JPH0415257A - Thermoplastic polyimide resin composition - Google Patents
Thermoplastic polyimide resin compositionInfo
- Publication number
- JPH0415257A JPH0415257A JP2119446A JP11944690A JPH0415257A JP H0415257 A JPH0415257 A JP H0415257A JP 2119446 A JP2119446 A JP 2119446A JP 11944690 A JP11944690 A JP 11944690A JP H0415257 A JPH0415257 A JP H0415257A
- Authority
- JP
- Japan
- Prior art keywords
- thermoplastic polyimide
- polyimide resin
- copolymer
- resin composition
- trifluoromethylpropene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 19
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 title claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 4
- VJOAJCOCCYFXPR-UHFFFAOYSA-N 3,3,3-trifluoro-2-methylprop-1-ene Chemical compound CC(=C)C(F)(F)F VJOAJCOCCYFXPR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 5
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 3
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical compound FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 abstract 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 abstract 2
- HIOSIQSHOMBNDE-UHFFFAOYSA-N 3-[1-(3-aminophenoxy)-4-phenylcyclohexa-2,4-dien-1-yl]oxyaniline Chemical group NC1=CC=CC(OC2(C=CC(=CC2)C=2C=CC=CC=2)OC=2C=C(N)C=CC=2)=C1 HIOSIQSHOMBNDE-UHFFFAOYSA-N 0.000 abstract 1
- 230000018044 dehydration Effects 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 abstract 1
- 229920005575 poly(amic acid) Polymers 0.000 abstract 1
- 229920001169 thermoplastic Polymers 0.000 abstract 1
- 239000004416 thermosoftening plastic Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012744 reinforcing agent Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012210 heat-resistant fiber Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 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
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 150000008430 aromatic amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 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
- 238000005485 electric heating Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 230000002787 reinforcement Effects 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
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、エンジニアリングプラスチック材料として
優れた特性を有する熱可塑性ポリイミド系樹脂組成物に
関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a thermoplastic polyimide resin composition having excellent properties as an engineering plastic material.
従来、熱可塑性ポリイミド樹脂は、耐熱性、難燃性、耐
薬品性などに優れたエンジニアリングプラスチック材料
として、特に電気・電子機器類、自動車等の車輌機器類
などの分野において使用されて来た。しかしこの樹脂は
、非粘着性、摺動特性、高温剛性が満足できるものでな
く、これらの特性が要求される複写機等の事務機器類の
分野においては、適用できるものでなかった。また、熱
可塑性ポリイミド樹脂に対して、ポリテトラフルオロエ
チレン、ポリ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、ポリテトラフルオロエチレン−パ
ーフルオロプロピレン共重合体などのフッ素樹脂を添加
することによる非粘着性および摺動特性の改良の試みが
なされている。Conventionally, thermoplastic polyimide resins have been used as engineering plastic materials with excellent heat resistance, flame retardance, chemical resistance, etc., particularly in the fields of electrical and electronic equipment and vehicle equipment such as automobiles. However, this resin does not have satisfactory non-adhesive properties, sliding properties, and high temperature rigidity, and cannot be applied in the field of office equipment such as copying machines, which require these properties. In addition, non-stick properties can be achieved by adding fluororesins such as polytetrafluoroethylene, polytetrafluoroethylene-hexafluoropropylene copolymer, and polytetrafluoroethylene-perfluoropropylene copolymer to thermoplastic polyimide resin. Attempts have also been made to improve the sliding properties.
この場合、充分な非粘着性および摺動特性を前記樹脂組
成物に付与するためには、前記したフッ素樹脂をかなり
多く添加する必要があるが、あまり過量のフッ素樹脂を
添加すると、樹脂組成物の具備すべき機械的強度、特に
高温剛性が維持できなくなる。この欠点を補うためにガ
ラス繊維や炭素繊維などの繊維状強化剤を併用すること
も考えられるが、前記した充分な強度を保持するために
は、これらを相当多量に添加せざるを得ず、その場合に
は、繊維状強化剤の配向に基づく異方性やそりが発生し
たり、摺動時に相手材が損傷し易く充分な潤滑性が得ら
れないという問題が新たに生ずる。In this case, in order to impart sufficient non-adhesion and sliding properties to the resin composition, it is necessary to add a considerable amount of the fluororesin described above, but if too much fluororesin is added, the resin composition Mechanical strength, especially high-temperature rigidity, which should be maintained cannot be maintained. In order to compensate for this drawback, it may be possible to use fibrous reinforcing agents such as glass fiber or carbon fiber, but in order to maintain the sufficient strength mentioned above, it is necessary to add a considerable amount of these reinforcing agents. In that case, new problems arise, such as anisotropy and warpage due to the orientation of the fibrous reinforcing agent, and the mating material being easily damaged during sliding, making it impossible to obtain sufficient lubricity.
