JP2007192242A - Piston ring made of melt-moldable thermoplastic polyimide resin - Google Patents
Piston ring made of melt-moldable thermoplastic polyimide resin Download PDFInfo
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- JP2007192242A JP2007192242A JP2006008215A JP2006008215A JP2007192242A JP 2007192242 A JP2007192242 A JP 2007192242A JP 2006008215 A JP2006008215 A JP 2006008215A JP 2006008215 A JP2006008215 A JP 2006008215A JP 2007192242 A JP2007192242 A JP 2007192242A
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- polyimide resin
- thermoplastic polyimide
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- 239000009719 polyimide resin Substances 0.000 title claims abstract description 68
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 67
- 239000003921 oil Substances 0.000 claims abstract description 37
- 229920001721 polyimide Polymers 0.000 claims abstract description 21
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 20
- 239000004917 carbon fiber Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 14
- 239000011342 resin composition Substances 0.000 claims abstract description 11
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 9
- 239000000314 lubricant Substances 0.000 claims description 11
- 239000004642 Polyimide Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 22
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- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
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- -1 aromatic diamine compounds Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
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- 125000003118 aryl group Chemical group 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 0 CC(c(cc(C)c(C)c1)c1C(*)=O)=O Chemical compound CC(c(cc(C)c(C)c1)c1C(*)=O)=O 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
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- 239000002964 rayon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YAOMTJDATJQJHF-UHFFFAOYSA-N CCC(C)(CC)c1cc(Oc(cc2)ccc2-c(cc2)ccc2Oc2cc(NC=O)ccc2)ccc1 Chemical compound CCC(C)(CC)c1cc(Oc(cc2)ccc2-c(cc2)ccc2Oc2cc(NC=O)ccc2)ccc1 YAOMTJDATJQJHF-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 125000006160 pyromellitic dianhydride group Chemical group 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
Images
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- Pistons, Piston Rings, And Cylinders (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
本発明は、溶融成形可能な熱可塑性ポリイミド樹脂組成物を溶融成形してなり、耐熱性、シール特性が良好であるピストンリングに関し、かつ該樹脂組成物を用いることで、製造コストが著しく安価なピストンリングに関する。 The present invention relates to a piston ring which is obtained by melt-molding a melt-moldable thermoplastic polyimide resin composition and has good heat resistance and sealing properties, and the use of the resin composition makes the production cost extremely low. It relates to the piston ring.
ピストンリングは、自動車部品、事務機器部品、コンプレッサー部品その他の摺動シール材に用いられている。その性能は、摩擦磨耗特性（自材の磨耗及び相手材の磨耗に対する特性）に優れ、かつシール性に優れていることである。ピストンリングは、通常、ピストン及びシリンダーの間に取り付けられており、金属を特殊処理した材質ものが多数使用されている。 Piston rings are used for sliding seal materials such as automobile parts, office equipment parts, compressor parts, and the like. The performance is excellent in the frictional wear characteristics (characteristics against the wear of the own material and the wear of the mating material) and the sealing performance. The piston ring is usually attached between the piston and the cylinder, and a number of materials made of specially processed metal are used.
近年、燃焼率向上、エネルギー効率の観点からピストンリングのシール性向上が着目されているが、従来の金属材料では弾性率が高く柔軟性に劣るためにシール性をより向上させることに限界が生じている。 In recent years, attention has been focused on improving the sealing performance of piston rings from the viewpoint of improving the combustion rate and energy efficiency. However, since conventional metal materials have high elastic modulus and poor flexibility, there is a limit to further improving sealing performance. ing.
シール性を向上させる手法として、樹脂製のピストンリングを用いることが、特開平１１−３３６９００公報（特許文献１）に記載されている。しかしながら、従来の熱可塑性樹脂では、自動車エンジンの内燃機関に代表されるように耐熱摺動を必要とする部品のシール部分に多く使用され、耐熱性が不足しているために、ピストンリングの材料としては、満足のいくものではなかった。 JP-A-11-336900 (Patent Document 1) describes that a piston ring made of resin is used as a method for improving the sealing performance. However, conventional thermoplastic resins are often used in seal parts of parts that require heat-resistant sliding as typified by internal combustion engines of automobile engines, and are insufficient in heat resistance. As it was not satisfactory.
一方で、熱硬化樹脂は、耐熱性に優れるが、溶融成形加工が出来ないために、ピストンリングに求められるような複雑な形状に対応できない問題が有り、耐熱性と溶融成形性を両立可能な樹脂材料が無かった。
本発明の課題は、溶融成形可能な熱可塑性ポリイミド樹脂組成物を溶融成形してなり、耐熱性、摩擦磨耗特性、シール特性が良好であるピストンリングを得ることにある。また、得られたピストンリングは、ポリイミド樹脂本来の特性である、耐薬品性、耐久性、優れた機械特性などを併せもつ、優れたピストンリングを提供することにある。 An object of the present invention is to obtain a piston ring which is obtained by melt-molding a melt-moldable thermoplastic polyimide resin composition and has good heat resistance, friction wear characteristics, and seal characteristics. Another object of the present invention is to provide an excellent piston ring that has chemical properties, durability, excellent mechanical properties, etc., which are inherent properties of polyimide resin.
本発明のピストンリングは、溶融成形可能な熱可塑性ポリイミド樹脂と炭素繊維からなる樹脂組成物に対し特定量の潤滑材を含有することによって提供される。具体的には以下の［１］〜［５］の記載により提供される。
［１］ 溶融成形可能な熱可塑性ポリイミド樹脂５０〜９９重量部と炭素繊維５０〜１重量部からなる樹脂組成物１００重量部に対し、フッ素樹脂、グラファイト、オイル、および二硫化モリブデンからなる潤滑材を少なくとも１成分を総量０．５〜５０重量部含有する熱可塑性ポリイミド樹脂組成物を溶融成形してなることを特徴とするピストンリング。
［２］ 熱可塑性ポリイミド樹脂が、化学式（１）の繰り返し構造単位を有する溶融成形可能な熱可塑性ポリイミド樹脂である前記［１］記載のピストンリング。
The piston ring of the present invention is provided by containing a specific amount of a lubricant with respect to a resin composition comprising a thermoplastic polyimide resin and carbon fiber that can be melt-molded. Specifically, the following [1] to [5] are provided.
[1] Lubricant comprising fluororesin, graphite, oil, and molybdenum disulfide with respect to 100 parts by weight of a resin composition comprising 50 to 99 parts by weight of a thermoplastic polyimide resin capable of being melt-molded and 50 to 1 part by weight of carbon fiber A piston ring obtained by melt-molding a thermoplastic polyimide resin composition containing at least one component in a total amount of 0.5 to 50 parts by weight.
[2] The piston ring according to [1], wherein the thermoplastic polyimide resin is a melt-moldable thermoplastic polyimide resin having a repeating structural unit of the chemical formula (1).
