JP5735401B2 - Polymeric monomer supply apparatus and method of operating the apparatus - Google Patents

Description

  The present invention relates to a supply device that vaporizes a polymerizable monomer in a vaporization chamber and supplies the vaporized monomer to a utilization section, and an operation method of the device, and more particularly to an operation content during a period in which the supply is temporarily stopped.

  An apparatus for vaporizing a liquid material with a vaporizer and utilizing it for forming a thin film or the like is known (see, for example, Patent Documents 1 and 2). In Patent Document 1, when the thin film forming process is stopped, the liquid raw material remaining in the supply line is removed by flowing a purge liquid through the supply line.

  In Patent Document 2, when a vaporizer is maintained, a solvent is passed through the vaporizer to dissolve and remove deposits in the vaporizer. The vaporizer is maintained at a constant temperature (for example, 250 ° C.). The solvent is introduced into the vaporizer from the supply line and vaporized. The evaporated solvent is discharged from the vent pipe. In an aspect in which a vacuum pump is connected to the supply line, the liquid material in the supply line and the vaporizer is sucked and discharged in advance by the vacuum pump. Subsequently, an inert gas is allowed to flow through the supply line. Thus, the solvent is supplied after sufficiently reducing the residual amount of the liquid raw material in the supply line and the vaporizer.

Japanese Patent Laid-Open No. 11-92939 JP 2000-192243 A

  When the liquid raw material is a polymerizable monomer, if the supply is temporarily stopped, the residual liquid of the polymerizable monomer causes a polymerization reaction in various equipment and piping such as a mass flow controller and a vaporizer on the supply line, and the supply line is blocked. There is a risk of being. Therefore, it is conceivable to allow the cleaning liquid to flow through the supply line during the temporary stop period. Thereafter, when the supply of the polymerizable monomer is resumed, if the cleaning liquid is removed by vacuum suction from the supply line, the polymerizable monomer can be flowed to the supply line in a short time after the completion of the cleaning step.

  However, when the supply of the cleaning liquid is stopped for vacuum suction, the temperature control of the vaporizer cannot be followed, and the vaporizer temperature may rise excessively. If it does so, components, such as a vaporizer, may deteriorate with heat, the polymerizable monomer after supply resumption may be overheated, a polymerization reaction may occur, and a supply line may be blocked.

In order to solve the above problems, the present invention device is a monomer supply device that executes a supply mode in which a liquid of a polymerizable monomer is vaporized and supplied to a monomer utilization unit,
A supply line extending to the monomer utilization section;
A monomer liquid supply section for delivering the polymerizable monomer to the supply line in a liquid state;
A vaporizer having a vaporization chamber provided on the supply line;
Temperature control means for adjusting the temperature of the vaporization chamber;
A cleaning liquid supply section for sending the cleaning liquid to the supply line;
A flow rate adjusting unit for adjusting the flow rate of the cleaning liquid;
A suction means for sucking fluid from a portion upstream of the vaporization chamber of the supply line;
In the supply mode, the cleaning liquid supply unit and the suction means are closed,
When the supply mode is temporarily stopped, the monomer liquid supply unit is closed and the cleaning liquid supply unit is communicated with the supply line to execute a cleaning mode in which the cleaning liquid flows through the supply line, and the flow rate adjustment The flow rate of the cleaning liquid in the latter stage of the cleaning mode is smaller than the flow rate of the cleaning liquid in the initial stage of the cleaning mode,
When the supply mode is resumed, the cleaning liquid supply unit is closed, and the supply mode is switched to the supply mode through a vacuuming mode in which the suction unit communicates with the supply line.

According to the apparatus of the present invention, when the supply mode is temporarily stopped, the remaining polymerizable monomer liquid in the supply line can be washed away with the cleaning liquid, and the supply line can be prevented from being blocked. When the supply mode is resumed, the cleaning liquid in the supply line can be sucked and removed, and the supply of the polymerizable monomer can be started in a short time. Furthermore, the vaporizer can vaporize the polymerizable monomer in the supply mode, and the cleaning liquid can be vaporized in the cleaning mode. Further, the amount of heat supplied from the temperature control means can be used for the heat of vaporization of the polymerizable monomer and the cleaning liquid.
And at the latter stage of the cleaning mode, the supply heat amount can be reduced by reducing the flow rate of the cleaning liquid, so even when the supply heat amount is not consumed as the vaporization heat of the cleaning liquid when switching from the cleaning mode to the vacuuming mode, It is possible to prevent the temperature of the vaporizing chamber from rising excessively. Therefore, it is possible to prevent the structural members such as the vaporizer from being deteriorated by heat. Moreover, even if the temperature of the vaporizing chamber rises temporarily, it can be returned to the set temperature in a short time. Therefore, it is possible to prevent the polymerizable monomer after the resumption of supply from causing a polymerization reaction in the vaporizing chamber, and it is possible to suppress or prevent the dirt from adhering to the inner wall of the vaporizing chamber or the supply line from being blocked.

