use with the polyethenol series caking agent of polyvinyl alcohol water solution as principal constituent.

In the polaroid 10 shown in Fig. 2 (b), on the table side of the TAC of side film 11 (with the face of the opposition side of the bonding bonding plane of PVA film 12), be laminated with hard coat 14 as functional layer.Also hard coat 14 be can replace and AR layer, other functional layers are laminated with.

TAC film 11 is low with the cementability of caking agent 13, and it constitutes difficult adhesive resin film.The cementability height of PVA film 12 and caking agent 13, it constitutes easy-adhesion resin molding.The TAC film 11 of difficult cementability when bonding, is being implemented surface treatment with the PVA film 12 of easy-adhesion in order to improve cementability.

Fig. 1 is the figure of the above-mentioned employed surface processing device 1 of surface treatment of expression.Surface processing device 1 has: Cement Composite Treated by Plasma portion 2 and process gas plenum system 3.Cement Composite Treated by Plasma portion 2 has pair of electrodes 21.It is the cylinder shape (cylindrical or round shape) of identical size each other that these electrodes 21 constitute, and make axis towards orthogonal axially with Fig. 1, and (orientation) arranges about the edge.Below, when distinguishing two electrodes 21 mutually, mark " L " on the Reference numeral of left electrodes 21, mark " R " on the Reference numeral of right electrodes 21.The space of the narrowest part periphery between the described electrode 21 constitutes near atmospheric processing space 22.Handle the both ends open up and down in space 22 and be communicated with atmosphere.The thickness of the narrowest part between the electrode 21 is about 0.5mm～number mm, and it is narrow to handle space 22.

An electrode in the pair of electrodes 21 is connected another electrode 21 ground connection with the HV Terminal of power supply 23.At this, the electrode 21L in left side is connected with power supply 23, and the electrode 21R ground connection on right side is connected electrode 21L ground connection with electrode 21R but also can constitute power supply 23.By from power supply 23 service voltages, between electrode 21,21, form electric field, above-mentioned processing space 22 constitutes near atmospheric discharge space.For example constitute pulse type from the voltage of power supply 23 supplies and the electric field between the electrode 21.Are preferably the rise time of pulse and/or fall time below the 10 μ s, strength of electric field is preferably 10～1000kV/cm, and frequency is preferably 0.5～100kHz.Applying the interrupted wae that voltage and electric field are not limited to pulse type, also can be continuous waves such as sine wave.

Roller electrode 21 is with as object being treated being the supporting device of TAC film 11 and the function of travel mechanism.Continuous flaky TAC film 11 is striden two roller electrodes 21,21, and lateral circle surface is for example reeled about half-turn on each roller electrode 21.Roller electrode 21,21 TAC film 11 each other passes to be handled space 22 and stretches out downwards and be wound in and a pair ofly turn back roller 27,27 and turn back.Utilize the rotation of two roller electrodes 21, TAC film 11 is carried to a direction (right-hand).By the speed of rotation of dancer rools electrode 21, can regulate the translational speed of TAC film 11.

Be incorporated with film temperature regulating mechanism 28 in the inside of each roller electrode 21.Film temperature regulating mechanism 28 is made of the temperature regulation stream.Circulate in the temperature regulation stream of the temperature regulation medium of specified temperature in roller electrode 21.As the temperature regulation medium, for example make water.Thus, temperature that can dancer rools electrode 21, and then can regulate TAC film 11 and temperature roller electrode 21 contacted parts.The temperature of TAC film 11 is preferably more than the room temperature.At this, room temperature is generally 20～25 ℃, is more typically 25 ℃.

Next, process gas plenum system 3 is described.

Process gas plenum system 3 has: polymerizable monomer supply source 30 and rare gas element supply source 31.Polymerizable monomer supply source 30 is made of thermostatic container (thermostatic bath).In thermostatic container 30, accumulating as the surface-treated reacted constituent has polymerizable monomer.Polymerizable monomer preferably has the functional group of unsaturated link(age) and regulation, more preferably possess hydrophilic property.As polymerizable monomer, more preferably use acrylic or methacrylic acid.At this,, use vinylformic acid (CH as polymerizable monomer ₂=CHCOOH).Vinylformic acid is the hydrophilic polymer monomer with ethene unsaturated double-bond and carboxyl.Vinylformic acid AA is incorporated in the thermostatic container 30 with liquid state.There is the acrylic acid saturated vapo(u)r from liquid propene acid AA gasification in the upper portion of the liquid level of the liquid propene acid AA in thermostatic container 30.

In thermostatic container 30, be incorporated with well heater 32 as gasification mechanism.Liquid propene acid AA in the container 20 utilizes well heater 32 to be heated and gasifies.According to the Heating temperature of liquid propene acid AA, can regulate acrylic acid amount of vaporization.Consider that the vinylformic acid steam has explosivity, the Heating temperature of vinylformic acid AA preferably is made as below 150 ℃, more preferably is made as less than acrylic acid flash-point (54 ℃), further preferably is made as room temperature (25 ℃)～about 80 ℃; If consider flash-point, room temperature (25 ℃)～about 50 ℃ more preferably then.Even if near room temperature, when the acrylic acid amount of vaporization amount of satisfying the demand, also can omit well heater 32.In addition, acrylic acid burning-point is 360 ℃.Acrylic acid flash-point is 54 ℃.By the way, the burning-point of methacrylic acid is 360 ℃.The flash-point of methacrylic acid is 77 ℃.

In rare gas element supply source 31, be filled with rare gas element.Rare gas element plays following effect: generate the effect of the plasma body generation of plasma body with gas as the effect of the carrier gas of carrying the polymerizable monomer steam with as being used in handling space 22.At this,, use nitrogen, but except that nitrogen, also can use other rare gas elementes such as argon gas, helium as rare gas element.

Carrier gas or plasma body generation are preferably with gas and do not contain aerobic in fact.

Rare gas element is supplied with stream 33 and is extended from rare gas element supply source 31.Rare gas element supply stream 33 branches into plasma body and generates with gas flow path 34 and current-carrying path 35.Be respectively arranged with flow control device 34v, 35v at these streams 34,35. Flow control device 34v, 35v are made of mass flow controller or flowrate control valve etc.Utilize these flow control devices 34v, 35v, regulate the splitting ratio of rare gas element to each road 34,35.

Current-carrying path 35 is connected with thermostatic container 30.The leading section in current-carrying path 35 inserts the inside of thermostatic container 30 and opening and be positioned at the upper portion of vinylformic acid AA liquid level.

Also the leading section in current-carrying path 35 can be extended to the liquid internal of vinylformic acid AA, nitrogen is bubbled.

The upper lateral part of polymerizable monomer steam stream 36 self-constant temperature containers 30 extends.Plasma body generates with gas flow path 34 and polymerizable monomer steam stream 36 and converges.Process gas stream 37 extends to Cement Composite Treated by Plasma portion 2 from the fluidic junction of above-mentioned stream 34,36.Be provided with gas temperature regulating mechanism 38 at polymerizable monomer steam stream 36 and process gas stream 37.Gas temperature regulating mechanism 38 for example is made of band heater, and the whole periphery that constitutes the pipe of polymerizable monomer steam stream 36 and process gas stream 37 is covered.Utilize gas temperature regulating mechanism 38, can be adjusted in the temperature of the gas that polymerizable monomer steam stream 36 and process gas stream 37 flow through.

Leading section at process gas stream 37 is provided with process gas nozzle 39.Process gas nozzle 39 is disposed at the upper portion between the pair of rolls electrode 21.The opening of process gas nozzle 39 front ends is down and with to handle space 22 relative.The leading section of process gas nozzle 39 attenuates more to downside more, and is inserted into the part that narrows down gradually between the roller electrode 21.

Though omit detailed diagram, process gas nozzle 39 is along extending axially and the roughly the same width of the width of TAC film 11 or longer than the width of TAC film 11 with the paper of Fig. 1 is orthogonal.In the inside of process gas nozzle 39, be formed with to make and supply with the gas of stream 37 along above-mentioned axially (the paper orthogonal directions of Fig. 1) homodisperse commutation path from process gas.Commutation path comprises along above-mentioned axially extended chamber or slit or along a plurality of apertures of above-mentioned axial dispersion configuration etc.Also can make rectification part separate and be disposed between the front end and process gas nozzle 39 of process gas stream 37 from process gas nozzle 39 with above-mentioned commutation path.The blow-off outlet of process gas nozzle 39 front ends links to each other with commutation path.The slit-shaped that the blow-off outlet formation edge and the orthogonal direction of the paper of Fig. 1 of process gas nozzle 39 extended.The blow-off outlet of process gas nozzle 39 also can constitute along with a plurality of small pore-like of the orthogonal direction of the paper of Fig. 1 across compartment of terrain configuration.