（化学式（１）において、Ｘは直接結合、−ＳＯ２−、−ＣＯ―、−Ｃ（ＣＨ３）２−、−Ｃ（ＣＦ３）２−、または−Ｓ―であり、Ｒ１、Ｒ２、Ｒ３、およびＲ４は、それぞれ水素原子、アルキル基、アルコシキ基、ハロゲン化アルキル基、ハロゲン化アルコキシ基またはハロゲン原子であり、またＹは、下記化学式（２）からなる群より選ばれる基である。） (In the chemical formula (1), X is a direct bond, —SO 2 —, —CO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, or —S—, and R1, R2, R3 and R4 are each a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a halogenated alkoxy group or a halogen atom, and Y is a group selected from the group consisting of the following chemical formula (2). )
［３］ 熱可塑性ポリイミド樹脂が、化学式（３）の繰り返し構造単位を有する溶融成形可能な熱可塑性ポリイミド樹脂である前記［１］記載のピストンリング。 [3] The piston ring according to [1], wherein the thermoplastic polyimide resin is a melt-moldable thermoplastic polyimide resin having a repeating structural unit of the chemical formula (3).
［４］ 熱可塑性ポリイミド樹脂が、化学式（４）および化学式（５）の繰り返し構造単位を有する溶融成形可能な熱可塑性ポリイミド共重合体樹脂である前記［１］記載のピストンリング。 [4] The piston ring according to [1], wherein the thermoplastic polyimide resin is a melt-moldable thermoplastic polyimide copolymer resin having repeating structural units represented by chemical formulas (4) and (5).
（ただし、化学式（４）中のｍおよび化学式（５）中のｎは、ポリイミド共重合体の共重合比を示し、ｍ／ｎ＝４から９９（モル％／モル％）の範囲である。）
［５］ 熱可塑性ポリイミド樹脂が、化学式（６）の繰り返し構造単位を有する溶融成形可能な熱可塑性ポリイミド樹脂である前記［１］記載のピストンリング。
(However, m in the chemical formula (4) and n in the chemical formula (5) indicate a copolymerization ratio of the polyimide copolymer, and m / n = 4 to 99 (mol% / mol%). )
[5] The piston ring according to [1], wherein the thermoplastic polyimide resin is a melt-moldable thermoplastic polyimide resin having a repeating structural unit represented by chemical formula (6).
溶融成形可能な熱可塑性ポリイミド樹脂と炭素繊維とからなる樹脂組成物に対し、特定量のフッ素樹脂及びグラファイト、オイル、および二硫化モリブデンからなる潤滑材を少なくとも１成分を含有する熱可塑性ポリイミド樹脂組成物を溶融成形してなるピストンリングは、耐熱性、自材及び相手材の磨耗が著しく少ないという摩擦磨耗特性、およびシール性で優れているので、自動車分野を代表例とする様々な分野の内燃機関で使用されるシール目的のピストンリングとして極めて有用であり、かつ様々な応用用途が可能である。 Thermoplastic polyimide resin composition containing at least one component of a specific amount of fluororesin and a lubricant comprising graphite, oil, and molybdenum disulfide with respect to a resin composition comprising melt-moldable thermoplastic polyimide resin and carbon fiber Piston rings formed by melt-molding products are excellent in heat resistance, frictional wear characteristics that the wear of their own material and counterpart material is remarkably low, and sealing performance. It is extremely useful as a piston ring for sealing used in engines, and can be used in various applications.
以下に、本発明を詳細に説明する。
［熱可塑性ポリイミド樹脂］
本発明における溶融成形可能な熱可塑性ポリイミド樹脂とは、加重たわみ温度２００℃以上を有するポリイミド樹脂のことである。
The present invention is described in detail below.
[Thermoplastic polyimide resin]
The melt-moldable thermoplastic polyimide resin in the present invention is a polyimide resin having a weighted deflection temperature of 200 ° C. or higher.
本発明において用いられる熱可塑性ポリイミド樹脂の対数粘度は特に限定されないが、一般的には０．３５〜１．３０ｄｌ／ｇ、より好ましくは０．４０〜１．２０の範囲が好ましい。対数粘度が０．３５ｄｌ／ｇ未満になると、熱可塑性ポリイミド樹脂の分子量が小さく、機械強度に劣る。また、対数粘度が１．３０ｄｌ／ｇ以上のものは、熱可塑性ポリイミド樹脂の分子量が大きすぎ、成形体を射出成形や押出成形によって製造するための流動性に難が生じる。 Although the logarithmic viscosity of the thermoplastic polyimide resin used in the present invention is not particularly limited, it is generally 0.35 to 1.30 dl / g, more preferably 0.40 to 1.20. When the logarithmic viscosity is less than 0.35 dl / g, the molecular weight of the thermoplastic polyimide resin is small and the mechanical strength is poor. In addition, when the logarithmic viscosity is 1.30 dl / g or more, the molecular weight of the thermoplastic polyimide resin is too large, resulting in difficulty in fluidity for producing a molded article by injection molding or extrusion molding.
本発明におけるポリマーの対数粘度の測定は、パラクロロフェノール／フェノール（９０／１０重量比）の混合溶媒中、濃度０．５ｇ／１００ｍｌの溶媒で２００℃に加熱した後、３５℃に冷却して測定される。対数粘度については、‘高分子ハンドブック’朝倉書店出版、日本分析化学学会片１９９５年度初版Ｐ５８にその定義が記載されている。 In the present invention, the logarithmic viscosity of the polymer was measured by heating to 200 ° C. with a solvent having a concentration of 0.5 g / 100 ml in a mixed solvent of parachlorophenol / phenol (90/10 weight ratio) and then cooling to 35 ° C. Measured. The definition of the logarithmic viscosity is described in “Polymer Handbook” published by Asakura Shoten, Japan Analytical Chemistry Society, 1995, first edition P58.
本発明において、溶融成形可能な熱可塑性ポリイミド樹脂とは、上記条件を満たせば特に限定されないが、好ましい例として、上記の化学式（１）、化学式（２）、化学式（３）、化学式（４）と化学式（５）とで表される共重合体、および化学式（６）で表される５種の熱可塑性ポリイミド樹脂が挙げられる。 In the present invention, the melt-moldable thermoplastic polyimide resin is not particularly limited as long as the above conditions are satisfied. Preferred examples include the chemical formula (1), the chemical formula (2), the chemical formula (3), and the chemical formula (4). And a copolymer represented by the chemical formula (5) and five thermoplastic polyimide resins represented by the chemical formula (6).
上記の化学式（１）〜（６）で表される５種の熱可塑性ポリイミド樹脂は、それらの構造式に示されている相当する芳香族ジアミン化合物と芳香族テトラカルボン酸二無水物とを原料として、有機溶媒の存在下または非存在下で反応させ、得られたポリアミド酸を化学式にまたは熱的にイミド化して製造できる。これらの具体的製造方法は、公知であるポリイミドの製造方法の条件をすべて利用することができる。 The five types of thermoplastic polyimide resins represented by the above chemical formulas (1) to (6) are made from the corresponding aromatic diamine compounds and aromatic tetracarboxylic dianhydrides shown in their structural formulas. As described above, the reaction can be carried out in the presence or absence of an organic solvent, and the resulting polyamic acid can be produced by chemical or thermal imidization. These specific production methods can utilize all the conditions of the known polyimide production methods.
