WO2007055207A1

WO2007055207A1 - Process and equipment for charging ethylene carbonate containing material

Info

Publication number: WO2007055207A1
Application number: PCT/JP2006/322189
Authority: WO
Inventors: Hiroshi Niizuma; Tomohisa Iinuma
Original assignee: Toagosei Co., Ltd.
Priority date: 2005-11-11
Filing date: 2006-11-07
Publication date: 2007-05-18
Also published as: JPWO2007055207A1; TW200724253A; CN101304921A

Abstract

The invention aims at providing a process for stably charging a high-quality ethylene carbonate containing material by determining the number of particles contained in the material which particles are solid at atmospheric temperature in handling (e.g., at ordinary temperatures) with high reproducibility easily and accurately; and equipment for charging the material. The process comprises passing an ethylene carbonate containing material from a material storage vessel through a charging pipe and then through a pipe for measuring particles, which pipe is a branch separated from the charging pipe at a midway point and is heated, continuously in line, determining the number of particles contained in the material with a particle measuring instrument connected to the pipe for measuring particles, and charging the material into a storage vessel through an outlet of the charging pipe when the number of particles of 0.2μm or larger has reached a level below the reference value.

Description

Specification

Filling method and filling apparatus for ethylene carbonate-containing material

Technical field

TECHNICAL FIELD [0001] The present invention relates to a method for filling an ethylene carbonate-containing material into a filling container and a filling apparatus therefor, specifically, a stripping solution for removing an organic film adhering to a substrate surface such as an electronic device substrate. In particular, a method for filling an ethylene carbonate-containing material with reduced particles (fine particles) and a filling apparatus useful as a stripping solution for removing a photoresist film used for semiconductor wafers, liquid crystal substrates, etc. (Filling system)

Background art

Conventionally, a method of using a stripping solution has been known for removing a photoresist film used for microfabrication of an oxide film or a polysilicon film. As the stripping solution, inorganic materials such as caustic soda and caustic potash are used. Strong alkaline aqueous solution, mixture of sulfuric acid and hydrogen peroxide, IPA (isopropyl alcohol), organic solvent such as NMP (N-methylpyrrolidone), monoethanolamine, organic such as TMAH (tetramethylammonium hydride) Basic substances and the like have been used.

However, in the stripping method using these stripping solutions, if the fire hazard and harmfulness of the stripping solution itself cannot be ignored, the dissolved resist film accumulates with force, and the stripping ability of the resist coating is reduced. There was a problem that use was restricted.

In recent years, in order to improve the reusability of the stripping solution, a method of decomposing a resist film by oxidizing the processing solution with ozone has been proposed. In this method, ethylene carbonate (hereinafter referred to as “EC”) is used as the processing solution. And Z or propylene carbonate are used (see JP-A-2001-345304, JP-A-2003-330206, JP-A-2003-305418).

[0003] For the above-mentioned applications, it is necessary to use EC with reduced fine particles (particles). When the EC produced in the EC production facility is filled and stored in a product container, the container container and the resist are stored. When filling the tank to be supplied to the coating stripping device, or when circulating through the device when the resist coating stripping device is in operation, the par It is necessary to measure and manage the tickle. For this purpose, the method for measuring the number of particles needs to be accurate, but the conventional measuring method is based on the system shown in FIG. 3, that is, the measuring sample bottle 1, the introduction pipes 4 and 6, and the particle measuring device. 3 and a syringe sampler 1, EC storage force is sampled in advance into the measurement sample bottle 1 and liquid EC is piped by suction using the syringe sampler 5 2 Then, the number of particles was measured by introducing the solution into the particle measuring apparatus 3 and then introducing it into the particle measuring apparatus 3. According to this method, since the number of particles is measured after sampling into the measurement sample bottle 1, there is a risk that the number of particles will increase due to contamination of the inner surface of the measurement sample bottle 1 and the opening of the pipe 2. As a result, the EC with a fixed number of particles could not be filled and wasted due to the time lag when measuring particles.

