JP2023153091A - resin composition - Google Patents
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- JP2023153091A JP2023153091A JP2023058604A JP2023058604A JP2023153091A JP 2023153091 A JP2023153091 A JP 2023153091A JP 2023058604 A JP2023058604 A JP 2023058604A JP 2023058604 A JP2023058604 A JP 2023058604A JP 2023153091 A JP2023153091 A JP 2023153091A
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- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 51
- 239000004917 carbon fiber Substances 0.000 claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000003365 glass fiber Substances 0.000 claims abstract description 28
- 239000000945 filler Substances 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 15
- -1 alkali metal titanate Chemical class 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
- 239000010439 graphite Substances 0.000 claims abstract description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 8
- 239000011295 pitch Substances 0.000 claims description 53
- 239000000835 fiber Substances 0.000 claims description 35
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 230000013011 mating Effects 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 26
- 230000003746 surface roughness Effects 0.000 abstract description 12
- 238000005299 abrasion Methods 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 15
- 239000000178 monomer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 229920006026 co-polymeric resin Polymers 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000007833 carbon precursor Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229920006361 Polyflon Polymers 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920009638 Tetrafluoroethylene-Hexafluoropropylene-Vinylidenefluoride Copolymer Polymers 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000011300 coal pitch Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- PEVRKKOYEFPFMN-UHFFFAOYSA-N 1,1,2,3,3,3-hexafluoroprop-1-ene;1,1,2,2-tetrafluoroethene Chemical group FC(F)=C(F)F.FC(F)=C(F)C(F)(F)F PEVRKKOYEFPFMN-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical class FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000011315 coal-based isotropic pitch Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical compound C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004058 oil shale Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011318 synthetic pitch Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、樹脂組成物に関する。 The present invention relates to a resin composition.
ポリテトラフルオロエチレン樹脂に代表されるテトラフルオロエチレン系樹脂は、耐熱性が高く、摩擦係数が低く、化学的にも極めて安定しているため、各種シール材、軸受、ベアリング等の摺動部材として広く利用されている。テトラフルオロエチレン系樹脂単独では、耐摩耗性、機械特性等に劣るため、通常は、充填剤を添加してこれらの特性を改善した樹脂組成物が使用されている。テトラフルオロエチレン系樹脂に添加される充填剤としては、黒鉛、炭素繊維、二硫化モリブデン、銅等が挙げられる。 Tetrafluoroethylene resins, typified by polytetrafluoroethylene resins, have high heat resistance, low friction coefficients, and are extremely chemically stable, so they are used as various sealing materials, bearings, and sliding members such as bearings. Widely used. Tetrafluoroethylene resin alone has poor abrasion resistance, mechanical properties, etc., and therefore resin compositions with fillers added to improve these properties are usually used. Examples of the filler added to the tetrafluoroethylene resin include graphite, carbon fiber, molybdenum disulfide, copper, and the like.
例えば、特許文献１では、所定のモース硬度及び平均粒径を有する粉末状の硬質材料を添加したシール材が記載されている。また、特許文献２には、チタン酸アルカリ金属の多孔質球状粒子を添加することが記載されている。 For example, Patent Document 1 describes a sealing material to which a powdery hard material having a predetermined Mohs hardness and average particle size is added. Furthermore, Patent Document 2 describes the addition of porous spherical particles of alkali metal titanate.
一方、自動車、建設機械等、多くの産業分野で機械部品の性能向上が図られている。したがって、テトラフルオロエチレン系樹脂を含む樹脂組成物及びその成形品において、より高負荷で使用可能な摺動部材を提供することが求められている。 On the other hand, efforts are being made to improve the performance of mechanical parts in many industrial fields such as automobiles and construction machinery. Therefore, there is a need to provide a sliding member that can be used under higher loads in resin compositions containing tetrafluoroethylene resins and molded products thereof.
本発明は、このような課題を解決しようとするものであり、高速の負荷がかかる場合にも良好な摺動特性を発現し、摩耗量が少なく、相手材の表面粗さを小さくし、摺動面近傍温度を低くすることができる樹脂組成物を提供することを目的とする。 The present invention aims to solve these problems, and exhibits good sliding characteristics even when high-speed loads are applied, reduces the amount of wear, reduces the surface roughness of the mating material, and improves sliding properties. It is an object of the present invention to provide a resin composition that can lower the temperature near the moving surface.
本発明者らは、上記課題を解決するために鋭意研究を行った結果、ガラス繊維とピッチ系炭素繊維とを組合せて使用することで、テトラフルオロエチレン系樹脂を含む樹脂組成物に対して、高速の負荷がかかる場合にも良好な摺動特性を発現し、摩耗量が少なく、相手材の表面粗さを小さくし、摺動面近傍温度を低くすることができることを見出した。本発明者らは、このような知見に基づきさらに研究を重ね、本発明を完成させた。即ち、本発明は、以下の構成を包含する。 The present inventors conducted extensive research to solve the above problems, and found that by using a combination of glass fiber and pitch-based carbon fiber, a resin composition containing a tetrafluoroethylene resin can be made. It has been discovered that even when high-speed loads are applied, good sliding characteristics are exhibited, the amount of wear is small, the surface roughness of the mating material is reduced, and the temperature near the sliding surface can be lowered. The present inventors conducted further research based on such knowledge and completed the present invention. That is, the present invention includes the following configurations.
項１．テトラフルオロエチレン系樹脂、充填剤及びピッチ系炭素繊維を含有し、
前記充填剤が、ガラス繊維、二硫化モリブデン、黒鉛、銅及びチタン酸アルカリ金属よりなる群から選ばれる少なくとも１種である、樹脂組成物。
Item 1. Contains tetrafluoroethylene resin, filler and pitch carbon fiber,
A resin composition, wherein the filler is at least one selected from the group consisting of glass fiber, molybdenum disulfide, graphite, copper, and alkali metal titanate.
項２．前記テトラフルオロエチレン系重合体が、ポリテトラフルオロエチレン樹脂を含有する、項１に記載の樹脂組成物。 Item 2. Item 2. The resin composition according to item 1, wherein the tetrafluoroethylene polymer contains a polytetrafluoroethylene resin.
項３．前記充填剤が、ガラス繊維、二硫化モリブデン及び黒鉛よりなる群から選ばれる少なくとも１種である、項１又は２に記載の樹脂組成物。 Item 3. Item 3. The resin composition according to Item 1 or 2, wherein the filler is at least one selected from the group consisting of glass fiber, molybdenum disulfide, and graphite.
