JP2013021130A - Processing tank for manufacturing process, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reaction tank in which a reaction product is not attached to the internal wall surface substantially after the continued use so as to increase production efficiency significantly; and moreover to provide a structure of a processing tank for manufacturing process and a method for producing the processing tank for manufacturing process using the structure, which can easily produce the structure of processing tank for manufacturing process in which a reaction product is not attached to the internal wall surface substantially after continued use and the processing tank for manufacturing process using the structure.SOLUTION: In a reaction tank of this invention, a film comprising PFA is formed in the internal surface of a tank body. In a method for producing the reaction tank and a structure of the reaction tank, a PFA film is formed in the internal wall surface by melting and remelting.

Description

  The present invention relates to a chemical reaction tank used for chemical synthesis such as polymer synthesis, organic polymerization, organic decomposition, or chemical decomposition, and a mixing tank / kneading tank used for mixing / kneading organic materials or organic / inorganic mixed materials. In addition, for example, in the manufacture of functional electronic devices (hereinafter referred to as semiconductor applied functional electronic devices) using semiconductor-related technologies such as semiconductor devices, liquid crystal display devices, solar cells, organic EL devices, and LEDs. The present invention relates to a processing tank for a manufacturing process, such as a vacuum processing tank used in a manufacturing apparatus used for carrying out a film process, or an electronic component manufacturing apparatus for the electronic device, and a manufacturing method thereof.

  For example, polymer latex is produced by an emulsion polymerization method. When polymerized while stirring with a stirring blade at the time of production, the polymer particles are aggregated and adhered to the inner wall of the reaction tank or the stirring blade. If deposits (referred to as “scale”) adhere to the inner wall of the reaction tank, the heat removal capability of the reaction tank will decrease, and if left untreated, the reaction control may become impossible. Therefore, it is necessary to periodically remove the scale in the reaction vessel. At the time of removing the scale, the polymerization reaction is stopped each time, the chemical material for polymerization in the reaction vessel is taken out, and then the inner wall of the reaction vessel is subjected to a cleaning treatment to remove the scale. Then, the chemical material for polymerization is reintroduced into the reaction vessel, and the polymerization is resumed. Due to the complexity of such interruption of polymerization and scale removal from the inner wall of the reaction vessel, the production efficiency is significantly reduced.

  On the other hand, in an electronic device such as a semiconductor, a flat display, or a solar cell, many functional films are provided in order to exhibit the function. These films are created by PVD (Physical Vapor Deposition) or CVD (Chemical Vapor Deposition), but the gas types used for the formation differ depending on the film, so individual film formation for each film Formed in a tank. Also, the dry etching process employed as necessary is carried out in each reaction tank because the type of etching gas used varies depending on the etching target.

  In the processing tanks for these manufacturing processes, for example, when the film forming process is repeated several times, the product generated by the reaction adheres to the inner wall of the reaction processing tank, and the attached product is peeled off from the inner wall and the reaction processing tank. May float inside. Therefore, there is a possibility that a film having a desired characteristic is not formed, for example, a floating product is taken into the film during the film formation process.

  Furthermore, proposals have been made to form a number of different films in a single reaction treatment tank. In this proposal, however, reaction products generated in the film formation process of the previous process and adhered to the inner wall are not detected. In addition, if the film formed in the subsequent process is taken in, the formed film cannot obtain the desired characteristics, and further, the inside of the reaction processing tank may be contaminated by the product generated in the previous film forming process. For example, there are many problems to be solved by conventional methods.

  In order to solve this problem, for example, there is a proposal to prevent adhesion of scale to the inner wall of the reaction tank by coating the inner wall of the reaction tank with a polymer having a specific fluorine-containing aliphatic ring structure (Patent Document 1). .

  As another example of preventing adhesion to the inner wall surface of the reaction processing tank, for example, the partition member can be installed and removed freely with a gap from the inner wall surface, and the reaction product is adhered to the inner wall surface of the partition member. There is a proposal for preventing the adhesion of an object to the inner wall of a reaction treatment tank. The partition member with the reaction product attached to the inner wall surface is taken out of the reaction processing tank and replaced with another partition member. The reaction product adhering to the inner wall surface of the partition member is removed by dry etching or mechanical scraping, and the partition member from which the reaction product has been removed is reused.

  In addition, there is a proposal to prevent the adhesion of reaction products by smoothing the inner wall surface of the reaction treatment tank. As a base material for the reaction treatment tank, stainless steel, aluminum, etc. are industrially adopted, and as one method for smoothing the inner wall surface, a relatively good smooth surface can be obtained. Polishing is adopted.

JP-A-5-023652

  However, in the invention described in Patent Document 1, it is certainly effective in preventing the adhesion of scale in the production of polymer latex, but the vacuum used when forming a high-functional film used for an electronic device or the like by a semiconductor technology. In the case of a reaction vessel, it is not always possible to completely prevent the reaction product from adhering to the inner wall of the vacuum reaction vessel.

  The reason is that, in the coating film of the polymer having a specific fluorine-containing aliphatic ring structure described in Patent Document 1, the smoothness of the free surface is not sufficiently obtained, and fine irregularities remain. It seems that adhesion of reaction products during the film formation process by the method cannot be reliably prevented. Furthermore, in the case of Patent Document 1, since the base material of the reaction vessel is glass, there is a concern that the heat conduction is bad and the heat generated by the reaction cannot be sufficiently radiated.

  In the example in which the partition member is provided, the film forming process is interrupted to replace the partition member each time, and the production efficiency is remarkably reduced. Also, in the case of a vacuum reaction tank, the reaction tank is opened to the atmosphere for replacement of the partition member. Therefore, the reaction tank may be contaminated unless it is handled carefully, and the reaction tank is depressurized to a film formation atmosphere again. It has to be complicated.

  Even when sufficient smoothness is ensured by electropolishing or the like, the following problems exist. Electropolishing exhibits its effect to the maximum with a uniform surface, but it is difficult to make use of its characteristics for a non-uniform surface. In fact, when manufacturing an object, many processes such as welding and bending are applied, so that the surface is not uniform.

  On the other hand, in mechanical polishing, even if a wrapping film having a size of 12000 is used, very fine streaks are observed when observed with an electron microscope. Even if it is said to be smooth, mechanical polishing does not eliminate the streaks, but small irregularities remain only by reducing it.

  On the other hand, in electropolishing, if polishing finish with about 600 fixed abrasive grains is performed in advance and then electropolishing is performed, no streak is seen at all. However, mechanical polishing is superior to polishing the entire large flat surface flatly. Electropolishing can create a smooth wavy surface but is difficult to planarize.

  Due to such technical limitations, reaction tanks generally have a dome shape or a cylindrical shape, and the surface to be polished is made relatively simple. For this purpose, it is necessary to divide into several parts, and the electropolished surface of the divided parts is formed as a smooth surface with few irregularities so that there is no place where the electric field concentrates locally, and then electropolishing is performed. It is common.

  However, even if processed in such a manner, the reaction product adheres to the inner wall surface of the reaction tank, but it has been an obstacle to the formation of a highly functional film. In particular, there is a problem that the obstacle becomes larger as the miniaturization progresses to 20 nm, 15 nm, and 10 nm in the future.

  The present application has been made in view of the above points, and has been aimed at solving the above-mentioned problems, and has solved the problems by diligently studying and researching the problems from various aspects.

（構造式１において、Ｒｆはパーフルオロアルキル基を示し、ｍ及びｎは正の整数を示す。） The treatment tank for the production process of the present invention is provided with a film of perfluoroalkoxyalkane (hereinafter referred to as “PFA”) represented by the following structural formula 1 on the outermost surface of the inner wall surface where the reaction product can adhere. (First treatment tank).

(In Structural Formula 1, Rf represents a perfluoroalkyl group, and m and n represent positive integers.)

  The processing tank for another manufacturing process of the present invention is characterized in that, in the first processing tank, the base material of the processing tank is a metal (second processing tank).

  Still another processing tank for a manufacturing process according to the present invention is characterized in that, in the second processing tank, the metal is an aluminum-based metal (third processing tank).

Another processing tank for the manufacturing process of the present invention is the processing tank of any one of the first processing tank to the third processing tank, wherein the PFA film is a film made of Ni or NiF ₂ . It is provided directly on the top (fourth treatment tank).

  Still another processing tank for the manufacturing process of the present invention is the processing tank of any one of the first processing tank to the fourth processing tank, wherein the PFA film is subjected to a remelting process. It is a film (fifth treatment tank).

  The manufacturing method of the processing tank for the manufacturing process of the present invention is the manufacturing method of the processing tank for the manufacturing process, wherein the structure for the processing tank is provided with a film made of PFA on the inner wall surface of the processing tank base material. The structure is exposed to a temperature atmosphere higher than the melting point of PFA to melt at least the free surface region of the film, and then exposed to a temperature lower than the melting point of PFA to form at least a free surface region. Solidify, then re-melt at least the free surface area by exposing to the melting point of PFA or an atmosphere around the melting point of PFA, and then lowering to a temperature sufficiently lower than the melting point of PFA And a step of improving the smoothness of the free surface of the solid film made of PFA (first production method).

Another manufacturing method of the processing tank for the manufacturing process of the present invention is the above first manufacturing method, in which Ni or NiF ₂ is provided before a film made of PFA is provided on the surface of the processing tank base material which is the inner wall surface of the tank. The method further comprises a step of providing a film made of (second production method).

Another manufacturing method of the structure for the processing tank for the manufacturing process of the present invention is the above-described first manufacturing method, in which a film made of PFA is provided on the surface of the processing tank base material which is the inner wall surface of the processing tank. The method further includes a step of providing a film made of Al ₂ O ₃ derived from nonporous anodic oxidation before (third manufacturing method).

  The manufacturing method of the structure of the processing tank for the manufacturing process of this invention prepares the structure for processing tanks which provided the film | membrane which consists of PFA in the surface used as the tank inner wall surface of a processing tank base material, and this structure is used. It is exposed to an atmosphere having a temperature higher than the melting point of PFA to melt at least the free surface region of the solid film, and is then exposed to a temperature lower than the melting point of PFA to solidify at least the portion that becomes the free surface region. A solid film made of PFA by re-melting at least the portion that becomes the free surface region by exposure to an atmosphere at a temperature around the melting point or the melting point of PFA, and then lowering it to a temperature sufficiently lower than the melting point of PFA (4th manufacturing method) characterized by having the process of improving the smoothness of the free surface.