化学式（１）で表される熱可塑性ポリイミド樹脂を取上げて、より具体的に説明すると、下記化学式（７）の芳香族ジアミン化合物と下記化学式（８）の芳香族テトラカルボン酸二無水物とを原料として用いる。 More specifically, taking a thermoplastic polyimide resin represented by the chemical formula (1) and explaining it more specifically, an aromatic diamine compound of the following chemical formula (7) and an aromatic tetracarboxylic dianhydride of the following chemical formula (8): Used as a raw material.
（化学式（７）において、Ｘ、およびＲ１〜Ｒ４は前記同様である。） (In the chemical formula (7), X and R1 to R4 are the same as above.)
（化学式（８）において、Ｙは前記同様である。）
化学式（１）及び（７）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４の具体例は、水素原子、メチル基、エチル基などのアルキル基、メトキシ基、エトキシ基などのアルコキシ基、フルオロメチル基、トリフルオロメチル基などのハロゲン化アルキル基、フルオロメトキシ基などのハロゲン化アルコキシ基、塩素原子、フッ素原子などのハロゲン原子が挙げられる。好ましくは、水素原子である。
(In chemical formula (8), Y is the same as above.)
In the chemical formulas (1) and (7), specific examples of R1, R2, R3, and R4 include a hydrogen atom, an alkyl group such as a methyl group and an ethyl group, an alkoxy group such as a methoxy group and an ethoxy group, a fluoromethyl group, and a trimethyl group. Examples thereof include halogenated alkyl groups such as a fluoromethyl group, halogenated alkoxy groups such as a fluoromethoxy group, and halogen atoms such as a chlorine atom and a fluorine atom. Preferably, it is a hydrogen atom.
化学式（１）及び（８）中、Ｙは、式（２）で表される４価の芳香族基であり、好ましくはベンゼン環であり、その場合、化学式（８）の芳香族テトラカルボン酸二無水物はピロメリット酸二無水物である。 In chemical formulas (1) and (8), Y is a tetravalent aromatic group represented by formula (2), preferably a benzene ring, in which case aromatic tetracarboxylic acid of chemical formula (8) The dianhydride is pyromellitic dianhydride.
本発明において、好ましく用いられる溶融成形可能な熱可塑性ポリイミド樹脂は、上記の化学式（１）、化学式（２）、化学式（３）、化学式（４）と化学式（５）とで表される共重合体、および化学式（６）で表される５種である。 In the present invention, the thermoplastic polyimide resin that can be preferably melt-molded is a co-polymer represented by the above chemical formula (1), chemical formula (2), chemical formula (3), chemical formula (4), and chemical formula (5). There are 5 types represented by the union and chemical formula (6).
本発明において、好ましく用いられる溶融成形可能な熱可塑性ポリイミド樹脂５種を製造するに際し、本発明の課題を害さない範囲で、原料となる他の芳香族ジアミン化合物や芳香族テトラカルボン酸二無水物を一種または複数を組み合わせて用いて共重合化することができる。 In the present invention, when producing five types of melt-moldable thermoplastic polyimide resins that are preferably used, other aromatic diamine compounds and aromatic tetracarboxylic dianhydrides as raw materials are used as long as they do not impair the problems of the present invention. Can be copolymerized using one or a combination of two or more.
また、本発明で好ましく用いられる溶融成形可能な熱可塑性ポリイミド樹脂同士、または他のポリイミド樹脂を用いて、本発明の課題を害さない範囲で任意にポリマーブレンドして用いても良い。 Further, melt-moldable thermoplastic polyimide resins preferably used in the present invention, or other polyimide resins may be used by arbitrarily polymer blending within a range that does not impair the problems of the present invention.
本発明において、好ましく用いられる溶融成形可能な熱可塑性ポリイミド樹脂５種の中で、特記すべきことは以下の通りである。 Of the five types of melt-moldable thermoplastic polyimide resins preferably used in the present invention, the following should be noted.
化学式（３）のポリイミド樹脂は、三井化学株式会社製：商品名ＡＵＲＵＭ（登録商標）として購入可能である。 The polyimide resin of the chemical formula (3) can be purchased as a product name AURUM (registered trademark) manufactured by Mitsui Chemicals, Inc.
化学式（４）と化学式（５）とで表されるポリイミド共重合体樹脂において、共重合比であるｍ／ｎは、４から９９（モル％／モル％）の範囲であるが、より好ましくは５から９９（モル％／モル％）、更に好ましくは６から９９（モル％／モル％）である。 In the polyimide copolymer resin represented by the chemical formula (4) and the chemical formula (5), the copolymerization ratio m / n is in the range of 4 to 99 (mol% / mol%), more preferably. 5 to 99 (mol% / mol%), more preferably 6 to 99 (mol% / mol%).
［炭素繊維］
本発明に用いられる炭素繊維は、原料／製造方法により分類すると、レーヨン系、ポリアクリロニトリル（ＰＡＮ）系、ピッチ系、気相成長炭素繊維（ＶＧＣＦ）などが挙げられる。好ましくは、レーヨン系、ＰＡＮ系、ピッチ系が挙げられる。炭素繊維の使用量は、熱可塑性ポリイミド樹脂と炭素繊維との合計量１００重量部中に５０〜１重量部である。その量より上回ると、摺動時に樹脂組成物中の炭素繊維が相手金属を著しく磨耗させ好ましくない。好ましくは、４０〜１重量部である。
[Carbon fiber]
When the carbon fibers used in the present invention are classified according to the raw material / manufacturing method, rayon-based, polyacrylonitrile (PAN) -based, pitch-based, vapor-grown carbon fiber (VGCF) and the like can be mentioned. Preferably, rayon type, PAN type, and pitch type are mentioned. The usage-amount of carbon fiber is 50-1 weight part in 100 weight part of total amounts of a thermoplastic polyimide resin and carbon fiber. If the amount exceeds this amount, the carbon fibers in the resin composition will wear out the other metal significantly during sliding, which is not preferable. Preferably, it is 40-1 weight part.
［フッ素樹脂］
本発明に用いられるフッ素樹脂は、次の（ａ）〜（ｆ）からなる群より選ばれた少なくとも１種であることが好ましい。
（ａ）分子内に、化学式−（ＣＦ２ＣＦ２）−で表される繰り返し構造単位を有する４フッ化エチレン樹脂。
（ｂ）分子内に、化学式−（ＣＦ２ＣＦ２）−および、化学式−〔ＣＦ（ＣＦ３）ＣＦ２〕−で表される繰り返し構造単位を有する４フッ化エチレン樹脂―六フッ化プロピレン共重合樹脂。
（ｃ）分子内に、化学式−（ＣＦ２ＣＦ２）及び化学式−〔ＣＦ（ＯＣｍＦ２ｍ＋１）ＣＦ２〕 （式中、ｍは正の整数）で表される繰り返し構造単位を有する４フッ化エチレン−パーフロロアルキルビニルエーテル共重合樹脂。
（ｄ）分子内に、化学式−（ＣＦ２ＣＦ２）−および化学式−（ＣＨ２ＣＨ２）−で表される繰り返し構造単位を有する４フッ化エチレンーエチレン共重合樹脂。
（ｅ）分子内に、化学式 −（ＣＨ２ＣＨ２）− および 化学式 −（ＣＦＣｌＣＦ２）−で表される繰り返し構造単位を有する３フッ化塩化エチレン−エチレン共重合樹脂。
（ｆ）分子内に、化学式−（ＣＦ２ＣＨ２）−で表される繰り返し構造単位を有するフッ化ビニリデン樹脂。
[Fluororesin]
The fluororesin used in the present invention is preferably at least one selected from the group consisting of the following (a) to (f).
