JP2003183412A - Crosslinked tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder and method for producing the same - Google Patents
Crosslinked tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder and method for producing the sameInfo
- Publication number
- JP2003183412A JP2003183412A JP2001390723A JP2001390723A JP2003183412A JP 2003183412 A JP2003183412 A JP 2003183412A JP 2001390723 A JP2001390723 A JP 2001390723A JP 2001390723 A JP2001390723 A JP 2001390723A JP 2003183412 A JP2003183412 A JP 2003183412A
- Authority
- JP
- Japan
- Prior art keywords
- fine powder
- crosslinked
- less
- hexafluoropropylene
- fep
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 65
- 229920001577 copolymer Polymers 0.000 title claims abstract description 11
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract 7
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000155 melt Substances 0.000 claims abstract description 4
- 230000005865 ionizing radiation Effects 0.000 claims description 13
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 16
- 238000005299 abrasion Methods 0.000 abstract description 8
- 239000010419 fine particle Substances 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102100022210 COX assembly mitochondrial protein 2 homolog Human genes 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 101000900446 Homo sapiens COX assembly mitochondrial protein 2 homolog Proteins 0.000 description 1
- 101000607626 Homo sapiens Ubiquilin-1 Proteins 0.000 description 1
- 102100039934 Ubiquilin-1 Human genes 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、架橋テトラフルオ
ロエチレン／ヘキサフルオロプロピレン系共重合体（以
下、「テトラフルオロエチレン／ヘキサフルオロプロピ
レン系共重合体」を「ＦＥＰ」という）微粉末及びその
製造方法に関するものである。TECHNICAL FIELD The present invention relates to a fine powder of crosslinked tetrafluoroethylene / hexafluoropropylene copolymer (hereinafter, “tetrafluoroethylene / hexafluoropropylene copolymer” is referred to as “FEP”) and its production. It is about the method.
【０００２】[0002]
【従来の技術】ふっ素樹脂、とりわけポリテトラフルオ
ロエチレン系重合体（以下「ＰＴＦＥ」という）は、耐
熱性、耐薬品性、耐溶剤性等に優れるため、その特徴を
生かして容器の内面コーティングの素材、電線被覆材、
流体移送用チューブ等の用途に用いられている。しか
し、ＰＴＦＥの耐摩耗性は必ずしも十分とはいえず、耐
摩耗性を向上させるために電離性放射線を照射して架橋
する方法が知られている。ＰＴＦＥの照射架橋は、ＰＴ
ＦＥの微粉末をその融点以上の温度に加熱し、実質的に
酸素不存在の雰囲気中で電離性放射線を照射して行われ
る方法が知られている。Fluorine resins, especially polytetrafluoroethylene-based polymers (hereinafter referred to as "PTFE") are excellent in heat resistance, chemical resistance, solvent resistance and the like, so that the characteristics of these properties are utilized to coat the inner surface of a container. Material, wire coating,
Used for applications such as fluid transfer tubes. However, the abrasion resistance of PTFE is not always sufficient, and a method of cross-linking by irradiating ionizing radiation to improve the abrasion resistance is known. Irradiation cross-linking of PTFE is PT
A method is known in which FE fine powder is heated to a temperature equal to or higher than its melting point and is irradiated with ionizing radiation in an atmosphere substantially free of oxygen.
【０００３】[0003]
【発明が解決しようとする課題】しかし、ＰＴＦＥ微粉
末をその融点以上の温度に加熱して電離性放射線を照射
して架橋を行った場合、ゴム弾性や粒界融着により架橋
後の微粉砕が困難となる。このような、粒径の大きな架
橋ＰＴＦＥ粉末を他材料と混合する場合、架橋ＰＴＦＥ
粉体を混合体中に均一に分散させるのが難しくなり、ま
た、架橋ＰＴＦＥ粉体をコーティング材に用いた場合は
表面の平滑性が損なわれるため、十分な耐摩耗性を得る
ことができず、使用範囲が限定されるという問題があ
る。However, when the PTFE fine powder is heated to a temperature above its melting point and irradiated with ionizing radiation to effect crosslinking, fine pulverization after crosslinking due to rubber elasticity and grain boundary fusion. Will be difficult. When such a crosslinked PTFE powder having a large particle size is mixed with another material, the crosslinked PTFE powder is
It becomes difficult to uniformly disperse the powder in the mixture, and when the cross-linked PTFE powder is used as the coating material, the smoothness of the surface is impaired, so that sufficient abrasion resistance cannot be obtained. However, there is a problem that the range of use is limited.