[0004] On the other hand, since EC is a solid at room temperature with a melting point as high as 36 ° C, filling is performed in advance by heating the EC to a liquid state. When sampling the EC for particle measurement, sampling is performed. It sometimes solidified in the piping and could not be sampled. Also, when measuring particles, if the inside of the sampling container and the sampling container force were solidified in the pipe to the measuring device, the number of particles could not be measured.

Powerful solidification of EC can be achieved by heating the sampling pipe, sampling container, measurement pipe, etc., or adding EC to a second component with a known number of particles (for example, propylene carbonate) to make a mixture. Can be prevented. In the case of using a mixed liquid, there is no need to heat pipes, etc., but the number of particles in EC is calculated based on the measured value, the number of particles in the second component, and the amount of added force. It is necessary to measure the number of particles every time, and it is troublesome, and if the second component is neglected, the measured value fluctuates.

Disclosure of the invention

Problems to be solved by the invention

[0005] The present invention measures the number of particles in an EC-containing raw material in a solid state at a handling environment temperature, for example, room temperature, simply, accurately and with good reproducibility, and uses an EC-containing material with excellent quality for products. Method for stably filling containers such as containers, and this EC-containing material It is an object of the present invention to provide a filling device (filling system).

Means for solving the problem

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that an EC-containing raw material storage unit that is a receiving tank of a manufacturing facility such as EC, and an outlet product of the EC-containing raw material storage unit. An apparatus comprising: a filling pipe connected to the inlet of a filling container such as a container, and a particle measuring pipe branched from the filling pipe and connected to a device for measuring the number of particles When the liquid EC-containing raw material is passed through, the particle measurement pipes are heated to prevent solidification of the EC-containing raw material, and a particle measurement value with less fluctuation is obtained. It was found that the EC-containing material suggested in the measurement value could be filled into the filling container, and the present invention was completed.

[0007] That is, the present invention is described below.

1. A method of filling an EC-containing material into a filling container, in which an EC-containing raw material is passed from an EC-containing raw material storage section to a filling pipe, and then branched from the middle of the filling pipe and heated. The EC-containing raw material is continuously passed in-line to the particle measurement pipe, and the number of particles in the EC-containing raw material is measured by a particle measuring device connected to the particle measurement pipe. Filling the EC-containing material with the EC-containing material from the outlet of the filling pipe when the number of particles of 0.2 m or more reaches a reference value or less. Method.

2. Measure the number of particles in the EC-containing material while controlling the flow rate of the EC-containing material so that the fluctuation of the flow rate of the EC-containing material in the particle measurement pipe is within ± 10%. The method for filling EC-containing material according to 1.

3. After the filling of the EC-containing material is completed, the inside of the particle measurement pipe is cleaned by introducing an inert gas and Z or water into the particle measurement pipe, and then the particle measurement pipe The method for filling an EC-containing material according to 1 above, wherein the inert gas or the water is retained in a state where the EC-containing raw material is removed, and the EC-containing raw material is again passed through the particle measurement pipe when filling is resumed. .

4. EC-containing raw material storage section for storing the EC-containing raw material, a filling container for filling the EC-containing material, and the EC-containing raw material are passed from the EC-containing raw material storage section to the filling container. A liquid filling pipe, a pipe for passing through the apparatus for measuring the number of particles in the EC-containing raw material, a particle measuring pipe branched from the middle of the filling pipe and heated; A device for measuring the number of particles in the EC-containing raw material, comprising: a particle measuring device connected to an outlet of the particle measurement pipe.

The invention's effect

[0008] According to the EC-containing material filling method of the present invention, the EC-containing raw material that is in a solid state at a handling and environmental temperature, for example, room temperature, is branched from the filling pipe and heated to measure the particle. The number of particles is controlled by the in-line method introduced and measured in the particle measuring device, and then filled into the filling container from the filling pipe. A number of EC-containing materials can be easily filled without consolidation. Since the EC-containing material in the filling container has controlled physical properties, it is useful as an organic coating that adheres to the surface of a substrate such as an electronic device substrate, particularly as a stripping solution for removing the resist coating.

According to the EC-containing material filling apparatus of the present invention, the number of particles in the EC-containing raw material can be measured easily, accurately and with good reproducibility, and the EC-containing material having excellent quality can be used as a filling container such as a product container. It can be filled stably.

