JPH04101838A - Novel container and material therefor - Google Patents

Abstract

PURPOSE:To enable a container to be used for ultra high pure water and ultra high pure compound, while the entrance of corrosive solution into the layer of outer wall is removed by a method in which the layer of the inner wall of the container is mainly made of the film containing fluorine plastic, and the layer of its outer wall is made of a metallic sheet. CONSTITUTION:The chemical treatment such as plating treatment, the film-coating treatment for metallic oxide and rust proof treatment etc., are applied onto the surface of a metallic sheet according to necessity. The film containing fluorine plastic is laminated on the heated metallic sheet, and the metallic sheet is covered by a press. Then the atmosphere of the lamination is preferably the atmosphere containing no oxygen. The sheet is continuously pressed by e.g. two rolls etc., and is covered firmly. In order to strengthen further the fusion-adhesion of the metallic sheet to the film in the obtained film-coated metallic sheet, said metallic sheet is heated again according to necessity. The heating temperature is set at the temperature of at least softening temperature (mp) of the film containing fluorine plastic, and preferably it is at least (mp+30) deg.C and at most thermal decomposition temperature thereof. The obtained bonded object of the metal and the film containing fluorine plastic is made into a through a cutting process, container-making process and bonding process etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel container and materials used therein, and more particularly to a novel container having an inner wall layer and an outer wall layer and materials used therein. .

A novel container according to claim 1.

6. The novel container according to any one of claims 1 and 5, wherein the metal plate has a thickness of 0.15 to 5.0 m/m.

7. Even when the container is storing and transporting ultra-high purity compounds, it has chemical resistance, oil resistance, solvent resistance, heat resistance, electrical properties, etc.
Studies have been made on fluororesins having excellent properties. However, these fluorine-containing resins, such as tetrafluoroethylene resin (PTFE), are difficult to process and mold, making it extremely difficult to mold complex and precise containers. Even if it were molded, it could hardly be used for pressure-resistant containers or large-capacity containers because its physical strength was not great. Therefore, it is only used sparingly as a small container that requires almost no pressure resistance.

It has been widely used. It is well known that all of these metal plates have poor corrosion resistance, causing the metal to melt and causing various problems. As a countermeasure to this problem, various fluorine-containing resins are sintered or coated on the surface of the metal plate, but pinholes are formed in the resin, which is a problem especially when used in containers for ultra-high purity chemicals.

[Problem to be solved by the invention]

The object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a novel container and materials used therefor that have been completely unknown heretofore.

[Means for solving problems]

The present invention has been made to solve the above-mentioned problems, and provides a novel container characterized in that at least the inner wall layer of the container is mainly made of a fluorine-containing resin film, and the outer wall layer is further made of a metal plate. It is intended to capture and provide information. The configuration of the present invention will be explained in more detail below.

The "fluorine-containing resin" as used in the present invention is not particularly regulated as long as it is a thermoplastic resin containing a fluorine atom in the molecular structure of the resin, but in terms of -C, the molecular structure of the resin is Tetrafluoroethylene resins having four fluorine atoms in the formula, trifluoroethylene resins, difluoroethylene resins, fluoroethylene resins, copolymers of these resins, mixtures, etc. Of these, tetrafluoroethylene resins and nifluoroethylene resins are preferred, and tetrafluoroethylene resins are more preferred. Here, the tetrafluoroenalene resins specifically include, for example, tetrafluoroethylene resins. polyethylene resin (PTFE), tetrafluoroethylene,
perfluoroalkoxyethylene copolymer (PFA),
There are tetrafluoroethylene/hexafluoropropylene/perfluoroalkoxyethylene copolymers (EPE) and tetrafluoroethylene/ethylene copolymers (ETFE), among which PFA and ETFE are preferred, and PFA is particularly preferred.
In addition, the above-mentioned trifluoroethylene resin is specifically:
For example, trifluorochlorinated ethylene resin (PCTFE) and trifluorochloroethylene/ethylene copolymer (ECTFE)
), among which PCTF'E is preferable, and the difluoroethylene and -fluoroethylene resins include, for example, vinylidene fluoride resin (PVDF).
and fluorinated vinyl resin (PVC).