【０００４】従って、本発明は、架橋後の微粉末状態の
実現が容易であり、優れた耐摩耗性を有する成形体を実
現できる架橋ＦＥＰ微粉末及びその製造方法の提供を目
的とする。Therefore, an object of the present invention is to provide a crosslinked FEP fine powder which can easily realize a fine powder state after crosslinking and can realize a molded article having excellent abrasion resistance, and a method for producing the same.
【０００５】[0005]
【課題を解決するための手段】本発明は上記の目的を達
成するため、平均粒径が１０μｍ以下で最大粒径が５０
μｍ以下であり、結晶化点が２３３℃以下で、且つ溶融
粘度が５０００Ｐａ・ｓ以上であることを特徴とする架
橋ＦＥＰ微粉末を提供する。ここで、結晶化点とは、架
橋ＦＥＰ微粉末を融点以上に加熱し、その後降温したと
きに再結晶化するときの温度をいう。In order to achieve the above object, the present invention has an average particle size of 10 μm or less and a maximum particle size of 50.
A crosslinked FEP fine powder characterized by having a crystallization point of 233 ° C. or less and a melt viscosity of 5000 Pa · s or more. Here, the crystallization point means a temperature at which the crosslinked FEP fine powder is heated to a temperature equal to or higher than the melting point and then recrystallized when the temperature is lowered.
【０００６】また、本発明は、平均粒径が１０μｍ以下
で最大粒径が５０μｍ以下であるテトラフルオロエチレ
ン／ヘキサフルオロプロピレン系共重合体微粉末に、８
０℃〜２８０℃の温度範囲で、且つ酸素濃度１０ｔｏｒ
ｒ以下の雰囲気中で、１ｋＧｙ〜１ＭＧｙの電離性放射
線を照射することを特徴とする架橋ＦＥＰ微粉末の製造
方法を提供する。The present invention also provides a tetrafluoroethylene / hexafluoropropylene copolymer fine powder having an average particle size of 10 μm or less and a maximum particle size of 50 μm or less.
Oxygen concentration of 10 torr in the temperature range of 0 ° C to 280 ° C
Provided is a method for producing a crosslinked FEP fine powder, which comprises irradiating an ionizing radiation of 1 kGy to 1 MGy in an atmosphere of r or less.
【０００７】[0007]
【発明の実施の形態】本発明において、架橋ＦＥＰ微粉
末の平均粒径を１０μｍ以下、最大粒径を５０μｍ以下
とするのは、他材料と混合する場合の分散の均一化を図
り、また、コーティング材に用いた場合は表面の平滑化
を図れるようにするためである。BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the average particle size of the crosslinked FEP fine powder is set to 10 μm or less and the maximum particle size is set to 50 μm or less in order to make the dispersion uniform when mixed with other materials. This is because when used as a coating material, the surface can be smoothed.
【０００８】本発明において、架橋ＦＥＰ微粉末の結晶
化点が２３３℃以下で、且つ溶融粘度が５０００Ｐａ・
ｓ以上とするのは、ＦＥＰに十分な架橋度を付与して優
れた耐摩耗性を実現するためである。In the present invention, the crystallization point of the crosslinked FEP fine powder is 233 ° C. or lower and the melt viscosity is 5000 Pa.
The reason for setting s or more is to impart a sufficient degree of crosslinking to FEP and realize excellent wear resistance.
