CN116867816A - Copolymer, molded body, injection molded body, and coated electric wire - Google Patents

Copolymer, molded body, injection molded body, and coated electric wire Download PDF

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Publication number
CN116867816A
CN116867816A CN202280016114.8A CN202280016114A CN116867816A CN 116867816 A CN116867816 A CN 116867816A CN 202280016114 A CN202280016114 A CN 202280016114A CN 116867816 A CN116867816 A CN 116867816A
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China
Prior art keywords
copolymer
present
tfe
molded article
temperature
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CN202280016114.8A
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Chinese (zh)
Inventor
井坂忠晴
善家佑美
山本有香里
津田早登
滨田博之
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority claimed from PCT/JP2022/003645 external-priority patent/WO2022181230A1/en
Publication of CN116867816A publication Critical patent/CN116867816A/en
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Abstract

The present invention provides a copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units, wherein the content of the perfluoro (propyl vinyl ether) units is 3.3 to 4.2% by mass relative to the total monomer units, the melt flow rate at 372 ℃ is 27.0g/10 min to 35.0g/10 min, and the number of functional groups is per 10 6 The number of carbon atoms of the main chain is 20 or less.

Description

Copolymer, molded body, injection molded body, and coated electric wire
Technical Field
The present invention relates to a copolymer, a molded body, an injection molded body, and a coated electric wire.
Background
Patent document 1 describes a covered wire which is obtained by covering a core wire with a TFE-based copolymer having a structure derived from tetrafluoroethylene [ TFE]TFE unit and from perfluoro (alkyl vinyl ether) [ PAVE ]]The PAVE unit of (2) is more than 5% by mass and 20% by mass or less based on the total monomer units, and the unstable terminal group is 1X 10 per unit 6 The TFE copolymer has a melting point of 260 ℃ or higher and has a carbon number of less than 10.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2009-059690
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a copolymer which can give an injection-molded article excellent in surface smoothness by an injection molding method at high productivity, and which can give a molded article excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, deterioration resistance to repeated loads, rigidity and ozone resistance at high temperature, being less likely to deform even at high temperature, being less likely to crack even when in contact with a reagent, and being less likely to cause fluorine ions to be dissolved into a reagent such as hydrogen peroxide.
Means for solving the problems
According to the present invention, there is provided a copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units, wherein the content of perfluoro (propyl vinyl ether) units is 3.3 to 4.2% by mass relative to the total monomer units, and wherein the melt temperature is 372 ℃The flow rate is 27.0g/10 min-35.0 g/10 min, and the number of functional groups is relative to every 10 6 The number of carbon atoms of the main chain is 20 or less.
The copolymer of the present invention preferably has a melt flow rate of 27.0g/10 min to 33.0g/10 min at 372 ℃.
Further, according to the present invention, there is provided an injection molded article comprising the copolymer.
Further, according to the present invention, there is provided a coated wire comprising a coating layer containing the copolymer.
Further, according to the present invention, there is provided a molded article comprising the copolymer, wherein the molded article is a wafer carrier, a gasket, or a wire coating.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, it is possible to provide a copolymer which can give an injection-molded article excellent in surface smoothness by an injection molding method at high productivity, and can give a molded article excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, deterioration resistance to repeated loads, excellent rigidity and ozone resistance at high temperature, less liable to deform even at high temperature, less liable to generate cracks even when in contact with a reagent, less liable to dissolve fluorine ions into a reagent such as hydrogen peroxide.
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments.
The copolymers of the present invention contain Tetrafluoroethylene (TFE) units and perfluoro (propyl vinyl ether) (PPVE) units.
Since a copolymer (PFA) containing TFE units and PPVE units is excellent in chemical resistance, it is used as a material for forming a wafer carrier used for transporting, storing, cleaning, drying, and the like. In recent years, wafers having a larger diameter have been used, and in order to improve the production efficiency of semiconductor manufacturing, a large-sized wafer carrier has been required. In addition, since the wafer carrier is in direct contact with the wafer, high cleanliness that does not contaminate the wafer is required for the wafer carrier. Further, the wafer carrier is required to have high durability so as not to be damaged even if washing with water or a reagent is repeatedly performed and drying with heating is performed. In the case of drying a wafer accommodated in a wafer carrier by using a spin dryer, durability against centrifugal force is also required.
Patent document 1 describes: in a TFE copolymer having TFE units derived from tetrafluoroethylene [ TFE ] and PAVE units derived from perfluoro (alkyl vinyl ether) [ PAVE ], the PAVE units are more than 5% by mass of the total monomer units, whereby melt processability is improved and crack resistance is improved. However, a copolymer capable of providing a molded article having high cleaning properties and high durability has not been known.
The discovery is as follows: by properly adjusting the content of PPVE units, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE units and PPVE units, the moldability of the copolymer is significantly improved, and at the same time, the water vapor low permeability is extremely excellent, whereby a molded article having excellent abrasion resistance at 150 ℃, nitrogen low permeability, reagent low permeability, high temperature tensile creep characteristics, deterioration resistance to repeated loads, rigidity and ozone resistance at high temperatures, being less likely to deform even at high temperatures, being less likely to crack even when in contact with a reagent, and being less likely to cause elution of fluorine ions into a reagent such as hydrogen peroxide can be obtained. Therefore, by using the copolymer of the present invention, a large wafer carrier excellent in surface smoothness can be produced with high productivity. Further, the wafer carrier obtained by using the copolymer of the present invention is less likely to contaminate wafers, be damaged even if washing with water, ozone water or a reagent and drying with heating are repeated, and be damaged even if centrifugal force is large.
Further, the copolymer of the present invention can form a thin and defect-free coating layer on a core wire having a small diameter at a high speed without causing breakage of the coating layer by an extrusion molding method. Thus, the copolymer of the present invention can be used not only as a material for a wafer carrier but also for a wide range of applications such as wire coating.
The copolymer of the present invention is a melt-processible fluororesin. Melt processability means that a polymer can be melted and processed using existing processing equipment such as an extruder and an injection molding machine.
The content of PPVE unit in the copolymer is 3.3-4.2% by mass relative to the total monomer units. The content of PPVE unit in the copolymer is preferably 3.4% by mass or more, more preferably 3.5% by mass or more, further preferably 3.6% by mass or more, particularly preferably 3.7% by mass or more, preferably 4.1% by mass or less, further preferably 4.0% by mass or less, further preferably 3.9% by mass or less. If the PPVE unit content of the copolymer is too large, the copolymer is liable to be deformed at high temperature, and is poor in water vapor permeability, nitrogen permeability, reagent permeability, high-temperature tensile creep characteristics and rigidity at high temperature. If the content of PPVE unit in the copolymer is too small, cracks tend to occur when the copolymer is brought into contact with a reagent, or abrasion resistance at 150 ℃ and deterioration resistance against repeated loads and ozone resistance are poor.
The TFE unit content of the copolymer is preferably 95.8 to 96.7 mass%, more preferably 95.9 mass% or more, further preferably 96.0 mass% or more, more preferably 96.6 mass% or less, further preferably 96.5 mass% or less, particularly preferably 96.4 mass% or less, and most preferably 96.3 mass% or less, based on the total monomer units. If the TFE unit content of the copolymer is too small, the copolymer may be easily deformed at high temperature, or the water vapor permeability, nitrogen permeability, reagent permeability, high-temperature tensile creep characteristics, and rigidity at high temperature may be poor. If the TFE unit content of the copolymer is too large, cracks tend to occur when the copolymer is brought into contact with a reagent, and abrasion resistance at 150 ℃ and deterioration resistance to repeated loads and ozone resistance may be deteriorated.
In the present invention, the content of each monomer unit in the copolymer is determined by 19 F-NMR measurement.
The copolymer may also contain monomer units derived from monomers copolymerizable with TFE and FAVE. In this case, the content of the monomer unit copolymerizable with TFE and PPVE is preferably 0 to 0.9 mass%, more preferably 0.05 to 0.6 mass%, and even more preferably 0.1 to 0.5 mass%, based on the total monomer units of the copolymer.
As a means ofMonomers copolymerizable with TFE and PPVE include Hexafluoropropylene (HFP) and CZ 1 Z 2 ＝CZ 3 (CF 2 ) n Z 4 (wherein Z is 1 、Z 2 And Z 3 Identical or different, H or F, Z 4 H, F or Cl, n represents an integer of 2 to 10), and CF) 2 ＝CF-ORf 1 (wherein Rf 1 Perfluoro (alkyl vinyl ether) [ PAVE ] represented by perfluoroalkyl group having 1 to 8 carbon atoms](except PPVE), and CF 2 ＝CF-OCH 2 -Rf 1 (wherein Rf 1 A perfluoroalkyl group having 1 to 5 carbon atoms. ) Alkyl perfluorovinyl ether derivatives shown and the like. Among them, HFP is preferable.
The copolymer is preferably at least one selected from the group consisting of a copolymer composed of only TFE units and PPVE units, and a TFE/HFP/PPVE copolymer, and more preferably a copolymer composed of only TFE units and PPVE units.
