WO2019017488A1

WO2019017488A1 - Tank, and chemical solution supply system

Info

Publication number: WO2019017488A1
Application number: PCT/JP2018/027359
Authority: WO
Inventors: 弘和山本; 宏貴伊丹; 勇野口; 忠和塚本; 昌秀加藤; 川戸　進
Original assignee: 東邦化成株式会社
Priority date: 2017-07-21
Filing date: 2018-07-20
Publication date: 2019-01-24
Also published as: KR102616116B1; CN110944920A; KR20200034761A; TWI772468B; JPWO2019017488A1; CN110944920B; JP6571304B2; TW201908208A

Abstract

The present invention provides a tank for handling various chemical solutions, wherein it is possible to prevent electrical charging of the tank contents and reduce contamination of the tank contents. This tank includes a tank outer housing, and a lining layer on the inner surface thereof. The lining layer at least partially includes a composite resin material including a fluororesin A and carbon nanotubes. The fluororesin A is selected from the group consisting of polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers, tetrafluoroethylene/hexafluoropropylene copolymers, tetrafluoroethylene/ethylene copolymers, polyvinylidene fluoride, polychlorotrifluoroethylene, chlorotrifluoroethylene/ethylene copolymers, and polyvinyl fluoride.

Description

Tank and chemical supply system

This patent application claims priority under the Paris Convention based on Japanese Patent Application No. 2017-142264 (filed on July 21, 2017) and Japanese Patent Application No. 2018-021649 (filed on February 9, 2018) The entire contents of the above application are incorporated herein by reference.
The present invention relates to a tank including a composite resin material including a fluorocarbon resin and a carbon nanotube in at least a part of a lining layer, and a chemical solution supply system using the tank.

Conventionally, in a tank used for storing various chemical solutions, the inner wall of a metal tank outer can for the purpose of preventing the corrosion of the inner wall of the tank due to the corrosiveness of the chemical solution or the contamination of the chemical solution due to the corrosion. The lining material which consists of chemical-resistant materials, such as polyvinyl chloride, rubber | gum, polyolefin resin, a fluorine resin, is bonded together.

Various studies have been made on chemical resistant materials contained in lining materials. For example, Patent Document 1 describes a fluororesin-lined tank lined with tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA). Patent Document 2 describes a lining material including a sheet base made of a polyolefin base. Patent Document 3 describes a lining sheet having a conductive tetrafluoroethylene resin layer formed of a tetrafluoroethylene resin and a conductive filler such as carbon black or graphite.

Japanese Patent Application Publication No. 2003-170994 JP, 2001-328209, A Japanese Patent Application Publication No. 06-270353

Chemical-resistant materials such as fluoroplastics, which are usually used as lining materials, have chargeability, so when friction occurs between the chemical-resistant material and the chemical solution that is the contents, static electricity is generated, and the content is There may be a problem of ignition of things. Furthermore, as described in, for example, Patent Document 3, when a conductive material such as carbon black is added to a chemical resistant material used as a lining material, a large amount of conductivity is achieved to achieve desired antistatic properties. It is necessary to add some sex material, and there is also the possibility of contamination of the tank contents. Further, the presence of the conductive material or the like on the bonding surface of the lining material and the inner wall of the tank causes a problem such as easy peeling of the lining material.

An object of the present invention is to provide a tank that handles various chemical solutions, which can prevent charging of the contents of the tank, and in which contamination of the contents of the tank is reduced. Another object of the present invention is to provide a chemical solution supply system using the tank.

The present inventors diligently studied the lining layer provided on the inner surface of the tank in order to solve the above-mentioned problems. As a result, it has been found that the above object can be achieved by providing a lining layer containing a composite resin material containing a fluorocarbon resin and a carbon nanotube in at least a part thereof, thereby completing the present invention.

That is, the present invention includes the following preferred embodiments.
[1] With tank cans,
And at least a lining layer provided on the inner surface of the tank outer can;
The lining layer comprises, at least in part, a composite resin material comprising fluorocarbon resin A and carbon nanotubes,
Fluororesin A is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) A tank selected from the group consisting of
[2] The tank according to the above [1], wherein the lining layer provided at a portion where the introduced chemical solution first contacts the inner surface of the tank outer case contains a composite resin material containing fluororesin A and carbon nanotubes.
[3] equipped with a chemical pipe that leads to the inside and the outside of the tank,
The chemical liquid pipe is a molded body of a composite resin material having a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the pipe and / or containing fluorocarbon resin B and carbon nanotubes ,
Fluororesin B is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) The tank according to the above [1] or [2], which is selected from the group consisting of
[4] equipped with a chemical pipe that connects the inside and the outside of the tank
The chemical liquid pipe includes a chemical liquid feed pipe for putting the chemical liquid into the tank,
The chemical liquid feed pipe has a nozzle at its end (or tip),
The nozzle is a molded body of a composite resin material having a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the nozzle and / or containing fluorocarbon resin B and carbon nanotubes,
Fluororesin B is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) The tank according to any one of the above [1] to [3], which is selected from the group consisting of
[5] The tank according to [4], wherein the nozzle is selected from the group consisting of a spray nozzle, a rotating nozzle, a straight forward nozzle, and a shower nozzle.
[6] It further has a hollow spherical shaped body at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes, wherein fluorocarbon resin C is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) Any one of the above [1] to [5] selected from the group consisting of polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) The tank described in.
[7] It further has a rod-like molded body at least partially containing a composite resin material containing fluorocarbon resin C and carbon nanotubes, and fluorocarbon resin C is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE ), Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF) Selected from the group consisting of polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF), any of the above [1] to [6] Description tank.
[8] It further has a stirring rod which at least partially contains a composite resin material containing fluorocarbon resin C and carbon nanotubes, wherein fluorocarbon resin C is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), poly It is selected from the group consisting of chlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF), according to any one of the above [1] to [7] tank.
[9] The tank according to the above [8], wherein the stirring rod has a propeller at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes.
[10] Any one of the above-mentioned [1] to [9], wherein the chemical solution contains at least one selected from organic solvents, flammable liquids, acidic liquids, basic liquids, neutral liquids, aqueous solutions and conductive liquids. The tank described in.
[11] The tank according to any one of the above [1] to [9], wherein the chemical solution contains an organic solvent.
[12] The tank according to any one of the above [1] to [9], wherein the chemical solution contains at least one selected from an acidic liquid, a basic liquid, and a conductive liquid.
[13] The tank according to any one of the above [1] to [12], wherein the fluororesin A is a modified polytetrafluoroethylene.
[14] Modified polytetrafluoroethylene is represented by formula (I):

And a tetrafluoroethylene unit represented by the formula (II):

[Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group]
And the amount of perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene The tank according to any one of the above [1] to [13].
[15] The composite resin material is a compression-molded product of composite resin particles having an average particle diameter of 5 μm to 500 μm, which contains any of fluororesins A to C and a carbon nanotube, according to the above [1] to [14] The tank described in either.
[16] The tank according to any one of the above [1] to [15], which is a chemical solution supply tank, a chemical solution storage tank, and / or a chemical solution transport tank.
[17] A chemical solution supply system including supplying a chemical solution using the tank according to any one of the above [1] to [16].
[18] A molded article for use in a tank according to any one of the above [1] to [16], which contains any of the fluororesins A to C and a carbon nanotube.
[19]
The molded article according to the above-mentioned [18], which is selected from a lining sheet, a drug solution tube, a hollow molded body, a rod-shaped molded body, a rod-shaped molded body holder, a stirring rod, a stirring blade, and a stirring rod adapter.
[20] A compression-molded article of composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less, which contains any of fluororesins A to C and a carbon nanotube.
[21] The compression-molded article according to the above [20], which is selected from a lining sheet, a chemical solution tube, a hollow shaped body, a rod-shaped compact, a rod-shaped compact holder, a stirring rod, a stirring blade, and a stirring rod adapter .

According to the present invention, it is a tank for handling various chemical solutions, which can prevent charging of the contents of the tank, and a tank in which the contamination of the tank contents is reduced, and a chemical solution supply using the tank A system is provided.

It is a longitudinal cross-sectional view of the tank of 1st Embodiment A of this invention. It is a longitudinal cross-sectional view of the tank of 1st Embodiment B of this invention. It is a longitudinal cross-sectional view of the tank of 2nd Embodiment of this invention. It is the schematic of the chemical | medical solution supply system of 3rd Embodiment of this invention. It is a figure which shows the measurement sample for measuring the welding strength of composite resin material. It is a figure for demonstrating the measuring method of the welding strength of a composite resin material.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described herein, and various modifications can be made without departing from the spirit of the present invention.

The tank of the present invention has at least an outer tank can and a lining layer provided on the inner surface of the outer tank can.

<Can of tank outside>
The material of the tank outer can is not particularly limited as long as it is a material having good corrosion resistance, heat resistance and mechanical strength, but is usually metal, and examples thereof include stainless steel, iron, carbon steel, titanium and the like. The shape, size, thickness and the like of the tank outer can are not particularly limited, and may be appropriately selected according to the application of the tank of the present invention.

<Lining layer>
A lining layer is provided on the inner surface of the tank outer can. The resin contained in the lining layer may, for example, be a fluorine resin, a vinyl chloride resin or a polyolefin resin. From the viewpoint of chemical resistance and heat resistance, the lining layer preferably contains a fluorine resin. As the fluorine resin, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), polyvinyl fluoride ( PVF).

The thickness of the lining layer is preferably 1.3 to 8 mm, more preferably 1.8 to 4 mm, still more preferably 2 to 4 mm, from the viewpoint of easily suppressing metal elution. The thickness of the lining layer is measured using a micrometer. In a preferred embodiment of the present invention, the lining layer is a laminate of glass cloth and a resin sheet, in which case the thickness of the glass cloth is preferably 0.3 to 3 mm, more preferably 0.3 to 1 mm, still more preferably The thickness is 0.5 to 1 mm, and the thickness of the resin sheet is preferably 1 to 5 mm, more preferably 1.5 to 3 mm.

In the tank of the present invention, the lining layer contains, at least in part, a composite resin material containing fluorocarbon resin A and carbon nanotubes. When the lining layer contains at least a part of the composite resin material, at least a part of the lining layer provided on the inner surface of the tank outer can may be made of the composite resin material, or the entire lining layer is a composite resin material May be composed of Further, the composite resin material may be contained in a part of the lining layer provided on the inner surface of the tank outer can, and the composite resin material is contained in the entire lining layer provided on the inner surface of the tank outer can. It is also good. From the viewpoint of efficiently imparting antistatic properties and reducing the manufacturing cost of the tank, part of the lining layer provided on the inner surface of the tank outer can is made of a composite resin material, or It is preferable that a part contains a composite resin material.

When the chemical solution is introduced into the tank of the present invention, friction occurs in a portion where the introduced chemical solution initially contacts the inner surface of the outer tank can, so that static electricity is generated and the chemical solution is likely to be charged. Therefore, from the viewpoint of efficiently preventing charging of the chemical solution, the lining layer provided on the portion where the introduced chemical solution first contacts the inner surface of the outer tank can is a composite resin material including fluororesin A and carbon nanotubes. It is preferable to contain, and it is more preferable that this lining layer is comprised with the composite resin material containing the fluororesin A and a carbon nanotube. From the same point of view, a composite resin material including a fluororesin A and a carbon nanotube, wherein the lining layer provided at the bottom of the inner surface of the outer tank can is likely to generate static electricity due to friction with the supplied chemical solution. It is preferable that the lining layer is made of a composite resin material containing fluorocarbon resin A and carbon nanotubes.

<Composite resin material>
In the tank of the present invention, the lining layer contains, at least in part, a composite resin material containing fluorocarbon resin A and carbon nanotubes. The composite resin material containing fluorocarbon resin A and carbon nanotubes is a molded article of composite resin particles in which fluorocarbon resin A and carbon nanotubes are composited. The composite resin particle is a material in which particles of fluorocarbon resin A and carbon nanotubes are complexed, and carbon nanotubes exist on at least the surface and / or surface layer of the particles of fluorocarbon resin A. For example, at least a part of carbon nanotubes is supported or buried on the particle surface of fluorocarbon resin A. The carbon nanotubes may be attached to and supported on the particle surface of the fluorocarbon resin A, or a part may be buried and supported, and the carbon nanotubes may be completely buried in the surface layer of the particles of the fluorocarbon resin It is also good. In a composite resin material which is a molded product of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, and the composite resin particles are integrated to form a composite resin material. It may be done.

