Solids, compositions and shaped bodies

Abstract

Technical problem of the present application is to provide a solid capable of forming a molded body having excellent surface properties, and to provide a composition containing the solid, a molded body obtained by molding the solid, and a molded body obtained by molding the composition. The solid of the present application contains a copolymer, a specific compound selected from the group consisting of a compound represented by formula (1) CX 1 2=CX 2 (CF2) m X 3 a compound represented by formula (2) CF2=CF‑O‑(CF2) n F, and a solvent, the copolymer containing a unit based on tetrafluoroethylene, a unit based on ethylene, and a unit based on the specific compound, the solvent being a compound different from the specific compound, the proportion of the content of the specific compound with respect to the total content of the solvent and the specific compound being 50.0 mass% or less.

Description

Technical Field

[0001] This invention relates to solids, compositions, and molded articles. Background Technology

[0002] Ethylene / tetrafluoroethylene copolymer (hereinafter also known as "ETFE") not only possesses excellent heat resistance, weather resistance, electrical insulation, non-adhesiveness, and water and oil repellency, but also exhibits high formability and mechanical strength among fluoropolymers. Therefore, it can be manufactured into a wide variety of molded products, such as wire sheaths, tubes, sheets, films, filaments, pump housings, connectors, encapsulations, liners, and coatings, through melt forming methods such as extrusion molding, blow molding, injection molding, and rotational molding. For example, Patent Document 1 discloses a method for recovering fluorinated ethers, which includes: a step of producing a wet copolymer by suspension polymerization, solution polymerization or bulk polymerization in the presence of a specified fluorinated ether; a step of heating the wet copolymer in a container to vaporize and discharge a vaporized substance containing the fluorinated ether; and a step of transferring the vaporized substance to a cooling mechanism for cooling. Existing technical documents Patent documents

[0003] Patent Document 1: Japanese Patent No. 5569660 Summary of the Invention The technical problem that the invention aims to solve

[0004] When using ETFE as a constituent material for molded articles, excellent performance is required, specifically the ability to manufacture molded articles with excellent surface properties. The inventors manufactured ETFE according to the method described in Patent Document 1 above, and evaluated the molded articles formed by the manufactured ETFE, and found that the surface properties of the obtained molded articles still have room for improvement.

[0005] Therefore, the technical problem to be solved by the present invention is to provide a solid article capable of forming a molded article with excellent surface properties. A further technical problem to be solved by the present invention is to provide a composition comprising the solid article, a molded article obtained by molding the solid article, and a molded article obtained by molding the composition. means of solving technical problems

[0006] The inventors conducted in-depth research on the above-mentioned technology and found that the following solid material can be used to form a molded body with excellent surface properties, thereby completing the present invention: that is, the solid material comprises a copolymer, a specific compound described later, and a solvent, wherein the copolymer contains tetrafluoroethylene-based units, ethylene-based units, and units based on the specific compound, the solvent is a compound different from the specific compound, and the content of the specific compound relative to the total content of the solvent and the specific compound is less than 50.0% by mass, thereby completing the present invention.

[0007] That is, the inventors discovered that the above-mentioned technical problems can be solved by the following configuration. [1] A solid comprising a copolymer, a specific compound selected from compounds represented by formula (1) and formula (2) described later, and a solvent, wherein the copolymer contains tetrafluoroethylene-based units, ethylene-based units, and units based on the specific compound, the solvent being a compound different from the specific compound, and the content of the specific compound being less than 50.0% by mass relative to the total content of the solvent and the specific compound. [2] The solid as described in [1], wherein the content of the tetrafluoroethylene-based unit is 48.00 to 64.90 mol relative to all units contained in the copolymer. [3] The solid as described in [1] or [2], wherein the content of the ethylene-based unit is 35.00 to 51.90 mol relative to all units contained in the copolymer. [4] The solid as described in any one of [1] to [3], wherein the content of the unit based on the particular compound in the copolymer is 0.10 to 5.00 mol relative to all units contained in the copolymer. [5] The solid as described in any one of [1] to [4], wherein the solvent comprises a fluorinated solvent. [6] The solid as described in [5], wherein the fluorinated solvent comprises at least one selected from chlorofluorocarbons, perfluorocarbons, hydrofluorocarbons and hydrofluoroethers. [7] The solid as described in any one of [1] to [6], wherein the solvent comprises water. [8] The solid as described in any one of [1] to [7], wherein the content of the solvent is 0.01 to 2 by mass relative to the total mass of the solid. [9] The solid as described in any one of [1] to [8], wherein the specific surface area of ​​the solid is 0.3 m². 2 / g or more.

[10] A composition comprising the solids described in any one of [1] to [9] and at least one component selected from resins other than the copolymers, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fillers, crosslinking agents, crosslinking aids and organic peroxides.

[11] A molded body obtained by molding a solid material as described in any one of [1] to

[10] .

[12] A molded body formed from the composition described in

[10] . Invention Effects

[0008] According to the present invention, a solid article capable of forming a molded article with excellent surface properties can be provided. According to the present invention, a composition comprising the solid article, a molded article obtained by molding the solid article, and a molded article obtained by molding the composition can also be provided. Detailed Implementation

[0009] The meanings of the terms used in this instruction manual are as follows. The numerical range indicated by "~" includes the ranges whose lower and upper limits are the values ​​listed before and after "~". In this specification, the upper or lower limit of a numerical range can be replaced by the upper or lower limit of another numerical range. Furthermore, the upper or lower limit of a numerical range described in this specification can be replaced by the values ​​shown in the embodiments. In this specification, each component may be used alone or in combination with two or more of the corresponding substances. Here, when each component is used with two or more substances, unless otherwise specified, the content of the component refers to the total content of the substances used together. In this specification, a combination of two or more preferred methods is a more preferred method.

[0010] "Unit" refers to the collective term for atomic groups derived directly from a monomer molecule formed by the polymerization of monomers, and atomic groups obtained by chemically transforming a portion of the monomer molecule. Additionally, in the following text, depending on the context, units derived from each monomer may sometimes be referred to by their monomer name followed by the name "unit". "TFE unit" refers to the tetrafluoroethylene-based unit of the copolymer, and "E unit" refers to the ethylene-based unit of the copolymer. In addition, "A unit" refers to the unit based on a specific compound described later. "Solvent" refers to a substance that is liquid at 25°C and 1013 hPa.

[0011] [solid] The solid article of the present invention (hereinafter also referred to as "the solid article") comprises a copolymer containing TFE units, E units and A units based on a specific compound described later, and also comprises the specific compound and a solvent, which is a compound different from the specific compound. In addition, this solid is characterized by a ratio of the content of a specific compound to the total content of the solvent and the specific compound (hereinafter also referred to as "ratio P") of less than 50.0% by mass.