(A) A tetrafluoroethylene resin having a repeating structural unit represented by the chemical formula-(CF 2 CF 2 )-in the molecule.
(B) A tetrafluoroethylene resin-propylene hexafluoride copolymer having a repeating structural unit represented by the chemical formula-(CF 2 CF 2 )-and the chemical formula-[CF (CF 3 ) CF 2 ]-in the molecule. Polymerized resin.
(C) In the molecule, there is a 4-fluoro having a repeating structural unit represented by the chemical formula-(CF 2 CF 2 ) and the chemical formula-[CF (OC m F2 m + 1 ) CF 2 ] (where m is a positive integer). Ethylene-perfluoroalkyl vinyl ether copolymer resin.
(D) A tetrafluoroethylene-ethylene copolymer resin having a repeating structural unit represented by a chemical formula — (CF 2 CF 2 ) — and a chemical formula — (CH 2 CH 2 ) — in the molecule.
(E) A trifluorochloroethylene-ethylene copolymer resin having a repeating structural unit represented by a chemical formula — (CH 2 CH 2 ) — and a chemical formula — (CFClCF 2 ) — in the molecule.
(F) Vinylidene fluoride resin having a repeating structural unit represented by the chemical formula — (CF 2 CH 2 ) — in the molecule.
［グラファイト］
本発明に用いられるグラファイトは、原料／製造方法により分類すると、人造黒鉛、天然黒鉛（鱗片状黒鉛、鱗状黒鉛、土状黒鉛）が挙げられるが、特に制限なく、いずれも使用することができる。但し、本発明に用いられるグラファイトは、炭素の純度が高いものが好ましく、固定炭素の純度が９５％以上のものがより好ましい。
[Graphite]
The graphite used in the present invention can be classified into artificial graphite and natural graphite (scale-like graphite, scale-like graphite, earth-like graphite) when classified according to the raw material / manufacturing method, and any of them can be used without any particular limitation. However, the graphite used in the present invention preferably has a high carbon purity, and more preferably has a fixed carbon purity of 95% or more.
［オイル］
本発明に用いられるオイルは、熱重量減量測定（ＤＴＡ−ＴＧ）において、３００℃における熱重量減量が１０重量％以下である耐熱性の優れたオイルが好ましく用いられる。上記を満足する優れた耐熱性を有すれば、オイルの種類に特に制限はないが、好ましい具体例は、シリコンオイル、パーフルオロポリエーテル油、フェニルエーテル油、フッ素系オイルが挙げられる。但し、これからのオイルは、耐熱性の優れたオイルであることが当然であるが、本樹脂組成物の増粘を促進しないものであることも条件である。耐熱性の劣るオイルを使用すると、オイルの分解により発生するガスボイドが成形品内に残存し、その結果、磨耗特性等の特性に悪影響を及ぼす。
[oil]
As the oil used in the present invention, an oil having excellent heat resistance, in which the thermal weight loss at 300 ° C. is 10% by weight or less in the thermal weight loss measurement (DTA-TG) is preferably used. The type of oil is not particularly limited as long as it has excellent heat resistance satisfying the above, but preferred specific examples include silicon oil, perfluoropolyether oil, phenyl ether oil, and fluorine oil. However, it is natural that the future oil is an oil having excellent heat resistance, but it is also a condition that it does not promote the thickening of the resin composition. When oil having poor heat resistance is used, gas voids generated by the decomposition of the oil remain in the molded product, and as a result, the properties such as wear characteristics are adversely affected.
［二硫化モリブデン］
本発明に用いられる二硫化モリブデンは、天然の鉱物を精製し、高純度化した市販品が使用可能である。
[Molybdenum disulfide]
As the molybdenum disulfide used in the present invention, a commercially available product obtained by purifying a natural mineral and purifying it can be used.
［潤滑材の量］
本発明において、熱可塑性ポリイミド樹脂と炭素繊維からなるポリイミド樹脂組成物にフッ素樹脂、グラファイト、オイル、および二硫化モリブデンからなる潤滑材を少なくとも１成分を配合することによりポリイミド樹脂本来の柔軟性を発現しつつ、より耐熱性、摩擦磨耗特性に優れたピストンリングが得られる。そしてその特性は、それぞれの最適組成内でないと発現されない。フッ素樹脂、グラファイト、オイル、二硫化モリブデンなどの潤滑材の量は、ポリイミド樹脂と炭素繊維との総量１００重量部に対して、０．５〜５０重量部である。このましくは０．５〜４５重量部、さらに好ましくは０．５〜４０重量部である。５０重量部を超えると樹脂の磨耗が著しく増大し好ましくない。０．５重量部未満では、摩擦磨耗特性に優れたピストンリングが得らない。
[Amount of lubricant]
In the present invention, the polyimide resin composition consisting of thermoplastic polyimide resin and carbon fiber exhibits the inherent flexibility of the polyimide resin by blending at least one component with a lubricant consisting of fluororesin, graphite, oil, and molybdenum disulfide. On the other hand, a piston ring having more excellent heat resistance and frictional wear characteristics can be obtained. And the characteristic is not expressed unless it is in each optimal composition. The amount of the lubricant such as fluororesin, graphite, oil, and molybdenum disulfide is 0.5 to 50 parts by weight with respect to 100 parts by weight of the total amount of polyimide resin and carbon fiber. This is preferably 0.5 to 45 parts by weight, more preferably 0.5 to 40 parts by weight. If it exceeds 50 parts by weight, the wear of the resin is remarkably increased, which is not preferable. If it is less than 0.5 part by weight, a piston ring having excellent frictional wear characteristics cannot be obtained.
［その他の添加材］
本発明のポリイミド樹脂組成物には必要に応じて本樹脂組成物の特性を損なわない範囲内で、ガラス繊維、チタン酸カリウム繊維、ホウ酸アルミ繊維、金属繊維、セラミック繊維、ボロン繊維、炭化ケイ素繊維、アスベスト繊維、ロックウール繊維、アラミド繊維からなる群より少なくとも１種以上を含有してもよい。
[Other additives]
The polyimide resin composition of the present invention may be made of glass fiber, potassium titanate fiber, aluminum borate fiber, metal fiber, ceramic fiber, boron fiber, silicon carbide as long as the characteristics of the resin composition are not impaired as required. You may contain at least 1 or more types from the group which consists of a fiber, asbestos fiber, rock wool fiber, and an aramid fiber.