【０００９】本発明において、ＦＥＰ微粉末を架橋する
ときの電離性放射線の照射は、酸素濃度１０ｔｏｒｒ以
下の真空中又は不活性ガス雰囲気中で行われ、また、そ
の照射線量は１ｋＧｙ〜１ＭＧｙの範囲内である。酸素
濃度が１０ｔｏｒｒを越える雰囲気下では、十分な架橋
効果を達成できず、又、電離性放射線の照射線量が１ｋ
Ｇｙ未満では十分な架橋効果を達成できず、１ＭＧｙを
越えると伸び等の著しい低下を招く。In the present invention, the irradiation of the ionizing radiation when the FEP fine powder is cross-linked is performed in a vacuum or an inert gas atmosphere with an oxygen concentration of 10 torr or less, and the irradiation dose is in the range of 1 kGy to 1 MGy. It is within. In an atmosphere where the oxygen concentration exceeds 10 torr, a sufficient crosslinking effect cannot be achieved, and the irradiation dose of ionizing radiation is 1 k.
When it is less than Gy, a sufficient crosslinking effect cannot be achieved, and when it exceeds 1 MGy, elongation and the like are remarkably reduced.
【００１０】本発明においては、電離性放射線として
は、γ線、電子線、Ｘ線、中性子線、あるいは高エネル
ギーイオン等が使用される。電離性放射線の照射を行う
に際してのＦＥＰ微粉末の温度は、８０℃〜２８０℃の
範囲であり、８０℃未満では効率よく架橋させることが
できず、２８０℃を越えるとＦＥＰ粉末同士が融着して
しまって架橋後の粉砕が困難になり、微粉末を得ること
ができなくなる。In the present invention, γ rays, electron rays, X rays, neutron rays, high energy ions, etc. are used as the ionizing radiation. The temperature of the FEP fine powder upon irradiation with ionizing radiation is in the range of 80 ° C to 280 ° C. If the temperature is lower than 80 ° C, crosslinking cannot be efficiently performed, and if the temperature exceeds 280 ° C, the FEP powders are fused to each other. As a result, pulverization after crosslinking becomes difficult and it becomes impossible to obtain fine powder.
【００１１】電離性放射線の照射を行うときの温度が比
較的低い温度であれば、架橋時のＦＥＰ粉末同士の融着
は極めて少ないが、高温になるとＦＥＰ粉末同士の融着
が生じる。融着が生じた場合でも、２８０℃以下の温度
で架橋した場合は、照射架橋後にジェットミル等を用い
た粉砕を行うことにより照射架橋前のＦＥＰ微粉末と同
程度の粒径の微粉末を得ることができる。If the temperature at which the ionizing radiation is irradiated is relatively low, the FEP powders will not be fused to each other during crosslinking, but at high temperatures, the FEP powders will be fused to each other. Even if fusion occurs, if crosslinking is performed at a temperature of 280 ° C. or lower, fine powder having a particle size similar to that of FEP fine powder before irradiation crosslinking is obtained by performing pulverization using a jet mill after irradiation crosslinking. Obtainable.
【００１２】本発明の架橋ＦＥＰ微粉末は、平均粒径が
１０μｍ以下で最大粒径が５０μｍ以下の架橋されたＦ
ＥＰ微粉末であり、これを所定形状に成形することによ
り優れた耐摩耗性を有する成形体を得ることができる。
架橋ＰＴＦＥ微粉末は、それ単独で、あるいは他の高分
子材料、充填剤、着色剤等と混合した後所定形状に成形
される。成形体とガラス繊維等との複合化も可能であ
る。また、適当な溶媒に分散させてディスパージョンと
し、コーティング等に使用できる。The crosslinked FEP fine powder of the present invention has a mean particle size of 10 μm or less and a maximum particle size of 50 μm or less.
It is EP fine powder, and by molding this into a predetermined shape, a molded product having excellent wear resistance can be obtained.
