JP6571304B2 - Tank and chemical supply system - Google Patents

Description

This patent application is a 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 contents of which are incorporated herein by reference in their entirety.
The present invention relates to a tank containing a composite resin material containing a fluororesin and a carbon nanotube in at least a part of a lining layer, and a chemical supply system using the tank.

  Conventionally, in tanks used for storing various chemicals, etc., in order to prevent corrosion of the inner wall of the tank due to the corrosive nature of the chemicals and contamination of the chemicals due to corrosion, A lining material made of a chemical resistant material such as polyvinyl chloride, rubber, polyolefin resin, or fluororesin is bonded.

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

JP 2003-170994 A JP 2001-328209 A Japanese Patent Laid-Open No. 06-270353

  Since chemical-resistant materials such as fluororesin that are usually used as lining materials have electrification properties, static electricity is generated when friction occurs between the chemical-resistant material and the chemical solution that is the contents. There may be problems with the ignition of objects. Further, as described in Patent Document 3, for example, when a conductive material such as carbon black is added to a chemical resistant material used as a lining material, a large amount of conductive material is used to achieve a desired antistatic property. It is necessary to add a functional material, and there is a possibility that contaminants are mixed in the tank contents. In addition, since these conductive materials and the like are present on the bonding surface between the lining material and the tank inner wall, there arises a problem that the lining material is easily peeled off.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a tank that handles various chemicals, can prevent charging of the tank contents, and has reduced contamination of the tank contents. Another object of the present invention is to provide a chemical supply system using the tank.

  In order to solve the above-mentioned problems, the present inventors have intensively studied the lining layer provided on the inner surface of the tank. As a result, the inventors have found that the above-mentioned problems can be achieved by providing a lining layer containing at least a part of a composite resin material containing a fluororesin and a carbon nanotube on the inner surface of the tank, and have completed the present invention.

で表されるテトラフルオロエチレン単位と、式（ＩＩ）：

［式中、Ｘは、炭素数１〜６のパーフルオロアルキル基または炭素数４〜９のパーフルオロアルコキシアルキル基を表す］
で表されるパーフルオロビニルエーテル単位とを有する化合物であり、式（ＩＩ）で表されるパーフルオロビニルエーテル単位の量は、変性ポリテトラフルオロエチレンの全質量に基づいて０．０１〜１質量％である、前記［１］〜［１３］のいずれかに記載のタンク。
［１５］複合樹脂材料は、フッ素樹脂Ａ〜Ｃのいずれかとカーボンナノチューブを含む、５μｍ以上５００μｍ以下の平均粒子径を有する複合樹脂粒子の圧縮成形体である、前記［１］〜［１４］のいずれかに記載のタンク。
［１６］薬液供給タンク、薬液貯蔵タンク、および／または、薬液運搬タンクである、前記［１］〜［１５］のいずれかに記載のタンク。
［１７］前記［１］〜［１６］のいずれかに記載のタンクを用いて薬液の供給を行うことを含む、薬液供給システム。
［１８］前記［１］〜［１６］のいずれか１に記載のタンクに使用される、フッ素樹脂Ａ〜Ｃのいずれかとカーボンナノチューブを含む成形体。
［１９］
ライニングシート、薬液管、中空形状の成形体、棒状の成形体、棒状成形体ホルダー、攪拌棒、攪拌羽根、及び攪拌棒アダプタから選択される、前記［１８］に記載の成形体。
［２０］フッ素樹脂Ａ〜Ｃのいずれかとカーボンナノチューブを含む、５μｍ以上５００μｍ以下の平均粒子径を有する複合樹脂粒子の圧縮成形体。
［２１］ライニングシート、薬液管、中空形状の成形体、棒状の成形体、棒状成形体ホルダー、攪拌棒、攪拌羽根、及び攪拌棒アダプタから選択される、前記［２０］に記載の圧縮成形体。That is, the present invention includes the following preferred embodiments.
[1] A tank outer can,
A lining layer provided on the inner surface of the tank outer can,
The lining layer includes, at least in part, a composite resin material containing a fluororesin A and carbon nanotubes,
Fluororesin A is composed of 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) ) Tank selected from the group consisting of:
[2] The tank according to [1], wherein the lining layer provided at a portion where the introduced chemical solution first comes into contact with the inner surface of the tank outer can includes a composite resin material including fluororesin A and carbon nanotubes.
[3] A chemical solution pipe connected to the inside and the outside of the tank is provided,
The chemical liquid pipe has a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the pipe, and / or is a molded body of a composite resin material containing fluororesin B and carbon nanotubes. ,
Fluororesin B is composed of 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 [1] or [2], selected from the group consisting of:
[4] Provided with a chemical pipe connected to the inside and outside of the tank,
The chemical liquid pipe includes a chemical liquid input pipe for putting the chemical liquid into the tank,
The chemical injection pipe has a nozzle at its end (or tip),
The nozzle has a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the nozzle, and / or is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
Fluororesin B is composed of 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 [1] to [3], 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 rotary nozzle, a straight nozzle, and a shower nozzle.
[6] A hollow spherical molded body that at least partially includes a composite resin material including a fluororesin C and a carbon nanotube, and the fluororesin C is made of 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), any one of [1] to [5] above The tank described in.
[7] A rod-shaped molded body that at least partially includes a composite resin material including a fluororesin C and carbon nanotubes, and the fluororesin C is made of 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). The described tank.
[8] A stirrer bar that at least partially includes a composite resin material including a fluororesin C and a carbon nanotube, wherein the 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), poly Any one of [1] to [7], selected from the group consisting of chlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF). tank.
[9] The tank according to [8], wherein the stirring rod has a propeller that at least partially includes a composite resin material including a fluororesin C and a carbon nanotube.
[10] Any of the above [1] to [9], wherein the chemical liquid includes 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 described in.
[11] The tank according to any one of [1] to [9], wherein the chemical solution includes an organic solvent.
[12] The tank according to any one of [1] to [9], wherein the chemical liquid includes at least one selected from an acidic liquid, a basic liquid, and a conductive liquid.
[13] The tank according to any one of [1] to [12], wherein the fluororesin A is modified polytetrafluoroethylene.
[14] The modified polytetrafluoroethylene has the formula (I):

A tetrafluoroethylene unit represented by formula (II):

[Wherein X represents a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms]
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. The tank according to any one of [1] to [13].
[15] The composite resin material according to [1] to [14], wherein the composite resin material is a compression molded body of composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less, including any one of fluororesins A to C and carbon nanotubes. A tank according to any one of the above.
[16] The tank according to any one of [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 supply system including supplying a chemical using the tank according to any one of [1] to [16].
[18] A molded article containing any one of fluororesins A to C and carbon nanotubes used for the tank according to any one of [1] to [16].
[19]
The molded body according to [18], which is selected from a lining sheet, a chemical liquid 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 body of composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less, including any one of fluororesins A to C and carbon nanotubes.
[21] The compression molded body according to [20], which is selected from a lining sheet, a chemical liquid 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. .

  According to the present invention, a tank for handling various chemical liquids, which can prevent the tank contents from being charged, a tank in which contamination of the tank contents is reduced, and a chemical liquid 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 a 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 embodiment described here, and various modifications can be made without departing from the spirit of the present invention.

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

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

<Lining layer>
A lining layer is provided on the inner surface of the tank outer can. Examples of the resin contained in the lining layer include a fluororesin, a vinyl chloride resin, and a polyolefin resin. From the viewpoint of chemical resistance and heat resistance, the lining layer preferably contains a fluororesin. Examples of the fluororesin include polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), and 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, and 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 a glass cloth and a resin sheet. In that case, the thickness of the glass cloth is preferably 0.3 to 3 mm, more preferably 0.3 to 1 mm, and still more preferably. 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 includes a composite resin material containing the fluororesin A and the carbon nanotubes at least partially. That the lining layer includes at least a part of the composite resin material means that at least a part of the lining layer provided on the inner surface of the tank outer can may be composed of the composite resin material, or the entire lining layer is a composite resin material. It may be comprised. 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, or the entire lining layer provided on the inner surface of the tank outer can contains the composite resin material. Also good. From the viewpoint of efficiently imparting antistatic properties and reducing the manufacturing cost of the tank, a part of the lining layer provided on the inner surface of the tank outer can is made of a composite resin material, or the lining layer It is preferable that a part includes a composite resin material.

  When the chemical solution is charged into the tank of the present invention, static electricity is generated due to friction generated at the portion where the charged chemical solution first contacts the inner surface of the tank outer can, and the chemical solution is likely to be charged. Therefore, from the viewpoint of efficiently preventing the chemical solution from being charged, the lining layer provided at the portion where the introduced chemical solution is first in contact with the inner surface of the tank outer can is made of a composite resin material containing fluororesin A and carbon nanotubes. Preferably, the lining layer is composed of a composite resin material containing the fluororesin A and carbon nanotubes. From the same point of view, a composite resin material in which the lining layer provided on the bottom of the inner surface of the tank outer can easily contains static electricity due to friction with the charged chemical solution, and includes a fluororesin A and carbon nanotubes. It is preferable that the lining layer is composed of a composite resin material containing the fluororesin A and carbon nanotubes.

<Composite resin material>
In the tank of the present invention, the lining layer includes a composite resin material containing the fluororesin A and the carbon nanotubes at least partially. The composite resin material containing the fluororesin A and the carbon nanotube is a molded body of composite resin particles in which the fluororesin A and the carbon nanotube are combined. The composite resin particle is a material in which the fluororesin A particles and the carbon nanotubes are combined, and the carbon nanotubes exist on at least the surface and / or the surface layer of the fluororesin A particles. For example, at least a part of the carbon nanotubes are supported or buried on the surface of the fluororesin A particles. The carbon nanotubes may be adhered to and supported on the surface of the fluororesin A particles, or may be partially embedded and supported, or may be completely embedded in the surface layer of the fluororesin A particles. Also good. In the composite resin material that is a molded body of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, or the composite resin particles are integrated to form a composite resin material. You may do it.

The average particle size of the composite resin particles is preferably 500 μm or less, more preferably 300 μm or less, further preferably 200 μm or less, particularly preferably 100 μm or less, very preferably 50 μm or less, and most preferably 30 μm or less. When the average particle diameter is not more than the above upper limit, the carbon nanotubes can be easily dispersed uniformly in the lining layer, and the volume resistivity of the lining layer should be sufficiently reduced even when the lining layer is thin. Can do. Although the minimum of the average particle diameter of composite resin material is not specifically limited, Usually, it is 5 micrometers or more. By producing a composite resin material constituting at least a part of the lining layer from composite resin particles having an average particle diameter in the above range, the volume resistivity of the lining layer can be easily reduced efficiently. In the present invention, the average particle size of the composite resin particles that give the composite resin material contained in the lining layer may be the average particle size of the composite resin particles used in the production of the composite resin material, and the average particle size is The median diameter (D ₅₀ ) means the particle diameter at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method, and is measured using a laser diffraction / scattering particle size distribution apparatus. In the tank of the present invention, the lining layer or the like preferably contains a composite resin material that is a molded body of composite resin particles having the above average particle diameter, and the composite resin material in the lining layer or the like is in the above preferred range. The composite resin particles having a particle diameter of 1 mm may be used, or the composite resin particles may be integrated to form a composite resin material and the particle shape may not be maintained.