また、本発明のポリイミド樹脂組成物には、必要に応じて、マイカ、ガラスビーズ、クレー、シリカ、アルミナ、ケイソウ、土、水和アルミナ、シラスバルーン、カーボンナノチューブ、炭酸カルシウム、ハイドロタルサイトなどの充填剤、あるいは滑剤、離型剤、安定剤、着色剤、結晶核剤、酸化防止剤、老化防止剤など一般的に樹脂に添加して用いられる材料を１種以上含有してもよい。 In addition, the polyimide resin composition of the present invention includes mica, glass beads, clay, silica, alumina, diatomaceous earth, soil, hydrated alumina, shirasu balloon, carbon nanotube, calcium carbonate, hydrotalcite, etc. One or more materials that are generally used by adding to a resin, such as fillers, lubricants, mold release agents, stabilizers, colorants, crystal nucleating agents, antioxidants, and anti-aging agents may be contained.
更に、各種種液晶ポリマー、ポリエーテルイミド、ポリエーテルニトリル、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルケトンケトン、ポリエーテルケトンエーテルケトンケトン、ポリアミドイミド、ポリエーテルスルホン、ポリスルホン、ポリアリレート及び／又はポリフェニレンスルフィドなどの熱可塑性樹脂、エポキシ樹脂、ポリベンゾイミダゾール樹脂、ポリイミド樹脂などの熱硬化性樹脂を本発明のポリイミド樹脂組成物の特性を損なわない範囲で併用してよい。 Furthermore, various kinds of liquid crystal polymers, polyetherimide, polyethernitrile, polyetherketone, polyetheretherketone, polyetherketoneketone, polyetherketoneetherketoneketone, polyamideimide, polyethersulfone, polysulfone, polyarylate and / or Thermosetting resins such as polyphenylene sulfide and the like, epoxy resins, polybenzimidazole resins, and polyimide resins may be used in combination as long as the characteristics of the polyimide resin composition of the present invention are not impaired.
［ポリイミド樹脂組成物の製法］
本発明の熱可塑性ポリイミド樹脂組成物の製造は、特に限定されず、公知の製造方法が全て用いることができる。通常、単軸あるいは多軸の押出機を用いて連続的に行っても、混錬ロール、ブラベンダー等のバッチ式方法も実施可能である。加工温度は、用いるポリイミド樹脂の種類によって異なる。すなわち、それらのガラス転移温度や融点より求める、あるいは溶融流動開始する温度をメルトインデックスス計やフローテスターで求めて、その温度を参考するなどにより、更には実際に加工を行いながら、決定することができる。おおむね、ポリイミド樹脂の場合は、３８０〜４４０℃である。
[Production method of polyimide resin composition]
The production of the thermoplastic polyimide resin composition of the present invention is not particularly limited, and all known production methods can be used. Usually, even if it carries out continuously using a single screw or a multi-screw extruder, batch methods, such as a kneading roll and a Brabender, can also be implemented. The processing temperature varies depending on the type of polyimide resin used. That is, determine from the glass transition temperature and melting point, or determine the temperature at which the melt flow starts with a melt index meter or a flow tester, and refer to the temperature, and further determine the actual processing. Can do. Generally, in the case of polyimide resin, the temperature is 380 to 440 ° C.
［ピストンリングの成形］
本発明のピストンリングの成形は、特に限定されず、公知の成形方法が全て用いることができる。通常、主に射出成形により成形加工することによって各種用途に使用が可能である。射出成形によって得られた成形品に切削加工を施し、最終形状に仕上げることで使用することも可能である。その他、押出成形、圧縮成形、及びトランスファー成形等の従来から知られる方法で成形加工することも可能である。成形加工温度は、上記の熱可塑性ポリイミド樹脂組成物の製造における加工温度と同様である。
[Molding piston ring]
The molding of the piston ring of the present invention is not particularly limited, and all known molding methods can be used. Usually, it can be used for various applications by molding mainly by injection molding. It can also be used by cutting the molded product obtained by injection molding to finish it into a final shape. In addition, it is also possible to perform molding by a conventionally known method such as extrusion molding, compression molding, and transfer molding. The molding processing temperature is the same as the processing temperature in the production of the thermoplastic polyimide resin composition.
［実施例］
以下、実施例によって本発明を具体的に説明するが、本発明はこれら実施例に限定されるものではない。また、実施例における樹脂組成物の評価は以下の要領で実施した。
１）磨耗量（自材の磨耗量、相手材の磨耗量）
鈴木式の摩擦磨耗試験に準じ、相手材としてＦＣ材（ＦＣＤ４５）を用い、室温下、オイル中（エンジンオイル）、６時間後の磨耗量を測定した。面圧は３ＭＰａ、速度は２５０ｍ／ｍｉｎにて行った。
２）摩擦係数
鈴木式の摩擦磨耗試験に準じ、相手材としてＦＣ材（ＦＣＤ４５）を用い、室温下、オイル中（エンジンオイル）、６時間後の磨摩擦係数を求めた。この時の、面圧は３ＭＰａ、速度は２５０ｍ／ｍｉｎにて行った。
３）限界ＰＶ値
鈴木式の摩擦磨耗試験に準じ、相手材としてＦＣ材（ＦＣＤ４５）を用い、室温下、速度（Ｖ）２５０ｍ／ｍｉｎ、オイル中（エンジンオイル）、６時間試験を行い樹脂組成物が座屈しない上限の面圧（Ｐ）を求め、そのときのＰ×Ｖ［（ＭＰａ）×（ｍ／ｍｉｎ）］の値を求めた。
４）オイル漏れ量（シール性）
直径５２ｍｍの熱可塑性ポリイミド樹脂ピストンリング（幅２．３ｍｍ、厚さ２．３ｍｍ、合い口０．３ｍｍ）をＦＣ材（鋳鉄 ＦＣＤ４５）製ピストン、ＦＣ材（鋳鉄 ＦＣＤ４５）製ハウジングで構成された往復運動部分に装着し、オイルとしてトヨタ純正エンジンオイルを用い、２ＭＰａの油圧と、ピストンストローク １００ｍｍ、２０００ｒｐｍの往復運動を与え、１００時間連続して試験を実施した。オイル温度は、１２０℃であった。１００時間後のリング磨耗量（側面、外周面、軸溝）、ハウジング磨耗量を測定した。オイル漏れ量は８０時間〜１００時間の間のオイル漏れ量より、１分間あたりの漏れ量（ｃｃ／ｍｉｎ）を算出した。オイル漏れ量を計測することによりピストンリングのシール性が把握可能である。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. Moreover, evaluation of the resin composition in an Example was implemented in the following ways.
1) Amount of wear (amount of wear of own material, amount of wear of mating material)
In accordance with the Suzuki friction wear test, FC material (FCD45) was used as the counterpart material, and the amount of wear in oil (engine oil) at room temperature was measured after 6 hours. The surface pressure was 3 MPa and the speed was 250 m / min.
2) Friction coefficient FC material (FCD45) was used as the counterpart material according to the Suzuki friction wear test, and the friction coefficient after 6 hours at room temperature in oil (engine oil) was determined. At this time, the surface pressure was 3 MPa and the speed was 250 m / min.