The crosslinked PTFE fine powder is molded into a predetermined shape by itself or after being mixed with other polymer materials, fillers, colorants and the like. It is also possible to form a composite of the molded body and glass fiber or the like. Further, it can be used as a dispersion by dispersing it in an appropriate solvent to form a dispersion.
【００１３】[0013]
【実施例】［実施例１］平均粒径６μｍ、最大粒径２２
μｍのＦＥＰパウダ（喜多村製、ＫＢ−０ＦＪ）を使用
し、酸素濃度０．５ｔｏｒｒの真空下、８０℃に加熱し
て線量率３ｋＧｙ／時間のγ線を５０ｋＧｙ照射した。
照射後のＦＥＰパウダをピンミル（奈良機械製作所製１
６０Ｚ）を用い、回転数が１４０００ｒｐｍ、微粉末の
供給量が７．０ｋｇ／時間の条件で粉砕して架橋ＦＥＰ
微粉末を得た。[Example] [Example 1] Average particle size 6 μm, maximum particle size 22
A μm FEP powder (KB-0FJ manufactured by Kitamura) was used, and heated to 80 ° C. under vacuum with an oxygen concentration of 0.5 torr and irradiated with 50 kGy of γ-ray with a dose rate of 3 kGy / hour.
Pin mill the FEP powder after irradiation (manufactured by Nara Machinery Co., Ltd. 1
60Z), the rotation speed is 14000 rpm, and the fine powder supply rate is 7.0 kg / hour.
A fine powder was obtained.
【００１４】この架橋ＦＥＰ微粉末について、粒度分
布、結晶化点、融点、溶融粘度を測定し、その結果を表
１に示した。各特性の測定方法は次の通りである。
粒度分布：マイクロトラック法により測定した。
結晶化点：パーキンエルマー社製の示差走査熱量計（Ｄ
ＳＣ）を用い、２０℃／分でもって３２０℃から降温し
たときの降温時のＤＳＣ曲線の発熱ピークから求めた。
溶融粘度：フローテスタ（ダイの長さ８mm、直径２mm）
を使用し、温度３８０℃、荷重１０ｋｇｆで測定した。The particle size distribution, crystallization point, melting point and melt viscosity of this crosslinked FEP fine powder were measured, and the results are shown in Table 1. The measuring method of each characteristic is as follows. Particle size distribution: Measured by the Microtrac method. Crystallization point: Differential scanning calorimeter (D
(SC) was used to determine from the exothermic peak of the DSC curve when the temperature was lowered from 320 ° C. at 20 ° C./min. Melt viscosity: Flow tester (die length 8 mm, diameter 2 mm)
Was used at a temperature of 380 ° C. and a load of 10 kgf.
【００１５】また、架橋ＦＥＰ微粉末を、電熱プレスで
圧縮成形して（３５０℃、１００ｋｇｆ／cm2で１分間
圧縮・保持）厚さ０．５mmシートを作製し、このシート
を用いて比摩耗量を測定し、その結果を表１に併せて示
した。比摩耗量の測定は、リングオンディスク型摩擦
摩耗試験装置（ＪＩＳＫ７２１８）を使用し、相手材に
表面粗さ０．８μｍのＳＵＳ３０４を用い、面圧０．３
９ＭＰａ、周速１２５ｍ／分、室温で行った。Further, the crosslinked FEP fine powder is compression-molded by an electrothermal press (compressed and held at 350 ° C. and 100 kgf / cm 2 for 1 minute) to prepare a 0.5 mm-thick sheet, which is used for specific wear. The amount was measured, and the results are also shown in Table 1. The specific wear amount was measured by using a ring-on-disc type friction wear tester (JISK7218), using SUS304 having a surface roughness of 0.8 μm as a mating material, and a surface pressure of 0.3.
The test was performed at 9 MPa, a peripheral speed of 125 m / min, and room temperature.
