Solids, compositions and shaped bodies

Abstract

The technical problem of the present invention is to provide a solid with excellent pulverization properties and to provide a composition comprising said solid, a molded article obtained by molding said solid, and a molded article obtained by molding said composition. The solid of the present invention comprises a copolymer selected from formula (1) CX. 1 2 = CX 2 (CF2) m The compound represented by F and formula (2) CF2=CF-O-(CF2) n F represents a specific compound, and the solid of the solvent, wherein the copolymer contains tetrafluoroethylene-based units, ethylene-based units, and units based on the specific compound, and the solvent comprises a fluorinated solvent having hydrogen atoms and fluorine atoms that may have ether bonds, and the fluorinated solvent comprises having formula (3)CF3(CF3)2). p The hydrofluorocarbon represented by the group -, wherein the total content of the hydrofluorocarbon and the specific compound is less than 90.0% by mass relative to the total content of the solvent and the specific compound.

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 of molded articles, excellent performance in all aspects is required. The inventors manufactured ETFE according to the method described in Patent Document 1 above, and evaluated the solid containing the manufactured ETFE, and found that there is still room for improvement in the pulverability of the solid.

[0005] Therefore, the technical problem to be solved by the present invention is to provide a solid with excellent pulverization properties. A further technical problem to be solved by the present invention is to provide a composition comprising the solid, a molded article obtained by molding the solid, 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 technical problems and found that the following solid is a solid with excellent pulverization properties, thereby completing the present invention: that is, the solid is a solid comprising 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, the solvent comprises a fluorinated solvent containing hydrogen atoms and fluorine atoms that may have ether bonds, the fluorinated solvent comprises hydrofluorocarbons having groups represented by formula (3) described later, and the total content of the hydrofluorocarbons and the specific compound is less than 90.0% by mass relative to the total content of the solvent and the specific compound.

[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 below, 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, the solvent comprising a fluorinated solvent having hydrogen and fluorine atoms having ether bonds, the fluorinated solvent comprising hydrofluorocarbons having groups represented by formula (3) described below, the total content of the hydrofluorocarbons and the specific compound being less than 90.0% 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 fluorinated solvent further comprises hydrofluoroether. [6] The solid as described in [5], wherein the hydrofluoroether comprises a compound represented by formula (4) described later. [7] The solid as described in any one of [1] to [6], wherein the solvent further 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 content of the hydrofluorocarbon is 0.001 to 1.5 by mass relative to the total mass of the solid.

[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 [9].

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

[10] . Invention Effects

[0008] According to the present invention, a solid with excellent pulverization properties can be provided. According to the present invention, a composition comprising the solid, a molded body formed from the solid, and a molded body formed from 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. The solid article comprises at least a hydrofluorocarbon having a group represented by formula (3) described later as a solvent. In addition, this solid is characterized by a total content of the above-mentioned hydrofluorocarbons and specific compounds relative to the total content of the solvent and specific compounds (hereinafter also referred to as "ratio S") of 90.0% by mass or less.

[0012] The details of why this solid is a highly pulverizable solid are not yet clear, but it is believed that this is because the total content of the specific compound and the compound represented by formula (3) described later in the composition used to manufacture the copolymer or solid is below a specified value. Since this specific compound and the compound represented by formula (3) described later have high lipophilicity, it is speculated that when included in the solid, they would easily cause the copolymer containing TFE, E, and A units to swell, thereby increasing the hardness of the solid. In this solid, by keeping the total content of the specific compound and the compound represented by formula (3) described later below a specified value, it is speculated that the copolymer is less prone to swelling, and the hardness of the solid is suitable for pulverization. Here, "excellent solid material pulverization" means that solid materials can be easily pulverized to produce powders with a narrow particle size distribution and uniform particle size.

[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).

[0016] CX 1 2 = CX 2 (CF2) m Formula F (1) CF2 = CF - O - (CF2) n Formula F (2) In equation (1), X 1 and X 2 Each can be used to represent a hydrogen atom or a fluorine atom, and m represents an integer from 1 to 6. In equation (2), n represents an integer from 1 to 6.

[0017] In the compound represented by formula (1), X 1 and X 2 From a polymerizability perspective, hydrogen atoms are preferred. m is preferably an integer from 2 to 6, more preferably an integer from 2 to 4, and even more preferably 4.

[0018] As the compound represented by formula (1), CH2=CH(CF2)2F, CH2=CH(CF2)4F, CH2=CH(CF2)6F or CH2=CF(CF2)4F are preferred, and CH2=CH(CF2)4F is more preferred (hereinafter also referred to as "PFBE").