[0012] This solid material enables the formation of molded articles with excellent surface properties. The detailed reasons for this are not yet clear, but it is believed that the content of a specific compound in the components used to manufacture the copolymer or solid material is below a specified value. This specific compound is considered to be prone to remaining in the solid material due to its high oleophilicity. In cases where the solid material contains more of this specific compound than the solvent, it is speculated that bubbles from the specific compound will be generated during the heating process when forming the molded article. As a result, it is speculated that traces of these bubbles, i.e., pores (voids), will be formed on the surface of the molded article. In contrast, in this solid, by keeping the content of a specific compound below a specified value relative to the total content of the solvent and the specific compound, it is presumed that the specific compound is less likely to remain in the solid. As a result, bubbles are less likely to be generated during molding, and the number of pores formed on the surface of the molded body is reduced, thus enabling the formation of a molded body with better surface properties. Here, a molded body with excellent surface properties refers to a molded body whose surface has suppressed the generation of pores (bubbles) caused by a specific compound.

[0013] The components contained in this solid are described below.

[0014] [Copolymer] This solid contains a copolymer comprising E units, TFE units and A units. Unless otherwise specified, the term "copolymer" hereafter refers to copolymers containing E units, TFE units, and A units.

[0015] The copolymer is a copolymer containing TFE units based on tetrafluoroethylene, E units based on ethylene, and A units based on a specific compound selected from the compounds represented by formula (1) and the compounds represented by formula (2). CX 1 2 = CX 2 (CF2) m X 3 (1) CF2 = CF - O - (CF2) n F (2) In equation (1), X 1 X 2 and X 3 Each can be used to represent a hydrogen atom or a fluorine atom independently, and m represents an integer from 1 to 6. In equation (2), n represents an integer from 1 to 6. In the compound represented by formula (1), X 1 From a polymerizability perspective, hydrogen atoms are preferred. X 2 From a polymerizability perspective, hydrogen atoms are preferred. X 3 Fluorine atoms are preferred. m is preferably an integer from 2 to 6, more preferably an integer from 3 to 6, and even more preferably 3 or 4. Examples of compounds represented by formula (1) include CH2=CH(CF2)2F, CH2=CH(CF2)4F (hereinafter also referred to as "PFBE"), CH2=CH(CF2)6F, CH2=CF(CF2)3F, and CH2=CF(CF2)4F, with PFBE, CH2=CH(CF2)6F or CH2=CF(CF2)3F being preferred, and PFBE being more preferred. Specific examples of compounds represented by formula (2) are any one of CF2=CF-O-(CF2)F, CF2=CF-O-(CF2)2F, CF2=CF-O-(CF2)3F, CF2=CF-O-(CF2)4F, CF2=CF-O-(CF2)5F, and CF2=CF-O-(CF2)6F. Among them, CF2=CF-O-(CF2)3F, which corresponds to the compound with n=3, is preferred. The copolymer may contain either a unit based on the compound represented by formula (1) (hereinafter also referred to as "A1 unit") or a unit based on the compound represented by formula (2) (hereinafter also referred to as "A2 unit") as A unit, or it may contain both A1 unit and A2 unit as A unit. That is, when the copolymer contains both A1 units and A2 units, "content of A units" means the total content of A1 units and A2 units. As copolymers, copolymers containing TFE units, E units and A1 units are preferred, or copolymers containing TFE units, E units and A2 units are preferred, and copolymers containing E units, TFE units and A1 units are more preferred from the viewpoint of excellent long-term bending resistance. The content of TFE units relative to all units contained in the copolymer is preferably 45.00 to 69.99 mol%, more preferably 48.00 to 64.90 mol%, and even more preferably 50.00 to 64.50 mol%. Above the lower limit of the above values, the heat resistance of the molded article is better, and below the upper limit of the above values, the mechanical properties of the molded article are better. The content of E units relative to all units contained in the copolymer is preferably 30.00 to 54.99 mol%, more preferably 35.00 to 51.90 mol%, and even more preferably 35.00 to 49.50 mol%. Above the lower limit, the mechanical properties of the molded article are superior, and below the upper limit, the heat resistance of the molded article is superior. The content of unit A relative to all units contained in the copolymer is preferably 0.01 to 10.00 mol%, more preferably 0.10 to 5.00 mol%, and even more preferably 0.50 to 4.00 mol%. At or above the lower limit, a molded article with excellent wear resistance can be formed, and at or below the upper limit, a molded article with excellent dimensional stability can be formed. In the copolymer, the total content of TFE units and E units is preferably 90.00 to 99.99 mol% relative to all units contained in the copolymer, more preferably 95.00 to 99.90 mol%, and even more preferably 96.00 to 99.50 mol%. The copolymer may also contain units based on monomers other than tetrafluoroethylene, ethylene, and certain compounds. Other specific examples of monomers include: fluoroolefins (such as fluoroethylene, vinylidene fluoride, trifluoroethylene, hexafluoropropylene, hexafluoroisobutylene, etc., except for certain compounds), CF2=CFORf 1 SO2Y 1 (where Rf) 1 It is a perfluoroalkylene group with 1 to 10 carbon atoms, and oxygen atoms may be present between the carbon atoms. 1 (is a halogen atom or hydroxyl group), CF2=CFORf 2 CO2 Y 2 (where Rf) 2 It is a perfluoroalkylene group with 1 to 10 carbon atoms, and the carbon atoms may contain oxygen atoms. 2 It consists of hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, CF2=CF(CF2). pOCF=CF2 (where p is 1 or 2), fluorinated monomers with cyclic structures (e.g., perfluoro(2,2-dimethyl-1,3-dioxacyclopentene), 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxacyclopentene, perfluoro(2-methylene-4-methyl-1,3-dioxacyclopentene), etc.), itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Preferably, itaconic acid, itaconic anhydride, citraconic acid, or citraconic anhydride are preferred, with itaconic anhydride being more preferred. When the copolymer contains units based on other monomers, the content of units based on other monomers is preferably 0.01 to 2.00 mol% relative to all units contained in the copolymer, more preferably 0.10 to 1.00 mol%. As a copolymer, the form composed of TFE units, E units and A units is preferred, and the form composed of TFE units, E units and Al units is more preferred. From the viewpoint of superior pulverability of the solid, the copolymer content in the solid is preferably 99% by mass or more, more preferably 99.5% by mass or more, and even more preferably 99.8% by mass or more. From the viewpoint of superior flexural strength of the molded article, the copolymer content in the solid is preferably 99.99% by mass or less. <Mel flow rate> The melt flow rate (hereinafter also referred to as "MFR") of the copolymer is preferably 1 to 60 g / 10 min, more preferably 2 to 50 g / 10 min. When the MFR of the copolymer is above the lower limit mentioned above, a molded article with excellent flowability during melt molding can be formed. When the MFR of the copolymer is below the upper limit mentioned above, a molded article with excellent wear resistance at high temperatures can be formed. As a specific example of a method to bring the MFR of the copolymer within the above-mentioned range, a method of adjusting the molecular weight of the copolymer can be cited. The larger the molecular weight of the copolymer, the smaller the MFR. The MFR of the copolymer is determined according to ASTM D3159 by measuring the mass of solids flowing out of an orifice with a diameter of 2 mm and a length of 8 mm over 10 minutes at a temperature of 297 °C and a load of 49 N. The copolymer is the main component of the solids, and the components other than the copolymer have almost no effect on the MFR determination. Therefore, the MFR value obtained by measuring the solids can be regarded as the MFR of the copolymer. <Melting Point> From the viewpoint of superior mechanical strength of the molded article under high temperature use, the melting point of the copolymer is preferably above 215°C, more preferably above 220°C. From the viewpoint