The average particle diameter of the composite resin particles is preferably 500 μm or less, more preferably 300 μm or less, still more preferably 200 μm or less, particularly preferably 100 μm or less, very preferably 50 μm or less, most preferably 30 μm or less. When the average particle size is less than the above upper limit, carbon nanotubes are easily dispersed uniformly in the lining layer, and in particular, the volume resistivity of the lining layer is sufficiently reduced even when the thickness of the lining layer is thin. Can. The lower limit of the average particle size of the composite resin material is not particularly limited, but is usually 5 μm or more. By producing the composite resin material that constitutes at least a part of the lining layer from the composite resin particles having an average particle diameter in the above range, the volume resistivity of the lining layer can be efficiently reduced. In the present invention, the average particle size of the composite resin particles giving the composite resin material contained in the lining layer may be the average particle size of the composite resin particles used for producing the composite resin material, and the average particle size is The median diameter (D ₅₀ ) which means the particle diameter at 50% of the integrated value in the particle size distribution determined by the laser diffraction / scattering method, and is measured using a laser diffraction scattering type particle size distribution device. In the tank of the present invention, the lining layer and the like preferably contain a composite resin material which is a molded body of the composite resin particles having the above average particle diameter, and the composite resin material in the lining layer and the like has the above-mentioned preferable range Composite resin particles having a particle diameter of 1 may be used, or the composite resin particles may not be integrated to form a composite resin material and not maintain the particle shape.

In the tank of the present invention, the lining layer contains at least a part of the composite resin material in which the fluororesin A and the carbon nanotube are complexed, thereby effectively reducing the volume resistivity of the lining layer and charging the lining layer. Prevention and / or conductivity can be imparted. For this reason, it is possible to prevent the content from being charged, and to prevent, for example, the ignition of a chemical solution such as an organic solvent. Further, by using the composite resin material, the volume resistivity can be effectively reduced by a small amount of carbon nanotubes, and therefore, the conductive material contained in the lining layer is mixed with the contents, thereby making the tank such as a chemical solution Contamination of the contents is suppressed and the cleanliness is excellent.

The amount of the fluororesin A contained in the composite resin material is preferably 98.0% by mass or more, more preferably 99.0% by mass or more, still more preferably 99.8% by mass or more based on the total amount of the composite resin material It is. When the amount of the fluororesin A is equal to or more than the above lower limit, mechanical properties and moldability of the composite resin material can be easily improved. The upper limit of the amount of the fluororesin A is not particularly limited, but is about 99.99% by mass or less. The amount of fluorocarbon resin A contained in the composite resin material is measured by carbon component analysis.

The amount of carbon nanotubes contained in the composite resin material is preferably 0.01 to 2.0% by mass, more preferably 0.02 to 0.5% by mass, still more preferably 0 based on the total amount of the composite resin material. It is .025 to 0.2% by mass. It is preferable for the amount of carbon nanotubes to be not less than the above lower limit, since it is easy to lower the volume resistivity in order to enhance the antistatic property or the conductivity. It is preferable for the amount of carbon nanotubes to be equal to or less than the above upper limit because the volume resistivity is easily reduced efficiently. The amount of carbon nanotubes contained in the composite resin material is measured by carbon component analysis.

The composite resin material is a molded article of composite resin particles, and the specific surface area of the composite resin particles is preferably 0.5 to 9.0 m ² / g, more preferably 0.8, as measured in accordance with JIS Z8830. It is -4.0 m ² / g, still more preferably 1.0 to 3.0 m ² / g. It is preferable from the viewpoint of easily improving the adhesion between the fluororesin A and the carbon nanotube that the specific surface area is the above lower limit or more, and it is preferable from the viewpoint of easiness of producing the composite resin material that it is the above upper limit. By manufacturing the composite resin material which comprises at least one part of a lining layer from the composite resin particle which has the specific surface area of the said range, it is easy to reduce the volume resistivity of a lining layer efficiently. In the present invention, the specific surface area of the composite resin particles giving the composite resin material contained in the lining layer may be the average particle diameter of the composite resin particles used for producing the composite resin material, and the average particle diameter is specifically Specifically, the specific surface area / pore distribution measuring apparatus (for example, BELSORP-miniII manufactured by Nippon Bell), which is a fixed capacity gas adsorption method, is used to measure by a BET method, which is a general measuring method of specific surface area. In the tank of the present invention, the lining layer and the like preferably contain a composite resin material which is a molded body of the composite resin particles having the above average particle diameter, and the composite resin material in the lining layer and the like has the above-mentioned preferable range Composite resin particles having a particle diameter of 1 may be used, or the composite resin particles may not be integrated to form a composite resin material and not maintain the particle shape.

The volume resistivity of the composite resin material is preferably 1.0 × 10 ⁸ Ω · cm or less, more preferably 1.0 × 10 ⁷ Ω · cm or less, as measured in accordance with JIS K 6911 from the viewpoint of antistatic properties. Still more preferably, it is 1.0 × 10 ⁶ Ω · cm or less. Favorable antistatic property is acquired as a volume resistivity is below the said upper limit. The lower limit value of the volume resistivity of the composite resin material is not particularly limited, and may be 0 or more, but is usually 10 Ω · cm or more. The volume resistivity of the composite resin material is measured by a resistivity meter (for example, "Lorrester" or "Hyrester" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using a molding material or a cut test piece according to JIS K6911. For example, it is preferable that the composite resin material exhibits the above-mentioned volume resistivity when measured using a test piece of φ110 × 10 mm produced by compression molding (compression molding).
When the composite resin material is contained in the lining layer, it is preferable that the lining layer of the portion containing the composite resin material has the above-mentioned antistatic property. In addition, the said volume resistivity is similarly applied about the composite resin material containing the fluororesin B or the fluororesin C mentioned later.

Here, assuming that the volume resistivity of the composite resin material is X Ω · cm, and the amount of carbon nanotubes contained in the composite resin material based on the total amount of the composite resin material is Y mass%, X and Y have the following formula (1) :
X / Y ^-14 4 4 x 10 ^-12 (1)
It is preferable to satisfy When the above relationship is satisfied, the volume resistivity of the composite resin material can be efficiently reduced. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, it is easy to enhance the cleanness of the lining layer containing the composite resin material. The value (X / Y ^-14 ) calculated from the above formula (1) is more preferably 10 ^-12 or less, and still more preferably 10 from the viewpoint of easily reducing the volume resistivity of the composite resin material. ^-13 or less. Although the lower limit value of the value (X / Y ^-14 ) calculated from the above formula (1) is not particularly limited, it is usually 10 ^-18 or more, preferably 10 ^-16 or more. The above relationship can be achieved by producing a molded body by a production method to be described later, or producing a composite resin material using composite resin particles preferable for effectively reducing the volume resistivity. The method for measuring the volume resistivity is as described above, and the amount of carbon nanotubes contained in the composite resin material is measured by a carbon component analysis method.

The tank of the present invention can achieve the desired antistatic properties with a small amount of carbon nanotubes, though the reason is not clear by using the lining layer containing the above-mentioned composite resin material. Therefore, the composite resin material of the present invention is excellent in cleanness. In addition, even when, for example, a molded body produced from the composite resin material of the present invention is used as part of a lining layer for welding, the amount of conductive material present on the welding surface is small, so the adhesion is lowered. It can be avoided. Furthermore, according to the composite resin material of the present invention, even in the case of having the volume resistivity in the above-mentioned preferable range, it is easy to maintain the mechanical strength which the resin originally has.

(Fluororesin A)
The fluororesin A contained in the composite resin material is, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / tetrafluoroethylene / Hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE) And polyvinyl fluoride (PVF).
The fluororesin A contained in the composite resin material is selected from the group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) Is preferred. The fluorine resin A is more preferably selected from the group consisting of polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE), from the viewpoint of easily enhancing the conductivity, and further, the conductivity is efficiently selected. In view of easiness of enhancing the properties and flexibility and weldability, modified polytetrafluoroethylene (modified PTFE) is more preferable.

Polytetrafluoroethylene (PTFE) is a homopolymer of tetrafluoroethylene.

Modified polytetrafluoroethylene (modified PTFE) is a compound of formula (I) derived from tetrafluoroethylene:

In addition to the tetrafluoroethylene units represented by

[Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group]
And the amount of the perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene Some modified polytetrafluoroethylenes can be mentioned.

Examples of X in the formula (II) include a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms. Examples of the perfluoroalkyl group having 1 to 6 carbon atoms include perfluoromethyl group, perfluoroethyl group, perfluorobutyl group, perfluoropropyl group, perfluorobutyl group and the like. Examples of the perfluoroalkoxyalkyl group having 4 to 9 carbon atoms include perfluoro 2-methoxypropyl group and perfluoro 2-propoxypropyl group. From the viewpoint of easily enhancing the thermal stability of the modified PTFE, X is preferably a perfluoropropyl group, a perfluoroethyl group, or a perfluoromethyl group, more preferably a perfluoropropyl group. The modified PTFE may have one type of perfluorovinylether unit represented by the formula (II) or may have two or more perfluorovinylether units represented by the formula (II) Good.

The amount of the perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is less than 1 mol%, preferably 0.001 mol% or more, based on the amount of all structural units contained in the modified PTFE It is less than 1 mol%. When the amount of the perfluorovinyl ether unit represented by the formula (II) is smaller than the above upper limit, physical properties close to those of the PTFE resin tend to be obtained. In addition, when the amount of the perfluorovinyl ether unit represented by the formula (II) is equal to or more than the above lower limit, the improvement of the flexibility, the weldability and the compression creepability is more excellent than the PTFE. The amount of the perfluorovinyl ether unit is measured, for example, by performing infrared spectroscopy in the range of 1040 to 890 cm ⁻¹ characteristic absorption. The amount of perfluorovinyl ether unit represented by the formula (II) contained in the modified PTFE is 0.01 to 1% by mass, preferably 0.03 to 0.2% by mass, based on the total mass of the modified PTFE is there.

The melting point of the modified PTFE is preferably 300 to 380 ° C., more preferably 320 to 380 ° C., and still more preferably 320 to 350 ° C. When the melting point is the above lower limit or more, the formability is preferably improved, and the melting point is preferably the above upper limit or the like because the optimum mechanical properties of the resin can be easily obtained. The melting point of the modified PTFE is a value determined as the temperature of the heat of fusion peak which can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D 4591.

The heat of crystallization of the modified PTFE is preferably 18.0 to 25.0 J / g, more preferably 18.0 to 23.5 J / g. The heat of crystallization is measured by a differential scanning calorimeter (for example, "DSC-50" manufactured by Shimadzu Corporation). Specifically, the temperature is raised to 250 ° C. at a rate of 50 ° C./min, and temporarily held, and then the crystal is melted by raising the temperature to 380 ° C. at a rate of 10 ° C./min. After that, the peak of the crystallization point measured when the temperature is lowered at a rate of 10 ° C./min is measured in terms of heat.

The tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) is a compound of formula (I) derived from tetrafluoroethylene:

In addition to the tetrafluoroethylene units represented by

[Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group]
And a compound having an amount of perfluorovinylether unit represented by the formula (II) is more than 1% by mass based on the total mass of PFA.

Examples of X in the formula (II) include the groups described above for the modified PTFE, and the same applies to the preferred descriptions. PFA may have one type of perfluorovinylether unit represented by formula (II), or may have two or more perfluorovinylether units represented by formula (II) .

The amount of the perfluorovinyl ether unit represented by the formula (II) contained in PFA is 1 mol% or more, preferably 1 to 3 mol%, based on the amount of all the structural units contained in PFA. When the amount of the perfluorovinyl ether unit represented by the formula (II) is within the above range, the moldability of the molded body obtained from the composite resin material can be easily improved. The amount of the perfluorovinyl ether unit is measured, for example, by performing infrared spectroscopy in the range of 1040 to 890 cm ⁻¹ characteristic absorption.

In particular, when the fluororesin is a modified PTFE, its melting point is preferably 300 to 380 ° C., more preferably 320 to 380 ° C., and still more preferably 320 to 350 ° C. When the melting point is the above lower limit or more, the formability is preferably improved, and the melting point is preferably the above upper limit or the like because the optimum mechanical properties of the resin can be easily obtained. The melting point of the modified PTFE is a value determined as the temperature of the heat of fusion peak which can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D 4591.

In particular, when the fluorocarbon resin is modified PTFE, the heat of crystallization is preferably 18.0 to 25.0 J / g, more preferably 18.0 to 23.5 J / g. The heat of crystallization is measured by a differential scanning calorimeter (for example, "DSC-50" manufactured by Shimadzu Corporation). Specifically, the temperature is raised to 250 ° C. at a rate of 50 ° C./min, and temporarily held, and then the crystal is melted by raising the temperature to 380 ° C. at a rate of 10 ° C./min. After that, the peak of the crystallization point measured when the temperature is lowered at a rate of 10 ° C./min is measured in terms of heat.

(carbon nanotube)
A carbon nanotube (hereinafter also referred to as “CNT”) contained in the composite resin material has a structure in which one or a plurality of graphene sheets composed of six-membered rings of carbon atoms are cylindrically wound. The CNT is a single-walled CNT (single-walled carbon nanotube) in which one graphene sheet is concentrically wound, or a multilayer CNT (multi-walled carbon nanotube) in which two or more graphene sheets are concentrically wound. It is. The above carbon nanomaterials may be used alone or in combination. It is more preferable that the carbon nanotube is a multi-walled carbon nanotube from the viewpoint of being easily complexed with the modified PTFE particles and easily lowering the volume resistivity.