〔発明が解決しようとする課題］
このように従来の技術においては、優れた耐熱性、難燃
性、耐薬品性などに加えて非粘着性に優れ、高温で機械
的強度が大きく、しかも摺動特性に優れた熱可〒性ポリ
イミド系樹脂組成物は得られていないという問題があり
、これらを解決することが課題となっていた。[Problems to be Solved by the Invention] As described above, in addition to excellent heat resistance, flame retardance, and chemical resistance, the conventional technology has excellent non-adhesiveness, high mechanical strength at high temperatures, and There is a problem that a thermoplastic polyimide resin composition with excellent dynamic properties has not been obtained, and it has been an issue to solve these problems.
〔課題を解決するための手段］
上記の問題を解決するため、この発明は式（１）％式％
で示される繰り返し単位からなる熱可塑性ポリイミド樹
脂１００重量部に対して、３，３．３− ）リフルオロ
−２−トリフルオロメチルプロペンと１．１−ジフルオ
ロエチレンとの共重合体を１０〜９１１部添加してポリ
イミド系樹脂組成物とする手段を採用したものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention provides that 3.3.3 parts by weight of a thermoplastic polyimide resin consisting of repeating units represented by formula (1)% -) A method is adopted in which 10 to 911 parts of a copolymer of refluoro-2-trifluoromethylpropene and 1,1-difluoroethylene is added to form a polyimide resin composition.
以下その詳細を述べる。The details will be described below.
まず、この発明で用いられる熱可塑性ポリイミド樹脂は
、前記式（Ｉ）で表わされるものであって、その製造方
法を特に限定するものでなく、たとえば式
で表わされる４、４−ビス（３−アミノフェノキシ）ビ
フェニルと、ピロメリット酸二無水物とを反応させるこ
とによってポリイミド酸を生成させ、そのポリイミド酸
を脱水環化して得ることができる。First, the thermoplastic polyimide resin used in the present invention is represented by the above formula (I), and the manufacturing method thereof is not particularly limited. For example, 4,4-bis(3- It can be obtained by reacting aminophenoxy)biphenyl with pyromellitic dianhydride to produce polyimide acid, and then cyclodehydrating the polyimide acid.
このような、熱可塑性ポリイミド樹脂の溶融粘度は、成
形時の形状及びそれが使用される用途別に、最適な値と
すればよく、０．３５〜０．８０ｄｌ／ｇ程度が望まし
く、０．４５〜０．５５ｄｌ／ｇ程度が特に好ましい。The melt viscosity of such a thermoplastic polyimide resin may be set to an optimal value depending on the shape during molding and the application for which it is used, and is preferably about 0.35 to 0.80 dl/g, and 0.45 to 0.80 dl/g. About 0.55 dl/g is particularly preferable.
つぎに、この発明に用いられる３、３．３゜トリフルオ
ロ−２−トリフルオロメチルプロペンと１．１−ノフル
オロユチレ／との共重合体は、式（Ｈ）で示される繰り
返し単位が単独で、またはこの繰り返し単位と共にＣＬ
ＣＦｚで示される繰り返し単位とが（ＩＩ）弐の共重合
体本来の特性が失われないように、２０モノマ一％未満
の割合で共存する共重合体である。 ３．３．３− ト
リフルオロ−２−トリフルオロメチルプロペンと１１−
ジフルオロエチレンとの共重合体の製造方法は、特公昭
４９−３２７８５号公報などに開示されているように、
３．３．３− トリフルオロ２−トリフルオロメチルプ
ロペンと１．１−ジフルオロエチレンとを所定溶媒中で
共重合することから製造され、その場合、両物質の配合
モル比は、１：９から９＝１の範囲とし、約−１５℃か
ら約８０°Ｃの温度範囲で共重合させる。このような共
重合体としては、たとえば、米国アウジモノト社製＝Ｃ
ＭＸを挙げることができる。Next, the copolymer of 3,3.3°trifluoro-2-trifluoromethylpropene and 1,1-nofluoroethylene used in the present invention has a repeating unit represented by the formula (H) singly, or with this repeating unit CL
It is a copolymer in which the repeating units represented by CFz coexist in a proportion of less than 1% of 20 monomers so as not to lose the original properties of the copolymer (II). 3.3.3- Trifluoro-2-trifluoromethylpropene and 11-
A method for producing a copolymer with difluoroethylene is disclosed in Japanese Patent Publication No. 49-32785, etc.
