JPH02185563A - Thermosetting resin composition - Google Patents
Thermosetting resin compositionInfo
- Publication number
- JPH02185563A JPH02185563A JP469189A JP469189A JPH02185563A JP H02185563 A JPH02185563 A JP H02185563A JP 469189 A JP469189 A JP 469189A JP 469189 A JP469189 A JP 469189A JP H02185563 A JPH02185563 A JP H02185563A
- Authority
- JP
- Japan
- Prior art keywords
- thermosetting resin
- resin
- para
- particles
- aromatic polyamide
- 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.)
- Pending
Links
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 24
- 239000011342 resin composition Substances 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 27
- 239000004760 aramid Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 abstract description 14
- 239000000314 lubricant Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 9
- 230000013011 mating Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000013585 weight reducing agent Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- -1 xylene modified phenol Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 125000004958 1,4-naphthylene group Chemical group 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- LVGKZTVMAHRVFR-UHFFFAOYSA-N 4-(phenoxazine-10-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C2OC2=CC=CC=C21 LVGKZTVMAHRVFR-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241001235534 Graphis <ascomycete fungus> Species 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- 235000013351 cheese Nutrition 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
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JYIZNFVTKLARKT-UHFFFAOYSA-N phenol;1,3,5-triazine-2,4,6-triamine Chemical compound OC1=CC=CC=C1.NC1=NC(N)=NC(N)=N1 JYIZNFVTKLARKT-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000002023 wood 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〕
本発明は、熱硬化性樹脂組成物に関する。更に詳しくは
、高温における機械的特性にすぐれ、電気部品、機械部
品等に好適な、及び優れた摺動特性を有する熱硬化性樹
脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermosetting resin composition. More specifically, the present invention relates to a thermosetting resin composition that has excellent mechanical properties at high temperatures, is suitable for electrical parts, mechanical parts, etc., and has excellent sliding properties.
近年、機器類の軽量化ニーズ、製造組立の容易性等のニ
ーズに伴って、金属製品に代って合成樹脂製品が機械部
品として数多く用いられて来ている。例えば、軸受等の
摺動部材においても多くの合成樹脂製品が使用され始め
ている。In recent years, synthetic resin products have been increasingly used as machine parts in place of metal products in response to the need for lighter weight equipment and ease of manufacturing and assembly. For example, many synthetic resin products are beginning to be used in sliding members such as bearings.
かかる摺動材においては、従来、摺動性の良い■
樹脂として、ポリアミド、ポリアセタール、フッ素系樹
脂等が用いられて来た。これらは、比較的低温の、低荷
重、低〜中速領域においては、無給油下でも要求される
摺動性を満足するが、高温における高荷重、高速領域に
なるに従って、焼き付きや、樹脂のフロー(塑性変形)
等が起こり、使用に耐え得ないものであった。In such sliding materials, polyamide, polyacetal, fluororesin, etc. have conventionally been used as resins with good sliding properties. At relatively low temperatures, low loads, and low to medium speeds, these materials satisfy the required sliding properties even without lubrication, but as they move to high temperatures, high loads, and high speeds, seizures and resin failure occur. Flow (plastic deformation)
etc., which made it unusable.
これらの欠点を改良する目的で、熱硬化性の樹脂とし、
固体潤滑剤として無機系の粉末、ガラス繊維、芳香族ポ
リアミド繊維あるいは炭素繊維等を加える方法が採られ
ているが、無機系の粉末を加える方法では、相手材を損
傷させること、繊維形状のものの添加にあっては、摺動
時に、フィブリル化、割れ、折れ等を生じ、摩耗粉を多
く堆積させて摺動性を低下させる等の問題を有するもの
であった。In order to improve these drawbacks, thermosetting resin is used,
Methods of adding inorganic powder, glass fiber, aromatic polyamide fiber, carbon fiber, etc. as solid lubricants have been adopted, but adding inorganic powder may damage the mating material or cause damage to the fiber-shaped material. When added, there are problems such as fibrillation, cracking, folding, etc., occurring during sliding, and a large amount of abrasion powder being deposited, resulting in a decrease in sliding properties.