of excellent formability of solids, the upper limit of the melting point of the copolymer is preferably below 290°C, more preferably below 280°C, and particularly preferably below 270°C. Specific examples of methods to bring the melting point of the copolymer within the aforementioned range include methods for lowering the polymerization temperature during copolymer manufacturing and methods for adjusting the content of A units in the copolymer. The melting point of a copolymer is the temperature corresponding to the endothermic peak after heating the solid in air at a rate of 10°C / min using a differential scanning calorimeter. Similar to MFR, the melting point obtained from the measurement of the solid can be regarded as the melting point of the copolymer. [Specific compound] This solid contains a specific compound. The specific examples and preferred forms of the particular compounds are the same as those of the specific compounds that are the source of Unit A as described above. The specific compound contained in this solid may be either the compound represented by formula (1) or the compound represented by formula (2), but preferably one of the compounds represented by formula (1) and the compound represented by formula (2), and more preferably the compound represented by formula (1). Furthermore, the specific compound that serves as the source of the A unit in the copolymer and the specific compound contained in this solid are preferably the same. For example, if the copolymer contains PFBE units as A units, this solid preferably contains PFBE as a specific compound. From the viewpoint of having better surface properties of the molded article, the content of the specific compound contained in this solid is preferably 0.05% by mass or less, more preferably 0.045% by mass or less, and even more preferably 0.04% by mass or less. Furthermore, from the viewpoint of superior bending resistance of the molded article, the content of the specific compound contained in this solid is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more. The contents of specific compounds and solvents (excluding water) contained in the solid can be determined by analyzing the volatile components after heating the solid to 240°C using a headspace GC / MS apparatus. [solvent] This solid contains a solvent. However, the solvent contained in this solid is a different compound from that of the specific compound. Specific examples of solvents contained in this solid include water and organic solvents such as hydrofluorocarbons, hydrofluoroethers, perfluorocarbons, chlorofluorocarbons, alcohols, and hydrocarbons. This solid preferably contains a fluorinated solvent as a solvent. A fluorinated solvent is an organic solvent containing at least one fluorine atom. Examples of fluorinated solvents include chlorofluorocarbons, perfluorocarbons, hydrofluorocarbons, and hydrofluoroethers. The number of carbon atoms in the fluorinated solvent is preferably 2 to 7, more preferably 2 to 6. The solid preferably contains at least one selected from chlorofluorocarbons, perfluorocarbons, hydrofluorocarbons and hydrofluoroethers, and more preferably contains at least one selected from hydrofluorocarbons and hydrofluoroethers. Hydrofluorocarbons are composed of hydrogen atoms, fluorine atoms, and carbon atoms, and are fluorinated solvents that do not contain heteroatoms other than fluorine atoms. The number of carbon atoms in hydrofluorocarbons is preferably 3 to 7, more preferably 4 to 6. Hydrofluoroethers preferably contain one ether bond. Specific examples of hydrofluorocarbons include CF3CFHCF2CF2CF3, CF3(CF2)4H, CF3CF2CFHCF2CF3, CF3CFHCFHCF2CF3, CF2HCFHCF2CF2CF3, CF3(CF2)5H, CF3CH(CF3)CF2CF2CF3, CF3CF(CF3)CFHCF2CF3, CF3CH(CF3)CFHCF2CF3, CF3CF2CH2CH3 and CF3(CF2)3CH2CH3, 1,1,2,2-tetrafluorocyclobutane, CF3CFHCFHCF3, CF3CF(CF3)CFHCFHCF3, CF3CH2CF2CH3, CF2ClCFCl2, CF2ClCCl2F and CF3CClFCFClCF3. Among them, CF3(CF2)5H or CF3CF2CH2CH3 are preferred. Hydrofluoroethers are fluorinated solvents containing hydrogen and fluorine atoms with ether bonds. The number of carbon atoms in hydrofluoroether is preferably 3 to 7, more preferably 4 to 6, and even more preferably 4 or 5. Hydrofluoroethers preferably contain one ether bond. Specific examples of hydrofluoroethers include CF3CH2OCF2CF2H, CF3(CF3)CFCF2OCH3, CF3(CF2)3OCH3, CF3(CF2)3OC2H5, CF3(CF2)2C3F7OCH3 and (CF3)2CFOCH3, with CF3CH2OCF2CF2H being the most preferred. When the solid contains a fluorinated solvent, the content of the fluorinated solvent relative to the total mass of the solid is preferably 0.0001 to 0.5% by mass, more preferably 0.0001 to 0.4% by mass. In addition, the solvent in this solid material preferably includes water. The handling during transfer is even better when the solid contains water. When the solid contains water, the water content is preferably 0.01 to 0.5% by mass relative to the total mass of the solid, more preferably 0.01 to 0.2% by mass. The water content in the solid was determined by the difference between the weight loss of the solid as measured by differential thermogravimetric analysis and the total content of solvents and specific compounds in the solid as measured by headspace GC / MS. More detailed determination methods are described in the examples described later. <Proportion P> As described above, the ratio of the content of a specific compound in this solid to the total content of the solvent and the specific compound (content of the specific compound) / (content of the solvent + content of the specific compound), i.e., the ratio P, is less than 50.0% by mass. The ratio P is preferably 0.1 to 50.0% by mass, more preferably 0.5 to 50.0% by mass. Below the aforementioned upper limit, a shaped body with superior surface properties can be formed; above the aforementioned lower limit, the cohesiveness of the solid decreases, and the fluidity is superior. In this solid, the solvent content is preferably 0.001 to 2.5% by mass relative to the total mass of the solid, more preferably 0.01 to 2% by mass, and even more preferably 0.01 to 1% by mass. This solid material can be in the form of granules (beads), particles, filaments, etc. [Specific surface area] The specific surface area of ​​the solid is preferably 0.3 m². 2 / g or more, preferably 0.5m 2 / g or higher, further optimized 5m 2 / g or more, with 10m being particularly preferred 2 / g or more, and preferably 40m 2 / g or less, preferably 30m 2 / g or less. If the specific surface area of ​​a solid is above the aforementioned lower limit, a shaped body with superior surface properties can be formed. The specific surface area of ​​a solid is the BET specific surface area per unit mass of the solid, determined by the BET method based on the amount of nitrogen adsorbed on its surface (unit: m²). 2 / g). The specific surface area of ​​a solid can be measured using a known specific surface area measuring device (e.g., Mykrotrak Co., Ltd.). The product was manufactured by Bello Corporation and is marketed under the brand name "BELSORP MINI X". The specific surface area of ​​a solid can be controlled, for example, by adjusting the drying conditions when drying the granules containing the copolymer in the solid manufacturing method described later. [Methods for manufacturing solids] This solid can be manufactured, for example, by the following method: polymerizing the above-mentioned monomers (tetrafluoroethylene, ethylene and a specific compound) in a polymerization solvent to produce a copolymer, granulating a mixture containing the copolymer, polymerization solvent and water while stirring and heating, and drying the resulting granules, wherein the drying of the granules involves a two-stage drying process, namely a first stage of drying under normal pressure and a second stage of drying under vacuum. The above method will now be described as an example of a method for manufacturing this solid object. <Copolymer Manufacturing> The copolymer can be manufactured by polymerization of the monomers (tetrafluoroethylene, ethylene and specific compounds) in a polymerization solvent using known methods such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., wherein solution polymerization is preferred. In the manufacture of copolymers, in addition to the monomers and polymerization solvents mentioned above, polymerization initiators, chain transfer agents, etc., can also be used. The polymerization initiator is preferably a free radical polymerization initiator with a half-life of 10 hours and a temperature of 