(Method of manufacturing composite resin material)
The manufacturing method of the composite resin material contained in a lining layer is demonstrated below. The fluorocarbon resin A may be a composite resin material containing fluorocarbon resin B and carbon nanotubes which may be contained in a chemical liquid pipe or the like, and a fluorocarbon resin C which may be contained in a hollow spherical molded body etc. By substituting resin B or fluorocarbon resin C, the following statements apply analogously.

The composite resin material contained in the lining layer is a material in which fluorocarbon resin A and carbon nanotubes are composited. The method for producing the composite resin material is not particularly limited as long as a material having a physical property as described above and in which a fluorocarbon resin and a carbon nanotube are composited is obtained. Preferably, the composite resin material contained in the lining layer is manufactured from composite resin particles in which fluorocarbon resin A and carbon nanotubes are composited. Here, the method for producing the composite resin particles is not particularly limited as long as a composite resin material in which carbon nanotubes exist on at least the surface and / or surface layer of the fluorocarbon resin A, fluorocarbon resin B or fluorocarbon resin C is obtained. For example, carbon dioxide in the subcritical or supercritical state is used as described in JP-A 2014-34591, or ketone solvent is used as described in JP-A 2015-30821. Composite resin particles can be produced by combining particles of fluorocarbon resin A, fluorocarbon resin B or fluorocarbon resin C with carbon nanotubes.

The method for producing composite resin particles, in which particles of fluororesin A and carbon nanotubes are complexed using carbon dioxide in a subcritical or supercritical state, will be specifically described below. In addition, the said method is similarly applied to the manufacturing method of the composite resin particle in the case of using the fluororesin B or the fluororesin C.

First, in the first step, carbon nanotubes are dispersed in a solvent to prepare a carbon nanotube dispersion. As the solvent, water, alcohol solvents (ethanol, n-butyl alcohol, isopropyl alcohol, ethylene glycol etc.), ester solvents (ethyl acetate etc.), ether solvents (diethyl ether, dimethyl ether etc.), ketone solvents (methyl ethyl ketone) , Acetone, diethyl ketone, methyl propyl ketone, cyclohexanone etc., aliphatic hydrocarbon solvents (hexane, heptane etc), aromatic hydrocarbon solvents (toluene, benzene etc), chlorinated hydrocarbon solvents (dichloromethane, chloroform) , Chlorobenzene, etc.). One type of solvent may be used, or two or more types of solvents may be used in combination. From the viewpoint of facilitating complexing of the fluororesin A and the carbon nanotube, it is preferable to use a solvent that easily swells the particle surface of the fluororesin A, and specifically, it is preferable to use a ketone-based solvent.

The amount of the solvent contained in the carbon nanotube dispersion is preferably 20,000 to 1, relative to 100 parts by mass of the carbon nanotubes contained in the carbon nanotube dispersion, from the viewpoint of facilitating single dispersion of the carbon nanotubes in the solvent. 000, 000 parts by weight, more preferably 30,000 to 300,000 parts by weight, even more preferably 50,000 to 200,000 parts by weight.

The carbon nanotubes used for producing the composite resin particles preferably have an average length of 50 to 600 μm, more preferably 50 to 300 μm, and still more preferably 100 to 200 μm. The average length of the carbon nanotubes is measured by a scanning electron microscope (SEM, FE-SEM) or a transmission electron microscope (TEM).

Carbon nanotubes can be produced by conventional production methods. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, vapor phase growth method such as CVD method, gas phase flow method, carbon monoxide is reacted with iron catalyst at high pressure and high pressure to be a gas phase Such as the HiPco method to grow by Commercially available carbon nanotubes such as "NC7000" from Nanocyl may be used.

When dispersing carbon nanotubes in a solvent, a dispersant may be used for the purpose of enhancing the dispersibility of carbon nanotubes. Examples of the dispersant include acrylic dispersants, synthetic polymers such as polyvinyl pyrrolidone and polyaniline sulfonic acid, DNA, peptides, organic amine compounds and the like. One dispersant may be used, or two or more dispersants may be used in combination. From the viewpoint of easily reducing the amount of the dispersant remaining in the finally obtained molded article, the dispersant preferably has a boiling point at a temperature lower than the molding temperature of the composite resin particles preferred for the present invention. When a dispersant is used, the amount of the dispersant contained in the carbon nanotube dispersion may be appropriately selected according to the type and the amount of the carbon nanotube, the solvent and the dispersant. For example, the amount of dispersant used is preferably 100 to 6,000 parts by mass, more preferably 200 to 3,000 parts by mass, and still more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of carbon nanotubes. It is.

When water is used as a solvent in the first step, the carbon nanotube dispersion is mixed with an alcohol solvent or the like before the second step described later. This is because the affinity between the fluororesin A added in the subsequent second step and water is low, and it is difficult to disperse the particles of the fluororesin A in the carbon nanotube dispersion using water as a solvent. Therefore, by mixing an alcohol solvent, the affinity between the particles of the fluorocarbon resin A and the carbon nanotube dispersion liquid can be enhanced.

Next, in the second step, particles of fluorocarbon resin A are added to the carbon nanotube dispersion and stirred to prepare a mixed slurry in which particles of carbon nanotube and fluorocarbon resin A are dispersed.

When particles of fluorocarbon resin A are added to the carbon nanotube dispersion liquid, carbon nanotubes in the dispersion liquid are gently adsorbed on the particle surfaces of fluorocarbon resin A. Here, by appropriately adjusting the temperature of the solvent, the dispersion concentration of the carbon nanotube and the fluorocarbon resin A, the addition rate of the fluorocarbon resin A, and the like, the carbon nanotube is fluorinated while maintaining a high dispersion state of the carbon nanotube and the fluorocarbon resin A. It can be adsorbed on the surface of resin A particles. By such a method, the carbon nanotubes can be uniformly dispersed on the particle surface of the fluororesin A even at a low addition concentration. Further, even in the case of using a long carbon nanotube, it can be uniformly dispersed on the particle surface of the fluorocarbon resin A without impairing its properties. The addition of the fluororesin A may be performed by adding the particles of the fluororesin A as it is or in the form of a dispersion in which the particles of the fluororesin A are dispersed in advance in a solvent.

The particles of the fluorocarbon resin A used for producing the composite resin particles preferred for the present invention are preferably 5 to 500 μm, more preferably 10 to 250 μm, still more preferably 10 to 100 μm, particularly preferably 10 to 50 μm, very preferably It has an average particle size of 15 to 30 μm. It is easy to increase the dispersibility of carbon nanotubes in a molded article (composite resin material) produced from composite resin particles such that the average particle diameter of the fluororesin A is not more than the above upper limit, and the antistatic property is uniformly and efficiently enhanced. It is preferable because it is easy. It is preferable from the viewpoint of easiness of production of the composite resin particles that the average particle diameter of the fluorine resin A is not less than the above lower limit. The average particle diameter of the fluororesin A is a median diameter (D ₅₀ ) which means the particle diameter at an integrated value of 50% in the particle size distribution determined by the laser diffraction / scattering method, using a laser diffraction scattering type particle size distribution apparatus It is measured.

The particles of the fluorocarbon resin A used for producing the composite resin particles are preferably 0.5 to 9.0 m ² / g, more preferably 0.8 to 4.0 m ² / g, and further more preferably measured according to JIS Z8830. Preferably, it has a specific surface area of 1.0 to 3.0 m ² / g. The specific surface area is preferably not more than the above upper limit from the viewpoint of easily improving the adhesion between the particles of fluorocarbon resin A and the carbon nanotube, and it is not less than the above lower limit, the viewpoint of easiness of producing composite resin particles It is preferable from Specifically, the specific surface area of the fluorine resin A particles is measured by the BET method, which is a general measurement method of specific surface area, using a specific surface area / pore distribution measuring apparatus, which is a fixed capacity gas adsorption method. Ru.

In the tank of the present invention, the description on the structure and the melting point of the fluorocarbon resin A described above for the fluorocarbon resin A in the composite resin material contained in at least a part of the lining layer refers to these before and after compounding, and production of the composite resin material Since the characteristics do not change before and after, the same applies to particles of fluororesin A used for producing composite resin particles. The same applies to fluororesins B and C.

There is no particular limitation on the method of producing the particles of the fluorocarbon resin A having an average particle diameter and specific surface area in the above preferable range, and the fluorocarbon resin A is produced by a conventionally known polymerization method, preferably suspension polymerization, and obtained by the above polymerization Method of spray-drying a dispersion containing a reactive polymer, method of mechanically pulverizing the obtained fluororesin A using a grinder such as a hammer mill, turbo mill, cutting mill, jet mill, etc., obtained fluororesin A And mechanical grinding at a temperature below room temperature. From the viewpoint of easily obtaining particles of fluororesin A having a desired average particle diameter and specific surface area, it is preferable to produce particles of fluororesin A using a pulverizer such as a jet mill.

The particles of the fluororesin A having an average particle diameter in the above preferable range may be manufactured by adjusting the average particle diameter by a classification step using a sieve or an air stream.

Next, in the third step, the mixed slurry obtained in the second step is supplied to the pressure container, and the carbon dioxide is specified while maintaining the temperature and pressure at which carbon dioxide becomes subcritical or supercritical in the pressure container. Supply at speed and fill the pressure vessel with carbon dioxide. As carbon dioxide, any of liquefied carbon dioxide, carbon dioxide in gas-liquid mixture, and gaseous carbon dioxide may be used. Here, carbon dioxide in the supercritical state refers to a temperature above the critical point and a pressure above the critical point, specifically, a temperature above 31.1 ° C. and a pressure above 72.8 atmospheres I say the state. Moreover, a subcritical state means the state which exists in the pressure below a critical point, and the temperature below a critical point.

In the third step, the solvent and the dispersant contained in the mixed slurry dissolve in carbon dioxide, and the carbon nanotubes dispersed in the mixed slurry adhere to the particles of the fluororesin A.

The feed rate of carbon dioxide is preferably, for example, preferably 1 mg of the dispersing agent contained in the mixed slurry from the viewpoint of suppressing aggregation of carbon nanotubes and allowing carbon nanotubes to be uniformly attached to the particle surface of fluororesin A. It is 25 g / min or less, more preferably 0.07 g / min or less, and even more preferably 0.05 g / min or less.

In the subsequent fourth step, carbon dioxide is discharged from the pressure container together with the solvent and dispersant dissolved in carbon dioxide while maintaining the temperature and pressure at which carbon dioxide is in the subcritical or supercritical state for a predetermined time.

Next, in the fifth step, entrainer having high affinity to the dispersant is added to the pressure container while maintaining the state of the fourth step. Thereby, the remaining dispersant can be efficiently removed. As the entrainer, for example, the solvent used in preparing the carbon nanotube dispersion in the first step may be used. Specifically, when an organic solvent is used in the first step, the same organic solvent may be used as an entrainer. When water is used as the solvent in the first step, it is preferable to use an alcohol solvent as the entrainer. The fifth step is an optional step for efficiently removing the dispersant, and is not an essential step. It is also possible to remove the dispersant, for example by maintaining the fourth step without adding an entrainer.

Next, in the sixth step, the pressure of the pressure resistant container is lowered to remove carbon dioxide in the pressure resistant container to obtain composite resin particles. Here, depending on the carbon dioxide removal method, carbon dioxide and a solvent may remain in the composite resin particles. Therefore, residual carbon dioxide and a solvent can be efficiently removed by exposing the composite resin particles obtained to vacuum or heating.

(Method of producing tank of the present invention)
The lining layer provided on the inner surface of the tank of the present invention contains, at least in part, a composite resin material containing fluorocarbon resin A and carbon nanotubes. The lining layer containing the composite resin material may be made of, for example, a lining sheet containing the above-mentioned composite resin material, or a laminate of the lining sheet containing the above-mentioned composite resin material and another sheet (for example, glass cloth) It may be. The lining sheet containing the composite resin material may be manufactured, for example, by melting the above-mentioned composite resin particles and forming it into a sheet, or forming the above-mentioned composite resin particles into a sheet by, for example, compression molding (compression molding). A body may be obtained, or a compact obtained by the compression molding may be cut out into a sheet, for example. From the viewpoint of improving the conductivity of the lining sheet efficiently, the composite resin particles are compression molded to obtain a sheet-like molded product, or the molded product obtained by the compression molding is cut out into, for example, a sheet. It is preferred to produce a lining sheet comprising the material. The reason why the conductivity of the lining sheet can be efficiently enhanced by the above preferred manufacturing method is not clear, but is considered to be due to the following mechanism. The tank of the present invention is not limited to the mechanism described later. In the composite resin particle, as described above, carbon nanotubes are present on at least the surface and / or surface layer of the fluorine resin, and these carbon nanotubes are considered to form a conductive network. The conductive network of the carbon nanotube is considered to be easily cut when the carbon nanotube is cut by the external force applied to the composite resin particles or the carbon nanotube is aggregated. Therefore, when manufacturing a lining sheet from composite resin particles, it is considered that the conductivity of the lining sheet can be efficiently enhanced by using a method in which the network is not cut as much as possible. The method of compression-molding composite resin particles to obtain a sheet-like formed body, and the method of cutting out the composite resin material obtained by the compression-molding into, for example, a sheet to manufacture lining sheets, melt-extrude the composite resin particles Thus, it is considered that the cutting of the carbon nanotube network can be suppressed more easily than the method of manufacturing the lining sheet, and as a result, the conductivity of the lining sheet can be efficiently enhanced.