これに対して、熱硬化性樹脂に、固体潤滑剤としてメク
配向芳香族ポリアミド粉末を添加する方法も既に知られ
ている。例えば、特開昭59−227924号公報、同
60−179418号公報、同63−6043号公報に
は、ビスマレイミド系の熱硬化性樹脂にフッ素系フィラ
ーと共に芳香族ポリアミド粉末を添加した組成物が開示
されている。しかしながら、メタ配向芳香族ポリアミド
扮末を用いる方法においては、高速領域の摺動に際して
、ある時期に摩耗量が急激に増大する、いわゆる異常摩
耗が発生することが判明した。即ち、高速領域での摺動
に際しては、メタ配向芳香族ポリアミドでは充分な耐熱
性を発揮出来ず、また本質的に固体潤滑剤としての硬度
が不足する結果、高速領域での使用に際して、ある時期
から異常摩耗が発生するものと推定される。On the other hand, a method of adding Mek-oriented aromatic polyamide powder as a solid lubricant to a thermosetting resin is already known. For example, JP-A-59-227924, JP-A No. 60-179418, and JP-A No. 63-6043 disclose compositions in which aromatic polyamide powder is added to a bismaleimide-based thermosetting resin together with a fluorine-based filler. Disclosed. However, in the method using meta-oriented aromatic polyamide powder, it has been found that during sliding in a high-speed region, so-called abnormal wear occurs in which the amount of wear increases rapidly at a certain period. In other words, when sliding at high speeds, meta-oriented aromatic polyamides cannot exhibit sufficient heat resistance, and as a result of their inherent lack of hardness as a solid lubricant, when used at high speeds, the It is presumed that abnormal wear occurs from this.
本発明の目的は、かかる問題点に鑑み、相手材を損傷さ
せることなく、かつ長時間使用による異常摩耗を起こさ
ない固体潤滑剤を提供することにある。In view of these problems, an object of the present invention is to provide a solid lubricant that does not damage mating materials and does not cause abnormal wear due to long-term use.
〔問題点を解決するための手段〕
即し、本発明は、熱硬化性樹脂100重量部に対してパ
ラ配向芳香族ポリアミ1粒子5〜300重量部を配合し
てなることを特徴とする熱硬化性樹脂組成物である。[Means for Solving the Problems] Accordingly, the present invention provides a thermosetting resin characterized in that 5 to 300 parts by weight of para-oriented aromatic polyamide particles are blended with 100 parts by weight of a thermosetting resin. It is a curable resin composition.
本発明に用いる熱硬化性樹脂とは、加熱、光あるいは放
射線等、あるいは過酸化物などのラジカル発生剤等々に
よって架橋反応を生じ得る樹脂をいい、具体的には、フ
ェノール樹脂、ユリア樹脂、メラミン樹脂、メラミン・
フェノール共縮合樹脂、キシレン変性フェノール樹脂、
グアナミン樹脂、ユリア・グアナミン共縮合樹脂、アミ
ン樹脂、アセトグアナミン樹脂、不飽和ポリエステル系
樹脂、ビスマレイミド等のポリイミド樹脂、キシレン樹
脂、エポキシ樹脂、エポキシアクリレート樹脂、等々を
あげることが出来る。本発明においては、かかる例示さ
れた樹脂単独の使用は勿論のこと、2種以」二の共重合
物、混合物も使用できるし、また、本発明の1」的に支
障をきたざない範囲で例えば、ポリエチレン、ポリプロ
ピレン、ポリアセクール、ポリアミ1等々の熱可塑性樹
脂との混合物としても使用することが出来る。The thermosetting resin used in the present invention refers to a resin that can undergo a crosslinking reaction by heating, light, radiation, etc., or a radical generator such as peroxide, etc. Specifically, it includes phenol resin, urea resin, melamine resin, etc. Resin, melamine
Phenol cocondensation resin, xylene modified phenol resin,
Examples include guanamine resin, urea-guanamine cocondensation resin, amine resin, acetoguanamine resin, unsaturated polyester resin, polyimide resin such as bismaleimide, xylene resin, epoxy resin, epoxy acrylate resin, and the like. In the present invention, not only can the exemplified resins be used alone, but also copolymers and mixtures of two or more of them can be used, and within the range of not interfering with the aspect of the present invention. For example, it can also be used as a mixture with thermoplastic resins such as polyethylene, polypropylene, polyacecool, polyamide 1, etc.