Still another method of manufacturing a structure for a processing tank for a manufacturing process according to the present invention is the above-described fourth manufacturing method, in which a film made of PFA is formed on the surface of the structure that forms the tank inner wall of the processing tank substrate. before providing further comprising a step of providing a film made of Ni or NiF ₂ (fifth production method).

Another manufacturing method of the structure for the processing tank for the manufacturing process according to the present invention is that in the fourth manufacturing method, a film made of PFA is provided on the surface of the processing tank base material which is the inner wall surface of the processing tank. before, characterized by further comprising the step of providing a film of Al ₂ O ₃ derived from the non-porous anodic oxidation (sixth production method).

  According to the treatment tank for manufacturing process composed of the structure (material) of the present invention, the reaction product does not substantially adhere to the inner wall surface even when continuously used, and the production efficiency is greatly increased. be able to. Moreover, even if many types of structural films are produced in one film-forming treatment tank, reaction products do not substantially adhere to the inner wall surface, so each film is always clean as expected. The film can be formed in an in-tank environment, and the resulting structure film has the characteristics as designed. Furthermore, according to the manufacturing method, the structure of the processing tank for the manufacturing process in which the reaction product does not substantially adhere to the inner wall surface even when continuously used, and the processing for the manufacturing process using the structure. A tank can be provided easily.

The typical sectional view for explaining an example of the processing tank for manufacturing processes concerning the present invention. In the Example of this invention, explanatory drawing for demonstrating the measurement of smoothness supplementarily. Typical sectional drawing for demonstrating another example of the processing tank for manufacturing processes which concerns on this invention.

  An example of the processing tank for the manufacturing process according to the present invention is shown in FIG.

  In the treatment tank main body 100 of FIG. 1, a film 102 made of PFA is provided on the inner wall surface of a treatment tank substrate 101 made of metal such as aluminum. The film 102 is formed through a process of melting and remelting after coating PFA on the inner wall surface of the base material 101, thereby imparting high smoothness to the free surface.

  The PFA of structural formula 1 (hereinafter referred to as “PFA (1)”) employed in the present invention is manufactured and sold by many companies. Among them, in the present invention, it is desirable that the melting point is 298 to 310 ° C. and the density is 2.12 to 2.17. Further, when it is necessary to consider the case of using at high temperature, it is desirable to select the highest continuous use temperature, preferably at least 260 ° C. When it is necessary to consider heat dissipation such as an exothermic reaction, the thermal conductivity is preferably 0.25 W / m · k or more, for example.

（構造式１において、Ｒｆはパーフルオロアルキル基を示し、ｍ及びｎは正の整数を示す。）
すなわち、本発明のＰＦＡは、構造式１のような構造を含む、テトラフルオロエチレンとパーフルオロアルキルビニルエーテルとの共重合体である。Ｒｆの例としてはフッ素原子を２以上有するアルキル基、例えば全フッ化アルキル基が挙げられる。Ｒｆの炭素数は特に限定されないが、１以上、好ましくは２以上であり、通常は１２以下、好ましくは６以下である。本発明のＰＦＡの重量平均分子量は特に限定されないが、上記のような融点及び密度特性を満たすものであることが好ましい。

(In Structural Formula 1, Rf represents a perfluoroalkyl group, and m and n represent positive integers.)
That is, the PFA of the present invention is a copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether containing a structure such as structural formula 1. Examples of Rf include an alkyl group having 2 or more fluorine atoms, for example, a fully fluorinated alkyl group. The number of carbon atoms in Rf is not particularly limited, but is 1 or more, preferably 2 or more, and is usually 12 or less, preferably 6 or less. The weight average molecular weight of the PFA of the present invention is not particularly limited, but preferably satisfies the above melting point and density characteristics.

  The melt viscosity of PFA is an important factor for forming a film having high surface smoothness and no waviness. If the melt viscosity is too high, it is difficult to obtain high surface smoothness and undulation is likely to occur. The melt viscosity of PFA in the present invention is preferably 10 g / 10 min or more, more preferably 20 g / 10 min or more, in accordance with ASTM D3307. Of course, if the coating is made uniform and the melting time is sufficiently long, a PFA film having high surface smoothness without waviness can be obtained even if it has a somewhat high melt viscosity.

  Specific examples of PFA that are shown below are preferably employed.

(1) Daikin Industries, Ltd. AC-5539 (for electrostatic coating polymer thick coating, powder)
Other AC sequences include AC-5600, ACX-21, ACX-31, ACX-31WH, ACX-34, and ACX-41.

  In addition, AD-2CRE (coating film thickness: 10 to 15 μm) and AW-5000L (coating film thickness: 30 to 40 μm) can be used.

  It is recommended by the manufacturer that AD-2CRE be used after filtration with a 100-150 mesh wire mesh and AW-5000L with a 60-80 mesh wire mesh after filtration. The coating conditions for AD-2CRE are preferably a spray gun nozzle diameter of 1.0 mmφ and an atomization pressure of 0.2 MPa as air spray conditions. The coating conditions of AW-5000L are preferably a spray gun nozzle diameter of 1.0 to 1.2 mmφ and an atomization pressure of 0.2 to 0.4 MPa as air spray conditions.

  Examples of the primer made by Daikin Industries, Ltd. that are preferably used in the present invention include the following.

As an aqueous primer, ED-1939D21L, EK-1908S21L, EK-1909S21L, EK-1959S21L, EK-1983S21L, EK-1208M1L, EK-1209BEL, EK-1209M10L, EK-1283S1L,
Solvent-based primers include TC-1509M1, TC-1559M2, TC-11000, and the like.

  For example, in the case of primer EK-1909S21L, these primers are roughened with Tosa Emery Extra # 80 / # 100 = 50 · 50 manufactured by Uji Electric Chemical Industry, and then air sprayed by about 10 μm. A PFA film is provided thereon.

  The primer coating conditions are, for example, a spray gun nozzle diameter of 1.0 to 1.2 mmφ, an atomization pressure of 0.2 to 0.4 MPa, or a spray gun nozzle diameter of 1.0 to 1.5 mmφ, and an atomization. The pressure is 0.2 to 0.3 MPa. Drying is performed at a temperature of 80 to 90 ° C. and a time of 10 to 15 minutes, for example.

(2) Mitsui DuPont Fluorochemical Co., Ltd. EM-500CL (for aqueous topcoat), EM-500GN (for aqueous topcoat), EM-700CL (for aqueous topcoat), EM-700GN (for aqueous topcoat), EM -700GY (for water-based topcoat), which are suitable for articles that cannot be electrostatically painted due to their complex shape.

In addition, the present invention can be used as follows:
MP-102 (for micro powder and top coat)
MP-103 (for micro powder, top coat),
MP-300 (fluorinated powder for top coat),
MP-310 (fluorinated powder for top coat),
MP-630 (conductive powder),
MP-642 (conductive powder),
MP-620 (high thermal conductivity),
MP-621 (high thermal conductivity),
MP-622 (high thermal conductivity),
MP-623 (high thermal conductivity),
MP-501 (for articles that cannot be electrostatically painted due to their complicated shape),
MP-502 (for articles that cannot be electrostatically coated due to their complicated shape),
SL-800BK (with carbon filler)
SL-800LT (with glass filler),
Etc.

  Among these, MP-103, MP-300, and MP-310 are preferable in the present invention because the resulting film is excellent in planar smoothness. Among them, MP-310 is particularly preferable because the spherulite control is about 5 μm and excellent in fineness and uniformity. SL-800BK is preferable in the present invention in terms of heat dissipation because it has good heat conduction and excellent heat dissipation. MP-630,642 (conductive micropowder) is also used as a preferred PFA material in the present invention in terms of good heat conduction and excellent heat dissipation.

Among these PFAs manufactured by Mitsui / DuPont Fluorochemicals, RFA in the structural formula 1 is “-CF ₂ CF ₂ CF ₃ ” with a molecular weight of several hundred thousand to one million. The melting point is 300 to 310 ° C., the viscosity is 104 to 105 poise (380 ° C.), and the maximum continuous use temperature is 260 ° C.

  As the primer, those of PFA primer PL-902 series sold as a general aqueous general-purpose primer and PFA primer PL-910 series sold as a primer excellent in heat resistance and corrosion resistance are preferable. Specifically, it is sold under the brand names PL-902YL, PL-902BN, PL-902AL, PL-910YL, PL-910BN, PL-910AL, and PL-914AL.

(3) Packing Land Co., Ltd. NK-108 (lubricity, standard film thickness 50 μm, heat-resistant temperature 260 ° C.),
NK-372 (lubrication, antistatic, standard film thickness 100, 300 μm, heat resistant temperature 260 ° C.),
NK-379 (lubrication, antistatic, standard film thickness 100, 300 μm, heat resistant temperature 260 ° C.),
NK-013 (wear resistance, standard film thickness 300 μm, heat-resistant temperature 150 ° C.),
NK-013C (wear resistance, standard film thickness 300 μm, heat-resistant temperature 150 ° C.),
Is mentioned.

(4) Nippon Fluoro Industry Co., Ltd. NF-015 (standard film thickness 50 μm), NF-015EC (standard film thickness 40 μm, antistatic), NF-020AC (standard film thickness 600 μm, antistatic).

  The shape, size, side wall thickness, and the like of the reaction vessel (also referred to as “treatment tank” in the present invention) in the present invention may be appropriately set according to the purpose of use and the use environment of the reaction vessel. . Moreover, the shaping | molding method of reaction container is not specifically limited, It shape | molds in a predetermined shape with various methods. If the reaction vessel is large or the shape is complicated, the structure may be divided into several parts and finally assembled.

  In the present invention, the base material processed into the processing vessel or the structure constituting the processing vessel is preferably processed with good heat conduction, such as stainless steel, aluminum metal such as aluminum or aluminum alloy, etc. A suitable metal substrate for the construction of the processing vessel is employed. For example, if the metal base material is for PCVD, a small one is formed in a dome shape or a bell jar shape, and a processing vessel is constituted by a base plate and a two-member structure. If it is large, a processing container is comprised by 3 member structure of an upper cover plate, a cylindrical side wall member, and a base plate.