The Melt Flow Rate (MFR) of the copolymer is 27.0g/10 min to 35.0g/10 min. The MFR of the copolymer is preferably 27.1g/10 min or more, more preferably 28.0g/10 min or more, still more preferably 29.0g/10 min or more, preferably 34.0g/10 min or less, more preferably 33.9g/10 min or less, still more preferably 33.3g/10 min or less, still more preferably 33.0g/10 min or less, particularly preferably 32.9g/10 min or less, particularly preferably 32.0g/10 min or less, very preferably 31.0g/10 min or less, and most preferably 30.0g/10 min or less. By setting the MFR of the copolymer in the above range, the moldability of the copolymer is improved, and the water vapor low permeability is extremely excellent, whereby a molded article having excellent abrasion resistance at 150 ℃, nitrogen low permeability, reagent low permeability, high-temperature tensile creep characteristics, resistance to repeated load, excellent rigidity and ozone resistance at high temperature, being less likely to deform even at high temperature, being less likely to crack even when in contact with a reagent, and being less likely to cause fluorine ions to be dissolved into a reagent such as hydrogen peroxide can be obtained. If the MFR is too low, it is difficult to obtain an injection-molded article excellent in surface smoothness when the copolymer is injected by injection molding, or a molded article obtained from the copolymer is poor in water vapor permeability, nitrogen permeability and rigidity at high temperature. If the MFR is too high, the molded article obtained from the copolymer is poor in abrasion resistance at 150 ℃ and ozone resistance, or cracks are likely to occur when the molded article is contacted with a reagent.
In the present invention, MFR is a value obtained as a mass (g/10 min) of a polymer flowing out from a nozzle having an inner diameter of 2.1mm and a length of 8mm at 372℃under a 5kg load every 10 minutes using a melt index meter according to ASTM D1238.
The MFR can be adjusted by adjusting the kind and amount of a polymerization initiator used in polymerizing the monomers, the kind and amount of a chain transfer agent, and the like.
In the present invention, every 10 of the copolymer 6 The number of functional groups having the number of main chain carbon atoms is 20 or less. Every 10 of the copolymer 6 The number of functional groups having the number of main chain carbon atoms is preferably 15 or less, more preferably 10 or less, and further preferably less than 6. By setting the number of functional groups of the copolymer in the above range, a molded article having excellent ozone resistance and being less likely to cause elution of fluorine ions into a reagent such as hydrogen peroxide can be obtained.
The identification of the kind of the functional group and the measurement of the number of functional groups may be performed by infrared spectroscopic analysis.
Specifically, the number of functional groups was measured by the following method. First, the copolymer was cold-molded to prepare a film having a thickness of 0.25mm to 0.3 mm. The film was analyzed by fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the above copolymer, and to obtain a differential spectrum from the fully fluorinated background spectrum without functional groups. The specific absorption peak of the specific functional group in the copolymer was calculated for every 1X 10 based on the following formula (A) 6 Number of functional groups N of carbon atoms.
N＝I×K/t (A)
I: absorbance of light
K: correction coefficient
t: film thickness (mm)
For reference, the absorption frequency, molar absorptivity, and correction factor are shown in table 1 for some functional groups. The molar absorptivity was determined from FT-IR measurement data of the low molecular weight model compound.
TABLE 1
TABLE 1
-CH 2 CF 2 H、-CH 2 COF、-CH 2 COOH、-CH 2 COOCH 3 、-CH 2 CONH 2 The absorption frequency ratios of (C) are shown in the tables respectively for-CF 2 H. -COF, free-COOH and bonded-COOH, -COOCH 3 、-CONH 2 Is tens of kesse (cm) -1 )。
For example, the functional group number of-COF means the number of functional groups derived from-CF 2 Absorption frequency of COF 1883cm -1 The number of functional groups obtained from the absorption peak at the site and the number of functional groups obtained from the absorption peak derived from-CH 2 Absorption frequency of COF 1840cm -1 The total number of functional groups obtained from the absorption peak at the position.
The functional groups are functional groups present at the main chain end or side chain end of the copolymer and functional groups present in the main chain or side chain. The number of functional groups may be-cf=cf 2 、-CF 2 H、-COF、-COOH、-COOCH 3 、-CONH 2 and-CH 2 Total number of OH.
The functional group is introduced into the copolymer, for example, by a chain transfer agent or a polymerization initiator used in producing the copolymer. For example, using alcohols as chain transfer agents, or using compounds having-CH 2 In the case of peroxides of OH structure as polymerization initiators, -CH 2 OH is introduced into the backbone end of the copolymer. In addition, the functional group is introduced into the terminal of the side chain of the copolymer by polymerizing a monomer having the functional group.
By subjecting the copolymer having such a functional group to fluorination treatment, a copolymer having the number of functional groups in the above range can be obtained. That is, the copolymer of the present invention is preferably a fluorinated copolymer. The copolymers of the invention also preferably have-CF 3 End groups.
The melting point of the copolymer is preferably 295℃to 315℃and more preferably 300℃or higher, still more preferably 303℃or higher, particularly preferably 304℃or higher, most preferably 305℃or higher, and still more preferably 310℃or lower. When the melting point is within the above range, a copolymer which provides a molded article having more excellent sealability particularly at high temperatures can be obtained.
In the present invention, the melting point can be measured using a differential scanning calorimeter [ DSC ].
The copolymer preferably has a water vapor permeability of 8.0 g.cm/m 2 The following is given. The copolymer of the present invention has very excellent low water vapor permeability because the content of PPVE unit, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE unit and PPVE unit are properly adjusted. Therefore, since moisture hardly permeates into the molded article formed of the copolymer, contamination of the wafer caused by outflow of the contaminant from the wafer carrier can be suppressed when the molded article is used as the wafer carrier.
In the present invention, the water vapor permeability can be measured at a temperature of 95℃for 30 days. Specific measurement of the water vapor permeability can be performed by the method described in examples.
The copolymer preferably has a nitrogen permeability coefficient of 240cm 3 ·mm/(m 2 24 h.atm) or less. The copolymer of the present invention has excellent nitrogen low permeability because the content of PPVE unit, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE unit and PPVE unit are appropriately adjusted.
In the present invention, the nitrogen permeability coefficient can be measured under the conditions of a test temperature of 70℃and a test humidity of 0% RH. The nitrogen permeability coefficient can be specifically measured by the method described in examples.
The Methyl Ethyl Ketone (MEK) transmittance of the copolymer is preferably 58.0mg cm/m 2 Day or less. The copolymer of the present invention has excellent MEK low permeability because the content of PPVE unit, melt Flow Rate (MFR) and the number of functional groups of the copolymer containing TFE unit and PPVE unit are appropriately adjusted. Namely, by using the copolymer of the present invention,a molded article which is less likely to be permeable to a reagent such as MEK can be obtained.
In the present invention, MEK transmittance can be measured at a temperature of 60 ℃ for 60 days. Specific measurement of MEK transmission can be performed by the methods described in examples.
The storage modulus (E') of the copolymer at 150℃is preferably 115MPa or more, more preferably 120MPa or more, further preferably 125MPa or more, preferably 1000MPa or less, more preferably 500MPa or less, further preferably 300MPa or less. By setting the storage modulus (E') of the copolymer at 150℃within the above range, a copolymer which provides a molded article which is not easily deformed even at high temperature can be obtained.
The storage modulus (E') can be measured by a dynamic viscoelasticity measurement at a temperature rising rate of 2 ℃/min and a frequency of 10Hz at a temperature ranging from 30 ℃ to 250 ℃. The storage modulus (E') at 150℃can be increased by adjusting the PPVE unit content and the Melt Flow Rate (MFR) of the copolymer.
The repulsion at 150℃of the copolymer is preferably 0.55MPa or more, more preferably 0.60MPa or more, still more preferably 0.65MPa or more, still more preferably 0.70MPa or more, particularly preferably 0.75MPa or more, particularly preferably 0.80MPa or more, most preferably 0.85MPa or more, and the upper limit is not particularly limited and may be 3.00MPa or less. The repulsive force at 150℃can be increased by adjusting the PPVE unit content, melt Flow Rate (MFR) and the number of functional groups of the copolymer. The high repulsive force means that the molded body formed of the copolymer is not easily deformed even at high temperature.
The repulsive force can be calculated as follows: the height of the test piece (height of the test piece after compression deformation) was measured after the test piece obtained from the copolymer was deformed at a compression deformation rate of 50%, left at 150℃for 18 hours, and released from the compressed state, and left at room temperature for 30 minutes, and calculated from the height of the test piece after compression deformation and the storage modulus (MPa) at 150℃by the following formula.
Repulsive force (MPa) = (t) at 150 °c 2 －t 1 )/t 1 ×E’
t 1 : original height of test piece before compression deformation(mm)×50％
t 2 : height (mm) of test piece after compression deformation
E': storage modulus (MPa) at 150 DEG C
The copolymer of the present invention can be produced by a polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization, or bulk polymerization. As the polymerization method, emulsion polymerization or suspension polymerization is preferable. In these polymerizations, the conditions such as temperature and pressure, polymerization initiator, and other additives may be appropriately set according to the composition and amount of the copolymer.