Further, by utilizing the present invention, an EC-containing material filling device is disposed in the resist film peeling apparatus, so that the EC-containing material being used can be actually used when the resist film peeling apparatus is in operation. Useful for liquid management.

Brief Description of Drawings

FIG. 1 is a schematic view showing an example of an EC-containing material filling apparatus according to the present invention.

FIG. 2 is a schematic view showing another example of the EC-containing material filling device of the present invention.

FIG. 3 is a schematic view showing a particle measurement system according to a conventional method.

Explanation of symbols

[0010] 1; Sample bottle for measurement

2; water bath

3; Particle counter 4; Introduction piping

5; Syringe sampler

6; Drain piping

7; Raw material containing EC

8; Clean bench

9; EC-containing raw material storage

10; liquid pump

11a; valve

lib; valve

12; Piping for filling

13a; valve

13b; valve

14; Pipe for particle measurement 15; Pressure gauge

16; valve

7; Valve for flow control 8; Particle counter 9; Flow meter

0; valve

1; Vanolev

2; Valve

3; Bypass valve

4; valve

5; Pipe for recycling EC-containing raw materials 6; Bypass line

7; valve

8; Filter part

9; Banolev 30; EC-containing material circulation pipe

31; inert gas supply device

32; water supply device

33; container for filling

BEST MODE FOR CARRYING OUT THE INVENTION

[0011] Hereinafter, the present invention will be described in detail.

The EC-containing material filling method of the present invention (hereinafter also referred to as “the filling method of the present invention”) is a method of filling an EC-containing material into a filling container, and the EC-containing raw material is stored in the EC-containing raw material storage. Then, the EC-containing raw material is continuously passed inline to the particle measurement pipe branched from the middle of the filling pipe and heated, and then passed through the filling pipe. The number of particles in the EC-containing raw material is measured by a particle measuring device connected to a pipe, and when the number of particles of 0.2 m or more reaches a reference value or less, the EC-containing material is The filling container is filled from the outlet of the filling pipe.

[0012] The material to be filled in the filling container, that is, the material stored in the EC-containing raw material storage unit is an EC-containing raw material that is in a solid state at a handling environment temperature, for example, normal temperature. Therefore, the EC-containing raw material may be EC alone or a mixture containing EC and other components and in a solid state (the content of EC is usually 50% by mass or more, preferably 60% by mass) Above, particularly preferably 70% by mass or more). The number of particles in the EC-containing raw material is preferably measured by a particle measuring device whose target is a liquid sample. The number of particles (fine particles of 0.2 m or more) in a liquid EC-containing raw material is usually 100 or less Z milliliters. The particle measuring device is preferably a light scattering type measuring device because it can measure the number of particles in a non-contact and non-destructive manner.

In the present invention, the following filling device is used for filling the EC-containing material.

The EC-containing material filling apparatus of the present invention (hereinafter referred to as “the filling apparatus of the present invention”) includes an EC-containing raw material storage section for storing EC-containing raw materials, and a filling container for filling the EC-containing materials. And passing the EC-containing raw material from the EC-containing raw material storage unit to the filling container. A liquid filling pipe, a pipe for passing through the apparatus for measuring the number of particles in the EC-containing raw material, a particle measuring pipe branched from the middle of the filling pipe and heated; A device for measuring the number of particles in the EC-containing raw material, comprising: a particle measuring device connected to an outlet of the particle measuring pipe.

[0014] A schematic diagram of the filling apparatus of the present invention is shown in FIG. That is, the filling apparatus in FIG. 1 includes an EC-containing raw material storage unit 9 for storing EC-containing raw materials, a filling container 33 for filling the EC-containing materials, the EC-containing raw materials, and the EC-containing raw materials. Filling pipe 12 for passing the liquid from the storage unit 9 to the filling container 33, and for particle measurement that branches from the middle of the filling pipe 12 and is heated and passes the EC-containing raw material to the particle measuring device 18. A pipe 14 and a particle measuring device 18 for measuring the number of particles in the EC-containing raw material into which the outlet force of the particle measuring pipe 14 is also introduced. The filling device of the present invention includes a liquid feed pump 10 for stably feeding the EC-containing raw material from the EC-containing raw material storage unit 9 in the filling pipe 12, and the particle measuring pipe 14. In addition to a part of the filter 28 located in the middle of the filling pipe 12 before branching to, a plurality of valves 11a, l ib, 13a, 13b, 16, 24¾_27, ¾ffiU nore br Noreb 23 may be provided. The piping may be heated not only for the filling pipe 12 but also for other pipes such as the filling pipe 12 from the EC-containing raw material storage unit 9 to the filling container 33. Therefore, the filling device of the present invention can be provided with a pipe heating means, for example, a means such as winding a self-controlling electric heater around the pipe.