Further, the method of the present invention is a supply step of sending a polymerizable monomer in a liquid state to a supply line, vaporizing the polymerizable monomer in a temperature-controlled vaporization chamber on the supply line, and supplying the vaporized monomer to a monomer utilization section. A method of operating a monomer supply device for performing
When the supply process is temporarily stopped, a cleaning process is performed in which the cleaning liquid is caused to flow in the supply line and vaporized in the vaporization chamber, and the flow rate of the cleaning liquid in the latter stage of the cleaning process is set to the initial value in the cleaning process. Smaller than the flow rate of the cleaning liquid,
When the supply process is resumed, the supply process is switched to a vacuum drawing process for sucking the fluid in the supply line.

According to the method of the present invention, when the supply process is temporarily stopped, the remaining polymerizable monomer liquid in the supply line can be washed away with the cleaning liquid, and the supply line can be prevented from being blocked. When the supply process is resumed, the cleaning liquid in the supply line can be sucked and removed, and the supply of the polymerizable monomer can be started in a short time.
In the latter stage of the cleaning process, the supply heat amount for vaporization and temperature control can be reduced by reducing the flow rate of the cleaning liquid. Therefore, when the switching from the cleaning process to the evacuation process is performed, the supply heat amount is the vaporization of the cleaning liquid. Even if it is not consumed as heat, it is possible to prevent the temperature of the vaporizing chamber from rising excessively. Therefore, it is possible to prevent the structural members such as the vaporizer from being deteriorated by heat. Moreover, even if the temperature of the vaporizing chamber rises temporarily, it can be returned to the set temperature in a short time. Therefore, it is possible to prevent the polymerizable monomer after the resumption of supply from causing a polymerization reaction in the vaporizing chamber, and it is possible to suppress or prevent the dirt from adhering to the inner wall of the vaporizing chamber or the supply line from being blocked.

  The flow rate adjusting unit maintains the flow rate of the cleaning liquid at the first flow rate at the initial stage of the cleaning mode, and sets the flow rate of the cleaning liquid to a second flow rate that is smaller than the first flow rate during the transition from the initial stage to the late stage. The flow rate of the cleaning liquid is preferably maintained at the second flow rate. In the cleaning step, the flow rate of the cleaning liquid is initially maintained at the first flow rate, and the flow rate of the cleaning liquid is set to a second flow rate smaller than the first flow rate during the transition from the initial stage to the later stage. It is preferable to keep the flow rate at the second flow rate. By maintaining the initial flow rate of the cleaning liquid in the cleaning mode (cleaning process) at the first flow rate, the temperature fluctuation of the vaporization chamber due to the change of the flowing liquid from the polymerizable monomer to the cleaning liquid is converged in a short time to reach a steady state. be able to. Furthermore, after the transition to the later stage, by keeping the cleaning liquid flow rate at the second flow rate, the temperature fluctuation of the vaporization chamber accompanying the reduction of the cleaning liquid flow rate can be converged in a short time to be in a steady state.

  It is preferable that the temperature adjusting means adjusts the temperature of the vaporizing chamber to be constant regardless of whether the supply mode is being executed or is temporarily stopped. It is preferable to adjust the temperature of the vaporizing chamber so as to be constant throughout the supplying process, the cleaning process, and the vacuuming process. Thereby, in the latter stage of the cleaning mode (cleaning process), the amount of supplied heat can be reliably reduced by reducing the flow rate of the cleaning liquid. Therefore, after that, it is possible to reliably suppress the excessive temperature increase in the vaporizing chamber during the vacuuming. Further, it is not necessary to readjust the set temperature of the vaporizing chamber when the supply mode is resumed, and the supply mode can be resumed promptly.

  Preferably, the flow rate adjusting unit is provided in the upstream portion of the supply line, and the flow rate of the polymerizable monomer is adjusted in the supply mode, and the flow rate of the cleaning liquid is adjusted in the cleaning mode. Thus, the flow rate of not only the polymerizable monomer liquid in the supply mode but also the cleaning liquid in the cleaning mode can be adjusted by one flow rate adjusting unit. In the cleaning mode, the flow rate adjusting unit can be cleaned by flowing the cleaning liquid through the flow rate adjusting unit, and the polymerizable monomer can be prevented from being polymerized inside the flow rate adjusting unit.

  Examples of the polymerizable monomer include monomers having an unsaturated bond and a predetermined functional group. The predetermined functional group is preferably selected from a hydroxyl group, a carboxyl group, an acetyl group, a glycidyl group, an epoxy group, an ester group having 1 to 10 carbon atoms, a sulfone group, and an aldehyde group. A hydrophilic group is preferred.

Examples of the monomer having an unsaturated bond and a hydroxyl group include ethylene glycol methacrylate, allyl alcohol, and hydroxyethyl methacrylate.
Examples of the monomer having an unsaturated bond and a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-methacryloylpropionic acid and the like.
Examples of the monomer having an unsaturated bond and an acetyl group include vinyl acetate.
Examples of the monomer having an unsaturated bond and a glycidyl group include glycidyl methacrylate.
Monomers having an unsaturated bond and an ester group include methyl acrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid. Examples include butyl, t-butyl methacrylate, isopropyl methacrylate, and 2-ethyl methacrylate.
Examples of the monomer having an unsaturated bond and an aldehyde group include acrylic aldehyde and crotonaldehyde.