  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 combined, thereby effectively reducing the volume resistivity of the lining layer and charging the lining layer. Preventive properties and / or conductivity can be imparted. For this reason, it is possible to prevent the contents from being charged, and to prevent ignition of a chemical solution such as an organic solvent. In addition, by using a composite resin material, the volume resistivity can be effectively reduced with a small amount of carbon nanotubes, so that a tank for chemicals and the like by mixing the conductive material contained in the lining layer into the contents Contamination of contents is suppressed, and 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, and even 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 not less than the above lower limit, the mechanical properties and moldability of the composite resin material are easily improved. Although the upper limit of the amount of the fluororesin A is not particularly limited, it is about 99.99% by mass or less. The amount of the fluororesin A contained in the composite resin material is measured by a carbon component analysis method.

  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, and even more preferably 0, based on the total amount of the composite resin material. 0.025 to 0.2% by mass. It is preferable for the amount of carbon nanotubes to be equal to or greater than the above lower limit because the volume resistivity is likely to be lowered in order to increase the antistatic property or 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 a carbon component analysis method.

The composite resin material is a molded body 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 according to JIS Z8830. It is -4.0m < ² > / g, More preferably, it is 1.0-3.0m < ² > / g. The specific surface area is preferably not less than the above lower limit from the viewpoint of easily improving the adhesion between the fluororesin A and the carbon nanotube, and the specific surface area is preferably not more than the above upper limit from the viewpoint of easy production of the composite resin material. By producing a composite resin material constituting at least a part of the lining layer from composite resin particles having a specific surface area in the above range, the volume resistivity of the lining layer can be easily reduced efficiently. In the present invention, the specific surface area of the composite resin particles that give the composite resin material contained in the lining layer may be the average particle diameter of the composite resin particles used in the production of the composite resin material, and the average particle diameter is Specifically, it is measured by a BET method, which is a general method for measuring a specific surface area, using a specific surface area / pore distribution measuring device (for example, BELSORP-miniII manufactured by Nippon Bell), which is a constant volume gas adsorption method. In the tank of the present invention, the lining layer or the like preferably contains a composite resin material that is a molded body of composite resin particles having the above average particle diameter, and the composite resin material in the lining layer or the like is in the above preferred range. The composite resin particles having a particle diameter of 1 mm may be used, or the composite resin particles may be integrated to form a composite resin material and the particle shape may not be maintained.

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 according to JIS K6911, from the viewpoint of antistatic properties. Even more preferably, it is 1.0 × 10 ⁶ Ω · cm or less. When the volume resistivity is not more than the above upper limit, good antistatic properties can be obtained. The lower limit 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, “Lorester” or “High Lester” manufactured by Mitsubishi Chemical Analytech) using a molding material or a cut test piece according to JIS K6911. For example, when measured using a test piece of φ110 × 10 mm produced by compression molding (compression molding), the composite resin material preferably exhibits the volume resistivity.
When the composite resin material is contained in the lining layer, the portion of the lining layer containing the composite resin material preferably has the antistatic property. In addition, the said volume resistivity is applied similarly about the composite resin material containing the fluororesin B or the fluororesin C mentioned later.

Here, when the volume resistivity of the composite resin material is XΩ · 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 are expressed by the following formula (1). :
X / Y ⁻¹⁴ ≦ 4 × 10 ⁻¹² (1)
It is preferable to satisfy. When satisfy | filling the said relationship, the volume resistivity of a composite resin material can be reduced efficiently. In addition, since the volume resistivity can be sufficiently reduced with a small amount of carbon nanotubes, it is easy to improve the cleanliness 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, more preferably 10 from the viewpoint of easily reducing the volume resistivity of the composite resin material. ^-13 or less. The lower limit value of the value (X / Y ^-14 ) calculated from the above formula (1) is not particularly limited, but is usually 10 ^-18 or more, preferably 10 ^-16 or more. The said relationship can be achieved by manufacturing a molded object with the manufacturing method mentioned later, or manufacturing a composite resin material using the composite resin particle preferable for reducing volume resistivity efficiently. The volume resistivity measurement method 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 property with a small amount of carbon nanotubes, although the reason is not clear, by using the lining layer containing the composite resin material. Therefore, the composite resin material of the present invention is excellent in cleanliness. Further, for example, even when a molded body produced from the composite resin material of the present invention is used for welding as a part of the lining layer, since the amount of the conductive material present on the weld surface is small, the adhesiveness is reduced. It can be avoided. Furthermore, according to the composite resin material of the present invention, it is easy to maintain the mechanical strength inherent to the resin even when the volume resistivity is in the above-mentioned preferable range.

(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 / 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). It is preferable. The fluororesin A is more preferably selected from the group consisting of polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE), from the viewpoint of easily increasing the conductivity efficiently, and further improving the conductivity efficiently. Of these, modified polytetrafluoroethylene (modified PTFE) is still more preferable from the viewpoints of easy improvement and flexibility and weldability.

  Polytetrafluoroethylene (PTFE) is a tetrafluoroethylene homopolymer.

で表されるテトラフルオロエチレン単位に加えて、例えば式（ＩＩ）：

［式中、Ｘは、炭素数１〜６のパーフルオロアルキル基又は炭素数４〜９のパーフルオロアルコキシアルキル基を表す］
で表されるパーフルオロビニルエーテル単位を含有する化合物であり、式（ＩＩ）で表されるパーフルオロビニルエーテル単位の量は、変性ポリテトラフルオロエチレンの全質量に基づいて０．０１〜１質量％である変性ポリテトラフルオロエチレンが挙げられる。Modified polytetrafluoroethylene (modified PTFE) is derived from the formula (I) derived from tetrafluoroethylene:

In addition to the tetrafluoroethylene unit represented by, for example, the formula (II):

[Wherein X represents a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms]
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. One modified polytetrafluoroethylene is mentioned.

  Examples of X in the formula (II) include a C 1-6 perfluoroalkyl group or a C 4-9 perfluoroalkoxyalkyl group. Examples of the C 1-6 perfluoroalkyl group include a perfluoromethyl group, a perfluoroethyl group, a perfluorobutyl group, a perfluoropropyl group, a perfluorobutyl group, and the like. Examples of the C 4-9 perfluoroalkoxyalkyl group include a perfluoro 2-methoxypropyl group and a perfluoro 2-propoxypropyl group. From the viewpoint of easily improving the thermal stability of the modified PTFE, X is preferably a perfluoropropyl group, a perfluoroethyl group, or a perfluoromethyl group, and more preferably a perfluoropropyl group. The modified PTFE may have one type of perfluorovinyl ether unit represented by the formula (II), or may have two or more types of perfluorovinyl ether 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 the 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, the physical properties close to those of the PTFE resin are easily obtained. Further, when the amount of the perfluorovinyl ether unit represented by the formula (II) is not less than the above lower limit, the flexibility, weldability, and compression creep property are improved more than PTFE. The amount of the perfluorovinyl ether unit is measured, for example, by performing infrared spectroscopic analysis in the range of characteristic absorption of 1040 to 890 cm ⁻¹ . The amount of the 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 even more preferably 320 to 350 ° C. If the melting point is not less than the above lower limit, it is preferable because the moldability is easily improved, and if it is not more than the above upper limit, it is preferable because optimum mechanical characteristics of the resin are easily obtained. The melting point of the modified PTFE is a value determined as the temperature of the heat of fusion peak that can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D4591.

  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, a sample of about 3 mg was heated to 250 ° C. at a rate of 50 ° C./min, held once, and further heated to 380 ° C. at a rate of 10 ° C./min to melt the crystal. After that, it is measured in terms of heat quantity from the peak of the crystallization point measured when the temperature is lowered at a rate of 10 ° C./min.

で表されるテトラフルオロエチレン単位に加えて、例えば式（ＩＩ）：

［式中、Ｘは、炭素数１〜６のパーフルオロアルキル基又は炭素数４〜９のパーフルオロアルコキシアルキル基を表す］
で表されるパーフルオロビニルエーテル単位を含有する化合物であり、式（ＩＩ）で表されるパーフルオロビニルエーテル単位の量が、ＰＦＡの全質量に基づいて１質量％より多い化合物が挙げられる。The tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) is derived from the formula (I) derived from tetrafluoroethylene:

In addition to the tetrafluoroethylene unit represented by, for example, the formula (II):

[Wherein X represents a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms]
And a compound in which the amount of the perfluorovinyl ether 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 preferable descriptions are similarly applied thereto. PFA may have one type of perfluorovinyl ether unit represented by the formula (II), or may have two or more types of perfluorovinyl ether units represented by the 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 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 spectroscopic analysis in the range of characteristic absorption of 1040 to 890 cm ⁻¹ .

  In particular, when the fluororesin is modified PTFE, the melting point is preferably 300 to 380 ° C, more preferably 320 to 380 ° C, and even more preferably 320 to 350 ° C. If the melting point is not less than the above lower limit, it is preferable because the moldability is easily improved, and if it is not more than the above upper limit, it is preferable because optimum mechanical characteristics of the resin are easily obtained. The melting point of the modified PTFE is a value determined as the temperature of the heat of fusion peak that can be measured using a differential scanning calorimeter (DSC) in accordance with ASTM-D4591.

  In particular, when the fluororesin 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, a sample of about 3 mg was heated to 250 ° C. at a rate of 50 ° C./min, held once, and further heated to 380 ° C. at a rate of 10 ° C./min to melt the crystal. After that, it is measured in terms of heat quantity from the peak of the crystallization point measured when the temperature is lowered at a rate of 10 ° C./min.

(carbon nanotube)
A carbon nanotube (hereinafter also referred to as “CNT”) included in the composite resin material has a structure in which one or a plurality of graphene sheets formed of a six-membered ring of carbon atoms are wound in a cylindrical shape. CNT is a single-wall CNT (single wall carbon nanotube) in which one graphene sheet is wound concentrically, or a multi-wall CNT (multi-wall carbon nanotube) in which two or more graphene sheets are wound in a concentric shape It is. The carbon nanomaterials described above may be used alone or in combination. The carbon nanotubes are more preferably multi-walled carbon nanotubes from the viewpoint of being easily combined with the modified PTFE particles and easily reducing the volume resistivity.

(Production method of composite resin material)
A method for producing a composite resin material contained in the lining layer will be described below. It should be noted that the fluororesin A can also be used for a composite resin material containing a fluororesin B and carbon nanotubes that can be contained in a chemical liquid tube, etc. By substituting the resin B or the fluororesin C, the following description applies similarly.