0 to 100°C, and particularly preferably a free radical polymerization initiator with a temperature of 20 to 90°C. Specific examples of polymerization initiators include various polymerization initiators illustrated in International Publication No. 2013 / 015202. Polymerization initiators can be used alone or in combination with two or more. The amount of polymerization initiator used relative to 100 parts by mass of monomer is preferably 0.01 to 0.9 parts by mass, and particularly preferably 0.05 to 0.5 parts by mass. Fluorinated solvents such as hydrofluorocarbons, hydrofluoroethers, perfluorocarbons, and chlorofluorocarbons can be used as polymerization solvents. Polymerization solvents can be used alone or in combination of two or more. As a polymerization solvent, fluorinated solvents are preferred, hydrofluorocarbons, hydrofluoroethers, perfluorocarbons or chlorofluorocarbons are more preferred, and hydrofluorocarbons or hydrofluoroethers are even more preferred. The amount of polymerization solvent used, in terms of mass ratio to the amount of monomer used, is preferably 5 times or more, more preferably 7 times or more. Furthermore, it is preferably 20 times or less, more preferably 17 times or less. Chain transfer agents can be used in the manufacture of copolymers, and are preferred to be used. Considering the large chain transfer constant and low addition amount, the following chain transfer agents are preferred as chain transfer agents: alcohols such as methanol, ethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoropropanol, 1,1,1,3,3,3-hexafluoroisopropanol, and 2,2,3,3,3-pentafluoropropanol; hydrofluorocarbons such as CF2H2; hydrocarbons such as n-pentane, n-hexane, and cyclohexane; ketones such as acetone; thiols such as methanethiol; esters such as methyl acetate and ethyl acetate; and ethers such as diethyl ether and methyl ethyl ether. From the perspective of higher chain transfer constant and higher stability of the terminal groups of the copolymer, at least one of alcohols, hydrocarbons, and hydrofluorocarbons is preferred, more preferably at least one of alcohols and hydrocarbons, and particularly preferred are alcohols. Among alcohols, methanol or ethanol is particularly preferred. Among these, methanol is particularly preferred from the perspective of reactivity and ease of acquisition. Two or more chain transfer agents can be used. The amount of chain transfer agent used is preferably 0.001 times or more, more preferably 0.005 times or more, by mass ratio to the amount of monomer used. Furthermore, it is preferably 5 times or less, more preferably 4 times or less. The polymerization temperature is preferably 15–90°C, more preferably 20–85°C, and particularly preferably 25–80°C. Polymerization properties are excellent when the polymerization temperature is above the lower limit of the above values. Polymerization temperatures below the upper limit of the above values ​​can increase the melting point of the copolymer. The polymerization pressure is preferably 0.5 to 3.0 MPa, and particularly preferably 0.9 to 2.5 MPa. The polymerization time is preferably 1 to 12 hours. <Granulation> Next, the mixture containing the copolymer, polymerization solvent and water is heated while being stirred to produce granules containing the copolymer. In granulation, a mixture comprising the copolymer, a polymerization solvent, and water is first prepared. This mixture can be prepared, for example, by mixing a slurry containing the copolymer and the polymerization solvent with water. In the preparation of the mixture, the slurry produced by the copolymer can be used directly, or a slurry obtained by concentrating the slurry can be used, or a slurry obtained by diluting the slurry with a diluting solvent can be used. The diluting solvent can be the same as or different from the solvent used as the polymerization solvent, but it is preferred to use the same solvent. The amount of water used in granulation can be 20 to 500 volumes relative to the total volume of the copolymer and the polymerization solvent, more preferably 50 to 300 volumes. The mixture can be prepared by adding water to a polymerization tank containing the slurry after copolymer production, or by transferring the slurry to a separate container (granulation tank) to mix it with water. Preferably, the slurry containing the copolymer and polymerization solvent is transferred from the polymerization tank to a granulation tank pre-filled with water for mixing. As a granulation tank, a sealable container can be used, which includes stirring blades for mixing the contents, a heating container or heating mechanism for the contents, and a discharge mechanism for expelling the separated gases. The stirring blades can be commonly used stirring blades such as turbine blades or anchor blades. Examples of heating devices include jacketed heating, hot water baths, oil baths, and steam heating. The heating temperature of the mixture during granulation is preferably in the range of 25 to 110°C, and more preferably in the range of 30 to 90°C. The internal pressure of the container during granulation is preferably 0.01 to 0.8 MPa, more preferably 0.01 to 0.7 MPa, and even more preferably 0.01 to 0.6 MPa. The pressure described in this instruction manual is gauge pressure based on atmospheric pressure. The granulation time can be, for example, 1 to 24 hours, preferably 1 to 15 hours. As an example of the end time of granulation, one can consider a period in which the volume of the mixture contained in the granulation tank does not decrease. If, within a specified period, the volume of the mixture in the granulation tank is confirmed to have reached a constant level without decreasing, it can be inferred that the solvents and other components discharged from the granulation tank during the aforementioned granulation period have been substantially discharged. <Drying> Next, the granulated material containing the copolymer is dried to produce the solid material containing the copolymer. From the viewpoint of manufacturing solids with a low proportion of P, it is preferable to manufacture solids containing copolymers by a two-stage drying process, which involves a first stage of drying under normal pressure and a second stage of drying under vacuum. Here, atmospheric pressure means that the pressure inside the container undergoing drying is 0 to 0.1 MPa, and vacuum means that the pressure inside the container undergoing drying is -0.01 to -0.1 MPa. The granules obtained by the above granulation contain moisture, polymerization solvent, and specific compounds (hereinafter collectively referred to as "vaporized substances"). During the subsequent drying process, these components vaporize, forming a solid with a porous surface. According to the inventors' research, when the granules are dried only under vacuum conditions, not at atmospheric pressure, a solid with a small specific surface area can be obtained. It is speculated that when the granules are dried only under vacuum conditions, the vaporized substances rapidly vaporize near the surface. Furthermore, the size of the pores formed near the surface becomes smaller, making it easier for the vaporized substances (especially the specific compounds) to remain inside the solid. In contrast, it has been found that when the granules are subjected to a two-stage drying process—first drying under atmospheric pressure and then drying under vacuum—a solid with a large specific surface area can be obtained. It is speculated that in the case of this two-stage drying, the size of the pores formed near the surface is large, drying also occurs inside the granules, and the vaporized substances rapidly vaporize and separate, resulting in a solid with a low proportion of P. As a specific example of a drying method, one can exemplify a method in which granules are transferred from a granulation container to a drying container such as a dryer, and the granules are heated under specified pressure conditions to vaporize and separate the gaseous substances contained in the granules. Examples of dryers used for drying include batch rotary dryers, indirect heating dryers, vacuum dryers, and hot air dryers. The pressure inside the container during the first stage of drying is preferably 0 to 0.1 MPa, more preferably 0 to 0.08 MPa. The drying temperature for the first stage is preferably in the range of 30 to 150°C, and more preferably in the range of 35 to 130°C. The drying time for the first stage is preferably 1 to 24 