3.3.3-Trifluoro Produced by copolymerizing 2-trifluoromethylpropene and 1,1-difluoroethylene in a specified solvent, in which case the molar ratio of both substances ranges from 1:9 to 1:9. 9=1, and the copolymerization is carried out in a temperature range of about -15°C to about 80°C. As such a copolymer, for example, =C manufactured by Aujimonoto Co., Ltd.
One example is MX.
以上述べた熱可塑性ポリイミド樹脂および３，３３−ト
リフルオロ−２−トリフルオロメチルプロペンと１．１
−ジフルオロエチレンの共重合体を配合するにあっては
、熱可塑性ポリイミド樹脂１００重量部に対して、この
共重合体を１０〜９４１部配合する。The above-mentioned thermoplastic polyimide resin and 3,33-trifluoro-2-trifluoromethylpropene and 1.1
- When blending a difluoroethylene copolymer, 10 to 941 parts of this copolymer is blended to 100 parts by weight of the thermoplastic polyimide resin.
なぜなら１０重量部未満の少量では、優れた非粘着性、
摺動特性が得られず、９０重量部を越える多量では、高
温剛性や機械的強度が非常に低くなるためである。Because in small amounts less than 10 parts by weight, excellent non-stick properties,
This is because sliding properties cannot be obtained, and if the amount exceeds 90 parts by weight, high temperature rigidity and mechanical strength will become extremely low.
なお、この発明の樹脂組成物には、一般の合成樹脂に対
して配合し得る汎用の充填材をこの発明の目的を阻害し
ない範囲の量で適宜配合することができる。このような
充填材の具体例としては、シリコーン樹脂、ポリエーテ
ルサルホン樹脂、芳香族ポリエステル樹脂、ポリイミド
樹脂等の耐熱性高分子材料、耐熱性繊維補強材（たとえ
ば、ガラス繊維、炭素繊維、グラファイト繊維、チタン
酸カリウムホイスカー、ウオラストナイト、セラミック
繊維、マグネンウムホイスカー、ホウ酸アルミニウムホ
イスカー、銅線、銅線、ステンレス銅線、炭化ケイ素繊
維その他の耐熱性無機質繊維または芳香族アミドなどの
耐熱性を線繊維）、熱伝導性改良材（グラファイト、亜
鉛、アルミニウム等の金属または酸化マグネシウム、酸
化亜鉛等の無機化合物の粉末）、断熱性向上剤（ガラス
ピーズ、シリカバルーン、珪藻土、炭酸マグネシウム粉
末、石綿等）、潤滑性向上剤（二硫化モリブデン、グラ
ファイト、カーボン、マイカ、タルク等の固体潤滑材）
、着色材（酸化鉄、硫化カドミニウム、セレン化カドミ
ニウムその他の無機顔料、カーボンブラック等）を例示
することができる。In addition, the resin composition of the present invention may contain a general-purpose filler that can be blended with common synthetic resins in an amount that does not impede the object of the present invention. Specific examples of such fillers include heat-resistant polymeric materials such as silicone resins, polyethersulfone resins, aromatic polyester resins, and polyimide resins, heat-resistant fiber reinforcement materials (e.g., glass fibers, carbon fibers, graphite Heat-resistant fibers, potassium titanate whiskers, wollastonite, ceramic fibers, magnenium whiskers, aluminum borate whiskers, copper wire, copper wire, stainless steel copper wire, silicon carbide fibers and other heat-resistant inorganic fibers or aromatic amides thermal conductivity improvers (powder of metals such as graphite, zinc, aluminum, or inorganic compounds such as magnesium oxide, zinc oxide), thermal insulation improvers (glass peas, silica balloons, diatomaceous earth, magnesium carbonate powder) , asbestos, etc.), lubricity improvers (solid lubricants such as molybdenum disulfide, graphite, carbon, mica, talc, etc.)