[0015] The EC-containing raw material storage unit 9 may be a receiving tank (having an EC-containing raw material inside) of a manufacturing facility such as EC, and a container (EC inside) It may contain) A liquid feed pump 10 can be provided to feed the EC-containing raw material from the EC-containing raw material storage unit. The liquid feed pump 10 can adjust the flow rate of the EC-containing raw material, but can also be performed by a valve 11a disposed on the downstream side thereof. After the number of particles in the EC-containing raw material reaches the reference value, the filling pipe 12 is filled and filled into the filling container 33. Further, in the filling pipe 12 between the outlet of the EC-containing raw material storage unit 9 and the inlet of the particle measuring pipe 14, the diameter is large. A filter part 28 that excludes particles, foreign matters, and the like can be provided. As the filter unit 28, for example, a filtration device including a filter having a mesh opening of 0.2 / zm (polypropylene, polytetrafluoroethylene, etc.) can be used. Note that the mesh opening, the core material, and the like are appropriately selected according to the purpose. A preferable filtration device is a cartridge type in which the filter can be easily replaced and arranged.

In the present invention, before the filling container 33 is filled, it is necessary to measure the number of particles in the EC-containing raw material that is passed through the filling pipe 12. For this purpose, the filling device of the present invention includes a pipe branched from the middle of the filling pipe 12. That is, a particle measuring pipe 14 connected to the particle measuring device 18 is provided. Thereby, between the EC-containing raw material storage unit 9 and the particle measuring device 18, it is possible to measure the number of particles with good accuracy in-line without mixing of particles with external force.

In addition, the filling apparatus of the present invention can prevent contamination of the working environment and the like where the EC-containing raw material is not diffused to the outside.

[0017] One of the features of the present invention is that when the EC-containing raw material is passed, the particle measurement pipe 14 is not heated to prevent it from solidifying before reaching the particle measurement device 18. The EC-containing material is filled into the filling container 33 when the number of particles having a diameter of 0 or more, measured using the particle measuring device 18, reaches a reference value or less. It is.

The temperature of the EC-containing raw material by heating the particle measurement pipe 14 is preferably in the range of 40 ° C to 80 ° C. When the heating temperature is less than 40 ° C, the EC-containing raw material may solidify inside the particulate measurement pipe 14 and inside the particle measuring device 18. Above 80 ° C, if the particle measuring device 18 uses a semiconductor sensor, the life of the sensor will be shortened. In addition, when the cell length detected by the sensor in the particle measuring device 18 is very small, the particle measuring pipe 14 before the particle measuring apparatus 18 and the drain pipe after the particle measuring apparatus 18 are heated. It is only possible to prevent the EC-containing raw material from solidifying in the particle measuring device 18. In addition, when filling the EC containing material into the above-mentioned filling container 33, the number power of particles of 0.2 m or more in the EC containing raw material is usually 80 Z milliliters or less, preferably 50 Z milliliters or less. And do the power. If an EC-containing material with a particle power of more than 100 milliliters of Z is used as a resist coating stripping solution, the productivity of electronic device substrates and the like may be reduced.

[0018] A specific operation procedure will be described below with reference to the drawing (Fig. 1).

In the present invention, the EC-containing raw material that is the material to be filled in the filling container 33 is liquefied by heating in the EC-containing raw material storage unit 9.