And,, be formed with temperature regulation stream (omitting diagram) in the inside of process gas nozzle 39.The temperature regulation medium of specified temperature flows through at the temperature regulation stream.As the temperature regulation medium, for example make water.Can utilize the temperature regulation medium that the tectosome of process gas nozzle 39 is maintained specified temperature, and then can regulate, and then can regulate the temperature of the gas that blows out from process gas nozzle 39 temperature of the gas that in process gas nozzle 39, passes through.

Illustrate that the 1 pair of TAC film of film surface processing device 11 that uses above-mentioned formation carries out the method for surface treatment and then manufacturing polaroid 10.

[process gas supplying step]

The nitrogen of rare gas element supply source 31 is supplied with stream 33 from rare gas element be assigned to plasma body generation usefulness gas flow path 34 and current-carrying path 35.Utilize flow control device 34v, 35v to regulate and distribute ratio.The nitrogen that is diverted to current-carrying path 35 is imported into thermostatic container 30, and the vinylformic acid steam of the liquid level upside of the liquid propene acid in the thermostatic container 30 is expressed into polymerizable monomer steam stream 36.At process gas stream 37, mix from the gas (nitrogen+vinylformic acid steam) of polymerizable monomer steam stream 36 and the nitrogen that generates with gas flow path 34 from plasma body, thereby generate process gas.Consider limits of explosion, the acrylic acid concentration in the process gas (vinylformic acid+nitrogen) is preferably below 2%, and more preferably about 1%.The partition ratio that the concentration of process gas can be distributed to two streams 34,35 according to nitrogen, regulate by acrylic acid Heating temperature of well heater 32 heating.This process gas is transported to process gas nozzle 39 through process gas stream 37.Process gas in process gas nozzle 39 along the width (the paper orthogonal directions of Fig. 1) of TAC film 11 homogenized after, blow out to handling space 22.

[plasma treatment step]

Supply with according to voltage, between electrode 21,21, form atmosphere pressure discharging, thereby inter-electrode space 22 is constituted discharge space from power supply 23.Thus, the nitrogen in the process gas is by plasma bodyization, and the vinylformic acid steam is activated, and causes the fracture, polymerization of two keys etc.In addition, contact, shine the ultraviolet ray (337nm) from nitrogen plasma to TAC film 11 by making nitrogen plasma, keys such as the C-C of the surface molecular of TAC film 11, C-O, C-H are cut off.Can consider in this key cut-out portion in conjunction with (graft polymerization) polymerizing acrylic acid thing or in conjunction with the COOH base that decomposes from vinylformic acid etc.Thus, form the cementability promoting layer on the surface of TAC film 11.

[temperature adjustment step]

And, utilizing gas temperature regulating mechanism 38, the gas temperature that will pass through in polymerizable monomer steam stream 36 and process gas stream 37 is adjusted to temperature desired.And utilize the temperature regulation stream in the process gas nozzle 39, the process gas temperature that will pass through in process gas nozzle 39 is adjusted to temperature desired.Thus, the temperature (hereinafter referred to as " blow out temperature ") of process gas when process gas nozzle 39 blows out can be made as design temperature.The upper limit that blows out temperature preferably sets the scope that can not produce thermal distortions such as swelling at TAC film 11.The ultimate temperature that TAC film 11 does not produce thermal distortions such as swelling also depends on treatment condition etc., for example is about 80 ℃.From preventing the viewpoint of dewfall in gas flow path 36,37 and nozzle 39, the lower limit that blows out temperature is preferably more than the room temperature.Blow out temperature and be preferably about 35 ℃～80 ℃, about more preferably 40 ℃～50 ℃.

And, utilize film temperature regulating mechanism 28, the temperature (hereinafter referred to as " film temperature ") of the part that contacts with roller electrode 21 of TAC film 11 is maintained blow out the low temperature desired of temperature than process gas.Be preferably, it is low more than 5 ℃ to make the film temperature ratio blow out temperature.More preferably, it is low more than 10 ℃ to make the film temperature ratio blow out temperature.By this temperature regulation, even if for example under the high speed transport condition more than the 10m/s, also can make vinylformic acid condensation effectively (supporting) on the surface of TAC film 11, and then, the cementability promoting layer that comprises acrylic acid graftomer can be formed on the surface of TAC film 11 effectively.

[mobile step]

With above-mentioned process gas supplying step and plasma treatment step side by side, roller electrode 21 clockwise direction in Fig. 1 is rotated continuously, with TAC film 11 to right-hand conveying.The each point of TAC film 11 (processed part) is wound on the roller electrode 21 in left side, after this be about to before the roller electrode 21 in this left side leaves by handling space 22, turn back after roller 27,27 turns back in utilization, twist on the roller electrode 21 on right side and once more by handling space 22.The each point of TAC film 11 (processed part) each when handling space 22 by Cement Composite Treated by Plasma.Therefore, can in a processing space 22, carry out twice surface treatment to TAC film 11.

[process gas flow regulating step]

At this, be accompanied by moving of TAC film 11 on the left roller electrode 21, the environmental gas (air) of these TAC film 11 peripheries is involved in this TAC film 11 to be handled in the space 22.Have following trend: the translational speed of TAC film 11 is big more, and then the amount of being involved in of air is big more.Therewith correspondingly, increase the supply flow rate of process gas.Be preferably, the article on plasma body generates and regulates with the flow of gas flow path 34 when keeping certain by the flow with current-carrying path 35, regulates the supply flow rate of process gas.Thus, be process gas (almost all being that nitrogen, surplus are the vinylformic acid steam) with the gas displacement of handling in the space 22, handle space 22 certainly air and then oxygen are driven out of.

In a word, in above-mentioned process gas supplying step, set the supply flow rate of process gas, so that the oxygen concn of handling in the space 22 is below the prescribed value.Particularly, make the oxygen concns of handling in the space 22 be preferably 3000ppm, more preferably 2000ppm, more preferably below the 1000ppm.Thus, the key that can prevent C-C, C-O, the C-H etc. of acrylic acid fracture in the article on plasma body treatment step or polymerization, TAC film 11 surface moleculars cuts off, the reaction such as combine between polymerizing acrylic acid thing or functional group and the above-mentioned key cut-out portion produces obstruction.Therefore, can form the cementability promoting layer effectively on the surface of TAC film 11, thereby can make the processing steady quality.And, can increase the transfer rate of TAC film 11 and not worry that air is involved in and handle in the space 22.Therefore, the treatment time can be shortened.

[bonding step]

To utilize caking agent 13 bonding by the TAC film 11 that as above step has been carried out the difficult adhesive resin of surface-treated with the PVA film 12 of easy-adhesion resin.Since be formed with the cementability promoting layer effectively on the surface of TAC film 11, therefore, can TAC film 11 and PVA film 12 is bonding securely.Thus, can obtain the good polaroid of quality 10.

Next, the surface processing device to other embodiments of the present invention describes.In the following embodiments, for constitute same Reference numeral of mark and omission explanation on figure with the first embodiment multiple.

Fig. 3 represents second embodiment of the present invention.In second embodiment, be provided with three roller electrodes 21 in plasma body generating unit 2.Three electrodes 21 constitute big or small each other identical cylinder shape (cylindrical), make axis towards also arranging about the edge with the orthogonal direction of Fig. 3.When three electrodes 21 are distinguished from each other, the electrode 21 in left side is labeled as " electrode 21L ", the electrode 21 of central authorities is labeled as " electrode 21C ", the electrode 21 on right side is labeled as " electrode 21R ".

The roller electrode 21C of central authorities is connected with power supply 23.About roller electrode 21L, 21R ground connection.By from power supply 23 service voltages, forming electric field between adjacent electrode 21L, the 21C and between electrode 21C, the 21R, the space of these the narrowest interelectrode part peripheries constitutes near atmospheric processing space 22.When two processing spaces 22 are distinguished from each other, the processing space 22 between electrode 21L, the 21C of left side and central authorities is labeled as " handling space 22A ", the processing space 22 between electrode 21C, the 21R on central authorities and right side is labeled as " handling space 22B ".

Continuous flaky TAC film 11 is striden three roller electrodes 21, for example reels about half-turn on the side face of each roller electrode 21 upside.Adjacent roller electrode 21 TAC film 11 to each other stretches out to handling 22 belows, space, is wound on a pair of roller 27,27 of turning back and turns back.Utilize the rotation of three roller electrodes 21, TAC film 11 is transferred towards a direction (right-hand).

In second embodiment,, be provided with the first process gas plenum system 3A and the second process gas plenum system 4 as gas supply system.The first process gas plenum system 3A constitutes the formation same with the process gas plenum system 3 of first embodiment.Process gas nozzle 39 is configured between roller electrode 21L, the 21C of left side and central authorities, and relative with discharge space 22A.The process gas that the first process gas plenum system 3A will contain the vinylformic acid steam supplies to discharge space 22A.

The second process gas plenum system 4 has: the second process gas supply source 41 and the second process gas nozzle 43.The second process gas supply source 41 is accumulated the nitrogen as second process gas.As second process gas, also can use other rare gas elementes such as argon, helium.Second process gas is supplied with stream 42 and is extended to Cement Composite Treated by Plasma portion 2 from the second process gas supply source 41.The second process gas nozzle 43 links to each other with the leading section of supplying with stream 42.The second process gas nozzle 43 is configured between roller electrode 21C, the 21R on central authorities and right side, and relative with discharge space 22B.The nitrogen of the second process gas supply source 41 is blown out to processing space 22B through supplying with stream 42 from nozzle 43.