Therefore, in the present invention, a composite resin material obtained by compression molding composite resin particles (for example, composite resin particles having an average particle diameter of 5 μm to 500 μm) including fluororesin A and carbon nanotubes is used as a lining layer A tank can be provided that includes at least in part.
The composite resin material contained in at least a part of the lining layer is formed by compression molding composite resin particles (for example, composite resin particles having an average particle diameter of 5 μm to 500 μm) including fluororesin A and carbon nanotubes. An embodiment tank can be provided which is a resulting compression molded body.

As a fluorine resin contained in a composite resin material, for example, polytetrafluoroethylene (PTFE) from the viewpoint of facilitating the production of a lining sheet through compression molding of composite resin particles and of efficiently enhancing the conductivity of the lining sheet , Modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE) And polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). As a fluorine resin contained in the composite resin material, a fluorine selected from the group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) It is preferable to use a resin.
The above manufacturing method has been described by way of example in the case of producing a sheet from a composite resin material, but also when producing a chemical liquid tube, a hollow spherical shaped body, etc., these composite resin particles are melt extruded. A molded body may be produced, or composite resin particles may be compression molded to obtain these molded bodies, or these molded bodies may be manufactured by cutting from the molded body obtained by the compression molding. Good. Here, as described above, it is easy to suppress the cutting of the carbon nanotube network, and as a result, the composite resin particles are subjected to compression molding from the viewpoint of easily enhancing the conductivity of the chemical solution tube etc. It is preferable to produce a drug solution tube and a hollow spherical shaped body.
From the viewpoint of being suitable for such a production method, the fluororesins B and / or C contained in the composite resin material are, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroethylene / perfluoroethylene Fluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene ( PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). A group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) as the fluorine resin B and / or C contained in the composite resin material It is preferred to be selected from

When the fluorine resin is a PTFE resin and a modified PTFE resin, a method of subjecting a preform obtained by compressing the composite resin particles to a firing treatment is mentioned as a method of producing the composite resin material by compression molding the composite resin particles. Be The preformed body before firing is produced by subjecting the composite resin particles to a suitable pretreatment (eg, preliminary drying, granulation, etc.) as necessary, and then placing the composite resin particles in a mold and compressing it. The pressure applied during compression to produce a preform before firing is preferably 0.1 to 100 MPa, more preferably 1 to 80 MPa, and still more preferably 5 to 50 MPa.

The preformed body obtained as described above is fired, for example, at a temperature equal to or higher than the melting point of the resin contained in the composite resin particles to produce a molded body. The firing temperature is preferably 345 to 400 ° C., more preferably 360 to 390 ° C., although it depends on the size of the preform before firing and the firing time. The preform before firing is placed in a firing furnace, and preferably fired at the above-mentioned firing temperature to produce a formed product.
The obtained molded product may be used as it is as a lining sheet or the like (for example, a rod-like molded product to be described later, a stirring rod or the like) or cut from the molded product to a lining sheet or the like (for example A hollow spherical shaped body, a rod-like shaped body, a stirring rod or the like may be produced.

When the fluorocarbon resin is PCTFE resin, PFA resin, FEP resin, ETFE resin, ECTFE resin, PVDF resin and PVF resin (other than PTFE resin and modified PTFE resin), a method of compression molding the composite resin particles to produce a composite resin material As the heat treatment, appropriate pre-treatment such as pre-drying is performed according to the size of the molding, and after pre-treatment, the mold is heated to 200 ° C. or higher, preferably 200 to 400 ° C., more preferably 210 to 380 ° C. The resin is melted by heating in a circulating electric furnace for 2 hours or more, preferably 2 to 12 hours. After heating for a predetermined time, the mold is taken out of the electric furnace, and the mold is cooled to around normal temperature while pressing and compressing with a hydraulic pressure and a surface pressure of 25 kg / cm ² or more, preferably 50 kg / cm ² or more. A molded article (resin material) of composite resin particles was obtained.
The obtained molded product may be used as it is as a lining sheet or the like (for example, a rod-like molded product to be described later, a stirring rod or the like) or cut from the molded product to a lining sheet or the like (for example A hollow spherical shaped body, a rod-like shaped body, a stirring rod or the like may be produced.

As a method of providing a lining layer on the inner surface of the tank outer can, a sheet obtained by etching one side of a sheet of a fluorine resin, or a sheet obtained by laminating glass cloth on one side of a sheet of a fluorine resin, The method of making it cut out according to, and bonding the cut-out sheet | seat to a tank inner surface using an epoxy adhesive etc. is mentioned. The gap between the sheets bonded to the inner surface of the tank may be welded, for example, using a rod-like welding material, preferably a PFA material, having a circular or triangular cross section with a diameter of 2 to 5 mm.

<Chemical liquid pipe>
The tank of the present invention can be provided with a chemical liquid pipe connected to the inside and the outside of the tank. Examples of the chemical liquid pipe include a chemical liquid introduction pipe for injecting a chemical liquid and a chemical liquid discharge pipe for discharging a chemical liquid. When the drug solution passes through the drug solution pipe, friction occurs between the inner surface of the drug solution pipe and the drug solution, and static electricity is generated, whereby the drug solution is likely to be charged. Therefore, from the viewpoint of efficiently preventing electrification of the chemical solution, the chemical solution tube has a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the chemical solution tube and / or It is preferable that the chemical liquid pipe be a molded body of a composite resin material containing fluorocarbon resin B and carbon nanotubes. Here, the fluorine resin B is, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene Copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and It can be selected from polyvinyl fluoride (PVF). The fluororesin B is preferably selected from the group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and tetrafluoroethylene / perfluoroalkylvinylether copolymer (PFA). The fluorine resin B is more preferably selected from the group consisting of polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE), from the viewpoint of facilitating efficient improvement of the conductivity, and further, the conductivity is efficiently selected. In view of easiness of enhancing the properties and flexibility and weldability, modified polytetrafluoroethylene (modified PTFE) is more preferable.

The composite resin material constituting the drug solution pipe or the composite resin material contained in the lining layer provided on the inner surface of the drug solution pipe is a molded body of composite resin particles in which the fluorocarbon resin B and the carbon nanotube are complexed. The composite resin particle is a material in which particles of fluorocarbon resin B and carbon nanotubes are complexed, and carbon nanotubes exist on at least the surface and / or surface layer of the particles of fluorocarbon resin B. For example, at least a part of carbon nanotubes is supported or buried on the particle surface of fluorocarbon resin B. The carbon nanotube may be attached to and supported on the particle surface of the fluorocarbon resin B, or a part may be buried and supported, or the carbon nanotube may be completely embedded in the surface layer of the fluorocarbon resin B particle. It is also good. In a composite resin material which is a molded product of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, and the composite resin particles are integrated to form a composite resin material. It may be done.

With regard to the composite resin material constituting the chemical solution pipe or the composite resin material contained in the lining layer provided on the inner surface of the chemical solution pipe, the description of the composite resin material containing the above-mentioned fluororesin A and carbon nanotubes applies similarly. Further, with respect to the fluorocarbon resin B, the description described for the fluorocarbon resin A applies in the same manner, and for the carbon nanotube, the description described above for the carbon nanotube applies similarly. The fluororesin B may be the same resin as the fluororesin A or may be a different resin.

As a method of providing a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of a chemical liquid pipe, for example, melt extrusion or compression molding of composite resin particles to prepare a sheet of composite resin material And a method of bonding the same to the inner surface of the drug solution pipe, and a method of cutting a molded composite resin particle into a tubular shape and bonding the same to the inner surface of the drug solution pipe. Regarding the method of producing the sheet of the composite resin material, the description described above for the method of producing the lining sheet applies similarly. As a method of bonding, when the drug solution pipe is made of metal, it is bonded to the inner surface of the drug solution pipe using an adhesive or the like, or when the drug solution pipe is made of resin, it is welded to the inner surface of the drug solution pipe. The method is mentioned.

<Nozzle>
The present invention comprises a chemical liquid pipe connected to the inside and the outside of the tank,
The chemical liquid pipe includes a chemical liquid feed pipe for putting the chemical liquid into the tank,
The chemical liquid feed pipe has a nozzle at its end (or tip),
The nozzle is a molded body of a composite resin material having a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the nozzle and / or containing fluorocarbon resin B and carbon nanotubes,
Fluororesin B includes polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) The tank can be provided, selected from the group consisting of

As used herein, the term "nozzle" refers to a pipe-like mechanical component used to determine the direction of fluid flow, and to control the properties of the fluid such as the flow rate, flow rate, direction and pressure of the flowing material. There is no particular restriction as long as it is a part that is used and is usually understood as a nozzle.
The nozzle can be selected, for example, from the group consisting of a spray nozzle, a rotary nozzle, a straight forward nozzle, and a shower nozzle.
With regard to the lining layer of the nozzle and the fluorocarbon resin B etc., those descriptions regarding the chemical liquid pipe can be referred to.

<Hollow spherical molded body>
The tank of the present invention may have a hollow spherical shaped body at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes. Such a hollow spherical molded body is usually used to float on the liquid surface of the chemical solution charged into the tank of the present invention and remove static electricity charged on the chemical solution from the liquid surface. In particular, when the chemical solution is stored in the tank according to the present invention, the chemical solution vibrates to cause friction with the inner surface of the tank to generate static electricity, which tends to cause the chemical solution to be charged. By using a hollow spherical shaped body that at least partially contains the composite resin material, static electricity generated in friction during transportation or the like can be efficiently removed. Fluororesin C includes polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) Is preferably selected from the group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and tetrafluoroethylene / perfluoroalkylvinyl ether It is more preferably selected from the group consisting of alcohol copolymer (PFA). Fluorine resin C is preferably selected from the group consisting of modified PTFE, PTFE and PFA from the viewpoint of molding processability, and from the viewpoint of easily enhancing the conductivity, more preferably from the group consisting of PTFE and modified PTFE It is more preferably modified PTFE from the viewpoint of being selected and capable of efficiently enhancing the conductivity and the viewpoint of flexibility and weldability.

The composite resin material at least partially contained in the hollow spherical molded body is a molded body of composite resin particles in which fluorocarbon resin C and carbon nanotubes are complexed. The composite resin particle is a material in which particles of fluorocarbon resin C and carbon nanotubes are complexed, and carbon nanotubes exist on at least the surface and / or surface layer of the particles of fluorocarbon resin C. For example, at least a part of carbon nanotubes is supported or buried on the particle surface of fluorocarbon resin C. The carbon nanotubes may be attached to and supported on the particle surface of the fluorocarbon resin C, or a part may be buried and supported, and the carbon nanotubes may be completely embedded in the surface layer of the particles of the fluorocarbon resin C. It is also good.

With respect to the composite resin material which is at least partially contained in the hollow spherical molded body, the description of the composite resin material containing the above-mentioned fluorocarbon resin A and carbon nanotube applies similarly. Moreover, as for the fluorine resin C, the description described for the fluorine resin A applies similarly. The fluorine resin C may be the same resin as the fluorine resin A or B, or may be a different resin. The same description as described above for carbon nanotubes applies to carbon nanotubes.

The aspect in which the hollow spherical molded body at least partially includes the composite resin material may be such that at least a part of the hollow spherical molded body includes the composite resin material containing the fluorocarbon resin C and the carbon nanotube, for example, resin An embodiment in which a lining material containing the above-mentioned composite resin material is lined on at least a part of the surface of the hollow spherical molded body, a hollow spherical molded body is a molded body composed of a composite resin material containing fluorocarbon resin C and carbon nanotubes. Aspects and the like are included.

<Rod-shaped compact>
In an embodiment of the present invention, there is provided a tank further comprising a rod-like molded body at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes.
Such a rod-like shaped body is generally used to remove static electricity, which is charged in the chemical solution, from the liquid surface of the chemical solution introduced into the tank of the present invention from the liquid surface and to remove it from the solution. In particular, when the chemical solution is stored in the tank according to the present invention, the chemical solution vibrates to cause friction with the inner surface of the tank to generate static electricity, which tends to cause the chemical solution to be charged. By using a rod-like compact containing at least a part of the composite resin material, static electricity generated in friction during transportation or the like can be efficiently removed. The dimensions (diameter and length) of the rod-shaped molded product, the shape (circular shape, hexagonal shape, etc.) of the cross section, the conductivity, and the like can be selected appropriately.

Fluororesin C includes polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) It is preferred to be selected from the group consisting of
The above description can be appropriately referred to for the “fluororesin C”, the “carbon nanotube”, the “composite resin material” and the like.

The rod-like shaped body can be connected to the ground wire. A rod-shaped molded product can be connected to the ground wire to more efficiently discharge electricity.
A holder (also referred to as a “rod-shaped molded body holder”) for providing a rod-shaped molded body in a tank can be used. The rod-shaped compact holder is generally cylindrical and the outer shape corresponds to the size of the hole of the tank, and the inner shape corresponds to the outer shape of the rod-shaped compact. The dimensions of the rod-shaped compact holder can be appropriately selected according to the dimensions of the rod-shaped compact and the dimensions of the hole of the tank.