[0019] Specific examples of the 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.

[0020] 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.

[0021] 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.

[0022] 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 molded article has better chemical resistance and heat resistance during long-term use, and below the upper limit of the above values, the molded article has better mechanical properties.

[0023] 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 and weather resistance of the molded article during long-term outdoor use are superior.

[0024] 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.

[0025] 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%.

[0026] 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 the carbon atoms may contain oxygen 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. 2It consists of hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, CF2=CF(CF2). p OCF=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.

[0027] 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%.

[0028] 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, more preferably 99.95% by mass or less.

[0029] <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.

[0030] <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 210°C, more preferably above 215°C, and even 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 measured by a differential scanning calorimeter after heating the solid in air at a rate of 10°C / min. Similar to MFR, the melting point obtained by measuring the solid can be regarded as the melting point of the copolymer.

[0031] [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.

[0032] 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.

[0033] From the viewpoint of better pulverability of solids, the content of the specific compound contained in the solid is preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and even more preferably 0.03% 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 0.002% by mass or more.

[0034] 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.

[0035] [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, alcohols, and hydrocarbons.

[0036] In this solid, the solvent comprises a fluorinated solvent (hereinafter also referred to as "solvent F") that may have hydrogen atoms and fluorine atoms having ether bonds. In addition, solvent F comprises a hydrofluorocarbon having the group represented by formula (3) (hereinafter also referred to as "solvent F3"). CF3 (CF2) p - (3) In equation (3), p represents an integer greater than or equal to 1. This indicates the bonding site with an adjacent atom. As for p, it is preferably an integer from 1 to 5, and more preferably an integer from 1 to 3.

[0037] Solvent F3 is preferably the compound represented by formula (3a). CF3 (CF2) p -R (3a) In formula (3a), R represents a hydrogen atom or a fluoroalkyl or alkyl group having 1 to 6 carbon atoms. Among the fluoroalkyl or alkyl groups represented by R, those with CF3 (CF2) are... p - A carbon atom with a basal bond is bonded to at least one hydrogen atom. The definition and preferred method of p in equation (3a) are the same as those of p in equation (3). R is preferably a hydrogen atom or a fluoroalkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom. In addition, the compound represented by formula (3a) preferably has 3 to 8 carbons, more preferably 4 to 7.

[0038] Specific examples of solvent F3 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, with CF3(CF2)5H being preferred.

[0039] The content of solvent F3 relative to the total mass of the solids is preferably 0.001 to 2.0% by mass, more preferably 0.001 to 1.5% by mass, and even more preferably 0.001 to 1.2% by mass. Below the aforementioned upper limit, the pulverization of solids is superior; above the aforementioned lower limit, the particle size of solids becomes more uniform, resulting in superior operability.

[0040] In this solid, solvent F preferably also contains hydrofluoroether. As a hydrofluoroether, a fluorinated solvent containing hydrogen atoms and fluorine atoms with ether bonds can be used. The hydrofluoroether preferably includes the compound represented by formula (4) (hereinafter also referred to as "solvent F4"). R 1 -OR 2 (4) In equation (4), R 1 R represents a fluoroalkyl group having 2 to 6 carbon atoms. 2 R represents a fluoroalkyl or alkyl group having 1 to 4 carbon atoms. 1 and R 2 The total number of carbon atoms is less than 8. When the solid contains hydrofluoroether (more preferably solvent F4), the bulk density of the solid increases, resulting in better transportability on the manufacturing line.

[0041] As R in equation (4) 1 The preferred fluoroalkyl group has 2 to 4 carbon atoms, and the more preferred fluoroalkyl group has 2 or 3 carbon atoms. As R in equation (4) 2 Preferably, it is a fluoroalkyl or alkyl group having 1 to 3 carbon atoms, more preferably a fluoroalkyl or alkyl group having 1 or 2 carbon atoms, and even more preferably a fluoroalkyl group having 2 carbon atoms. R in equation (4) 1 and R 2 The total number of carbon atoms is preferably 3 to 7, more preferably 4 to 6, and even more preferably 4 or 5.

[0042] Specific examples of solvent F4 include CF3CH2OCF2CF2H, CF3(CF3)CFCF2OCH3, CF3(CF2)3OCH3, CF3(CF2)3OC2H5, CF3(CF2)2C3F7OCH3 and (CF3)2CFOCH3, with CF3CH2OCF2CF2H being the most preferred.

[0043] When the solid contains solvent F4, the content of solvent F4 relative to the total mass of the solid is preferably 0.0001 to 0.4% by mass, more preferably 0.0001 to 0.3% by mass. In addition, when the solid contains hydrofluoroether, the content of hydrofluoroether 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.