Preferably, the polymerizable monomer is a monomer having an ethylenically unsaturated double bond and a carboxyl group. Examples of such monomers include acrylic acid (CH ₂ ═CHCOOH) and methacrylic acid (CH ₂ ═C (CH ₃ ) COOH). The polymerizable monomer is preferably acrylic acid or methacrylic acid. Thereby, the adhesiveness of a hardly-adhesive resin film can be improved reliably. More preferably, the polymerizable monomer is acrylic acid.

The cleaning liquid preferably satisfies the following conditions (a) to (d).
(A) It must be compatible with the polymerizable monomer.
(B) It is easy to vaporize or has low viscosity, and hardly remains in the vaporizer and the supply line when the vacuuming mode (evacuation step) is performed.
(C) Be safe (do not explode or burn easily)
(D) Be inexpensive.
From the above viewpoint, it is preferable to use ethanol, IPA (isopropyl alcohol), water, n-hexane, diethyl ether, polyethylene glycol or the like as the cleaning liquid.

  According to the present invention, it is possible to prevent the temperature of the vaporizing chamber from excessively rising during evacuation prior to restarting the supply of the polymerizable monomer. Therefore, it is possible to prevent the structural members such as the vaporizer from being deteriorated by heat. And it can prevent that the polymerizable monomer after supply resumption raise | generates a polymerization reaction in a vaporization chamber. Furthermore, the cleaning liquid can be saved and the cost can be reduced.

FIG. 1 is a configuration diagram of a monomer supply apparatus according to an embodiment of the present invention. FIG. 2 is a time chart explaining the operation of the monomer supply apparatus. FIG. 3A is a time chart showing a modification of the flow rate change of the cleaning liquid in the cleaning process. FIG. 3B is a time chart showing another modification of the flow rate change of the cleaning liquid in the cleaning process.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 shows a monomer supply apparatus 1 according to an embodiment of the present invention. The monomer supply device 1 includes a monomer liquid supply unit 2 and a supply line 10. The monomer liquid supply unit 2 stores a polymerizable monomer in a liquid state. A supply line 10 is drawn from the monomer liquid supply unit 2 and extends to the monomer utilization unit 3. In the supply mode described later, the monomer liquid supply unit 2 sends the polymerizable monomer to the supply line 10 in a liquid state. The polymerizable monomer is vaporized on the supply line 10 and then supplied to the monomer utilization unit 3.

  In this embodiment, acrylic acid (AA) is used as the polymerizable monomer. The polymerizable monomer is not limited to acrylic acid, and may be methacrylic acid. In addition, itaconic acid, maleic acid, 2-methacryloylpropionic acid, ethylene glycol methacrylate, allyl alcohol, hydroxyethyl methacrylate, vinyl acetate. , Glycidyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, t-butyl methacrylate , Isopropyl methacrylate, 2-ethyl methacrylate, acrylic aldehyde, crotonaldehyde, acetaldehyde, vinyl alcohol, styrene sulfonic acid, acrylamide, methacrylamide, N, N-dimethylamino Propylacrylamide, N, N-dimethylamide, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-cyclopentene, 1-cyclohexene, 1-cycloheptene, 1-cyclooctene, cyclopentadiene, dicyclopentadiene (DCPD) or the like may be used.

A mixed liquid of plural kinds of polymerizable monomers may be sent to the supply line 10. In this case, the monomer liquid supply unit 2 may store a plurality of types of polymerizable monomers in a mixed liquid state, and the monomer liquid supply unit 2 stores a plurality of types of polymerizable monomer liquids in separate tanks. A suitable amount of the polymerizable monomer liquid may be taken out from each tank and mixed.

  The monomer utilization unit 3 performs various operations such as surface treatment, preparation, production, and processing using a polymerizable monomer. The monomer utilization unit 3 in this embodiment is configured by a surface treatment apparatus. The processing target is, for example, a protective film 9 for a polarizing plate for a liquid crystal panel display. The protective film 9 is composed of a TAC film mainly composed of triacetate cellulose (TAC). The film to be treated is not limited to TAC, but polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyimide (PI), or other various resin films may be used.

The monomer utilization unit, that is, the film surface treatment apparatus 3 includes a pair of roll electrodes 3a and 3a. A continuous sheet-like processed film 9 is wound around the upper peripheral surface of each roll electrode 3a. As the roll electrodes 3a, 3a rotate, the film 9 to be processed is conveyed. An electric field is applied between the pair of electrodes 3a, 3a, and plasma near atmospheric pressure is generated in the interelectrode space 3c. A discharge gas nozzle 3d faces the interelectrode space 3c. A discharge generating gas such as nitrogen (N ₂ ) is supplied from the nozzle 3d to the interelectrode space 3c. Here, the vicinity of the atmospheric pressure refers to a range of 1.013 × 10 ^{4 to} 50.663 × 10 ⁴ Pa, and considering the ease of pressure adjustment and the simplification of the apparatus configuration, 1.333 × 10 ⁴ to 10.664 × 10 ⁴ Pa is preferable, and 9.331 × 10 ^{4 to} 10.9797 × 10 ⁴ Pa is more preferable.