<Agitator bar>
In an embodiment of the present invention, there is provided a tank further comprising a stir bar at least partially comprising a composite resin material comprising fluorocarbon resin C and carbon nanotubes.
Such a stirring rod is generally used to enter the inside of the chemical solution from the liquid surface of the chemical solution introduced into the tank of the present invention and is used to stir the chemical solution. It is used to remove static electricity from the solution. The dimensions (diameter and length) of the stirring rod, the shape of the cross section (circle, hexagon, etc.), conductivity, etc. can be selected appropriately.

The stirring rod can have a propeller (or a stirring blade) at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes. The stirring rod and the propeller may be integral, but the stirring rod may be separable from the propeller. When the stirring rod has a propeller, the chemical solution can be stirred more efficiently. The dimensions (size) and shape (eg, crescent shape), conductivity, etc. of the stirring rod can be appropriately selected.
The above description can be appropriately referred to for “fluororesin C”, “carbon nanotube” and “composite resin material” relating to a propeller.
In the case where the stirring rod has a propeller, both of the stirring rod and the propeller may indicate the desired diselectrification.

The stir bar can optionally be connected to the ground wire. A stirrer can be connected to the ground wire to more efficiently discharge electricity.
An adapter for providing a stir bar in the tank (also referred to as a "stir bar adapter") can be used. The stir bar adapter is generally cylindrical and the outer shape corresponds to the size of the hole in the tank, and the inner shape corresponds to the outer shape of the stir bar. The dimensions of the stir bar adapter can be selected appropriately depending on the dimensions of the stir bar and the dimensions of the hole in the tank.

<Tank>
Although the application of the tank of the present invention is not particularly limited, for example, a tank containing a drug solution is mentioned, and specifically, it is a drug solution supply tank, a drug solution storage tank and / or a drug solution transport tank. The chemical solution supply tank is, for example, a tank used in a system for supplying a chemical solution described later. The chemical solution supply tank is used to allow the chemical solution to pass through the tank and be supplied to another tank. Therefore, the chemical solution supply tank is usually provided with a chemical solution input pipe and a chemical solution discharge pipe, and it is also possible to simultaneously input and discharge the chemical solution. The chemical solution storage tank is a tank for storing the chemical solution inside. Therefore, the chemical solution storage tank may have at least one opening. The chemical solution transport tank is a tank transported in a state in which the chemical solution is stored as contents. When the chemical solution is transported, static electricity is easily generated due to the vibration of the chemical solution, but the static electricity can be removed by using the tank of the present invention. The tank of the present invention may be a tank for supplying, storing, transporting or the like of a chemical solution, or may be a tank having two or more of these purposes.

<Chemical solution>
The chemical solutions stored in the tank of the present invention include aqueous solutions such as hydrochloric acid, nitric acid, hydrofluoric acid, hydrogen peroxide water, sulfuric acid, isopropyl alcohol (IPA), ethanol, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), etc. Organic solvents and water can be mentioned. The chemical solution contained in the tank is preferably an organic solvent. The organic solvent is, for example, a chemical solution used in semiconductor manufacturing, etc., and in applications of semiconductor production, even if it is a problem caused by static electricity or a trace of contaminants charged in the chemical solution, the advantage of the tank of the present invention It is easier to

<Chemical solution>
The chemical solution stored in the tank according to the embodiment of the present invention is not particularly limited as long as it can be stored. The chemical solution can include, for example, at least one selected from an organic solvent, a flammable liquid, an acidic liquid, a basic liquid, a neutral liquid, an aqueous solution, and a conductive liquid.
The organic solvent includes, for example, isopropyl alcohol (IPA), ethanol, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK) and the like.
Flammable liquids include, for example, isopropyl alcohol (IPA), ethanol, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK) and the like.
The acidic liquid includes, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, hydrogen peroxide water and the like.
The basic liquid includes, for example, ammonia water and the like.
The neutral liquid includes, for example, ozone water, so-called water, ultrapure water, pure water, deionized water, ion exchanged water, distilled water and the like.
The aqueous solution includes, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, aqueous ammonia, aqueous hydrogen peroxide, ozone water and the like.
The conductive liquid includes, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, hydrogen peroxide water, ammonia water, so-called water, ion exchanged water, deionized water, pure water and the like.
The chemical solution contained in the tank may be, for example, an organic solvent. The organic solvent is, for example, a chemical solution used in semiconductor manufacturing, etc., and in applications of semiconductor production, even if it is a problem caused by static electricity or a trace of contaminants charged in the chemical solution, the advantage of the tank of the present invention It is easier to
The chemical contained in the tank can be used even if it is a conductive liquid.

<Chemical solution supply system>
The present invention also provides a chemical solution supply system including the supply of a chemical solution using the tank of the present invention. The application of the chemical solution supply system of the present invention is not particularly limited, but from the viewpoint of easily utilizing the advantage of the chemical solution supply system of the present invention that contamination of the chemical solution is reduced and the cleanness is high. It is preferable that it is a chemical | medical solution supply system used for these. In a preferred embodiment of the present invention, the chemical solution supply system of the present invention comprises a chemical solution transport tank, a chemical solution storage tank of a semiconductor factory line, a pump for pumping a chemical solution from the chemical solution transport tank to the chemical solution storage tank, and each line from the chemical solution storage tank. The pump according to the present invention may be used as the chemical solution transport tank and / or the chemical solution storage tank, including a pump for pressure-feeding the chemical solution. According to the preferred chemical solution supply system of the present invention of this aspect, specifically, the chemical solution transport tank (for example, ISO tank) is transported to the semiconductor factory by the tank truck, and the pump is carried out from the chemical solution transport tank to the chemical solution storage tank in the semiconductor factory line. Thus, a series of chemical solutions can be supplied such that the chemical solution is pressure-fed and the chemical solution is sent from the chemical solution storage tank to each line. The chemical solution supply system of the present invention is a device for supplying the contents of the tank of the present invention in addition to the tank of the present invention, for example, a compressed gas source or chemical solution for delivering inert gas such as nitrogen gas under high pressure. A supply pump may be provided, or a filter or the like may be provided to filter a chemical solution to remove impurities and the like.

<Molded body>
The present invention can provide a molded body,
It can be used for tanks where chemical solutions are handled.
The tank may have a layer of lining sheets.
The molded body may be a compression molded body which can be obtained by compression molding composite resin particles containing a fluorocarbon resin and a carbon nanotube. The fluorine resin may be, for example, any of the fluorine resins AC described herein. The description of the present specification relating to any of the composite resin particles, the fluororesins A to C and the carbon nanotubes can be referred to for each of the composite resin particles of the molded body, any of the fluororesins A to C and the carbon nanotubes.
The formed body that can be used for the tank can include, for example, the above-mentioned lining sheet, a drug solution tube, a hollow formed body, a rod-shaped formed body, a rod-shaped formed body holder, a stirring rod, a stirring blade, a stirring blade adapter, and the like.

Embodiment
Next, the present invention will be described in detail by the following embodiments. In the following, in describing the configuration shown in the drawings, terms indicating directions such as “upper”, “lower”, “left”, “right” and the like, and other terms including those will be used. The purpose of using these terms is to facilitate the understanding of the embodiments through the drawings. Therefore, those terms are not limited to those indicating the direction in which the embodiment of the present invention is actually used, and the technical scope of the invention described in the claims is not limited by these terms.

First Embodiment
The tank of the first embodiment of the present invention includes the tanks of the first embodiment A and the first embodiment B.
The tank according to the first embodiment A of the present invention is, as shown in FIG. 1A, a tank outer can 1, a lining layer 2 provided on the inner surface of the tank outer can 1, and a chemical solution input for introducing a chemical solution into the tank. The tube 3 has a chemical solution discharge tube 4 for discharging the chemical solution to the outside of the tank, and a hollow spherical shaped body 5 for removing static electricity which is charged in the chemical solution by floating on the liquid surface of the chemical solution. 6 is stored. As a method of providing the lining layer 2 on the inner surface of the tank outer can 1, a lining sheet obtained by etching one side of a sheet of a fluorine resin, or a lining sheet obtained by laminating glass cloth on one side of a sheet of a fluorine resin The method of making it cut out according to the shape of 1 inner surface, and bonding the cut-out sheet to the tank inner surface using an epoxy adhesive etc. is mentioned. The gap between the sheets bonded to the inner surface of the tank may be welded, for example, using a rod-like welding material, preferably a PFA material, having a circular or triangular cross section with a diameter of 2 to 5 mm. The tank in the first embodiment A includes the chemical solution inlet pipe 3, the chemical solution outlet pipe 4, and the hollow spherical shaped body 5, but these are not essential components for the tank of the present invention, and at least one of them is used. It may or may not have any of these.

In the tank according to the first embodiment A of the present invention, from the viewpoint of efficiently removing static electricity, at least when the chemical solution is introduced into the tank, a portion where the introduced chemical solution first contacts the inner surface of the tank outer can ( It is preferable that a lining layer including lining sheet 8 provided in liquid contact portion 7) in FIG. 1A includes a composite resin material including fluorocarbon resin A and carbon nanotubes, and the lining sheet includes fluorocarbon resin A and carbon nanotubes. It is more preferable that it is a molded object comprised with the composite resin material containing. From the viewpoint of further improving the antistatic property, it is preferable that the lining layer including the lining sheet 10 (including the lining sheet 8) provided on the tank bottom 9 includes the composite resin material including the fluororesin A and the carbon nanotube. More preferably, the lining sheet is a molded body composed of a composite resin material containing fluorocarbon resin A and carbon nanotubes. An earth wire 11 is connected to the lining sheet 8 or the lining sheet 10, and the static electricity flowing from the chemical solution into the lining sheet 8 or 10 having a low volume resistivity flows into the ground or the like via the earth wire 11 and is removed. The lining sheet containing the composite resin material containing fluorocarbon resin A and carbon nanotubes is, for example, thinly cut out the molded composite resin particle produced as described above into a sheet, or extruding the composite resin particles into a sheet Manufactured by molding. By lining the lining sheet containing the composite resin material thus obtained on the inner surface of the tank at the liquid contact portion 7 or tank bottom portion 9 in the same manner as the method for providing the lining layer 2 described above, the efficiency of the chemical solution 6 is obtained. Static charge removal is possible.

The tank according to the first embodiment A of the present invention, as shown in FIG. 1A, includes a chemical solution inlet pipe 3 and a chemical solution outlet pipe 4 provided on the upper portion of the tank. The discharge port of the drug solution input pipe 3 is provided at a position higher than the liquid level 12 of the drug solution 6, and the suction port of the drug solution discharge pipe 4 is provided at a position near the bottom of the tank. Although the tank in the first embodiment A has the chemical solution inlet pipe 3 and the chemical solution outlet pipe 4 at the above position, when the tank includes the chemical solution inlet pipe 3 and / or the chemical solution outlet pipe 4, these positions are particularly limited. Alternatively, the upper portion of the tank may have a chemical supply pipe and the tank bottom may have a chemical discharge pipe, or these pipes may be located on the side of the tank. The positions of the discharge port of the chemical liquid feed pipe and the suction port of the chemical liquid discharge pipe may be set appropriately. The tank according to the first embodiment A is not shown in FIG. 1A, but other configurations common to the tank, for example, a further liquid chemical pipe provided at an arbitrary position such as an upper portion, a lateral portion, a lower portion, a safety valve, It may further have a vent or the like.

Lining layers 31 and 41 containing a composite resin material containing fluorocarbon resin B and carbon nanotubes are provided on the inner surfaces of the chemical solution inlet tube 3 and the chemical solution outlet tube 4, respectively. The chemical solution input pipe 3 and the chemical solution discharge pipe 4 provided with the lining layers 31 and 41 containing the above-mentioned composite resin material on the inner surface of the pipe, for example, cut a formed body of composite resin particles into a tubular shape and made of metal It manufactures by the method of joining to piping inner surface, or the method of welding with resin piping inner surfaces. The chemical solution input pipe 3 and the lining layers 31 and 41 of the chemical liquid discharge pipe 4 are electrically connected to the ground wire 11, respectively, and the static electricity charged when passing through the chemical liquid input pipe 3 and the chemical liquid discharge pipe 4 In particular, it is removed via the ground wire 11. Each of lining layers 31 and 41 may have a ground wire different from ground wire 11. The chemical solution input pipe 3 and the chemical liquid discharge pipe 4 shown in FIG. 1A are provided with a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on a part of the inner surface. It may be a molded body made of a composite resin material containing fluorocarbon resin B and carbon nanotubes, and a tube obtained by cutting the molded body of the composite resin particle into a tubular shape is used as it is as a chemical liquid feed pipe and a chemical liquid discharge pipe. It is also good.