Mutually distinguishing when supplying to two gases of handling space 22A, 22B, be labeled as " first process gas ", will supply to the gas (nitrogen) of handling space 22B and be labeled as " second process gas " supplying to the gas (vinylformic acid steam+nitrogen) of handling space 22A.

First, second process gas supply source 31,41 also can be made of shared rare gas element supply source.

In second embodiment, to the left and the discharge space 22A between roller electrode 21L, the 21C of central authorities supply with first process gas (vinylformic acid+nitrogen) and carry out plasma bodyization, thereby form the adhesion promoter layer that contains polymerizing acrylic acid thing etc. on the surface of TAC film 11.At this moment, set the flow of first process gas, so that the oxygen concn in the discharge space 22A is preferably following, the 1000ppm more preferably of 1000ppm.

Then, the discharge space 22B between roller electrode 21C, the 21R on central authorities and right side carries out plasma bodyization and it is contacted with TAC film 11 second process gas (nitrogen is only arranged).Thus, can make the unreacted vinylformic acid activation on TAC film 11 surfaces, thereby can form the adhesion promoter layer more reliably.Therefore, can improve the cementability of TAC film 11 effectively.

Fig. 4 and Fig. 5 represent the 3rd embodiment of the present invention.The plasma surface processing device 1 of the 3rd embodiment has handling the occluding mechanism 7 that space 22 is stopped up.Occluding mechanism 7 comprises a counter-lateral quadrents plug members 71,72. Sidepiece plug members 71,72 is configured in the both sides of above-below direction (with the axial and orthogonal orthogonal directions of orientation of electrode 21) across handling space 22.The strip that the axially parallel of above-mentioned plug members 71,72 formations and electrode 21 extends.

The sidepiece plug members 71 of upside is configured to across the side face of processing space 22 upsides of roller electrode 21,21 each other.Sidepiece plug members 71 with the orthogonal section constitution of length direction for along with attenuating towards the below front end.The bottom of sidepiece plug members 71 is inserted near pair of electrodes 21, the 21 the narrowest position to each other, in other words is inserted near the discharge space.The lower surface of sidepiece plug members 71 marks off the upper end of handling space 22 with handling space 22 to face mutually.Utilize sidepiece plug members 71, the upper lateral part of handling space 22 is roughly stopped up.

Sidepiece plug members 71 towards the below and the left and right sides face of the part that front end attenuates constitutes the concave curved surface 73 of local barrel surface shape respectively.The radius-of-curvature of concave curved surface 73 is bigger slightly than the radius of each electrode 21.The center of curvature of the concave curved surface 73 in left side is roughly consistent with the axis of the electrode 21L in left side.The center of curvature of the concave curved surface 73 on right side is roughly consistent with the axis of the electrode 21R on right side.

The concave curved surface 73 in left side is along the side face of the electrode 21L in left side.Between the side face of the concave curved surface 73 in left side and electrode 21L, be formed with sidepiece gap 73e.Utilize gap 73e, allow processed film 11 to reel to electrode 21L.The concave curved surface 73 on right side is along the side face of the electrode 21R on right side.Between the side face of the concave curved surface 73 on right side and electrode 21R, be formed with sidepiece gap 73f.Utilize gap 73f, allow processed film 11 to reel to electrode 21R.

The sidepiece plug members 72 of downside constitutes the sidepiece plug members 71 formed shapes of the upside that turns upside down substantially.Details are as follows: promptly, the sidepiece plug members 72 of downside is configured to across the side face of processing space 22 downsides of roller electrode 21,21 each other.Sidepiece plug members 72 with the orthogonal section constitution of length direction for along with attenuating towards the top front end.The upper end of sidepiece plug members 72 is inserted near pair of electrodes 21, the 21 the narrowest position to each other, in other words is inserted near the discharge space.The upper surface of sidepiece plug members 72 marks off the lower surface of handling space 22 with handling space 22 to face mutually.Utilize sidepiece plug members 72, handle the lower side in space 22 and roughly stopped up.Utilize sidepiece plug members 71,72, both sides cover and handle space 22 up and down certainly.

Sidepiece plug members 72 towards the top and the left and right sides face of the part that front end attenuates constitutes the concave curved surface 74 of local barrel surface shape respectively.The radius-of-curvature of concave curved surface 74 is bigger slightly than the radius of each electrode 21.The center of curvature of the concave curved surface 74 in left side is roughly consistent with the axis of the electrode 21L in left side.The center of curvature of the concave curved surface 74 on right side is roughly consistent with the axis of the electrode 21R on right side.

The concave curved surface 74 in left side is along the side face of the electrode 21L in left side.Between the side face of the concave curved surface 74 in left side and electrode 21L, be formed with sidepiece gap 74e.Utilize gap 74e, allow processed film 11 to reel to electrode 21L.The concave curved surface 74 on right side is along the side face of the electrode 21R on right side.Between the side face of the concave curved surface 74 on right side and electrode 21R, be formed with sidepiece gap 74f.Utilize gap 74f, allow processed film 11 to reel to electrode 21R.

The thickness of gap 73e, 73f, 74e, 74f is bigger than the thickness of processed film 11, and its size is configured to fully to suppress the degree that environmental gas is on every side invaded in handling space 22.The thickness t of gap 73e, 73f, 74e, 74f is preferably (t 〉=g), more preferably handle below the thickness in space 22 below the interval g at the narrowest position between the electrode 21,21 at least.At this, the size of the thickness of handling space 22 after for the double thickness that deducts processed film 11 from above-mentioned interval g.For example, the thickness t of gap 73e, 73f, 74e, 74f is preferably about t=0.05mm～0.5mm, more preferably about t=0.2～0.3mm.The thickness of the thickness of gap 73e, 73f and gap 74e, 74f both can be mutually the same, also can differ from one another.

In addition, to be preferably double thickness than processed film 11 big and for below the 3mm, more preferably below the 1mm for the interval g at the narrowest position between the electrode 21,21.

In addition, in Fig. 4 and Fig. 5, the diagram that electrode 21 temperature inside are regulated stream 28, the gas temperature regulating mechanism 38 that reaches process gas plenum system 3, power supply 23 etc. is omitted.(omit too among Fig. 6～Figure 14) at after this embodiment.

In the sidepiece plug members 71,72 at least one constitutes the process gas nozzle of process gas plenum system 3 downstream end.At this, the plug members 71 that upside is provided is as the process gas nozzle.Plug members 71 is corresponding to the process gas nozzle 39 of first embodiment (Fig. 1).

Be provided with rectification part 75 at the hold concurrently upside of plug members 71 of nozzle.The front end of process gas stream 37 is connected with rectification part 75.Rectification part 75 is extended with the orthogonal direction of the paper of Fig. 4 on the edge abreast with plug members 71.Though omit detailed diagram, be provided with in rectification part 75 and make from the gas of process gas stream 37 commutation path of (with the orthogonal direction of the paper of Fig. 4) homogenizing vertically.Commutation path comprises along above-mentioned axially extended chamber or slit or along a plurality of apertures of above-mentioned axial dispersion configuration etc.

Be formed with and blow out stream 76 in the hold concurrently inside of plug members 71 of nozzle.Blow out stream 76 and constitute the slit-shaped of (with the orthogonal direction of the paper of Fig. 4) extension vertically.The downstream end that blows out stream 76 arrives the lower surface and the opening of plug members 71, thereby constitutes blow-off outlet.

And, be formed with temperature regulation stream 79 in the hold concurrently inside of plug members 71 of nozzle.Temperature regulation stream 79 (with the orthogonal direction of the paper of Fig. 4) vertically extends.Regulate stream 79 by making the water equitemperature regulate the medium flow excess temperature, can regulate the nozzle temperature of plug members 71 of holding concurrently.

The plug members 72 of downside is a nominal nozzle, has and the nozzle of the upside identical face shaping of plug members 71 of holding concurrently, and does not blow out stream and temperature regulation stream but form in inside.Plug members 72 also can similarly have the stream of blowing out and temperature regulation stream with the nozzle plug members 71 of holding concurrently, and also can utilize stopper etc. that the blow-off outlet of this plug members 72 is stopped up.In addition, sidepiece plug members 71,72 does not have venting port or the attraction mouth that is used to discharge process gas.

According to the 3rd embodiment, the process gas that comprises polymerizable monomer is imported into rectification part 75 and homogenized along the length direction of rectification part 75 from process gas stream 37.Process gas after the homogenizing blows out and is imported into processing space 22 from blowing out stream 76.In handling space 22, process gas contacts by plasma bodyization and with processed film 11.Thus, can improve the cementability on processed film 11 surfaces.After this, process gas flows out towards handling 22 outsides, space from the length direction of handling space 22 (orthogonal axially with the paper of Fig. 4) openings at two ends 22e.And, a part of process gas via up and down plug members 71,72 and about the side face of electrode 21L, 21R between gap 73e, 73f, 74e, 74f flow out towards the outside.