項４．前記ガラス繊維の平均繊維長が２０～３００μｍである、項３に記載の樹脂組成物。 Item 4. Item 4. The resin composition according to Item 3, wherein the glass fibers have an average fiber length of 20 to 300 μm.
項５．前記樹脂組成物の総量を１００体積％として、前記充填剤の含有量が１．０～２８．０体積％である、項１～４のいずれか１項に記載の樹脂組成物。 Item 5. Item 5. The resin composition according to any one of Items 1 to 4, wherein the filler content is 1.0 to 28.0 volume % when the total amount of the resin composition is 100 volume %.
項６．前記ピッチ系炭素繊維が、等方性ピッチ系炭素繊維である、項１～５のいずれか１項に記載の樹脂組成物。 Item 6. Item 6. The resin composition according to any one of Items 1 to 5, wherein the pitch-based carbon fiber is an isotropic pitch-based carbon fiber.
項７．前記ピッチ系炭素繊維の平均繊維長が２０～３００μｍである、項１～６のいずれか１項に記載の樹脂組成物。 Section 7. Item 7. The resin composition according to any one of items 1 to 6, wherein the pitch-based carbon fiber has an average fiber length of 20 to 300 μm.
項８．前記樹脂組成物の総量を１００体積％として、前記ピッチ系炭素繊維の含有量が１．０～２８．０体積％である、項１～７のいずれか１項に記載の樹脂組成物。 Section 8. Item 8. The resin composition according to any one of Items 1 to 7, wherein the content of the pitch-based carbon fiber is 1.0 to 28.0 volume % when the total amount of the resin composition is 100 volume %.
項９．摺動部材用樹脂組成物である、項１～８のいずれか１項に記載の樹脂組成物。 Item 9. The resin composition according to any one of Items 1 to 8, which is a resin composition for a sliding member.
項１０．項１～９のいずれか１項に記載の樹脂組成物を用いた成形品。 Item 10. A molded article using the resin composition according to any one of Items 1 to 9.
項１１．摺動部材である、項１０に記載の成形品。 Item 11. Item 11. The molded article according to item 10, which is a sliding member.
本発明によれば、高速の負荷がかかる場合にも良好な摺動特性を発現し、摩耗量が少なく、相手材の表面粗さを小さくし、摺動面近傍温度を低くすることができる樹脂組成物を提供することができる。 According to the present invention, the resin exhibits good sliding characteristics even when high-speed loads are applied, has little wear, reduces the surface roughness of the mating material, and can lower the temperature near the sliding surface. A composition can be provided.
本明細書において、「含有」は、「含む（comprise）」、「実質的にのみからなる（consist essentially of）」、及び「のみからなる（consist of）」のいずれも包含する概念である。 In this specification, "contain" is a concept that includes all of "comprise," "consist essentially of," and "consist of."
また、本明細書において、数値範囲を「Ａ～Ｂ」で示す場合、Ａ以上Ｂ以下を意味する。 Furthermore, in this specification, when a numerical range is expressed as "A to B", it means greater than or equal to A and less than or equal to B.
本発明の樹脂組成物は、テトラフルオロエチレン系樹脂、充填剤及びピッチ系炭素繊維を含有し、前記充填剤が、ガラス繊維、二硫化モリブデン、黒鉛、銅及びチタン酸アルカリ金属よりなる群から選ばれる少なくとも１種である。 The resin composition of the present invention contains a tetrafluoroethylene resin, a filler, and pitch-based carbon fiber, and the filler is selected from the group consisting of glass fiber, molybdenum disulfide, graphite, copper, and alkali metal titanate. At least one type of
１．テトラフルオロエチレン系樹脂
本発明で使用するテトラフルオロエチレン系樹脂は、一部又は全部の繰り返し単位としてテトラフルオロエチレン（ＴＦＥ）を有する樹脂を意味している。つまり、テトラフルオロエチレン系樹脂としては、テトラフルオロエチレン（ＴＦＥ）の単独重合体であるポリテトラフルオロエチレン樹脂（ＰＴＦＥ樹脂）の他、テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体が繰り返し単位として含まれるテトラフルオロエチレン共重合体樹脂も使用できる。
1. Tetrafluoroethylene Resin The tetrafluoroethylene resin used in the present invention means a resin having tetrafluoroethylene (TFE) as some or all repeating units. In other words, tetrafluoroethylene resins include polytetrafluoroethylene resin (PTFE resin), which is a homopolymer of tetrafluoroethylene (TFE), as well as repeating monomers that can be copolymerized with tetrafluoroethylene (TFE). Tetrafluoroethylene copolymer resins contained as units can also be used.
テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体が繰り返し単位として含まれるテトラフルオロエチレン共重合体樹脂（変性ＰＴＦＥ樹脂）を採用する場合、テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体の含有量は、特に制限はなく、例えば、０．１～５０モル％、好ましくは０．２～３０モル％、より好ましくは０．３～１０モル％、さらに好ましくは０．４～５モル％とすることができる。 When employing a tetrafluoroethylene copolymer resin (modified PTFE resin) containing a monomer copolymerizable with tetrafluoroethylene (TFE) as a repeating unit, the monomer copolymerizable with tetrafluoroethylene (TFE) is used. The content is not particularly limited, and is, for example, 0.1 to 50 mol%, preferably 0.2 to 30 mol%, more preferably 0.3 to 10 mol%, and even more preferably 0.4 to 5 mol%. It can be expressed as mol%.
テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体が繰り返し単位として含まれるテトラフルオロエチレン共重合体樹脂（変性ＰＴＦＥ樹脂）を採用する場合、テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体としては、特に制限はなく使用できるが、耐熱性、耐摩耗性、化学的安定性等のテトラフルオロエチレン系樹脂の優れた性能を維持しやすい観点からは、フッ素含有単量体を使用することが好ましく、炭素数３以上（好ましくは３～６）のパーフルオロアルケン、炭素数１～６のパーフルオロ（アルキルビニルエーテル）、ハロゲン化トリフルオロエチレン等が挙げられる。テトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体としては、具体的には、エチレン、ヘキサフルオロプロピレン（ＨＦＰ）、パーフルオロ（メチルビニルエーテル）（ＰＭＶＥ）、パーフルオロ（エチルビニルエーテル）（ＰＥＶＥ）、パーフルオロ（プロピルビニルエーテル）（ＰＰＶＥ）、パーフルオロ（ブチルビニルエーテル）（ＰＢＶＥ）、クロロトリフルオロエチレン等が挙げられる。これらのテトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体は、単独で用いることもでき、２種以上を組合せて用いることもできる。 When employing a tetrafluoroethylene copolymer resin (modified PTFE resin) containing a monomer copolymerizable with tetrafluoroethylene (TFE) as a repeating unit, the monomer copolymerizable with tetrafluoroethylene (TFE) is used. Although there are no particular restrictions on the use of monomers, fluorine-containing monomers are preferred from the standpoint of easily maintaining the excellent performance of tetrafluoroethylene resins such as heat resistance, abrasion resistance, and chemical stability. Preferred examples include perfluoroalkenes having 3 or more carbon atoms (preferably 3 to 6 carbon atoms), perfluoro(alkyl vinyl ethers) having 1 to 6 carbon atoms, and halogenated trifluoroethylenes. Specifically, monomers copolymerizable with tetrafluoroethylene (TFE) include ethylene, hexafluoropropylene (HFP), perfluoro(methyl vinyl ether) (PMVE), and perfluoro(ethyl vinyl ether) (PEVE). , perfluoro(propyl vinyl ether) (PPVE), perfluoro(butyl vinyl ether) (PBVE), chlorotrifluoroethylene, and the like. These monomers copolymerizable with tetrafluoroethylene (TFE) can be used alone or in combination of two or more.
このようなテトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体を有するテトラフルオロエチレン共重合体樹脂としては、例えば、テトラフルオロエチレン－ヘキサフルオロプロピレン共重合体樹脂（ＦＥＰ樹脂）、テトラフルオロエチレン－パーフルオロアルキルビニルエーテル樹脂（ＰＦＡ樹脂）、エチレン－テトラフルオロエチレン共重合体樹脂（ＥＴＦＥ樹脂）、テトラフルオロエチレン－ヘキサフルオロプロピレン－フッ化ビニリデン共重合体樹脂（ＴＨＶ樹脂）等が挙げられる。これらのテトラフルオロエチレン（ＴＦＥ）と共重合可能な単量体を有するテトラフルオロエチレン共重合体樹脂は、単独で用いることもでき、２種以上を組合せて用いることもできる。 Examples of the tetrafluoroethylene copolymer resin having a monomer copolymerizable with tetrafluoroethylene (TFE) include tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP resin), tetrafluoroethylene - Perfluoroalkyl vinyl ether resin (PFA resin), ethylene-tetrafluoroethylene copolymer resin (ETFE resin), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer resin (THV resin), and the like. These tetrafluoroethylene copolymer resins having monomers copolymerizable with tetrafluoroethylene (TFE) can be used alone or in combination of two or more.
なかでも、テトラフルオロエチレン系樹脂としては、耐熱性、耐摩耗性、化学的安定性、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）等の観点から、ポリテトラフルオロエチレン樹脂（ＰＴＦＥ樹脂）が好ましい。 Among these, tetrafluoroethylene resins are preferred from the viewpoint of heat resistance, abrasion resistance, chemical stability, and sliding properties (amount of wear, aggressiveness to mating materials, temperature near sliding surfaces, etc.). Tetrafluoroethylene resin (PTFE resin) is preferred.
本発明の樹脂組成物において、テトラフルオロエチレン系樹脂の含有量は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、本発明の樹脂組成物の総量を１００体積％として、４４．０～９８．０体積％が好ましく、６５．０～９６．８体積％がより好ましく、７８．０～９５．５体積％がさらに好ましい。 In the resin composition of the present invention, the content of the tetrafluoroethylene resin is determined from the viewpoints of sliding properties (amount of wear, attack on mating material, temperature near the sliding surface, etc.), dispersibility, etc. The total amount of the resin composition is 100% by volume, preferably 44.0 to 98.0% by volume, more preferably 65.0 to 96.8% by volume, and even more preferably 78.0 to 95.5% by volume.
２．充填剤
充填剤としては、特に制限はなく、上記したテトラフルオロエチレン系樹脂に対して充填剤として添加することができるピッチ系炭素繊維以外の充填剤を採用することができる。このような充填剤としては、具体的には、ガラス繊維、二硫化モリブデン、黒鉛、銅、チタン酸アルカリ金属（２チタン酸ナトリウム、２チタン酸カリウム、３チタン酸ナトリウム、３チタン酸カリウム、４チタン酸ナトリウム、４チタン酸カリウム、トンネル構造型チタン酸ナトリウム、トンネル構造型チタン酸カリウム、６チタン酸ナトリウム、６チタン酸カリウム、８チタン酸ナトリウム、８チタン酸カリウム）等が挙げられる。なかでも、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、ガラス繊維、二硫化モリブデン、黒鉛等が好ましい。
2. Filler The filler is not particularly limited, and fillers other than pitch-based carbon fibers that can be added as a filler to the above-mentioned tetrafluoroethylene resin can be employed. Specifically, such fillers include glass fiber, molybdenum disulfide, graphite, copper, alkali metal titanates (sodium dititanate, potassium dititanate, sodium trititanate, potassium trititanate, Examples include sodium titanate, potassium tetratitanate, tunnel structure type sodium titanate, tunnel structure type potassium titanate, sodium hexatitanate, potassium hexatitanate, sodium octitanate, potassium octitanate), and the like. Among these, glass fiber, molybdenum disulfide, graphite, etc. are preferred from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near sliding surface, etc.), dispersibility, etc.
充填剤としてガラス繊維を使用する場合、ガラス繊維の平均繊維長は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、２０～３００μｍが好ましく、４０～２００μｍがより好ましく、５０～１５０μｍがさらに好ましい。 When using glass fiber as a filler, the average fiber length of the glass fiber is 20 to 300 μm from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near the sliding surface, etc.), dispersibility, etc. is preferable, 40 to 200 μm is more preferable, and even more preferably 50 to 150 μm.
なお、平均繊維長（Ｌｖ）は、以下の式のように定義される。
Ｌｖ＝（ｌ１×ｌ１＋ｌ２×ｌ２＋…＋ｌｎ×ｌｎ）／（ｌ１＋ｌ２＋…＋ｌｎ）
ここで、ｌ１～ｌｎは、それぞれ１～ｎ番目の繊維の長さを示す。ガラス繊維の平均繊維長は、（株）ＫＥＹＥＮＣＥ社製のマイクロスコープＶＨＸ－７０００と、付属の画像解析ソフトを使用し、６０００個のガラス繊維の長さを測定し、上記式により算出する。
Note that the average fiber length (Lv) is defined as in the following formula.
Lv=(l 1 ×l 1 +l 2 ×l 2 +…+l n ×l n )/(l 1 +l 2 +…+l n )
Here, l 1 to l n indicate the lengths of the 1st to nth fibers, respectively. The average fiber length of the glass fibers is calculated using the above formula by measuring the length of 6000 glass fibers using a microscope VHX-7000 manufactured by KEYENCE Co., Ltd. and the attached image analysis software.