As the polymerization initiator, an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used.
The oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, and the following are exemplified as typical examples:
Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, and di-2-ethoxyethyl peroxydicarbonate;
peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate;
dialkyl peroxides such as di-t-butyl peroxide;
di [ fluoro (or fluoro chloro) acyl ] peroxides; etc.
As bis [ fluoro (or fluoro chloro) acyl groups]The peroxides include [ (RfCOO) & lt- & gt ]] 2 (Rf is perfluoroalkyl, omega-hydroperfluoroalkyl or fluorochloroalkyl).
Examples of the di [ fluoro (or fluorochloroacyl ] peroxides include di (ω -hydro-dodecafluoroheptanoyl) peroxide, di (ω -hydro-hexadecanoyl) peroxide, di (perfluoropropionyl) peroxide, di (perfluorobutanoyl) peroxide, di (perfluoropentanoyl) peroxide, di (perfluorohexanoyl) peroxide, di (perfluoroheptanoyl) peroxide, di (perfluorooctanoyl) peroxide, di (perfluorononanoyl) peroxide, di (ω -chloro-hexafluorobutanoyl) peroxide, di (ω -chloro-dodecafluoroheptanoyl) peroxide, di (ω -chloro-dodecafluorooctanoyl) peroxide, ω -hydro-dodecafluoroheptanoyl-peroxide, ω -chloro-hexafluorobutanoyl-peroxide, ω -hydrododecafluoroheptanoyl-perfluorobutanoyl-peroxide, di (perfluoroheptanoyl) peroxide, di (dichloro-heptanoyl) peroxide, di (dichloro-dodecanoyl) peroxide, and di (dichloro-dodecanoyl) dodecanoyl peroxide.
The water-soluble radical polymerization initiator may be a known water-soluble peroxide, and examples thereof include ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, and percarbonic acid, potassium salts, sodium salts, disuccinic acid peroxide, and organic peroxides such as dipentaerythritol peroxide, t-butyl peroxymaleate, and t-butyl hydroperoxide. The reducing agent such as sulfite may be used in combination with the peroxide in an amount of 0.1 to 20 times the amount of the peroxide.
In the polymerization, a surfactant, a chain transfer agent and a solvent may be used, and conventionally known ones may be used, respectively.
As the surfactant, a known surfactant can be used, and for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant, and the like can be used. Among them, the fluorinated anionic surfactant is preferable, and the fluorinated anionic surfactant having 4 to 20 carbon atoms, which may be linear or branched, and which may or may not contain ether-bonded oxygen (i.e., may have an oxygen atom interposed between carbon atoms), is more preferable. The amount of the surfactant to be added (relative to the polymerization water) is preferably 50ppm to 5000ppm.
Examples of the chain transfer agent include: hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatic compounds such as toluene and xylene; ketones such as acetone; acetate esters such as ethyl acetate and butyl acetate; alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and methyl chloride; etc. The amount of the chain transfer agent to be added may vary depending on the amount of the chain transfer constant of the compound to be used, and is usually in the range of 0.01 to 20% by mass relative to the polymerization solvent.
Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.
In the suspension polymerization, a fluorine-based solvent may be used in addition to water. As the fluorine-based solvent, CH may be mentioned 3 CClF 2 、CH 3 CCl 2 F、CF 3 CF 2 CCl 2 H、CF 2 ClCF 2 Hydrochlorofluoroalkanes such as CFHCl; CF (compact flash) 2 ClCFClCF 2 CF 3 、CF 3 CFClCFClCF 3 Isophlorofluoroalkanes; CF (compact flash) 3 CFHCFHCF 2 CF 2 CF 3 、CF 2 HCF 2 CF 2 CF 2 CF 2 H、CF 3 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 Hydrofluoroalkanes such as H; CH (CH) 3 OC 2 F 5 、CH 3 OC 3 F 5 CF 3 CF 2 CH 2 OCHF 2 、CF 3 CHFCF 2 OCH 3 、CHF 2 CF 2 OCH 2 F、(CF 3 ) 2 CHCF 2 OCH 3 、CF 3 CF 2 CH 2 OCH 2 CHF 2 、CF 3 CHFCF 2 OCH 2 CF 3 Isohydrofluoroethers; perfluorocyclobutane, CF 3 CF 2 CF 2 CF 3 、CF 3 CF 2 CF 2 CF 2 CF 3 、CF 3 CF 2 CF 2 CF 2 CF 2 CF 3 Among them, perfluoroalkanes are preferable. The amount of the fluorine-based solvent to be used is preferably 10 to 100% by mass based on the aqueous medium in view of suspension property and economy.
The polymerization temperature is not particularly limited, and may be 0 to 100 ℃. The polymerization pressure is appropriately determined depending on the kind and amount of the solvent used, the vapor pressure, the polymerization temperature, and other polymerization conditions, and may be generally 0 to 9.8MPaG.
When an aqueous dispersion containing a copolymer is obtained by polymerization, the copolymer contained in the aqueous dispersion can be precipitated, washed, and dried to recover the copolymer. In addition, in the case where the copolymer is obtained as a slurry by polymerization, the copolymer can be recovered by taking out the slurry from the reaction vessel, washing it, and drying it. The copolymer can be recovered in the form of a powder by drying.
The copolymer obtained by polymerization may be molded into pellets. The molding method for molding the pellets is not particularly limited, and conventionally known methods can be used. For example, a method of melt-extruding a copolymer using a single screw extruder, a twin screw extruder, or a tandem extruder, cutting the copolymer into a predetermined length, and molding the copolymer into pellets, and the like can be mentioned. The extrusion temperature at the time of melt extrusion is required to be changed depending on the melt viscosity of the copolymer and the production method, and is preferably from +20℃to +140℃of the melting point of the copolymer. The method of cutting the copolymer is not particularly limited, and conventionally known methods such as a wire cutting method, a thermal cutting method, an underwater cutting method, and a sheet cutting method can be employed. The volatile components in the pellets may also be removed by heating the resulting pellets (degassing treatment). The obtained pellets may be treated by contacting them with warm water at 30 to 200 ℃, steam at 100 to 200 ℃ or hot air at 40 to 200 ℃.
The copolymer obtained by polymerization may also be subjected to a fluorination treatment. The fluorination treatment may be performed by contacting the copolymer that has not been subjected to the fluorination treatment with a fluorine-containing compound. By fluorination treatment, the-COOH, -COOCH-of the copolymer can be obtained 3 、-CH 2 OH、-COF、-CF＝CF 2 、-CONH 2 Isothermally labile functional groups and relatively thermally stable-CF 2 Conversion of functional groups such as H to extremely thermally stable-CF 3 . As a result, the-COOH, -COOCH-of the copolymer can be used 3 、-CH 2 OH、-COF、-CF＝CF 2 、-CONH 2 and-CF 2 The total number of H (the number of functional groups) is easily adjusted to be within the above-mentioned range.
The fluorine-containing compound is not particularly limited, and examples thereof include those at the place of fluorinationA source of fluorine radicals that generates fluorine radicals under physiological conditions. As the fluorine radical source, F may be mentioned 2 Gas, coF 3 、AgF 2 、UF 6 、OF 2 、N 2 F 2 、CF 3 OF, fluorinated halogens (e.g. IF 5 、ClF 3 ) Etc.
F 2 The fluorine radical source such as gas may be used at a concentration of 100%, but from the viewpoint of safety, it is preferably used by mixing with an inactive gas and diluting to 5 to 50% by mass, more preferably 15 to 30% by mass. The inert gas may be nitrogen, helium, argon, or the like, and nitrogen is preferable from the viewpoint of economy.
The conditions of the fluorination treatment are not particularly limited, and the copolymer in a molten state may be brought into contact with the fluorine-containing compound, but may be usually conducted at a temperature of 20 to 240℃and more preferably 100 to 220℃below the melting point of the copolymer. The fluorination treatment is generally carried out for 1 to 30 hours, preferably 5 to 25 hours. The fluorination treatment preferably involves reacting the copolymer which has not been subjected to the fluorination treatment with fluorine gas (F 2 Gas) contact.
The copolymer of the present invention may be mixed with other components as needed to obtain a composition. Examples of the other components include fillers, plasticizers, processing aids, mold release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, ultraviolet absorbers, antioxidants, foaming agents, perfumes, oils, softeners, dehydrofluorination agents, and the like.
Examples of the filler include silica, kaolin, clay, organized clay, talc, mica, alumina, calcium carbonate, calcium terephthalate, titanium oxide, calcium phosphate, calcium fluoride, lithium fluoride, crosslinked polystyrene, potassium titanate, carbon, boron nitride, carbon nanotubes, and glass fibers. Examples of the conductive agent include carbon black. Examples of the plasticizer include dioctyl phthalate and pentaerythritol. Examples of the processing aid include carnauba wax, sulfone compound, low molecular weight polyethylene, and fluorine-based aid. Examples of the dehydrofluorination agent include organic onium and amidines.