【００１６】［実施例２］加熱温度を２００℃、照射線
量を１００ｋＧｙとした以外は実施例１と同様にして照
射し、その後粉砕して架橋ＦＥＰ微粉末を得、実施例１
と同様の評価を行った。[Example 2] Irradiation was carried out in the same manner as in Example 1 except that the heating temperature was 200 ° C and the irradiation dose was 100 kGy, and then crushed to obtain crosslinked FEP fine powder.
The same evaluation as was done.
【００１７】［実施例３］加熱温度を２８０℃、照射線
量を１５０ｋＧｙとした以外は実施例１と同様にして照
射し、その後粉砕して架橋ＦＥＰ微粉末を得、実施例１
と同様の評価を行った。Example 3 Irradiation was carried out in the same manner as in Example 1 except that the heating temperature was 280 ° C. and the irradiation dose was 150 kGy, and then crushed to obtain crosslinked FEP fine powder.
The same evaluation as was done.
【００１８】［実施例４］加熱温度を２００℃、照射線
量を８０ｋＧｙとした以外は実施例１と同様にして照射
して、架橋ＦＥＰ微粉末を得、実施例１と同様の評価を
行った。なお、比摩耗量の測定は、架橋ＦＥＰ微粉末５
０重量部とＰＴＦＥモールディングパウダ（住友３Ｍ社
製、ＴＦＭ−１７００）５０重量部をヘンシェルミキサ
によって混合し、ホットフォーミング成形（予備成形圧
力：５００ｋｇｆ／cm2、焼成温度：３６０℃、冷却圧
力：３５０ｋｇｆ／cm2）したものを厚さ０．５mmのシ
ートにスカイビングしたものを使用した。[Example 4] Crosslinked FEP fine powder was obtained by irradiation in the same manner as in Example 1 except that the heating temperature was 200 ° C and the irradiation dose was 80 kGy, and the same evaluation as in Example 1 was performed. . In addition, the measurement of the specific wear amount was conducted by using the crosslinked FEP fine powder 5
0 parts by weight and 50 parts by weight of PTFE molding powder (Sumitomo 3M, TFM-1700) were mixed by a Henschel mixer, and hot forming (preforming pressure: 500 kgf / cm 2 , firing temperature: 360 ° C., cooling pressure: 350 kgf). / Cm 2 ) which was skived into a sheet having a thickness of 0.5 mm was used.
【００１９】［実施例５］加熱温度を２００℃、照射線
量を１００ｋＧｙとした以外は実施例１と同様にして照
射して、架橋ＦＥＰ微粉末を得、実施例１と同様の評価
を行った。比摩耗量の測定は、架橋ＦＥＰ微粉末１５重
量部とＰＦＡディスパージョン（ダイキン社製、ＡＣＸ
−３１）８５重量部を混合し、静電粉体塗装によりアル
ミニウム板にスプレーし、３４０℃に３０分間保持する
ことにより焼成したものについて、リングオンディスク
型摩擦摩耗試験装置（ＪＩＳＫ７２１８）を使用し、相
手材に表面粗さ０．８μｍのＳＵＳ３０４を用い、面圧
０．１ＭＰａ、周速５０ｍ／分、室温で行った。 な
お、塗装面の表面粗さＲａは０．４８μｍであった。[Example 5] Crosslinked FEP fine powder was obtained by irradiation in the same manner as in Example 1 except that the heating temperature was 200 ° C and the irradiation dose was 100 kGy, and the same evaluation as in Example 1 was performed. . 15 parts by weight of crosslinked FEP fine powder and PFA dispersion (manufactured by Daikin Co., ACX
-31) 85 parts by weight were mixed, sprayed on an aluminum plate by electrostatic powder coating, and baked by holding at 340 ° C. for 30 minutes, using a ring-on-disc type friction and abrasion tester (JISK7218). The SUS304 having a surface roughness of 0.8 μm was used as the mating material, and the surface pressure was 0.1 MPa, the peripheral speed was 50 m / min, and the test was performed at room temperature. The surface roughness Ra of the coated surface was 0.48 μm.