Furthermore, it goes without saying that the fluororesin film used for the inner wall layer in the present invention should not have any damage such as pinholes, but should also completely cover the metal plate that will become the outer wall layer. The IBi ff may be any value, but for boat fishing, it is 30 to 500μ, preferably 50 to 500μ.
It is 400μ, more preferably 60 to 300μ. These fluorine-containing resin films can be produced by conventional methods, such as hot melt extrusion, casting, etc., and if necessary, Pigments, dyes, glass powder, glass peas, fillers such as glass fibers, aluminum oxide, talc, mica, erythrium, and the like can be blended.

Furthermore, the "metal plate" in the present invention is not particularly limited, and any metal plate can be used, but -fG
For example, iron-based, aluminum-based, copper-based, titanium-based, and nickel-based metal plates, among which iron-based, aluminum-based, and copper-based metal plates are preferred, and aluminum-based metal plates are particularly preferred. The above-mentioned iron-based metal plate may be any metal plate as long as it is a gold RIA plate whose composition mainly contains iron, and specifically, for example, a cold rolled steel plate, a galvanized steel plate, a zinc alloy plated plate, etc. There are steel plates, aluminum plated steel plates, copper plated steel plates, stainless steel plates, phosphoric acid treated steel plates, aluminum-zinc alloy plated steel plates, etc. Among them, galvanized steel plates, zinc alloy plated steel plates, aluminum plated lead steel plates, aluminum-zinc alloy plated steel plates. and stainless steel plates are preferred.

Further, as the aluminum-based metal plate, any metal plate may be used as long as the metal plate mainly contains aluminum metal in its composition, but generally, for example,
It is an aluminum plate described in pages 13 to 22 of "Aluminum Handbook (2nd edition)" published by the Light Metals Association of Japan on September 30, 2007, and specifically, pure aluminum, (AI
-Cu) system, (AI-Mn) system, (AI-3i) system, (
AI-Mg) system, (A, l-Mg-3i) system and (AI
-Zn-Mg) type plates, among which pure aluminum type, (AI-Mn) type and (Al-Mg) type plates are preferable.

Further, as the copper-based metal plate, any metal plate may be used as long as the metal plate mainly contains copper in terms of composition.
Generally, metal plates such as pure copper, brass, bronze, and brass are available.

The thickness of the metal plate in the present invention is not particularly limited, but generally, for example, 0.75 to 5 m/m,
Preferably 0.2 to 4 m/m s, more preferably 0
．． 5-3 ny'm.

Next, the fluorine-containing resin film that becomes the inner wall layer and the metal plate that becomes the outer wall layer do not necessarily need to be integrated, but in actual use, they are joined and are substantially integrated. As a bonding method which is desirable, there is mainly a method of bonding the film by heat fusion welding.

Films can be bonded by heat fusion welding using conventional methods, but generally, for example,
It can be obtained through processes such as a pretreatment process, a heating process, film lamination, a pressurizing process, a reheating process, and a cooling process. The above steps will be explained below.

(1) Pre-treatment step This step is performed as necessary to more strongly coat the metal plate and the fluorine-containing resin film.

■ Pre-treatment process of metal plates The purpose of pre-treatment of metal plates is to remove oily substances that adhere to the surface.
Cleaning and removing foreign substances, oxide films, etc., exposing bare metal to the surface by polishing, etc., surface plating,
Apply surface treatment such as acid treatment, and if necessary,
Add roughness to the surface, etc.

89 Surface cleaning There are no particular limitations, and conventional cleaning methods used for specific metals may be used. For example, as a degreasing method,
Degrease and clean using organic solvents, alkaline aqueous solutions, surfactants, etc.

50 Surface Polishing The surface can be polished to expose the bare metal on the surface, for example, by mechanical and chemical polishing.

C9 Surface treatment If necessary, chemical conversion treatments such as plating, coating with a metal oxide film layer, and rust prevention treatment can be performed on the surface to be coated with the film.0 For example, chemical conversion treatment of iron-based metals. Specific examples include phosphate treatment with zinc phosphate, calcium phosphate, etc., and chromate treatment with reactive chromate, coating type chromate, and the like.

46 Surface Roughening Roughening the surface by a surface roughening method by physical means such as brushing, sandblasting, and shitblasting, or by a surface roughening method by chemical or electrochemical etching method, or by combining these &[l,'z. I can do it.