hours, more preferably 1 to 12 hours. The pressure inside the container during the second stage of drying is preferably -0.01 to -0.1 MPa, more preferably -0.02 to -0.1 MPa. The drying temperature in the second stage is preferably in the range of 50 to 150°C, and more preferably in the range of 60 to 150°C. The drying time for the second stage is preferably 1 to 24 hours, more preferably 1 to 12 hours. In addition, relative to the overall drying time, it is preferable that the drying time of the first stage is 30-70% and the drying time of the second stage is 70-30%, and more preferably that the drying time of the first stage is 30-60% and the drying time of the second stage is 40-70%. The dried solid material can also be melt-extruded using an extruder to form other solid materials such as granules or filaments. [Composition] The composition of the present invention (hereinafter also referred to as "the composition") comprises the above-described solid and at least one selected from resins other than copolymers, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fillers, crosslinking agents, crosslinking aids, and organic peroxides (hereinafter also referred to as "other components"). Because the composition contains the solid, it is possible to form molded articles with excellent surface properties by using the composition. This composition is preferably in solid form. The content of this solid relative to the total mass of the composition is preferably 50% by mass or more and less than 100% by mass, more preferably 70% by mass or more and less than 100% by mass, and even more preferably 90% by mass or more and less than 100% by mass. This composition preferably does not contain solvents and specific compounds other than those derived from the solid. In this composition, the ratio of the content of a specific compound to the total content of the solvent and the specific compound is preferably 0.1 to 50.0% by mass, more preferably 0.5 to 50.0% by mass. The content of the above-mentioned "other components" in this composition is preferably 0.0000001 to 70 parts by mass relative to 100 parts by mass of the copolymer in this composition, more preferably 0.0000005 to 60 parts by mass, and even more preferably 0.000001 to 50 parts by mass. As a method for manufacturing this composition, an example is a method of melting and mixing the solid or the powder obtained by pulverizing the solid with the other components mentioned above as needed using a known method. This solid material can be pulverized using known pulverizers such as rotary mills, hammer mills, turbine mills, and jet mills. [molded body] The molded article of the present invention is obtained by molding the above-described solid material or the above-described composition. Because the molded article of the present invention is formed using the solid material, it has a low number of pores on the surface and excellent surface properties. Specific examples of forming methods include injection molding, extrusion molding, blow molding, pressure molding, rotational molding, electrostatic coating, and spray molding. The molded body of the present invention may also be a coating film formed using the solid or the composition. Examples of methods for forming the coating film include forming a coating film using powder obtained by pulverizing the solid or a composition containing the powder by rotational forming, electrostatic coating, or spray forming. The thickness of the coating is preferably 1μm to 10mm, more preferably 50μm to 5mm, and even more preferably 100μm to 3mm. Specific examples of the molded bodies of the present invention include nuts, bolts, joints, membranes, bottles, gaskets, wire sheaths, tubes, hoses, pipes, valves, sheets, seals, encapsulations, cans, rollers, containers, stopcocks, connectors, filter housings, filter cages, flow meters, pumps, wafer carriers, and wafer boxes. This solid, the composition of the present invention, or the molded article described above can be used for the following purposes. Food packaging films, lining materials for fluid transport lines used in food manufacturing processes, encapsulation components, sealing materials, and sheet materials, etc., are fluid transport components used in food manufacturing equipment. Drug stoppers, packaging films, lining materials for fluid transport lines used in drug manufacturing processes, encapsulation components, sealing materials, and sheet-like components for transporting liquid drugs; Inner lining components for pharmaceutical tanks and piping in chemical or semiconductor plants; O-rings, pipes, seals, valve cores, hoses and sealing materials used in automobile fuel systems and peripheral devices, as well as hoses and sealing materials used in automobile AT systems and other fuel delivery components. Flange gaskets, shaft seals, valve stem oil seals, sealing materials and hoses used in automobile engines and peripheral devices, as well as other automobile components such as brake hoses, air conditioning hoses, radiator hoses and wire sheathing materials; O-rings, tubes, packages, valve cores, hoses, sealing materials, rollers, gaskets, diaphragms, and connectors for semiconductor manufacturing equipment, etc. Coating and ink components for coating equipment, such as coating rollers, hoses, tubes, and ink containers; Food and beverage tubing or flexible tubing, as well as hoses, belts, sealing components and connectors, food packaging materials, and glass cooking equipment; Components for waste liquid transportation, such as pipes and hoses. Pipes and hoses, and other components for transporting high-temperature liquids; Steam piping components, such as pipes and hoses for steam piping; Corrosion-resistant tape for piping, such as the tape wound around the piping on the deck of a ship; Various coating materials, such as wire coating materials, optical fiber coating materials, and transparent surface coating materials and back coating materials applied to the light incident side surface of photovoltaic elements of solar cells; The diaphragm and various encapsulation components of the diaphragm pump; Agricultural films, as well as various roofing materials and sidewalls and other weather-resistant covering materials; Interior decoration materials used in the construction field, as well as glass covering materials such as non-combustible fire-resistant safety glass; Laminated steel sheets and other lining materials used in the home appliance industry, etc. Carrier membrane for fuel cells. From the viewpoint of excellent surface properties, the molded articles of the present invention are particularly suitable for liquid delivery components and coating materials for semiconductor devices. Example The present invention will now be described in detail with examples. Examples 1 to 12 are embodiments, and Examples 13 to 14 are comparative examples. However, the present invention is not limited to these examples. The various measurement and evaluation methods are as follows. [Measurement] <Content of solvents and specific compounds in solids> The content of residual solvents and specific compounds in the solid was determined by analyzing the gaseous components present in the headspace gas phase after the solid was heated to 240°C using a headspace GC / MS instrument, and determining the content (mass %) of each component relative to the total mass of the copolymer. The water content in the solid was calculated as the difference between the weight loss of the solid as determined by differential thermogravimetric analysis (TG-DTA) and the total content of solvents and specific compounds in the solid as determined by headspace GC / MS. The weight loss of the solid was determined by heating the solid from 30°C to 550°C at a heating rate of 10°C / min using TG-DTA and measuring the weight of the solid before and after heating. <Content of each unit in the copolymer> The content (mol%) of each unit in the copolymer was calculated based on the results of perfluorination determination and melt F-NMR analysis. Specifically, the content of E units in the copolymer was determined by... 1 H and 13 Calculated by C-NMR measurements. <MFR (Mel Flow Rate)> The mass (g) of solids flowing out of an orifice with a diameter of 2 mm and a length of 8 mm within 10 minutes was measured using a melt flow indexer (manufactured by Techno7 Co., Ltd.) according to ASTM D3159 at a temperature of 297°C and a load of 49 N. The measured value is the MFR (g / 10min) of the copolymer. <Melting Point> The melting