[0044] This solid may also contain fluorinated solvents containing hydrogen and fluorine atoms but not in solvent F3 and hydrofluoroethers (hereinafter also referred to as "other fluorinated solvents"). Specific examples of other fluorinated solvents include hydrofluorocarbons other than solvent F3, such as 1,1,2,2-tetrafluorocyclobutane, CF3CFHCFHCF3, CF3CF(CF3)CFHCFHCF3, CF3CH2CF2CH3(HFC-365mfc), CF2ClCFCCl2, CF2 ClCCl2F and CF3CClFCFClCF3, with CF3CH2CF2CH3 being preferred.

[0045] When the solid contains other fluorinated solvents, the content of the other fluorinated solvents relative to the total mass of the solid is preferably 0.0001 to 0.4% by mass, more preferably 0.0001 to 0.3% by mass.

[0046] The solvent in this solid preferably also includes water. When this solid contains water, its mechanical properties and formability are even better.

[0047] 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 0.1% 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.

[0048] <Proportion S> As described above, the ratio of the total content of solvent F3 and the specific compound in this solid to the total content of solvent and specific compound (content of solvent F3 + content of specific compound) / (content of solvent + content of specific compound), i.e., the ratio S, is less than 90.0% by mass. The ratio S is preferably 0.5 to 60.0% by mass, more preferably 1.0 to 50.0% by mass, and even more preferably 1.0 to 12.0% by mass. Below the aforementioned upper limit, the solid material exhibits superior pulverability; above the aforementioned lower limit, the solid material exhibits reduced cohesion and superior fluidity.

[0049] In this solid, the solvent content is preferably 0.01 to 2% by mass relative to the total mass of the solid, more preferably 0.01 to 1.5% by mass.

[0050] This solid material can be in the form of granules (beads), particles, filaments, etc.

[0051] Methods for manufacturing solids This solid can be manufactured, for example, by the following manufacturing method: polymerizing the above-mentioned monomers (tetrafluoroethylene, ethylene and a specific compound) in a polymerization solvent to produce a copolymer, heating a mixture containing the copolymer, polymerization solvent and water while stirring, granulating the copolymer, and separating the polymerization solvent and unreacted monomers from the mixture, wherein a two-stage heating process is performed when heating the mixture, namely, a first stage of heating at a lower temperature and a second stage of heating at a higher temperature. The above method will now be described as an example of a method for manufacturing this solid object.

[0052] <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.

[0053] 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.

[0054] Fluorinated solvents such as hydrofluorocarbons, hydrofluoroethers, and perfluorocarbons can be used as polymerization solvents. Polymerization solvents can be used alone or in combination of two or more. As a polymerization solvent, solvent F is preferred, solvent F3 is more preferred, solvent F3 and hydrofluoroether are even more preferred, and solvent F3 and solvent F4 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.

[0055] 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.

[0056] The polymerization temperature is preferably 15–90°C, more preferably 20–80°C, and particularly preferably 25–75°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.

[0057] <Granulation> Next, the mixture containing the copolymer, polymerization solvent and water is heated while being stirred, thereby separating the polymerization solvent and unreacted monomers from the container and granulating the copolymer-containing granules.

[0058] In granulation, a mixture comprising the copolymer, polymerization solvent, and water is first prepared. This mixture can be prepared, for example, by mixing a slurry containing the copolymer and 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.

[0059] 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.

[0060] From the viewpoint of producing solids with a low proportion S, it is preferable to perform a first-stage granulation by heating at a lower temperature and venting gas at a lower venting rate while stirring and granulating a mixture containing copolymer, polymerization solvent and water, and a second-stage granulation by heating at a higher temperature and venting gas at a higher venting rate. When unreacted monomers and polymerization solvents are separated from the copolymer by vaporization during granulation through a single heating process, it is presumed that the vaporization of these substances will generate bubbles within the mixture, particularly in granules with incompletely defined shapes. Furthermore, it is speculated that solvent F3, which has high oleophilicity and affinity for the copolymer constituting the granules, and certain other compounds may easily remain within these spaces. In the aforementioned two-stage granulation process, divided into a first stage and a second stage, it is speculated that in the first stage, unreacted gaseous raw material components such as tetrafluoroethylene and ethylene are mainly separated from the mixture and discharged from the container. In the subsequent second stage, unreacted specific compounds and polymerizing solvents dissolved in the mixture are mainly vaporized, and these vaporized substances are discharged from the container. In this case, during the first stage, granules that have solidified to a certain extent are formed while gases that easily cause bubbles are slowly removed. Then, in the second stage, unreacted specific compounds and polymerizing solvents are rapidly vaporized and removed. Therefore, it is speculated that the generation of uneven spaces within the granules can be suppressed, and the residue of solvent F3 and specific compounds within the granules can be suppressed.