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

  A method for producing composite resin particles in which fluororesin A particles and carbon nanotubes are composited using carbon dioxide in a subcritical or supercritical state will be specifically described below. In addition, the said method is applied similarly 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. Solvents include 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, etc.) , Chlorobenzene, etc.). One kind of solvent may be used, or two or more kinds of solvents may be used in combination. From the viewpoint of easily combining 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 solvent.

  The amount of the solvent contained in the carbon nanotube dispersion is preferably 20,000 to 1, with respect to 100 parts by mass of the carbon nanotube contained in the carbon nanotube dispersion, from the viewpoint of easily dispersing the carbon nanotubes in the solvent. It is 000,000 mass parts, More preferably, it is 30,000-300,000 mass parts, More preferably, it is 50,000-200,000 mass parts.

  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 even more preferably 100 to 200 μm. The average length of the carbon nanotube 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, carbon dioxide catalytic hydrogen reduction, arc discharge method, laser evaporation method, vapor phase growth method such as CVD method, gas phase flow method, carbon monoxide reacts with iron catalyst at high temperature and high pressure, and gas phase The HiPco method, the oil furnace method, etc., which are grown by the above method. Commercially available carbon nanotubes such as “NC7000” manufactured by Nanocyl may be used.

  When carbon nanotubes are dispersed in a solvent, a dispersant may be used for the purpose of enhancing the dispersibility of the carbon nanotubes. Examples of the dispersant include acrylic dispersants, synthetic polymers such as polyvinyl pyrrolidone and polyaniline sulfonic acid, DNA, peptides, and organic amine compounds. One type of dispersant may be used, or two or more types of 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 lower than the molding temperature of the composite resin particles preferred in the present invention. When using a dispersant, the amount of the dispersant contained in the carbon nanotube dispersion may be appropriately selected depending on the types and amounts of the carbon nanotube, the solvent, and the dispersant. For example, the amount of the dispersant used is preferably 100 to 6,000 parts by mass, more preferably 200 to 3,000 parts by mass, and even more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the carbon nanotubes. It is.

  When water is used as the 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 fluororesin A particles in the carbon nanotube dispersion using water as a solvent. Therefore, by mixing an alcohol solvent, the affinity between the fluororesin A particles and the carbon nanotube dispersion can be increased.

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

  When the fluororesin A particles are added to the carbon nanotube dispersion, the carbon nanotubes in the dispersion are gently adsorbed on the surface of the fluororesin A particles. Here, by appropriately adjusting the temperature of the solvent, the dispersion concentration of the carbon nanotubes and the fluororesin A, the addition rate of the fluororesin A, etc., the carbon nanotubes are fluorinated while maintaining a high dispersion state of the carbon nanotubes and the fluororesin A. It can be adsorbed on the particle surface of the resin A. By such a method, the carbon nanotubes can be uniformly dispersed on the surface of the fluororesin A particles even at a low addition concentration. Even when long carbon nanotubes are used, they can be uniformly dispersed on the surface of the fluororesin A particles without impairing their properties. The fluororesin A may be added as it is, or the fluororesin A particles may be added in the form of a dispersion in which the fluororesin A particles are previously dispersed in a solvent.

The fluororesin A particles used for the production of the composite resin particles preferred in the present invention are preferably 5 to 500 μm, more preferably 10 to 250 μm, even more preferably 10 to 100 μm, particularly preferably 10 to 50 μm, and most preferably It has an average particle size of 15-30 μm. When the average particle diameter of the fluororesin A is not more than the above upper limit, the dispersibility of the carbon nanotubes in the molded body (composite resin material) produced from the composite resin particles can be easily improved, and the antistatic property can be improved uniformly and efficiently. It is preferable because it is easy. The average particle diameter of the fluororesin A is preferably not less than the above lower limit from the viewpoint of easy production of the composite resin particles. The average particle diameter of the fluororesin A is a median diameter (D ₅₀ ) that means a particle diameter at an integrated value of 50% in the particle size distribution obtained by the laser diffraction / scattering method, and using a laser diffraction / scattering particle size distribution apparatus. Measured.

The particles of fluororesin A used for the production of the composite resin particles are preferably 0.5 to 9.0 m ² / g, more preferably 0.8 to 4.0 m ² / g, even more as 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 fluororesin A particles and the carbon nanotubes, and being not less than the above lower limit is easy to produce composite resin particles. To preferred. Specifically, the specific surface area of the particles of the fluororesin A is measured by a BET method, which is a general method for measuring the specific surface area, using a specific surface area / pore distribution measuring device which is a constant volume gas adsorption method. The

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

  The production method of the fluororesin A particles having an average particle diameter or specific surface area in the above preferred range is not particularly limited, and the fluororesin A is produced by a conventionally known polymerization method, preferably suspension polymerization, and obtained by the above polymerization. A method of spray-drying a dispersion containing a reactive polymer, a method of mechanically pulverizing the obtained fluororesin A using a pulverizer such as a hammer mill, turbo mill, cutting mill, jet mill, etc., and a fluororesin A obtained And freeze pulverization in which the material is mechanically pulverized at a temperature below room temperature. From the viewpoint of easily obtaining fluororesin A particles having a desired average particle diameter and specific surface area, it is preferable to produce fluororesin A particles using a pulverizer such as a jet mill.

  The fluororesin A particles having an average particle size in the above preferred range may be produced by adjusting the average particle size by a classification process using a sieve or an air flow.

  Next, in the third step, the mixed slurry obtained in the second step is supplied to the pressure vessel, and while maintaining the temperature and pressure at which the carbon dioxide becomes a subcritical or supercritical state in the pressure vessel, the carbon dioxide is specified. Supply at a speed to fill the pressure vessel with carbon dioxide. As carbon dioxide, any of liquefied carbon dioxide, gas-liquid mixed carbon dioxide, and gaseous carbon dioxide may be used. Here, the supercritical state of carbon dioxide refers to a state at a temperature above the critical point and a pressure above the critical point, specifically, at a temperature of 31.1 ° C. or higher and a pressure of 72.8 atm or higher. State. The subcritical state refers to a state where the pressure is higher than the critical point and the temperature is lower than the critical point.

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

  The supply rate of carbon dioxide is preferably 0 with respect to 1 mg of the dispersant contained in the mixed slurry, for example, from the viewpoint of suppressing aggregation of the carbon nanotubes and facilitating the uniform attachment of the carbon nanotubes on the surface of the fluororesin A particles. 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, the carbon dioxide is discharged from the pressure vessel together with the solvent and dispersant dissolved in the carbon dioxide while maintaining the temperature and pressure at which the carbon dioxide is in a subcritical or supercritical state for a predetermined time.

  Next, in the fifth step, an entrainer having a high affinity with the dispersant is added to the pressure vessel while maintaining the state of the fourth step. Thereby, the remaining dispersing agent can be removed efficiently. 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, a similar organic solvent may be used as an entrainer. When water is used as the solvent in the first step, an alcohol solvent is preferably used as the entrainer. The fifth step is an optional step for efficiently removing the dispersant and is not an essential step. For example, it is possible to remove the dispersant by maintaining the fourth step without adding an entrainer.

  Next, in the sixth step, by reducing the pressure in the pressure vessel, carbon dioxide in the pressure vessel is removed, and composite resin particles can be obtained. Here, depending on the carbon dioxide removal method, carbon dioxide and a solvent may remain in the composite resin particles. Therefore, the remaining carbon dioxide and solvent can be efficiently removed by subjecting the resulting composite resin particles to vacuum or heating.

(Manufacturing method of the tank of the present invention)
The lining layer provided on the inner surface of the tank of the present invention includes at least a composite resin material containing the fluororesin A and carbon nanotubes. The lining layer containing the composite resin material may be composed of, for example, a lining sheet containing the composite resin material, or a laminate of the lining sheet containing the composite resin material and another sheet (for example, glass cloth). There may be. The lining sheet containing the composite resin material may be produced, for example, by melting the composite resin particles and molding the composite resin particles into a sheet shape, or by forming the composite resin particles, for example, by compression molding (compression molding). A molded body may be obtained, or a molded body obtained by the compression molding may be cut into a sheet, for example. From the viewpoint of easily increasing the conductivity of the lining sheet, a composite resin particle is compression molded to obtain a sheet-shaped molded body, or the molded body obtained by the compression molding is cut into a sheet shape, for example, to form a composite resin It is preferable to produce a lining sheet containing the material. The reason why it is easy to efficiently increase the conductivity of the lining sheet by the above preferable manufacturing method is not clear, but is considered to be due to the following mechanism. In addition, the tank of this invention is not limited to the mechanism mentioned later at all. In the composite resin particles, as described above, carbon nanotubes are present on at least the surface and / or the surface layer of the fluororesin, and these carbon nanotubes are considered to form a conductive network. The conductive network of carbon nanotubes is considered to be easily cut when the carbon nanotubes are cut or aggregated by an external force applied to the composite resin particles. Therefore, when manufacturing a lining sheet from composite resin particles, it is considered that the conductivity of the lining sheet can be efficiently increased by using a method in which the network is not cut as much as possible. A method of obtaining a sheet-like molded body by compression molding composite resin particles, and a method of producing a lining sheet by cutting out the composite resin material obtained by compression molding into, for example, a sheet form include melt extrusion of composite resin particles. This makes it easier to suppress the cutting of the network of carbon nanotubes than the method of manufacturing the lining sheet, and as a result, it is considered that the conductivity of the lining sheet is easily improved.

Therefore, the present invention provides a composite resin material obtained by compression molding composite resin particles containing fluororesin A and carbon nanotubes (for example, composite resin particles having an average particle diameter of 5 μm or more and 500 μm or less). A tank comprising at least a portion can be provided.
The composite resin material contained in at least a part of the lining layer is obtained by compression molding composite resin particles containing fluororesin A and carbon nanotubes (for example, composite resin particles having an average particle diameter of 5 μm to 500 μm). The tank of an embodiment which is the compression-molded body obtained can be provided.

From the viewpoint of easily producing a lining sheet through compression molding of composite resin particles and easily improving the conductivity of the lining sheet, as a fluororesin contained in the composite resin material, 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 polyvinyl fluoride (PVF). Fluorine resin contained in the composite resin material is 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.
In addition, although the said manufacturing method was demonstrated to the case where the sheet | seat is manufactured from composite resin material as an example, when manufacturing a chemical | medical solution tube, a hollow spherical molded object, etc., these composite resin particle | grains are melt-extruded and these are carried out. A molded body may be manufactured, composite resin particles may be compression molded to obtain these molded bodies, or these molded bodies may be manufactured by cutting from a molded body obtained by the compression molding. Good. Here, as described above, it is easy to suppress the cutting of the network of carbon nanotubes, and as a result, from the viewpoint of easily enhancing the conductivity of the chemical solution tube, etc., through compression molding the composite resin particles, It is preferable to produce a chemical liquid tube and a hollow spherical molded body.
From the viewpoint of being suitable for such a production method, the fluororesin B and / or C contained in the composite resin material is, for example, polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene / 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). The group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA) as the fluororesin B and / or C contained in the composite resin material Is preferably selected from.