3) Limit PV value According to Suzuki's frictional wear test, FC material (FCD45) is used as the counterpart material, speed (V) 250m / min, in oil (engine oil), 6 hours test at room temperature, resin composition The upper limit surface pressure (P) at which the object does not buckle was determined, and the value of P × V [(MPa) × (m / min)] at that time was determined.
4) Oil leakage (sealability)
52mm diameter thermoplastic polyimide resin piston ring (2.3mm wide, 2.3mm thick, 0.3mm mating joint) made of FC material (cast iron FCD45) piston and FC material (cast iron FCD45) housing The test was carried out for 100 hours continuously, using Toyota engine oil as oil, applying 2MPa hydraulic pressure, reciprocating motion of piston stroke 100mm, 2000rpm. The oil temperature was 120 ° C. The ring wear amount (side surface, outer peripheral surface, shaft groove) and housing wear amount after 100 hours were measured. The amount of oil leakage was calculated from the amount of oil leakage between 80 hours and 100 hours (cc / min) per minute. By measuring the amount of oil leakage, the sealing performance of the piston ring can be grasped.
［実施例１〜５］
化学式（３）の熱可塑性ポリイミド樹脂（三井化学（株）社製、商品名オーラム（登録商標）ＰＤ４５０）とフッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）を表１に示すような割合でミキサーを用いてドライブレンドし、その後、２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表１に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表１に示す。
[Examples 1 to 5]
A thermoplastic polyimide resin of chemical formula (3) (Mitsui Chemicals, Inc., trade name Aurum (registered trademark) PD450) and a fluororesin (Asahi Glass Fluoropolymers, trade name, Aflon PTFE L-180) are shown. 1 is dry-blended using a mixer at a ratio shown in FIG. 1, and then PAN-based carbon fiber (trade name Besfight HTA-C6-UH, manufactured by Toho Tenax Co., Ltd.) in Table 1 using a twin-screw extruder. It is supplied from the side feeder at the rate shown and extruded and granulated at 400 to 420 ° C., and the resulting pellets are supplied to an injection molding machine (cylinder temperature 400 to 420 ° C., injection pressure 230 MPa, mold temperature 190 ° C.). A test piece defined by each test method described above was molded. The results are shown in Table 1.
［実施例６］
潤滑材としてフッ素樹脂の替わりにオイル（信越化学 シリコンオイル ＫＦ９６５−１００）を用いる以外は、実施例１〜５と同様な方法によって行った。結果を表１に示す。
[Example 6]
It was carried out by the same method as in Examples 1 to 5, except that oil (Shin-Etsu Chemical Silicon Oil KF965-100) was used instead of fluororesin as the lubricant. The results are shown in Table 1.
［実施例７］
潤滑材としてフッ素樹脂の替わりにグラファイト（日本黒鉛 ＡＣＰ）を用いる以外は、実施例１〜５と同様な方法によって行った。結果を表１に示す。
[Example 7]
The same method as in Examples 1 to 5 was performed except that graphite (Nippon Graphite ACP) was used instead of the fluororesin as the lubricant. The results are shown in Table 1.
［実施例８］
潤滑材としてフッ素樹脂の替わりに市販されている二硫化モリブデンを用いる以外は、実施例１〜５と同様な方法によって行った。結果を表１に示す。
[Example 8]
It carried out by the same method as Examples 1-5 except using commercially available molybdenum disulfide instead of a fluororesin as a lubricant. The results are shown in Table 1.
［実施例９］
表１の実施例９に示す組成物を用い、かつ炭素繊維としてピッチ系炭素繊維（クレハ化学社製：Ｍ１０７）を用いる以外は実施例1〜５と同様な方法によって行った。結果を表１に示す。
[Example 9]
It was carried out by the same method as in Examples 1 to 5 except that the composition shown in Example 9 in Table 1 was used and pitch-based carbon fiber (manufactured by Kureha Chemical Co., Ltd .: M107) was used as the carbon fiber. The results are shown in Table 1.
［実施例１０］
表１の実施例１０に示す組成物を用い、かつフッ素樹脂としてフッ素樹脂（ダイキン工業社製：ルブロンＬ−５）を用いる以外は実施例１〜５と同様な方法によって行った。結果を表１に示す。
[Example 10]
The same procedure as in Examples 1 to 5 was performed except that the composition shown in Example 10 of Table 1 was used and a fluororesin (Daikin Industries, Ltd .: Lubron L-5) was used as the fluororesin. The results are shown in Table 1.
［実施例１１〜１５］
化学式（４）および（５）で示される熱可塑性ポリイミド共重合体樹脂（三井化学（株）社製、商品名オーラム（登録商標）ＰＤ５００Ａ）とフッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）表２に示すような割合でミキサーを用いてドライブレンドし、その後２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表２に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表２に示す。
[Examples 11 to 15]
Thermoplastic polyimide copolymer resin represented by chemical formulas (4) and (5) (Mitsui Chemicals Co., Ltd., trade name Aurum (registered trademark) PD500A) and fluororesin (Asahi Glass Fluoropolymers Co., Ltd., commercial product) Name Aflon PTFE L-180) Dry blend using a mixer at a ratio as shown in Table 2, and then using a twin screw extruder, PAN-based carbon fiber (manufactured by Toho Tenax Co., Ltd., trade name Besfight HTA-) C6-UH) Supplied from the side feeder at a rate as shown in Table 2, extruded and granulated at 400 to 420 ° C., and the resulting pellets were injection molded (cylinder temperature 400 to 420 ° C., injection pressure 230 MPa, mold) The test piece defined in each test method described above was molded. The results are shown in Table 2.
［実施例１６〜２０］
芳香族ジアミン化合物として１，３−ビス（４−アミノフェノキシ）ベンゼン、芳香族テトラカルボン酸二無水物として３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を原料とし、得られたポリアミド酸を熱的に熱的にイミド化して、化学式（６）の熱可塑性ポリイミド樹脂を得た。得られたポリイミド粉の対数粘度（ηｉｎｈ）は、０．９ｄｌ／ｇであった。この化学式（６）である熱可塑性ポリイミド樹脂とフッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）表３に示すような割合でミキサーを用いてドライブレンドし、その後２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表３に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表３に示す。
[Examples 16 to 20]
Obtained using 1,3-bis (4-aminophenoxy) benzene as an aromatic diamine compound and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as raw materials as an aromatic tetracarboxylic dianhydride The resulting polyamic acid was thermally imidized thermally to obtain a thermoplastic polyimide resin of the chemical formula (6). The logarithmic viscosity (ηinh) of the obtained polyimide powder was 0.9 dl / g. The thermoplastic polyimide resin having the chemical formula (6) and the fluororesin (manufactured by Asahi Glass Fluoropolymers Co., Ltd., trade name Aflon PTFE L-180) were dry blended using a mixer at the ratio shown in Table 3, and then 2 PAN-based carbon fiber (manufactured by Toho Tenax Co., Ltd., trade name Besfight HTA-C6-UH) was supplied from the side feeder at a rate as shown in Table 3 and extruded at 400 to 420 ° C. The pellets obtained were granulated and supplied to an injection molding machine (cylinder temperature of 400 to 420 ° C., injection pressure of 230 MPa, mold temperature of 190 ° C.), and the test pieces defined in each test method described above were molded. The results are shown in Table 3.