point (°C) of the copolymer was determined by detecting the endothermic peak after heating the solid to 300°C in air at a heating rate of 10°C / min using a scanning differential thermal analyzer (DSC 7020 manufactured by SII Corporation). Specific surface area The specific surface area of ​​solids was determined using a BET specific surface area measuring device (manufactured by Macquarie Ltd., trade name "BELSORP MINI X", etc.) based on the amount of nitrogen adsorbed on the particle surface by the BET method. Based on the measured specific surface area values, the specific surface area of ​​each solid was evaluated according to the following criteria. (Evaluation Criteria) ◎: Specific surface area measured at 20m² 2 / g or more. ○: Specific surface area measured at 10m² 2 / g or more and less than 20m 2 / g. △: The measured specific surface area is within 0.3m². 2 / g or more and less than 10m 2 / g. ×: The measured specific surface area is less than 0.3 m². 2 / g. [Evaluation Test] <Surface properties> Using an injection molding machine (ROBOSHOT α-50C, manufactured by FANUC Corporation), the mold is sculpted to obtain a molded body with a design size of 12mm wide, 120mm long and 3mm thick, and the gate uses a tunnel gate with a front diameter of 1.0mm. Under molding conditions of 310°C barrel temperature, 150°C mold temperature, 20 mm / sec injection speed, 78.4 MPa holding pressure, 3 seconds holding time, and 30 seconds cooling time, the solids obtained in each example were molded to obtain molded bodies. The injection molded bodies were visually observed and evaluated according to the following criteria. (Evaluation Criteria) ○: No pores were generated, and no defects in appearance were produced. ×: Pores are formed. [Example 1] After evacuating a 1.3L stainless steel polymerization tank equipped with a stirrer and jacket, add 0.8L of CF3CH2CF2CH3 (hereinafter referred to as "HFC-365mfc"), 8.7g of methanol, 12.1g of the specific compound CH2=CH(CF2)4F(PFBE), and 0.4g of CF2=CFO(CF2)2CF3 (hereinafter referred to as "PPVE"). While stirring the mixture, add a mixture of TFE and E with a molar ratio of 83 / 17 (mol%), 155g of tetrafluoroethylene (TFE) / ethylene (E), to pressurize the inside of the polymerization tank to 1.5MPaG (gauge pressure) and maintain the temperature of the polymerization tank at 72°C (polymerization temperature). After the temperature stabilizes, inject 17mL of a 1% (w / w) solution of tert-butyl peroxypentanoate (hereinafter referred to as "PBPV") (solvent: CF3CH2OCF2CF2H (hereinafter referred to as "AE-3000")) to begin polymerization. During polymerization, a TFE / E mixture with a molar ratio of 54 / 46 (mol%) was added to maintain a constant internal pressure of 1.5 MPaG. Furthermore, for every 10 g of TFE / E mixture consumed during polymerization, 1.2 mL of PFBE was added (equivalent to an amount of 3.1 mol% relative to the total molar percentage of TFE and E). After adding 100 g of the TFE / E mixture, the polymerization tank was cooled, and polymerization was terminated, yielding a copolymer of TFE, ethylene, PFBE, and PPVE. Then, the remaining monomer gas was purged from the polymerization tank to 0.01 MPa, and the slurry was transferred to a 2.6 L container, with the same volume of water added. The slurry was heated while stirring to vaporize the solvent, simultaneously producing (granulating) granules containing the copolymer. During granulation, the inside of the container was heated within the range of 30–100 °C. Granulation was stopped at a point when the volume of the mixture containing the granules in the container was visually confirmed to have reached a constant level without decreasing, yielding the granules. The obtained granules were placed in an oven heated to 120 °C and dried at atmospheric pressure (0.01 MPa) for 90 minutes. Then, the pressure inside the oven was reduced, and the granules were dried under vacuum (-0.07 MPa) for 60 minutes to obtain granular solid 1. Furthermore, the results measured by the above method confirmed that solid 1 contained water, HFC-365mfc, PFBE and PPVE. [Example 2] When initially feeding the polymerization tank, the amount of methanol was changed to 10.6 g, the amount of PFBE was changed to 9.6 g, and PPVE was not added to the polymerization tank. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 13 mL. Moreover, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 1.0 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 1. Then, after obtaining granules containing the copolymer in the same manner as in Example 1, the obtained granules were placed in an oven heated to 120°C and dried for 150 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 180 minutes under vacuum of -0.05 MPa to obtain granular solid 2. The results obtained by the above method confirmed that solid 2 contained water, HFC-365mfc and PFBE. [Example 3] When initially feeding the polymerization tank, the amount of methanol was changed to 4.6 g and the amount of PFBE was changed to 3.4 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 5 mL. Moreover, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.4 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing the copolymer in the same manner as in Example 1, the obtained granules were placed in an oven heated to 120°C and dried for 180 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 240 minutes under vacuum of -0.09 MPa to obtain granular solid 3. The results obtained by the above method confirmed that solid 3 contained water, HFC-365mfc and PFBE. [Example 4] When initially feeding the polymerization tank, 0.8 L of 2,3-dichlorooctafluorobutane was added instead of 0.8 L of HFC-365mfc, the amount of methanol was changed to 20.8 g, and the amount of PFBE was changed to 5.9 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 5 mL. Also, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.4 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing the copolymer in the same manner as in Example 1, the resulting granules were placed in an oven heated to 120°C and dried at atmospheric pressure of 0.01 MPa for 95 minutes. Then, the pressure inside the oven was reduced and dried at vacuum of -0.09 MPa for 85 minutes to obtain granular solid 4. The results determined by the above method confirmed that solid 4 contained water, 2,3-dichlorooctafluorobutane and PFBE. [Example 5] When initially feeding the polymerization tank, the amount of methanol was changed to 16.6 g and the amount of PFBE was changed to 6.7 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 9 mL. Also, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.7 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing copolymers in the same manner as in Example 1, the resulting granules were placed in an oven heated to 120°C and dried at atmospheric pressure of 0.01 MPa for 85 minutes. Then, the pressure inside the oven was reduced and dried at vacuum of -0.07 MPa for 120 minutes to obtain granular solids 5. The results obtained by the above method confirmed that solid 5 contained water, HFC-365mfc and PFBE. [Example 6] When initially feeding the polymerization tank, the amount of methanol was changed to 10.4 g and the amount of PFBE was changed to 7.1 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 10 mL. Also, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.8 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing the copolymer in the same manner as in Example 1, the obtained granules were placed in an oven heated to 120°C and dried for 150 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 180 minutes under vacuum of -0.05 MPa to obtain granular solid 6. The results obtained by the above method confirmed that solid 6 contained water, HFC-365mfc and PFBE. [Example 7] When initially feeding the polymerization tank, the amount of methanol was changed to 15.8 g and the amount of PFBE was changed to 5.9 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 8 mL. Also, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.7 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing copolymers in the same manner as in Example 1, the resulting granules were placed in an oven heated to 120°C and dried for 140 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 140 minutes under vacuum of -0.05 MPa to obtain granular solid 7. The results obtained by the above method confirmed that solid 7 contained water, HFC-365mfc and PFBE. [Example 8] When initially feeding the polymerization tank, 0.8 L of CF3(CF2)4CF2H (hereinafter