, colorants (iron oxide, cadmium sulfide, cadmium selenide and other inorganic pigments, carbon black, etc.).
この発明における上記した諸原料の配合、加熱、混合な
どの諸操作は、特に限定されるものではなく、たとえば
、ヘンシェルミキサー、タンブラ−ミキサー等の混合機
によって乾式混合した後に、直接、射出成形機や溶融押
出機に供給して成形してもよく、また、熱ロール、ニー
グー、溶融押出機などで溶融混合してもよい、このとき
の溶融温度は３８０〜４５０ ’Ｃ１好ましくは、３９
０〜４２０℃が適当であるにの発明の組成物を成形する
にあたっては、その方法を特に限定するものではなく、
圧縮成形、押出成形、射出成形などが可能である。The various operations such as blending, heating, and mixing of the above-mentioned raw materials in this invention are not particularly limited. The melting temperature may be 380 to 450' C1, preferably 39
There are no particular limitations on the method for molding the composition of the invention, which is suitable at 0 to 420°C.
Compression molding, extrusion molding, injection molding, etc. are possible.
また、この発明の樹脂組成物は、溶融混合した後、ジェ
ットミル、冷凍粉砕機等によって粉砕し、そのままもし
くは所望の粒径毎に分級した粉末とし、この粉末を用い
て、流動浸漬塗装、＃電粉体塗装などを行うことができ
る。In addition, the resin composition of the present invention can be melt-mixed and then pulverized by a jet mill, frozen pulverizer, etc., either as it is or as a powder classified into desired particle sizes, and this powder can be used for fluidized dip coating, # Electro-powder coating etc. can be applied.
また、得られた成形品に対して所定の熱処理を施すこと
により、さらに高温剛性が高く、寸法安定性に優れた成
形体に改質することも可能である。Further, by subjecting the obtained molded product to a predetermined heat treatment, it is possible to modify the molded product into a molded product with even higher high temperature rigidity and excellent dimensional stability.
特に２４０°Ｃ以上の高温使用に耐え、且つ過酷な摺動
条件、具体的には面圧（ｋｇ／ｃｄ）と速度（ｍ ／
ｍｎ）の積が６００（ｋｇ／ｃｄ−ｗａ ／５ｉｎ）を
超えるような条件下の使用においては、所定の熱処理を
施したものが効果的である。この熱処理は、２５０°Ｃ
以上で３２０°Ｃ以下、好ましくは、２７０〜３１０’
Ｃの範囲で行なう、なぜなら３２０°Ｃを超える温度で
は、フ。In particular, it can withstand high-temperature use of 240°C or higher, and is subject to harsh sliding conditions, specifically surface pressure (kg/cd) and speed (m/m/cd).
When used under conditions where the product of mn) exceeds 600 (kg/cd-wa/5in), it is effective to use a material that has been subjected to a predetermined heat treatment. This heat treatment is carried out at 250°C
above and below 320°C, preferably between 270 and 310'
C range, because at temperatures above 320 °C, the temperature is too high.
素樹脂が溶融して好ましくなく、２５Ｑ’Ｃより低い温
度では、耐熱変形性の向上は得られないからである。ま
た、上記熱処理に要する時間は、加熱する温度により２
分〜数週間必要となるが、その目安としては成形材料中
の熱可塑性ポリイミド成分の密度が少くとも１．５％以
上の密度増加をするに足りる時間を熱処理時間とすれば
よい。さらにこれを具体的に示せば、２７０’Ｃの加熱
下では１２時間以上、２８０°Ｃの加熱下では一時間以
上、３００’Ｃの加熱下では１０分間以上である。This is because the base resin melts, which is undesirable, and the heat deformation resistance cannot be improved at a temperature lower than 25Q'C. In addition, the time required for the above heat treatment depends on the heating temperature.
The heat treatment time may take from minutes to several weeks, but as a rough guide, the heat treatment time should be sufficient to increase the density of the thermoplastic polyimide component in the molding material by at least 1.5%. More specifically, the heating time is 12 hours or more under heating at 270'C, one hour or more under heating at 280°C, and 10 minutes or more under heating at 300'C.