Utilize the plug members 71 of upside, can roughly stop up the upper lateral part of handling space 22.Utilize the plug members 72 of downside, can roughly stop up the lower side of handling space 22.Thus, even if reduce the supply flow rate of process gas, the side face that the side face that also can prevent or suppress outside environmental gas self-electrode 21,21 upsides reaches downside is to each other invaded to each other and is handled in the space 22.And.Because of above-mentioned process gas flows out from axle head opening 22e and gap 73e, 73f, 74e, 74f, therefore, can prevent that outside environmental gas from invading and handling in the space 22 through axle head opening 22e and gap 73e, 73f, 74e, 74f.Thus, can effectively the oxygen concns in the processing space 22 be set at prescribed level is below the 3000ppm.Therefore, can improve the cementability of processed film 11 effectively.

Fig. 6 represents the variation of the 3rd embodiment.In the sidepiece plug members up and down of this variation, not only the plug members 71 to upside constitutes the process gas nozzle, and also constitutes the process gas nozzle for the plug members 72A of downside.Be provided with rectification part 77 in the hold concurrently bottom of plug members 72A of nozzle.Rectification part 77 (with the orthogonal direction of the paper of Fig. 6) is vertically extended.Process gas stream 37 is connected with rectification part 77.In rectification part 77, similarly be provided with rectification part 75 and make the process gas commutation path of homogenizing vertically.Process gas stream 37 from shared polymerizable monomer supply source 30 (with reference to Fig. 1) also can carry out branch, and is connected via hold concurrently plug members 71,72A of rectification part 75,77 and nozzle respectively.Hold concurrently plug members 71,72A of nozzle also can be connected with different each other gas supply source.Be preferably, one in the different each other gas supply source is polymerizable monomer supply source 30, and another in the different each other gas supply source is the rare gas element supply source 41 (with reference to Fig. 2) of nitrogen or rare gas etc.

In the inside that nozzle is held concurrently plug members 72A, be formed with and blow out stream 78 and temperature regulation stream 79.The above-mentioned commutation path of rectification part 77 with blow out stream 78 and link to each other.Blow out stream 78 and constitute the slit-shaped of (with the orthogonal direction of the paper of Fig. 6) extension vertically.Blow out stream 78 and arrive upper surface and the opening that nozzle is held concurrently plug members 72A, thereby constitute blow-off outlet.The hold concurrently blow-off outlet of plug members 72A of nozzle has identical length and the width of blow-off outlet with the spray nozzle clogging parts 71 of upside.

Thus, process gas not only is imported into and handles space 22 from the nozzle of the upside plug members 71 of holding concurrently, and is imported into and handles space 22 from the nozzle of the downside plug members 72A that holds concurrently.Preferably be identical size each other from the flow that plug members 71,72A blow out of holding concurrently of nozzle up and down.Thus, can exert pressure to handling in the space 22 equably.In handling space 22, after this flow out from the axle head opening 22e that handles space 22 and gap 73e, 73f, 74e, 74f for the surface-treated process gas of processed film 11.Utilize flowing of this process gas, can prevent that outside environmental gas from entering and handling in the space 22 from axle head opening 22e and gap 73e, 73f, 74e, 74f.By exerting pressure to handling in the space 22 equably, can prevent that outside environmental gas is from the concentrated processing space 22 that flows into of the part of gap 73e, 73f, 74e, 74f.Thus, can effectively the oxygen concn of handling in the space 22 be set at below the prescribed value (3000ppm).Therefore, can improve the cementability of processed film 11 effectively.In addition, sidepiece plug members 71,72A do not have venting port or the attraction mouth that is used for the process gas discharge.

Fig. 7～Fig. 9 represents the 4th embodiment of the present invention.

In this embodiment, except that the sidepiece plug members 71,72 of the 3rd embodiment (Fig. 4 and Fig. 5), also be provided with axle head plug members 80.As shown in Figure 8, axle head plug members 80 is disposed at the axial both ends of electrode 21,21 respectively.As shown in Figure 7, each axle head plug members 80 is across between the end of a mutually the same side pair of electrodes 21,21 and a counter-lateral quadrents plug members 71,72, on axially, and covers the end 22e that handles space 22 above-mentioned same side in the axial direction.

As Fig. 8 and shown in Figure 9, axle head plug members 80 has front plate 81 and pair of side plates 82, is コ shape (U-shaped, ∏ shape) when overlooking.Front plate 81 constitutes the tabular of extending up and down.Edge is provided with side plate 82 respectively in the left and right sides of front plate 81.Each side plate 82 and front plate 81 quadratures.

The end face of front plate 81 self-electrodes 21 leaves towards the axial outside.As shown in Figure 7, from the axial outside, front plate 81 has strides left and right sides electrode 21L, 21R width dimensions to each other, and from the axial outside, front plate 81 has sidepiece plug members 71,72 size up and down to each other under stepping up.From the axial outside, front plate 81 covers the end 22e that handles space 22.

As shown in Figure 9, left plate 82 is outstanding towards the end face of electrode 21L from front plate 81.Right side plate 82 is outstanding towards the end face of electrode 21R from front plate 81.

It is outstanding towards the axial outside that sidepiece plug members 71,72 is compared electrode 21, and the inside of inserting axle head plug members 80.The medial surface of the axial end portion butt front plate 81 of sidepiece plug members 71,72, and utilize bolt 89 fixing.Thus, axle head plug members 80 is supported in sidepiece plug members 71,72.Between the axial end of the upper lateral part of front plate 81 and sidepiece plug members 71, do not form the gap.Between the axial end of the lower side of front plate 81 and sidepiece plug members 72, do not form the gap.

About the upper lateral part butt of concave curved surface 73 of the last ora terminalis of each side plate 82 and sidepiece plug members 71.Between ora terminalis on each side plate 82 and sidepiece plug members 71, do not form the gap.The lower side butt of the following ora terminalis of each side plate 82 and the concave curved surface 74 of sidepiece plug members 72.Between the following ora terminalis of each side plate 82 and sidepiece plug members 72, do not form the gap.

In addition, also can between the ora terminalis up and down of side plate 82 and sidepiece plug members 71,72, be formed with the gap.

As shown in Figure 9, the electrode 21 that originates from that is in electrode 21 end face sides of each side plate 82 leaves about.Between the axial end of side plate 82 and electrode 21, be formed with end play 82e.Thus, can prevent that when electrode 21 rotations side plate 82 and electrode 21 from producing friction.The thickness t 8 of gap 82e is preferably about t8=0.05mm～0.5mm, more preferably about t8=0.1mm.

In the 4th embodiment, not only can utilize 71,72 inhibition of sidepiece plug members or prevent that outside environmental gas from entering in the processing space 22 from the both sides up and down of handling space 22, and, handle space 22 end 22e in the axial direction because axle head plug members 80 covers, can suppress or prevent therefore that outside environmental gas is in end 22e enters processing space 22.Therefore, can further reduce the supply flow rate of process gas.And process gas is handled process gap 73e, 73f, 74e, the 74f outflow of sidepiece up and down in the space 22 certainly, and also from axial crest clearance 82e outflow.Utilize flowing of this process gas, can prevent that outside environmental gas is in sidepiece gap 73e, 73f, 74e, 74f and end play 82e enter processing space 22.Even if outside environmental gas enters the inside of axle head plug members 80 through end play 82e, also can make the environmental gas that enters be diffused into the internal space of axle head plug members 80 to reduce the concentration of this environmental gas.Thus, can effectively the oxygen concns in the processing space 22 be set in below the prescribed level is below the 3000ppm.Therefore, can improve the cementability of processed film 11 effectively.

Figure 10 and Figure 11 represent the 5th embodiment of the present invention.In the 5th embodiment, substitute the axle head plug members 80 of コ shape (U-shaped) and be provided with tabular axle head plug members 90.Axle head plug members 90 is separately positioned on the axial both ends of electrode 21,21.Each axle head plug members 90 is across between the end of a mutually the same side pair of electrodes 21,21 and a counter-lateral quadrents plug members 71,72, on axially, and covers the end 22e that handles space 22 above-mentioned same side in the axial direction.

The axial end of sidepiece plug members 71,72 than electrode 21 towards axially outstanding a little (about for example outstanding 0.1mm).The axial end butt of the upper lateral part of axle head plug members 90 and sidepiece plug members 71 also utilizes bolt 99 to link.The axial end butt of the lower side of axle head plug members 90 and sidepiece plug members 72 also utilizes bolt 99 to link.Thus, axle head plug members 90 is by sidepiece plug members up and down 71,72 supportings.