(2) In the film pre-treatment process, treatments such as providing an oxide film or the like and applying various surface treatment agents such as aminosilane, vinylsilane, mercaptonelan, etc. can be performed.

(2) Heating process This is a process in which the pretreated metal plate is heat treated in the air or in an atmosphere substantially free of oxygen. In the present invention, the latter is preferred, and if necessary, a film may also be added. This is a process of heat treatment at the same time.

■Heating atmosphere The “substantially oxygen-free atmosphere J” mentioned above is
There are no particular restrictions on the atmosphere as long as it can heat the metal plate and film while substantially maintaining the surface condition of the metal plate and film that underwent the pretreatment process, but specifically, the atmosphere may have an oxygen content of 1% or less, The atmosphere is preferably 0.5% or less, more preferably 0.2% or less, particularly preferably 0.01% or less. To create this heating atmosphere, it can be filled with an inert gas or heated in a vacuum state. Any type of inert gas may be used; however, for boat fishing, nitrogen gas, argan gas, neon gas, helium gas, etc. are preferred, among which nitrogen gas and argon gas are preferred, with nitrogen gas being particularly preferred.

Further, the vacuum state is 5 Torr or less, preferably 1 Torr or less, and more preferably 0.1 Torr or less.

■ Heating temperature The optimum heating temperature is determined depending on the type of fluorine-containing resin film and metal plate to be coated.
Above, preferably (mp+30) 1 or more, more preferably (mp+50) 1 or more, and below the thermal decomposition temperature. Specifically, in the case of a fluororesin film, tetrafluoroethylene perfluoroalkoxy In tyrene copolymer, -a 280~400°C5 ethylene-
For tetrafluoroethylene copolymers, -&H? 260 to 370°C for ethylene-chlorotrifluoroethylene copolymer, 220 to 350°C for −C, and 250 to 300°C for polyvinylene fluoride.

■ Heating time The heating time is not something that should be specified in particular, but it must be the time required for at least the surface of the metal plate to reach the heating temperature, and may be determined as appropriate depending on the type and thickness of the metal plate. , -C for 1 to 20 minutes, preferably 3 to 15 minutes
minutes, more preferably about 5 to 10 minutes.

(3) Lamination step This step is a step of covering a heated metal plate with a fluorine-containing resin film using a Mi layer and press.

■ Lamination atmosphere The lamination atmosphere is not particularly limited, but it is desirable that the atmosphere be substantially free of oxygen, at least until the film is laminated and placed on the heated metal plate. It is preferable to follow the previous step (2), (2).

■ Pressing is a strong coating process. Here, the roll in contact with the film is preferably a roll that does not stick to the film, such as a rubber roll or a metal roll, and the pressing force is 5 to 30 kg.
/cd, preferably 10 to 20 words/c1! It is.

(4) Reheating process This process is a reheating process that is carried out as necessary in order to further strengthen the fusion force between the metal plate and the film of the film-coated metal plate obtained in the previous process. It is.

(2) Heating Atmosphere The heating atmosphere is not particularly limited, and may be in the air, but is preferably an atmosphere similar to that in the preceding step (2), (2).

■ Heating Temperature The heating temperature should be determined as appropriate depending on the type of fluorine-containing resin film and metal plate to be coated. - For boat fishing, the temperature should be at least the softening point temperature (mp) of the fluororesin film, preferably at least (mp + 20) 1, more preferably at least (mp + 30) °C, and at most the thermal decomposition temperature. Specifically, in the case of a fluorine-containing resin film, for a tetrafluoroethylene/perfluoroalkoxyethylene copolymer, - 280 to 400 °C for boat fishing,
In the ethylene-tetrafluoroethylene copolymer, -
260-360℃ for boat fishing, 220-350℃ for boat fishing with ethylene-chlorotrifluoroethylene copolymer
and 200 to 250°C for polyvinylidene fluoride.

■Heating time Heating time is not something that should be specified in particular, but it needs to be the time required for at least the surface of the metal plate to reach the heating temperature, and may be determined as appropriate depending on the type and thickness of the metal plate. , -m for 1 to 20 minutes, preferably 3 to 10 minutes
minutes, more preferably 5 to 7 minutes.