[0061] In the first stage, the discharge rate of gas from the container is preferably 0.01 to 0.50 kg / L / h, more preferably 0.01 to 0.40 kg / L / h, and even more preferably 0.01 to 0.30 kg / L / h. If the gas discharge rate in the first stage is below the aforementioned upper limit, the proportion of solid matter S can be further suppressed by inhibiting the vaporization of unreacted monomers and polymerization solvents in the first stage and suppressing the generation of bubbles in the formation of granules. In addition, the above-mentioned gas discharge rate is the unit volume of the container used in granulation and the mass of gas discharged per hour.

[0062] The heating temperature in the first stage is preferably in the range of 25–95°C, more preferably in the range of 30–90°C, and even more preferably in the range of 30–90°C. It is preferable to adjust the heating temperature in the first stage so that the rate of gas discharge from the container in the first stage is within the above-mentioned range.

[0063] In the first stage, the pressure inside the container is preferably 0.01 to 0.80 MPa, more preferably 0.01 to 0.70 MPa, and even more preferably 0.01 to 0.60 MPa. The pressure described in this instruction manual is gauge pressure based on atmospheric pressure.

[0064] The implementation time for the first phase can be, for example, 1 to 8 hours, preferably 1 to 6 hours. As an example of the time when the first stage ends and the second stage begins, consider a scenario where the pressure inside the container remains constant for the same period as in the first stage. Once the pressure inside the container is confirmed to have reached a constant point, it can be inferred that the gaseous components contained within the container under the conditions of the first stage have been largely expelled.

[0065] In the second stage, the discharge rate of the gas discharged from the container is preferably 0.05 to 0.80 kg / L / h, more preferably 0.10 to 0.80 kg / L / h, and even more preferably 0.15 to 0.80 kg / L / h. If the gas discharge rate in the second stage is above the lower limit mentioned above, specific compounds and polymerization solvents can be rapidly removed from the granules, resulting in a solid with a lower proportion S. If the gas discharge rate in the second stage is below the upper limit mentioned above, a solid with excellent shape stability can be produced.

[0066] The difference between the discharge rate of the gas discharged from the container in the second stage and the discharge rate of the gas discharged from the container in the first stage is preferably 0.1 kg / L / h or more, more preferably 0.15 kg / L / h or more, and preferably 0.9 kg / L / h or less. If the difference in gas discharge rates is above the aforementioned lower limit, then a solid with a lower proportion S can be produced.

[0067] The heating temperature in the second stage is preferably in the range of 30 to 110°C, more preferably in the range of 30 to 90°C, and even more preferably in the range of 35 to 90°C. The heating temperature in the second stage is preferably adjusted so that the discharge rate of the gas discharged from the container in the second stage, or the difference between the discharge rate of the gas discharged from the container in the second stage and the discharge rate of the gas discharged from the container in the first stage, is within the above range. In the second stage, the pressure inside the container is preferably 0.01–1.00 MPa, more preferably 0.01–0.80 MPa, and even more preferably 0.01–0.70 MPa. This pressure can be gauge pressure.

[0068] The implementation time for the second phase can be, for example, 0.5 to 8 hours, preferably 1 to 6 hours. As an example of the end of the second stage, consider a period in which the amount of solvent discharged and recovered from the container during the second stage does not increase. When it is confirmed that the amount of recovered solvent reaches a constant point, it can be inferred that, under the conditions of the second stage, the solvent and other components discharged from the mixture containing the granules have been substantially discharged.

[0069] The granules obtained by the above granulation process can be recovered from the container and dried as needed. Preferably, the solid is produced by drying the recovered granules. As a specific example of drying, one method is to transfer the recovered granules to a dryer for heating. Through drying, substances such as water and solvents inside the granules can be further vaporized and removed.

[0070] Examples of dryers used for drying include batch rotary dryers, indirect heating dryers, vacuum dryers, and hot air dryers.

[0071] The drying temperature is preferably in the range of 60 to 250°C, and more preferably in the range of 100 to 160°C. The drying time is preferably in the range of 1 to 48 hours, more preferably in the range of 1 to 24 hours.

[0072] The solids obtained by drying or granulation can also be melt-extruded using an extruder to form granules, filaments, or other forms of solids.

[0073] [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.

[0074] 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.

[0075] 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.