As the other components, other polymers than the above copolymers may be used. Examples of the other polymer include a fluororesin other than the above copolymer, a fluororubber, a nonfluorinated polymer, and the like.
The method for producing the composition includes: a method of dry-mixing the copolymer with other components; a method in which the copolymer and other components are mixed in advance by a mixer, and then melt-kneaded by a kneader, a melt extruder, or the like; etc.
The copolymer or the composition of the present invention can be used as a processing aid, a molding material, or the like, and is preferably used as a molding material. Aqueous dispersions, solutions, suspensions, and copolymer/solvent systems of the copolymers of the present invention may also be utilized, which may be applied as coatings or used for encapsulation, impregnation, film casting. However, the copolymer of the present invention is preferably used as the molding material because it has the above-mentioned characteristics.
The copolymer of the present invention or the above composition may be molded to obtain a molded article.
The method for molding the copolymer or the composition is not particularly limited, and examples thereof include injection molding, extrusion molding, compression molding, blow molding, transfer molding, rotational molding, and roll lining molding. Among the molding methods, extrusion molding, compression molding, injection molding or transfer molding is preferable, and injection molding is more preferable because a molded article can be produced with high productivity. That is, the molded article is preferably an extrusion molded article, a compression molded article, an injection molded article or a transfer molded article, and more preferably an injection molded article, an extrusion molded article or a transfer molded article, and even more preferably an injection molded article, since it can be produced at high productivity. By molding the copolymer of the present invention by injection molding, an injection molded article excellent in surface smoothness can be obtained with high productivity.
Examples of molded articles containing the copolymer of the present invention include nuts, bolts, joints, films, bottles, gaskets, wire coatings, pipes, hoses, pipes, valves, sheets, seals, gaskets, tanks, rolls, containers, taps, connectors, filter housings, filter covers, flow meters, pumps, wafer carriers, wafer cassettes, and the like.
The copolymer, the composition or the molded article of the present invention can be used for the following purposes, for example.
A film for packaging food, a lining material for a fluid transfer line used in a food manufacturing process, a gasket, a sealing material, a fluid transfer member for a food manufacturing apparatus such as a sheet;
reagent delivery members such as plugs for chemicals, packaging films, liners for fluid delivery lines used in chemical manufacturing processes, gaskets, seals, sheets, etc.;
inner lining members of reagent tanks and piping of chemical equipment and semiconductor factories;
fuel delivery members such as hoses and sealing materials used in AT devices of automobiles such as O (square) rings/tubes/gaskets, valve core materials, hoses and sealing materials used in fuel systems and peripheral devices of automobiles;
flange gaskets, shaft seals, stem seals, sealing materials, brake hoses for automobiles such as hoses, air conditioning hoses, radiator hoses, wire coating materials, and other automobile components used in engines and peripheral devices of automobiles;
A reagent transporting member for a semiconductor device, such as an O-ring, a tube, a gasket, a valve body material, a hose, a sealing material, a roller, a gasket, a diaphragm, and a joint of a semiconductor manufacturing apparatus;
coating and ink members such as coating rolls, hoses, tubes, ink containers for coating equipment;
pipes such as pipes for food and drink, hoses, belts, gaskets, joints, and other food and drink conveying members, food packaging materials, and glass cooking devices;
a waste liquid transporting member such as a tube or a hose for transporting waste liquid;
high-temperature liquid transmission members such as pipes and hoses for high-temperature liquid transmission;
a member for steam piping such as a pipe or a hose for steam piping;
a corrosion-resistant belt for piping such as a belt wound around piping such as a deck of a ship;
various coating materials such as a wire coating material, an optical fiber coating material, a transparent surface coating material provided on a light incidence side surface of a photovoltaic element of a solar cell, and a back surface agent;
sliding components such as diaphragms and various gaskets of the diaphragm pump;
weather resistant covers for agricultural films, various roofing materials, sidewalls, and the like;
glass-like coating materials such as interior materials and incombustible fire-resistant safety glass used in the construction field;
Lining materials such as laminated steel sheets used in the field of home appliances and the like.
Further examples of the fuel delivery member used in the fuel system of the automobile include a fuel hose, a filler hose, and an evaporator hose. The fuel delivery member can be used as a fuel delivery member for acid-resistant gasoline, alcohol-resistant fuel, and fuel to which a gasoline additive such as methyl t-butyl ether or amine-resistant additive is added.
The above-mentioned chemical stopper and packaging film have excellent chemical resistance to acids and the like. The reagent transporting member may be an anti-corrosive tape wound around a piping of a chemical apparatus.
Examples of the molded article include radiator chambers, reagent tanks, bellows, separators, rolls, gasoline tanks, waste liquid transport containers, high-temperature liquid transport containers, fishery and fish farming tanks, and the like of automobiles.
Further, examples of the molded article include a bumper, a door trim, an instrument panel, a food processing device, a cooking machine, water/oil resistant glass, a lighting-related instrument, an indication board and a housing for OA instruments, an electric lighting sign, a display screen, a liquid crystal display, a cellular phone, a printer chassis, electric and electronic parts, sundries, a dustbin, a bathtub, an entire bathroom, a ventilator, a lighting frame, and the like.
The molded article containing the copolymer of the present invention is excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, resistance to repeated loads, rigidity at high temperature, ozone resistance, and the like, is not easily deformed even at high temperature, is not easily cracked even when in contact with a reagent, and is not easily eluted with a reagent such as hydrogen peroxide, and therefore can be suitably used for nuts, bolts, joints, gaskets, valves, taps, connectors, filter housings, filter covers, flow meters, pumps, and the like.
The molded article containing the copolymer of the present invention is excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, resistance to repeated load, rigidity at high temperature, ozone resistance, and the like, is not easily deformed even at high temperature, is not easily cracked even when in contact with a reagent, and is not easily eluted with a reagent such as hydrogen peroxide, and therefore can be suitably used as a compressed member such as a gasket or a gasket.
The compressed member of the present invention exhibits a high repulsive force even if deformed at a high compression deformation rate. The compressed member of the present invention can be used in a state of being compressed and deformed at a compression deformation rate of 10% or more, and can be used in a state of being compressed and deformed at a compression deformation rate of 20% or more or 25% or more. By deforming the compressed member of the present invention at such a high compression set, a certain rebound resilience can be maintained for a long period of time, and sealing properties and insulating properties can be maintained for a long period of time.
The compressed member of the present invention exhibits a high storage modulus, a high recovery amount, and a high repulsive force even when deformed at a high compression deformation rate at a high temperature. The compressed member of the present invention can be used in a state of being compressed and deformed at a compression deformation rate of 10% or more at 150 ℃ or more, and can be used in a state of being compressed and deformed at a compression deformation rate of 20% or more or 25% or more at 150 ℃. By deforming the compressed member of the present invention at such a high temperature with a high compression deformation rate, a certain rebound resilience can be maintained for a long period of time even at a high temperature, and sealing properties and insulating properties at a high temperature can be maintained for a long period of time.
The compression set is the compression set at the portion where the compression set is the largest when the compressed member is compressed. For example, when a flat compressed member is used in a state compressed in the thickness direction, the compression set is the compression set in the thickness direction. For example, when the member is used in a state where only a part of the member is compressed, the member is a part having the highest compression set among compression sets of the compressed part.
The size and shape of the compressed member of the present invention may be appropriately set according to the application, and are not particularly limited. The compressed member of the present invention may be annular in shape, for example. The compressed member of the present invention may have a circular shape, an elliptical shape, a quadrangular shape with rounded corners, or the like in a plan view, and may have a through hole in a central portion thereof.
The compressed member of the present invention is preferably used as a member for constituting a nonaqueous electrolyte battery. The compressed member of the present invention is excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, resistance to repeated load deterioration, rigidity at high temperature, ozone resistance, and sealability at high temperature, and is therefore particularly suitable as a member used in contact with a nonaqueous electrolyte in a nonaqueous electrolyte battery. That is, the compressed member of the present invention may have a liquid receiving surface of the nonaqueous electrolyte in the nonaqueous electrolyte battery.
The compressed member of the present invention is not easily permeable to water vapor. Therefore, by using the compressed member of the present invention, the permeation of water vapor from the outside through the secondary battery can be suppressed. As a result, by using the compressed member of the present invention, deterioration in battery performance and short lifetime of the nonaqueous electrolyte battery can be suppressed.
Since the nonaqueous electrolyte battery can be further suppressedDeterioration of battery performance and reduction of lifetime, the water vapor permeability of the compressed member of the present invention is preferably 8.8 g.cm/m 2 Hereinafter, it is more preferably 8.4 g.cm/m 2 The following is more preferably 8.0 g.cm/m 2 The following is given. The water vapor permeability of the compressed member can be measured at a temperature of 95℃for 30 days.
The nonaqueous electrolyte battery is not particularly limited as long as it is a battery provided with a nonaqueous electrolyte, and examples thereof include a lithium ion secondary battery and a lithium ion capacitor. Further, as a member constituting the nonaqueous electrolyte battery, a sealing member, an insulating member, and the like can be given.