充填剤としてガラス繊維を使用する場合、ガラス繊維の平均繊維径は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、４～２４μｍが好ましく、５～２０μｍがより好ましく、６～１５μｍがさらに好ましい。なお、ガラス繊維の平均繊維径は、（株）ＫＥＹＥＮＣＥ社製のマイクロスコープＶＨＸ－７０００と、付属の画像解析ソフトを使用し、繊維長と同時に測定する。 When using glass fiber as a filler, the average fiber diameter of the glass fiber should be 4 to 24 μm from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near the sliding surface, etc.), dispersibility, etc. is preferable, 5 to 20 μm is more preferable, and even more preferably 6 to 15 μm. Note that the average fiber diameter of the glass fibers is measured at the same time as the fiber length using a microscope VHX-7000 manufactured by KEYENCE Co., Ltd. and the attached image analysis software.
充填剤としてガラス繊維を使用する場合、ガラス繊維の平均アスペクト比は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、２～７５が好ましく、２～４０がより好ましく、３～２５がさらに好ましい。なお、ガラス繊維の平均アスペクト比は、上記により算出した平均繊維長及び平均繊維径を用いて、平均繊維長／平均繊維径により算出する。 When using glass fiber as a filler, the average aspect ratio of the glass fiber is 2 to 75 from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near the sliding surface, etc.), dispersibility, etc. is preferable, 2 to 40 is more preferable, and 3 to 25 is even more preferable. Note that the average aspect ratio of the glass fibers is calculated as average fiber length/average fiber diameter using the average fiber length and average fiber diameter calculated above.
充填剤として二硫化モリブデン、黒鉛、銅、チタン酸アルカリ金属等を使用する場合、これら充填剤の平均粒子径は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、０．５～３０μｍが好ましく、１．５～１５μｍがより好ましく、２～１０μｍがさらに好ましい。 When using molybdenum disulfide, graphite, copper, alkali metal titanate, etc. as a filler, the average particle diameter of these fillers is determined by the sliding characteristics (amount of wear, aggressiveness to mating material, temperature near the sliding surface, etc.) ), preferably from 0.5 to 30 μm, more preferably from 1.5 to 15 μm, even more preferably from 2 to 10 μm, from the viewpoint of dispersibility and the like.
本発明の樹脂組成物において、充填剤の含有量は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、本発明の樹脂組成物の総量を１００体積％として、１．０～２８．０体積％が好ましく、１．２～１５．０体積％がより好ましい。 In the resin composition of the present invention, the content of the filler is determined from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near sliding surface, etc.), dispersibility, etc. The total amount is 100% by volume, preferably 1.0 to 28.0% by volume, more preferably 1.2 to 15.0% by volume.
３．ピッチ系炭素繊維
ピッチ系炭素繊維としては、ピッチを炭素前駆体とする炭素繊維を意味する。なかでも、テトラフルオロエチレン系樹脂に対して充填剤として添加することができるものを採用することができるが、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）等の観点から、等方性ピッチを炭素前駆体とする等方性ピッチ系炭素繊維が好ましい。特に、等方性ピッチ系炭素繊維は、炭素六角網面からなる結晶子が小さく、且つ、ランダムに並んでいるため、機械的強度及び硬度が比較的低い。そのため、等方性ピッチ系炭素繊維は摺動により、さらに適度な破壊が起こりやすく、炭素繊維の結晶子を含んだ良質な摺動皮膜を形成しやすいため、摺動特性を向上させやすい。なお、等方性とは、光学的に等方性であって、分子や分子の集団が無秩序に配向している場合も包含する。また、炭素前駆体とは、目的とする最終炭素製品であるピッチ系炭素繊維の前の段階にある一連の炭素化中間体を意味する。
3. Pitch-based carbon fiber Pitch-based carbon fiber refers to carbon fiber that uses pitch as a carbon precursor. Among these, those that can be added as fillers to tetrafluoroethylene resins can be used, but the sliding properties (amount of wear, aggressiveness to mating materials, temperature near the sliding surface, etc.) etc. From this point of view, isotropic pitch-based carbon fibers using isotropic pitch as a carbon precursor are preferred. In particular, isotropic pitch-based carbon fibers have relatively low mechanical strength and hardness because the crystallites consisting of carbon hexagonal mesh planes are small and randomly arranged. Therefore, isotropic pitch-based carbon fibers are more likely to undergo moderate destruction due to sliding, and are easy to form a high-quality sliding film containing carbon fiber crystallites, making it easier to improve sliding properties. Note that isotropy includes optically isotropic, and also includes cases where molecules or groups of molecules are oriented in a disordered manner. Also, carbon precursor refers to a series of carbonization intermediates that precede the desired final carbon product, pitch-based carbon fiber.
炭素前駆体であるピッチとは、木材、石炭等の乾留の際に得られる液状タール、オイルサンドから得られるビチューメン、オイルシェールの乾留によって得られる油分、原油の蒸留による残渣油、石油留分のクラッキングによって生成するタール等を熱処理及び重合して得られる常温で固体状のものである。具体的には、原材料によって、石炭系ピッチ、石油系ピッチ、ナフタレン等の芳香族化合物を重合した合成ピッチ等が挙げられる。ピッチは、化学的には無数の縮合多環芳香族化合物の混合物である。石炭を原料として得られる石炭系ピッチとしては、コークス炉から生じるコールタールを熱処理して得られるピッチ等が挙げられる。本発明におけるピッチは、特に限定されないが、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）等の観点から、等方性ピッチが好ましく、石炭系等方性ピッチ（石炭を原料として得られる等方性ピッチ）がより好ましい。 Pitch, which is a carbon precursor, refers to liquid tar obtained during the carbonization of wood, coal, etc., bitumen obtained from oil sands, oil obtained by carbonization of oil shale, residual oil from distillation of crude oil, and petroleum fractions. It is solid at room temperature and is obtained by heat-treating and polymerizing tar generated by cracking. Specifically, depending on the raw material, examples include coal-based pitch, petroleum-based pitch, and synthetic pitch obtained by polymerizing aromatic compounds such as naphthalene. Pitch is chemically a mixture of countless fused polycyclic aromatic compounds. Examples of coal-based pitch obtained using coal as a raw material include pitch obtained by heat-treating coal tar generated from a coke oven. The pitch in the present invention is not particularly limited, but from the viewpoint of sliding characteristics (amount of wear, aggressiveness to mating material, temperature near the sliding surface, etc.), an isotropic pitch is preferable, and a coal-based isotropic pitch is preferable. (Isotropic pitch obtained using coal as a raw material) is more preferable.