[0076] This solid material can be pulverized using known pulverizers such as rotary mills, hammer mills, turbine mills, and jet mills. Because of the excellent pulverability of this solid, for example, powder obtained by pulverizing this solid can be used to manufacture molded articles with excellent surface smoothness. In addition, by heating and melting the powder obtained by pulverizing this solid, molded articles with a small number of pores can be manufactured.

[0077] [molded body] The molded article of the present invention is obtained by molding the above-described solid material or the above-described composition. The molded article of the present invention is formed using the solid material, therefore it has excellent surface properties. Specific examples of forming methods include injection molding, extrusion molding, blow molding, pressure molding, rotational molding, electrostatic coating, and spray molding.

[0078] 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.

[0079] 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.

[0080] 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

[0081] The present invention will now be described in detail with examples. Examples 1 to 17 are embodiments, and Examples 18 to 19 are comparative examples. However, the present invention is not limited to these examples. The various measurement and evaluation methods are as follows.

[0082] [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.

[0083] <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. Furthermore, the content of IAH units in the copolymer was determined by the following method. A 200 μm film was obtained by press molding the copolymer. In the infrared absorption spectrum, the absorption peak of the C=O stretching vibration of the IAH units in the copolymer appeared at 1870 cm⁻¹. -1 The absorbance of this absorption peak is measured, and the content M (mol%) of IAH units is determined using the formula M = aL. Here, L is 1870 cm⁻¹. -1 The absorbance at that point is given by a coefficient. Using IAH as a model compound, a = 0.87 is used as a coefficient.

[0084] <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.

[0085] <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).

[0086] [Evaluation Test] <Powder Manufacturing> The solid samples obtained in each example were pulverized using a rotary mill (Fritsch, Rotor Speedill P-14) at a speed of 1300 rpm to obtain solid powder.

[0087] <Preparation of Coating Test Pieces> The surface of a 40mm long, 150mm wide, and 2mm thick SUS304 stainless steel plate was sandblasted using 60-mesh alumina particles to achieve a surface roughness Ra of 5–10 μm. The plate was then cleaned with ethanol to create a test substrate. A liquid primer (AGC Co., Ltd., "Fluon IL-300J") was applied to the surface of the test substrate using an air spray gun (manufactured by Meiji Machinery Co., Ltd.). The substrate with the liquid primer coating was suspended in an oven and fired at 300°C for 30 minutes to form a 23μm thick primer layer, resulting in a primer-coated substrate. Next, solid powder was electrostatically sprayed onto the entire surface of the substrate with the primer layer, and then fired at 275°C for 15 minutes. This electrostatic coating and firing process was repeated three times to form a top coating layer, resulting in a coating test piece. The thickness of the top coating layer was 200 μm.

[0088] <Appearance Evaluation (Surface Smoothness)> The top coating of the coated test piece was confirmed by visual inspection and tactile examination. The appearance of the coated test piece was evaluated according to the following evaluation criteria. The higher the appearance evaluation of the coated test piece, the better its pulverizability.

[0089] (Appearance Evaluation Criteria) ◎: The topcoat is formed on the entire surface of the substrate. The surface of the topcoat is visually smooth and glossy. The surface of the topcoat is tactilely smooth and does not feel uneven. ○: A topcoat is formed on the entire surface of the substrate. The surface of the topcoat is visually uneven, but no gloss is visible. The surface of the topcoat is not noticeably uneven to the touch. ×: The surface of the top coating can be felt as uneven by touch. In addition, some areas on the substrate that have not formed a top coating due to foaming or other reasons can be visually identified.

[0090] [Example 1] After evacuating a 1.3L stainless steel polymerization tank equipped with a stirrer and jacket, add 614g of CF3CH2CF2CH3 (hereinafter referred to as "HFC-365mfc"), 54g of CF3(CF2)4CF2H (hereinafter referred to as "C6H"), 10.2g of methanol, and 7.5g of the specific compound CH2=CH(CF2)4F(PFBE). While stirring the mixture, add 146g of tetrafluoroethylene (TFE) and 8.7g of ethylene (E), then allow hot water to flow through the jacket to maintain the temperature in the polymerization tank at 66℃ (polymerization temperature). The pressure in the polymerization tank at this time is 1.5MPaG (gauge pressure). After the temperature stabilizes, inject 7mL of a 1% (w / w) solution of tert-butyl peroxypentanoate (hereinafter referred to as "PBPV") (solvent: CF3CH2CF2CH3) to begin polymerization. During polymerization, a TFE / E mixture with a molar ratio of 54 / 46 is added to maintain a constant internal pressure of 1.5 MPaG. Furthermore, for every 10 g of TFE / E mixture consumed during polymerization, 1.0 mL of PFBE is added (equivalent to an amount of 1.0 mol% relative to the total molar percentage of TFE and E). 210 minutes after the start of the reaction, the polymerization tank was cooled after adding 100g of a mixed gas with a TFE / E molar ratio of 54 / 46, and the polymerization was terminated.