本発明においては、バラ配向芳香族ポリアミド粒子が用
いられることが極めて重要である。即ち、高速領域での
高い摺動性と、長時間安定した摺動特性を得るためには
、固体潤滑剤自体が高い耐熱性を有する必要があるから
である。又、相手材に損傷を与えることなく摩耗特性を
高めるためには、適度な硬度が要求されるからである。In the present invention, it is extremely important that loosely oriented aromatic polyamide particles are used. That is, in order to obtain high sliding properties in a high-speed range and stable sliding properties for a long time, the solid lubricant itself needs to have high heat resistance. Further, in order to improve the wear characteristics without damaging the mating material, appropriate hardness is required.
芳香族ポリアミドが、一般に耐熱性に優れることは既に
知られており、メタ配向芳香族ポリアミドも従来汎用の
ポリアミド他のポリマーに対しては高い耐熱性を有する
ものであるが、バラ配向芳香族ポリアミドは、その分子
鎖構造からの予想される通り、極めて高い耐熱性と、そ
れにも増して優れた機械的特性を有するものであり、メ
タ配向芳香族ポリアミドとは、その特性面において際立
った相違を有するポリマーである。It is already known that aromatic polyamides generally have excellent heat resistance, and meta-oriented aromatic polyamides also have higher heat resistance than conventional general-purpose polyamides and other polymers. As expected from its molecular chain structure, polyamide has extremely high heat resistance and even better mechanical properties, and it is markedly different from meta-oriented aromatic polyamide in terms of its properties. It is a polymer with
本発明においては、かかる特性を有するパラ配向芳香族
ポリアミド粒子を用いることに重要な意味があり、これ
によって上述の固体潤滑剤に要求される機能が初めて満
足されたのである。In the present invention, it is important to use para-oriented aromatic polyamide particles having such characteristics, and the above-mentioned functions required of a solid lubricant are satisfied for the first time.
本発明において、「パラ配向芳香族ポリアミド」とは、
アミ1結合(−C−N−)によって、バラH
位に2価の結合手が位置する芳香族基が連結されてなる
ポリアミドをいい、該芳香族基は具体的には、2価の結
合手がI、4−フェニレン(バラフェニレン)や4,4
′−ビフェニレン、1,4ナフチレンの如く、芳香族環
より同軸的に反対方向に、または1.5−ナフチレンや
2,6−ナフチレンの如く、平行軸的に反対方向に配置
されているような芳香族基を意味する。これらの芳香族
基には、メチル基やエチル基等の低級アルキル基やメト
キシ基、エトキシ基等のアルコキシ基、クロル基等のハ
ロケン基等が1個または2個以上含まれていでもよい。In the present invention, "para-oriented aromatic polyamide" means
Refers to a polyamide in which aromatic groups in which a divalent bond is located at the rose H position are connected by an amide bond (-C-N-), and the aromatic group specifically refers to a divalent bond. The hand is I, 4-phenylene (bara phenylene) or 4,4
'-Biphenylene, 1,4-naphthylene, etc., which are coaxially opposite to the aromatic ring, or 1,5-naphthylene, 2,6-naphthylene, which are arranged in the opposite direction parallel to the aromatic ring. means an aromatic group. These aromatic groups may contain one or more lower alkyl groups such as methyl and ethyl groups, alkoxy groups such as methoxy and ethoxy groups, and haloken groups such as chlorine.