なお、ピッチからピッチ系炭素繊維を製造する方法は特に制限されず、常法にしたがって行うことができる。 Note that the method for producing pitch-based carbon fiber from pitch is not particularly limited, and can be carried out according to a conventional method.
ピッチ系炭素繊維の平均繊維長は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、２０～３００μｍが好ましく、４０～２００μｍがより好ましく、５０～１５０μｍがさらに好ましい。 The average fiber length of the pitch-based carbon fiber is preferably 20 to 300 μm, more preferably 40 to 200 μm, from the viewpoint of sliding properties (amount of wear, attack on mating material, temperature near sliding surface, etc.) and dispersibility. Preferably, 50 to 150 μm is more preferable.
なお、平均繊維長（Ｌｖ）は、以下の式のように定義される。
Ｌｖ＝（ｌ１×ｌ１＋ｌ２×ｌ２＋…＋ｌｎ×ｌｎ）／（ｌ１＋ｌ２＋…＋ｌｎ）
ここで、ｌ１～ｌｎは、それぞれ１～ｎ番目の繊維の長さを示す。ピッチ系炭素繊維の平均繊維長は、（株）ＫＥＹＥＮＣＥ社製のマイクロスコープＶＨＸ－７０００と、付属の画像解析ソフトを使用し、６０００個のピッチ系炭素繊維の長さを測定し、上記式により算出する。
Note that the average fiber length (Lv) is defined as in the following formula.
Lv=(l 1 ×l 1 +l 2 ×l 2 +…+l n ×l n )/(l 1 +l 2 +…+l n )
Here, l 1 to l n indicate the lengths of the 1st to nth fibers, respectively. The average fiber length of pitch-based carbon fibers was determined by measuring the length of 6,000 pitch-based carbon fibers using a microscope VHX-7000 manufactured by KEYENCE Co., Ltd. and the attached image analysis software, and using the above formula. calculate.
ピッチ系炭素繊維の平均繊維径は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、５～２０μｍが好ましく、７～１８μｍがより好ましく、１０～１５μｍがさらに好ましい。なお、ピッチ系炭素繊維の平均繊維径は、（株）ＫＥＹＥＮＣＥ社製のマイクロスコープＶＨＸ－７０００と、付属の画像解析ソフトを使用し、繊維長と同時に測定する。 The average fiber diameter of the pitch-based carbon fiber is preferably 5 to 20 μm, more preferably 7 to 18 μm, from the viewpoint of sliding properties (amount of wear, attack on mating material, temperature near the sliding surface, etc.) and dispersibility. Preferably, 10 to 15 μm is more preferable. Note that the average fiber diameter of the pitch-based carbon fiber is measured at the same time as the fiber length using a microscope VHX-7000 manufactured by KEYENCE Co., Ltd. and the attached image analysis software.
ピッチ系炭素繊維の平均アスペクト比は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、２～６０が好ましく、２～３０がより好ましく、３～１５がさらに好ましい。なお、ピッチ系炭素繊維の平均アスペクト比は、上記により算出した平均繊維長及び平均繊維径を用いて、平均繊維長／平均繊維径により算出する。 The average aspect ratio of the pitch-based carbon fiber is preferably 2 to 60, more preferably 2 to 30, from the viewpoint of sliding properties (amount of wear, attack on mating material, temperature near the sliding surface, etc.) and dispersibility. Preferably, 3 to 15 are more preferable. Note that the average aspect ratio of the pitch-based carbon fibers is calculated as average fiber length/average fiber diameter using the average fiber length and average fiber diameter calculated above.
本発明の樹脂組成物において、ピッチ系炭素繊維の含有量は、摺動特性（摩耗量、相手材への攻撃性、摺動面近傍温度等）、分散性等の観点から、本発明の樹脂組成物の総量を１００体積％として、１．０～２８．０体積％が好ましく、２．０～２０．０体積％がより好ましい。 In the resin composition of the present invention, the content of pitch-based carbon fiber is determined from the viewpoint of sliding properties (amount of wear, aggressiveness to mating material, temperature near sliding surface, etc.), dispersibility, etc. The total amount of the composition is 100% by volume, preferably 1.0 to 28.0% by volume, more preferably 2.0 to 20.0% by volume.
４．樹脂組成物及び成形品
本発明の樹脂組成物は、上記のとおり、テトラフルオロエチレン系樹脂、ガラス繊維及びピッチ系炭素繊維を含有するものであるが、これ以外に、各種添加剤、例えば、ピッチ系炭素繊維以外の炭素材料（黒鉛等）、二硫化モリブデン、銅、チタン酸アルカリ金属（チタン酸ナトリウム、チタン酸カリウム等）、各種分散剤等を含ませることも可能である。
4. Resin composition and molded article As mentioned above, the resin composition of the present invention contains a tetrafluoroethylene resin, glass fiber, and pitch-based carbon fiber, but it also contains various additives such as pitch. It is also possible to include carbon materials other than carbon fibers (graphite, etc.), molybdenum disulfide, copper, alkali metal titanates (sodium titanate, potassium titanate, etc.), various dispersants, and the like.
本発明の樹脂組成物に、上記した添加剤を含ませる場合、添加剤の含有量は、本発明の効果を損なわない範囲で適宜設定することができ、本発明の樹脂組成物の総量を１００体積％として、０．１～１０．０体積％（好ましくは０．２～５．０体積％）とすることができる。 When the resin composition of the present invention contains the above-mentioned additives, the content of the additives can be set as appropriate within a range that does not impair the effects of the present invention, and the total amount of the resin composition of the present invention is 100% The volume % can be 0.1 to 10.0 volume % (preferably 0.2 to 5.0 volume %).
本発明の樹脂組成物は、上記したテトラフルオロエチレン系樹脂、ガラス繊維及びピッチ系炭素繊維を含有していればよく、その製造方法は特に制限されないが、例えば、テトラフルオロエチレン系樹脂、ガラス繊維及びピッチ系炭素繊維、並びに必要に応じて添加剤を、常法により混合することができる。 The resin composition of the present invention only needs to contain the above-described tetrafluoroethylene resin, glass fiber, and pitch-based carbon fiber, and the manufacturing method thereof is not particularly limited. and pitch-based carbon fiber, and additives if necessary, can be mixed by a conventional method.
混合方法は特に制限されず、タンブラーミキサー、ヘンシェルミキサー等を用いて乾式で行うことができる。 The mixing method is not particularly limited, and can be carried out in a dry manner using a tumbler mixer, a Henschel mixer, or the like.