[0091] Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–90°C to ensure a gas purging rate X1 / V of 0.02 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.1 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 85–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.58 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solid 1. Wherein, the above-mentioned discharge rate X1 / V is the average value of the gas discharge rate during the first stage, and the above-mentioned discharge rate X2 / V is the average value of the discharge rate during the second stage.

[0092] The results of the above measurements show that the MFR of copolymer 1 contained in solid 1 is 14 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.08 / 44.60 / 2.32 (molar percentages respectively), and the melting point is 249 °C. The proportion S of the obtained solid 1 is 6.3 by mass.

[0093] [Example 2] Except for changes to the types and amounts of the components used in the polymerization and the polymerization conditions, as shown in Table 1, TFE, ethylene, and PFBE were copolymerized in the same manner as in Example 1. "AE-3000" in Table 1 represents CF3CH2OCF2CF2H. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.06 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.2 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–90°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.79 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solid 2. The results of the above measurements show that the MFR of copolymer 2 contained in solid 2 is 6 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.41 / 45.58 / 1.01 (molar percentages respectively), and the melting point is 261℃. The proportion S of the obtained solid 1 is 34.9% by mass.

[0094] [Example 3] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure a gas purging rate X1 / V of 0.05 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.4 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–95°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.78 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 3. The results of the above measurements show that the MFR of copolymer 3 contained in solid 3 is 12 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.36 / 45.10 / 1.54 (molar percentages respectively), and the melting point is 256 °C. The proportion of solid 3 obtained is 44.9% by mass.

[0095] [Example 4] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure a gas purging rate X1 / V of 0.06 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–95°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.79 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 4. The results of the above measurements show that the MFR of copolymer 4 contained in solid 4 is 11 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.40 / 45.50 / 1.10 (molar percentages respectively), and the melting point is 261℃. The proportion of the obtained solid 4 to S is 10.9 by mass.

[0096] [Example 5] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure a gas purging rate X1 / V of 0.04 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.81 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 5. The results of the above measurements show that the MFR of copolymer 5 contained in solid 5 is 23 g / 10 min, with a composition of TFE units / E units / PFBE units = 53.23 / 44.70 / 2.07 (molar percentages), and a melting point of 251 °C. The proportion S of the obtained solid 5 is 15.3% by mass.

[0097] [Example 6] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure a gas purging rate X1 / V of 0.05 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.1 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–105°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.21 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 6. The results of the above measurements show that the MFR of copolymer 6 contained in solid 6 is 25 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 58.00 / 38.50 / 3.50 (molar percentages respectively), and the melting point is 233 °C. The proportion S of the obtained solid 6 is 5.1 by mass.

[0098] [Example 7] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.05 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.43 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 7. The results of the above measurements show that the MFR of copolymer 7 contained in solid 7 is 13 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 58.10 / 38.40 / 3.50 (molar percentages respectively), and the melting point is 233℃. The proportion S of the obtained solid 7 is 17.2 by mass.

[0099] [Example 8] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.10 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–105°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.78 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 8. The results of the above measurements show that the MFR of copolymer 8 contained in solid 8 is 38 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 57.48 / 38.92 / 3.60 (molar percentages respectively), and the melting point is 233℃. The proportion of the obtained solid 8 to S is 6.1 by mass.

[0100] [Example 9] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank until atmospheric pressure was reached. The slurry was transferred to a 2.6L container, and water of the same volume as the slurry was added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.03 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.4 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–97°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.78 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 9. The results of the above measurements show that the MFR of copolymer 9 contained in solid 9 is 11 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 57.80 / 38.20 / 4.00 (molar percentages respectively), and the melting point is 227 °C. The proportion of the obtained solid 9 to S is 20.3 by mass.

[0101] [Example 10] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.05 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.2 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.56 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 10. The results of the above measurements show that the MFR of copolymer 10 contained in solid 10 is 23 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 58.52 / 39.34 / 2.14 (molar percentages respectively), and the melting point is 244 °C. The resulting solid content 10 had a mass ratio S of 16.0%.

[0102] [Example 11] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure a gas purging rate X1 / V of 0.25 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.49 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 11. The results of the above measurements show that the MFR of copolymer 11 contained in solid 11 is 5 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 58.30 / 38.50 / 3.20 (molar percentages respectively), and the melting point is 231℃. The proportion S of the obtained solid 11 is 28.8% by mass.