このような熱処理は、所定温度下の加熱装置の中に成形
品を置いて行なうが、その加熱装置は電気加熱方式によ
るものが便利であり、装置内の雰囲気としては、たとえ
ば、熱風循環式や熱風流通式などであってもよい。Such heat treatment is carried out by placing the molded product in a heating device at a predetermined temperature, but it is convenient to use an electric heating method, and the atmosphere inside the device can be, for example, a hot air circulation type or A hot air flow type or the like may be used.
［作用〕
この発明における熱可塑性ポリイミド系樹脂組成物は、
射出成形その他の手法で成形された成形体表層部に、３
，３．３− トリフルオロ−２−トリフルオロメチルプ
ロペンと１．１−ジフルオロエチレンとの共重合体であ
るフッ素樹脂が高密度ムこ分布するようになり、非粘着
性および優れた潤滑性、耐摩耗性を示すと共に、このフ
ッ素樹脂の強度、剛性によって、成形体全体が優れた強
度および高温剛性を示すようになると推定される。[Function] The thermoplastic polyimide resin composition in this invention has the following properties:
3 on the surface layer of a molded product molded by injection molding or other methods.
The fluororesin, which is a copolymer of 3.3-trifluoro-2-trifluoromethylpropene and 1.1-difluoroethylene, has a high-density mucodistribution, resulting in non-adhesion and excellent lubricity. In addition to exhibiting abrasion resistance, it is presumed that due to the strength and rigidity of this fluororesin, the entire molded article exhibits excellent strength and high-temperature rigidity.
実施例および比較例に使用した原材料を一括５て示すと
つぎのとおりである。なお、〔〕内に略号を記入し、ま
た配合割合はすべて重量部である。The raw materials used in the Examples and Comparative Examples are listed below. In addition, the abbreviations are written in [ ], and all compounding ratios are parts by weight.
■ 熱可塑性ポリイミド樹脂（三井東圧化学社製： Ｎ
ＩＪ ＴＰＩ） （ＴＰＩ）
■３，３．３− １−リフルオロ−２−トリフルオロメ
チルプロペンと１．■−ノフルオロエチレンの共重合体
（米国アウジモノト社製： ＣＭ−Ｘ） （ＣＭ−Ｘ
〕■ ポリテトラフルオロエチレン（三井デュポンフ
ロロケミカル社製：テフロン７Ｊ） ［ＰＴＦＩｌ■
ポリ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（三井デュポンフロロケミカル社製： ＦＥ
Ｒｌｏｏ） （ＦＥＰ）■ ポリテトラフルオロエチ
レン−パーフルオロプロピレン共重合体（三井デュポン
フロロケミカル社製： ＰＦＡ−３４０Ｊ） ＣＰＰ
Ａ ）■ グラファイト（日本黒鉛社製： ＡＣＰ）
（ＧＲＰ）第 １ 表
実施例１〜５：
第１表に示す配合割合で配合し、よく混合した諸原料を
二輪溶融押出機（池貝鉄工社製： ＰＣＭ−３０）に供
給し、シリンダー温度４００℃、スクリュー回転数８Ｏ
ｒｐｍの条件で溶融混合すると共に、押出し造粒した。■ Thermoplastic polyimide resin (manufactured by Mitsui Toatsu Chemical Co., Ltd.: N
IJ TPI) (TPI) ■3,3.3- 1-lifluoro-2-trifluoromethylpropene and 1. ■-Nofluoroethylene copolymer (manufactured by Aujimonoto, USA: CM-X) (CM-X
]■ Polytetrafluoroethylene (Mitsui DuPont Fluorochemical Co., Ltd.: Teflon 7J) [PTFIl■
Polytetrafluoroethylene-hexafluoropropylene copolymer (Mitsui DuPont Fluorochemical Co., Ltd.: FE
Rloo) (FEP)■ Polytetrafluoroethylene-perfluoropropylene copolymer (manufactured by DuPont Mitsui Fluorochemicals: PFA-340J) CPP
A) Graphite (manufactured by Nippon Graphite Co., Ltd.: ACP)
(GRP) Table 1 Examples 1 to 5: The various raw materials blended in the proportions shown in Table 1 and mixed well were supplied to a two-wheel melt extruder (manufactured by Ikegai Iron Works: PCM-30), and the cylinder temperature was 400. ℃, screw rotation speed 8O
The mixture was melt-mixed under rpm conditions and extruded and granulated.