【００２０】［比較例１］平均粒径６μｍのＦＥＰパウ
ダ（喜多村製、ＫＢ−０ＦＪ）について、未架橋状態で
実施例１と同様の評価を行った。また、このＦＥＰパウ
ダを、電熱プレスで圧縮成形して（３００℃、１００ｋ
ｇｆ／cm2で１分間圧縮・保持）厚さ０．５mmシートを
作製し、実施例１と同様にして比摩耗量を測定した。Comparative Example 1 An FEP powder having an average particle size of 6 μm (KB-0FJ manufactured by Kitamura) was evaluated in the same manner as in Example 1 in an uncrosslinked state. In addition, this FEP powder was compression-molded by an electrothermal press (300 ° C., 100 k
A sheet having a thickness of 0.5 mm was prepared by compressing and holding at gf / cm 2 for 1 minute, and the specific wear amount was measured in the same manner as in Example 1.
【００２１】［比較例２］加熱温度を５０℃、照射線量
を２００ｋＧｙとした以外は実施例１と同様にして照射
し、その後粉砕して架橋ＦＥＰ微粉末を得、実施例１と
同様の評価を行った。[Comparative Example 2] Irradiation was carried out in the same manner as in Example 1 except that the heating temperature was 50 ° C. and the irradiation dose was 200 kGy, and then crushed to obtain a crosslinked FEP fine powder. Evaluation similar to that in Example 1 I went.
【００２２】［比較例３］加熱温度を３００℃、照射線
量を１５０ｋＧｙとした以外は実施例１と同様にして照
射した。その後ジェットミルで粉砕を試みたが、照射時
の温度が高すぎたため粉末同士が融着し、粉砕できなか
った。[Comparative Example 3] Irradiation was performed in the same manner as in Example 1 except that the heating temperature was 300 ° C and the irradiation dose was 150 kGy. After that, an attempt was made to pulverize with a jet mill, but because the temperature during irradiation was too high, the powder particles fused together and could not be pulverized.
【００２３】［比較例４］平均粒径２５μｍ、最大粒径
１５０μｍのＦＥＰパウダ（喜多村製、粗粉砕品）を使
用し、加熱温度を２００℃、照射線量を８０ｋＧｙとし
た以外は実施例１と同様にして照射し、その後粉砕して
架橋ＦＥＰ粉末を得、実施例１と同様の評価を行った。
なお、比摩耗量の測定は、架橋ＦＥＰ粉末５０重量部と
ＰＴＦＥモールディングパウダ（住友３Ｍ社製、ＴＦＭ
−１７００）５０重量部を使用し、実施例４と同様にし
て作製したシートについて行った。[Comparative Example 4] The same as Example 1 except that an FEP powder (coarse crushed by Kitamura) having an average particle size of 25 μm and a maximum particle size of 150 μm was used, the heating temperature was 200 ° C., and the irradiation dose was 80 kGy. Irradiation was performed in the same manner, and then pulverization was performed to obtain a crosslinked FEP powder, and the same evaluation as in Example 1 was performed.
The specific wear amount was measured by 50 parts by weight of crosslinked FEP powder and PTFE molding powder (Sumitomo 3M TFM, TFM).
-1700) 50 parts by weight was used for the sheet prepared in the same manner as in Example 4.
【００２４】［比較例５］平均粒径６μｍのＦＥＰパウ
ダ（喜多村製、ＫＢ−０ＦＪ）の未架橋状態のもの１５
重量部とＰＦＡディスパージョン（ダイキン社製、ＡＣ
Ｘ−３１）８５重量部を混合し、実施例５と同様に焼成
したものについて、実施例５と同様にして比摩耗量を測
定した。なお、塗装面の表面粗さＲａは０．４４μｍで
あった。[Comparative Example 5] FEP powder (KB-0FJ manufactured by Kitamura) having an average particle size of 6 μm in an uncrosslinked state 15
Parts by weight and PFA dispersion (Daikin Co., AC
X-31) 85 parts by weight were mixed and fired in the same manner as in Example 5, and the specific wear amount was measured in the same manner as in Example 5. The surface roughness Ra of the coated surface was 0.44 μm.