  In the case of a reaction vessel that handles a reaction having a relatively high reaction temperature, it is desirable to select an aluminum-based metal as the base material for the treatment vessel in order to further enhance the heat dissipation effect.

  As the base material made of stainless steel, a material made of a material is appropriately selected according to the purpose and conditions of use of the reaction vessel. In the present invention, SCM440 and S45 are important for hardness, SUS316 is important for corrosion resistance, SUS316L for low carbon steel, and SUS316L-EP whose surface is smoothed by electrolytic polishing in advance. However, it is not limited to these substrates as long as they meet the purpose and conditions of use.

  As the aluminum base material, an aluminum alloy containing other metals in addition to pure aluminum is employed in the present invention.

  The aluminum alloy in the present invention is made of a metal mainly composed of aluminum. The metal containing aluminum as a main component is a metal that usually contains 50% by mass or more of aluminum. Preferably, the metal contains 80% by mass or more of aluminum, more preferably 90% by mass or more, and still more preferably 94% by mass of aluminum. % Or more is desirable.

  A preferable metal contained in the aluminum alloy includes at least one metal selected from the group consisting of magnesium, titanium, and zirconium. Of these, magnesium is particularly preferred because it has the advantage of improving the strength of the aluminum alloy.

  In the present invention, the aluminum alloy may be a metal mainly composed of high-purity aluminum in which the content of a specific element (iron, copper, manganese, zinc, chromium) is suppressed. The total content of these specific elements is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less.

  The aluminum alloy containing high-purity aluminum as a main component may contain one or more other metals that can form an alloy with aluminum, if necessary. Such a metal is not particularly limited as long as it is other than the above-mentioned specific element, but preferred metals include at least one metal selected from the group consisting of magnesium, titanium and zirconium. Of these, magnesium is particularly preferred because it has the advantage of improving the strength of the aluminum alloy. The magnesium concentration is not particularly limited as long as it can form an alloy with aluminum, but is usually 0.5% by mass or more, preferably 1.0% by mass or more, in order to provide sufficient strength improvement. Preferably it is 1.5 mass% or more. In order to form a uniform solid solution with aluminum, it is preferably 6.5% by mass or less, more preferably 5.0% by mass, still more preferably 4.5% by mass or less, and most preferably 3% by mass. It is as follows.

  The aluminum alloy in the present invention may contain other metal components as a crystal modifier in addition to the above metals. There is no particular limitation as long as it has a sufficient effect on crystal control, but zirconium or the like is preferably used.

  In the present invention, the individual content of metals other than aluminum positively contained in the aluminum alloy is usually 0.01% by mass or more, preferably 0%, based on the entire aluminum alloy. 0.05% by mass or more, and more preferably 0.1% by mass or more. The lower limit of this content is necessary for fully expressing the characteristics of the contained metal. However, it is usually 20% by mass or less, preferably 10% by mass or less, more preferably 6% by mass or less, particularly preferably 4.5% by mass or less, and most preferably 3% by mass or less. This upper limit is necessary in order for aluminum and other metal components other than aluminum to form a uniform solid solution and maintain good material properties.

  The surface which becomes the processing container inner wall of these substrates, which are the processing members for the processing container of the present invention, is smoothed by means such as electrolytic polishing, mechanical polishing, or both to give the desired smoothness. Is preferred. When the PFA powder is electrostatically applied to the polished surface, the smoothness of the polished surface at this stage is preferably equal to or less than the average particle size of the PFA powder. However, this need not be the case when the PFA film is not provided directly on the polished surface of the substrate.

In order to more easily and reliably improve the smoothness and film quality of the free surface of the PFA film to be formed, a film 103 (referred to as “underlayer film”) made of Al ₂ O ₃ , Ni or NiF ₂ is previously used as a base material. It is desirable to provide it on the polished surface. If a film made of Ni or NiF ₂ is previously provided on the polished surface of the substrate, the effect of suppressing thermal decomposition of PFA is great when melting or remelting the PFA film provided thereon, A film with better quality than other base materials can be obtained. Further, the Ni film has high corrosion resistance and high adhesiveness with the PFA film, and therefore is preferable as a base film for the PFA film.

  In order to provide the Ni film on the polished surface of the substrate, for example, an electroless nickel plating method or a plasma sputtering method in which Ni is sputtered to form a film is employed. In addition, MOCVD using an Ni complex is used. It can also be adopted.

  In the case of the electroless nickel plating method, the plating solution contains a reducing agent, but P (phosphorus) or B (boron) can be contained in the obtained Ni film depending on the reducing agent used. When hypophosphite is used as the reducing agent, P (phosphorus) can be contained in the obtained Ni film, and when dimethylamine borane (DMAB) is used, B (boron) is contained in the Ni film. I can do it. When B (boron) is contained in the Ni film, the hardness of the film can be increased and the electric resistance of the film can be lowered as compared with the case where P (phosphorus) is contained in the Ni film. It can be used properly according to.

  The use of hydrazine as the reducing agent is advantageous because it does not generate hydrogen gas during the reaction unlike hypophosphorous acid or DMAB.

  The amount of P (phosphorus) contained in the Ni film is appropriately determined depending on the use of the reaction vessel, but is preferably a chemical composition, Ni: 83 to 98%, P: 2 to 15%, and others: It is desirable to be 0 to 2%.

  In the case of B (boron), it is desirable that the chemical composition is Ni: 97 to 99.7%, B: 0.3 to 3%, and other: 0 to 2.7%.

  Although the object of the present invention can be achieved even if an electroless nickel plating is processed by a third party based on a desired specification, the electroless nickel plating solution itself is commercially available or can be prepared by itself. You may go by yourself. Commercially available electroless nickel plating solutions are manufactured or sold by, for example, Tool System Co., Ltd., World Metal Co., Ltd., Metal Processing Technology Laboratory, etc. The companies that perform electroless nickel plating processing include Nippon Kanisen Co., Ltd., Hitachi Kyowa Engineering Co., Ltd., Sanwa Plating Industry Co., Ltd., Kodama Co., Ltd., Shimizu Naga Metal Industry Co., Ltd., Daiwa Electric Industry Co., Ltd., Nishina Industrial Co., Ltd. Company, Fujima Seiren Co., Ltd.

In order to provide the NiF ₂ film on the polished surface of the substrate, the free surface of the Ni film provided on the polished surface of the substrate may be fluorinated. In the fluorination treatment, for example, a base material provided with a Ni film on the surface is set in a vacuum container, and after reaching a predetermined degree of vacuum, F ₂ gas is supplied into the vacuum container and the Ni film surface is exposed to F ₂ gas. Exposure to In this case, by controlling the exposure time to F ₂ gas, the entire Ni film can be made into a NiF ₂ film, or it can be made into a two-layer structure such that the inside is a Ni film and the outermost part is a NiF ₂ film. You can also. Alternatively, the distribution of F atoms in the thickness direction of the film can be changed. For example, the distribution amount of F atoms in the film from the free surface toward the inside of the film can be continuously reduced. In this case, the close contact with the substrate and the close contact with the PFA film can be further strengthened. Of course, in the NiF ₂ film obtained by fluorinating the Ni film by containing P (phosphorus) or B (boron) as described above, P (phosphorus) or B (boron) is formed by the above chemical composition. Needless to say, it is included.

  When a Ni film and a Ni-based film are provided as a base film, after the electroless plating process, annealing is performed for a desired time at a desired temperature in an atmosphere such as a rare gas or a nitrogen gas, whereby the film is applied to the substrate. Since the adhesion force and hardness can be greatly increased, this method is a preferred undercoat post-treatment method in the present invention. Preferably, for example, it is desirable to perform annealing for about 1 hour in a temperature range of 260 to 350 ° C. in a nitrogen atmosphere.

In order to provide an Al ₂ O ₃ film as a base film on the surface of an aluminum substrate, a production method appropriately selected according to the use of the reaction vessel and the use conditions (reaction temperature, reaction raw materials, reaction products, etc.) Is adopted.

The anodic oxidation method that can form a nonporous Al ₂ O ₃ film is preferably employed in the present invention. This anodized film is anodized in the chemical composition having a predetermined composition, or an anodized surface which will be described later on the inner surface of the aluminum reaction vessel itself, or at least the inner surface of the aluminum structure constituting the aluminum reaction vessel. Formed by law.

This Al ₂ O ₃ anodic oxide film is a film made of a metal oxide mainly composed of aluminum, and can be easily formed with a thickness of 10 nm or more. Since this film is a passive film, when it is formed on the inner surface of the aluminum reaction vessel body, it exhibits high performance as a protective film.

The thickness of the Al ₂ O ₃ anodized film is preferably 100 μm or less. If the film is thick, cracks are likely to occur and outgas is likely to be released. Therefore, the film thickness of the Al ₂ O ₃ anodized film is more preferably 10 μm or less, further preferably 1 μm or less, still more preferably 0.8 μm or less, and particularly preferably 0.6 μm or less. The lower limit of the film thickness is desirably 10 nm or more. If the film thickness is too thin, sufficient corrosion resistance cannot be obtained. The thickness of the Al ₂ O ₃ anodized film is more preferably 20 nm or more, and even more preferably 30 nm or more.

The non-porous Al ₂ O ₃ film in the present invention is superior in corrosion resistance to a porous Al ₂ O ₃ film having a porous structure that has been used conventionally, and has fine pores and pores. There is an advantage that it does not or hardly adsorbs moisture or the like because it has no or almost no (substantially).

The Al ₂ O ₃ anodized film is obtained by anodizing the inner surface of an aluminum container main body or structure using a chemical conversion solution having a pH of 4 to 10. According to this method, there is an advantage that a dense and non-porous anodic oxide film can be easily obtained.