also referred to as "C6H") was added instead of 0.8 L of HFC-365mfc, the amount of methanol was changed to 9.4 g, and the amount of PFBE was changed to 4.3 g. Furthermore, 6 mL of a 1% by mass solution of PBPV (solvent: C6H) was injected into the polymerization tank after heating and pressurizing the TFE / E mixed gas instead of a 1% by mass solution of PBPV (solvent: AE-3000). Moreover, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 0.5 mL. Except for the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after the solvent was vaporized in the same manner as in Example 1, the resulting solid was placed in an oven heated to 130°C and dried for 90 minutes under normal pressure of 0.001 MPa. Then, the pressure inside the oven was reduced and dried for 60 minutes under vacuum of -0.1 MPa to obtain granular solid 8. The results obtained by the above method confirm that solid 8 contains water, C6H and PFBE. [Example 9] After evacuating a 1.3L stainless steel polymerization tank equipped with a stirrer and jacket, 0.8L of C6H, 3.9g of methanol, and 14.2g of the specific compound PFBE were added. While stirring the mixture, a mixture of TFE and E with a molar ratio of 88 / 12 (mol%) was added to pressurize the inside of the polymerization tank to 1.5MPaG and maintain the temperature at 66°C (polymerization temperature). After the temperature stabilized, 19mL of a 1% (w / w) solution of PBPV (solvent: C6H) was forced in to begin polymerization. During polymerization, a TFE / E mixture with a molar ratio of 60 / 40 (mol%) was added to maintain a constant internal pressure of 1.5 MPaG. Furthermore, for every 10 g of TFE / E mixture consumed during polymerization, 1.4 mL of PFBE was added (equivalent to an amount of 1.4 mol% relative to the total molar percentage of TFE and E). After adding 100 g of the TFE / E mixture, the polymerization tank was cooled, and the polymerization was terminated, yielding a copolymer of TFE, ethylene, and PFBE. Then, the remaining monomer gas was purged from the polymerization tank to 0.005 MPa (atmospheric pressure), and the slurry was transferred to a 2.6 L container. Water of the same volume as the slurry was added. The slurry was heated while stirring to vaporize the solvent, simultaneously producing (granulating) granules containing the copolymer. During granulation, the inside of the container was heated within the range of 30–100 °C. Granulation was stopped at a point when the volume of the mixture containing the granules in the container was visually confirmed to have reached a constant level without decreasing, yielding the granules. The obtained granules were placed in an oven heated to 120 °C and dried at 0.008 MPa (atmospheric pressure) for 150 minutes. Then, the pressure inside the oven was reduced, and the granules were dried at -0.05 MPa (vacuum) for 180 minutes to obtain granular solid 9. The results obtained by the above method confirmed that solid 9 contained water, C6H and PFBE. [Example 10] When initially feeding the polymerization tank, 0.8 L of AE-3000 was added instead of 0.8 L of HFC-365mfc, the amount of methanol was changed to 7.7 g, and the amount of PFBE was changed to 9.6 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) that was heated and pressurized with the added TFE / E mixed gas was changed to 13 mL. Also, during polymerization, the amount of PFBE added for every 10 g of TFE / E mixed gas consumed was changed to 1 mL. Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 2. Then, after the solvent was vaporized in the same manner as in Example 1, the resulting solid was placed in an oven heated to 130°C and dried for 150 minutes under normal pressure of 0.01 MPa. Next, the pressure inside the oven was reduced and dried for 180 minutes under vacuum of -0.05 MPa to obtain granular solid 10. The results obtained by the above method confirm that solid 10 contains water, AE-3000 and PFBE. [Example 11] After evacuating a 1.3L stainless steel polymerization tank equipped with a stirrer and jacket, add 0.8L of AE-3000, 11.3g of methanol, and 4.7g of a specific compound CH2=CF(CF2)2CF2H (hereinafter also referred to as "C3olf"). While stirring the mixture, add a mixture of TFE and E with a molar ratio of 86 / 14 (mol%) to pressurize the inside of the polymerization tank to 1.5MPaG and maintain the temperature at 72℃ (polymerization temperature). After the temperature stabilizes, inject 8mL of a 1% (w / w) solution of PBPV (solvent: AE-3000) to begin polymerization. During polymerization, a TFE / E mixture with a molar ratio of 57 / 43 (mol%) was added to maintain a constant internal pressure of 1.5 MPaG. Furthermore, for every 10 g of TFE / E mixture consumed during polymerization, 0.7 mL of C3olf (equivalent to 1.6 mol% of the total molar percentage of TFE and E) was added. After adding 100 g of the TFE / E mixture, the polymerization tank was cooled, and the polymerization was terminated, yielding a copolymer of TFE, ethylene, and PFBE. Then, after the solvent was vaporized in the same manner as in Example 1, the resulting solid was placed in an oven heated to 130°C and dried for 85 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 60 minutes under vacuum of -0.09 MPa to obtain granular solid 11. The results of the above method confirmed that solid 11 contained water, AE-3000 and C3olf. [Example 12] When initially feeding the polymerization tank, 9.0 g of a specific compound CH2=CH(CF2)5CF3 (hereinafter also referred to as "C6olf") was added instead of 4.7 g of C3olf, and the amount of methanol was changed to 12.5 g. Furthermore, the amount of a 1% by mass solution of PBPV (solvent: AE-3000) injected into the polymerization tank after heating and pressurizing the TFE / E mixed gas was changed to 7 mL. Moreover, during polymerization, the amount of C6olf added for every 10 g of TFE / E mixed gas consumed was changed to 0.5 mL (equivalent to an amount of 1.4 mol% relative to the total molar percentage of TFE and E). Apart from the above changes, a copolymer of TFE, ethylene, and PFBE was produced in the same manner as in Example 11. Then, after the solvent was vaporized in the same manner as in Example 1, the resulting solid was placed in an oven heated to 130°C and dried for 90 minutes under normal pressure of 0.01 MPa. Then, the pressure inside the oven was reduced and dried for 60 minutes under vacuum of -0.09 MPa to obtain granular solid 12. The results determined by the above method confirmed that solid 12 contained water, AE-3000 and C6olf. [Example 13] A copolymer of TFE, ethylene and PFBE was produced in the same manner as in Example 2. Then, after obtaining granules containing copolymers in the same manner as in Example 1, the resulting granules were placed in an oven heated to 120°C and dried under vacuum conditions of -0.05 MPa for 330 minutes to obtain granular solids 13. The results determined by the above method confirmed that solid 13 contained water, HFC-365mfc, PFBE and PPVE. [Example 14] A copolymer of TFE, ethylene and PFBE was produced in the same manner as in Example 9. Then, after obtaining granules containing copolymers in the same manner as in Example 1, the resulting granules were placed in an oven heated to 120°C and dried under vacuum conditions of -0.05 MPa for 330 minutes to obtain granular solids 14. The results determined by the above method confirmed that solid 14 contained water, HFC-365mfc, PFBE and PPVE. For the solids manufactured in each example, the MFR, composition, and melting point of the copolymer contained in the solids, as well as the content, proportion P, and specific surface area of ​​each component of the solids, were determined by the above method. The results are shown in Table 1 below. Table 1 shows the composition and physical properties of the copolymers obtained in each example, as well as the determination and evaluation results of the solids. In the table, the "TFE Unit", "E Unit", and "A Unit" columns represent the content (unit: mol%) of each unit relative to the total number of units contained in the solid in each example. Table 1 As shown in the table, it was confirmed that solids with a content of a specific compound relative to the total content of the solvent and the specific compound of less than 50.0% by mass can be used to manufacture molded articles with excellent surface properties (Examples 1 to 12). Furthermore, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2023-221100, filed on December 27, 2023, are incorporated herein by reference as a disclosure of this invention.