得られたベレントをシリンダー温度４１０℃、射出圧１
１００ｋｇ／ｃ４、金型温度１８０’Ｃの条件下で射出
成形した。その際、実施例１〜４についてはそのまま、
実施例５については２８０°Ｃで８時間熱処理をして摩
擦摩耗試験片（内径１７ｍ、外径２１ｍ、長さ１０■）
および曲げ試験片（ＡＳＴＭ−０７９０に準拠）、引張
り弾性率試験片（幅４■、長さ２５■、厚さ１■）及び
接触角試験片（直径１０■、厚さ３■）を作製した。得
られた試験片に対する各試験方法はつぎのとおりである
。The obtained berent was heated at a cylinder temperature of 410°C and an injection pressure of 1
Injection molding was carried out under conditions of 100 kg/c4 and a mold temperature of 180'C. At that time, Examples 1 to 4 were as they were.
For Example 5, a friction and wear test piece was heat-treated at 280°C for 8 hours (inner diameter 17 m, outer diameter 21 m, length 10 cm)
A bending test piece (according to ASTM-0790), a tensile modulus test piece (width 4cm, length 25cm, thickness 1cm), and a contact angle test piece (diameter 10cm, thickness 3cm) were prepared. . The test methods for the obtained test pieces are as follows.
１）摩擦摩耗試験
スラスト型摩擦摩耗試験機により相手材を軸受鋼（５Ｕ
Ｊ２）とし、滑り速度毎分３２ｍ、荷重６．２５ｋｇ／
ｄの条件のもとに摩擦係数および摩耗係数（ｃｄ眩・■
）を求めた。1) Friction and wear test Using a thrust type friction and wear tester, the mating material was tested using bearing steel (5U
J2), sliding speed 32 m/min, load 6.25 kg/
Under the conditions of d, the coefficient of friction and the coefficient of wear (cd dazzling・■
) was sought.
２）曲げ強度試験 ４５７Ｍ−０７９０に準拠する方法を用いた。2) Bending strength test A method according to 457M-0790 was used.
３）引張り弾性率試験（弾性率の保持率）東洋精機製作
断裂の動的粘弾性測定装置を用いて周波数１０七で引張
り応力を加え、温度変化に対する引張り弾性率の変化を
２５°Ｃおよび２００°Ｃで求めた。3) Tensile modulus test (retention rate of elastic modulus) Tensile stress was applied at a frequency of 107 using a fracture dynamic viscoelasticity measuring device manufactured by Toyo Seiki, and the change in tensile modulus with respect to temperature changes was measured at 25°C and 200°C. Determined in °C.
４）非粘着性（水に対する接触角）試験エルマ光学社製
ゴニオメータ式接触角測定器Ｇ−１型を用いて水に対す
る接触角を求めた。4) Non-adhesion (contact angle to water) test The contact angle to water was determined using a goniometer type contact angle measuring instrument G-1 manufactured by Elma Optical Co., Ltd.
比較例１〜５：
諸原料を第１表に示す配合割合で混合した以外は、実施
例１と全く同し操作を行なって試験片を作製して前記各
試験を行ない、得られた結果を第１表に併記した。Comparative Examples 1 to 5: Test pieces were prepared in the same manner as in Example 1, except that the raw materials were mixed at the proportions shown in Table 1, and the above tests were conducted. It is also listed in Table 1.
この表から実施例１〜５は、曲げ強度、引張り弾性率に
も優れると共に、非粘着性が著しく優れており、また摺
動性、耐摩耗性に大変優れている。As can be seen from this table, Examples 1 to 5 have excellent bending strength and tensile modulus, as well as extremely good non-adhesiveness, and very good sliding properties and abrasion resistance.