  When the fluororesin is a PTFE resin or a modified PTFE resin, a method for producing a composite resin material by compression molding composite resin particles includes a method of subjecting a preformed product obtained by compressing composite resin particles to a firing treatment. It is done. The preformed body before firing is produced by subjecting the composite resin particles to an appropriate pretreatment (for example, preliminary drying, granulation, etc.) as necessary, and then placing the composite resin particles into a mold for compression. As pressurization at the time of compressing to produce a preform before firing, it is preferably 0.1 to 100 MPa, more preferably 1 to 80 MPa, and even more preferably 5 to 50 MPa.

The preformed body obtained as described above is fired at a temperature equal to or higher than the melting point of the resin contained in the composite resin particles, for example, 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 dimensions of the preform before firing and the firing time. The preformed body before firing is placed in a firing furnace and preferably fired at the firing temperature to produce a formed body.
The obtained molded body may be used as it is as a lining sheet or the like (for example, a rod-shaped molded body, a stirring bar, etc., which will be described later). You may produce a hollow spherical molded object, a rod-shaped molded object, a stirring bar, etc.).

When the fluororesin 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 producing a composite resin material by compression molding of composite resin particles As for hot air which performed suitable pretreatments, such as preliminary drying, according to the size of a forming object, and carried out pretreatment, a mold was set at 200 ° C or more, preferably 200-400 ° C, more preferably 210-380 ° 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, take out the mold from the electric furnace, and after cooling the mold to near room temperature while compressing with a surface pressure of 25 kg / cm ² or more, preferably 50 kg / cm ² or more using a hydraulic press. A molded body (resin material) of composite resin particles was obtained.
The obtained molded body may be used as it is as a lining sheet or the like (for example, a rod-shaped molded body, a stirring bar, etc., which will be described later). You may produce a hollow spherical molded object, a rod-shaped molded object, a stirring bar, etc.).

  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 fluororesin sheet, or a sheet in which a glass cloth is laminated on one side of a fluororesin sheet, the shape of the inner surface of the tank outer can And a method of bonding the cut sheet to the tank inner surface using an epoxy adhesive or the like. The gap between the sheets bonded to the inner surface of the tank may be welded using, for example, a rod-shaped welding material having a circular or triangular cross section with a diameter of 2 to 5 mm, preferably a PFA material.

<Chemical solution tube>
The tank of this invention can be equipped with the chemical | medical solution tube connected with the inside and the exterior of a tank. Examples of the chemical solution pipe include a chemical solution input tube for supplying the chemical solution and a chemical solution discharge tube for discharging the chemical solution. When the chemical solution passes through the chemical solution tube, friction is generated between the inner surface of the chemical solution tube and the chemical solution, and the chemical solution is easily charged by generating static electricity. Therefore, from the viewpoint of efficiently preventing the chemical solution from being charged, the chemical solution tube has a lining layer containing a composite resin material containing the fluororesin B and the carbon nanotubes on at least a part of the inner surface of the chemical solution tube, and / or The chemical liquid tube is preferably a molded body of a composite resin material containing fluororesin B and carbon nanotubes. Here, the fluororesin 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 / perfluoroalkyl vinyl ether copolymer (PFA). The fluororesin B is more preferably selected from the group consisting of polytetrafluoroethylene (PTFE) and modified polytetrafluoroethylene (modified PTFE) from the viewpoint of easily increasing the conductivity efficiently, and further improving the conductivity efficiently. Of these, modified polytetrafluoroethylene (modified PTFE) is still more preferable from the viewpoints of easy improvement and flexibility and weldability.

  The composite resin material constituting the chemical liquid tube or the composite resin material contained in the lining layer provided on the inner surface of the chemical liquid tube is a molded body of composite resin particles in which the fluororesin B and the carbon nanotube are combined. The composite resin particles are a material in which the fluororesin B particles and the carbon nanotubes are combined, and the carbon nanotubes exist on at least the surface and / or the surface layer of the fluororesin B particles. For example, at least a part of the carbon nanotube is supported or buried on the surface of the fluororesin B particles. The carbon nanotubes may be carried by adhering to the surface of the fluororesin B particles, may be partly buried and carried, or may be completely buried in the surface layer of the fluororesin B particles. Also good. In the composite resin material that is a molded body of such composite resin particles, at least a part of the composite resin particles may be contained while maintaining the particle shape, or the composite resin particles are integrated to form a composite resin material. You may do it.

  The description of the composite resin material containing the fluororesin A and the carbon nanotube is similarly applied to the composite resin material constituting the chemical liquid tube or the composite resin material included in the lining layer provided on the inner surface of the chemical liquid tube. For the fluororesin B, the description for the fluororesin A applies similarly, and for the carbon nanotube, the description 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 fluororesin B and carbon nanotubes on at least a part of the inner surface of the chemical liquid tube, for example, a composite resin material sheet is prepared by melt extrusion and compression molding And the method of bonding this to the inner surface of a chemical | medical solution pipe | tube, The method of cutting the molded object of a composite resin particle into a pipe shape, and bonding this to the inner surface of a chemical | medical solution pipe | tube is mentioned. Regarding the method for producing a sheet of composite resin material, the description of the method for producing a lining sheet in the above applies similarly. As a method of bonding, when the chemical solution tube is made of metal, it is bonded to the inner surface of the chemical solution tube using an adhesive or the like, or when the chemical solution tube is made of resin, it is welded to the inner surface of the chemical solution tube. A method is mentioned.

<Nozzle>
The present invention comprises a chemical solution pipe connected to the inside and the outside of the tank,
The chemical liquid pipe includes a chemical liquid input pipe for putting the chemical liquid into the tank,
The chemical injection pipe has a nozzle at its end (or tip),
The nozzle has a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the nozzle, and / or is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
Fluororesin B is composed of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE) and 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:

In this specification, the “nozzle” means a pipe-like mechanical part used to determine the direction of fluid flow, and controls the characteristics of the fluid such as the flow rate, flow rate, direction and pressure of the flowing material. There is no particular limitation as long as it is a component that is used and is usually understood as a nozzle.
The nozzle can be selected from the group consisting of, for example, a spray nozzle, a rotary nozzle, a straight nozzle, and a shower nozzle.
Regarding the lining layer of the nozzle and the fluororesin B, those descriptions relating to the chemical liquid tube can be referred to.

<Hollow spherical molded body>
The tank of the present invention may have a hollow spherical molded body that at least partially contains a composite resin material containing fluororesin C and carbon nanotubes. Such a hollow spherical molded body is usually used for removing static electricity charged on the chemical liquid floating on the liquid surface of the chemical liquid charged in the tank of the present invention. In particular, when transporting or the like in a state where the chemical solution is stored in the tank of the present invention, the chemical solution vibrates, causing friction with the tank inner surface, generating static electricity and easily charging the chemical solution. By using a hollow spherical molded body that at least partially contains the composite resin material, static electricity generated by friction during transportation or the like can be efficiently removed. The fluororesin C is composed of 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) Are preferably selected from the group consisting of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), and tetrafluoroethylene / perfluoroalkyl vinyl ether. It is more preferably selected from the group consisting of alcohol copolymer (PFA). The fluororesin C is preferably selected from the group consisting of modified PTFE, PTFE and PFA from the viewpoint of molding processability, and more preferably from the group consisting of PTFE and modified PTFE from the viewpoint of easily improving the conductivity. From the viewpoint of being easily selected and enhancing the conductivity efficiently, and from the viewpoint of flexibility and weldability, more preferred is modified PTFE.

  The composite resin material at least partially contained in the hollow spherical molded body is a molded body of composite resin particles in which a fluororesin C and a carbon nanotube are combined. The composite resin particle is a material in which the fluororesin C particles and the carbon nanotubes are combined, and the carbon nanotubes exist on at least the surface and / or the surface layer of the fluororesin C particles. For example, at least a part of the carbon nanotubes are supported or buried on the surface of the fluororesin C particles. The carbon nanotubes may be carried by adhering to the surface of the fluororesin C particles, or may be partly buried and carried, or may be completely buried in the surface layer of the fluororesin C particles. Also good.

  The description of the composite resin material containing the fluororesin A and the carbon nanotubes applies to the composite resin material at least partially contained in the hollow spherical molded body. Regarding the fluororesin C, the description of the fluororesin A applies similarly. The fluororesin C may be the same resin as the fluororesin A or B, or may be a different resin. The description regarding the carbon nanotube is similarly applied to the carbon nanotube.

  The embodiment in which the hollow spherical molded body includes at least a part of the composite resin material is acceptable as long as at least a part of the hollow spherical molded body includes the composite resin material containing the fluororesin C and the carbon nanotubes. An embodiment in which the lining material containing the composite resin material is lined on at least a part of the surface of the hollow spherical molded body, and the hollow spherical molded body is a molded body composed of a composite resin material containing a fluororesin C and a carbon nanotube. Embodiments and the like are included.

<Bar-shaped compact>
In an embodiment of the present invention, there is provided a tank further having a rod-shaped molded body at least partially containing a composite resin material containing a fluororesin C and carbon nanotubes.
Such a rod-shaped molded body is usually used for removing static electricity charged in the chemical liquid from the liquid surface of the chemical liquid charged in the tank of the present invention and charged in the chemical liquid. In particular, when transporting or the like in a state where the chemical solution is stored in the tank of the present invention, the chemical solution vibrates, causing friction with the tank inner surface, generating static electricity and easily charging the chemical solution. By using a rod-shaped molded body that at least partially contains the composite resin material, static electricity generated by friction during transportation or the like can be efficiently removed. The dimensions (diameter and length) of the rod-shaped molded body, the cross-sectional shape (circular, hexagonal, etc.), conductivity, etc. can be appropriately selected.

The fluororesin C is composed of 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) Are preferably selected from the group consisting of:
For the “fluororesin C”, “carbon nanotube”, “composite resin material” and the like, the above description can be referred to as appropriate.

The rod-shaped molded body can be connected to a ground wire. The rod-shaped molded body can be connected to the ground wire for more efficient charge removal.
A holder (also referred to as “rod-shaped molded body holder”) for providing a rod-shaped molded body in the tank can be used. The rod-shaped molded body holder 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 rod-shaped molded body. The dimensions of the rod-shaped molded body holder can be appropriately selected according to the dimensions of the rod-shaped molded body and the dimensions of the tank holes.

<Stir bar>
In an embodiment of the present invention, there is provided a tank further having a stirring bar at least partially containing a composite resin material containing a fluororesin C and carbon nanotubes.
Such a stirring bar is usually used to stir the chemical liquid from the liquid level of the chemical liquid charged into the tank of the present invention, and can be generated in the chemical liquid during the stirring. Used to remove static electricity from the liquid. The dimensions (diameter and length) of the stirring rod, the shape of the cross section (circular, hexagonal, etc.), conductivity, etc. can be selected as appropriate.