[0103] [Example 12] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.03 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.2 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–105°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.58 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 12. The results of the above measurements show that the MFR of copolymer 12 contained in solid 12 is 7 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 48.60 / 48.50 / 2.90 (molar percentages respectively), and the melting point is 248℃. The resulting solid 12 had a mass ratio S of 10.4.

[0104] [Example 13] After evacuating a 1.3L stainless steel polymerization tank equipped with a stirrer and jacket, add 1148g of CF3CH2CCF2H (AE-3000), 23g of CF3(CF2)4CF2H(C6H), 5.5g of methanol, and 7.0g of CH2=CHCF2CF3 (as a specific compound). While stirring the mixture, add 155g of TFE and 5g of ethylene (E), then allow hot water to flow through the jacket to maintain the polymerization temperature at 66℃ (polymerization temperature). The pressure inside the polymerization tank at this point is 1.5MPaG. After the temperature stabilizes, inject 17mL of a 1% (w / w) solution of tert-butyl peroxypentanoate (PBPV) (solvent: CF3CH2OCF2CH3) to begin polymerization. During polymerization, a TFE / E mixture with a molar ratio of 60 / 40 is added to maintain a constant internal pressure of 1.5MPaG. Simultaneously with the addition of the mixed gas, CH2=CHCF2 CF3 and itaconic anhydride (hereinafter also referred to as "IAH"), in amounts equivalent to 2.0 mol% of the total molar percentage of TFE and E, were continuously added. 360 minutes after the start of the reaction, the polymerization tank was cooled after the addition of 100 g of the mixed gas with a TFE / E ratio of 60 / 40, thus ending the polymerization.

[0105] Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.02 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.2 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.30 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 13. The results of the above measurements show that the MFR of copolymer 13 contained in solid 13 is 25 g / 10 min, and the composition is TFE unit / E unit / CH2=CHCF2CF3 unit / IAH unit = 53.40 / 43.75 / 2.10 / 0.75 (molar percentages respectively), and the melting point is 236℃. The resulting solid content 13 had a mass ratio S of 18.0%.

[0106] [Example 14] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–85°C to ensure that the gas purging rate X1 / V was 0.03 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.2 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 80–100°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.65 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 14. The results of the above measurements show that the MFR of copolymer 14 contained in solid 14 is 28 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 58.00 / 38.49 / 3.51 (molar percentages respectively), and the melting point is 236 °C. The proportion S of the obtained solid 14 is 50.4 by mass.

[0107] [Example 15] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 40–95°C to ensure a gas purging rate X1 / V of 0.03 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.3 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 95–110°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.18 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 15. The results of the above measurements show that the MFR of copolymer 15 contained in solid 15 is 7 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.10 / 45.96 / 0.94 (molar percentages respectively), and the melting point is 261 °C. The proportion S of the obtained solid 15 is 2.4 by mass.

[0108] [Example 16] Except for the changes in the types and amounts of the components used in the polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene and PFBE were copolymerized in the same manner as in Example 1. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–80°C to ensure a gas purging rate X1 / V of 0.05 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.4 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 70–88°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.42 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 16. The results of the above measurements show that the MFR of copolymer 16 contained in solid 16 is 10 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.10 / 45.30 / 1.60 (molar percentages respectively), and the melting point is 253 °C. The proportion S of the obtained solid 16 is 83.5 by mass.

[0109] [Example 17] Except for changes to the types and amounts of the components used for polymerization and the polymerization conditions as shown in Table 1, TFE, ethylene, and CF2=CFO(CF2)2CF3 were copolymerized in the same manner as in Example 1. Furthermore, in Example 17, 10.4 g of CF2=CFO(CF2)2CF3 was used to replace 7.5 g of PFBE. Additionally, "Novec7100" shown in Table 1 indicates F(CF2)4OCH3. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with the same volume of water added. The slurry was heated while stirring, as the first stage, to remove only the gas. At this time, the internal temperature of the container was adjusted within the range of 30–75°C to ensure a gas purging rate X1 / V of 0.09 kg / L / h. The first stage ended when the pressure inside the container was confirmed to be constant at 0.5 MPa. Next, as the second stage, the slurry is heated to vaporize and discharge the solvent. During this process, the internal temperature of the container is adjusted within the range of 70–90°C to ensure that the discharge rate (X2 / V) of the vaporized solvent is 0.3 kg / L / h. Furthermore, a cooling mechanism is used to recover the solvent discharged from the container into a tank. The second stage ends when the amount of recovered solvent reaches a constant level, yielding granules. The resulting granules are then dried in an oven at 150°C to obtain granular solids 17. The results of the above measurements show that the MFR of copolymer 17 contained in solid 17 is 15 g / 10 min, the composition is TFE unit / E unit / CF2=CFO(CF2)2CF3 unit=53.24 / 44.35 / 2.41 (molar percentages respectively), and the melting point is 248℃. The proportion S of the obtained solid 17 is 88.4% by mass.