これに対して、ＣＭ−Ｘを添加していない比較例１は、
非粘着性、摺動性（摩ＷＩ係数）、耐摩耗性の点で劣っ
ていた。また、添加されるフッ素樹脂がそれぞれＰＴＦ
Ｅ、 ＦＥＰ 、、ＰＦＡである比較例２〜４は、曲げ
強度が小さく、また、高温剛性（２００”Ｃにおける引
張り弾性率）に劣り、潤滑性、耐摩耗性もあまり良くな
い。さらに、フン素樹脂（ＣＭ−Ｘ）を用いているが、
添加量が過量（１００重量部）の比較例５は、曲げ強度
、高温剛性に劣り、耐摩耗性もあまり良くなかった。On the other hand, in Comparative Example 1 in which CM-X was not added,
It was inferior in non-adhesion, sliding properties (friction WI coefficient), and abrasion resistance. In addition, each fluororesin added is PTF.
Comparative Examples 2 to 4, which are E, FEP, and PFA, have low bending strength, poor high temperature rigidity (tensile modulus at 200"C), and poor lubricity and wear resistance. Although base resin (CM-X) is used,
Comparative Example 5 in which the amount added was excessive (100 parts by weight) was inferior in bending strength and high temperature rigidity, and the abrasion resistance was also not very good.
この発明の熱可塑性ポリイミド系樹脂組成物は、ポリイ
ミド樹脂本来の優れた機械的、熱的、電気的特性を損な
うことなく非粘着性に優れ、しかもきわめて好ましい摺
動特性を発揮するので、高温下で使用される摺動部材と
して最適である。したがって、その優れた非粘着性を活
かして、潤滑および非粘着性を必要とする用途、たとえ
ば、付着性の強いトナーに接触する複写機内の軸受、ヒ
ートローラや感光体のような回転体から複写紙を剥離す
る爪部材などの格好の素材になり、この発明の意義はき
わめて大きいといえる。The thermoplastic polyimide resin composition of the present invention has excellent non-stick properties without impairing the excellent mechanical, thermal, and electrical properties inherent to polyimide resins, and also exhibits extremely favorable sliding properties, so it can be used at high temperatures. Ideal as a sliding member used in Therefore, its excellent non-adhesive properties can be used for applications that require lubrication and non-adhesive properties, such as bearings in copiers that come into contact with highly adhesive toner, and copying from rotating bodies such as heat rollers and photoreceptors. This invention can be said to be of great significance as it can be used as a suitable material for claw members for peeling off paper.
Claims (1)
脂１００重量部に対して、３，３，３−トリフルオロ−
２−トリフルオロメチルプロペンと１，１−ジフルオロ
エチレンとの共重合体を１０〜９０重量部添加したこと
を特徴とする熱可塑性ポリイミド系樹脂組成物。(1) Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼For 100 parts by weight of a thermoplastic polyimide resin consisting of repeating units shown in (I), 3,3,3-trifluoro-
A thermoplastic polyimide resin composition comprising 10 to 90 parts by weight of a copolymer of 2-trifluoromethylpropene and 1,1-difluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2119446A JP2796543B2 (en) | 1990-05-09 | 1990-05-09 | Thermoplastic polyimide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2119446A JP2796543B2 (en) | 1990-05-09 | 1990-05-09 | Thermoplastic polyimide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0415257A true JPH0415257A (en) | 1992-01-20 |
| JP2796543B2 JP2796543B2 (en) | 1998-09-10 |
Family
ID=14761602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2119446A Expired - Fee Related JP2796543B2 (en) | 1990-05-09 | 1990-05-09 | Thermoplastic polyimide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796543B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709750B2 (en) | 2005-05-13 | 2010-05-04 | Tatsuta System Electronics Co, Ltd. | Shielding film, shielded printed circuit board, shielded flexible printed circuit board, method of manufacturing shielding film, and method of manufacturing shielded printed circuit board |
| JP2019112502A (en) * | 2017-12-21 | 2019-07-11 | 信越ポリマー株式会社 | High heat-resistant and high slidable film and method for producing the same |
-
1990
- 1990-05-09 JP JP2119446A patent/JP2796543B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7709750B2 (en) | 2005-05-13 | 2010-05-04 | Tatsuta System Electronics Co, Ltd. | Shielding film, shielded printed circuit board, shielded flexible printed circuit board, method of manufacturing shielding film, and method of manufacturing shielded printed circuit board |
| JP2019112502A (en) * | 2017-12-21 | 2019-07-11 | 信越ポリマー株式会社 | High heat-resistant and high slidable film and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2796543B2 (en) | 1998-09-10 |
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