  A monomer nozzle 3e is provided above the electrode 3a on the upstream side (left side in FIG. 1) in the transport direction. In parallel with the plasma generation, a polymerizable monomer is introduced from the supply line 10 into the monomer nozzle 3e. This polymerizable monomer is sprayed from the monomer nozzle 3e to the film 9 to be processed, and is condensed on the surface of the film 9 to be processed and causes a plasma polymerization reaction in the discharge space 3a. As a result, an adhesion promoting layer made of a polymerized monomer film can be formed on the surface of the film 9 to be treated.

  The surface-treated film 9 is bonded to a polarizing film made of a PVA film. An aqueous adhesive such as an aqueous PVA solution is used as the adhesive. By pre-treating the film 9 in advance, good adhesiveness can be expressed.

The configuration of the monomer supply apparatus 1 will be described in further detail.
The supply line 10 is provided with a flow rate adjusting unit 30 and a vaporizer 40. The supply line 10 includes a liquid path 11 between the monomer liquid supply unit 2 and the vaporizer 40 and a gas path 13 between the vaporizer 40 and the film processing unit 3.

The flow rate adjusting unit 30 is disposed in the liquid path 11 (portion upstream of the vaporization chamber 41 of the supply line 10). The flow rate adjusting unit 30 is configured by a liquid mass flow controller (MFC), and adjusts the mass flow rate of the liquid flowing through the liquid path 11 to be a predetermined value.
Instead of the mass flow controller, a flow rate control valve that adjusts the volume flow rate of the fluid may be used as the flow rate adjustment unit 30.

The vaporizer 40 includes a vaporization chamber 41 and a discharge unit 42. The discharge unit 42 is configured by, for example, an ejector nozzle and faces the vaporization chamber 41. The downstream end of the liquid path 11 is connected to the discharge unit 42. Further, a carrier supply unit 60 is connected to the discharge unit 42 via a carrier supply path 61. The supply unit 40 pumps nitrogen (N ₂ ) as a carrier gas to the supply path 61. The carrier supply path 61 is provided with a carrier supply path on / off valve 62 and a carrier flow rate adjusting unit 63 that are electromagnetic on / off valves. The flow rate adjusting unit 63 is configured by a mass flow controller, but may be configured by a flow rate control valve. The discharge unit 42 mists the liquid from the liquid path 11 and discharges it into the vaporization chamber 41 together with the carrier gas from the carrier supply path 61. This discharged liquid is vaporized in the vaporizing chamber 41. Although not shown, the carrier supply unit 60 is directly connected to the gas path 13 via a direct passage without going through the vaporization chamber 41. By adjusting the flow rate ratio between the carrier gas passing through the supply passage 41 and the carrier gas passing through the straight passage, the concentration of the vaporized liquid can be adjusted.
The carrier gas may be a rare gas such as argon or helium or other inert gas instead of nitrogen.

  Temperature control means 50 is incorporated in the vaporizer 40. The temperature adjustment means 50 includes a controller 51, a heater 52, and a temperature sensor 53. The heater 52 heats the vaporization chamber 41. The temperature sensor 53 detects the temperature of the vaporization chamber 41. The controller 51 includes an input / output signal processing unit, a microcomputer, a heater driving unit, and the like. Based on the temperature detected by the temperature sensor 53, the controller 51 adjusts the temperature of the vaporizing chamber 41 to be constant by turning on / off or increasing / decreasing the output of the heater 52. The set temperature of the vaporizing chamber 41 is preferably a temperature at which both the polymerizable monomer and the cleaning liquid described later can be vaporized. For example, when the polymerizable monomer is acrylic acid and the cleaning liquid is ethanol, the set temperature of the vaporizing chamber 41 is preferably 140 ° C. to 200 ° C., more preferably about 170 ° C.

Furthermore, the monomer supply apparatus 1 includes a cleaning liquid supply unit 4 and a suction unit 5. The cleaning liquid is stored in the cleaning liquid supply unit 4. Ethanol is used as the cleaning liquid. Ethanol has the advantage that it is compatible with acrylic acid (polymerizable monomer), is easily vaporized, and is safe and inexpensive.
In addition, instead of ethanol, IPA (isopropyl alcohol), water, n-hexane, diethyl ether, polyethylene glycol, or the like may be used as the cleaning liquid.

  A cleaning liquid supply path 14 extends from the cleaning liquid supply unit 4 to the supply line 10. The cleaning liquid supply path 14 is provided with a cleaning liquid supply path on / off valve 24 composed of an electromagnetic on / off valve. A merging portion 11 a is provided in the liquid path 11 upstream (on the monomer liquid supply unit 2 side) from the mass flow controller 30. The cleaning liquid supply path 14 joins the joining portion 11a. A line upstream end opening / closing valve 21 including an electromagnetic opening / closing valve is provided in the liquid path 11 upstream (on the monomer liquid supply unit 2 side) from the merging portion 11a.

  A branch portion 11 b is provided in the liquid path 11 between the mass flow controller 30 and the vaporizer 40. The suction path 15 branches from the branch portion 11b. In the suction path 15, a suction path opening / closing valve 25 including an electromagnetic opening / closing valve and a suction means 5 are sequentially provided from the branching portion 11b side. The suction means 5 is constituted by a vacuum pump. The liquid passage 11 between the branching portion 11b and the vaporizer 40 is provided with a vaporizer introduction side open / close valve 22 including an electromagnetic open / close valve.