［比較例１〜３］
化学式（３）の熱可塑性ポリイミド樹脂（三井化学（株）社製、商品名オーラム（登録商標）ＰＤ４５０）と フッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）表４に示すような割合でミキサーを用いてドライブレンドし、その後２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表４に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表４に示す。
[Comparative Examples 1-3]
Thermoplastic polyimide resin of chemical formula (3) (Mitsui Chemicals, Inc., trade name: Aurum (registered trademark) PD450) and fluororesin (Asahi Glass Fluoropolymers, Inc., trade name: Aflon PTFE L-180) Table 4 As shown in Table 4, PAN-based carbon fiber (product name: Besfight HTA-C6-UH, manufactured by Toho Tenax Co., Ltd.) using a twin-screw extruder is used. It is supplied from the side feeder at a proper ratio, extruded and granulated at 400 to 420 ° C., and the obtained pellets are supplied to an injection molding machine (cylinder temperature 400 to 420 ° C., injection pressure 230 MPa, mold temperature 190 ° C.). A test piece defined in each test method was molded. The results are shown in Table 4.
［比較例４〜６］
化学式（４）および（５）で示される熱可塑性ポリイミド共重合体樹脂（三井化学（株）社製、商品名オーラム（登録商標）ＰＤ５００Ａ、ｍ／ｎ＝９）とフッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）表５に示すような割合でミキサーを用いてドライブレンドし、その後２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表５に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表５に示す。
[Comparative Examples 4 to 6]
Thermoplastic polyimide copolymer resins represented by chemical formulas (4) and (5) (trade name Aurum (registered trademark) PD500A, m / n = 9, manufactured by Mitsui Chemicals, Inc.) and fluororesin (Asahi Glass Fluoropolymers ( Co., Ltd., trade name: Aflon PTFE L-180) Dry blend using a mixer in the proportions shown in Table 5, and then using a twin-screw extruder, PAN-based carbon fiber (manufactured by Toho Tenax Co., Ltd.) Product name Besfight HTA-C6-UH) Supplied from the side feeder at a ratio as shown in Table 5, extruded and granulated at 400 to 420 ° C., and the resulting pellets were injection molded (cylinder temperature 400 to 420 ° C., An injection pressure of 230 MPa and a mold temperature of 190 ° C. were supplied, and a test piece defined in each test method described above was molded. The results are shown in Table 5.
［比較例７〜９］
芳香族ジアミン化合物として１，３−ビス（４−アミノフェノキシ）ベンゼン、芳香族テトラカルボン酸二無水物として３，３’，４，４’−ビフェニルテトラカルボン酸二無水物を原料とし、得られたポリアミド酸を熱的に熱的にイミド化して、化学構造式が（６）の熱可塑性ポリイミド樹脂を得た。得られたポリイミド粉の対数粘度（ηｉｎｈ）は、０．９ｄｌ／ｇであった。この化学構造式が（６）である熱可塑性ポリイミド樹脂とフッ素樹脂（旭硝子フロロポリマーズ（株）社製、商品名アフロンＰＴＦＥ Ｌ−１８０）表６に示すような割合でミキサーを用いてドライブレンドし、その後２軸押出機を用いてＰＡＮ系炭素繊維（東邦テナックス（株）社製、商品名ベスファイトＨＴＡ−Ｃ６−ＵＨ）表６に示すような割合でサイドフィーダーより供給し４００〜４２０℃で押出して造粒し、得られたペレットを射出成形機（シリンダー温度４００〜４２０℃、射出圧力２３０ＭＰａ、金型温度１９０℃）に供給し、前述した各試験法に定められた試験片を成形した。結果を表６に示す。
[Comparative Examples 7 to 9]
Obtained using 1,3-bis (4-aminophenoxy) benzene as an aromatic diamine compound and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride as raw materials as an aromatic tetracarboxylic dianhydride The resulting polyamic acid was thermally imidized thermally to obtain a thermoplastic polyimide resin having a chemical structural formula (6). The logarithmic viscosity (ηinh) of the obtained polyimide powder was 0.9 dl / g. This chemical structural formula (6) is a thermoplastic polyimide resin and fluororesin (Asahi Glass Fluoropolymers Co., Ltd., trade name Aflon PTFE L-180). Then, using a twin screw extruder, PAN-based carbon fiber (manufactured by Toho Tenax Co., Ltd., trade name Besfight HTA-C6-UH) is supplied from the side feeder at a rate as shown in Table 6 at 400 to 420 ° C. The pellets obtained by extrusion were granulated, and the obtained pellets were supplied to an injection molding machine (cylinder temperature 400 to 420 ° C., injection pressure 230 MPa, mold temperature 190 ° C.), and the test pieces defined in each test method described above were molded. . The results are shown in Table 6.
本発明の溶融成形可能な熱可塑性ポリイミド樹脂組成物を成形してなるピストンリングは、自材及び相手材の磨耗が著しく少ない摩擦磨耗特性、およびシール性も優れているので極めて有用であり、様々な分野のシール目的のピストンリングとして応用が可能である。また、本発明のピストンリングは、高圧、高速の条件でも使用可能で、使用時のシール性がＦＣ材などの金属材料と比較し著しく改良され、さらには、ピストン本体に組み付ける際のかじり及び変形がなく実用的である。更には、本ピストンリングは、実使用前（組み付け前）に熱処理すると効果的で、熱処理により結晶化度の上昇や寸法安定化などの効果が期待できる。 The piston ring formed by molding the melt-moldable thermoplastic polyimide resin composition of the present invention is extremely useful because it has excellent frictional wear characteristics and sealability with extremely low wear of the self-material and the counterpart material. It can be applied as a piston ring for sealing purposes in various fields. In addition, the piston ring of the present invention can be used under high pressure and high speed conditions, and the sealing performance during use is remarkably improved as compared with metal materials such as FC materials, and further, galling and deformation when assembled to the piston body. There is no practical. Furthermore, this piston ring is effective if it is heat-treated before actual use (before assembly), and effects such as an increase in crystallinity and dimensional stability can be expected by heat treatment.
上記の優れた特性を有する本発明のピストンリングは、具体的に例えば、自動車部品では、エンジン内のピストンリング、過給機（ターボ）、エアーコンプレッサー、ＡＢＳ、ＥＳＣ、オイルポンプなどのシールを目的としたシール材料、産業用では、空気、窒素、水素などの各種気体圧縮用コンプレッサーのピストンリングや建築機械のダンパー用のウェアーリングなどに用いる事が可能である。 The piston ring of the present invention having the above-mentioned excellent characteristics is specifically intended to seal piston rings in engines, turbochargers, air compressors, ABS, ESC, oil pumps, etc. In the industrial use, it can be used for piston rings of compressors for compressing various gases such as air, nitrogen and hydrogen, and wear rings for dampers of building machines.