In addition, since this method has a function of repairing defects caused by non-uniformity of the metal surface, there is an advantage that a dense and smooth anodic oxide film can be formed. As described above, the lower limit of the pH value of the chemical conversion solution is 4 or more, preferably 5 or more, and more preferably 6 or more. Further, the upper limit of the pH value of the chemical conversion liquid is usually 10 or less, preferably 9 or less, more preferably 8 or less. In order to reliably prevent dissolution of the Al ₂ O ₃ anodic oxide film formed by anodic oxidation in the chemical conversion solution, the pH value is neutral or near neutral, or as close as possible to neutral. It is desirable.

  In the present invention, the chemical conversion solution is preferably in the range of pH 4 to 10 in order to buffer the concentration fluctuation of various substances during anodic oxidation and keep the pH within a predetermined range (buffering action). Therefore, it is desirable to include a compound such as an acid or salt exhibiting a buffering action (hereinafter sometimes referred to as “compound (A)”). The type of such a compound is not particularly limited, but is preferably at least one selected from the group consisting of boric acid, phosphoric acid, organic carboxylic acid, and salts thereof from the viewpoint of high solubility in the chemical conversion solution and good dissolution stability. is there. More preferably, it is an organic carboxylic acid or a salt thereof that hardly contains boron or phosphorus elements in the anodic oxide coating 2.

  The concentration of these compounds (A) may be appropriately selected according to the purpose, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass with respect to the whole chemical conversion liquid. That's it. Increasing the electrical conductivity is desirable in order to sufficiently form the anodic oxide film. However, it is usually 30% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less. In order to keep the performance of the anodic oxide film high and to reduce the cost, it is desirable that it be less than this.

The chemical conversion liquid in the present invention preferably contains a non-aqueous solvent. The use of a chemical conversion solution containing a non-aqueous solvent has an advantage that it can be processed at a high throughput because the time required for the constant current conversion is shorter than that of an aqueous chemical conversion solution. In addition, when an aqueous solution is used as a chemical conversion solution, OH ⁻ ions generated by electrolysis of water etch the anodic oxide film to make it porous, so that the main solvent having a low dielectric constant that can suppress water electrolysis Is preferably used.

  The type of the non-aqueous solvent is not particularly limited as long as it can be anodized satisfactorily and has sufficient solubility in a solute, but a solvent having one or more alcoholic hydroxyl groups and / or one or more phenolic hydroxyl groups, Or an aprotic organic solvent is preferable. Among these, a solvent having an alcoholic hydroxyl group is preferable from the viewpoint of storage stability.

  Examples of the compound having an alcoholic hydroxyl group include monohydric alcohols such as methanol, ethanol, propanol, isopropanol, 1-butanol, 2-ethyl-1-hexanol, and cyclohexanol; ethylene glycol, propylene glycol, butane-1,4. -Dihydric alcohols such as diol, diethylene glycol, triethylene glycol, and tetraethylene glycol; trihydric or higher polyhydric alcohols such as glycerin and pentaerythritol can be used. Moreover, the solvent which has functional groups other than alcoholic hydroxyl group in a molecule | numerator can also be used. Among these, those having two or more alcoholic hydroxyl groups are preferable in view of miscibility with water and vapor pressure, more preferably dihydric alcohols and trihydric alcohols, and particularly preferably ethylene glycol, propylene glycol, and diethylene glycol.

  These compounds having an alcoholic hydroxyl group and / or a phenolic hydroxyl group may further have other functional groups in the molecule. For example, a solvent having an alkoxy group together with an alcoholic hydroxyl group such as methyl cellosolve and cellosolve can also be used.

  As the aprotic organic solvent, either a polar solvent or a nonpolar solvent may be used.

  The polar solvent is not particularly limited, but examples thereof include cyclic carboxylic acid esters such as γ-butyrolactone, γ-valerolactone, and δ-valerolactone; chain carboxylic acid esters such as methyl acetate, ethyl acetate, and methyl propionate. Cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate; chain carbonates such as dimethyl carbonate, ethylmethyl carbonate, diethyl carbonate, N-methylformamide, N-ethylformamide, N, N- Amides such as dimethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, glutaronitrile, adiponitrile, methoxyacetate Nitrile, 3-methoxy nitriles such as propionitrile; trimethyl phosphate, phosphates such as triethyl phosphate.

  Although it does not specifically limit as a nonpolar solvent, For example, hexane, toluene, silicone oil, etc. are mentioned.

  These solvents may be used alone or in combination of two or more. Particularly preferred as the non-aqueous solvent for the chemical conversion liquid used for forming the anodic oxide film is ethylene glycol, propylene glycol, or diethylene glycol, which may be used alone or in combination. Moreover, if it contains the nonaqueous solvent, you may contain water.

  The non-aqueous solvent is usually contained in an amount of 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 55% by mass or more, and usually 95% by mass or less, based on the whole chemical conversion liquid. , Preferably 90% by mass or less, particularly preferably 85% by mass or less.

  When the chemical conversion liquid contains water in addition to the non-aqueous solvent, the content thereof is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% with respect to the whole chemical conversion liquid. The content is usually at least 85% by mass, preferably at most 50% by mass, particularly preferably at most 40% by mass.

  The ratio of water to the non-aqueous solvent is preferably 1% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, particularly preferably 10% by mass or more, and usually 90% by mass or less, preferably 60%. It is not more than mass%, more preferably not more than 50 mass%, particularly preferably not more than 40 mass%.

  The chemical conversion liquid may contain other additives as necessary. For example, you may contain the additive for improving the film formability and film | membrane characteristic of an anodic oxide film. The additive is not particularly limited and may be used by adding one or more substances selected from known additives and other substances. At this time, there is no special restriction | limiting in the addition amount of an additive, What is necessary is just to consider an effect and cost, etc.

  The electrolytic method for anodization is not particularly limited. As the current waveform, for example, in addition to direct current, a pulse method in which an applied voltage is periodically interrupted, a PR method in which the polarity is inverted, other alternating current, AC / DC superimposition, incomplete rectification, a modulation current such as a triangular wave, or the like can be used. However, preferably a direct current is used.

  The method for controlling the current and voltage for anodization is not particularly limited, and conditions for forming an oxide film on the inner surface of the aluminum alloy container body 1 can be appropriately combined. Usually, it is preferable to anodize at a constant current and a constant voltage. In other words, it is preferable that the formation is performed at a constant current up to a predetermined formation voltage Vf, and after the formation voltage is reached, the voltage is held for a certain period of time to perform anodization.

At this time, in order to efficiently form an oxide film, the current density is usually 0.001 mA / cm ² or more, preferably 0.01 mA / cm ² or more. However, in order to obtain an oxide film with good surface flatness, the current density is usually 100 mA / cm ² or less, preferably 10 mA / cm ² or less.

  The formation voltage Vf is usually 3 V or higher, preferably 10 V or higher, more preferably 20 V or higher. Since the obtained oxide film thickness is related to the formation voltage Vf, it is preferable to apply the voltage or more in order to give a certain thickness to the oxide film. However, it is usually 1000 V or less, preferably 700 V or less, more preferably 500 V or less. Since the obtained oxide film has high insulating properties, it is preferable to carry out at the voltage or lower in order to form a high-quality oxide film without causing high dielectric breakdown. Alternatively, a method may be used in which an alternating current having a constant peak current value is used instead of the direct current power source until the formation voltage is reached, and when the formation voltage is reached, the direct current voltage is switched to the direct current voltage and held for a certain period of time.

  Other conditions for the anodization are not particularly limited. However, the temperature at the time of anodization is set to a temperature range in which the chemical conversion liquid exists stably as a liquid. Usually, it is −20 ° C. or higher, preferably 5 ° C. or higher, more preferably 10 ° C. or higher. In consideration of production, energy efficiency, and the like at the time of anodization, it is preferable to perform the treatment at the temperature or higher. However, it is usually 150 ° C. or lower, preferably 100 ° C. or lower, more preferably 80 ° C. or lower. In order to maintain the composition of the chemical conversion solution and perform uniform anodic oxidation, the treatment is preferably performed at the temperature or lower.

  The anodization includes a first step in which an inner surface of the aluminum reaction vessel main body or the structure thereof and a counter electrode (for example, platinum) are disposed in the chemical conversion liquid, and the aluminum reaction vessel main body or the structure thereof. A positive voltage to the electrode, a negative voltage is applied to the electrode and a constant current is allowed to flow for a predetermined time, and a constant voltage is applied between the electrode and the aluminum reaction vessel body or the structure for a predetermined time. It is preferable to include the 3rd process to apply.

The predetermined time of the second step is until the voltage between the aluminum reaction vessel body or its structure and a predetermined electrode reaches a predetermined value (for example, 200 V when ethylene glycol is used). It is preferable that The predetermined time of the third step is preferably set until a current between the aluminum alloy container body or its structure and a predetermined electrode reaches a predetermined value. The current value rapidly decreases when the voltage reaches the predetermined value, and then gradually decreases with time (referred to as “residual current”). However, in order to fall below the predetermined current value at the end of the constant voltage process, for example, 24 It takes time. However, the quality of the Al ₂ O ₃ anodized film obtained is equivalent to that obtained by heat treatment. Further, the smaller the residual current, the better the quality of the Al ₂ O ₃ anodized film. In consideration of these matters, in order to increase productivity, it is desirable to stop the constant voltage treatment at an appropriate time and perform heat treatment (annealing) in the next step. The heat treatment is preferably performed at 150 ° C. or more, more preferably at about 300 ° C. for 0.5 to 1 hour. Although depending on the continuation of the residual current, if the duration of the residual current is not so long, the constant voltage process may be continuously performed, and if it is long, the process may be switched to the heat treatment.

  In the second step, it is desirable to pass a current of 0.01 to 100 mA, preferably 0.1 to 10 mA, more preferably 0.5 to 2 mA per square centimeter. As described above, in the third step, the voltage is set such that the chemical conversion liquid does not cause electrolysis.

Although not bound by any theory, from the knowledge obtained by the present inventors, the nonporous Al ₂ O ₃ anodized film formed during the chemical conversion treatment has an amorphous structure as a whole. Therefore, it is considered that there are almost no grain boundaries such as crystals. Further, by adding a compound having a buffering action or using a non-aqueous solvent as a solvent, a trace amount of carbon component is taken into the anodized film and the bonding strength of Al-O is weakened. This presumably stabilizes the amorphous structure of the entire film.