(5) Cooling Step This step is a step of cooling the reheated film-coated metal plate to room temperature, and can be cooled using, for example, air cooling, water, or the like. If non-uniform cooling is performed here, distortion and deformation will occur in the plate, so uniform cooling is desirable.

The film-coated metal plate of the present invention obtained by the above process is produced by heating the metal plate and the fluorine-containing resin film in an atmosphere substantially free of oxygen to fuse and bond the metal plate and the fluorine-containing resin film. The resin film is hardly affected by oxidative deterioration, and therefore the metal plate and the fluorine-containing resin film exhibit strong adhesive strength and are expected to be usable for a long period of time.

The step of forming the bonded body of the metal and fluorine-containing resin film obtained through the above steps into a container involves conventional steps such as a cutting step, a container forming step, and, if necessary, a bonding step. There is.

The forming process of the fluororesin film Mi layer metal plate includes cutting into the desired shape by shearing, cutting (milling, sawing), etc. (cutting process), followed by bending, drawing and ironing. After forming into a container shape by processing, spatula drawing, etc. (container forming process), welding (arc welding, plasma welding, electron beam welding), brazing, soldering, riveting, etc. as necessary. The joining process (joining process) can be performed with

In the thus obtained container of the present invention, the inner wall layer is a continuous uniform layer of fluorine-containing resin film without any pinholes, so that corrosive solutions are prevented from penetrating the gold i-layer, which is the outer wall layer. As a result, corrosion resistance is considered to be extremely excellent. Taking advantage of this characteristic,
This container is used as a container for various compounds such as strong acid compounds such as aqua regia, concentrated sulfuric acid, and concentrated nitric acid, and strong basic compounds such as caustic soda, caustic potash, and aqueous ammonia, and also contains impurities from the metal layer and inner wall layer. Since there is very little elution of water, it is used not only as a container for ultra-high purity water but also as a container for ultra-high purity compounds. Specific uses of these containers include, for example:
There are various types of storage containers, transportation containers, pressure vessels, chemical reaction containers, chemical experiment equipment, chemical measurement equipment, etc. Also,
Since the inner wall layer of the container of the present invention is made of a thin fluorine-containing resin film, it is lightweight and has excellent thermal conductivity.
It is used in chemical reaction tanks, heat exchange equipment, etc., and its contribution to industry is extremely large.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but it goes without saying that the present invention should not be limited only to the Examples.

Example A (Preparation of container) Example 1 As shown in Table 1, commercially available phosphate-treated electrogalvanized steel sheet (Nippon Steel: Bonde Steel FiEGC1 thickness 7.0 m)
/m) with an alkaline degreaser (manufactured by Nippon Parr Ising,
The surface was washed with Fine Cleaner 301 at 60°C for 3 minutes, then washed with water and dried. This steel plate was placed in a nitrogen-substituted heating furnace with an oxygen concentration of 0.1%.
After heat treatment at 0°C for 6 minutes, 10 kg/a of PFΔ film with a jγ diameter of 0.1 m/m was deposited using a pair of silicon rolls also placed in a nitrogen atmosphere with the same oxygen concentration.
! It was heat fused at a pressure of . Furthermore, this heat-sealed steel plate was reheated at 390° C. for 7 minutes in a nitrogen atmosphere, and cooled by being left indoors to obtain a PFA film-coated steel plate.

Next, this coated steel plate was drawn using a hydraulic press machine and a mold to obtain a size of 1.8jl! A container was prepared (hereinafter referred to as “
).

Example 2 As shown in Table 1, Al specified in JISA4000
100P-Hl 4 (Aluminum: plate thickness 15.0
m/m) The surface of the plate was cut using a milling machine to which a circular metal plate with a diameter of 50 mm was attached with a sand vapor with a roughness of No. 80, and the rotation speed of the milling machine was 1100 rpm and the scribing speed was 100 cm/min. I processed the brats. The scribing depth of the obtained linear scribing pattern was 1 μm.

After degreasing the surface of the scribed aluminum plate with a 1% aqueous solution of caustic soda, the same thickness as in Example 1 was prepared.
By heat-sealing a 1m/m PFA film, P
An FA resin coated metal plate was obtained.

The above heat fusion bonding conditions are as follows: The aluminum plate and the film, which have been preheated to 390°C, are pressed with a pressure of 100 kg using a silicone roll with a diameter of 10 cm, and then heated at 390°C for 10 minutes. It performs processing.