The fluororesin C is composed of 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) Are preferably selected from the group consisting of:
For the “fluororesin C”, “carbon nanotube”, “composite resin material” and the like, the above description can be referred to as appropriate.

The stirring rod may have a propeller (or stirring blade) that at least partially includes a composite resin material including the fluororesin C and the carbon nanotubes. The stir bar and propeller may be integral, but the stir bar may be separable from the propeller. When the stirring bar has a propeller, the chemical solution can be stirred more efficiently. The size (size) and shape (crescent shape, etc.), conductivity, etc. of the stirring bar can be selected as appropriate.
For the “fluorine resin C”, “carbon nanotube”, and “composite resin material” related to the propeller, the above description can be referred to as appropriate.
When the stirrer has a propeller, both the stirrer and the propeller need only exhibit the desired charge removal performance.

The stir bar can be connected to a ground wire as appropriate. By connecting the stirring bar to the ground wire, it is possible to remove electricity more efficiently.
An adapter (also referred to as “stirring bar adapter”) for providing a stirring bar in the tank can be used. The stir bar adapter is generally cylindrical and the outer shape corresponds to the size of the tank hole and the inner shape corresponds to the outer shape of the stir bar. The size of the stirring rod adapter can be selected as appropriate according to the size of the stirring rod and the size of the tank hole.

<Tank>
Although the use of the tank of the present invention is not particularly limited, for example, a tank containing a chemical solution as a content is exemplified, and specifically, a chemical solution supply tank, a chemical solution storage tank, and / or a chemical solution transport tank. The chemical liquid supply tank is a tank used in a system for supplying a chemical liquid, which will be described later, for example. The chemical liquid supply tank is used for the chemical liquid 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 tube and a chemical solution discharge tube, and the chemical solution can be charged and discharged simultaneously. The chemical solution storage tank is a tank intended to store a chemical solution inside. Therefore, the chemical solution storage tank only needs to have at least one opening. The chemical solution transport tank is a tank that is transported in a state where the chemical solution is stored as the contents. When the chemical solution is transported, static electricity is likely to be generated by the vibration of the chemical solution, but static electricity can be removed by using the tank of the present invention. The tank of the present invention may be a tank for the purpose of supplying, storing or transporting a chemical solution, or a tank having two or more of these purposes.

<Chemical solution>
Examples of the chemical solution stored in the tank of the present invention include hydrochloric acid, nitric acid, hydrofluoric acid, hydrogen peroxide solution, sulfuric acid and other aqueous solutions, isopropyl alcohol (IPA), ethanol, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), and the like. An organic solvent and water are mentioned. The chemical solution contained in the tank is preferably an organic solvent. The organic solvent is a chemical solution used in, for example, semiconductor manufacturing. In the semiconductor manufacturing application, even if the chemical solution is contaminated by static electricity or a small amount of contaminants, the advantage of the tank of the present invention Is easier to demonstrate.

<Chemical solution>
If the chemical | medical solution accommodated in the tank of embodiment of this invention is a chemical | medical solution which can be accommodated, it will not restrict | limit in particular. The chemical liquid 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.
Examples of the organic solvent include isopropyl alcohol (IPA), ethanol, acetone, tetrahydrofuran (THF), methyl ethyl ketone (MEK), and the like.
The combustible liquid includes, 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, aqueous ammonia.
The neutral liquid includes, for example, ozone water, so-called water, ultrapure water, pure water, deionized water, ion exchange water, distilled water, and the like.
The aqueous solution contains, for example, hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, ammonia water, hydrogen peroxide water, ozone water and the like.
Examples of the conductive liquid include hydrochloric acid, nitric acid, hydrofluoric acid, sulfuric acid, hydrogen peroxide water, ammonia water, so-called water, ion exchange water, deionized water, and pure water.
The chemical solution contained in the tank may be an organic solvent, for example. The organic solvent is a chemical solution used in, for example, semiconductor manufacturing. In the semiconductor manufacturing application, even if the chemical solution is contaminated by static electricity or a small amount of contaminants, the advantage of the tank of the present invention Is easier to demonstrate.
The chemical liquid 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 supplying a chemical solution using the tank of the present invention. The use of the chemical solution supply system of the present invention is not particularly limited, but from the viewpoint of easily utilizing the advantages of the chemical solution supply system of the present invention that the contamination of the chemical solution that is the content is reduced and the cleanness is high, It is preferable that the chemical solution supply system used in the above. In a preferred embodiment of the present invention, the chemical solution supply system of the present invention includes a chemical solution transport tank, a chemical solution storage tank of a semiconductor factory line, a pump for pumping the chemical solution from the chemical solution transport tank to the chemical solution storage tank, and each line from the chemical solution storage tank. The tank of the present invention may be used as the chemical solution transport tank and / or the chemical solution storage tank. According to the preferable chemical supply system of the present invention of this aspect, specifically, a chemical transport tank (for example, an ISO tank) is transported to a semiconductor factory by a tank lorry, and is pumped from the chemical transport tank to the chemical storage tank in the semiconductor factory line. Thus, a series of chemical liquid supply can be performed in which the chemical liquid is pumped and the chemical liquid is fed from the chemical liquid storage tank to each line. In addition to the tank of the present invention, the chemical solution supply system of the present invention is a device for supplying the contents of the tank of the present invention, for example, a compressed gas source or a chemical solution for sending an inert gas such as nitrogen gas under high pressure. A supply pump may be provided, or a filter for filtering the chemical solution to remove impurities and the like may be provided.

<Molded body>
The present invention can provide a molded body,
It can be used for tanks where chemicals are handled.
The tank may have a layer of lining sheets.
The molded body may be a compression molded body that can be obtained by compression molding composite resin particles containing a fluororesin and a carbon nanotube. The fluororesin can be, for example, any of fluororesins A to C described in this specification. The description of this specification regarding 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, the fluororesins A to C, and the carbon nanotubes of the molded body.
The molded body that can be used for the tank can include, for example, the above-described lining sheet, chemical solution tube, hollow molded body, rod-shaped molded body, rod-shaped molded body holder, stirring rod, stirring blade, stirring rod 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 “up”, “down”, “left”, “right”, and other terms including them will be used. The purpose of using these terms is to facilitate understanding of the embodiments through the drawings. Therefore, these terms do not necessarily indicate the direction in which the embodiments of the present invention are actually used, and the technical scope of the invention described in the claims is not limited by these terms.

(First embodiment)
The tank according to the first embodiment of the present invention includes the tank according to the first embodiment A and the first embodiment B.
As shown in FIG. 1A, the tank according to the first embodiment A of the present invention includes 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 supplying a chemical solution into the tank. The tube 3 has a chemical solution discharge tube 4 for discharging the chemical solution outside the tank, and a hollow spherical molded body 5 for removing static electricity that floats on the liquid surface of the chemical solution and is charged in 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 fluororesin sheet or a lining sheet in which a glass cloth is laminated on one side of a fluororesin sheet can be used. The method of cutting out according to the shape of 1 inner surface, and bonding the cut-out sheet | seat on 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 using, for example, a rod-shaped welding material having a circular or triangular cross section with a diameter of 2 to 5 mm, preferably a PFA material. The tank in the first embodiment A has a chemical solution input tube 3, a chemical solution discharge tube 4, and a hollow spherical molded body 5. However, these are not essential components for the tank of the present invention, and at least one of them is provided. You may have, and it is not necessary to have any of these.

  In the tank of 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, the introduced chemical solution is first in contact with the inner surface of the tank outer can ( It is preferable that the lining layer including the lining sheet 8 provided in the liquid contact portion 7) in FIG. 1A includes a composite resin material including the fluororesin A and the carbon nanotube, and the lining sheet includes the fluororesin A and the carbon nanotube. More preferably, it is a molded body composed of a composite resin material. From the viewpoint of further improving the antistatic property, the lining layer including the lining sheet 10 (including the lining sheet 8) provided on the tank bottom 9 preferably includes a composite resin material including the fluororesin A and the carbon nanotube. More preferably, the lining sheet is a molded body made of a composite resin material containing fluororesin A and carbon nanotubes. A ground wire 11 is connected to the lining sheet 8 or the lining sheet 10, and static electricity that has flowed from the chemical into the lining sheet 8 or 10 having a low volume resistivity flows into the ground or the like through the ground wire 11 and is removed. The lining sheet containing the composite resin material containing the fluororesin A and the carbon nanotube is obtained by, for example, thinly cutting the composite resin particle molded body produced as described above into a sheet, or extruding the composite resin particles into a sheet. Manufactured by molding. The lining sheet containing the composite resin material thus obtained is lined in the same manner as the method for providing the lining layer 2 on the inner surface of the tank in the liquid contact part 7 or the tank bottom part 9, thereby improving the efficiency of the chemical liquid 6. Static charge removal is possible.

  The tank of 1st Embodiment A of this invention is equipped with the chemical | medical solution injection | pouring pipe | tube 3 and the chemical | medical solution discharge pipe 4 which were provided in the tank upper part, as shown to FIG. 1A. The discharge port of the chemical solution input tube 3 is provided at a position higher than the liquid level 12 of the chemical solution 6, and the suction port of the chemical solution discharge tube 4 is provided at a position near the bottom of the tank. The tank in the first embodiment A has the chemical solution input tube 3 and the chemical solution discharge tube 4 at the above positions, but when the tank includes the chemical solution input tube 3 and / or the chemical solution discharge tube 4, these positions are particularly limited. Alternatively, a chemical solution input pipe may be provided at the top of the tank and a chemical discharge tube may be provided at the bottom of the tank, or these pipes may be located on the side of the tank. The position of the discharge port of the chemical solution input tube and the suction port of the chemical solution discharge tube may be set as appropriate. The tank of the first embodiment A is not shown in FIG. 1A, but other general configurations of the tank, for example, additional chemical pipes, safety valves, and the like provided at arbitrary positions such as an upper part, a lateral part, and a lower part, A vent may be further provided.

  Lining layers 31 and 41 containing a composite resin material containing a fluororesin B and a carbon nanotube are provided on the inner surfaces of the chemical solution input tube 3 and the chemical solution discharge tube 4, respectively. The chemical solution input tube 3 and the chemical solution discharge tube 4 in which the lining layers 31 and 41 containing the composite resin material are provided on the inner surface of the tube, for example, are obtained by cutting a molded body of composite resin particles into a tubular shape, It is manufactured by a method of bonding to the inner surface of the pipe or a method of welding to the inner surface of the resin pipe. The lining layers 31 and 41 of the chemical solution input tube 3 and the chemical solution discharge tube 4 are electrically connected to the ground wire 11, respectively. The static electricity charged when passing through the chemical solution input tube 3 and the chemical solution discharge tube 4 is It is removed via the ground wire 11. Each of the lining layers 31 and 41 may have a ground wire different from the ground wire 11. In addition, although the chemical | medical solution injection | pouring pipe | tube 3 and the chemical | medical solution discharge pipe 4 which are shown by FIG. 1A are provided with the lining layer containing the composite resin material containing fluororesin B and a carbon nanotube in a part of inner surface, these pipe | tubes are A molded body composed of a composite resin material containing fluororesin B and carbon nanotubes may be used, and a tube obtained by cutting a molded body of composite resin particles into a tubular shape is used as it is as a chemical solution input tube and a chemical solution discharge tube. Also good.