The Al ₂ O ₃ anodized film manufactured as described above is preferably subjected to heat treatment for the purpose of completely removing moisture in the film. In particular, an anodic oxide film of Al formed on an aluminum alloy base material mainly composed of high-purity aluminum that does not substantially contain the specific element has a high thermal stability and is difficult to form voids or gas reservoirs. There is. For this reason, even when annealing at about 300 ° C. or higher, almost no voids or seams are generated in the Al anodic oxide film, so that elution of aluminum into the reaction solution due to generation of particles and exposure of aluminum can be suppressed.

The temperature of the heat treatment is not particularly limited, but is usually 100 ° C. or higher, preferably 200 ° C. or higher, more preferably 250 ° C. or higher. In order to sufficiently remove moisture on the surface and inside of the Al ₂ O ₃ anodized film by heat treatment, it is desirable to perform the treatment at the above temperature or more. However, it is usually 600 ° C. or lower, preferably 550 ° C. or lower, more preferably 500 ° C. or lower. In order to maintain the amorphous structure of the Al ₂ O ₃ anodized film and maintain the flatness of the surface, it is desirable to perform the treatment at the above temperature.

The time for the heat treatment is not particularly limited, and may be appropriately set in consideration of surface roughness due to the heat treatment, productivity, etc., but is usually 1 minute or more, preferably 5 minutes or more, particularly preferably 15 minutes or more. is there. In order to sufficiently remove moisture on the surface and the inside of the Al ₂ O ₃ anodized film, it is preferable to perform the treatment for at least the above time. However, it is usually 180 minutes or less, preferably 120 minutes or less, more preferably 60 minutes or less. In order to maintain the Al ₂ O ₃ anodic oxide film structure and the surface flatness, it is desirable to perform the treatment within the above time.

  The atmosphere in the furnace during the annealing treatment is not particularly limited, but usually nitrogen, oxygen, or a mixed gas thereof can be appropriately used. Of these, an atmosphere having an oxygen concentration of 18 vol% or higher is preferable, a condition of 20 vol% or higher is more preferable, and a condition of oxygen concentration of 100 vol% is most preferable.

  It is desirable to perform primer treatment of PFA on the base surface on which the PFA film is directly provided in order to increase the adhesion with the base surface.

In the present invention, the thickness of the base film is determined so that the smoothness of the surface on which the PFA film is provided can be sufficiently ensured as desired, the smoothness of the polished surface of the substrate, the average particle diameter of the PFA powder used, or the PFA In view of the average particle diameter of the PFA particles dispersed in the paint, it is selected as desired in a timely manner.
In the present invention, it is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and still more preferably 2 to 15 μm.

  In order to provide a PFA film on the polishing surface or the base film surface of the base material (referred to as “PFA film formation surface” together), it is also described in Experiments 1 and 2 and Examples below. The following is preferred.

  When forming the PFA film, the prepared PFA includes a fine powder for electrostatic coating and a liquid similar to a general paint. In the present invention, it is preferable to use a fine powder form for electrostatic coating because a coating film with a uniform thickness can be easily formed even if the shape of the structure of the processing container has a somewhat complicated uneven shape.

  As for the painting method, in the case of liquid paints as well as general paints, it is desirable to paint by spray coating, but depending on the substrate, it is painted by dip coating, dip spin coating, roll coating, and spin flow coating. It is also adopted as appropriate. Further, it is desirable that the powder coating is processed by electrostatic powder coating or electrostatic fluid dipping.

  The PFA paint thus coated is baked onto the PFA film forming surface of the base material for the processing vessel. At that time, a melting and re-melting process is applied, and finally the desired smoothing performance is achieved. A PFA coating film having

The method of processing a coating film on the PFA film-forming surface of the processing container substrate varies depending on the type of substrate, application, and the type of paint to be selected, but it is preferable to perform processing in the following steps.
(1) Preparation of metal base material (coating material) (electropolished) ⇒ (2) Degreasing or calcining ⇒ (3) Roughening (blasting) or / and base film formation ⇒ (4) Clean ⇒ (5) Primer coating ⇒ (6) Pre-drying ⇒ (7) Top coat (PFA) coating ⇒ (8) Pre-drying ⇒ (9) Primary firing (melting) ⇒ (10) Primary cooling (melting point of PFA used) ⇒ (11) Secondary firing (remelting) ⇒ (12) Secondary cooling (room temperature)

  When a thick topcoat layer is provided, the desired thickness can be obtained by repeatedly performing “(7) Topcoat (PFA) coating ⇒ (8) Predrying ⇒ (9) Primary firing (melting)” in the above process. In addition, a top coat layer can be formed. The coating thickness per time in this case is the form of PFA to be used (powder or paint), the viscosity at the time of melting treatment, the dispersion concentration and particle size of PFA in the case of paint, the particle size of powder in the case of powder, Etc. In the present invention, the thickness is preferably 1 to 100 μm.

  In the case of multiple coatings, the primary firing temperature in the first and intermediate coatings is set as the intermediate primary firing temperature, and the primary firing temperature in the final coating is set as the final primary firing temperature. Depending on the type of PFA and the number of coatings, the intermediate primary firing temperature and the final primary firing temperature may be set to the same temperature. Preferably, the intermediate primary firing temperature is set lower than the final primary firing temperature. It is desirable to be done.

  (3) The processing of (5) and (6) is omitted in some cases. For example, even if a top coat is provided directly on the surface of the base material, if there is sufficient adhesion between the base material surface and the top coat surface, the processing steps (3), (5) and (6) can be omitted. If the substrate and the top coat are firmly bonded by the primer by applying the primer, the processing (3) can be omitted.

  The primary firing temperature and firing time in the present invention are important factors for obtaining sufficient smoothness to achieve the object of the present invention in the secondary firing, and the PFA and metal substrate used, as required. It is determined appropriately according to the specification of the primer to be employed.

  The temperature and time of the primary firing in the present invention include impurities (low molecular weight components, unfluorinated end groups) contained in the PFA material (available in powder form or paint form) by primary firing from the coated PFA film. It is desirable that the temperature and time be sufficient for discharging components, products during synthesis, additives such as surfactants, etc.) out of the membrane. The upper limit of the primary firing temperature is a temperature at which PFA having a molecular weight necessary to constitute a PFA film giving high smoothness is not decomposed (referred to as “PFA decomposition temperature”), or a temperature slightly higher than the decomposition temperature (“ It is desirable to be referred to as “Th”. Th is determined in relation to the time for holding the PFA coating film at the temperature in the primary firing.

  Th in the present invention is preferably set to 30 to 70 ° C. higher than the melting point of PFA to be used. If the set temperature is too low, sufficient smoothness may not be obtained in secondary firing, and if it is too high, decomposition of PFA may be promoted. More preferably, it is 35-60 degreeC, More preferably, it is desirable to set it as 40-50 degreeC.

  The primary firing time in the present invention includes a time for raising the temperature to the primary firing temperature (primary firing temperature raising time) and a time for maintaining the primary firing temperature (primary firing temperature holding time). In the primary firing temperature raising time, the temperature raising speed is controlled by the control device so that heat is uniformly transmitted to any part of the PFA coating film and the PFA coating film is uniformly fired. The primary firing temperature holding time is a time for melting the entire free surface of the PFA coating film as uniformly as possible so that the local non-uniformity cannot be seen visually. In the present invention, the primary firing temperature holding time depends on the thickness and size of the PFA coating film, and thus is appropriately determined each time depending on the thickness and size of the PFA coating film. Minutes, more preferably 15 to 40 minutes.

  In primary firing, the smoothness of the film obtained through the secondary firing depends on the firing temperature, the temperature rise speed to the firing temperature and the setting of the holding time at the firing temperature, so the firing temperature in the primary firing The heating speed up to the firing temperature and the holding time at the firing temperature are appropriately determined in consideration of the substrate, the type of PAF, the thickness of the PFA coating film and the coating area.

  In the primary firing, it is considered that impurities contained in the PFA material (available in powder form or paint form) are decomposed and removed from the PFA film. It is thought that the smoothness of the PFA film that has been subjected to the secondary baking is remarkably improved by removing unnecessary impurities from the PFA film by the primary baking.

In the present invention, the primary firing is performed in a gas atmosphere in which oxygen is mixed with a rare gas, such as a 20 vol% O ₂ / Ar gas atmosphere. The atmosphere gas for the primary firing is preferably a rare gas / oxygen mixed gas, but is not limited to this in the present invention, and may be an oxygen gas alone or a nitrogen / oxygen mixed gas. It may be used a mixed gas of NO and NO ₂ and oxygen instead of nitrogen. NO and NO ₂ may be used alone. Ozone can be used instead of oxygen gas.

  When the primary firing is completed, the sample is cooled to a temperature not higher than the melting point of the PFA to be used (referred to as “Tl”) and solidified (primary cooling / solidification). The temperature Tl below the melting point at this time is preferably 5 to 60 ° C., more preferably 10 to 50 ° C., and even more preferably 20 to 50 ° C. lower than the melting point of the PFA to be used. When the melting point varies depending on the molecular weight distribution of PFA, the mixing of a plurality of PFAs having different molecular weights, etc., the primary firing temperature is appropriately selected as desired in the above range with respect to the lowest temperature within the range of the width. If the width of the temperature lower than the melting point of PFA is too small, smooth solidification cannot be expected, and if it is too large, it takes too much time to reach re-melting and the production efficiency is lowered.

  The temperature below the melting point (primary cooling / solidification temperature) Tl is the temperature raising speed for raising the temperature from the Tl to the secondary firing temperature and the holding time at the secondary firing temperature is free of the PFA film obtained by secondary cooling to room temperature. It is set so that the smoothness of the surface is sufficiently secured.

  The secondary firing temperature is a temperature for remelting the PFA film once solidified through the primary firing treatment, and solidifies through a temperature lowering process to room temperature where the PFA coating film subjected to the primary firing treatment is next applied. It is the temperature that promotes smoothing during the process.

  The secondary firing is preferably performed at the melting point of the PFA to be used or at a temperature within 15 ° C. higher than this melting point. It is more preferable to carry out at a temperature slightly different from the melting point of the PFA to be used or the melting point before and after that.