The tank according to the first embodiment A of the present invention has a hollow spherical shaped body 5 as shown in FIG. 1A. The number of hollow spherical shaped articles 5 is not particularly limited, and may be appropriately selected according to the size of each shaped article 5 and the required charging effect. An earth wire 13 is connected to each of the molded bodies 5, and the earth wire exits from the lid 14 to the outside of the tank and is connected to the ground. The static electricity charged in the chemical solution 6 flows into the compact 5 having a low volume resistivity, and is removed via the ground wire 13. The hollow spherical molded body 5 is obtained by thinly cutting out a molded body of a composite resin material containing fluorocarbon resin C and carbon nanotubes, or attaching a sheet produced by extruding the composite resin material into a sheet shape into a hollow spherical body. You may manufacture by putting together. Although the tank of this embodiment has the lid 14, the lid 14 is not essential. Although the ground wire 13 extends from the lid 14 in the first embodiment A, the ground wire 13 may be electrically connected to the ground wire 11.

The tank according to the first embodiment B of the present invention is similar in shape to the tank according to the first embodiment A, and provided on the inner surface of the tank outer can 1 and the tank outer can 1 as shown in FIG. 1B. The lining layer 2, the chemical solution input pipe 3 for introducing the chemical solution into the tank, the nozzle 36 provided at the end of the chemical solution input pipe 3, the chemical solution discharge pipe 4 for discharging the chemical solution outside the tank, the static electricity in the chemical solution A rod-like shaped body 52 inserted in the chemical solution for removing the chemical substances, and a stirring rod 56 for stirring the chemical solution are provided, and the chemical solution 6 is stored in the tank.
The method of providing the lining layer 2 in the inner surface of the tank outer can 1 can use the method similar to the method described by the tank of 1st Embodiment A.
The tank according to the first embodiment B includes the chemical solution inlet pipe 3, the chemical solution outlet pipe 4, the rod-like molded body 52, and the stirring rod 56, but these are not essential components of the tank according to the present invention. It may have one or none of these.

Also in the tank according to the first embodiment B of the present invention, the liquid contact portion 7, the lining layer including the lining sheet 8, the lining layer including the lining sheet 10 (including the lining sheet 8) provided on the tank bottom 9, and the ground wire Have eleven. About these, the description of the tank of 1st Embodiment A can be referred, and the efficient static elimination of the chemical | medical solution 6 is attained.

The tank according to the first embodiment B of the present invention is also provided with the chemical solution inlet pipe 3 and the chemical solution outlet pipe 4 provided on the upper portion of the tank, as shown in FIG. 1B. The description regarding the tank of the first embodiment A can be referred to for the chemical liquid inlet pipe 3 and the chemical liquid outlet pipe 4.
The tank according to the first embodiment B is also not shown in FIG. 1B, but other configurations common to the tank, such as a further liquid chemical pipe provided at an arbitrary position such as the upper part, the lateral part, and the lower part, a safety valve, It may further have a vent or the like.

The tank of the first embodiment B of the present invention has a nozzle 36 provided at the end of the drug solution feed pipe 3 as shown in FIG. 1B. The dimensions of the nozzle 36 are not particularly limited, and the length, the thickness, the shape of the cross section, and the like may be appropriately selected according to the required charging effect. Although the ground wire may be connected to the nozzle 36, the chemical solution feed pipe 3 can function as the ground wire. It is preferable because the static electricity of the chemical solution passing through the nozzle can be reduced before entering the tank.
The nozzle 36 may be manufactured by cutting out a molded body of the composite resin material containing the fluorocarbon resin B and the carbon nanotube into a tubular shape, or extruding the composite resin material into a tubular shape.

The tank of the first embodiment B of the present invention can have a rod-like formed body 52 as shown in FIG. 1B. The dimensions of the rod-like molded body 52 are not particularly limited, and the length, the thickness, the shape of the cross section, etc. may be appropriately selected according to the required charging effect. An earth wire 53 is connected to the rod-like molded body 52 and is connected to the ground. The static electricity of the chemical solution 6 flows into the rod-like compact 52 having a low volume resistivity, and is removed via the ground wire 53.
The rod-like shaped body 52 may be manufactured by cutting out a shaped body of the composite resin material containing the fluorocarbon resin C and the carbon nanotube into a rod-like shape, or extruding the composite resin material into a rod-like shape.
The tank according to the embodiment B of the present invention preferably has a rod-shaped holder 54 (hereinafter also referred to as a “rod-shaped holder”), and the holder 54 preferably holds the rod-shaped molding 52. The molded object holder 54 "is not essential. The dimensions of the outside of the rod-shaped molded body holder 54 can be appropriately selected in consideration of the dimensions of the hole provided in the tank.

The tank of the first embodiment B of the present invention can have a stirring rod 56 as shown in FIG. 1B. The dimensions of the stirring rod 56 are not particularly limited, and the length, the thickness, the shape of the cross section, etc. may be appropriately selected according to the required charging effect and stirring effect. The stirring rod 56 can be provided with a propeller (or stirring blade) 57 at its end. The stirring rod 56 and the propeller 57 may be integral or separable. A ground wire (not shown) can be contacted with the stir bar 56 and connected to the ground. The static electricity of the chemical solution 6 flows into the stirring rod 56 having a low volume resistivity and can be removed through the ground wire.
The stirring rod 56 may be manufactured by cutting out a molded body of the composite resin material containing the fluorocarbon resin C and the carbon nanotube into a rod or extruding the composite resin material into a rod.
The propeller 57 can be manufactured by cutting out a molded body of the composite resin material containing the fluorocarbon resin C and the carbon nanotube at least partially including the composite resin material containing the fluorocarbon resin C and the carbon nanotube into a propeller shape.
The tank according to Embodiment B of the present invention has a stirring rod adapter 58 (hereinafter also referred to as “stirring rod adapter”), and the adapter 58 preferably holds the stirring rod 56, but “the stirring rod adapter 58” Not required. The external dimensions of the stirring rod adapter 58 can be selected appropriately in consideration of the dimensions of the holes provided in the tank.
The stirring rod adapter may be manufactured by cylindrically cutting out a molded product of a composite resin material containing fluorocarbon resin C and carbon nanotubes, or extruding the composite resin material into a cylindrical shape. Additionally, a ground wire may be connected to the stir bar adapter.

Second Embodiment
In the tank according to the second embodiment of the present invention, as shown in FIG. 2, the tank outer can 1, the lining layer 2 provided on the inner surface of the tank outer can 1, and the chemical solution for charging or discharging the chemical solution into the tank. A tube 15 has a hollow spherical molded body 5 for removing static electricity which is suspended in the liquid surface of the chemical solution and charged in the chemical solution, and the chemical solution 6 is stored in the tank. As a method of providing the lining layer 2 on the inner surface of the tank outer can 1, a lining sheet obtained by etching one side of a sheet of a fluorine resin, or a lining sheet obtained by laminating glass cloth on one side of a sheet of a fluorine resin The method of making it cut out according to the shape of 1 inner surface, and bonding the cut-out sheet to the tank inner surface using an epoxy adhesive etc. is mentioned. The gap between the sheets bonded to the inner surface of the tank may be welded, for example, using a rod-like welding material, preferably a PFA material, having a circular or triangular cross section with a diameter of 2 to 5 mm. The tank in the present embodiment has the drug solution pipe 15 and the hollow spherical shaped body 5, but these are not essential components of the tank of the present invention, and may have at least one of them. It is not necessary to have any of these.

In the tank according to the second embodiment of the present invention, from the viewpoint of efficiently removing static electricity, at least when the chemical solution is introduced into the tank, a portion where the introduced chemical solution first contacts the inner surface of the tank outer can (see FIG. It is preferable that a lining layer including lining sheet 8 provided in liquid contact portion 7 in 2 includes a composite resin material including fluororesin A and carbon nanotubes, and the lining sheet includes fluororesin A and carbon nanotubes. More preferably, it is a molded product of a composite resin material. From the viewpoint of further improving the antistatic property, it is preferable that the lining layer including the lining sheet 10 (including the lining sheet 8) provided on the tank bottom 9 includes the composite resin material including the fluororesin A and the carbon nanotube. More preferably, the lining sheet is a molded article of a composite resin material containing fluororesin A and carbon nanotubes. The grounding wire 11 is connected to the lining sheet 8 or the lining lining sheet 10, and the static electricity flowing from the chemical solution into the lining sheet 8 or 10 having a low volume resistivity flows into the ground or the like via the grounding wire 11 and is removed. . The lining sheet containing the composite resin material containing the fluorocarbon resin A and the carbon nanotube is, for example, thinly cut out the molded product of the composite resin material manufactured as described above into a sheet, or extruding the composite resin material into a sheet Manufactured by molding. By lining the lining sheet containing the composite resin material thus obtained on the inner surface of the tank at the liquid contact portion 7 or tank bottom portion 9 in the same manner as the method for providing the lining layer 2 described above, the efficiency of the chemical solution 6 is obtained. Static charge removal is possible.

The tank of 2nd Embodiment of this invention has the chemical | medical solution pipe 15 as shown in FIG. A lining layer 151 containing a composite resin material containing fluorocarbon resin B and carbon nanotubes is provided on the inner surface of the drug solution tube 15. The chemical liquid pipe 15 in which the lining layer 151 containing the above-mentioned composite resin material is provided on the inner surface of the pipe is, for example, a method of cutting a molded body of the composite resin material into a tubular shape and bonding it to the inner surface of metal pipe , Manufactured by a method of welding to the inner surface of a resin pipe. The lining layer 151 of the drug solution tube 15 is electrically connected to the ground wire 11, and static electricity charged when passing through the drug solution tube 15 is finally removed via the ground wire 11. The lining layer 151 may have a ground wire different from the ground wire 11. The chemical liquid pipe 15 shown in FIG. 2 is provided with a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on a part of the inner surface, but a composite resin material containing fluorocarbon resin B and carbon nanotubes The pipe | tube which cut-processed the molded object of composite resin material in the tubular form may be used as it is as a chemical | medical solution pipe.

The tank according to the second embodiment of the present invention has a hollow spherical shaped body 5 as shown in FIG. The number of hollow spherical shaped articles 5 is not particularly limited, and may be appropriately selected according to the size of each shaped article 5 and the required charging effect. An earth wire 13 is connected to each of the molded bodies 5, and the earth wire exits from the lid 14 to the outside of the tank and is connected to the outside. The static electricity charged in the chemical solution 6 flows into the compact 5 having a low volume resistivity, and is removed via the ground wire 13. The hollow spherical molded body 5 is obtained by thinly cutting out a molded body of a composite resin material containing fluorocarbon resin C and carbon nanotubes, or attaching a sheet produced by extruding the composite resin material into a sheet shape into a hollow spherical body. You may manufacture by putting together. Although the tank of this embodiment has the lid 14, the lid 14 is not essential. Further, although the ground wire 13 extends from the lid 14 in the present embodiment, the ground wire 13 may be electrically connected to the ground wire 11.

The tank according to the second embodiment of the present invention has a shape as shown in FIG. 2 and is used, for example, as a chemical solution transport tank. In particular, it may be a tank container as known as an ISO tank. Tank containers are containers used when cargo is liquid in freight transportation such as ships, railways, automobiles and the like. In particular, when the chemical solution is transported by the tank container, the liquid inside the tank vibrates due to the vibration at the time of transportation, and such vibration may cause friction to charge the chemical solution. According to the tank of the present embodiment, it is possible to efficiently remove the static electricity generated in the chemical solution. The tank according to the present embodiment is not shown in FIG. 2, but other configurations common to the tank, such as additional liquid chemical pipes provided at arbitrary positions such as upper, horizontal and lower parts, safety valves and vents And the like. Moreover, the conveyance means of the tank of this embodiment is not specifically limited, You may be conveyed by conveyance vehicles, such as a tank lorry and a freight train, and a ship.

Third Embodiment
Next, an embodiment of the supply system of the present invention is shown in FIG. 3 as a third embodiment. The supply system of the present invention in this embodiment, as shown in FIG. 3, has a chemical solution transport tank 16 and a chemical solution supply tank 22, and is a system for supplying a chemical solution to each use point 18 (POU, point of use). It is. At least one of the chemical solution transport tank 16 and the chemical solution supply tank 22 may be the tank of the present invention, and any of them may be the tank of the present invention. The chemical solution transport tank 16 may be, for example, a tank of the embodiment shown in FIG. The chemical solution transport tank 16 has a chemical solution as its content, is loaded on the transport vehicle 17 and transported. The chemical solution transported by the chemical solution transport tank 16 is finally transported to each use point 28 by the operation of the pump 24. First, the chemical solution transport tank 16 is connected to the chemical solution supply tank 22 via the coupler 20 in the pass box 19 and the

connection pipes

18 and 21, for example, in a semiconductor manufacturing plant. The chemical solution in the chemical solution transport tank 16 passes through the connection pipe 18, is connected by the coupler 20, and is transported to the chemical liquid supply tank 22 via the connection pipe 21. The pump 24 is connected to the chemical solution supply tank 22, and the chemical solution carried from the chemical solution supply tank 22 via the

connection pipes

23 and 25 passes through the filter 26 to be finely contained in the chemical solution. Contaminants are removed and transported to each point of use 28 via connection tube 27. In the third embodiment shown in FIG. 3, the liquid supply is performed using the pump 24, but the position of the pump 24 is not limited to the illustrated position. Also, multiple pumps 24 may be used. Furthermore, the chemical solution may be supplied by a pressurization system or the like without using a pump.