Next, this PFA-coated metal plate was treated in the same manner as in Example 1, and 1.81! (hereinafter referred to as "container series 2").

Example 3 In Example 2, the thickness of the aluminum plate used was 2.0 m/m, and the thickness of the PFA film was 0 m/m.
．． 1.81 in the same manner as in Example 2 except that it was set to 2 m/m.
! , a container was prepared (hereinafter referred to as "container series 3")
.

Example 4 1.81 containers were prepared in the same manner as in Example 3, except that the PFA film 1 in Example 3 was replaced with an ETFE film (film thickness 0.2 m/m) (hereinafter referred to as "container series"). 4
).

Comparative Example 1 As in Example 1, an epoxy resin adhesive side (manufactured by Ciba Geigi, Araldite X183/
2315) and dried to create an epoxy resin adhesive layer (layer thickness 0.02 m/m ) as an intermediate layer.
A TFE film (II' ffl, 6.0 m/m) was laminated and crimped to obtain a PTFE-coated steel plate.

Comparative Example 2 In Example 1, 1.82 containers were prepared using this steel plate in the same manner as in Example 1 (hereinafter referred to as "container series 5"). The thickness of PFA film is 0.02
1.81 containers were prepared in the same manner as in Example 1 except that the ratio was m/m (hereinafter referred to as "container series 6").

Comparative Example 3 A PVdF resin paint (Gainer 203, manufactured by Pennwalt) was applied on a steel plate pretreated as in Example 1, dried, and coated with an IEJ thickness of 0.03 m/m (7) to form a PVdF layer. A steel plate having the following properties was obtained.

Next, 181 containers were prepared using this steel plate in the same manner as in Example 1 (hereinafter referred to as "container series 7").

Example B (RW value of container) Regarding the volumes HNCL 1 to 7 prepared in Example A, the overall heat transfer coefficient that determines the thermal conductivity was determined, and the corrosion resistance by aqua regia and the weight of the fluororesin-coated metal container were determined. It was measured and the results are listed in Table-1.

The measurement method was as follows.

(1) Overall heat transfer coefficient 1 / U -1 / h o +1
/ h i −+−Σ (ti/ λ
1 ) + 17 r o +1 / r i .

Here, each coefficient was set as follows.

ho -5000 outer membrane heat transfer coefficient hi = 300 inner membrane heat transfer coefficient ro
= 2500 Outer wall dirt coefficient rl = 20
00 Inner wall dirt coefficient t+ Thickness of i-th wall P1λ1 Thermal conductivity of 1st wall (
2) Aqua regia test Aqua regia at 70°C was placed in a container for 3 days, and metal elution (2) thereafter was measured by atomic absorption spectrometry.

(3) Weight The weight of a certain area was peeled off and converted to 1r+(weight per area).

It is clear from Table 1 that containers 1 to 4 have excellent thermal conductivity and corrosion resistance, and are lightweight.On the other hand, 2SN11L5 has excellent thermal conductivity, and containers N16 to 7 have excellent corrosion resistance, respectively. It was significantly inferior.

Claims (1)

[Scope of Claims] 1. A novel container characterized in that at least the inner wall layer of the container mainly consists of a fluorine-containing resin film, and the outer wall layer further consists of a metal plate. 2. The novel container according to claim 1, wherein the fluorine-containing resin is a tetrafluorinated resin. 3. The novel container according to claim 2, wherein the tetrafluorinated resin is a tetrafluoroethylene/perfluoroalkoxyethylene copolymer (PFA). 4. The novel container according to claim 1, wherein the film has a thickness of 30 to 500μ. 5. The novel container according to claim 1, wherein the metal of the metal plate is an aluminum metal plate. 6. The novel container according to any one of claims 1 and 5, wherein the metal plate has a thickness of 0.15 to 5.0 m/m. 7. A novel container according to any one of claims 1 to 6, wherein the container is a container for storing, transporting, and reacting ultra-high purity compounds. 8. The novel container according to claim 7, wherein the ultra-high purity compound is ultra-high purity water. 9. A material used for a container, which is a metal plate to which a fluorine-containing resin film is mainly bonded to at least the surface that will become the inner wall of the container.