  The gas path 13 is provided with a branch portion 13c. The purge path 16 branches from the branch portion 13c. A gas downstream end opening / closing valve 23 composed of an electromagnetic opening / closing valve is provided in the gas passage 13 downstream (on the monomer utilization unit 3 side) from the branching portion 13c. The purge path 16 is provided with a purge path on / off valve 26 comprising an electromagnetic on / off valve. The downstream ends of the suction path 15 and the purge path 16 merge to form a discharge path 17.

An operation method of the monomer supply apparatus 1 configured as described above will be described with reference to the flowchart of FIG.
[Supply mode (supply process)]
The monomer supply apparatus 1 executes a supply mode (supply process) during normal processing. In the supply mode, the on-off valves 21, 22, and 23 on the supply line 10 are opened to open the entire supply line 10, and the on-off valves 24, 25, and 26 are closed, and the cleaning liquid supply unit 4 and the suction unit 5 are connected. Close. Further, the on-off valve 62 is opened to open the carrier supply path 61. Then, the polymerizable monomer is sent from the monomer liquid supply unit 2 to the supply line 10 in a liquid state. The flow rate of the polymerizable monomer liquid is adjusted by the mass flow controller 30 so as to be a predetermined flow rate. The polymerizable monomer liquid after the flow rate adjustment is introduced into the vaporizer 40 and discharged from the discharge portion 42 into the vaporization chamber 41 while being mixed with the carrier gas from the carrier supply portion 60 to be vaporized. In order to promote vaporization, the heater 52 is operated. Part or much of the amount of heat supplied from the heater 52 is provided as heat of vaporization of the polymerizable monomer. Furthermore, the temperature control means 50 operates the output of the heater 52 to maintain the temperature in the vaporization chamber 41 constant. Thereby, the vaporization amount of the polymerizable monomer can be stabilized.

  The monomer-containing gas containing the vaporized polymerizable monomer and the carrier gas is supplied to the monomer utilization unit 3 including the film surface treatment apparatus via the gas path 13. Then, a monomer-containing gas is sprayed on the protective film 9 to form a condensed layer of a polymerizable monomer on the surface of the film 9, and further a plasma polymerization reaction of the condensed layer is caused in the discharge space 3c to form a polymerized film. To do. Thereby, the adhesiveness at the time of bonding the protective film 9 with a polarizing film can be improved.

  When some trouble occurs in the film surface treatment apparatus 3 or the polarizing plate production facility downstream thereof, or when the production is temporarily or temporarily suspended, the mode of the monomer supply apparatus 1 is changed from the supply mode to the cleaning mode. Switch to. That is, the supply mode is temporarily stopped and the cleaning mode is started. When the production of the polarizing plate is resumed, the mode of the monomer supply device 1 is switched from the cleaning mode to the supply mode through the vacuuming mode.

The operation during the suspension period of the supply mode will be described in further detail.
[Cleaning mode (cleaning process)]
In the cleaning mode (cleaning process), the on-off valves 21, 23, 25 are closed and the on-off valves 24, 22, 26 are opened. As a result, the monomer liquid supply section 2 is closed and the monomer utilization section 3 is shut off from the supply line 10, while the cleaning liquid supply section 4 is communicated with the liquid path 11 and the purge path 16 is communicated with the gas path 13. Moreover, the on-off valve 62 is maintained in an open state. Then, the cleaning liquid is delivered from the cleaning liquid supply unit 4 and introduced into the liquid path 11 via the cleaning liquid supply path 14. By introducing the cleaning liquid, the residual liquid of the polymerizable monomer in the liquid passage 11 can be pushed out to the vaporizing chamber 41 and vaporized. Alternatively, the residual liquid can be dissolved in the cleaning liquid. As a result, the liquid path 11 can be cleaned and the liquid path 11 can be prevented from being blocked. In particular, the mass flow controller 30 on the liquid path 11 can be cleaned, the residual liquid can be prevented from being polymerized in a narrow flow rate detection path in the mass flow controller 30, and the mass flow controller 30 can be prevented from being blocked.

  Further, the flow rate of the cleaning liquid is adjusted by the mass flow controller 30. Accordingly, the mass flow controller 30 adjusts the flow rate of the polymerizable monomer in the supply mode, and adjusts the flow rate of the cleaning liquid in the cleaning mode. Details of the flow rate adjustment of the cleaning liquid will be described later. After the flow rate is adjusted, the cleaning liquid is introduced into the vaporizer 40 and discharged from the discharge portion 42 into the vaporization chamber 41 while being mixed with the carrier gas from the carrier supply portion 60 to be vaporized. By the discharge flow of the cleaning liquid, the residual liquid of the polymerizable monomer in the discharge part 42 can be reliably pushed out, and the inside of the discharge part 42 can be reliably prevented from being blocked by the polymerization of the residual liquid. Further, by vaporizing the cleaning liquid, it is possible to prevent the cleaning liquid from being accumulated in the vaporizing chamber 41 in a liquid state. The heater 52 is operated to promote the vaporization of the cleaning liquid. Part or much of the amount of heat supplied from the heater 52 is provided as the heat of vaporization of the cleaning liquid. Further, the output of the heater 52 is operated by the temperature adjusting means 50, and feedback control is performed so that the temperature in the vaporizing chamber 41 is maintained constant. The set temperature of the vaporizing chamber 41 in the cleaning mode is preferably equal to the set temperature of the vaporizing chamber 41 in the supply mode. Furthermore, it is preferable that the temperature adjusting means 50 adjusts the temperature of the vaporizing chamber 41 to be a constant temperature regardless of whether the supply mode is being executed or is temporarily stopped.