Before measuring the number of particles in the EC-containing raw material, in order to make the EC-containing raw material in the pipe uniform, the pipe for filling 12 and the pipe for particle measurement up to just before the particle measuring device 18 14 Purge the EC-containing material. In this operation, with the valves lla, 13a, 13b and 23 opened and the valves 16, 20 and 27 closed, the EC-containing raw material in the EC-containing raw material storage unit 9 is transferred by the liquid feed pump 10. The liquid is passed through the filling pipe 12, and then, the liquid is passed from the filling pipe 12 toward the particle measuring device 18 and discharged from the bypass line 26. By purging the inside of the pipe up to just before the particle measuring device 18 with the EC-containing material, it is possible to remove or reduce particles that may be generated by the opening and closing operation of the nozzle.

Next, in order to measure the number of particles by the particle measuring device 18, the valve 23 is closed, the valves 16 and 24 and the flow rate control valve 17 are opened, and the EC-containing material is introduced into the particle measuring device 18. Measure the number of Since the principle of measuring the number of particles varies depending on the type of particle measuring device 18, the introduction rate of the EC-containing raw material is within the specified range. Therefore, the flow rate of the EC-containing raw material is adjusted by adjusting the opening of the valves lla, 13a, 13b and 16 and the flow control valve 17 while observing the indicated value of the pressure gauge 15 and the indicated value of the flowmeter 19. Is controlled.

[0019] Another feature of the present invention is that, as described above, a flow rate control valve 17 is installed in the particle measurement pipe 14, preferably in front of the particle measurement device 18, so It is possible to control the flow rate of the EC-containing raw material to be introduced. Specifically, the EC-containing raw material flow in the particle measurement pipe 14 is as follows. The flow rate of the EC-containing raw material is controlled so that the amount fluctuation is preferably within ± 10%. For this control, the flow control valve 17 is a control valve linked to the indicated value of the flow meter 19, or a manual-single dollar valve that can adjust the minute flow rate, and the indicated value of the flow meter 19 This can be done by manual adjustment. Note that if the flow rate of the EC-containing material fluctuates by more than ± 10% of the set flow rate, the measured value of the number of particles may change greatly, and the true value may not be obtained. The pressure is preferably less than the pressure resistance of the particle measuring device!

[0020] The measured value of the number of particles is a value when the number of parts measured by the particle measuring device 18 is continuously monitored and the numerical value is stabilized. When the number of particles with a measured value of 0.2 μχη or more reaches the reference value or less, that is, when 80 particles Ζ milliliter or less, the nozzle 13a is closed, the valve 27 is opened, and the EC-containing raw material is filled 12 Then, filling of the EC-containing material into the filling container 33 is started. When the number of particles by the particle measuring device 18 is large, the valve 16 is closed again, the valve 23 is opened, and the EC containing material is purged.

The filling container 33 may have a shape, size, etc. according to the purpose. Before filling with the EC-containing material, the filling may be started in a state filled with an inert gas such as nitrogen gas, or the initial EC-containing material from which the outlet force of the filling pipe 12 is also discharged is used. After the washing, filling may be started.

[0021] Another feature of the present invention is that in order to facilitate reuse of the filling apparatus of the present invention when filling of the EC-containing material is completed and when continuous measurement of the number of particles is interrupted and stopped. The inside of the particle measuring pipe 14 is cleaned. That is, after the EC-containing raw material stops flowing, an inert gas such as nitrogen gas and water such as Z or ultrapure water are introduced from upstream of the particle measurement pipe 14 to measure the particle. The inside of pipe 14 is cleaned. In order to perform this step, the filling device of the present invention can include an inert gas supply device 31 and a water supply device (ultra pure water supply device) 32 (see FIG. 1). When using these devices, for example, first, nitrogen gas is supplied from the inert gas supply device 31, and the EC-containing raw material remaining inside the particle measurement pipe 14 and the particle measurement device 18 is removed. Blow and then above the water supply device 32 Residue can be removed by supplying pure water or the like. When the operation is stopped by the operation, the residual EC-containing material solidified by the temperature drop of the particle measurement pipe 14 expands in volume when remelted by reheating, and the particle measurement pipe 14 and the particle Damage to the sensor of the measuring device 18 can be prevented beforehand. In addition, when passing ultrapure water or the like, it is preferable to monitor the number of particles and pass it until the level is equal to the number of particles in the ultrapure water stock solution.