混合後、得られる本発明の樹脂組成物を常法で成形し、成形品を製造することができる。例えば、粉末状の本発明の樹脂組成物を金型に投入し、１０～６０ＭＰａ程度に加圧して圧粉体を得た後に、金型から取り出し、２５０～４００℃程度で熱処理して成形することができる。また、熱処理の際に圧縮成形することもできるし、ラム押出機等によって連続成形することもできる。 After mixing, the resulting resin composition of the present invention can be molded in a conventional manner to produce a molded article. For example, the powdered resin composition of the present invention is put into a mold and pressurized to about 10 to 60 MPa to obtain a green compact, which is then taken out from the mold and heat-treated at about 250 to 400°C to form it. be able to. Further, compression molding can be performed during heat treatment, or continuous molding can be performed using a ram extruder or the like.
このようにして得られる本発明の成形品は、高速の負荷がかかる場合にも良好な摺動特性を発現し、摩耗量が少なく、相手材の表面粗さを小さくし、摺動面近傍温度を低くすることができる特性を生かして、各種シール材、軸受、ベアリング等の摺動部材として有用である。つまり、本発明の樹脂組成物は、摺動部材用樹脂組成物として有用である。 The molded product of the present invention obtained in this way exhibits good sliding characteristics even when high-speed loads are applied, has low wear, reduces the surface roughness of the mating material, and has a temperature near the sliding surface. It is useful as various sealing materials, bearings, and sliding members such as bearings by taking advantage of its ability to reduce the friction. That is, the resin composition of the present invention is useful as a resin composition for sliding members.
本発明の樹脂組成物を用いた成形品を摺動部材として使用する場合、相手部材としては、金属又は金属合金であれば特に制限なく採用することができ、なお、相手部材が金属又は金属合金である場合、通常は、わずかに摩耗した金属片が研磨材として作用し相手部材の摩耗が顕著になりやすい。しかしながら、本発明の樹脂組成物を用いた成形品を摺動部材として使用する場合は、そのような場合であっても、摺動部材及び相手部材への摩耗量を有効に低減することができる。 When a molded article using the resin composition of the present invention is used as a sliding member, any metal or metal alloy can be used as the mating member without particular restriction; In this case, the slightly worn metal piece usually acts as an abrasive, and the wear of the mating member tends to become noticeable. However, when a molded article using the resin composition of the present invention is used as a sliding member, even in such a case, the amount of wear on the sliding member and the mating member can be effectively reduced. .
本発明の樹脂組成物を用いた成形品を摺動部材として使用する場合、相手部材としては、例えば、アルミニウム、ステンレス、鉄、銅、亜鉛、ニッケル等や、これらの合金等が挙げられる。 When a molded article using the resin composition of the present invention is used as a sliding member, examples of the mating member include aluminum, stainless steel, iron, copper, zinc, nickel, and alloys thereof.
以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例の態様に限定されない。 EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. However, the present invention is not limited to the embodiments.
（実施例１）
テトラフルオロエチレン樹脂（ダイキン工業（株）製 ポリフロンＭ－１１１）に、ガラス繊維（セントラルグラスファイバー（株）製 ＥＦＨ－５０－３１ 平均繊維径１１μｍ、平均繊維長５０μｍ、平均アスペクト比４．５）を８体積％、等方性ピッチ系炭素繊維（大阪ガスケミカル（株）製 ＳＧ－２４１ 平均繊維径１３μｍ、平均繊維長１４０μｍ、平均アスペクト比１０．８）を２体積％になるように配合した。この配合物をヘンシェルミキサーを用いて１２００ｒｐｍで２分間混合した。得られた樹脂組成物を常温でプレス成形して、１２５ｍｍ×１２５ｍｍ×（厚み）３ｍｍ程度の平板とした。このときプレスは、１５ＭＰａで５分間保持した後、３０ＭＰａで１５分間保持することによって行った。得られた平板をオーブンに入れて３５０℃程度の温度で加熱し、成形品を得た。得られた成形品のかさ密度は、２．２０ｇ／ｃｍ３であった。
(Example 1)
Glass fiber (EFH-50-31, manufactured by Central Glass Fiber Co., Ltd., average fiber diameter 11 μm, average fiber length 50 μm, average aspect ratio 4.5) was added to tetrafluoroethylene resin (Polyflon M-111 manufactured by Daikin Industries, Ltd.). 8% by volume, and 2% by volume of isotropic pitch-based carbon fiber (SG-241 manufactured by Osaka Gas Chemical Co., Ltd., average fiber diameter 13 μm, average fiber length 140 μm, average aspect ratio 10.8). . This formulation was mixed using a Henschel mixer at 1200 rpm for 2 minutes. The obtained resin composition was press-molded at room temperature to form a flat plate of approximately 125 mm x 125 mm x (thickness) 3 mm. At this time, pressing was performed by holding at 15 MPa for 5 minutes and then holding at 30 MPa for 15 minutes. The obtained flat plate was placed in an oven and heated at a temperature of about 350°C to obtain a molded product. The bulk density of the obtained molded article was 2.20 g/cm 3 .
（実施例２）
ガラス繊維を５体積％、等方性ピッチ炭素繊維を５体積％になるように配合した以外は実施例１と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．１７ｇ／ｃｍ３であった。
(Example 2)
A molded article was obtained in the same manner as in Example 1, except that glass fiber was blended at 5% by volume and isotropic pitch carbon fiber was blended at 5% by volume. The bulk density of the obtained molded article was 2.17 g/cm 3 .
（実施例３）
ガラス繊維を２体積％、等方性ピッチ炭素繊維を８体積％になるように配合した以外は実施例１と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．１５ｇ／ｃｍ３であった。
(Example 3)
A molded article was obtained in the same manner as in Example 1, except that glass fiber was blended at 2% by volume and isotropic pitch carbon fiber was blended at 8% by volume. The bulk density of the obtained molded article was 2.15 g/cm 3 .
（比較例１）
等方性ピッチ炭素繊維を使用せず、ガラス繊維を１０体積％になるように配合した以外は実施例１と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．２１ｇ／ｃｍ３であった。
(Comparative example 1)
A molded article was obtained in the same manner as in Example 1, except that isotropic pitch carbon fiber was not used and glass fiber was blended at 10% by volume. The bulk density of the obtained molded article was 2.21 g/cm 3 .