  The cleaning gas containing the vaporized cleaning liquid and the carrier gas is discharged from the vaporizing chamber 41 in the order of the gas path 13, the purge path 16, and the discharge path 17. Thereby, the monomer-containing gas remaining inside the vaporizing chamber 41 and the gas passage 13 can be purged. Therefore, it is possible to prevent the polymerizable monomer vapor in the residual gas from condensing and polymerizing in the vaporizing chamber 41 or the gas passage 13, and dirt is attached to the inner wall of the vaporizing chamber 41 or the gas passage 13 is blocked. Can be prevented.

[Flow rate adjustment in cleaning mode (cleaning process)]
Details of the flow adjustment of the cleaning liquid by the mass flow controller 30 will be described.
In the initial stage of the cleaning mode (cleaning process), the flow rate of the cleaning liquid (first flow rate Q ₁ ) is set so that the amount of heat required for vaporizing the cleaning liquid is approximately the same as the amount of heat required for vaporizing the polymerizable monomer in the supply mode. It is preferable to do. Thereby, as shown in FIG. 2, when the supply mode is switched to the cleaning mode, the temperature fluctuation of the vaporization chamber 41 can be suppressed. In FIG. 2, the temperature of the vaporization chamber 41 changes to the low temperature side, but may change to the high temperature side. This temperature variation is detected by the temperature sensor 53. Based on this detected temperature, the controller 51 adjusts the output of the heater 52, so that the temperature of the vaporizing chamber 41 eventually converges to the set temperature. By keeping the cleaning liquid flow in the cleaning mode initial constant value Q _1, it may be a steady state is converged in a short time the temperature variation of the vaporization chamber 41 due to the mode switching.

As shown in FIG. 2, the mass flow controller 30 reduces the flow rate of the cleaning liquid as the cleaning mode (cleaning process) proceeds. Here, as the period until time t ₁ with the start of the cleaning mode (washing step) elapses and washed Mode Initial (washing step initial), washed mode late time t ₁ later (cleaning step late), washed Mode The flow rate of the cleaning liquid at the later stage is made smaller than the flow rate of the cleaning liquid at the initial stage of the cleaning mode. Preferably, the initial cleaning mode keeps the flow rate of the cleaning liquid to the first flow rate Q _1, the first flow rate the flow rate of the cleaning solution during the transition from the initial to the late Q ₁ is less than the second flow rate _{Q 2 (Q 2 <Q 1} ) to the late keeps the flow rate of the cleaning liquid to the second flow rate Q _2. The duration _{t 1} of the cleaning mode initial is _preferably t 1 = _10min~40min, t 1 = about 20min, more preferably. In this embodiment, the flow rate of the cleaning solution during the transition from the initial to the late from the first flow rate Q ₁ stepwise and reduced to the second flow rate Q _2, which may be gradually reduced (see FIG. 3 (b) reference). The second flow rate Q ₂ is preferably 20% to 60% (Q ₂ = Q ₁ × 0.2 to 0.6) with respect to the first flow rate Q ₁ , and 50% (Q ₂ = Q ₁ ×). More preferably, it is about 0.5).

The amount of heat required for vaporization of the cleaning liquid in the latter stage of the cleaning mode is reduced by the amount of reduction in the flow rate. Therefore, immediately after the transition to the late cleaning mode, the amount of heat supplied to the heater 52 becomes excessive, and the temperature of the vaporizing chamber 41 temporarily rises. This temperature rise is detected by the temperature sensor 53, and the controller 51 adjusts the output of the heater 52 based on the detected temperature. As a result, the temperature of the vaporizing chamber 41 decreases with the passage of time and converges to the set temperature after the above increase. After the transition to late, by keeping the washing solution flow rate at a constant value Q _2, can be a steady state is converged in a short time the temperature variation of the vaporization chamber 41 due to the fact that reducing the cleaning liquid flow. The output (supplied heat amount) of the heater 52 in the latter steady state is smaller than the output (supplied heat amount) of the heater 52 at the initial stage by the amount of decrease in the flow rate of the cleaning liquid.

Since the flow rate of not only the polymerizable monomer liquid in the supply mode (supply process) but also the cleaning liquid in the cleaning mode can be adjusted by one mass flow controller 30 (flow rate adjusting unit), the apparatus configuration can be simplified.
Moreover, compared with the case where the flow rate of the cleaning liquid is maintained at the initial flow rate, the cleaning liquid can be saved and the cost required for cleaning can be reduced.