It is preferable to hold the inert gas or the ultrapure water in a state in which the EC-containing raw material in the particle measurement pipe 14 is removed after the inside of the particle measurement pipe 14 is cleaned. When refilling of the material is resumed, it is preferable to again pass the liquid into the particle measurement pipe 14, that is, purge the EC-containing raw material.

[0022] The specific operation is as follows. That is, after filling the filling container 33, the operation of the liquid feed pump 10 is stopped, the valve 13a is closed, and the flow of the EC-containing raw material to the particle measuring device 18 is stopped. Thereafter, when introducing an inert gas such as high purity nitrogen gas, the valves 20 and 21 are opened, and when introducing ultrapure water or the like, the valves 20 and 22 are opened. Both inert gas and ultrapure water can be introduced simultaneously. As a normal operation, first, valves 22 and 23 are closed, valves 20, 21 and 24 are opened, and high-purity nitrogen gas is supplied to remain in the particle measurement pipe 14 and the particle measurement device 18. Eject the EC-containing material and blow the piping. The completion of the blow is determined by confirming that no liquid has come out from the outlet of the particle measuring device 18. Thereafter, the valves 21 and 23 are closed, the valves 22 and 24 are opened, and ultrapure water or the like is passed through the same line to clean the inside of the particle measuring pipe 14 and the particle measuring apparatus 18.

When the particle measurement is stopped after completion of the cleaning, it is preferable to close the valves 20, 21, 22 and 24 and fill the particle measurement pipe 14 with ultrapure water or the like until the next measurement.

[0023] In the present invention, since the amount of the EC-containing raw material used when measuring the number of particles in the EC-containing raw material may be small, the valve 29 and the EC-containing raw material as shown in FIG. It is necessary to use a device further equipped with an EC-containing material circulation pipe 30 to be sent to the storage unit 9. it can. In the circulation device of Fig. 2, in order to measure the number of particles in the EC-containing raw material, a part of the EC-containing raw material is passed through the particle measuring device 18, and the remaining EC-containing raw material is used for circulating the EC-containing raw material. It is a device that can return the filtered EC-containing raw material to the EC-containing raw material storage unit 9 through the pipe 30.

Example

Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that the present invention is not limited to these examples.

In Examples 1 and 2 below, using the filling apparatus shown in FIG. 1, after measuring particles only for EC (hereinafter referred to as “EC raw material”), the EC material is used as a filling container. Filled.

The filling device shown in Fig. 1 includes an EC-containing raw material storage unit 9 (tank installed in the EC manufacturing device) in which EC raw material heated to 60 ° C and liquefied is stored, and this EC-containing raw material storage EC feed from EC 9 at a flow rate of 5m ³ Z, feed container 33 for filling EC material, EC feed from EC containing feed stock 9 A filling pipe 12 (diameter 1 inch) for passing liquid to the filling container 33 and a filter part 28 (before opening of the filling pipe 12 made of polytetrafluoroethylene having a mesh size of 0.2 m). Filter), and a halfway force in the filling pipe 12 is branched and heated, and the particle measurement pipe 14 (diameter 1 inch) that passes the EC raw material to the particle measuring device 18 and the outlet port of the particle measurement pipe 14 A particle measuring device that measures the number of particles in the EC raw material introduced 18 (manufactured by Lion) -28 type "). Incidentally, a conversion joint is used from the particle measurement pipe 14 to the introduction port of the particle measurement device 18, and the introduction port has a diameter of mm. The filling pipe 12 is heated to about 80 ° C. by steam tracing, and the particle measuring pipe 14 is heated to about 70 ° C. by rolling a ribbon heater.

In addition, as shown in this figure: U, Nonreb 13a, 13b, 16, 20, 24 and 27, flow control valve 17, bypass valve 23, pressure gauge 15, flow meter 19, bypass Line 26, an inert gas supply device 31 (supplying high-purity nitrogen gas) used for cleaning the particle measurement pipe 14, and a water supply device 32 (supplying ultrapure water) are provided. Example 1

Before measuring the number of particles in the EC raw material and before filling the EC material filling container 33, in the pipe from the filling pipe 12 to the particle measuring pipe 14 immediately before the particle measuring device 18, The EC raw material was purged.