Hereinafter, the present invention will be described in more detail by way of examples, but these do not limit the scope of the present invention.

<Measurement of Average Particle Size D ₅₀ >
Fluorine resin particles used in the preparation of the composite resin particles, and an average particle diameter of the composite resin particles, the particle size distribution measured by a laser diffraction scattering particle size distribution analyzer (manufactured by Nikkiso "MT3300II"), the average particle diameter D ₅₀ Obtained.

<Measurement of specific surface area>
The measurement of the specific surface area of the fluorocarbon resin particles used in the production of the composite resin particles and the composite resin particles was carried out using a specific surface area / pore distribution measuring apparatus (BELSORP-miniII manufactured by Nippon Bell) in accordance with JIS Z8830.

<Measurement of heat of crystallization>
The heat of crystallization of the fluorine resin particles used for producing the composite resin particles was measured using a differential scanning calorimeter ("DSC-50" manufactured by Shimadzu Corporation). 10 mg of the measurement sample is heated to 250 ° C. at a rate of 50 ° C./min and temporarily held, and then the crystal is melted by raising the temperature to 380 ° C. at a rate of 10 ° C./min. The peak of the crystallization point measured when the temperature was lowered at a rate of ° C./min was measured in terms of heat.

<Measurement of melting point>
The measurement of the melting point of the fluorocarbon resin particles used for producing the composite resin particles was determined as the temperature of the heat of fusion peak which can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D4591.

<Preparation of composite resin material>
The composite resin particles obtained in the production example described later were subjected to pretreatment (eg, preliminary drying, granulation, etc.) as necessary, and then uniformly filled in a predetermined amount in a molding die. The preparation procedure after filling varies depending on the type of fluororesin.
When the fluorocarbon resin was a PTFE resin and a modified PTFE resin, the composite resin particles were compressed by pressing at 15 MPa and holding for a certain period of time to obtain a preformed body. The obtained preform is taken out of the molding die, fired in a hot air circulating electric furnace set at 345 ° C. or more for 2 hours or more, slowly cooled, taken out from the electric furnace, and a molded product of composite resin particles ( Composite resin material) was obtained.
When the fluorocarbon resin is PCTFE resin, PFA resin, FEP resin, ETFE resin, ECTFE resin, PVDF resin, and PVF resin (other than PTFE resin and modified PTFE resin), hot air circulation type electricity having a mold set at 200 ° C. or higher The furnace is heated for 2 hours or more to melt the resin. After heating for a predetermined time, the mold is taken out of the electric furnace, and the mold is cooled to around normal temperature while pressing and compressing with a hydraulic press at a surface pressure of 25 kg / cm ² or more. The material was obtained.

<Measurement of volume resistivity>
A test piece of φ110 × 10 mm was produced from the composite resin material (molded body) obtained as described above from the composite resin particles, and used as a measurement sample. The measurement of volume resistivity was performed using a resistivity meter ("Loresta" or "Hiresta" manufactured by Mitsubishi Chemical Analytech Co., Ltd.) according to JIS K6911.

<Measurement of welding strength of composite resin material>
A test piece 10 mm thick × 30 mm wide × 100 mm long is prepared from the composite resin material (molded body) obtained as described above from the composite resin particles, and the test piece is 50 mm long and about 1 mm deep. The V groove was cut. Next, a PFA welding rod with a diameter of 3 mm is welded to the groove portion so that the length of the portion to be fused is 50 mm using a hot air type welding machine, and the test specimen for welding strength measurement as shown in FIG. It was created. Next, as shown in FIG. 5, the test piece for measuring welding strength is set in a tensile tester so that the folded portion of the fused PFA welding rod is on the lower side, and the welding rod remains unfused Set the part on the upper chuck of the tensile tester. Tension was performed at a speed of 10 mm / min using a tensile tester (“Tensilon universal material tester” manufactured by A & D Co., Ltd.), and the maximum stress was measured to obtain welding strength.

<Measurement of metal elution amount of composite resin material>
The degree of metal contamination in the molded body due to the addition of the carbon nanotube was evaluated by measuring the metal elution amount of the metal-based 17 element using an ICP mass spectrometer ("ELAN DRCII" manufactured by Perkin Elmer). Specifically, a test piece of 10 mm × 20 mm × 50 mm obtained by cutting from the composite resin material obtained as described above is converted into 0.5 L of 3.6% hydrochloric acid (EL-UM grade made by Kanto Chemical) for about 1 hour. Immerse, take out after immersion for 1 hour, flush with ultra pure water (specific resistance: 118.0 MΩ · cm) and wash, immerse the entire test piece in 0.1 L of 3.6% hydrochloric acid, and under a room temperature environment Stored for 24 hours and 168 hours. After the specified time elapsed, the entire amount of the immersion liquid was recovered, and the metal impurity concentration of the immersion liquid was analyzed.

<Measurement of carbon dropout of composite resin material>
The degree of desorption of carbon nanotubes from the composite resin material was evaluated by measuring TOC using a total organic carbon meter (“TOCvwp” manufactured by Shimadzu Corporation). Specifically, a test piece of 10 mm × 20 mm × 50 mm obtained by cutting from the composite resin material obtained as described above is converted into 0.5 L of 3.6% hydrochloric acid (EL-UM grade made by Kanto Chemical) for about 1 hour. Immerse, take out after immersion for 1 hour, flush with ultra pure water (specific resistance value: 118.0 MΩ · cm) and wash, immerse the entire test piece in ultra pure water, room temperature environment for 24 hours and 168 I saved time. After the specified time elapsed, the entire amount of the immersion liquid was recovered, and the total organic carbon analysis was performed on the immersion liquid.

<Evaluation of chemical resistance of composite resin material>
The weight of a 10 mm × 20 mm × 50 mm test piece obtained by cutting the composite resin material obtained as described above was measured using an electronic balance (A & D electronic balance for analysis “BM-252”). Then, the test pieces were subjected to SPM (H ₂ SO ₄ : H ₂ O ₂ = 1: 2 (mass ratio)), FPM (HF: H ₂ O ₂ = 1: 2 (mass ratio)), APM (SC− 1) Immerse in each solution of (NH ₄ OH: H ₂ O ₂ : H ₂ O = 1: 1: 5 (mass ratio)), ozone water (50 ppm) for 168 hours, allow to dry, and test after immersion The weight of the piece was measured using an electronic balance in the same manner as before immersion. The weight change before and after immersion was calculated by the following equation and used as an index of chemical resistance.
Weight change (%) = [(weight after immersion-weight before immersion) / weight before immersion] x 100

[Production of Composite Resin Particles]
In the following examples and comparative examples, modified PTFE particles or polytetrafluoroethylene (PTFE) particles shown in the following Table 1 were used. In the modified

PTFE particles

1 and 2 shown in Table 1, X in the above formula (II) is a perfluoropropyl group, and the amount of perfluorovinylether unit is based on the total mass of the modified polytetrafluoroethylene. It was confirmed to be 0.01 to 1% by mass.

Production Example 1
To 500 g of a carbon nanotube dispersion liquid (dispersant = 0.15 mass%, carbon nanotube = 0.025 mass%) using water as a solvent, 3,500 g of ethanol was added for dilution. Furthermore, 1,000 g of modified PTFE particles 1 were added to prepare a mixed slurry.
Next, the prepared mixed slurry is supplied to the pressure container, liquefied carbon dioxide is supplied at a supply rate of 0.03 g / min to 1 mg of the dispersant contained in the mixed slurry in the pressure container, and the pressure in the pressure container is adjusted. The pressure was raised and raised to a temperature of 50 ° C. at 20 MPa. While maintaining the above pressure and temperature for 3 hours, carbon dioxide was discharged from the pressure vessel together with the solvent (water, ethanol) dissolved in carbon dioxide and the dispersant.
Subsequently, the pressure and temperature in the pressure resistant vessel were lowered to atmospheric pressure and normal temperature to remove carbon dioxide in the pressure resistant vessel, whereby CNT composite resin particles 1 were obtained.

Production Example 2
A CNT composite resin particle 2 was obtained in the same manner as in Production Example 1-1 except that the amount of CNT was set to 0.05% by mass based on the total amount of the composite resin particles.

Production Example 3
A CNT composite resin particle 3 was obtained in the same manner as in Production Example 1-1 except that the amount of CNT was set to 0.1% by mass based on the total amount of the composite resin particles.

Production Example 4
A CNT composite resin particle 4 was obtained in the same manner as in Production Example 1 except that the modified PTFE 2 was used in place of the modified PTFE 1.

Production Example 5
A CNT composite resin material 5 was obtained in the same manner as in Production Example 2 except that the modified PTFE 2 was used in place of the modified PTFE 1.

[Resin particles 6 for comparison (Production Example 6)]
The modified PTFE 1 in which the CNTs were not complexed was used as the resin particle 6 for comparison.

[Resin particle 7 for comparison (Production Example 7)]
The modified PTFE 2 in which the CNTs were not complexed was used as the resin particle 7 for comparison.

[Resin particle 8 for comparison (Production Example 8)]
PTFE particles not composited with CNTs were used as resin particles 8 for comparison

The average particle size and the specific surface area of the resin particles obtained in the above Production Examples 1 to 8 were measured according to the above measurement method. The results are shown in Table 2. Moreover, the volume resistivity and welding strength which were measured about the molded object produced according to said method using the resin particle obtained by said manufacture example 1-8 are shown in Table 2, and the result of chemical resistance evaluation is shown in Table 3. Show. Furthermore, from the amount of CNT and the volume resistivity of the resin material, the following equation:
A = X / Y ^-14
The value A obtained by the above is also shown in Table 2. In the above formula, X is the volume resistivity [Ω · cm] of the resin material, and Y is the amount of CNT contained in the resin material [mass%] (equal to the amount of CNT used for the production of the resin material) is there.
In the following, composite resin materials prepared from the composite resin particles 1 to 5 according to the above method are also referred to as composite resin materials 1 to 5, respectively, They are also referred to as comparative resin materials 6 to 8 respectively. Also, the amount of CNTs in the composite resin particles or resin particles is equal to the amount of CNTs in the composite resin material or resin material obtained therefrom.

For the resin materials obtained from the

composite resin materials

1 and 2 and the resin material 6 for comparison, evaluation of metal elution amount and carbon dropout was performed. The obtained results are shown in Table 4. In addition, about elements (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn) other than the element described in the column of the metal elution amount in Table 4, the metal elution amount is The results are not shown in Table 4 because the measurements were taken but at the instrument detection limit (ND). Also, the results in Table 4 are all after immersion for 24 hours.

A test piece of 10 mm × 10 mm × 2 mm in thickness was obtained from the composite resin material 2 produced using the composite resin particles obtained in Production Example 2 according to the production method of the composite resin material. The test pieces were immersed in various chemicals shown in Table 5, and weight changes before and after immersion for about one week (1 W) and about one month (1 M) were measured. The obtained results are shown in Table 5. In addition, the immersion test to APM in Table 5 was performed on temperature conditions of 80 degreeC, and the immersion test to another chemical | medical solution was performed on room temperature conditions. Moreover, the detail of each chemical | medical solution in Table 5 is as showing in Table 6.

Production Example 9 and Composite Resin Material 9
A CNT composite resin particle 9 was obtained in the same manner as in Production Example 2 except that PCTFE (average particle diameter 10 μm, specific surface area 2.9, volume resistivity 10 ² Ω · cm) was used instead of the modified PTFE 1. Using the obtained CNT composite resin particles 9, a composite resin material 9 was produced according to the production method of the above composite resin material, and a test piece of 10 mm × 10 mm × thickness 2 mm was obtained. Likewise, the test pieces were subjected to the immersion tests in various chemical solutions shown in Table 5. The obtained results are shown in Table 5.

[Resin materials 10 to 12 for comparison]
A commercially available molded article in which 15% by weight of graphite is added to PTFE is used as the resin material 10 for comparison, and a commercially available molded article in which 15% by weight of carbon fiber is added to PTFE is used as the resin material 11 for comparison. Further, a commercially available composite material (composite material of PFA resin and carbon fiber) was used as the resin material 12 for comparison. The immersion test to the various chemical | medical solutions shown in Table 5 was similarly done about the test piece which has the said size of these materials. The obtained results are shown in Table 5.

[Production of composite resin particles (PCTFE)]
Composite resin particles were produced using polychlorotetrafluoroethylene (PCTFE) particles shown in Table 7 below.

Production Example 13 Production of CNT Composite Resin Particles 13
A CNT composite resin particle 13 was obtained in the same manner as in Production Example 1 except that PCTFE particles 2 were used instead of the modified PTFE particles 1.

Production Example 14 Production of CNT Composite Resin Particles 14
CNT composite resin particles 14 were obtained in the same manner as in Production Example 2 except that PCTFE particles 2 were used instead of the modified PTFE particles 1.