【００２５】[0025]
【表１】 [Table 1]
【００２６】表１から明らかな通り、実施例１〜５の架
橋ＦＥＰ微粉末は、粒径、結晶化点及び溶融粘度のいず
れも本発明で規定する範囲にある架橋された微粉末であ
り、単独使用の場合（実施例１〜３）及び他材料と混合
して使用した場合（実施例４、５）のいずれにおいても
耐摩耗性に優れている。比較例１は、非架橋のＦＥＰ微
粉末であり、粒径は小さいものの、耐摩耗性が劣ってい
る。比較例２は、ＦＥＰ加熱温度を低くして電離性放射
線を照射したものであり、架橋よりも分子切断が優性と
なり、粒径は小さいものの耐摩耗性が劣っている。比較
例３は、ＦＥＰ加熱温度を高くして電離性放射線を照射
したものであり、耐摩耗性は優れるものの粉末同士の融
着が著しく微粉砕が不可能であった。比較例４は、粒径
の大きいＦＥＰ微粉末を使用したものであり、ＰＴＦＥ
パウダ中への分散が悪く、耐摩耗性が劣っている。比較
例５は、非架橋のＦＥＰ微粉末を他材料と混合してコー
ティングしたものであり、表面粗さは低いものの耐摩耗
性が劣っている。As is clear from Table 1, the crosslinked FEP fine powders of Examples 1 to 5 are crosslinked fine powders whose particle size, crystallization point and melt viscosity are all within the ranges specified by the present invention. It has excellent wear resistance both when used alone (Examples 1 to 3) and when mixed with other materials (Examples 4 and 5). Comparative Example 1 is a non-crosslinked FEP fine powder having a small particle size but poor wear resistance. In Comparative Example 2, the FEP heating temperature was lowered and the ionizing radiation was irradiated, and the molecular cleavage was more dominant than the crosslinking, and the particle size was small, but the abrasion resistance was poor. In Comparative Example 3, the FEP heating temperature was raised and the ionizing radiation was irradiated, and although the abrasion resistance was excellent, the fusion of the powder particles was remarkable and the pulverization was impossible. Comparative Example 4 uses FEP fine powder having a large particle size,
Dispersion in powder is poor and wear resistance is poor. Comparative Example 5 is prepared by mixing non-crosslinked FEP fine powder with another material and coating the mixture. The surface roughness is low but the wear resistance is poor.
【００２７】[0027]
【発明の効果】以上説明してきた通り、本発明は、平均
粒径が１０μｍ以下で最大粒径が５０μｍ以下であり、
結晶化点が２３３℃以下で、且つ溶融粘度が５０００Ｐ
ａ・ｓ以上である架橋ＦＥＰ微粉末を提供するものであ
り、これを使用することにより、優れた耐摩耗性を有す
る成形体を容易に実現できるようになる。As described above, according to the present invention, the average particle size is 10 μm or less and the maximum particle size is 50 μm or less.
Crystallization point is below 233 ° C and melt viscosity is 5000P
The present invention provides a crosslinked FEP fine powder having a / s or more, and by using this, a molded product having excellent wear resistance can be easily realized.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 浅野 健次 東京都千代田区大手町一丁目６番１号 日 立電線株式会社内 Ｆターム(参考） 4F070 AA24 AB01 DA41 DA47 DC02 DC07 DC13 GA04 GB02 GB03 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kenji Asano 1-6-1, Otemachi, Chiyoda-ku, Tokyo Standing Wire Co., Ltd. F-term (reference) 4F070 AA24 AB01 DA41 DA47 DC02 DC07 DC13 GA04 GB02 GB03
Claims (3)
μｍ以下であり、結晶化点が２３３℃以下で、且つ溶融
粘度が５０００Ｐａ・ｓ以上であることを特徴とする架
橋テトラフルオロエチレン／ヘキサフルオロプロピレン
系共重合体微粉末。1. An average particle diameter of 10 μm or less and a maximum particle diameter of 50.