  The tank of the first embodiment A of the present invention has a hollow spherical molded body 5 as shown in FIG. 1A. The number of hollow spherical molded bodies 5 is not particularly limited, and may be appropriately selected according to the size of each molded body 5 and the required charging effect. A ground wire 13 is connected to each of the molded bodies 5, and the ground wire exits from the lid body 14 to the outside of the tank and is connected to the ground. Static electricity charged in the chemical solution 6 flows into the molded body 5 having a low volume resistivity and is removed through the ground wire 13. The hollow spherical molded body 5 is formed by thinly cutting a composite resin material molded body containing a fluororesin C and carbon nanotubes, or by sticking a sheet produced by extruding the composite resin material into a sheet into a hollow spherical shape. You may manufacture by combining. Although the tank of this embodiment has the cover body 14, the cover body 14 is not essential. In the first embodiment A, the ground wire 13 extends from the lid body 14, but the ground wire 13 may be electrically connected to the ground wire 11.

The tank of the first embodiment B of the present invention is similar in shape to the tank of the first embodiment A, and is provided on the tank outer can 1 and the inner surface of the tank outer can 1 as shown in FIG. 1B. The lining layer 2, the chemical solution input tube 3 for supplying the chemical solution into the tank, the nozzle 36 provided at the end of the chemical solution input tube 3, the chemical solution discharge tube 4 for discharging the chemical solution outside the tank, the static electricity in the chemical solution There are a rod-shaped molded body 52 inserted in the chemical solution and a stirring rod 56 for stirring 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 method similar to the method described in the tank of the first embodiment A can be used.
The tank according to the first embodiment B includes the chemical liquid input pipe 3, the chemical liquid discharge pipe 4, the rod-shaped molded body 52, and the stirring bar 56, but these are not essential components of the tank of the present invention, and at least of these. One may be present, or none of these may be present.

  The tank according to the first embodiment B of the present invention also includes 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. 11. 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.

As shown in FIG. 1B, the tank according to the first embodiment B of the present invention also includes a chemical liquid input pipe 3 and a chemical liquid discharge pipe 4 provided at the upper part of the tank. For the chemical solution input tube 3 and the chemical solution discharge tube 4, the description related to the tank of the first embodiment A can be referred to.
The tank of the first embodiment B is not shown in FIG. 1B, but other general configurations of the tank, for example, additional chemical pipes, safety valves, and the like provided at arbitrary positions such as an upper part, a lateral part, and a lower part, A vent may be further provided.

The tank according to the first embodiment B of the present invention has a nozzle 36 provided at the end of the chemical liquid supply tube 3 as shown in FIG. 1B. The dimensions of the nozzle 36 are not particularly limited, and the length, thickness, cross-sectional shape, and the like may be appropriately selected according to the required charging effect. A ground wire may be connected to the nozzle 36, but the chemical solution feeding pipe 3 can function as a ground wire. It is preferable because the static electricity of the chemical liquid 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 fluororesin B and the carbon nanotubes into a cylindrical shape, or extruding the composite resin material into a cylindrical shape.

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

The tank of the first embodiment B of the present invention can have a stirring bar 56 as shown in FIG. 1B. The dimensions of the stirring rod 56 are not particularly limited, and the length, thickness, cross-sectional shape, and the like 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 integrated or separable. A ground wire (not shown) is brought into contact with the stirring rod 56 and can be connected to the ground. The static electricity of the chemical solution 6 flows into the stirring bar 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 a composite resin material containing the fluororesin C and the carbon nanotubes into a rod shape, or extruding the composite resin material into a rod shape.
The propeller 57 includes at least a part of a composite resin material containing a fluororesin C and carbon nanotubes, and can be manufactured by cutting a molded body of the composite resin material containing the fluororesin C and carbon nanotubes into a propeller shape.
The tank of the embodiment B of the present invention has a stirring bar adapter 58 (hereinafter also referred to as “stirring bar adapter”) and preferably holds the stirring bar 56 by the adapter 58. Not required. The outer dimension of the stirring rod adapter 58 can be appropriately selected in consideration of the dimension of the hole provided in the tank.
The stirring rod adapter may be manufactured by cutting a molded body of the composite resin material containing the fluororesin C and the carbon nanotube into a cylindrical shape, or extruding the composite resin material into a cylindrical shape. Further, a ground wire may be connected to the stirring rod adapter.

(Second Embodiment)
As shown in FIG. 2, the tank according to the second embodiment of the present invention includes a tank outer can 1, a lining layer 2 provided on the inner surface of the tank outer can 1, and a chemical for charging or discharging the chemical into the tank. The tube 15 has a hollow spherical shaped body 5 for removing static electricity floating on the liquid surface of the chemical liquid and charged in the chemical liquid, and the chemical liquid 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 fluororesin sheet or a lining sheet in which a glass cloth is laminated on one side of a fluororesin sheet can be used. The method of cutting out according to the shape of 1 inner surface, and bonding the cut-out sheet | seat on 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 using, for example, a rod-shaped welding material having a circular or triangular cross section with a diameter of 2 to 5 mm, preferably a PFA material. The tank in the present embodiment includes the chemical liquid tube 15 and the hollow spherical molded body 5, but these are not essential components of the tank of the present invention, and may include at least one of these, None of these may be present.

  In the tank of 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, the introduced chemical solution is first in contact with the inner surface of the tank outer can (see FIG. It is preferable that the lining layer including the lining sheet 8 provided in the liquid contact portion 7) in 2 includes the composite resin material including the fluororesin A and the carbon nanotube, and the lining sheet includes the fluororesin A and the carbon nanotube. A molded body of a composite resin material is more preferable. From the viewpoint of further improving the antistatic property, the lining layer including the lining sheet 10 (including the lining sheet 8) provided on the tank bottom 9 preferably includes a composite resin material including the fluororesin A and the carbon nanotube. More preferably, the lining sheet is a molded body of a composite resin material containing fluororesin A and carbon nanotubes. A ground wire 11 is connected to the lining sheet 8 or the lining lining sheet 10, and 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 ground wire 11 and is removed. . For a lining sheet containing a composite resin material containing fluororesin A and carbon nanotubes, for example, the composite resin material produced as described above is thinly cut into a sheet, or the composite resin material is extruded into a sheet shape. Manufactured by molding. The lining sheet containing the composite resin material thus obtained is lined in the same manner as the method for providing the lining layer 2 on the inner surface of the tank in the liquid contact part 7 or the tank bottom part 9, thereby improving the efficiency of the chemical liquid 6. Static charge removal is possible.

  The tank of the second embodiment of the present invention has a chemical liquid tube 15 as shown in FIG. A lining layer 151 including a composite resin material including fluororesin B and carbon nanotubes is provided on the inner surface of the chemical liquid tube 15. The chemical liquid pipe 15 provided with the lining layer 151 containing the composite resin material on the inner surface of the pipe is, for example, a method in which a molded body of the composite resin material is cut into a tubular shape and this is joined to the inner surface of a metal pipe, or It is manufactured by a method of welding to the inner surface of a resin pipe. The lining layer 151 of the chemical liquid tube 15 is electrically connected to the ground wire 11, and the static electricity charged when passing through the chemical liquid 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. 2 is provided with a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on a part of the inner surface thereof, the composite resin material containing fluororesin B and carbon nanotubes is provided. A molded body of a composite resin material may be used as it is as a chemical liquid tube.

  The tank of the second embodiment of the present invention has a hollow spherical shaped body 5 as shown in FIG. The number of hollow spherical molded bodies 5 is not particularly limited, and may be appropriately selected according to the size of each molded body 5 and the required charging effect. A ground wire 13 is connected to each molded body 5, and the ground wire goes out of the tank from the lid body 14 and is connected to the outside. Static electricity charged in the chemical solution 6 flows into the molded body 5 having a low volume resistivity and is removed through the ground wire 13. The hollow spherical molded body 5 is formed by thinly cutting a composite resin material molded body containing a fluororesin C and carbon nanotubes, or by sticking a sheet produced by extruding the composite resin material into a sheet into a hollow spherical shape. You may manufacture by combining. Although the tank of this embodiment has the cover body 14, the cover body 14 is not essential. In the present embodiment, the ground wire 13 extends from the lid body 14, but the ground wire 13 may be electrically connected to the ground wire 11.

  The tank of 2nd Embodiment of this invention has a shape as shown in FIG. 2, and is used as a tank for chemical | medical solution conveyance, for example. Specifically, it may be a tank container known as an ISO tank. A tank container is a container used when cargo is liquid in cargo transportation such as ships, railroads, and automobiles. In particular, when a chemical solution is transported in a tank container, the liquid inside the tank vibrates due to vibration during transportation, and friction may be generated by the vibration, and the chemical solution may be charged. According to the tank of this embodiment, static electricity generated in the chemical solution can be efficiently removed. The tank of the present embodiment is not shown in FIG. 2, but other general configurations of the tank, for example, additional chemical pipes, safety valves, and vents provided at arbitrary positions such as an upper part, a lateral part, and a lower part Etc. may further be included. In addition, the tank transporting means of the present embodiment is not particularly limited, and may be transported by transporting vehicles such as tank trucks and freight trains, ships, and the like.

(Third embodiment)
Next, an embodiment of the supply system of the present invention is shown in FIG. 3 as a third embodiment. As shown in FIG. 3, the supply system of the present invention in this embodiment includes a chemical solution transport tank 16 and a chemical solution supply tank 22, and 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, the tank of the embodiment shown in FIG. The chemical solution transport tank 16 contains the chemical solution as a content, and is loaded on the transport vehicle 17 and transported. The chemical liquid transported in the chemical liquid 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 and the connecting pipes 18 and 21 in the pass box 19 in, for example, a semiconductor manufacturing factory. The chemical solution in the chemical solution transport tank 16 passes through the connection pipe 18, is connected by the coupler 20, and is conveyed to the chemical solution supply tank 22 through the connection pipe 21. A pump 24 is connected to the chemical liquid supply tank 22, and the chemical liquid carried from the chemical liquid supply tank 22 through the connection pipes 23 and 25 passes through the filter 26, thereby being finely contained in the chemical liquid. Contaminants are removed and transported to each point of use 28 via connecting tube 27. In the third embodiment shown in FIG. 3, the liquid is supplied using the pump 24, but the position of the pump 24 is not limited to the illustrated location. A plurality of pumps 24 may be used. Further, the chemical solution may be supplied by a pressurizing system or the like without using a pump.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these do not limit the scope of the present invention.