At first, this was closed, and Noreb 16, 20 and 27 were closed, and Noreb lla, 13a and 13b were placed side by side. After that, while the liquid feed pump 10 is operated and the inside is published, the EC raw material is passed from the EC-containing raw material storage 9 into the particle measurement pipe 14 (at a flow rate of 5 m ³ Z), and the nozzle is opened and closed. Removed the particles that were generated. Next, the valves 16 and 24 and the flow control valve 17 were opened, the bypass valve 23 was closed, and the EC raw material was passed through the particle measuring device 18. The pressure of the EC raw material to the particle measuring device 18 was 0.26 MPa, and the allowable pressure of the particle measuring device 18 was 0.3 MPa or less.

After that, the flow rate control valve 17 was adjusted so that the EC raw material flowing in the particle measurement pipe 14 would have a flow rate of 10 ml Z with a flow meter. As a result, the fluctuation force of the flow rate of the EC raw material in the particle measurement pipe 14 was within 10%. Thereafter, the number of particles detected by the particle measuring device 18 was taken in every minute, and changes in measured values were monitored. After starting continuous measurement, after about 10 to 15 minutes have passed since the start of liquid flow through the piping due to the solidification of the EC raw material, the number of particles became almost steady, and the measured values shown in Table 1 Got.

[table 1]

table 1

As shown in Table 1, since the number of particles of 0.2 m or more became 50 Zml or less, valve 13a was closed, valve 27 was opened, and EC raw material was passed through filling pipe 12. The EC material was filled into a filling container 33.

Example 2 After completion of filling in Example 1, the operation of the liquid feed pump 10 was stopped, and liquid feeding of the EC raw material was stopped. After that, the valve 13a is closed, the valves 20 and 21 are opened, and high purity nitrogen gas is vented from the inert gas supply device 31 so that the residual EC in the particle measurement pipe 14 and the particulate measurement device 18 are retained. Expelled raw materials. After confirming that the EC raw material flow was stopped, the valve 21 was closed, the valve 22 was opened, and ultrapure water was passed through the water supply device 32. After monitoring the number of particles in the waste liquid of ultrapure water that was passed through and confirming that the number of particles was equivalent to the number of particles in the ultrapure water stock solution, the EC raw material was again processed in the same procedure as described in Example 1. The liquid was passed through. Next, in the same manner as in Example 1, the valves 20, 23 and 27 were closed, the valves 13a, 13b and 16, and the flow control valve 17 were opened, the EC raw material was fed, and the particle value was measured. . As a result, the measured values shown in Table 2 were obtained. From Table 1 and Table 2, it was confirmed that there was reproducibility by repeated measurement.

[Table 2]

Table 2

Comparative Example 1

Samples of EC raw materials for batch measurement were sampled from the EC-containing raw material storage unit 9 of the filling device shown in FIG. 1, and the number of particles in the EC raw material was measured using the system shown in FIG. The number of particles was measured with a notch type measuring device (“KS-58 type” manufactured by Rion). Details are shown below.

At first, this was closed, and Noreb 16, 20 and 27 were closed, and Noreb lla, 13a and 13b were placed side by side. Thereafter, the liquid feed pump 10 was operated, and while publishing the inside, the EC raw material was passed from the EC-containing raw material storage section 9 to the particle measurement pipe 14 to remove particles generated by opening and closing the valve. Next, 5 sample bottles were sampled from the 26th bypass line under the Taline booth.

Then, the measurement sample bottle 1 containing the EC raw material is placed in the water in the clean bench. It was immersed in one bath 2 and heated to 60 ° C (see Fig. 3). Similarly, a ribbon heater was wound around the introduction pipe 4 and the drain pipe 6 to heat and keep the temperature at about 60 ° C. Thereafter, the EC raw material was introduced into the particle measuring device 3 with a syringe sampler 5 at an injection speed of 10 ml Z, and the number of particles was measured. The results are shown in Table 3. In addition, the number of particles shown in Table 4 was obtained by changing the date from the start of the EC raw material sampler to particle measurement. In both cases, although the EC product was sampled from the same product tank (EC-containing raw material storage unit 9), the reproducibility of the measured values is large and fluctuations are large, so the true value cannot be determined. I helped. Therefore, the filling of the filling container 33 could not be started.