[0110] [Example 18] TFE, ethylene, and PFBE were copolymerized in the same manner as in Example 2. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with an equal volume of water added. The slurry was heated while stirring to expel the gas and vaporized solvent. The internal temperature of the container was adjusted within the range of 30–95°C to maintain a gas expulsion rate of 0.25 kg / L / h. The solvent expelled from the container was then recovered into the tank using a cooling mechanism. Heating was stopped when the amount of recovered solvent reached a constant level, yielding granules. The resulting granules were then dried in an oven at 150°C to obtain granular solid 18. The results of the above measurements show that the MFR of copolymer 18 contained in solid 18 is 6 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.41 / 45.58 / 1.01 (molar percentages respectively), and the melting point is 261℃. The proportion S of the obtained solid 18 is 95.3 by mass.

[0111] [Example 19] TFE, ethylene, and PFBE were copolymerized in the same manner as in Example 3. Then, the remaining monomer gas was purged from the polymerization tank to atmospheric pressure, and the slurry was transferred to a 2.6L container, with an equal volume of water added. The slurry was heated while stirring to expel the gas and vaporized solvent. The internal temperature of the container was adjusted within the range of 30–105°C to maintain a gas expulsion rate of 0.90 kg / L / h. The solvent expelled from the container was then recovered into the tank using a cooling mechanism. Heating was stopped when the amount of recovered solvent reached a constant level, yielding granules. The resulting granules were then dried in an oven at 150°C to obtain granular solid 19. The results of the above measurements show that the MFR of copolymer 19 contained in solid 19 is 12 g / 10 min, the composition is TFE unit / E unit / PFBE unit = 53.40 / 45.06 / 1.54 (molar percentages respectively), and the melting point is 256 °C. The proportion of the obtained solid 19 to S is 97.6% by mass.

[0112] Table 1 shows the compounds used to manufacture the copolymers, the polymerization conditions of the copolymers, and the manufacturing conditions of the solids in each example. Table 2 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 columns “TFE Unit”, “E Unit”, “A Unit” and “IAH Unit” represent the content (unit: mol%) of each unit relative to all units contained in the resulting copolymer in each example. In the table, the "Solvent" column for "Solids" indicates the ratio (in mass%) of the total amount of solvent contained in the solids to the total mass of the solids obtained in each example. Among them, the solids in Examples 1 to 17 all contain water. The solids in Examples 2 to 16 all contain CF3CH2OCF2CF2H, which is equivalent to solvent F4, and the solid in Example 17 contains F(CF2)4OCH3, which is equivalent to solvent F4.

[0113] Table 1

[0114] Table 2

[0115] Table 3

[0116] As shown in the table, it was confirmed that solids with a total content of solvent F3 and a specific compound of less than 90.0% by mass relative to the total content of solvent and specific compound exhibited excellent pulverization properties (Examples 1 to 17).

[0117] Furthermore, the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2023-220827, 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 solvent includes fluorinated solvents that may have ether bonds containing hydrogen atoms and fluorine atoms. The fluorinated solvent comprises hydrofluorocarbons having the group represented by formula (3), The total content of the hydrofluorocarbon and the specific compound relative to the total content of the solvent and the specific compound is less than 90.0% by mass. CX 1 2=CX 2 (CF2) m F (1) CF2=CF-O-(CF2) n F (2) CF3(CF3)2) p - (3) In equation (1), X 1 and X 2 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. In equation (3), p represents an integer greater than or equal to 1. This indicates the bonding site with an adjacent atom.

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 fluorinated solvent also includes hydrofluoroethers.

6. The solid as described in claim 5, wherein, The hydrofluoroether includes the compound represented by formula (4). R 1 -O-R 2 (4) In equation (4), R 1 R represents a fluoroalkyl group having 2 to 6 carbon atoms. 2 R represents a fluoroalkyl or alkyl group having 1 to 4 carbon atoms. 1 and R 2 The total number of carbon atoms is less than 8.

7. The solid as described in claim 1 or 2, wherein, The solvent also 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 content of the hydrofluorocarbon is 0.001 to 1.5% of the total mass of the solid.

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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