  Next, an example of the melting and remelting steps will be described below.

When Rf in the structural formula 1 is “—CF ₂ CF ₂ CF ₃ ” (melting point is 310 ° C.), for example, a PFA fine powder is applied to the PFA film forming surface of the processing container substrate by a predetermined thickness by electrostatic coating. Then, it is heated to 345 ° C. at a programmed heating rate, and this state of 345 ° C. is maintained for 30 minutes (melting step). This melting step is performed in a 20 vol% O ₂ / Ar gas atmosphere. Next, the atmosphere is switched to a 100 vol% argon atmosphere, the temperature is lowered to 280 ° C. at a predetermined rate, and when the temperature reaches 280 ° C., the temperature is maintained for 30 minutes. Subsequently, it is heated again to 310 ° C. at a predetermined rate (remelting step), and this temperature is maintained for 30 minutes. After holding for 30 minutes, the temperature is lowered to room temperature by stopping heating and allowing to stand naturally. By passing through such a process, a PFA film having a very smooth free surface can be formed.

When Rf is PFA of “—CF ₂ CF ₂ CF ₃ ”, the melting point is said to be 310 ° C., but melting has already started between 295 ° C. and 305 ° C. Accordingly, a temperature in the range of 295 ° C. to 315 ° C. can be selected as the temperature of the remelting step. Preferably, a temperature in the range of 305 ° C to 315 ° C is selected.

  The smoothness is the best at 310 ° C. or a temperature slightly different from the melting point before and after that, but in order to obtain smoothness suitable for the purpose of the present invention, it is in the range of 305 ° C. to 315 ° C. It is desirable to remelt at temperature.

  Hereinafter, the present invention will be specifically described by experiments and examples, but the present invention is not limited to these experiments and examples. In addition, the part and% in this experiment and an Example are mass references | standards unless it mentions specially.

[Experiment 1] PFA melting and remelting experiment on plate-like substrate and smoothness measurement Plate-shaped SUS substrate (SUS316L-EP: 10 cm × 10 cm, which has been subjected to a predetermined polishing treatment after mirror polishing treatment) Two sheets (base materials 1 and 2) having a thickness of 2 mm) were prepared. When the surface smoothness of the mirror-finished surface of these base materials was measured with a commercially available surface roughness measuring device (dektak 6M manufactured by Veeco), the surface roughness Ra was 0.006 μm in any case.

A Ni film (thickness: 2 μm) was provided by electroless plating on the surface of one of them (base material 1) on which the surface smoothness was measured. The electroless plating conditions are described below.
Electroless plating solution (A):
Nickel sulfate ... 26.3g / L
Sodium hypophosphite ... 21.2g / L
Citric acid ... 25.0g / L
Acetic acid ... 12.5g / L
Lossell salt ... 16.0 g / L
Urea ... 12.5g / L
pH ... 6.0
Bath temperature: 80 ° C

  The mirror-finished surface of the substrate 1 was subjected to the following treatment, and then immersed in a bath of the electroless plating solution (A) to form a Ni film.

  The base material 1 was immersed in a commercially available degreasing agent (OPC-370 Condy Clean M / trade name: manufactured by Okuno Pharmaceutical Co., Ltd.) at 60 ° C. for 5 minutes. Next, the mirror-finished surface was sufficiently washed with ultrapure water for semiconductors withdrawn from the degreasing agent. Then, it was immersed in a commercially available catalyst imparting agent (OPC-80 catalyst / trade name: Okuno Pharmaceutical Co., Ltd.) at 25 ° C. for 5 minutes. Subsequently, the mirror-finished surface was sufficiently washed with ultrapure water for semiconductors by pulling it up from the catalyst imparting agent. After this washing, it was immersed in a commercially available activation liquid (OPC-505 accelerator / trade name: manufactured by Okuno Pharmaceutical Co., Ltd.) at 35 ° C. for 5 minutes. Next, the mirror-finished surface was sufficiently washed with ultrapure water for semiconductors by pulling up from the activation liquid.

  The substrate 1 treated in this way was immersed in the electroless plating solution (A) for 70 minutes. Next, it was lifted from the electroless plating solution (A) and sufficiently washed with ultrapure water for semiconductors. When visually observed, the Ni film was uniformly formed on the entire mirror-finished surface, and the free surface was extremely smooth. When the smoothness of the free surface of the Ni film was measured with the above-mentioned commercially available apparatus, Ra = 0.006 μm, which was a surface roughness that was the same as the mirror-finished surface of the substrate.

  The base material 1 provided with the Ni film as described above and the base material 2 are placed in a commercially available degreasing agent (OPC-370 Condy Clean M / trade name: manufactured by Okuno Pharmaceutical Co., Ltd.) at 60 ° C. for 5 minutes. A degreasing treatment was performed by dipping. Subsequently, it pulled up from the inside of a degreasing agent and fully washed with the ultrapure water for semiconductors.

The pre-coating material (primer) is applied to the Ni film surface (Ni film free surface) of the base material 1 subjected to such treatment and the surface of the base material 2 on which the smoothness is measured (mirror finish surface) under the following conditions. And dried.
Precoat material (primer): EK-1908S21L (manufactured by Daikin Industries, Ltd.)
・ Painting conditions: Nozzle diameter of spray gun ... 1.2mmφ
Atomization pressure: 0.3 MPa
-Drying conditions: 85 ° C, 15 minutes

Next, after a PFA powder film is formed on the precoated material treated surfaces of the substrates 1 and 2 to a thickness of about 120 μm by electrostatic coating under the following conditions, these substrates are accommodated in an infrared heating furnace. It installed in the made container (quartz container).
・ Topcoat material: AC-5600 (manufactured by Daikin Industries, Ltd.)
・ Electrostatic coating device (Landsburg Co., Ltd.):
Handgun: REA90 / L
High pressure controller 9040
Number of overcoating ... 3 times Coating amount per time ... 120 ± 10μm
Intermediate firing between paintings Approx. 340 ° C, 15 minutes

  In the infrared heating furnace used in this experiment, even when not in use, the cleanliness of the inside is maintained by constantly flowing 100% argon at a flow rate of 1 L / min inside the quartz container. In this infrared heating furnace, a thermocouple is attached to the outer periphery of the quartz vessel, and the output of the infrared light source is controlled by a temperature controller so that the temperature will be as programmed based on the temperature information from this thermocouple. It is the composition to do. The quartz vessel is provided with a gas pipe for introducing a gas from outside the furnace. For example, a gas such as 100 vol% argon and argon mixed with 20 vol% oxygen is introduced into the furnace. The inside can be adjusted to a desired atmosphere.

Two substrates 1 and 2 treated with PFA coating are placed in a quartz container, the door is closed to shut off the atmosphere, and 20 vol% O ₂ / Ar gas is introduced into the infrared heating furnace at a flow rate of 1 L / min. Supply started. This state was kept waiting for the atmospheric temperature of the space near the quartz container installation and the temperature of the quartz container to become constant. After the temperature became constant, the infrared light source was turned on. The temperature of the quartz container immediately before turning on the infrared light source was 25 ° C.

  Subsequently, the output of the infrared light source was gradually increased, and the temperature was raised in a substantially linear function to 345 ° C. in 1 hour. Subsequently, this state of 345 ° C. was maintained for 30 minutes. Thereafter, the gas was switched to Ar 100 vol%, and this gas was allowed to flow at a flow rate of 5 L / min for 10 minutes, so that the temperature of the quartz container was 280 ° C. This state was maintained for 30 minutes. When the PFA-treated surfaces of the substrates 1 and 2 were visually observed, surface irregularities were observed. After holding for 30 minutes, the flow rate of Ar 100 vol% gas was set to 1 L / min, and the temperature was raised from 280 ° C. to 310 ° C. in 6 minutes. When the temperature reached 310 ° C., the output of the infrared light source was controlled and the state was maintained for 30 minutes. Thereafter, the substrates 1 and 2 were moved to a place not exposed to infrared light in the quartz container and allowed to cool naturally.

  After the temperature was lowered to room temperature by natural cooling, the substrates 1 and 2 were taken out. When the PFA-treated surfaces of the substrates 1 and 2 at this time were visually observed, they were close to a mirror surface.

  The base materials 1 and 2 were set in the surface smoothness measuring apparatus used in Experiment 1, and the smoothness of the PFA surface was measured. At this time, for convenience, the base material 1 is referred to as a sample 1-1, and the base material 2 is referred to as a sample 1-2. In the measurement, the free surface of the PFA film of each material was divided into 5 parts every 2 cm in parallel to one side (referred to as X-axis direction for convenience), and each divided surface was measured on a straight line from end to end of the sample. Next, the smoothness in the direction perpendicular to the straight line (referred to as the Y-axis direction for convenience) was also measured in each divided region by dividing the free surface of the PFA film of each material into 5 parts every 2 cm (see FIG. 2). The measurement results are shown in Table 1.

[Experiment 2] PFA melting and remelting experiment on curved substrate and measurement of smoothness In place of the plate-like substrate in Experiment 1, the inner surface is a cylindrical concave surface (curvature radius: 20 ^cmΦ , 10 cm × 10 cm) Except for the above, each sample was subjected to Ni treatment or PFA treatment in the same manner as in Experiment 1, and samples 2-1 for smoothness measurement (Ni treatment was applied), 2-2 (Ni treatment was performed) Not applied). For these, the smoothness was measured in the same manner as in Experiment 1. The results are shown in Tables 2-1 and 2-2.

[Experiment 3] Experiment on presence / absence of re-melting of PFA film and smoothness measurement Prepare two plate-like SUS substrates (SUS316L-EP: 2 cm × 5 cm) (samples 3-1 and 3-2) that are mirror-polished. In the same manner as in Experiment 1, a Ni film was provided on the mirror-polished surface of the SUS substrate. Similar to Experiment 1, when the surface roughness of the mirror-polished surface and the Ni film surface of the two SUS substrates was measured, the same results as in Experiment 1 were obtained.