The axial end of axle head plug members 90 self-electrodes 21,21 a little disposes with leaving.Between axle head plug members 90 and electrode 21,21, be formed with gap 91.Thus, can prevent that when electrode 21 rotations axle head plug members 90 and electrode 21 from producing friction.The overhang that the thickness in gap 91 is given prominence to corresponding to sidepiece plug members 71,72 self-electrodes 21.The thickness t 9 in gap 91 is preferably about t9=0.05mm～0.5mm, more preferably about t9=0.1mm.

In the 5th embodiment, axle head plug members 90 covers the axial end portion 22e that handles space 22, thereby can suppress or prevent that outside environmental gas is in end 22e enters processing space 22.Thus, even if the supply flow rate of process gas reduces, also can effectively the oxygen concn of handling in the space 22 be set at below the prescribed value (3000ppm).Therefore, can improve the cementability of processed film 11 effectively.

Figure 12 and Figure 13 represent the variation of the 5th embodiment.In this variation, between the electrode 21L in tabular axle head plug members 92 and left side, be formed with labyrinth 93.Between the electrode 21R on axle head plug members 92 and right side, be formed with labyrinth 94.

Details are as follows, and promptly as shown in figure 14, the left part of the face of (towards a side of electrode 21) in axle head plug members 90 inboards is formed with a plurality of circular-arc or part cyclic protuberances 95.The axis that these part annular convex 95 constitute each other with the electrode 21 in left side is the concentric circles at center.The right side part of the face of (electrode 21 sides) in axle head plug members 90 inboards is formed with a plurality of circular-arc or part cyclic protuberances 96.The axis that these part annular convex 96 constitute each other with the electrode 21 on right side is the concentric circles at center.

As Figure 12 and shown in Figure 13, the axial both ends of the surface at the electrode 21L in left side are formed with a plurality of cyclic grooves 97 respectively.These annular recess 97 formations are the concentric circles at center with the axis of electrode 21L each other.Annular recess 97 is corresponding one by one with the part annular convex 95 of axle head plug members 90.Each several part annular convex 95 is inserted in the corresponding annular recess 97.Constitute labyrinth 93 by part annular convex 95 and annular recess 97.

Axial both ends of the surface at the electrode 21R on right side are formed with a plurality of cyclic grooves 98 respectively.These annular recess 98 formations are the concentric circles at center with the axis of electrode 21R each other.Annular recess 98 is corresponding one by one with the part annular convex 96 of axle head plug members 90.Each several part annular convex 96 is inserted in the corresponding annular recess 98.Constitute labyrinth 94 by part annular convex 96 and annular recess 98.

The quantity of part annular convex 95,96 and annular recess 97,98 is respectively two in the drawings, but is not limited thereto, and can have respectively more than three, also can have one respectively.From the viewpoint of the stopping property that improves labyrinth 93,94, more preferably the quantity of part annular convex 95,96 and annular recess 97,98 is more.

As labyrinth, also can form part cyclic groove at axle head plug members 90, and in the end face formation of electrode 21 and the annular convex of above-mentioned engagement.

Utilize labyrinth 93,94, can will be between each electrode 21 and the axle head plug members 90 sealing, thereby can suppress more effectively or prevent that outside environmental gas is through between each electrode 21 and the axle head plug members 90 and enter in the processing space 22.Thus, even if reduce the supply flow rate of process gas, also can more effectively the oxygen concn of handling in the space 22 be set at below the prescribed value (300ppm).Therefore, can improve the cementability of processed film 11 effectively.

The present invention is not limited to above-mentioned embodiment, can carry out various changes in the scope of its main idea.

For example, in the process gas flow regulating step,, also can regulate the flow in current-carrying path 35, regulate the supply flow rate of process gas with this except that plasma body generates with the Flow-rate adjustment of gas flow path 34.Also can when the flow maintenance of the plasma body generation being used gas flow path 34 is certain, regulate the flow in current-carrying path 35, regulate the supply flow rate of process gas with this.Also can to make plasma body generate flow with gas flow path 34 be zero and regulate the flow in current-carrying path 35, regulates the supply flow rate of process gas with this.

Be replaced into rare gas element (for example nitrogen) by the environmental gas that will handle space 22 and periphery thereof, the oxygen concn of handling space 22 can be adjusted to below the prescribed value, below the promptly preferred 3000ppm, more preferably below following, the further preferred 1000ppm of 2000ppm.Also can utilize chamber to surround and handle space 22 and periphery thereof, be rare gas element (for example nitrogen) by the gas displacement with chamber interior, thereby the oxygen concn that will handle space 22 is adjusted to below the prescribed value.

Form the gas curtain (ガ ス カ one テ Application) of rare gas element (for example nitrogen) at the peripheral part of handling space 22, utilize this gas curtain to stop or suppress environmental gas such as air to enter and handle in the space 22, thus can regulate handle space 22 oxygen concn to normality.

Though process gas does not preferably contain aerobic, if described process gas be preferably 3000ppm following, more preferably below the 1000ppm, then also can contain aerobic.

The electrode structure of Cement Composite Treated by Plasma portion 2 is not limited to the roller electrode structure, it also can be parallel plate electrode structure (with reference to Figure 15) with pair of plates shape electrode, can also be the structure that makes plate electrode and roller electrode contraposition, can also be to make the electrode with concave curved surface and the structure of roller electrode contraposition.

As the polymerizable monomer in the process gas, also can instead of propylene acid and use methacrylic acid, can also use other hydrophilic polymerizable monomers.

Difficult adhesive resin film 11 is not limited to the TAC film, also can use the resin molding of difficult cementabilities such as COP, PP, PE, PET.

Also can constitute and make difficult adhesive resin film 11 motionless and mobile processing spaces 22.

Also can not make difficult adhesive resin film 11 and processing space 22 carry out Cement Composite Treated by Plasma with relatively moving.

The Cement Composite Treated by Plasma portion of embodiment is so-called direct type plasma processing apparatus, promptly handle space 22 and be discharge space, and to being disposed at the processed film 11 direct irradiation plasma bodys of handling space 22, but the present invention also goes for following so-called distance type plasma processing apparatus, promptly handling space and discharge space separately constitutes, handling the space links to each other with discharge space, after discharge space makes the process gas plasma bodyization, blow out, and it is contacted with the processed film 11 of processing spatial to handling the space.In so-called distance type plasma processing apparatus, will handle the spatial oxygen concn and be preferably set to 3000ppm, more preferably be set at 2000ppm and then more preferably be set at 1000ppm.

Also the gas that comprises the polymerizable monomer steam can be supplied to difficult adhesive resin film and make it on the surface of difficult adhesive resin film, support (condensation etc.), after this, make with above-mentioned other the different plasma bodys of polymerizable monomer gas that contain to generate and use gaseous plasmaization, and it is contacted with the part that supports above-mentioned polymerizable monomer of difficult adhesive resin film.Perhaps, also can make plasma body generate and it is contacted with difficult adhesive resin film, after this, polymerizable monomer be contacted with the above-mentioned plasma body contact part of above-mentioned difficult adhesive resin film with gaseous plasmaization.The carrier gas that plasma body generates with gas and polymerizable monomer steam both can be made of same composition (for example nitrogen), also carrier gas can be also used as plasma body generation gas.

After plasma treatment step, before the bonding step, can utilize aqueous rinsing liquid to clean difficult adhesive resin film.

Purposes outside the manufacturing that the surface treatment method of difficult adhesive resin film and surface processing device also can be applied to polaroid.

Sidepiece plug members 72 can be made of the attraction nozzle that the gas of handling space 22 is attracted.At this moment, following aspect is noted: outside environmental gas is sucked into easily to handle in the space 22 or be not attracted nozzle easily with processed film 11 period of contact at the spike of polymerizable monomer and attracts.

Also the key element of a plurality of embodiments can be made up mutually.The occluding mechanism 7 of the 3rd～the 5th embodiment or their variation for example, also can be set in second embodiment (Fig. 3).At this moment, occluding mechanism 7 is provided with corresponding to handling the processing space 22A among space 22A, the 22B at least.

Axle head plug members 80,90,92 also can only be arranged at axial one-sided.

Embodiment 1

Embodiment below is described, but the present invention is not limited to these embodiment.

In embodiment 1, the subtend discharge space is sneaked into the oxygen mixed volume of oxygen and the relation between the cementability is studied.Figure 15 represents that the summary of employed surface processing device constitutes.

The pure nitrogen gas of rare gas element supply source 31 is imported thermostatic containers 30 through rare gas element stream 33, thereby obtain the process gas that constitutes by nitrogen and acrylic acid mixed gas.The flow of nitrogen and the flow of process gas are made as 10L/min.The temperature of liquid propene acid AA in the thermostatic container 30 is made as 40 ℃.