１：ＦＣＤ４５製ピストン（往復部）
２：ピストンリング
３：ＦＣＤ４５製ハウジング
４：油圧計
５：オイル供給管
６：オイルポンプ
７：オイルバス
８：オイル漏れ量測定用バルブ
９：オイル漏れ量測定用オイル排出管
１０：メスシリンダー
1: FCD45 piston (reciprocating part)
2: Piston ring 3: Housing made of FCD45 4: Hydraulic gauge 5: Oil supply pipe 6: Oil pump 7: Oil bath 8: Valve for measuring oil leakage amount 9:
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006008215A JP2007192242A (en) | 2006-01-17 | 2006-01-17 | Piston ring made of melt-moldable thermoplastic polyimide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006008215A JP2007192242A (en) | 2006-01-17 | 2006-01-17 | Piston ring made of melt-moldable thermoplastic polyimide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007192242A true JP2007192242A (en) | 2007-08-02 |
Family
ID=38448112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006008215A Pending JP2007192242A (en) | 2006-01-17 | 2006-01-17 | Piston ring made of melt-moldable thermoplastic polyimide resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007192242A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012070401A1 (en) | 2010-11-24 | 2012-05-31 | 旭硝子株式会社 | Sliding member for sheet-shaped recording material detachment, seal ring for automobile, and seal ring and sliding member for industrial gas compressor |
| WO2012105538A1 (en) * | 2011-02-03 | 2012-08-09 | 株式会社リケン | Combined piston ring |
| WO2013171325A1 (en) * | 2012-05-16 | 2013-11-21 | Solvay Specialty Polymers Usa, Llc | Tribological aromatic polyimide compositions |
| JP2015067726A (en) * | 2013-09-30 | 2015-04-13 | 住友化学株式会社 | Resin composition for sliding member |
| US9429149B2 (en) | 2012-05-15 | 2016-08-30 | Sabic Global Technologies B.V. | Polyetherimide pump |
| EP3109471A1 (en) * | 2015-06-26 | 2016-12-28 | Danfoss A/S | Water-hydraulic machine |
| WO2018034112A1 (en) * | 2016-08-15 | 2018-02-22 | 株式会社リケン | Piston ring |
| WO2020066969A1 (en) * | 2018-09-26 | 2020-04-02 | 住友化学株式会社 | Resin composition and molded product |
| WO2023017833A1 (en) * | 2021-08-11 | 2023-02-16 | Ntn株式会社 | Piston ring |
| WO2025000811A1 (en) * | 2023-11-08 | 2025-01-02 | 江苏徐工工程机械研究院有限公司 | Thermoplastic polyimide and supporting ring prepared from same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316424A (en) * | 1994-05-26 | 1995-12-05 | Mitsui Toatsu Chem Inc | Oil-impregnated polyimide resin composition for sliding materials |
| JPH0848887A (en) * | 1994-08-04 | 1996-02-20 | Mitsui Toatsu Chem Inc | Resin composition |
| JPH0881629A (en) * | 1994-09-13 | 1996-03-26 | Mitsui Toatsu Chem Inc | Oil seal ring |
| JPH0989111A (en) * | 1995-09-29 | 1997-03-31 | Ntn Corp | Synthetic resin made seal ring |
| JPH1182741A (en) * | 1997-09-04 | 1999-03-26 | Teikoku Piston Ring Co Ltd | Combination of piston and compression ring |
| JP2004346143A (en) * | 2003-05-21 | 2004-12-09 | Mitsui Chemicals Inc | Conductive plastic film |
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2006
- 2006-01-17 JP JP2006008215A patent/JP2007192242A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07316424A (en) * | 1994-05-26 | 1995-12-05 | Mitsui Toatsu Chem Inc | Oil-impregnated polyimide resin composition for sliding materials |
| JPH0848887A (en) * | 1994-08-04 | 1996-02-20 | Mitsui Toatsu Chem Inc | Resin composition |
| JPH0881629A (en) * | 1994-09-13 | 1996-03-26 | Mitsui Toatsu Chem Inc | Oil seal ring |
| JPH0989111A (en) * | 1995-09-29 | 1997-03-31 | Ntn Corp | Synthetic resin made seal ring |
| JPH1182741A (en) * | 1997-09-04 | 1999-03-26 | Teikoku Piston Ring Co Ltd | Combination of piston and compression ring |
| JP2004346143A (en) * | 2003-05-21 | 2004-12-09 | Mitsui Chemicals Inc | Conductive plastic film |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9388009B2 (en) | 2010-11-24 | 2016-07-12 | Asahi Glass Co., Ltd. | Sliding member for sheet-shaped recording material detachment, seal ring for automobile, and seal ring and sliding member for industrial gas compressor |
| KR20130107333A (en) | 2010-11-24 | 2013-10-01 | 아사히 가라스 가부시키가이샤 | Sliding member for sheet-shaped recording material detachment, seal ring for automobile, and seal ring and sliding member for industrial gas compressor |
| WO2012070401A1 (en) | 2010-11-24 | 2012-05-31 | 旭硝子株式会社 | Sliding member for sheet-shaped recording material detachment, seal ring for automobile, and seal ring and sliding member for industrial gas compressor |
| WO2012105538A1 (en) * | 2011-02-03 | 2012-08-09 | 株式会社リケン | Combined piston ring |
| JP2012163118A (en) * | 2011-02-03 | 2012-08-30 | Riken Corp | Combined piston ring |
| US9429149B2 (en) | 2012-05-15 | 2016-08-30 | Sabic Global Technologies B.V. | Polyetherimide pump |
| WO2013171325A1 (en) * | 2012-05-16 | 2013-11-21 | Solvay Specialty Polymers Usa, Llc | Tribological aromatic polyimide compositions |
| CN104470981A (en) * | 2012-05-16 | 2015-03-25 | 索尔维特殊聚合物美国有限责任公司 | friction polymer composition |
| JP2015067726A (en) * | 2013-09-30 | 2015-04-13 | 住友化学株式会社 | Resin composition for sliding member |
| US9932459B2 (en) | 2013-09-30 | 2018-04-03 | Sumitomo Chemical Company, Limited | Resin composition for sliding member |
| EP3109471A1 (en) * | 2015-06-26 | 2016-12-28 | Danfoss A/S | Water-hydraulic machine |
| WO2018034112A1 (en) * | 2016-08-15 | 2018-02-22 | 株式会社リケン | Piston ring |
| JP2018028332A (en) * | 2016-08-15 | 2018-02-22 | 株式会社リケン | piston ring |
| CN109563930A (en) * | 2016-08-15 | 2019-04-02 | 株式会社理研 | piston ring |
| WO2020066969A1 (en) * | 2018-09-26 | 2020-04-02 | 住友化学株式会社 | Resin composition and molded product |
| WO2023017833A1 (en) * | 2021-08-11 | 2023-02-16 | Ntn株式会社 | Piston ring |
| EP4386208A4 (en) * | 2021-08-11 | 2024-12-11 | NTN Corporation | Piston ring |
| WO2025000811A1 (en) * | 2023-11-08 | 2025-01-02 | 江苏徐工工程机械研究院有限公司 | Thermoplastic polyimide and supporting ring prepared from same |
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