<Measurement of average particle diameter _{D 50>}
The average particle size of the fluororesin particles and the composite resin particles used for the production of the composite resin particles was measured with a laser diffraction / scattering particle size distribution device (“MT3300II” manufactured by Nikkiso), and the average particle size D ₅₀ was calculated. Obtained.

<Measurement of specific surface area>
The measurement of the specific surface area of the fluororesin particles and the composite resin particles used for the production of the composite resin particles was performed using a specific surface area / pore distribution measuring device (BELSORP-mini II manufactured by Nippon Bell) according to JIS Z8830.

<Measurement of heat of crystallization>
The heat of crystallization of the fluororesin particles used for the production of the composite resin particles was measured using a differential scanning calorimeter (“DSC-50” manufactured by Shimadzu Corporation). A sample of 3 mg was heated to 250 ° C. at a rate of 50 ° C./min, held once, and further heated to 380 ° C. at a rate of 10 ° C./min, and then the crystals were melted. It was measured by converting into a calorie from the peak of the crystallization point measured when the temperature was lowered at a rate of ° C / min.

<Measurement of melting point>
The melting point of the fluororesin particles used for the production of the composite resin particles was determined as the temperature of the melting heat peak that can be measured using a differential scanning calorimeter (DSC) according to ASTM-D4591.

<Production of composite resin material>
The composite resin particles obtained in the production examples described later were pretreated (for example, pre-dried, granulated, etc.) as necessary, and then were uniformly filled in a molding die. The preparation procedure after filling differs depending on the type of fluororesin.
When the fluororesin was a PTFE resin or a modified PTFE resin, the composite resin particles were compressed by pressurizing at 15 MPa and holding for a certain period of time to obtain a preform. The obtained preform is taken out from the molding die, baked in a hot air circulation type electric furnace set at 345 ° C. or more for 2 hours or more, slowly cooled, then taken out from the electric furnace, and a composite resin particle compact ( Composite resin material) was obtained.
When the fluororesin 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 electric with the mold set at 200 ° C or higher Heat in a furnace for 2 hours or more to melt the resin. After heating for a predetermined time, the mold is taken out from the electric furnace, and after cooling the mold to near room temperature while compressing and compressing with a hydraulic press at a surface pressure of 25 kg / cm ² or more, a molded body of composite resin particles (resin Material).

<Measurement of volume resistivity>
A test piece of φ110 × 10 mm was prepared from the composite resin material (molded body) obtained as described above from the composite resin particles, and used as a measurement sample. The volume resistivity was measured using a resistivity meter (“Loresta” or “Hiresta” manufactured by Mitsubishi Chemical Analytech) in accordance with JIS K6911.

<Measurement of welding strength of composite resin material>
A test piece having a thickness of 10 mm, a width of 30 mm, and a length of 100 mm is prepared from the composite resin material (molded body) obtained as described above from the composite resin particles, and the test piece has a length of 50 mm and a depth of about 1 mm. The V groove was cut. Next, a PFA welding rod having a diameter of 3 mm was welded to the groove portion using a hot air type welding machine so that the length of the portion to be fused was 50 mm, and a test piece for measuring welding strength as shown in FIG. It was created. Next, as shown in FIG. 5, the test piece for measuring the welding strength is set on a tensile tester so that the folded portion of the fused PFA welding rod is on the lower side, and the welding rod remains without being fused. Set the part on the upper chuck of the tensile tester. Tensile testing was performed at a rate of 10 mm / min using a tensile testing machine (“Tensilon Universal Material Testing Machine” manufactured by A & D Co., Ltd.), the maximum stress was measured, and the welding strength was obtained.

<Measurement of metal elution from composite resin material>
The degree of metal contamination in the molded product due to the addition of carbon nanotubes was evaluated by measuring the metal elution amount of 17 metal elements using an ICP mass spectrometer (“ELAN DRCII” manufactured by PerkinElmer). Specifically, a 10 mm × 20 mm × 50 mm test piece obtained by cutting from the composite resin material obtained as described above was added to 0.5 L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto Chemical) for about 1 hour. Immerse, take out after immersion for 1 hour, wash by pouring with ultrapure water (specific resistance: ≧ 18.0 MΩ · cm), immerse the entire test piece in 0.1 L of 3.6% hydrochloric acid, and at room temperature Stored for 24 hours and 168 hours. The total amount of the immersion liquid was collected after the lapse of the specified time, and the metal impurity concentration of the immersion liquid was analyzed.

<Measurement of carbon loss of composite resin material>
The degree of carbon nanotube desorption from the composite resin material was evaluated by measuring TOC using a total organic carbon meter (“TOCvwp” manufactured by Shimadzu Corporation). Specifically, a 10 mm × 20 mm × 50 mm test piece obtained by cutting from the composite resin material obtained as described above was added to 0.5 L of 3.6% hydrochloric acid (EL-UM grade manufactured by Kanto Chemical) for about 1 hour. Immerse, take out after immersion for 1 hour, wash by pouring with ultrapure water (specific resistance value ≧ 18.0 MΩ · cm), immerse the entire test piece in ultrapure water for 24 hours and 168 at room temperature. Saved for hours. The total amount of the immersion liquid was collected after the lapse of the specified time, 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 from the composite resin material obtained as described above was measured using an electronic balance (A & D Analytical Balance “BM-252”). Then the test _{piece, 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) Immersion in each solution of (NH ₄ OH: H ₂ O ₂ : H ₂ O = 1: 1: 5 (mass ratio)) and ozone water (50 ppm), dry and test after immersion The weight of the piece was measured using an electronic balance in the same manner as before immersion. The change in weight before and after immersion was calculated by the following formula and used as an index of chemical resistance.
Weight change (%) = [(weight after immersion−weight before immersion) / weight before immersion] × 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 perfluorovinyl ether unit is based on the total mass of the modified polytetrafluoroethylene, It confirmed that it was 0.01-1 mass%.

[Production Example 1]
Dilution was performed by adding 3,500 g of ethanol to 500 g of a carbon nanotube dispersion (dispersant = 0.15 mass%, carbon nanotube = 0.025 mass%) using water as a solvent. Further, 1,000 g of the modified PTFE particles 1 was added to prepare a mixed slurry.
Next, the prepared mixed slurry is supplied to a pressure vessel, 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 vessel, and the pressure in the pressure vessel is reduced. The pressure was increased and the temperature was increased to 20 MPa and the temperature to 50 ° C. While maintaining the above pressure and temperature for 3 hours, carbon dioxide was discharged from the pressure vessel together with the solvent (water, ethanol) and the dispersant dissolved in the carbon dioxide.
Subsequently, the carbon dioxide in the pressure vessel was removed by lowering the pressure and temperature in the pressure vessel to atmospheric pressure and room temperature, and CNT composite resin particles 1 were obtained.

[Production Example 2]
CNT composite resin particles 2 were obtained in the same manner as in Production Example 1-1 except that the amount of CNTs was 0.05% by mass based on the total amount of composite resin particles from which the amount of CNTs was obtained.

[Production Example 3]
CNT composite resin particles 3 were obtained in the same manner as in Production Example 1-1 except that the amount of CNT was 0.1% by mass based on the total amount of composite resin particles from which the amount of CNT was obtained.

[Production Example 4]
CNT composite resin particles 4 were obtained in the same manner as in Production Example 1 except that modified PTFE2 was used instead of modified PTFE1.

[Production Example 5]
A CNT composite resin material 5 was obtained in the same manner as in Production Example 2 except that modified PTFE2 was used instead of modified PTFE1.

[Comparative Resin Particle 6 (Production Example 6)]
Modified PTFE 1 that was not combined with CNT was used as comparative resin particles 6.

[Comparative Resin Particles 7 (Production Example 7)]
Modified PTFE 2 not composited with CNT was used as comparative resin particles 7.

[Comparative Resin Particles 8 (Production Example 8)]
The PTFE particles not combined with CNT were used as comparative resin particles 8.

The average particle diameter and specific surface area of the resin particles obtained in Production Examples 1 to 8 were measured according to the 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 examples 1-8 are shown in Table 2, and the result of chemical-resistance evaluation is shown in Table 3. Show. Further, from the amount of CNT and the volume resistivity of the resin material, the following formula:
A = X / Y- ¹⁴
Table 2 also shows the value A obtained by the above. X in the above formula is the volume resistivity [Ω · cm] of the resin material, and Y is the amount of CNT contained in the resin material [% by mass] (equal to the amount of CNT used in the production of the resin material). is there.
In the following, composite resin materials prepared from composite resin particles 1 to 5 according to the above method are also referred to as composite resin materials 1 to 5, respectively, and resin materials prepared from comparative resin particles 6 to 8 according to the above method, These are also referred to as comparative resin materials 6 to 8, respectively. Further, the amount of CNT in the composite resin particles or resin particles is equal to the amount of CNT in the composite resin material or resin material obtained therefrom.

The resin materials obtained from the composite resin materials 1 and 2 and the comparative resin material 6 were evaluated for metal elution and carbon loss. Table 4 shows the obtained results. For elements other than the elements described in the column of metal elution amount in Table 4 (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn), Although the measurement was performed and the device detection limit (ND) was reached, the results are not shown in Table 4. Moreover, all the results in Table 4 are the results 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 in accordance with the production method of the composite resin material. The test piece was immersed in various chemical solutions shown in Table 5, and the weight change before immersion and after immersion for about 1 week (1 W) and about 1 month (1 M) was measured. The results obtained are shown in Table 5. In addition, the immersion test in APM in Table 5 was performed under a temperature condition of 80 ° C., and the immersion test in other chemicals was performed under a room temperature condition. The details of each chemical solution in Table 5 are as shown in Table 6.

[Production Example 9 and composite resin material 9]
CNT composite resin particles 9 were 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 modified PTFE 1. Using the obtained CNT composite resin particles 9, a composite resin material 9 was prepared according to the above-described composite resin material preparation method, and a 10 mm × 10 mm × 2 mm thick test piece was obtained. Similarly, the test pieces were subjected to immersion tests in various chemical solutions shown in Table 5. The results obtained are shown in Table 5.

[Comparative resin materials 10-12]
A commercial molded body in which 15% by weight of graphite was added to PTFE was used as the comparative resin material 10, and a commercial molded body in which 15% by weight of carbon fiber was added to PTFE was used as the comparative resin material 11. A commercially available composite material (composite material of PFA resin and carbon fiber) was used as the comparative resin material 12. Similarly, test pieces having the above sizes of these materials were subjected to immersion tests in various chemical solutions shown in Table 5. The results obtained are shown in Table 5.

[Manufacture of composite resin particles (PCTFE)]
Using the polychlorotetrafluoroethylene (PCTFE) particles shown in the following Table 7, composite resin particles were produced.

[Production Example 13: Production of CNT composite resin particles 13]
CNT composite resin particles 13 were obtained in the same manner as in Production Example 1 except that PCTFE particles 2 were used in place 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 in place of the modified PTFE particles 1.