Process gas (vinylformic acid+nitrogen) self-constant temperature container 30 is passed out to process gas supply with stream 37.Make oxygen sneak into stream 51 and converge, will sneak into the process gas of supplying with stream 37 from the oxygen of sneaking into stream 51 with process gas supply stream 37.The oxygen concn of the mixed volume of oxygen in the process gas that makes after sneaking into is in the scope of 0～2 volume % to be regulated.This process gas is blown out towards handling space 22 from nozzle 39.The temperature that blows out of process gas is 32 ℃.The electrode structure of Cement Composite Treated by Plasma portion 2 constitutes the parallel plate electrode structure that is made of opposed pair of plates electrode 24,25 up and down.At the sidepiece configuration process gas supplying-nozzle 39 of the electrode 24 of upside, be provided with in the other side of electrode 24 and attract nozzle 62, utilize to attract nozzle 62 to suck the gas of handling in the spaces 22 of having handled, and discharge from air-releasing mechanism 61.

Power supply 23 is connected with the electrode 24 of upside, and makes electrode 25 ground connection of downside.Electric power to electrode 24 inputs is 110V.

On the electrode 25 of downside, place TAC film 11.The temperature and the film temperature of electrode 25 are adjusted to 25 ℃.Therefore, the temperature head of process gas and TAC film is 7 ℃.

Make in the electrode 24,25 one relatively move back and forth (sweeping) with respect to another.Translational speed is made as 10m/min, and reciprocal time is made as once (twice sweeping).

TAC film after the surface treatment 11 and PVA film 12 is bonding.As caking agent, use solution as described below: with the aqueous solution of (A) polyvinyl alcohol 5wt% and (B) aqueous solution of Xylo-Mucine 2wt% with (A): (B)=20: 1 volume ratio carries out mixed solution.The mean polymerisation degree of polyvinyl alcohol (A) is 500.

Then, carried out the cementability evaluation.The cementability evaluation hand evaluation that to be the trier peel off TAC film and PVA film with hand.

Above operation is carried out 3 times repeatedly, for the tentative data of identical conditions (oxygen mixed volume), respectively obtains three.

The result represents in table 1." ◎ " expression cementability of this table 1 is very good." zero " expression cementability is good." △ " expression cementability is good slightly." * " expression cementability is poor.

[table 1]

Oxygen concn (vol%)

2

1

0.5

0.3

0.2

0.1

0.05

0

Tentative data 1

×

×

×

○

○

◎

◎

◎

Tentative data 2

×

×

×

△

○

◎

◎

◎

Tentative data 3

×

×

×

○

○

◎

◎

◎

Oxygen concn in the process gas after oxygen is sneaked into is 0.5vol% when above, is bonding bad.When oxygen concn was 0.3vol%, plurality was bonding good.Oxygen concn is 0.2vol% when following, is bonding good.Oxygen concn is 0.1vol% when following, and cementability is very good.Find out thus, for obtain good cementability, handle oxygen concns in the space 22 be preferably below the 3000ppm, more preferably below the 2000ppm and then more preferably below the 1000ppm.

Embodiment 2

Used the device of Fig. 3.The width of TAC film 11 is 33cm.Each thickness thickness of narrow position (interelectrode) of handling space 22A, 22B is 1mm.Each is handled space 22A, 22B length up and down and is about 10cm.Each volume of handling space 22A, 22B is about 0.3L.Shown in condition (1)～(4) of table 2,, and make first process gas (vinylformic acid steam+nitrogen) proportional to the transfer rate of the supply flow rate of handling space 22A supply and TAC film 11 in the transfer rate of the range regulation TAC of 10m/min～30m/min film 11.In addition, the flow of gas flow path 34 is 0.Therefore, the supply flow rate of above-mentioned first process gas equates with the flow in current-carrying path 35.The temperature that blows out of first process gas is made as 40 ℃, and the temperature of TAC film 11 is made as 25 ℃.Nitrogen all is made as 10L/min to handling corresponding following four conditions (1)～(4) of flow that space 22B supplies with.The electric power of supplying with to electrode 22C and interelectrode to apply corresponding each condition (1)～(4) of voltage as described below.

(1) supply capability: 918W (direct current of 270V, 3.4A is converted to interchange)

Apply voltage: Vpp=15.3kV

(2) supply capability: 891W (direct current of 270V, 3.3A is converted to interchange)

Apply voltage: Vpp=15.3kV

(3) supply capability: 864W (direct current of 270V, 3.2A is converted to interchange)

Apply voltage: Vpp=15kV

(4) supply capability: 810W (direct current of 270V, 3A is converted to interchange)

Apply voltage: Vpp=14.8kV

One end, the other end and the central part of the width of the TAC film after Cement Composite Treated by Plasma respectively downcuts two coupons respectively, the coupons of this TAC film is bonded in coupons two-sided of PVA film, makes polaroid sample with Fig. 2 (a) same cross-sectional structure.The PVA of the polymerization degree 500 uses 5% the aqueous solution as the evaluation caking agent.Corresponding to each condition (1)～(4), make a plurality of (two～three) polaroid sample.The drying conditions of caking agent is made as at 80 ℃ and kept 5 minutes.After the adhesive hardens, utilize floating roll method (JIS K6854) that bonding strength is measured.Consequently, as shown in table 2, be that the sample under which condition in condition (1)～(4) is all damaged, thereby obtained enough bonding strengths.

[table 2]

In condition (1)～(4), because the transfer rate of TAC film 11 and the supply flow rate of first process gas (vinylformic acid steam+nitrogen) are proportional, therefore, treatment capacity should be regarded as mutually the same, but confirm to have following trend: transfer rate and supply flow rate are big more, and then bonding strength becomes good more.Therefore, can think if the size of supply flow rate that makes process gas for more than to a certain degree, even if then transfer rate increase also can suppress the amount of being involved in of air, thereby can guarantee bonding strength.

[comparative example 1]

As a comparative example 1, the flow in current-carrying path 35 that will be in Fig. 3 is made as 0, makes nitrogen flow through gas flow path 33,34,37,39 successively with 10L/min and supplies to and handle space 22A and carry out plasma bodyization.Therefore, the acrylic acid content in first process gas of comparative example 1 is 0.The temperature that blows out of first process gas is made as 40 ℃, the temperature of TAC film 11 and is made as 25 ℃.In addition, as second process gas, nitrogen is supplied to processing space 22B with 10L/min.The transfer rate of TAC film is made as 2m/min.Supply capability is 1107W (direct current of 270V, 4.1A is converted to interchange).The interelectrode voltage that applies is Vpp=15.6kV.Similarly to Example 1, attempt the TAC film after the Cement Composite Treated by Plasma and PVA film are carried out bonding, but almost not bonding.

Embodiment 3

In embodiment 3, used the device 1 of Fig. 3.The width of TAC film 11, respectively to handle thickness and the volume of space 22A, 22B identical with embodiment 2.In the scope of V=5m/min～30m/min, regulate the transfer rate V of TAC film 11, and in the scope of Q=5L～33L, regulated first process gas (vinylformic acid steam+nitrogen) to the supply flow rate Q that handles space 22A.In addition, the flow of gas flow path 34 is made as 0.Therefore, the supply flow rate Q of above-mentioned first process gas equates with the flow in current-carrying path 35.The temperature that blows out of first process gas is made as 40 ℃, the temperature of TAC film 11 and is made as 25 ℃.Nitrogen is made as 10L/min to the supply flow rate of handling space 22B.

The probe of configuration oxygen concentration determination device is measured the oxygen concn of handling space 22A below processing space 22A.As the oxygen concentration determination device, use commodity oxygen analyser by name, the model LC-850KS of eastern beautiful corporate system.Figure 16 ecbatic.

When the supply flow rate (transverse axis of the graphic representation of Figure 16) of first process gas was certain and less relatively value, by increasing translational speed, the oxygen concn of handling space 22A increased.This situation is represented: translational speed is big more, and then the be involved in amount of air in handling space 22A increases more.And under the certain situation of translational speed, along with the supply flow rate increase of first process gas, the oxygen concn of handling space 22A reduces.This situation is represented: by increasing the supply flow rate of first process gas, can be first process gas with the gas displacement of handling in the 22A of space.If the supply flow rate of first process gas surpasses 20L, then irrelevant with translational speed, the oxygen concn of handling space 22A becomes below the 1000ppm, thereby becomes below the 3000ppm reliably.And if the supply flow rate of first process gas surpasses 30L, then irrelevant with translational speed, the oxygen concn of handling space 22A roughly becomes 0ppm.This situation represents that the gas of handling in the 22A of space roughly fully is replaced into first process gas.

According to above embodiment 1～3, can distinguish: by regulating the supply flow rate of process gas, be preferably 3000ppm following, more preferably 2000ppm and then 1000ppm more preferably so that handle the oxygen concn of space 22A, thereby can obtain good bonding strength.Can confirm that when translational speed was big, the supply flow rate by increasing process gas thus, can carry out high speed processing so that oxygen concn is in the above-mentioned scope gets final product.

Embodiment 4

In embodiment 4, use that (the identical in fact device of device of Fig. 7～Fig. 9) is studied the relation between the oxygen concn in the translational speed of the flow of process gas and processed film 11 and processing space 22 with the 4th embodiment.

The width of processed film 11 (along the axial size of electrode 21) is 330mm, and the thickness of film 11 is 0.1mm.