[Evacuation mode (evacuation process)]
When resuming the supply mode (supply process), prior to that, the cleaning mode (cleaning process) is terminated and the evacuation mode (evacuation process) is executed. In the vacuuming mode, the on-off valves 21, 22, 24, and 26 are closed, and the on-off valve 25 is opened. Thus, the monomer liquid supply unit 2 and the cleaning liquid supply unit 4 are closed and the vaporizer 40 is shut off from the liquid path 11, while the suction unit 5 is communicated with the liquid path 11. Then, the suction means 5 sucks the fluid in the liquid passage 11 through the suction passage 15 and discharges it from the discharge passage 17. Accordingly, the cleaning liquid remaining in the liquid path 11 at the end of the cleaning process can be removed from the liquid path 11.

  In the evacuation mode, the supply of the cleaning liquid is stopped by closing the cleaning liquid supply unit 4, and the vaporization of the cleaning liquid in the vaporizing chamber 41 is stopped. Therefore, the amount of heat supplied from the heater 52 is not consumed as heat of vaporization. Therefore, when switching from the cleaning mode to the evacuation mode, the amount of heat supplied to the heater 52 becomes excessive, and the temperature of the vaporization chamber 41 temporarily rises. However, since the amount of heat supplied is small, the temperature increase width of the vaporization chamber 41 can be suppressed to a small value. Therefore, it is possible to prevent the constituent members of the vaporizer 40 from being thermally damaged. In addition, in the feedback control by the temperature control means 50, the time required to follow the operation amount of the heater 52 can be shortened. Therefore, at the end of the evacuation mode (evacuation process), the temperature of the vaporization chamber 41 can be converged to the set temperature.

  Further, in the evacuation mode, the on-off valves 62 and 23 are opened, the carrier gas is caused to flow in the order of the vaporization chamber 41 and the gas passage 13 and blown out from the nozzle 3e. Therefore, the carrier gas is always circulated through all modes. By flowing the carrier gas to the vaporizing chamber 41 even in the evacuation mode, it is possible to more reliably prevent an excessive temperature rise in the vaporizing chamber 41 and to reliably shorten the time required for the heater output to follow.

The set temperature of the vaporizing chamber 41 in the evacuation mode is preferably the same as the set temperature of the vaporizing chamber 41 in the supply mode and the cleaning mode. In other words, the set temperature of the vaporization chamber 41 is preferably constant throughout the supply mode (supply process), the cleaning mode (cleaning process), and the evacuation mode (evacuation process). As a result, the amount of heat supplied to the heater 52 can be reliably reduced as the flow rate of the cleaning liquid is reduced and the flow is stopped, and the excessive temperature rise of the vaporization chamber 41 can be reliably suppressed during evacuation. Furthermore, when the supply mode to be described later is restarted, it is not necessary to readjust the set temperature of the vaporizing chamber 41, and it is possible to quickly shift to the supply mode.
The duration _{t 3} of the vacuuming _mode, preferably t 3 = _3min~20min, t 3 = about 10min, more preferably.

  The two-dot chain line in FIG. 2 is vaporized by switching to the evacuation mode (evacuation process) when it is assumed that the flow rate of the cleaning liquid is maintained at the initial size throughout the entire period of the cleaning mode (cleaning process). It shows how the temperature of the chamber 41 fluctuates. In this case, since the heater 52 is switched to the evacuation mode (evacuation process) with a relatively high output, the temperature rise degree of the vaporization chamber 41 is large, and even when the evacuation mode (evacuation process) ends. The vaporization chamber 41 still tends to be overheated.

[Resumption of supply mode (supply process)]
After the evacuation mode (evacuation process), the supply mode (supply process) is resumed. Specifically, the on-off valves 21, 22, 23, 62 are opened and the on-off valves 24, 25, 26 are closed, and the polymerizable monomer is sent from the monomer liquid supply unit 2 to the supply line 10. Then, after the flow rate is adjusted in the mass flow controller 30, the polymerizable monomer is introduced into the vaporizer 40 and vaporized, and further supplied to the monomer utilization unit 3. Prior to this supply mode, the residual cleaning liquid in the liquid passage 11 is removed in advance in the vacuum mode, so that the polymerizable monomer can be supplied in a shorter time than when the vacuum mode is not performed. You can start. In addition, when the supply mode is resumed, the temperature of the vaporizing chamber 41 has converged to the set temperature, so that the polymerizable monomer is not overheated. Therefore, it is possible to prevent the polymerization reaction of the polymerizable monomer from occurring in the vaporizing chamber 41, and it is possible to prevent dirt from adhering to the inner wall of the vaporizing chamber 41 or blocking the gas passage 13.
In the case of the above-described comparative example of the two-dot chain line in FIG. 2, since the vaporization chamber 41 is in an overheated state when the supply mode (supply process) is restarted, the polymerizable monomer is polymerized in the vaporization chamber 41. There is a risk of soiling or clogging.

The present invention is not limited to the above-described embodiment, and various modifications can be employed without departing from the spirit of the present invention.
For example, as shown in FIG. 3 (a), in the cleaning mode (cleaning step), the flow rate of the cleaning liquid is decreased stepwise (discontinuously) over a plurality of times (two times in the figure), thereby The flow rate may be smaller than the initial flow rate of the cleaning liquid. As shown in FIG. 3B, in the cleaning mode (cleaning process), the flow rate of the cleaning liquid is gradually (continuously) decreased with the passage of time, so that the flow rate of the cleaning liquid in the later stage is smaller than the flow rate of the cleaning liquid in the initial stage. May be. The flow rate of the cleaning liquid in the later stage may be made smaller than the initial flow rate of the cleaning liquid by gradually decreasing the flow rate of the cleaning liquid over almost the entire period of the cleaning mode (cleaning process).