（実施例４）
テトラフルオロエチレン樹脂（ダイキン工業（株）製 ポリフロンＭ－１１１）に、二硫化モリブデン（（株）ダイゾー製 Ｔパウダー 平均粒子径３．５μｍ）を８体積％、等方性ピッチ系炭素繊維（大阪ガスケミカル（株）製 ＳＧ－２４１ 平均繊維径１３μｍ、平均繊維長１４０μｍ、平均アスペクト比１０．８）を２体積％になるように配合した。この配合物をヘンシェルミキサーを用いて１２００ｒｐｍで２分間混合した。得られた樹脂組成物を常温でプレス成形して、１２５ｍｍ×１２５ｍｍ×（厚み）３ｍｍ程度の平板とした。このときプレスは、１５ＭＰａで５分間保持した後、３０ＭＰａで１５分間保持することによって行った。得られた平板をオーブンに入れて３５０℃程度の温度で加熱し、成形品を得た。得られた成形品のかさ密度は、２．６５ｇ／ｃｍ３であった。
(Example 4)
8% by volume of molybdenum disulfide (T powder, average particle size 3.5 μm, manufactured by Daizo Corporation) was added to tetrafluoroethylene resin (Polyflon M-111 manufactured by Daikin Industries, Ltd.), and an isotropic pitch-based carbon fiber (Osaka SG-241 manufactured by Gas Chemical Co., Ltd. (average fiber diameter 13 μm, average fiber length 140 μm, average aspect ratio 10.8) was blended at 2% by volume. This formulation was mixed using a Henschel mixer at 1200 rpm for 2 minutes. The obtained resin composition was press-molded at room temperature to form a flat plate of approximately 125 mm x 125 mm x (thickness) 3 mm. At this time, pressing was performed by holding at 15 MPa for 5 minutes and then holding at 30 MPa for 15 minutes. The obtained flat plate was placed in an oven and heated at a temperature of about 350°C to obtain a molded product. The bulk density of the obtained molded article was 2.65 g/cm 3 .
（実施例５）
二硫化モリブデンを５体積％、等方性ピッチ炭素繊維を５体積％になるように配合した以外は実施例４と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．４７ｇ／ｃｍ３であった。
(Example 5)
A molded article was obtained in the same manner as in Example 4, except that molybdenum disulfide was blended at 5% by volume and isotropic pitch carbon fiber was blended at 5% by volume. The bulk density of the obtained molded article was 2.47 g/cm 3 .
（実施例６）
二硫化モリブデンを２体積％、等方性ピッチ炭素繊維を８体積％になるように配合した以外は実施例４と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．２７ｇ／ｃｍ３であった。
(Example 6)
A molded article was obtained in the same manner as in Example 4, except that molybdenum disulfide was blended at 2% by volume and isotropic pitch carbon fiber was blended at 8% by volume. The bulk density of the obtained molded article was 2.27 g/cm 3 .
（比較例２）
等方性ピッチ炭素繊維を使用せず、二硫化モリブデンを１０体積％になるように配合した以外は実施例４と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．７６ｇ／ｃｍ３であった。
(Comparative example 2)
A molded article was obtained in the same manner as in Example 4, except that isotropic pitch carbon fiber was not used and molybdenum disulfide was blended at 10% by volume. The bulk density of the obtained molded article was 2.76 g/cm 3 .
（実施例７）
テトラフルオロエチレン樹脂（ダイキン工業（株）製 ポリフロンＭ－１１１）に、黒鉛粉（新越化成工業（株）製 ＢＦ－５Ａ 平均粒子径５．０μｍ）を８体積％、等方性ピッチ系炭素繊維（大阪ガスケミカル（株）製 ＳＧ－２４１ 平均繊維径１３μｍ、平均繊維長１４０μｍ、平均アスペクト比１０．８）を２体積％になるように配合した。この配合物をヘンシェルミキサーを用いて１２００ｒｐｍで２分間混合した。得られた樹脂組成物を常温でプレス成形して、１２５ｍｍ×１２５ｍｍ×（厚み）３ｍｍ程度の平板とした。このときプレスは、１５ＭＰａで５分間保持した後、３０ＭＰａで１５分間保持することによって行った。得られた平板をオーブンに入れて３５０℃程度の温度で加熱し、成形品を得た。得られた成形品のかさ密度は、２．１６ｇ／ｃｍ３であった。
(Example 7)
Tetrafluoroethylene resin (Polyflon M-111, manufactured by Daikin Industries, Ltd.) was added with 8% by volume of graphite powder (BF-5A, manufactured by Shin-etsu Chemical Industries, Ltd., average particle size 5.0 μm), and isotropic pitch-based carbon was added. Fibers (SG-241 manufactured by Osaka Gas Chemical Co., Ltd., average fiber diameter 13 μm, average fiber length 140 μm, average aspect ratio 10.8) were blended at 2% by volume. This formulation was mixed using a Henschel mixer at 1200 rpm for 2 minutes. The obtained resin composition was press-molded at room temperature to form a flat plate of approximately 125 mm x 125 mm x (thickness) 3 mm. At this time, pressing was performed by holding at 15 MPa for 5 minutes and then holding at 30 MPa for 15 minutes. The obtained flat plate was placed in an oven and heated at a temperature of about 350°C to obtain a molded product. The bulk density of the obtained molded article was 2.16 g/cm 3 .
（実施例８）
黒鉛粉を５体積％、等方性ピッチ炭素繊維を５体積％になるように配合した以外は実施例７と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．１５ｇ／ｃｍ３であった。
(Example 8)
A molded article was obtained in the same manner as in Example 7, except that graphite powder was blended at 5% by volume and isotropic pitch carbon fiber was blended at 5% by volume. The bulk density of the obtained molded article was 2.15 g/cm 3 .
（実施例９）
黒鉛粉を２体積％、等方性ピッチ炭素繊維を８体積％になるように配合した以外は実施例７と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．１４ｇ／ｃｍ３であった。
(Example 9)
A molded article was obtained in the same manner as in Example 7, except that graphite powder was blended at 2% by volume and isotropic pitch carbon fiber was blended at 8% by volume. The bulk density of the obtained molded article was 2.14 g/cm 3 .
（比較例３）
等方性ピッチ炭素繊維を使用せず、黒鉛粉を１０体積％になるように配合した以外は実施例７と同様な方法で成形品を得た。得られた成形品のかさ密度は、２．１７ｇ／ｃｍ３であった。
(Comparative example 3)
A molded article was obtained in the same manner as in Example 7, except that isotropic pitch carbon fiber was not used and graphite powder was blended at 10% by volume. The bulk density of the obtained molded article was 2.17 g/cm 3 .