Plug members 71,72 length and electrode 21,21 length vertically vertically is 330mm.The diameter of electrode 21,21 is 310mm.The interval at the narrowest position of electrode 21,21 (handling the thickness in space 22) is 0.7mm.

Make the hold concurrently lower surface of plug members 71 of nozzle be positioned at the position of leaving 21.5mm with respect to the horizontal plane of the axis that disposes electrode 21,21 upward.Make the upper surface of plug members 72 be positioned at the position of leaving 21.5mm with respect to above-mentioned horizontal plane downwards.Therefore, the above-below direction in processing space 22 is of a size of 43mm.Handling space 22 and the sectional area orthogonal cross section of axis is 72.97mm ²The volume of handling space 22 is 0.02408L.

The thickness t of sidepiece gap 73e, 73f, 74e, 74f is made as about t=0.5mm respectively.

The thickness t 8 of gap 82e between side plate 82 and electrode 21 end faces is made as t8=0.1mm.

The length of axle head plug members about in the of 80 is that the width (along the size of electrode 21,21 orientations) of 134mm, axle head plug members 80 is 48mm.The axle head plug members 80 axial 35mm that are of a size of.

At first, the environmental gas of handling part 2 peripheries and then the gas that will handle in the space 22 are utilized nitrogen (N ₂) 80vol%, oxygen (O ₂) mixed gas of 20vol% replaces.After this, as simulation process gas, the gas of nitrogen 100% is held concurrently plug members 71 to handling space 22 supplies from the nozzle of upside.Simulation process gas (N ₂100%) supply flow rate is made as these four kinds of 10slm, 20slm, 30slm, 40slm.The supply flow rate of the per unit length axially is these four kinds of 30slm/m, 61slm/m, 91slm/m, 121slm/m.When supply flow rate was 10slm, the gas per minute of handling in the space 22 was changed 415 times.When supply flow rate was 20slm, the gas per minute of handling in the space 22 was changed 830 times.When supply flow rate was 30slm, the gas per minute of handling in the space 22 was changed 1245 times.When supply flow rate was 40slm, the gas per minute of handling in the space 22 was changed 1661 times.

Carry out following operation in the lump with above-mentioned gas supply: electrode 21,21 is rotated in a clockwise direction with transport membrane 11 in Fig. 7.Or rotating electrode 21,21 not, make film 11 motionless.The transfer rate of film 11 is made as these four kinds of 0m/min, 10m/min, 20m/min, 30m/min.

Do not carry out electrode 21 and the nozzle temperature regulation of plug members 71 of holding concurrently.

At self simulation process gas (N ₂100%) begins to have supplied with moment, the oxygen concn of handling space 22 has been carried out instrumentation through 120 seconds.As oxymeter, used the system LC-850KS of Dongli Engineering Co., Ltd (guaranteeing precision (repeatability) 0.05ppm).Following instrumentation hole is set, and this instrumentation hole connects from the axial central part of plug members 72 upper surfaces of the downside bottom surface to this plug members 72, and the probe of above-mentioned oxymeter is connected with the opening towards above-mentioned bottom surface in this instrumentation hole.Utilization sucks and imports above-mentioned oxymeter at the built-in suction pump of above-mentioned oxymeter with the gas of handling space 22 from above-mentioned instrumentation hole, measure oxygen concn.The attraction flow of above-mentioned oxymeter is made as 200ml/min.

Represent measurement result in the table 3.

[table 3]

Handle the oxygen concn (ppm) in the space

Along with transfer rate increases, the oxygen concn of handling in the space 22 increases.Can think that the oxygenated environment gas with periphery of moving according to film 11 is involved in and handles in the space 22.

When the supply gas flow was 10slm, if transfer rate is 0～10m/min, the oxygen concns of then handling in the space 22 were the ppm concentration of 2 figure places, but if transfer rate is made as 20m/min～30m/min, and then oxygen concn increases significantly and becomes the ppm concentration of 5 figure places.

When the supply gas flow is 20slm,, also oxygen concn can be maintained the ppm concentration of 2 figure places even if transfer rate is made as 20m/min～30m/min.

When the supply gas flow was 30slm～40slm, even if increase transfer rate, oxygen concn also changed hardly.

Can confirm according to above result: if the supply gas flow is made as (per unit length axially is about more than the 60slm/m) more than the 20slm, even if then the transfer rate of film 11 is about 30m/min, also can prevent being involved in of environmental gas, thereby oxygen concn can be maintained below the prescribed value (3000ppm) fully.Therefore, we can say by utilizing plug members 71,72,80 will handle space 22 and surround, oxygen concn can be maintained below the normality, meanwhile,, can shorten the treatment time by high speed transport membrane 11.And, as can be known the supply gas flow of the per unit length on axially be preferably 60slm above, more preferably more than the 90slm.Consider that transfer rate has limit this point and if then there is the possibility this point that wastes in a large amount of supply gas, axially the upper limit of the supply gas flow of the per unit length on is preferably 180slm.

Owing to can think and enter the axial length that the flow of handling the environmental gas in the space 22 does not rely on electrode 21 from axle head opening 22e, therefore, be speculated as width (above-mentioned axial size) at axial length of electrode 21 and film 11 bigger than 330mm, during for example for the 1500mm left and right sides, can further reduce the oxygen concn of handling in the space 22.

Embodiment 5

In embodiment 5,, plug members 71 or 72 positions have been regulated at above-below direction to the device of embodiment 4.Thus, the thickness t of counter-lateral quadrents gap 73e, 73f or 74e, 74f is regulated.Particularly, the plug members 72 of downside is fixed in height among the embodiment 4, with hold concurrently position more than the height of position adjustments in the embodiment 4 of plug members 71 of the nozzle of upside.Nozzle is held concurrently the height of plug members 71 with respect to the height among the embodiment 4, is made as these four kinds of 0mm, 0.1mm, 0.2mm, 0.5mm.When the height of plug members 71 was 0mm, the thickness t of sidepiece gap 73e, 73f was about t=0.5mm.When the height of plug members 71 was 0.1mm, the thickness t of sidepiece gap 73e, 73f was about t=0.6mm.When the height of plug members 71 was 0.2mm, the thickness t of sidepiece gap 73e, 73f was about t=0.7mm.When the height of plug members 71 was 0.5mm, the thickness t of sidepiece gap 73e, 73f was about t=1.0mm.

Axle head plug members 80 constitutes can be according to the altitude mixture control of plug members 71,72 and flexible up and down structure.That is, as shown in figure 17, axle head plug members 80 constitutes epimere parts 83, stage casing parts 84 and hypomere parts 85 these three-stage structures.Each parts 83,84,85 is コ shape (U-shaped, ∏ shape) respectively when overlooking, epimere parts 83 are big or small each other identical with hypomere parts 85, and stage casing parts 84 are bigger slightly than epimere parts 83 and hypomere parts 85.Epimere parts 83 can be slided up and down to embed the upper lateral part of stage casing parts 84, by being screwed into bolt 86, can be with epimere parts 83 with respect to the stationkeeping of stage casing parts 84 at above-below direction.Hypomere parts 85 can be slided up and down to embed the lower side of stage casing parts 84, by being screwed into bolt 87, can be with hypomere parts 85 with respect to the stationkeeping of stage casing parts 84 at above-below direction.

In addition, the hole 83b of epimere parts 83 is used for and the hold concurrently axial end portion banded bolt hole of plug members 71 of nozzle.The hole 85b of hypomere parts 85 is the axial end portion banded bolts hole that are used for the plug members 72 of downside.

Device size outside the thickness t of the height of plug members 71,72 and gap 73e, 73f, 74e, 74f constitutes identical with embodiment 4.

Then, similarly to Example 4, the environmental gas of handling part 2 peripheries and then the gas that will handle in the space 22 are utilized nitrogen (N ₂) 80vol%, oxygen (O ₂) mixed gas of 20vol% replaces.After this, as simulation process gas, the gas of nitrogen 100% is held concurrently plug members 71 to handling space 22 supplies from the nozzle of upside.Simulation process gas (N ₂100%) supply flow rate is made as these three kinds of 10slm, 20slm, 30slm.

Carry out following operation in the lump with above-mentioned gas supply: make electrode 21,21 in Fig. 7, be rotated in a clockwise direction transport membrane 11.The transfer rate of film 11 is made as these three kinds of 10m/min, 20m/min, 30m/min.

Do not carry out electrode 21 and the nozzle temperature regulation of plug members 71 of holding concurrently.

Certainly beginning to supply with simulation process gas (N ₂100%) rises the moment of passing through 120 seconds, the oxygen concn of handling space 22 has been carried out instrumentation.It is identical with embodiment 4 that employed oxygen concn is taken into account measuring method.