A crosslinked tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder having a crystallization point of 233 ° C. or less and a melt viscosity of 5000 Pa · s or more.
μｍ以下であるテトラフルオロエチレン／ヘキサフルオ
ロプロピレン系共重合体微粉末に、８０℃〜２８０℃の
温度範囲で、且つ酸素濃度１０ｔｏｒｒ以下の雰囲気中
で、１ｋＧｙ〜１ＭＧｙの電離性放射線を照射すること
を特徴とする架橋テトラフルオロエチレン／ヘキサフル
オロプロピレン系共重合体微粉末の製造方法。2. An average particle diameter of 10 μm or less and a maximum particle diameter of 50.
Irradiating the tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder having a particle diameter of μm or less with ionizing radiation of 1 kGy to 1 MGy in an atmosphere having a temperature range of 80 ° C. to 280 ° C. and an oxygen concentration of 10 torr or less. A method for producing a fine powder of a crosslinked tetrafluoroethylene / hexafluoropropylene copolymer, which comprises:
μｍ以下であるテトラフルオロエチレン／ヘキサフルオ
ロプロピレン系共重合体微粉末に、８０℃〜２８０℃の
温度範囲で、且つ酸素濃度１０ｔｏｒｒ以下の雰囲気中
で、１ｋＧｙ〜１ＭＧｙの電離性放射線を照射し、その
後粉砕することを特徴とする架橋テトラフルオロエチレ
ン／ヘキサフルオロプロピレン系共重合体微粉末の製造
方法。3. An average particle diameter of 10 μm or less and a maximum particle diameter of 50.
The tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder having a size of μm or less is irradiated with ionizing radiation of 1 kGy to 1 MGy in an atmosphere having a temperature range of 80 ° C. to 280 ° C. and an oxygen concentration of 10 torr or less, A method for producing a crosslinked tetrafluoroethylene / hexafluoropropylene-based copolymer fine powder, which is characterized by pulverizing thereafter.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3348610A4 (en) * | 2015-09-07 | 2019-05-22 | Sumitomo Electric Fine Polymer, Inc. | METHOD FOR MANUFACTURING MOLDED POLYTETRAFLUOROETHYLENE BODY AND MOLDED POLYTETRAFLUOROETHYLENE BODY |
| EP3348601A4 (en) * | 2015-09-07 | 2019-05-29 | Sumitomo Electric Fine Polymer, Inc. | POLYTETRAFLUOROETHYLENE MOLDED BODY AND MANUFACTURING METHOD THEREOF |
| US10731015B2 (en) | 2012-07-05 | 2020-08-04 | Daikin Industries, Ltd. | Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article |
-
2001
- 2001-12-25 JP JP2001390723A patent/JP3731536B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10731015B2 (en) | 2012-07-05 | 2020-08-04 | Daikin Industries, Ltd. | Modified fluorine-containing copolymer, fluorine resin molded article, and method for manufacturing fluorine resin molded article |
| EP3348610A4 (en) * | 2015-09-07 | 2019-05-22 | Sumitomo Electric Fine Polymer, Inc. | METHOD FOR MANUFACTURING MOLDED POLYTETRAFLUOROETHYLENE BODY AND MOLDED POLYTETRAFLUOROETHYLENE BODY |
| EP3348601A4 (en) * | 2015-09-07 | 2019-05-29 | Sumitomo Electric Fine Polymer, Inc. | POLYTETRAFLUOROETHYLENE MOLDED BODY AND MANUFACTURING METHOD THEREOF |
| US10858487B2 (en) | 2015-09-07 | 2020-12-08 | Sumitomo Electric Fine Polymer, Inc. | Polytetrafluoroethylene formed product, and manufacturing method therefor |
| US11326034B2 (en) | 2015-09-07 | 2022-05-10 | Sumitomo Electric Fine Polymer | Method for manufacturing polytetrafluoroethylene formed product, and polytetrafluoroethylene formed product |
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