The nonaqueous electrolyte is not particularly limited, and 1 or 2 or more of known solvents such as propylene carbonate, ethylene carbonate, butylene carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, dimethyl carbonate, diethyl carbonate, and methylethyl carbonate may be used. The nonaqueous electrolyte battery may further include an electrolyte. The electrolyte is not particularly limited, and LiClO may be used 4 、LiAsF 6 、LiPF 6 、LiBF 4 、LiCl、LiBr、CH 3 SO 3 Li、CF 3 SO 3 Li, cesium carbonate, and the like.
The compressed member of the present invention can be preferably used as a sealing member such as a gasket or a packing, or an insulating member such as an insulating gasket or an insulating packing, for example. The sealing member is used to prevent leakage of liquid or gas or intrusion of liquid or gas from the outside. The insulating member is a member used for electrical insulation. The compressed member of the present invention may be a member used for both sealing and insulation purposes.
The compressed member of the present invention exhibits a high storage modulus, a high recovery amount, and a high repulsive force even when deformed at a high compression deformation rate at a high temperature, and thus can be suitably used in a high-temperature environment. For example, the compressed member of the present invention is preferably used in an environment where the maximum temperature is 40 ℃ or higher. For example, the compressed member of the present invention is preferably used in an environment where the maximum temperature is 150 ℃. As a case where the compressed member of the present invention can be brought to such a high temperature, for example, a case where after the compressed member is mounted to a battery in a compressed state, another battery member is mounted to the battery by welding; a case where the nonaqueous electrolyte battery generates heat; etc.
The compressed member of the present invention is excellent in low water vapor permeability, and exhibits a high storage modulus, a high recovery amount, and a high repulsive force even when deformed at a high compression deformation rate at a high temperature, and therefore can be suitably used as a sealing member for a nonaqueous electrolyte battery or an insulating member for a nonaqueous electrolyte battery. For example, in the case of charging a battery such as a nonaqueous electrolyte secondary battery, the temperature of the battery may be temporarily 40 ℃ or higher, in particular, temporarily 150 ℃ or higher. The compressed member of the present invention is used in a battery such as a nonaqueous electrolyte secondary battery by deforming at a high compression deformation rate even at a high temperature, and does not deteriorate high rebound resilience even when it is in contact with a nonaqueous electrolyte at a high temperature. Therefore, in the case where the compressed member of the present invention is used as a sealing member, it has excellent sealing properties and can maintain the sealing properties for a long period of time even at high temperatures. In addition, the compressed member of the present invention has excellent insulating properties because it contains the copolymer. Therefore, when the compressed member of the present invention is used as an insulating member, the compressed member is firmly adhered to 2 or more conductive members, and short-circuiting can be prevented for a long period of time.
By molding the copolymer of the present invention by extrusion molding, even in the case where the diameter of the core wire is small, the coating layer can be formed thin on the core wire having a small diameter at a high drawing speed without causing breakage of the coating layer, and the coating layer having excellent electrical characteristics can be formed, and therefore can be suitably used as a material for forming the wire coating layer. Therefore, the coated wire having the coating layer containing the copolymer of the present invention has almost no defects such as spark generation even when the diameter of the core wire is small and the coating layer is thin, and is excellent in electrical characteristics.
The coated wire comprises a core wire and a coating layer provided around the core wire and containing the copolymer of the present invention. For example, an extrusion molded article obtained by melt-extruding the copolymer of the present invention on a core wire may be used as the coating layer. The covered wire is suitable for a LAN Cable (ethernet Cable), a high-frequency transmission Cable, a flat Cable, a heat-resistant Cable, and the like, and is suitable for a transmission Cable such as a LAN Cable (ethernet Cable), a high-frequency transmission Cable, and the like.
As the material of the core wire, for example, a metal conductor material such as copper or aluminum can be used. The core wire preferably has a diameter of 0.02mm to 3mm. The diameter of the core wire is more preferably 0.04mm or more, still more preferably 0.05mm or more, and particularly preferably 0.1mm or more. The diameter of the core wire is more preferably 2mm or less.
Specific examples of the core wire include AWG (American wire gauge) -46 (solid copper wire with a diameter of 40 μm), AWG-26 (solid copper wire with a diameter of 404 μm), AWG-24 (solid copper wire with a diameter of 510 μm), AWG-22 (solid copper wire with a diameter of 635 μm), and the like.
The thickness of the coating layer is preferably 0.1mm to 3.0mm. The thickness of the coating layer is also preferably 2.0mm or less.
As the high-frequency transmission cable, a coaxial cable may be mentioned. The coaxial cable generally has a structure in which an inner conductor, an insulating coating layer, an outer conductor layer, and a protective coating layer are laminated in this order from a core portion to an outer peripheral portion. The molded article containing the copolymer of the present invention can be suitably used as an insulating coating layer containing the copolymer. The thickness of each layer in the above-described structure is not particularly limited, and in general, the diameter of the inner conductor is about 0.1mm to 3mm, the thickness of the insulating coating layer is about 0.3mm to 3mm, the thickness of the outer conductor layer is about 0.5mm to 10mm, and the thickness of the protective coating layer is about 0.5mm to 2mm.
The coating may contain bubbles, which are preferably uniformly distributed in the coating.
The average cell diameter of the bubbles is not limited, and is, for example, preferably 60 μm or less, more preferably 45 μm or less, further preferably 35 μm or less, further preferably 30 μm or less, particularly preferably 25 μm or less, and particularly preferably 23 μm or less. The average cell diameter is preferably 0.1 μm or more, more preferably 1 μm or more. The average bubble diameter can be obtained by obtaining an electron microscope image of a wire cross section, calculating the diameter of each bubble by image processing, and averaging.
The foaming ratio of the coating layer may be 20% or more. More preferably 30% or more, still more preferably 33% or more, still more preferably 35% or more. The upper limit is not particularly limited, and is, for example, 80%. The upper limit of the foaming ratio may be 60%. The foaming ratio was obtained as ((specific gravity of wire coating material-specific gravity of coating layer)/specific gravity of wire coating material) ×100. The foaming ratio can be appropriately adjusted according to the application by, for example, adjusting the amount of gas inserted into an extruder to be described later, or by selecting the type of dissolved gas.
The coated wire may further include a different layer (outer layer) around the coating layer, and a different layer may be provided between the core wire and the coating layer. When the coating layer contains bubbles, the electric wire of the present invention may have a 2-layer structure (skin-foam) in which a non-foam layer is interposed between the core wire and the coating layer; a 2-layer structure (foam-skin) having a non-foam layer coated on the outer layer; further, the outer layer of the skin-foam was covered with a 3-layer structure (skin-foam-skin) of a non-foam layer. The non-expanded layer is not particularly limited, and may be a resin layer composed of a polyolefin resin such as TFE/HFP copolymer, TFE/PAVE copolymer, TFE/ethylene copolymer, vinylidene fluoride polymer, polyethylene [ PE ], or a resin such as polyvinyl chloride [ PVC ].
The coated wire can be produced, for example, by heating the copolymer using an extruder, extruding the copolymer onto the core wire in a molten state, and forming a coating layer.
In forming the coating layer, the gas may be introduced into the copolymer in a molten state by heating the copolymer, thereby forming the coating layer containing bubbles. As the gas, for example, a gas such as difluoromethane, nitrogen, carbon dioxide, or the like, or a mixture of the above gases can be used. The gas may be introduced into the heated copolymer as a pressurized gas or may be produced by mixing a chemical blowing agent into the copolymer. The gas is dissolved in the copolymer in a molten state.
In addition, the copolymer of the present invention can be suitably used as a material for a product for high-frequency signal transmission.
The product for transmitting a high-frequency signal is not particularly limited as long as it is a product for transmitting a high-frequency signal, and examples thereof include (1) a molded plate such as an insulating plate for a high-frequency circuit, an insulating material for a connecting member, and a printed wiring board, (2) a molded body such as a base or a radome for a high-frequency vacuum tube, and (3) a covered wire such as a coaxial cable or a LAN cable. The high-frequency signal transmission product can be suitably used for satellite communication equipment, mobile telephone base stations, and other equipment utilizing microwaves, particularly microwaves of 3GHz to 30 GHz.
In the above-mentioned high-frequency signal transmission product, the copolymer of the present invention is suitable for use as an insulator in view of low dielectric loss tangent.
The molded plate (1) is preferably a printed wiring board in terms of obtaining good electrical characteristics. The printed wiring board is not particularly limited, and examples thereof include printed wiring boards for electronic circuits of mobile phones, various computers, communication devices, and the like. As the molded article (2), a radome is preferable in terms of low dielectric loss.
The copolymer of the present invention is molded by injection molding, and a sheet excellent in surface smoothness can be obtained with high productivity. The molded article containing the copolymer of the present invention is excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, resistance to deterioration under repeated load, rigidity at high temperature, ozone resistance, and the like, and is not easily deformed even at high temperature, is not easily cracked even when it is in contact with a reagent, and is not easily eluted with a reagent such as hydrogen peroxide. Therefore, the molded article containing the copolymer of the present invention can be suitably used as a film or sheet.