On the Ni film of the SUS substrate provided with Ni films on two surfaces, PFA was coated according to the specifications by outsourcing.
Subcontractor: Nippon Fluoro Industry Co., Ltd. Topcoat material: ACX-31 (Daikin Industries, Ltd.)
Coating method: Electrostatic coating PFA coating thickness: 20μm

  Next, the two SUS substrates coated with PFA were baked in the following steps. The same furnace used in Experiment 1 was used as the firing furnace.

For two samples, a SUA substrate in which PFA powder was electrostatically applied to a quartz cocoon was placed in a quartz container, and baked in the following procedure.
(1) Flow 20% O ₂ / Ar at a flow rate of 1 L / min and raise the temperature from room temperature to 345 ° C. over 1 hour.
(2) Maintain the atmosphere at 345 ° C. for 30 minutes.
(3) Ar100% is flowed at a flow rate of 5 L / min and lowered to 280 ° C. in 10 minutes. At this stage, the sample 3-2 is moved to the non-heated position so that the subsequent heating history (remelting) does not occur.
(4) Maintain the atmosphere at 280 ° C. for 30 minutes.
(5) The temperature is raised from 280 ° C. to 310 ° C. in 6 minutes by changing the atmosphere to 100% Ar and a flow rate of 1 L / min.
(6) Hold 310 ° C. for 30 minutes while maintaining the atmosphere.
(7) Turn off the heating and move the quartz insulator (sample 3-1) to the non-heated position to allow it to cool naturally.

The temperature program is shown below.

The smoothness of the free surface of the PFA films of Sample 3-1 (with remelting history) and Sample 3-2 (without remelting history) on which the PFA film was formed in this way was measured in the same manner as in Experiment 1. As shown in the results, the sample 3-1 had very good smoothness and no swell was observed.
Sample 3-1: Ra = 0.061 μm, PV = 0.302 μm
Sample 3-2: Ra = 0.354 μm, PV = 2.141 μm

[Experiment 4] PFA variation experiment A PFA film was provided on the mirror-polished surface of the plate-like SUS substrate in the same manner as in Experiment 1 except that the topcoat material was changed and the conditions described in Table 4 were used. The smoothness of the PFA film surface was measured in the same manner as in Experiment 1. The results are shown in Table 4.
Top coat material:
MP-310 (Mitsui / DuPont Fluorochemicals),
EM-500CL (Mitsui / DuPont Fluorochemicals),
EM-700CL (Mitsui / DuPont Fluorochemicals)
AW-5000L (Daikin Industries, Ltd.)

[Example A]

  A SUS base material (SUS316L-EP) is precision machined, and as a structural member for a reactor, an upper lid plate 302 (diameter: 100 cm, thickness: 15 mm), a cylindrical side wall member 303 (diameter: 100 cm, height: 50 cm) 15 mm) and a base plate 304 (diameter: 150 cm, thickness: 20 mm).

  In the same manner as in Experiment 1, after pre-treatment, a Ni plating film was formed to a thickness of 2 μm by electroless plating on the surfaces serving as the inner walls. Then, a PFA film was provided on the Ni film surface of each member in the same manner as in Experiment 1. Thus, when the smoothness of the PFA free surface of the three structural members provided with the PFA film was measured in the same manner as in Experiment 1, the same results as in Experiment 1 were obtained.

  Thereafter, the reactor 301 was formed by setting the three structural members provided with the PFA film in a plasma processing apparatus 300 obtained by modifying a commercially available plasma CVD (PCVD) processing apparatus for experiments. Reference numeral 305 denotes a sealing material for a vacuum device such as an O-ring. A schematic diagram of the reaction furnace 301 is shown in FIG.

Using this reactor 301, Si film (film thickness: 2 μm) / P ⁺ Si film (film thickness: 0.2 μm) / SiO film (film thickness: 2 μm) / P ⁺ Si under the conditions shown in Table 5-1 A three-layer structure film of film (film thickness: 0.2 μm) / SiN film (film thickness: 2 μm) was formed on a glass substrate (3 cm × 3 cm) provided with an Au electrode on the surface. By repeating this film formation continuously, the same kind of three-layer structure films were formed on five kinds of glass substrates.

  Thereafter, the vacuum in the reaction furnace 301 was broken and the inner wall of the furnace 301 was observed, and no product was found attached.

  Each sample was provided with an Au electrode on the uppermost layer of the obtained three-layer structure film so that the electrical characteristics could be measured. As shown in Table 5-2, each sample was confirmed to have the desired characteristics, and no variation was observed between the films.

マイクロ波パワー：Ｓｉ、Ｐ^＋・・・８２０Ｗ
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Microwave power: Si, P ⁺ ... 820W
SiO, SiN ... 1500W

[Example B1]
(Create reaction vessel)
<Creation of container body>
A cylindrical container body was prepared by bending and arc welding a plate (3 mm thick) of aluminum alloy A5083.

<Formation of anodized film>
After dissolving 1.8 parts of tartaric acid in 39.5 parts of water, 158 parts of ethylene glycol (EG) was added and mixed with stirring. While this solution was stirred, 29% aqueous ammonia was added until the pH of the solution reached 7.1 to prepare a chemical conversion solution a.

In this chemical conversion solution, the container body was formed at a constant current of 1 mA / cm ² up to a chemical conversion voltage of 50 V, and after reaching 50 V, anodization was performed by holding at a constant voltage for 30 minutes.

  After the reaction, the product was sufficiently washed with pure water and then dried at room temperature. The obtained aluminum sample piece with an oxide film was annealed in an IR furnace at 300 ° C. for 1 hour, then opened to the atmosphere and left at room temperature for 48 hours. The thickness of the nonporous metal oxide film was measured and found to be 0.08 μm.

<Formation of PFA film>
The surface of the anodized film is degreased with an organic solvent, and PES primer 462-Z-68501 manufactured by DuPont is spray-coated so that the thickness after firing is 8 μm, and dried at 100 ° C. for 10 minutes. On top of this, PFA paint AC-5600 manufactured by Daikin Industries, Ltd. was applied in the same manner as in Experiment 1 so that the thickness after firing was 25 μm, and then a PFA film was formed in the same manner as in Experiment 1.

  Thus, an aluminum alloy reaction vessel of the present invention was obtained. Separately from the above, a glass five-hole separable cover was prepared as a reaction vessel lid, and a cooling device, a thermometer, and a stirring blade were attached thereto to constitute a reaction apparatus.

(Production of polymer: Test example 1)
In an emulsification tank equipped with a stirrer, 50 parts of water, 31 parts of butadiene, 32 parts of styrene, 10.5 parts of methyl methacrylate, 6 parts of acrylonitrile, 0.5 part of acrylic acid, 0.6 part of t-dodecyl mercaptan and dodecylbenzenesulfone 0.3 parts of sodium acid salt was added and stirred to obtain a monomer emulsion.

  Separately from the preparation of the monomer emulsion, 70 parts of water, 4 parts of butadiene, 7 parts of styrene, 4 parts of methyl methacrylate, in the aluminum alloy reaction vessel (internal volume 3 liters) prepared in Example B1, 2 parts of acrylonitrile, 2 parts of itaconic acid, 1 part of acrylic acid, 0.3 part of sodium dodecylbenzenesulfonate, 1 part of potassium persulfate and 0.6 part of n-dodecyl mercaptan are added and reacted at 70 ° C. for 2 hours. It was.

  Subsequently, the monomer emulsion prepared above was continuously supplied to the reactor over 5 hours to perform polymerization. In order to complete the polymerization, the reaction was further continued for 4 hours after the completion of the supply of the monomer emulsion to obtain a copolymer latex having a polymerization conversion rate of 98%. After cooling, the pH was adjusted to 8.5 using 5% sodium hydroxide. A copolymer latex having a solid content concentration of 45.2% and a viscosity of 80 mPa · s was obtained. The amount of polymerization scale was 0.0003%, and the amount of fine solidified product was 0.0015%.

(Production of polymer: Test example 2)
In an emulsification tank equipped with a stirrer, 30 parts of water, 35 parts of butadiene, 39 parts of styrene, 14.5 parts of methyl methacrylate, 8 parts of acrylonitrile, 0.5 part of acrylic acid, 0.6 part of t-dodecyl mercaptan and dodecylbenzenesulfone 0.3 parts of sodium acid salt was added and stirred to obtain a monomer emulsion.

  Separately from the preparation of the monomer emulsion, 70 parts of water, 0.3 part of sodium dodecylbenzenesulfonate, 2 parts of itaconic acid are contained in the reaction vessel made of aluminum alloy (internal volume 3 liters) prepared in Example B1. Parts, 1 part of acrylic acid and 5.5 parts of styrene-acrylic acid copolymer latex (average particle size 0.05 micron) were charged and heated to 70 ° C. Next, 1 part of potassium persulfate was added to initiate the polymerization. Subsequently, the monomer emulsion prepared above was continuously supplied to the reactor over 5 hours to perform polymerization. In order to complete the polymerization, the reaction was further continued for 4 hours after the completion of the monomer emulsion supply to obtain a copolymer latex having a polymerization conversion rate of 98%. After cooling, the pH was adjusted to 8.5 using 5% sodium hydroxide. A copolymer latex having a solid content concentration of 50.5% and a viscosity of 120 mPa · s was obtained. The amount of polymerization scale was 0.0004%, and the amount of fine coagulum was 0.0018%.

[Amount of polymerization scale]
After completion of the polymerization reaction, the polymerization scale attached to the reaction vessel wall and the stirring blade is collected, and the mass (scale amount) after drying is measured. The ratio of the scale amount to the total mass of the monomers used for the polymerization is expressed as a percentage.

[Amount of fine solidified product]
The precisely weighed copolymer latex (W2) having a solid content of 45% is filtered through a 325 mesh wire mesh, the coagulum remaining on the wire mesh is dried in an infrared oven for 20 minutes, and its weight (W3) is precisely weighed. Expressed as a ratio of W3 to W2.

[Example B2]
In preparing the reaction vessel of Example B1, an aluminum alloy reaction vessel was prepared by forming a PFA coating directly on the vessel body without forming an anodic oxide coating.

  A polymerization reaction was carried out in the same manner as in Example B1, except that the obtained reaction vessel was used. A copolymer latex having a polymerization conversion of 98%, a solid content concentration of 45.1% and a viscosity of 80 mPa · s was obtained. The latex pH was adjusted to 8.5 using 5% sodium hydroxide. The amount of polymerization scale was 0.0005%, and the amount of fine coagulum was 1.5%.