In addition, the spray nozzle clogging parts 71 of upside are fixed in height among the embodiment 4, below the position adjustments of the plug members 72 of the downside height to the embodiment 4.Plug members 72 is made as these four kinds of 0mm, 0.1mm, 0.2mm, 0.5mm with respect to the slippage of the height among the embodiment 4.When the slippage of plug members 72 was 0mm, the thickness t of sidepiece gap 74e, 74f was about t=0.5mm.When the slippage of plug members 72 was 0.1mm, the thickness t of sidepiece gap 74e, 74f was about t=0.6mm.When the slippage of plug members 72 was 0.2mm, the thickness t of sidepiece gap 74e, 74f was about t=0.7mm.When the slippage of plug members 72 was 0.5mm, the thickness t of sidepiece gap 74e, 74f was about t=1.0mm.

And, when carrying out altitude mixture control with plug members 71 that said nozzle is held concurrently similarly, instrumentation handle the oxygen concn in space 22.

The measurement result of embodiment 5 is as shown in table 4.

[table 4]

Handle the oxygen concn (ppm) in the space

In table 4, the hurdle except that descending most the hurdle is with the stationkeeping of the plug members 72 of downside and the data the when plug members 71 of upside is risen.To descend most the hurdle be with the stationkeeping of the plug members 71 of upside and the data the when plug members 72 of downside is descended.

Transfer rate is 10m/min and supply gas flow when being 10slm, and along with the position of increasing plug members 71, the oxygen concns of handling in the space 22 increase significantly.Only make the height of plug members 71 rise 0.1mm on the position of 0mm, oxygen concn has just surpassed 3000ppm.

Relative therewith, if making transfer rate is 20slm for the 10m/min identical with above-mentioned transfer rate makes the supply gas flow, then irrelevant with the height of plug members 71, the oxygen concn of handling in the space 22 does not almost change, and can maintain below the 30ppm.

This trend when transfer rate is made as 20m/min too.Promptly, when transfer rate is that 20m/min and supply gas flow are when being 10slm, handling space 22 interior oxygen concns becomes the ppm concentration of 5 figure places, but if keep transfer rate is that the constant supply gas flow that makes of 20m/min is 20slm, then irrelevant with the height of plug members 71, the oxygen concns in the processing space 22 can be maintained the roughly certain value below the 30ppm.

Transfer rate is made as 30m/min, the supply gas flow is made as 30slm, even if when the height to plug members 71 has carried out adjusting, irrelevant with the height of plug members 71, also the oxygen concns in the processing space 22 can be maintained the roughly certain value below the 30ppm.

Transfer rate is made as 30m/min, the supply gas flow is made as 30slm, even if when the height to the plug members 72 of downside has carried out adjusting, irrelevant with the height of plug members 72, also the oxygen concn of handling in the space 22 can be maintained double-digit ppm concentration.In addition, in this case, compare with identical transfer rate and identical supply gas flow the plug members 71 of upside has been carried out the situation of altitude mixture control, it is big that oxygen concn becomes a little.

Can confirm according to above result: if the supply gas flow is made as (more than the about 60slm/m of per unit length) more than the 20slm, even if then the thickness t of sidepiece gap 73e, 73f, 74e, 74f increases a little, even and if then increase the transfer rate of film 11, also oxygen concn fully can be maintained below the prescribed value (3000ppm).

Description of reference numerals

1 plasma surface processing device

10 polaroids

11 TAC films (difficult adhesive resin film)

12 PVA films (easy-adhesion resin molding)

13 caking agents

14 hard coats

2 Cement Composite Treated by Plasma portions

The 21 electrodes travel mechanism of holding concurrently

The electrode in 21L left side

The electrode of 21C central authorities

The electrode on 21R right side

22 handle space (discharge space)

22A handles space (discharge space)

22B handles space (discharge space)

22e axle head opening

23 power supplys

The plate electrode of 24 upsides

The plate electrode of 25 downsides

27 rollers (travel mechanism of difficult adhesion film) of turning back

28 film temperature regulating mechanisms

3 process gas plenum systems

The 03A first process gas plenum system

30 thermostatic containers (polymerizable monomer supply source)

31 rare gas element supply sources

32 well heaters

33 rare gas elementes are supplied with stream

34 plasma bodys generate uses gas flow path

The 34v flow control device

35 current-carrying paths

The 35v flow control device

36 polymerizable monomer steam streams

37 process gas streams

38 gas temperature regulating mechanisms

39,39A process gas nozzle

4 second process gas plenum systems

41 second process gas supply sources

43 second process gas nozzles

42 second process gass are supplied with stream

51 oxygen are sneaked into stream

61 air-releasing mechanisms

62 attract nozzle

7 occluding mechanisms

The sidepiece plug members of 71 dual-purpose process gas nozzles

72 sidepiece plug members

The sidepiece plug members of 72A dual-purpose process gas nozzle

73 concave curved surfaces

73e, 73f sidepiece gap

74 concave curved surfaces

74e, 74f sidepiece gap

75 rectification part

76 blow out stream

The rectification part of 77 downsides

78 downsides blow out stream

79 temperature regulation streams

80 axle head plug members

81 front plate

82 side plates

The 82e end play

90 axle head plug members

91 end plaies

92 axle head plug members

93 labyrinths

94 labyrinths

95 part cyclic protuberances

96 part cyclic protuberances

97 annular recess

98 annular recess

Claims (14)

1. film surface treatment method, to handling with the surface of the bonding difficult adhesive resin film of easy-adhesion resin molding, described film surface treatment method is characterised in that,

Utilize plasma body to make polymerizable monomer activation and make it and be configured near the described difficult adhesive resin film reaction of atmospheric processing spatial,

Oxygen concn in the described processing space is set at below the 3000ppm.

2. film surface treatment method as claimed in claim 1 is characterized in that,

In described processing space, produce discharge, the process gas that will contain the steam of described polymerizable monomer supplies in the described processing space, and the supply flow rate of described process gas is set at the oxygen concn that makes in the described processing space becomes supply flow rate below the 3000ppm.

3. film surface treatment method as claimed in claim 2 is characterized in that,

Described process gas does not contain oxygen in fact.

4. as each described film surface treatment method in the claim 1～3, it is characterized in that,

Oxygen concn in the described processing space is set at below the 2000ppm.

5. as each described film surface treatment method in the claim 1～4, it is characterized in that,

Oxygen concn in the described processing space is set at below the 1000ppm.

6. as each described film surface treatment method in the claim 1～5, it is characterized in that,

Described difficult adhesive resin film is relatively moved with respect to described processing space, the described speed that relatively moves is made as more than the 10m/min.

7. as each described film surface treatment method in the claim 1～6, it is characterized in that,

Described polymerizable monomer is acrylic or methacrylic acid.

8. the manufacture method of a polaroid is characterized in that,

Described difficult adhesive resin film is transparent protective membrane; described easy-adhesion resin molding is a polarizing coating; after each described film surface treatment method, that described difficult adhesive resin film is bonding via transparent caking agent and easy-adhesion resin molding in implementing claim 1～7.

9. film surface processing device, to handling with the surface of the bonding difficult adhesive resin film of easy-adhesion resin molding, this film surface processing device is characterised in that,

Have Cement Composite Treated by Plasma portion, this plasma body handling part utilizes plasma body to make the polymerizable monomer activation and it is contacted with being disposed at the difficult adhesive resin film of approaching atmospheric processing spatial,

Oxygen concn in the described processing space is below the 3000ppm.

10. film surface processing device as claimed in claim 9 is characterized in that,

Described Cement Composite Treated by Plasma portion has the pair of electrodes that produces discharge in described processing space,

Also has the process gas plenum system, the process gas that this process gas plenum system will contain the steam of described polymerizable monomer supplies in the described processing space, and the supply flow rate of the process gas of described process gas plenum system is set to the oxygen concn that makes in the described processing space becomes the following supply flow rate of 3000ppm.

11. film surface processing device as claimed in claim 10 is characterized in that,

Described pair of electrodes constitutes respectively makes axis towards axial cylindric, and along being arranged in parallel with described axial orthogonal orientation, described electrode the narrowest position and periphery thereof each other constitutes described processing space,

And, has a counter-lateral quadrents plug members, this counter-lateral quadrents plug members be arranged at across described processing space with described axially and the both sides of the orthogonal orthogonal directions of described orientation and extend axially along described, a described counter-lateral quadrents plug members across the described side face of described pair of electrodes each other, and and the side face of described each electrode between form allow described difficult adhesive resin film to described each electrode roll around the gap, at least one in the described counter-lateral quadrents plug members constitutes the process gas nozzle of the downstream end of described process gas plenum system.

12. film surface processing device as claimed in claim 11 is characterized in that,

Also have the axle head plug members, this axle head plug members is across between the end of the mutually the same side on an axially described pair of electrodes and a described counter-lateral quadrents plug members, described, and covers the end of described processing space in described described same side on axially.

13. as each described film surface processing device in the claim 9～12, it is characterized in that,

Also have the travel mechanism that described difficult adhesive resin film is relatively moved with respect to described processing space, the described speed that relatively moves of being undertaken by described travel mechanism is more than the 10m/min.

14. as each described film surface processing device in the claim 9～13, it is characterized in that,

Described polymerizable monomer is acrylic or methacrylic acid.

Images