The film of the present invention is useful as a release film. The release film can be produced by molding the copolymer of the present invention by melt extrusion molding, calender molding, press molding, casting molding, or the like. From the viewpoint of obtaining a uniform film, a release film can be produced by melt extrusion molding.
The film of the present invention can be applied to the surface of a roll used in an OA apparatus. The copolymer of the present invention can be molded into a desired shape by extrusion molding, compression molding, press molding, etc., and formed into a sheet, film, tube shape, etc., for use as a surface material for OA equipment rolls, OA equipment belts, etc. In particular, thin-walled tubes and films can be produced by melt extrusion.
The molded article containing the copolymer of the present invention is excellent in low water vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, high-temperature tensile creep characteristics, resistance to repeated load, rigidity at high temperature and ozone resistance, is not easily deformed even at high temperature, is not easily cracked even when in contact with a reagent, and is not easily eluted with a reagent such as hydrogen peroxide, and therefore can be suitably used as a bottle or a tube. The bottle or tube of the present invention can easily visually confirm the content, and is not easily damaged in use.
The copolymer of the present invention can be molded into injection-molded articles by injection molding with high productivity. Further, the obtained molded article is excellent in surface smoothness, extremely excellent in low vapor permeability, abrasion resistance at 150 ℃, low nitrogen permeability, low reagent permeability, excellent in high-temperature tensile creep characteristics, deterioration resistance to repeated loads, rigidity at high temperature and ozone resistance, is not easily deformed even at high temperature, is not easily cracked even when in contact with a reagent, and is not easily eluted fluorine ions into a reagent such as hydrogen peroxide, and therefore can be suitably used for a valve. Therefore, the valve containing the copolymer of the present invention can be produced with high productivity, is less likely to be damaged even if repeatedly opened and closed at a high frequency, and is excellent in low reagent permeability, sealability at high temperatures, and low water vapor permeability. In the valve of the present invention, at least the liquid receiving portion may be composed of the above-mentioned copolymer. The valve of the present invention may be a valve having a housing containing the copolymer.
While the embodiments have been described above, it will be understood that various changes in form and details may be made therein without departing from the spirit and scope of the claims.
Examples
Next, embodiments of the present invention will be described with reference to examples, but the present invention is not limited to the examples.
The values of the examples were measured by the following methods.
(content of monomer units)
The content of each monomer unit was measured by an NMR analyzer (for example, AVANCE300 high temperature probe manufactured by Bruker Biospin Co.).
(melt flow Rate (MFR))
The mass (G/10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2.1mm and a length of 8mm per 10 minutes was determined by using a melt index analyzer G-01 (manufactured by Toyo Seisakusho-Sho Co., ltd.) at 372℃under a 5kg load in accordance with ASTM D1238.
(number of functional groups)
The pellets of the copolymer were cold-molded to prepare a film having a thickness of 0.25mm to 0.3 mm. By Fourier transform infrared Spectrum analysis device [ FT-IR (Spectrum One manufactured by Perkinelmer Co.)]The film was scanned 40 times and analyzed to obtain an infrared absorption spectrum and a differential spectrum from a fully fluorinated background spectrum without functional groups. The absorbance peak of the specific functional group shown by the differential spectrum was calculated for every 1X 10 in the sample according to the following formula (A) 6 Number of functional groups N of carbon atoms.
N＝I×K/t (A)
I: absorbance of light
K: correction coefficient
t: film thickness (mm)
For reference, regarding the functional groups in the present invention, the absorption frequency, molar absorptivity, and correction coefficient are shown in table 2. The molar absorptivity was determined from FT-IR measurement data of the low molecular weight model compound.
TABLE 2
TABLE 2
(melting point)
The melting point was determined from the melting curve peak generated during the 2 nd heating process by performing the 1 st heating from 200℃to 350℃at a heating rate of 10℃per minute using a differential scanning calorimeter (trade name: X-DSC7000, manufactured by Hitachi High-Tech Science Co., ltd.), then cooling from 350℃to 200℃at a cooling rate of 10℃per minute, and performing the 2 nd heating from 200℃to 350℃again at a heating rate of 10℃per minute.
Example 1
After adding 33.4L of pure water to a 174L-volume autoclave and sufficiently performing nitrogen substitution, 33.4kg of perfluorocyclobutane, 0.83kg of perfluoro (propyl vinyl ether) (PPVE) and 2.26kg of methanol were added, and the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.6MPa, and then 0.066kg of a 50% methanol solution of di-n-propyl dicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.042kg of PPVE was added to each 1kg of TFE fed, and polymerization was continued for 20.3 hours. TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 33kg of powder.
The obtained powder was melt-extruded at 360℃by a screw extruder (trade name: PCM46, manufactured by Mitsui Co., ltd.) to obtain pellets of TFE/PPVE copolymer. Using the pellets obtained, the PPVE content was determined by the method described above. The results are shown in Table 3.
The obtained pellets were placed in a vacuum vibration type reaction apparatus VVD-30 (manufactured by Dachuan origin Co., ltd.) and heated to 210 ℃. After evacuation, N for introduction 2 F gas dilution to 20 vol% 2 The gas is brought to atmospheric pressure. From F 2 After 0.5 hour from the time of gas introduction, the mixture was once evacuated and F was introduced again 2 And (3) gas. After 0.5 hour, the mixture was again evacuated and F was introduced again 2 And (3) gas. Thereafter, F is as described above 2 The gas introduction and evacuation operations were continued for 1 time within 1 hour, and the reaction was carried out at 210℃for 10 hours. After the reaction, the inside of the reactor was fully replaced with N 2 And (3) ending the fluorination reaction by using the gas. Using fluorineThe pellets thus formed were measured for various physical properties by the above-mentioned method. The results are shown in Table 3.
Example 2
Fluorinated pellets were obtained in the same manner as in example 1, except that PPVE was changed to 0.80kg, methanol was changed to 2.42kg, PPVE was changed to 0.041kg added per 1kg of TFE supplied, and the polymerization time was changed to 19.3 hours. The results are shown in Table 3.
Example 3
34.0L of pure water was charged into a 174L-volume autoclave, and after sufficient nitrogen substitution, 30.4kg of perfluorocyclobutane, 0.71kg of perfluoro (propyl vinyl ether) (PPVE) and 2.05kg of methanol were charged, and the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.6MPa, and then 0.060kg of a 50% methanol solution of di-n-propyl dicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.040kg of PPVE was added to each 1kg of TFE fed, and polymerization was continued for 18.5 hours. TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 30g of powder.
The obtained powder was melt-extruded at 360℃by a screw extruder (trade name: PCM46, manufactured by Mitsui Co., ltd.) to obtain pellets of TFE/PPVE copolymer. Using the pellets obtained, the PPVE content was determined by the method described above. The results are shown in Table 3.
The obtained pellets were placed in a vacuum vibration type reaction apparatus VVD-30 (manufactured by Dachuan origin Co., ltd.) and heated to 210 ℃. After evacuation, N for introduction 2 F gas dilution to 20 vol% 2 The gas is brought to atmospheric pressure. From F 2 After 0.5 hour from the time of gas introduction, the mixture was once evacuated and F was introduced again 2 And (3) gas. After 0.5 hour, the mixture was again evacuated and F was introduced again 2 And (3) gas. Thereafter, F is as described above 2 The gas introduction and evacuation operations were continued for 1 time within 1 hour, and the reaction was carried out at 210℃for 10 hours. After the reaction, the inside of the reactor was fully replaced with N 2 And (3) ending the fluorination reaction by using the gas. Each was determined by the method described above using fluorinated pelletsPhysical properties. The results are shown in Table 3.
Example 4
Fluorinated pellets were obtained in the same manner as in example 3 except that PPVE was changed to 0.68kg, methanol was changed to 1.85kg, PPVE was changed to 0.038kg added per 1kg of TFE supplied, and the polymerization time was changed to 18 hours. The results are shown in Table 3.
Example 5
Fluorinated pellets were obtained in the same manner as in example 3 except that PPVE was changed to 0.66kg, methanol was changed to 1.80kg, PPVE was changed to 0.037kg added per 1kg of TFE supplied, and the polymerization time was changed to 18 hours. The results are shown in Table 3.
Example 6
Fluorinated pellets were obtained in the same manner as in example 3 except that PPVE was changed to 0.63kg, methanol was changed to 1.90kg, PPVE was changed to 0.036kg added per 1kg of TFE supplied, and the polymerization time was changed to 18 hours. The results are shown in Table 3.