[Example B3]
In the production of the reaction vessel of Example B1, a cylindrical vessel body was produced by bending and arc welding using a SUS electrolytic polishing plate (3 mm thick) instead of the plate of aluminum alloy A5083. A SUS reaction vessel was prepared in the same manner as in Example B1 except that this vessel body was used.

  A polymerization reaction was carried out in the same manner as in Example B1, except that the obtained reaction vessel was used. A copolymer latex having a polymerization conversion of 98%, a solid content concentration of 44.8% and a viscosity of 80 mPa · s was obtained. The latex pH was adjusted to 8.5 using 5% sodium hydroxide. The amount of polymerization scale was 0.0005% and the amount of fine coagulum was 0.0025%, which was as good as Example B1.

[Comparative Example B1]
In the preparation of the reaction vessel of Example B1, after forming the anodized film, an aluminum alloy reaction vessel was prepared without forming the PFA film.

  A polymerization reaction was carried out in the same manner as in Example B1, except that the obtained reaction vessel was used. A copolymer latex having a polymerization conversion rate of 95%, a solid content concentration of 44.3%, and a viscosity of 80 mPa · s was obtained. The latex pH was adjusted to 8.5 using 5% sodium hydroxide. The amount of polymerization scale was 0.5%, and the amount of fine coagulum was 0.20%.

The results are shown in Table 6.

[Example C1]
(Production of slurry composition for secondary battery negative electrode)
Carboxymethyl cellulose (CMC, “BSH-12” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was prepared as a thickener. The polymerization degree of the thickener was 1700, and the etherification degree was 0.65.

  To the reaction vessel prepared in Example B1, 100 parts of artificial graphite (average particle size: 24.5 μm) as a negative electrode active material and 1 part of a 1% aqueous solution of the above thickener were added, respectively, and the solid content concentration was determined with ion-exchanged water. After adjusting to 55%, the mixture was mixed at 25 ° C. for 60 minutes. Next, after adjusting the solid content concentration to 52% with ion-exchanged water, the mixture was further mixed at 25 ° C. for 15 minutes to obtain a mixed solution.

  1 part (solid content basis) of the polymer latex prepared in Test Example 1 of Example B1 and ion-exchanged water are added to the above mixed solution, and adjusted to a final solid content concentration of 42%, and further for 10 minutes. Mixed. This was defoamed under reduced pressure to obtain a slurry composition for a secondary battery negative electrode having good fluidity.

(Manufacture of batteries)
The slurry composition for secondary battery negative electrode was applied on a copper foil having a thickness of 20 μm with a comma coater so that the film thickness after drying was about 200 μm, and dried for 2 minutes (0.5 m / min). Speed, 60 ° C.) and heat treatment (120 ° C.) for 2 minutes to obtain an electrode raw material. This raw electrode was rolled with a roll press to obtain a secondary battery negative electrode having a negative electrode active material layer thickness of 80 μm.

  The negative electrode is cut into a disk shape with a diameter of 15 mm, and a separator made of a disk-shaped polypropylene porous film with a diameter of 18 mm and a thickness of 25 μm, a metallic lithium used as the positive electrode, and an expanded metal are sequentially laminated on the negative electrode active material layer surface side of the negative electrode. This was stored in a stainless steel coin-type outer container (diameter 20 mm, height 1.8 mm, stainless steel thickness 0.25 mm) provided with polypropylene packing. The electrolyte is poured into the container so that no air remains, and the outer container is fixed with a 0.2 mm thick stainless steel cap through a polypropylene packing, and the battery can is sealed, and the diameter is A half cell (secondary battery) having a thickness of 20 mm and a thickness of about 2 mm was produced.

In addition, as an electrolytic solution, LiPF ₆ was added at 1 mol / liter in a mixed solvent obtained by mixing ethylene carbonate (EC) and diethyl carbonate (DEC) at EC: DEC = 1: 2 (volume ratio at 20 ° C.). A solution dissolved at a concentration was used. Table 7 shows the evaluation results of the charge / discharge cycle characteristics of this half cell.

[Example C2]
A half cell was prepared in the same manner as in Example C1, except that the reaction container and polymer latex prepared in Example B2 were used as the reaction container and polymer latex used in the preparation of the slurry composition. The results are shown in Table 7.

[Comparative Example C1]
A half cell was prepared in the same manner as in Example C1, except that the reaction container and polymer latex prepared in Comparative Example B1 were used as the reaction container and polymer latex used in the preparation of the slurry composition. The results are shown in Table 7.

[Example C3]
A half cell was prepared in the same manner as in Example C1, except that the reaction container and polymer latex prepared in Example B3 were used as the reaction container and polymer latex used in the preparation of the slurry composition. The results are shown in Table 7.

[Charge / discharge cycle characteristics]
Using the secondary batteries obtained in the examples and comparative examples, each battery was charged at a constant current until it reached 4.2 V by a constant current constant voltage charging method of 0.1 C at 25 ° C., and then charged at a constant voltage. Moreover, the charge / discharge cycle which discharges to 3.0V with a constant current of 0.1 C was performed. The charge / discharge cycle was performed up to 100 cycles, and the ratio of the discharge capacity at the 50th cycle to the initial discharge capacity was taken as the capacity maintenance rate, and the determination was made based on the number of batteries generated with this capacity maintenance rate of 80% or less. The discharge capacity at the 50th cycle was defined as the battery capacity, and the test was performed with 50 batteries each manufactured. It shows that it is excellent in charging / discharging cycling characteristics, so that this number is small.

DESCRIPTION OF SYMBOLS 100 ... Reaction tank main body 101 ... Base material 102 ... PFA film 300 ... Plasma processing apparatus 301 ... Processing furnace 302 ... Upper lid plate 303 ... Cylindrical side wall member 304 ... Base plate 305 ... Sealing member

  The treatment tank for manufacturing process composed of the structure (material) of the present invention does not substantially adhere to the reaction product on the inner wall surface even when continuously used, and can greatly increase the production efficiency. Because it can, industrial applicability is very high.

  Moreover, even if many types of structural films are produced in one film-forming treatment tank, reaction products do not substantially adhere to the inner wall surface, so each film is always clean as expected. Films can be formed in the container environment, and the resulting structural film has the characteristics as designed, so the film processing equipment and the production system incorporating it can be significantly reduced in size, saving energy, saving space, and saving energy. In terms of resources, industrial applicability is extremely high.

Claims (13)

In the treatment tank for the manufacturing process, a film of perfluoroalkoxyalkane (hereinafter referred to as “PFA”) represented by the following structural formula 1 is provided on the outermost surface of the inner wall surface of the treatment tank where the reaction product can adhere. A processing tank for a manufacturing process, characterized in that it exists.

(In Structural Formula 1, Rf represents a perfluoroalkyl group, and m and n represent positive integers.)   The said processing tank is a processing tank for manufacturing processes of Claim 1 whose base material is a metal.   The processing tank for a manufacturing process according to claim 2, wherein the metal is an aluminum-based metal. The PFA film, the treatment tank for the production process according to any one of claims 1 to 3 is provided directly on the film made of Ni or NiF _2. The processing tank for a manufacturing process according to any one of claims 1 to 3, wherein the PFA film is directly provided on a film made of Al ₂ O ₃ derived from nonporous anodization.   The processing tank for a manufacturing process according to any one of claims 1 to 5, wherein the PFA film is a film subjected to a remelting process.   In the manufacturing method of a processing tank for a manufacturing process, a structure for a processing tank in which a film made of PFA is provided on a surface that becomes a tank inner wall surface of a processing tank base is prepared, and the structure is higher than the melting point of PFA Exposure to a temperature atmosphere melts at least the free surface region of the film, then exposes to a temperature lower than the melting point of the PFA to solidify at least the free surface region, and then melts the PFA or PFA melting point The surface of the solid film made of PFA is re-melted by exposing it to an atmosphere at a temperature exceeding about 1, and then remelting at least the portion that becomes the free surface region, and then lowered to a temperature sufficiently lower than the melting point of PFA. The manufacturing method of the processing tank for manufacturing processes characterized by having the process to raise. The method for producing a treatment tank for a production process according to claim 7, further comprising a step of providing a film made of Ni or NiF ₂ before providing a film made of PFA on a surface which becomes a tank inner wall surface of the treatment tank base material. . 8. The manufacturing process according to claim 7, further comprising a step of providing a film made of Al ₂ O ₃ by nonporous anodic oxidation before providing a film made of PFA on a surface to be a tank inner wall surface of the treatment tank base material. Method of manufacturing treatment tank.   In a method for manufacturing a structure of a processing tank for a manufacturing process, a structure for a processing tank in which a film made of PFA is provided on a surface that becomes a tank inner wall surface of a processing tank base is prepared, and the structure is melted by PFA Exposure to an atmosphere at a temperature higher than the point to melt at least the free surface region of the film, then exposure to a temperature lower than the melting point of the PFA to solidify at least the free surface region, and then the melting point of the PFA or the PFA Of the free surface of the solid film made of PFA by re-melting at least the portion that becomes the free surface region by exposure to an atmosphere around the melting point of the PFA, and then lowering the temperature to a temperature sufficiently lower than the melting point of the PFA. The manufacturing method of the structure of the processing tank for manufacturing processes characterized by having the process which improves smoothness. The structure of the processing tank for the manufacturing process according to claim 10, further comprising a step of providing a film made of Ni or NiF ₂ before providing a film made of PFA on a surface that becomes a tank inner wall surface of the processing tank base material. Body manufacturing method. 8. The manufacturing process according to claim 7, further comprising a step of providing a film made of Al ₂ O ₃ by nonporous anodic oxidation before providing a film made of PFA on a surface to be a tank inner wall surface of the treatment tank base material. Of manufacturing the structure of the treatment tank.   It is a manufacturing method of the structure of the processing tank for manufacturing processes of any one of Claims 10 thru | or 12, Comprising: The several structure bodies from which a shape differs are prepared, These structure bodies are combined, and it is for manufacturing processes. A method for producing a treatment tank for a production process, comprising producing a treatment tank.

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