(Production Example 15: Production of CNT Composite Resin Particles 15)
The CNT composite resin particles 15 were obtained in the same manner as in Production Example 14 except that the amount of CNTs was 0.1% by mass based on the total amount of the composite resin particles.

Production Example 16 Production of CNT Composite Resin Particles 16
CNT composite resin particles 16 were obtained in the same manner as in Production Example 14 except that the amount of CNTs was 0.125% by mass based on the total amount of composite resin particles.

Production Example 17 Production of CNT Composite Resin Particles 17
A CNT composite resin particle 17 was obtained in the same manner as in Production Example 14 except that the amount was set to 0.15% by mass based on the total amount of composite resin particles capable of obtaining the amount of CNT.

Production Example 18 Production of CNT Composite Resin Particles 18
CNT composite resin particles 18 were obtained in the same manner as in Production Example 15, except that PCTFE particles 3 were used in place of PCTFE particles 2.

(Production Example 19: Production of CNT Composite Resin Particles 19)
CNT composite resin particles 19 were obtained in the same manner as in Production Example 15 except that PCTFE particles 1 were used instead of PCTFE particles 2.

(Production Example 20: Resin Particles 20 for Comparison)
PCTFE 2 in which CNTs were not complexed was used as the resin particle 20 for comparison.

The average particle size and the specific surface area of the composite resin particles obtained in the above Production Examples 13 to 20 and the resin particles for comparison were measured according to the above-mentioned measuring method. The results are shown in Table 8. Table 8 also shows volume resistivity measured for composite resin materials (molded bodies) 13 to 19 and a comparative resin material (molded body) 20 prepared according to the above method using the above-mentioned resin particles. Furthermore, from the amount of CNT and the volume resistivity of the resin material, the following equation:
A = X / Y ^-14
The value A obtained by the above is also shown in Table 8. In the above formula, X is the volume resistivity [Ω · cm] of the resin material, and Y is the amount of CNT contained in the resin material [mass%] (equal to the amount of CNT used for the production of the resin material) is there. The composite resin materials prepared according to the above method from the composite resin particles 13-19 are also referred to as composite resin materials 13-19, respectively, and the composite resin material prepared according to the above method from the resin particles 20 for comparison is a resin material for comparison It is also called 20.

For the

composite resin materials

14 and 15 and the comparative resin material 20, evaluation of metal elution amount and carbon dropout was performed. The obtained results are shown in Table 9. In addition, about elements (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn) other than the element described in the column of the metal elution amount in Table 9, the metal elution amount is The results are not shown in Table 9, as the measurements were taken but at the instrument detection limit (ND). In addition, the results in Table 9 are all after immersion for 24 hours.

The chemical resistance of the

composite resin materials

14 and 15 and the comparative resin material 20 were evaluated according to the above-mentioned method. The obtained results are shown in Table 10.

The above-mentioned

composite resin materials

14 and 15 were subjected to sulfuric acid / hydrogen peroxide immersion treatment (SPM treatment) under the above conditions, and the volume resistivity after the treatment was measured. As a result, as shown in Table 11 below, it was confirmed that the

composite resin materials

14 and 15 did not increase in volume resistivity even when SPM treatment was performed.

[Production of lining sheet 1 containing composite resin material]
A method for producing the language sheet 1 including the composite resin material from the composite resin particles obtained as described above will be described. The production method varies depending on the used fluorine resin. When the fluorine resin is polytetrafluoroethylene (PTFE) or modified polytetrafluoroethylene (modified PTFE), the composite resin particles obtained in Production Example 2 are pretreated, if necessary, (eg, predrying, granulation, etc.) Then, the composite resin material was compressed by uniformly filling a fixed amount in a molding die and pressing at 15 MPa and holding for a fixed time to obtain a preform. The obtained preform is taken out of the molding die, fired in a hot air circulating electric furnace set at 345 ° C. or more for 2 hours or more, gradually cooled, taken out from the electric furnace, and block-shaped composite resin material A molded body was obtained. (In the case where the fluorocarbon resin is tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) which is not shown in the Examples and Comparative Examples, there are compression molding method, compression molding method, sheet extrusion molding method etc. In this case, the CNT composite resin particles are subjected to pretreatment (eg, preliminary drying, granulation, etc.) if necessary, and then uniformly filled in a predetermined amount in a molding die, and an electric furnace set at 300 ° C. or higher After firing for 2 hours or more, the product is removed from the electric furnace and pressure-cooled at 5 MPa or more with a hydraulic press to obtain a block-like molded product of the composite resin material. A sheet with a thickness of 2.4 mm was made. The obtained sheet was laminated with a glass cloth having a thickness of 0.5 mm and heat-fused to obtain a lining sheet 1. The volume resistivity of the obtained lining sheet 1 was 10 ² Ω · cm.

[Production of lining sheet 2 not containing composite resin material]
A lining sheet 2 was obtained in the same manner as the lining sheet 1 except that the resin particle 6 for comparison (Production Example 6) was used in place of the composite resin particles obtained in Production Example 2.

[Manufacturing of the drug solution tube 1 containing a composite resin material]
The method for manufacturing the drug solution pipe 1 containing a composite resin material from the composite resin particles obtained as described above will be described. The composite resin particles obtained in Production Example 2 are subjected to pretreatment (eg, preliminary drying, granulation, etc.) if necessary, and then uniformly filled in a predetermined amount in a molding die, pressurized at 15 MPa, constant The composite resin material was compressed by holding for a time to obtain a preform. The obtained preform is taken out of the molding die, fired in a hot air circulating electric furnace set at 345 ° C. or more for 2 hours or more, gradually cooled, taken out from the electric furnace, and block-shaped composite resin material A molded body was obtained. The obtained molded body was cut using a CNC ordinary lathe (“TAC-510” manufactured by Takizawa Iron Works Ltd.) to produce a chemical liquid pipe having a diameter of 2 inches. The volume resistivity of the obtained drug solution tube 1 was 5.0 × 10 ² Ω · cm.

[Manufacturing of the drug solution tube 2 containing a composite resin material]
A drug solution pipe 2 was obtained in the same manner as the production of the drug solution pipe 1 except that the resin particle 6 for comparison (Production Example 6) was used instead of the composite resin particles obtained in Production Example 2.

[Production of hollow sphere 1 containing composite resin material]
The method for manufacturing the drug solution pipe 1 containing a composite resin material from the composite resin particles obtained as described above will be described. The composite resin particles obtained in Production Example 2 are subjected to pretreatment (eg, preliminary drying, granulation, etc.) if necessary, and then uniformly filled in a predetermined amount in a molding die, pressurized at 15 MPa, constant The composite resin material was compressed by holding for a time to obtain a preform. The obtained preform is taken out of the molding die, fired in a hot air circulating electric furnace set at 345 ° C. or more for 2 hours or more, gradually cooled, taken out from the electric furnace, and block-shaped composite resin material A molded body was obtained. The obtained molded product was cut and welded using a machining center to produce a hollow spherical molded product having a diameter of 50 mm. The volume resistivity of the obtained hollow spherical molded body was 5.0 × 10 ² Ω · cm.

[Production of hollow sphere 2 containing composite resin material]
A hollow sphere 2 was obtained in the same manner as in the production of the hollow sphere 1 except that the resin particle 6 for comparison (Production Example 6) was used instead of the composite resin particle obtained in Production Example 2.

Example 1
The lining sheet 1 was bonded to the inner side surface of the 50 L capacity tank using an adhesive (for example, epoxy type). The joints between the sheets were sealed using PFA welding rods of φ5 mm. The chemical solution pipe 1 was attached to the tank, and a plurality of hollow spheres 1 were disposed inside the tank.

Comparative Example 1
Comparative Example 1 was obtained in the same manner as in Example 1 except that the lining sheet 2, the drug solution pipe 2, and the hollow sphere 2 were used instead of the lining sheet 1, the drug solution pipe 1, and the hollow sphere 1.

Evaluation of Antistatic Property 10 L of thinner (NTX Eco Thinner manufactured by Sankyo Kagaku Co., Ltd.) is put into the tank manufactured in Example 1 and Comparative Example 1, and a stirrer having a sales expansion blade made of PTFE is used. Stirring was carried out for 10 minutes at the number of revolutions of the above, and the charging potential of the lining sheet was measured using an electrometer (FMX-003 manufactured by SIMCO) to evaluate the antistatic property of the organic solvent. As a result, Comparative Example 1 was charged rapidly by stirring, and the charging potential tended to increase with the passage of time (about 1.5 kV in about 5 minutes). On the other hand, Example 1 had a value below the measurement limit (-0.01 kV), and it was confirmed that the tank of Example 1 is superior to the tank of Comparative Example 1 in the antistatic property. .

Reference Signs List 1 tank outer can 2 lining layer 3 chemical solution feeding pipe 31 lining layer 4 chemical solution discharging pipe 41 lining layer 5 hollow spherical molded body 6 chemical solution 7 wetted portion 8 lining sheet 9 tank bottom portion 10 lining sheet 11 ground wire 12 liquid surface 13 ground wire 14 lid 15 chemical liquid pipe 151 lining layer 16 chemical liquid transport tank 17 transportation vehicle 18 connecting pipe 19 pass box 20 coupler 21 connecting pipe 22 chemical liquid supply tank 24 circulating pump 25 connecting pipe 26 filter 27 connecting pipe 28 point of use 29 PFA welding rod 30 Test piece 31 groove 32 lower chuck 33 upper chuck 36 nozzle 52 rod shaped body 53 ground wire 54 holder 56 stirring bar 57 propeller 58 adapter

Claims

With the can outside the tank,
And at least a lining layer provided on the inner surface of the tank outer can;
The lining layer comprises, at least in part, a composite resin material comprising fluorocarbon resin A and carbon nanotubes,
Fluororesin A is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) A tank selected from the group consisting of
The tank according to claim 1, wherein a lining layer provided at a portion where the introduced chemical solution first contacts the inner surface of the tank outer case comprises a composite resin material containing fluororesin A and carbon nanotubes.
It has a chemical pipe that leads to the inside and the outside of the tank,
The drug solution pipe has a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the drug solution pipe, and / or is a molded body of a composite resin material containing fluorocarbon resin B and carbon nanotubes. Yes,
Fluororesin B is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) The tank according to claim 1 or 2, selected from the group consisting of
It has a chemical pipe that leads to the inside and the outside of the tank,
The chemical liquid pipe includes a chemical liquid feed pipe for putting the chemical liquid into the tank,
The chemical feed tube has a nozzle at its end,
The nozzle is a molded body of a composite resin material having a lining layer containing a composite resin material containing fluorocarbon resin B and carbon nanotubes on at least a part of the inner surface of the nozzle and / or containing fluorocarbon resin B and carbon nanotubes,
Fluororesin B is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP) ), Tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF) A tank according to any of the preceding claims, selected from the group consisting of
5. The tank according to claim 4, wherein the nozzle is selected from the group consisting of a spray nozzle, a rotary nozzle, a straight forward nozzle, and a shower nozzle.
It further has a hollow spherical shaped body at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes, wherein fluorocarbon resin C is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), Tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), poly The tank according to any of the preceding claims, selected from the group consisting of chlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).
It further has a rod-like shaped body at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes, and fluorocarbon resin C is made of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetragonal Fluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychloro The tank according to any of the preceding claims, selected from the group consisting of trifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).
It further has a stirring rod at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes, wherein fluorocarbon resin C is polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoro A tank according to any of the preceding claims, selected from the group consisting of ethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).
The tank according to claim 8, wherein the stirring rod has a propeller at least partially including a composite resin material containing fluorocarbon resin C and carbon nanotubes.
The tank according to any one of claims 1 to 9, wherein the chemical solution contains at least one selected from an organic solvent, a flammable liquid, an acidic liquid, a basic liquid, a neutral liquid, an aqueous solution, and a conductive liquid.
The tank according to any one of claims 1 to 10, wherein the fluororesin A is modified polytetrafluoroethylene.
Modified polytetrafluoroethylene is represented by formula (I):

And a tetrafluoroethylene unit represented by the formula (II):

[Wherein, X represents a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group]
And the amount of perfluorovinyl ether unit represented by the formula (II) is 0.01 to 1% by mass based on the total mass of the modified polytetrafluoroethylene A tank according to any one of the preceding claims.
The tank according to any one of claims 1 to 12, wherein the composite resin material is a compression-molded body of composite resin particles having an average particle diameter of 5 μm to 500 μm, which contains any of fluororesins AC and carbon nanotubes. .
The tank according to any one of claims 1 to 13, which is a chemical solution supply tank, a chemical solution storage tank, and / or a chemical solution transport tank.
A chemical solution supply system comprising supplying a chemical solution using the tank according to any one of claims 1 to 14.
A molded article comprising any of the fluororesins A to C and a carbon nanotube, which is used in the tank according to any one of claims 1 to 14.
17. The shaped body according to claim 16, which is selected from lining sheets, chemical tubes, hollow shaped bodies, rod shaped bodies, rod shaped body holders, stirring bars, stirring blades, and stirring bar adapters.