Comparative example 1
After filling a 174L autoclave with 51.8L of pure water and sufficiently replacing the pure water with nitrogen, 40.9kg of perfluorocyclobutane, 1.79kg of perfluoro (propyl vinyl ether) (PPVE) and 6.61kg of methanol were charged, the temperature in the system was kept at 35℃and the stirring speed was kept at 200rpm. Subsequently, tetrafluoroethylene (TFE) was introduced under pressure to 0.64MPa, and then 0.051kg of a 50% methanol solution of di-n-propyl peroxydicarbonate was introduced to start polymerization. Since the pressure in the system decreased as polymerization proceeded, TFE was continuously fed so that the pressure became constant, and 0.042kg of PPVE was additionally fed per 1kg of TFE fed. When the additional amount of TFE fed reached 40.9kg, polymerization was terminated. Unreacted TFE was discharged, and after the autoclave was allowed to return to atmospheric pressure, the obtained reaction product was washed with water and dried to obtain 41.0kg of powder.
Using the obtained powder, a fluorination reaction was performed in the same manner as in example 1 to obtain fluorinated pellets. The results are shown in Table 3.
Comparative example 2
Fluorinated pellets were obtained in the same manner as in example 3 except that PPVE was changed to 0.73kg, methanol was changed to 3.49kg, PPVE was changed to 0.040kg per 1kg of TFE supplied, and the polymerization time was changed to 20 hours. The results are shown in Table 3.
Comparative example 3
Fluorinated pellets were obtained in the same manner as in example 3 except that the flow rate of pure water was changed to 26.6L, the flow rate of PPVE was changed to 0.77kg, the flow rate of methanol was changed to 5.10kg, TFE was pressed to 0.58MPa, the flow rate of 50% methanol solution of di-n-propyl peroxydicarbonate was changed to 0.011kg, the flow rate of PPVE was changed to 0.031kg per 1kg of TFE supplied, the polymerization time was changed to 11 hours, and 15kg of dry powder was obtained. The results are shown in Table 3.
Comparative example 4
Fluorinated pellets were obtained in the same manner as in example 3 except that the flow rate of pure water was changed to 26.6L, the flow rate of PPVE was changed to 1.40kg, the flow rate of methanol was changed to 3.00kg, TFE was fed to 0.57MPa, the flow rate of 50% methanol solution of di-n-propyl peroxydicarbonate was changed to 0.014kg, PPVE was changed to 0.048kg added per 1kg of TFE fed, and the polymerization time was changed to 21 hours. The results are shown in Table 3.
Comparative example 5
Fluorinated pellets were obtained in the same manner as in example 3 except that PPVE was changed to 0.86kg, methanol was changed to 1.50kg, 0.046kg was added per 1kg of TFE supplied, the polymerization time was changed to 21 hours, the temperature of the vacuum vibration reactor was changed to 160 ℃, and the reaction was changed to 5 hours at 160 ℃. The results are shown in Table 3.
TABLE 3
TABLE 3 Table 3
The expression "< 6" in Table 3 means that the number of functional groups is less than 6.
Next, using the obtained pellets, the following characteristics were evaluated. The results are shown in Table 4.
(reagent impregnation crack test)
About 50g of the pellets were put into a mold (inner diameter: 120mm, height: 38 mm), heated at 360℃for 20 minutes by a hot plate press, and then water-cooled while being pressurized under a pressure of 1MPa, to prepare a molded article having a thickness of about 2 mm. The resulting sheet was die cut using 13.5mm by 38mm rectangular dumbbell, thereby obtaining 3 test pieces. A notch was cut into the center of the long side of each test piece obtained by using a blade of 19mm X0.45 mm according to ASTM D1693. In a 100mL polypropylene bottle, 3 notched test pieces and 25g of a 40 mass% aqueous solution of tetrabutylammonium hydroxide were placed, and after heating at 100℃for 20 hours in an electric furnace, the notched test pieces were taken out. The obtained 3 notched test pieces were mounted on a stress crack test jig according to ASTM D1693, and the number of cracks was counted by visually observing the notches and the periphery thereof.
O: the number of cracks is 0
X: the number of cracks is 1 or more
(vapor permeability)
A sheet-like test piece having a thickness of about 0.2mm was produced using the pellets and a hot press molding machine. In a test cup (permeation area 12.56 cm) 2 ) The inside was filled with 18g of water, covered with a sheet-like test piece, and fastened and sealed with a PTFE gasket interposed therebetween. The sheet-like test piece was brought into contact with water, kept at a temperature of 95℃for 30 days, taken out, left at room temperature for 2 hours, and then the mass reduction was measured. The water vapor permeability (g.cm/m) was measured by the following formula 2 )。
Water vapor permeability (g.cm/m) 2 ) =mass reduction amount (g) ×thickness (cm)/transmission area (m) of sheet-like test piece 2 )
(storage modulus (E')
The dynamic viscoelasticity was measured by using DVA-220 (manufactured by IT meter control Co.). As a sample test piece, a hot press molded piece having a length of 25mm, a width of 5mm and a thickness of 0.2mm was used, and the storage modulus (MPa) at 150℃was measured in a range of 30℃to 250℃under a temperature rising rate of 2℃per minute and a frequency of 10 Hz.
(recovery amount)
Determination of recovery according to ASTM D395 or JIS K6262: 2013.
About 2g of the pellets were put into a mold (inner diameter: 13mm, height: 38 mm), melted at 370℃for 30 minutes by a hot plate press, and then water-cooled while being pressurized with a pressure of 0.2MPa (resin pressure), to prepare a molded article having a height of about 8 mm. Thereafter, the obtained molded article was cut to prepare a test piece having an outer diameter of 13mm and a height of 6 mm. The test piece thus produced was compressed to a compression set of 50% at normal temperature (i.e., a test piece having a height of 6mm was compressed to a height of 3 mm) using a compression device. The compressed test piece was left standing in an electric furnace in a state of being fixed to a compression device, and left standing at 150℃for 18 hours. The compression device was taken out of the electric furnace, cooled to room temperature, and then the test piece was taken out. After the recovered test piece was left at room temperature for 30 minutes, the height of the recovered test piece was measured, and the recovery amount was determined by the following formula.
Amount of recovery (mm) =t 2 －t 1
t 1 : height of spacer (mm)
t 2 : height (mm) of test piece removed from compression device
In the above test, t 1 ＝3mm。
(repulsive force at 150 ℃ C.)
The repulsive force at 150℃was obtained by the following formula from the results of the compression set test at 150℃and the results of the storage modulus measurement at 150 ℃.
Repulsive force (MPa) = (t) at 150 °c 2 －t 1 )/t 1 ×E’
t 1 : height of spacer (mm)
t 2 : height (mm) of test piece removed from compression device
E': storage modulus (MPa) at 150 DEG C
The molded article having a large repulsive force at 150 ℃ is not easily deformed even at high temperature, and is excellent in sealing property at high temperature.
(injection moldability)
The copolymer was injection molded using an injection molding machine (manufactured by Sumitomo mechanical industries Co., ltd., SE50 EV-A) at Sup>A cylinder temperature of 390 ℃, sup>A mold temperature of 170 ℃ and an injection speed of 50 mm/s. As a die, a die (100 mm. Times.100 mm. Times.2.5 mmt) in which Cr plating was performed on HPM38 was used. The surface of the injection-molded article was visually observed, and the surface smoothness was evaluated according to the following criteria.
2: no roughness and smoothness of the surface was observed.
1: roughness was observed only on the surface of the portion of the mold in the vicinity of the gate.
0: roughness was observed in most of the surface.
(wire coating Forming conditions)
By means ofA wire coating molding machine (manufactured by Takara Shuzo Co., ltd.) was used to extrude a coating copolymer onto a copper conductor having a conductor diameter of 0.50mm at the following coating thickness to obtain a coated wire. The wire coating extrusion molding conditions were as follows.
a) Core conductor: conductor diameter 0.50mm
b) Coating thickness: 0.15mm
c) Coated wire diameter: 0.80mm
d) Wire drawing speed: 150 m/min
e) Extrusion conditions:
single screw extrusion moulding machine with barrel shaft diameter=30mm, l/d=22
Die (inner diameter)/sheet (outer diameter) =8.0 mm/5.0mm
Set temperature of extruder: barrel section C-1 (330 ℃), barrel section C-2 (360 ℃), barrel section C-3 (375 ℃), head section H (390 ℃), die section D-1 (405 ℃) and die section D-2 (395 ℃). The core wire preheating was set at 80 ℃.
(spark)
A spark tester (DENSOK HIGH FREQ SPARK TESTER) was provided on-line on the wire coating, and the presence or absence of damage to the wire coating was evaluated at a voltage of 1500V. The molding was continued for 1 hour, and the case where the spark was zero was found to be acceptable (o), and the case where the spark was detected to be unacceptable (x).
(coating off)
The coating molding of the electric wire was continuously performed, and the case where the coating was broken 1 or more times within 1 hour was regarded as discontinuous molding (x), and the case where the coating was not broken was regarded as continuous molding (o).
(abrasion test)
Using the pellets and a hot press molding machine, a sheet-like test piece having a thickness of about 0.2mm was produced, from which a 10 cm. Times.10 cm test piece was cut. The test piece thus prepared was fixed on a test stand of a taber abrasion tester (No. 101 model taber abrasion tester, manufactured by An Tian refiner manufacturing company), and abrasion test was performed using the taber abrasion tester under conditions of a test piece surface temperature of 150 ℃, a load of 500g, an abrasion wheel CS-10 (20 revolutions ground with grinding paper # 240), and a rotational speed of 60 rpm. The test piece weight after 1000 revolutions was measured, and the test piece weight was further measured after 5000 revolutions test with the same test piece. The abrasion loss was determined by the following formula.