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

(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 CNT was 0.125% by mass based on the total amount of composite resin particles from which the amount of CNT was obtained.

(Production Example 17: Production of CNT composite resin particles 17)
CNT composite resin particles 17 were obtained in the same manner as in Production Example 14 except that the amount of CNT was 0.15% by mass based on the total amount of composite resin particles from which the amount of CNT was obtained.

(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 the PCTFE particles 3 were used in place of the 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: Comparative resin particle 20)
PCTFE2 not combined with CNT was used as a resin particle 20 for comparison.

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

The composite resin materials 14 and 15 and the comparative resin material 20 were evaluated for metal elution amount and carbon loss. Table 9 shows the obtained results. For elements other than the elements described in the column of metal elution amount in Table 9 (Ag, Cd, Co, Cr, K, Li, Mn, Na, Ni, Pb, Ti, Zn), Although the measurement was performed and the device detection limit (ND) was reached, the results are not shown in Table 9. Moreover, all the results in Table 9 are the results after immersion for 24 hours.

The composite resin materials 14 and 15 and the comparative resin material 20 were evaluated for chemical resistance according to the above method. Table 10 shows the obtained results.

The composite resin materials 14 and 15 were subjected to sulfuric acid / water immersion treatment (SPM treatment) under the above conditions, and the volume resistivity after the treatment was measured. As a result, as shown in the following Table 11, it was confirmed that the composite resin materials 14 and 15 did not increase in volume resistivity even when the SPM treatment was performed.

[Manufacture of lining sheet 1 containing composite resin material]
A method for manufacturing the Rheing sheet 1 containing the composite resin material from the composite resin particles obtained as described above will be described. The manufacturing method varies depending on the fluororesin used. When the fluororesin is polytetrafluoroethylene (PTFE) or modified polytetrafluoroethylene (modified PTFE), the composite resin particles obtained in Production Example 2 are pretreated as necessary (for example, preliminary drying, granulation, etc.) After that, a predetermined amount and uniformly filled in the molding die, and the composite resin material was compressed by pressurizing at 15 MPa and holding for a certain period of time to obtain a preform. The obtained preform is taken out from the molding die, baked in a hot air circulation type electric furnace set at 345 ° C. or more for 2 hours or more, slowly cooled and then taken out from the electric furnace, and the composite resin material block shape is obtained. A molded body was obtained. (Although not shown in Examples and Comparative Examples, when the fluororesin is a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), there are compression molding methods, compression molding methods, sheet extrusion molding methods, etc., In this case, the CNT composite resin particles are pretreated as necessary (for example, pre-drying, granulation, etc.), and then are uniformly filled in a molding die and set to 300 ° C. or higher. And then taking out from the electric furnace and pressure-cooling with a hydraulic press at 5 MPa or more to obtain a block-shaped molded body of composite resin material.) The molded body is cut (peeled), A sheet having a thickness of 2.4 mm was prepared. The obtained sheet was laminated with a glass cloth having a thickness of 0.5 mm and heat-sealed to obtain a lining sheet 1. The volume resistivity of the obtained lining sheet 1 was 10 ² Ω · cm.

[Manufacture of lining sheet 2 containing no composite resin material]
A lining sheet 2 was obtained in the same manner as the production of the lining sheet 1 except that the comparative resin particles 6 (Production Example 6) were used in place of the composite resin particles obtained in Production Example 2.

[Manufacture of chemical tube 1 containing composite resin material]
A method for producing the chemical liquid tube 1 containing the 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 pretreated (for example, pre-dried, granulated, etc.) as necessary, and are then uniformly filled in a molding die in a certain amount and pressurized at 15 MPa to be constant. The composite resin material was compressed by holding for a time to obtain a preform. The obtained preform is taken out from the molding die, baked in a hot air circulation type electric furnace set at 345 ° C. or more for 2 hours or more, slowly cooled and then taken out from the electric furnace, and the composite resin material block shape is obtained. A molded body was obtained. The obtained molded body was cut using a CNC ordinary lathe (“TAC-510” manufactured by Takizawa Iron Works Co., Ltd.) to produce a chemical tube having a diameter of 2 inches. The volume resistivity of the obtained chemical liquid tube 1 was 5.0 × 10 ² Ω · cm.

[Manufacture of chemical tube 2 containing composite resin material]
A chemical solution tube 2 was obtained in the same manner as the production of the chemical solution tube 1 except that the comparative resin particles 6 (Production Example 6) were used in place of the composite resin particles obtained in Production Example 2.

[Production of hollow sphere 1 containing composite resin material]
A method for producing the chemical liquid tube 1 containing the 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 pretreated (for example, pre-dried, granulated, etc.) as necessary, and are then uniformly filled in a molding die in a certain amount and pressurized at 15 MPa to be constant. The composite resin material was compressed by holding for a time to obtain a preform. The obtained preform is taken out from the molding die, baked in a hot air circulation type electric furnace set at 345 ° C. or more for 2 hours or more, slowly cooled and then taken out from the electric furnace, and the composite resin material block shape is obtained. A molded body was obtained. A hollow spherical molded body having a diameter of 50 mm was manufactured by cutting and welding the obtained molded body using a machining center. 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 the production of the hollow sphere 1 except that the comparative resin particles 6 (Production Example 6) were used instead of the composite resin particles obtained in Production Example 2.

Example 1
The lining sheet 1 was bonded to the inner surface of a tank with a capacity of 50 L using an adhesive (for example, epoxy). The seam between the sheets was sealed using a PFA welding rod of φ5 mm. A chemical solution tube 1 was attached to the tank, and a plurality of hollow spheres 1 were arranged 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 chemical liquid tube 2 and the hollow sphere 2 were used instead of the lining sheet 1, the chemical liquid tube 1 and the hollow sphere 1.

Evaluation of antistatic property 10 L of thinner (NTX Eco thinner manufactured by Sankyo Chemical Co., Ltd.) was put in the tank manufactured in Example 1 and Comparative Example 1, and 285 rpm in a stirrer having a PTFE sales blade. The antistatic property with respect to the organic solvent was evaluated by measuring the charging potential of the lining sheet using an electrometer (SIMX FMX-003). As a result, Comparative Example 1 was rapidly charged by stirring, and the charging potential tended to increase with time (about 1.5 kV in about 5 minutes). On the other hand, Example 1 has a value less than the measurement limit (−0.01 kV), and it was confirmed that the tank of Example 1 is superior in antistatic property to the tank of Comparative Example 1. .

DESCRIPTION OF SYMBOLS 1 Tank outer can 2 Lining layer 3 Chemical solution injection pipe 31 Lining layer 4 Chemical solution discharge pipe 41 Lining layer 5 Hollow spherical molded body 6 Chemical solution 7 Liquid contact part 8 Lining sheet 9 Tank bottom part 10 Lining sheet 11 Ground wire 12 Liquid surface 13 Ground wire DESCRIPTION OF SYMBOLS 14 Lid 15 Chemical liquid pipe 151 Lining layer 16 Chemical liquid transport tank 17 Transport vehicle 18 Connection pipe 19 Pass box 20 Coupler 21 Connection pipe 22 Chemical liquid supply tank 24 Circulation pump 25 Connection pipe 26 Filter 27 Connection pipe 28 Use point 29 PFA welding rod 30 Specimen 31 Groove 32 Lower chuck 33 Upper chuck 36 Nozzle 52 Rod shaped body 53 Ground wire 54 Holder 56 Stirring rod 57 Propeller 58 Adapter

Claims (18)

A tank outside can,
A lining layer provided on the inner surface of the tank outer can,
The lining layer includes, at least in part, a composite resin material containing a fluororesin A and carbon nanotubes,
Fluororesin A is composed of 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 selected from the group consisting of,
The tank , wherein the lining layer is provided at least partially using a lining sheet containing a composite resin material, and a gap between the lining sheets is welded using a PFA material .   2. The tank according to claim 1, wherein the lining layer provided in a portion where the introduced chemical solution first comes into contact with the inner surface of the tank outer can contains a composite resin material containing fluororesin A and carbon nanotubes. It has a chemical tube that connects the inside and outside of the tank,
The chemical liquid tube has a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the chemical liquid pipe, and / or is a molded body of a composite resin material containing fluororesin B and carbon nanotubes. Yes,
Fluororesin B is composed of 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, which is selected from the group consisting of: It has a chemical tube that connects the inside and outside of the tank,
The chemical liquid pipe includes a chemical liquid input pipe for putting the chemical liquid into the tank,
The chemical injection pipe has a nozzle at its end,
The nozzle has a lining layer containing a composite resin material containing fluororesin B and carbon nanotubes on at least a part of the inner surface of the nozzle, and / or is a molded body of a composite resin material containing fluororesin B and carbon nanotubes,
Fluororesin B is composed of 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, which is selected from the group consisting of:   The tank according to claim 4, wherein the nozzle is selected from the group consisting of a spray nozzle, a rotary nozzle, a straight nozzle, and a shower nozzle.   A hollow spherical molded body that at least partially includes a composite resin material including a fluororesin C and a carbon nanotube, and the 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), poly The tank according to claim 1, which is selected from the group consisting of chlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).   It further has a rod-shaped molded body that at least partially contains a composite resin material containing a fluororesin C and carbon nanotubes. The fluororesin C is made of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetra Fluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychloro The tank according to claim 1, which is selected from the group consisting of trifluoroethylene (PCTFE), chlorotrifluoroethylene / ethylene copolymer (ECTFE), and polyvinyl fluoride (PVF).   It further has a stirrer bar at least partially containing a composite resin material containing a fluororesin C and carbon nanotubes. The fluororesin C is composed of polytetrafluoroethylene (PTFE), modified polytetrafluoroethylene (modified PTFE), tetrafluoroethylene. / Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoro The tank according to any one of claims 1 to 7, 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 that at least partially includes a composite resin material including fluororesin C and carbon nanotubes.   The tank according to any one of claims 1 to 9, wherein the chemical liquid includes 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. The modified polytetrafluoroethylene has the formula (I):

A tetrafluoroethylene unit represented by formula (II):

[Wherein X represents a perfluoroalkyl group having 1 to 6 carbon atoms or a perfluoroalkoxyalkyl group having 4 to 9 carbon atoms]
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. The tank according to any one of claims 1 to 11.   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, including any one of fluororesins A to C and carbon nanotubes. .   The tank according to claim 1, which is a chemical solution supply tank, a chemical solution storage tank, and / or a chemical solution transport tank. Furthermore, the tank in any one of Claims 1-14 containing a ground wire . Using tank according to any one of claims 1 to 15 comprising performing the supply of the chemical, the chemical liquid supply system. The molded object containing any one of fluororesin AC used for the tank of any one of Claims 1-15 , and a carbon nanotube. The molded body according to claim 17 , wherein the molded body is selected from a lining sheet, a chemical liquid 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.

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