The circuit configuration of the monomer supply apparatus 1 can be changed as appropriate. For example, a flow rate adjusting unit for adjusting the flow rate of the cleaning liquid may be provided in the cleaning liquid supply path 14 or the cleaning liquid supply unit 4 separately from the flow rate adjusting unit for adjusting the flow rate of the polymerizable monomer.
Instead of the on-off valves 21 and 24, a three-way valve may be provided in the junction portion 11a. Instead of the on-off valves 22 and 25, a three-way valve may be provided at the branch portion 11b. Instead of the on-off valves 23 and 26, a three-way valve may be provided at the branch portion 13c.

The utilization unit 3 is not limited to the surface treatment of the resin film, and may be one that applies a polymerizable monomer to a substrate, cloth, or the like.
The present invention is not limited to the surface treatment of a protective film for a polarizing plate, but can be applied to a treatment for forming a polymer film of a polymerizable monomer on various resin films.

  The present invention is applicable, for example, to the manufacture of a polarizing plate for a flat panel display (FPD).

DESCRIPTION OF SYMBOLS 1 Monomer supply apparatus 2 Monomer liquid supply part 3 Film processing part (Monomer utilization part)
3a Electrode 3c Interelectrode space 3d Discharge gas nozzle 3e Monomer nozzle 4 Cleaning liquid supply part 5 Suction means 9 Film to be processed 10 Supply line 11 Liquid path (upstream part)
11a Merge section 11b Branch section 13 Gas path 13c Branch section 14 Cleaning liquid supply path 15 Suction path 16 Purge path 17 Discharge paths 21-26 On-off valve 30 Mass flow controller (flow rate control section)
40 Vaporizer 41 Vaporization Chamber 42 Discharge Unit 50 Temperature Control Unit 51 Controller 52 Heater 53 Temperature Sensor 60 Carrier Supply Unit 61 Carrier Supply Path 62 On-off Valve 63 Carrier Flow Rate Control Unit

Claims (6)

A monomer supply device that executes a supply mode in which a liquid of a polymerizable monomer is vaporized and supplied to a monomer utilization unit,
A supply line extending to the monomer utilization section;
A monomer liquid supply section for delivering the polymerizable monomer to the supply line in a liquid state;
A vaporizer having a vaporization chamber provided on the supply line;
Temperature control means for adjusting the temperature of the vaporization chamber;
A cleaning liquid supply section for sending the cleaning liquid to the supply line;
A flow rate adjusting unit for adjusting the flow rate of the cleaning liquid;
A suction means for sucking fluid from a portion upstream of the vaporization chamber of the supply line;
In the supply mode, the cleaning liquid supply unit and the suction means are closed,
When the supply mode is temporarily stopped, the monomer liquid supply unit is closed and the cleaning liquid supply unit is communicated with the supply line to execute a cleaning mode in which the cleaning liquid flows through the supply line, and the flow rate adjustment The flow rate of the cleaning liquid in the latter stage of the cleaning mode is smaller than the flow rate of the cleaning liquid in the initial stage of the cleaning mode,
When the supply mode is resumed, the monomer supply device is switched to the supply mode through a vacuuming mode in which the cleaning liquid supply unit is closed and the suction means is communicated with the supply line.   The flow rate adjusting unit maintains the flow rate of the cleaning liquid at the first flow rate at the initial stage of the cleaning mode, and sets the flow rate of the cleaning liquid to a second flow rate that is smaller than the first flow rate during the transition from the initial stage to the late stage. The monomer supply device according to claim 1, wherein the flow rate of the cleaning liquid is maintained at the second flow rate.   The flow rate adjusting unit is provided in the upstream portion of the supply line, and adjusts the flow rate of the polymerizable monomer in the supply mode, and adjusts the flow rate of the cleaning liquid in the cleaning mode. Item 3. The monomer supply apparatus according to Item 1 or 2. A monomer supply device that sends a polymerizable monomer in a liquid state to a supply line, performs a supply step of vaporizing the polymerizable monomer in a temperature-controlled vaporization chamber on the supply line and supplying the vaporized monomer to a monomer utilization unit An operating method,
When the supply process is temporarily stopped, a cleaning process is performed in which the cleaning liquid is caused to flow in the supply line and vaporized in the vaporization chamber, and the flow rate of the cleaning liquid in the latter stage of the cleaning process is set to the initial value in the cleaning process. Smaller than the flow rate of the cleaning liquid,
When the supply process is restarted, the monomer supply apparatus is switched to the supply process through a vacuuming process for sucking the fluid in the supply line.   In the cleaning step, initially, the flow rate of the cleaning liquid is maintained at the first flow rate, and the flow rate of the cleaning liquid is set to a second flow rate smaller than the first flow rate during the transition from the initial stage to the later stage. The operation method according to claim 4, wherein the second flow rate is maintained. 6. The operating method according to claim 4, wherein the temperature of the vaporizing chamber is adjusted to be constant throughout the supplying step, the cleaning step, and the vacuuming step.

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