Abrasion loss (mg) =m1-M2
M1: test piece weight after 1000 revolutions (mg)
M2: weight of 5000 rpm test piece (mg)
(nitrogen permeability coefficient)
A sheet-like test piece having a thickness of about 0.1mm was produced using the pellets and a hot press molding machine. Using the obtained test piece, the test piece was prepared according to JIS K7126-1:2006, nitrogen permeability was measured using a differential pressure type gas permeability meter (L100-5000 type gas permeability meter, manufactured by Systemech ilinois Co.). Obtaining a permeation area of 50.24cm 2 The nitrogen permeability at a test temperature of 70℃and a test humidity of 0% RH. Using the obtained nitrogen permeation rate and the thickness of the test piece, the nitrogen permeation coefficient was calculated by the following formula.
Nitrogen permeability coefficient (cm) 3 ·mm/(m 2 ·24h·atm))＝GTR×d
GTR: nitrogen permeability (cm) 3 /(m 2 ·24h·atm))
d: test piece thickness (mm)
(methyl ethyl ketone (MEK) transmittance)
A sheet-like test piece having a thickness of about 0.1mm was produced using the pellets and a hot press molding machine. In a test cup (permeation area 12.56 cm) 2 ) 10g of MEK was placed in the container, and the container was covered with a sheet-like test piece, and fastened and sealed with a PTFE gasket interposed therebetween. The sheet-like test piece was contacted with MEK at a temperature of 60 DEG CAfter 60 days of holding, the sample was taken out and left at room temperature for 1 hour, and the mass reduction was measured. The MEK transmittance (mg.cm/m) was determined by the following formula 2 Day).
MEK transmittance (mg cm/m) 2 Day) = [ mass reduction (mg) ×thickness (cm) of sheet-like test piece]Transmission area (m) 2 ) Days (Tian)]
(95 ℃ C. Load deflection rate)
Using the pellets and a hot press molding machine, a sheet-like test piece having a thickness of about 3mm was produced, from which a test piece having a thickness of 80X 10mm was cut, and heated at 100℃for 20 hours by an electric furnace. The test was carried out using a thermal deformation tester (manufactured by An Tian refiner) according to the method described in JIS K-K7191, except for the test piece obtained, under conditions of a test temperature of 30 to 150 ℃, a temperature rising rate of 120 ℃/hr, a bending stress of 1.8MPa, and a flat-bed (flat-bed) method. The load deflection was obtained by the following method. The sheet having a small deflection under load at 95℃has excellent rigidity at high temperatures.
Load deflection (%) =a2/a1×100
a1: thickness of test piece before test (mm)
a2: deflection (mm) at 95 DEG C
(tensile creep test)
The tensile creep strain was measured using TMA-7100 manufactured by Hitachi high technology Co. Using the pellets and a hot press molding machine, a sheet having a thickness of about 0.1mm was produced, and a sample having a width of 2mm and a length of 22mm was produced from the sheet. The sample was mounted to the measuring jig at a distance of 10mm from the jig. For the sample, the cross-sectional load was 3.32N/mm 2 The sample was subjected to a load at 200℃and the displacement (mm) of the length of the sample was measured from the time 90 minutes after the start of the test to the time 1320 minutes after the start of the test, and the ratio (tensile creep strain (%)) of the displacement (mm) of the length to the initial sample length (10 mm) was calculated. The sheet having a small tensile creep strain (%) measured at 200℃for 1320 minutes is less likely to be elongated even under a long-term tensile load under a high-temperature environment and has excellent long-term tensile creep characteristics.
(6 ten thousand times tensile Strength maintenance)
The tensile strength maintenance rate was measured 6 ten thousand times by using a fatigue tester MMT-250NV-10 manufactured by Shimadzu corporation. A sheet having a thickness of about 2.4mm was produced using a pellet and a hot press molding machine, and a sample having a dumbbell shape (thickness: 2.4mm, width: 5.0mm, measuring section length: 22 mm) was produced using an ASTM D1708 micro dumbbell. The sample was mounted on a measurement jig, and the measurement jig was set in a constant temperature bath at 150 ℃. The uniaxial stretching was repeated at a stroke of 0.2mm and a frequency of 100Hz, and the tensile strength (tensile strength at +0.2mm in stroke) was measured for each stretching, and the tensile strength maintenance ratio was calculated from the measured values for 6 ten thousand times according to the following formula.
Tensile strength maintenance ratio (%) =tensile strength (6 ten thousand) (mN)/tensile strength (5 thousand) (mN) ×100 for 6 ten thousand times
The 6-thousand tensile strength retention is the ratio of the tensile strength under 6-thousand repeated loads to the tensile strength under 5-thousand repeated loads. The sheet having a high retention of tensile strength for 6 ten thousand times maintains initial tensile strength even after 6 ten thousand times of load, and is excellent in resistance to deterioration by repeated load.
(Hydrogen peroxide impregnation test)
25g of the pellets were immersed in 50g of a 3 wt% hydrogen peroxide solution, heated at 90℃for 20 hours in an electric furnace, further heated at 121℃for 1 hour in a sterilizer, and cooled to room temperature. The pellet was taken out of the aqueous solution, and a TISAB solution (10) (manufactured by kanto chemical company) was added to the remaining aqueous solution, and the fluoride ion concentration in the obtained aqueous solution was measured by a fluoride ion meter. From the obtained measurement values, the fluoride ion concentration (eluted fluoride ion amount) per weight of the pellet was calculated.
Dissolved fluoride ion amount (mass ppm) =measurement value (mass ppm) ×aqueous solution amount (g)/pellet weight (g)
(ozone exposure test)
The copolymer was compression molded at 350℃under a pressure of 0.5MPa to prepare a sheet having a thickness of 1mm, from which a 10X 20mm sample was cut out to prepare a sample for ozone exposure test. Ozone gas (ozone/oxygen=10/90 capacity%) generated by an ozone generating device (trade name: SGX-A11MN (modified), manufactured by Sumitomo industries Co., ltd.) and ion-exchanged water were mixed The PFA container was connected, and after adding steam to the ozone gas by bubbling in ion-exchanged water, the sample was exposed to the humid ozone gas at room temperature by passing through a PFA cell containing the sample at 0.7 liter/min. After 30 days from the initial exposure, the sample was taken out, the surface was gently rinsed with ion-exchanged water, and then a portion having a depth of 5 μm to 200 μm from the sample surface was observed at a magnification of 100 times by using a transmission optical microscope, taken together with a standard scale, and the surface of the sample was measured every 1mm 2 The number of cracks having a length of 10 μm or more was evaluated according to the following criteria.
O: the number of cracks is less than 10
X: the number of cracks is more than 10
(dielectric loss tangent)
The pellets were melt-molded to prepare a cylindrical test piece having a diameter of 2 mm. The test piece thus fabricated was set in a cavity resonator for 6GHz manufactured by kanto electronics application development company, and measured by a network analyzer manufactured by agilent technologies. The measurement result was analyzed by analysis software "CPMA" manufactured by Kanto electronic application development Co., ltd. On a personal computer connected to the network analyzer, to thereby determine the dielectric loss tangent (tan. Delta.) at 20℃and 6 GHz.
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Claims (5)

1. A copolymer comprising tetrafluoroethylene units and perfluoro (propyl vinyl ether) units,
the content of perfluoro (propyl vinyl ether) unit is 3.3 to 4.2 mass% relative to the total monomer units,
the melt flow rate at 372 ℃ is 27.0g/10 min-35.0 g/10 min,
the number of functional groups per 10 6 The number of carbon atoms of the main chain is 20 or less.
2. The copolymer of claim 1, wherein the melt flow rate at 372 ℃ is from 27.0g/10 min to 33.0g/10 min.
3. An injection molded article comprising the copolymer according to claim 1 or 2.
4. A coated wire comprising a coating layer comprising the copolymer according to claim 1 or 2.
5. A molded body comprising the copolymer of claim 1 or 2, wherein the molded body is a wafer carrier, a gasket, or a wire coating.
CN202280016114.8A 2021-02-26 2022-01-31 Copolymer, molded body, injection molded body, and coated electric wire Pending CN116867816A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2021-031096 2021-02-26
JP2021162078 2021-09-30
JP2021-162078 2021-09-30
PCT/JP2022/003645 WO2022181230A1 (en) 2021-02-26 2022-01-31 Copolymer, molded body, injection molded body, and coated electrical wire

Publications (1)

Publication Number Publication Date
CN116867816A true CN116867816A (en) 2023-10-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
CN202280016114.8A Pending CN116867816A (en) 2021-02-26 2022-01-31 Copolymer, molded body, injection molded body, and coated electric wire

Country Status (1)

Country Link
CN (1) CN116867816A (en)

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