［摺動試験］
実施例１～９及び比較例１～３について摺動試験を実施した。摺動試験は、各成形体から３０ｍｍ×３０ｍｍ×３ｍｍの試験片を切り出し、（株）エー・アンド・デイ製摩擦摩耗試験機「ＭＯＤＥＬ ＥＦＭ－ＩＩＩ－Ｈ」を用いてＪＩＳ Ｋ７２１８Ａ法に準拠して行った。相手材は、ＳＵＳ３０４リング（中心線平均表面粗さＲａ：０．０７μｍ程度）を用いた。試験環境は、２３℃±２℃、５０％ＲＨ±５％ＲＨであった。
[Sliding test]
Sliding tests were conducted for Examples 1 to 9 and Comparative Examples 1 to 3. For the sliding test, a test piece of 30 mm x 30 mm x 3 mm was cut out from each molded body, and tested in accordance with the JIS K7218A method using a friction and wear tester "MODEL EFM-III-H" manufactured by A&D Co., Ltd. I went. A SUS304 ring (center line average surface roughness Ra: about 0.07 μm) was used as the mating material. The test environment was 23°C±2°C, 50%RH±5%RH.
試験（１）：一定の滑り速度で段階的に圧力を上げて摺動させた場合の摩耗量の測定（ＰＶ試験）
この試験では、滑り速度（Ｖ）２ｍ／ｓの下、初期圧力（Ｐ）２５０ｋＰａから、荷重ステップ１２５ｋＰａ／１０分、すなわち、１０分毎に１２５ｋＰａ圧力を上げて、試験を行った。試験片の摩耗量は、試験片を押さえているトルク軸に取り付けられている金属板との変位を、渦流式変位センサーで検知することにより求めた。摩耗量が急に多くなり始める直前の値、すなわち限界ＰＶ値を求めた。ここで、ＰＶ値とは圧力と滑り速度の積である。
Test (1): Measurement of the amount of wear when sliding at a constant sliding speed while increasing the pressure in stages (PV test)
In this test, the test was carried out under a sliding speed (V) of 2 m/s, from an initial pressure (P) of 250 kPa, at a load step of 125 kPa/10 minutes, that is, by increasing the pressure by 125 kPa every 10 minutes. The amount of wear on the test piece was determined by detecting the displacement of the test piece with a metal plate attached to the torque shaft using an eddy current displacement sensor. The value immediately before the amount of wear suddenly started to increase, that is, the limit PV value was determined. Here, the PV value is the product of pressure and sliding speed.
表１～３に限界ＰＶ値、限界ＰＶ値における摩擦係数、及び摺動面近傍の温度を示す。 Tables 1 to 3 show the limit PV value, the friction coefficient at the limit PV value, and the temperature near the sliding surface.
試験（２）：一定の滑り速度及び圧力下に長時間摺動させた場合の摩耗量の測定（摩耗試験）
この試験では、滑り速度２ｍ／ｓの下、圧力５００ｋＰａで４０ｋｍ摺動させ、試験片の比摩耗量、摩擦係数及び摺動面近傍の温度を測定した。なお、比摩耗量とは、一定滑り距離後の摩耗量を、滑り距離及び加重で除した値を意味する。また、試験終了後の相手材ＳＵＳ３０４の平均表面粗さＲａを、表面粗さ計を用いて測定した。
Test (2): Measurement of wear amount when sliding for a long time under constant sliding speed and pressure (wear test)
In this test, the specimen was slid for 40 km at a sliding speed of 2 m/s and a pressure of 500 kPa, and the specific wear amount, friction coefficient, and temperature near the sliding surface of the specimen were measured. Note that the specific wear amount refers to the value obtained by dividing the wear amount after a certain sliding distance by the sliding distance and the load. Moreover, the average surface roughness Ra of the mating material SUS304 after the test was completed was measured using a surface roughness meter.
表１～３に、動摩擦係数、比摩耗量、相手材の表面粗さＲａ及び摺動面近傍の温度を示す。 Tables 1 to 3 show the dynamic friction coefficient, specific wear amount, surface roughness Ra of the mating material, and temperature near the sliding surface.
表１の結果から分かるように、実施例１では比較例１で配合されるガラス繊維のうち、２体積％を等方性ピッチ炭素繊維に置き換えることで限界ＰＶ値が向上している。等方性ピッチ炭素繊維の配合比を５体積％に増やした実施例２ではさらに限界ＰＶ値が向上し、動摩擦係数、比摩耗量、相手材の表面粗さ及び摺動面近傍温度が小さくなり、優れた摺動性を示した。等方性ピッチ炭素繊維の配合比を８体積％に増やした実施例３では限界ＰＶ値は実施例２と同等であったが、動摩擦係数、比摩耗量、相手材の表面粗さ及び摺動面近傍温度が小さくなり、実施例２よりもさらに優れた摺動性を示した。このため、実施例１～３は比較例１と比較し、高速の負荷がかかる場合にも良好な摺動特性を発現し、摩耗量が少なく、相手材の表面粗さを小さくし、摺動面近傍温度を低くすることができるうえに、等方性ピッチ炭素繊維の含有量が多い場合にはさらに好ましいことが理解できる。また、表２～３においても、同様の傾向が見られた。 As can be seen from the results in Table 1, in Example 1, the limit PV value was improved by replacing 2% by volume of the glass fibers blended in Comparative Example 1 with isotropic pitch carbon fibers. In Example 2, in which the blending ratio of isotropic pitch carbon fiber was increased to 5% by volume, the limit PV value was further improved, and the dynamic friction coefficient, specific wear amount, surface roughness of the mating material, and temperature near the sliding surface were reduced. , showed excellent sliding properties. In Example 3, in which the blending ratio of isotropic pitch carbon fiber was increased to 8% by volume, the limit PV value was the same as in Example 2, but the coefficient of dynamic friction, specific wear amount, surface roughness of the mating material, and sliding The temperature near the surface was lower, and the sliding properties were even better than in Example 2. Therefore, in comparison with Comparative Example 1, Examples 1 to 3 exhibit good sliding characteristics even when high-speed loads are applied, have less wear, and reduce the surface roughness of the mating material. It can be understood that it is more preferable if the near-plane temperature can be lowered and the content of isotropic pitch carbon fibers is large. Similar trends were also observed in Tables 2 and 3.
Claims (13)
前記充填剤が、ガラス繊維、二硫化モリブデン、黒鉛、銅及びチタン酸アルカリ金属よりなる群から選ばれる少なくとも１種である、樹脂組成物。 Contains tetrafluoroethylene resin, filler and pitch carbon fiber,
A resin composition, wherein the filler is at least one selected from the group consisting of glass fiber, molybdenum disulfide, graphite, copper, and alkali metal titanate.
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