In Tables 3 and 4, σ represents the standard deviation. CV (%) is a coefficient of variation and is calculated using the following formula.

CV (%) = (σ Ζ average number of particles) X 100

[Table 3]

Table 3

[Table 4]

Table 4

Comparative Example 2

Under a clean booth, industrial propylene carbonate (hereinafter referred to as “PC”) used as an additive component for preventing solidification was filtered through a 0.1 m filter (number of samples: 5). Thereafter, the number of particles in the filtration PC was measured in the same manner as in Comparative Example 1. Next, in the same way as in Comparative Example 1, EC for notch measurement (EC raw material) was sampled, and 5 particles were measured in the clean booth from the bypass line 26. A sample container was sampled so that the EC content was about 60% by mass.

Thereafter, in the same manner as in Comparative Example 1, the number of particles of the mixture raw material consisting of EC and PC in the measurement sample bottle 1 was measured. In addition, since there was no concern about blockage of the piping due to EC solidification, the mixture raw material, the introduction piping 4 and the drain piping 6 were not heated.

The number of particles in the EC was calculated from the measured values in the mixture raw material, the measured values in the PC, and the EC content ratio in the mixed raw material, and the results shown in Table 5 were obtained. In addition, when the EC (EC raw material) sampling and particle measurement operations were carried out at different days, the number of particles was as shown in Table 6. In all cases, the true value can be determined because the reproducibility of the measured values is large even though the same product tank (EC containing raw material storage unit 9) is also sampled EC (EC raw material). I helped.

[Table 5]

Table 5

[Table 6]

Table 6

Industrial applicability

According to the EC-containing material filling method of the present invention, an EC-containing material with reduced particles can be stably filled and stored in a container for filling, so that it can be used for electronic devices such as semiconductor wafers and liquid crystal substrates. By measuring the number of particles in the EC-containing material that contributes to improving the productivity of the substrate, it is possible to prevent the EC-containing material from being released into the atmosphere and polluting the environment.

Claims

The scope of the claims

[1] A method of filling an ethylene carbonate-containing material into a filling container,

The ethylene carbonate-containing raw material is passed through the filling pipe from the ethylene carbonate-containing raw material storage section,

Thereafter, the ethylene carbonate-containing raw material is continuously passed in-line into the particle measurement pipe branched from the middle of the filling pipe and heated, and the particle measurement apparatus connected to the partition measurement pipe By measuring the number of particles in the ethylene carbonate-containing raw material,

Next, when the number of particles of 0.2 m or more reaches a reference value or less, the ethylene carbonate-containing material is filled into the filling container from the outlet of the filling pipe. Material filling method.

[2] While controlling the flow rate of the ethylene carbonate-containing raw material so that the flow rate variation of the ethylene carbonate-containing raw material in the particle measurement pipe is within ± 10%, the particles of the ethylene carbonate-containing raw material The method for filling an ethylene carbonate-containing material according to claim 1, wherein the number is measured.

[3] After the filling of the ethylene carbonate-containing material is completed, the inside of the particle measurement pipe is washed by introducing an inert gas and Z or water into the particle measurement pipe, and then the particle measurement is performed. The above inert gas or water is retained in a state where the ethylene carbonate-containing raw material in the piping is removed, and when the filling is resumed, the ethylene carbonate-containing raw material is again passed through the particle measuring pipe. The method for filling an ethylene carbonate-containing material according to claim 1.

[4] An ethylene carbonate-containing raw material storage section for storing an ethylene carbonate-containing raw material, a filling container for filling the ethylene carbonate-containing material, and the ethylene carbonate-containing raw material, A filling pipe that passes through the filling container and a pipe that passes through an apparatus for measuring the number of particles in the ethylene carbonate-containing raw material, and is branched from the middle of the filling pipe and heated. A particle measuring pipe and an apparatus for measuring the number of particles in the ethylene carbonate-containing raw material and connected to the outlet of the particle measuring pipe An apparatus for filling ethylene carbonate-containing material.