Claims

1. A solid comprising a copolymer, a specific compound selected from compounds represented by formula (1) and compounds represented by formula (2), and a solvent, The copolymer contains tetrafluoroethylene-based units, ethylene-based units, and units based on the specific compound. The solvent is a compound different from the specific compound. The content of the specific compound relative to the total content of the solvent and the specific compound is less than 50.0% by mass. CX 1 2=CX 2 (CF2) m X 3 (1) CF2=CF-O-(CF2) n F (2) In equation (1), X 1 X 2 and X 3 Each can be used independently to represent a hydrogen atom or a fluorine atom, where m represents an integer from 1 to 6. In equation (2), n represents an integer from 1 to 6.

2. The solid as described in claim 1, wherein, The content of the tetrafluoroethylene-based unit is 48.00 to 64.90 mol relative to all units contained in the copolymer.

3. The solid as described in claim 1 or 2, wherein, The content of the ethylene-based unit is 35.00 to 51.90 mol relative to all units contained in the copolymer.

4. The solid as described in claim 1 or 2, wherein, The content of the unit based on the specific compound in the copolymer is 0.10 to 5.00 mol relative to all units contained in the copolymer.

5. The solid as described in claim 1 or 2, wherein, The solvent includes fluorinated solvents.

6. The solid as described in claim 5, wherein, The fluorinated solvent contains at least one selected from chlorofluorocarbons, perfluorocarbons, hydrofluorocarbons, and hydrofluoroethers.

7. The solid as described in claim 1 or 2, wherein, The solvent contains water.

8. The solid as described in claim 1 or 2, wherein, The solvent content is 0.01 to 2% of the total mass of the solids.

9. The solid as described in claim 1 or 2, wherein, The specific surface area of ​​the solid is 0.3 m². 2 / g or more.

10. A composition comprising the solid of claim 1 or 2 and at least one component selected from resins other than the copolymer, heat stabilizers, antioxidants, colorants, ultraviolet absorbers, fillers, crosslinking agents, crosslinking aids, and organic peroxides.

11. A shaped article formed from the solid article of claim 1 or 2.

12. A molded article formed from the composition of claim 10.

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