これらのパラ配向芳香族ポリアミドの典型的なものとし
ては、ポリ−バラベンズアミド、ポリバラフェニレンテ
レフタルアミド、ポリ−4,4′シアミノヘンズアニリ
ドテレフクルアミド、ボIJ−N、N’−p−フェニレ
ンビス(p−ベンズアミド)テレフタルアミド、ポリー
バラフエニレンー26−ナフタリンアミド、コポリ−バ
ラフェニレン/3.4’ (オキシジフェニレン)テ
レフタルアミド、コポリ−バラフェニレン/4,4’(
33′−ジメチルビフェニレン)−テレフタルアミド、
ポリ−2−クロロ−バラフェニレンテレフタルアミF等
があげられる。これらのうち、ポリ−パラフェニレンテ
レフタルアミド、またはポリマーを構成する繰返し単位
の40モル%以上が、バラフェニレンテレフタルアミド
単位であるコポリマーは、寸法安定性、耐熱性、耐薬品
性の点から好ましい。Typical of these para -oriented aromatic fragrances Poramide include polybarabens amide, polybarafenylene telepramide, poly -4,4 'Ciamino Hens Annilid Televo Kuramide, Bo IJ -N, N' -P - Phenylene bis(p-benzamide) terephthalamide, polyvaraphenylene-26-naphthalamide, copoly-varaphenylene/3,4' (oxydiphenylene) terephthalamide, copoly-varaphenylene/4,4'(
33'-dimethylbiphenylene)-terephthalamide,
Examples include poly-2-chloro-bara phenylene terephthalamide F and the like. Among these, poly-paraphenylene terephthalamide or a copolymer in which 40 mol% or more of the repeating units constituting the polymer are paraphenylene terephthalamide units is preferred from the viewpoint of dimensional stability, heat resistance, and chemical resistance.
かかるバラ配向芳香族ポリアミlは、相当する芳香族環
性ジアミン及び芳香族環性二塩基酸ハライドとから、い
わゆる低温溶液重合法(例えば、特公昭35−1439
9号公報等参照)によって高収率で高重合度ポリマーと
して得られる。Such a randomly oriented aromatic polyamyl is produced by a so-called low-temperature solution polymerization method (for example, Japanese Patent Publication No. 35-1439) from a corresponding aromatic cyclic diamine and an aromatic cyclic dibasic acid halide.
9, etc.), it can be obtained in high yield as a polymer with a high degree of polymerization.
本発明において用いられるパラ配向芳香族ポリアミド“
の重合度は、特に制限を受りるものではないが、通常は
対数粘度(ηinh )で0.8以上のものが用いられ
る。Para-oriented aromatic polyamide used in the present invention
The degree of polymerization is not particularly limited, but one having an logarithmic viscosity (ηinh) of 0.8 or more is usually used.
かかるパラ配向芳香族ポリアミドから粒子を得るには、
単離精製されたポリマーを通常汎用的に用いられる機械
的粉砕手段、例えばボールミル、ハンマーミル、ジエ・
ントミル等により粉砕することによって得られる。又、
例えば特開昭62−32123号公報に開示された方法
によっても微細な粒子を得ることができる。本発明にお
いては、粒子を得る手段は特に制限を受けるものではな
い。To obtain particles from such para-oriented aromatic polyamides,
The isolated and purified polymer is usually milled using commonly used mechanical grinding means such as ball mills, hammer mills, die mills, etc.
Obtained by grinding with a mill or the like. or,
For example, fine particles can also be obtained by the method disclosed in JP-A-62-32123. In the present invention, the means for obtaining particles is not particularly limited.
本発明において用いられる芳香族ポリアミド粒子の粒子
径(平均粒子径を表わし、以後単に粒径と略称する)は
、摺動利とした時の相手側の材質等により多少は異なる
か、通常100μm以下のものが好ましく用いられる。The particle size (representing the average particle size, hereinafter simply referred to as particle size) of the aromatic polyamide particles used in the present invention may vary depending on the material of the other side when used as a sliding joint, but is usually 100 μm or less. Those are preferably used.
特に高い摺動特性を得る為には、粒径が5へ・50μm
の範囲にある粒子を用いるのがよい。In order to obtain particularly high sliding properties, the particle size must be increased to 5 or 50 μm.
It is preferable to use particles within this range.
粒子の形状は、球状、リン片状、棒状等々いずれのもの
であってもす(れた摺動特性を得ることが出来るが、特
にずくれた摺動特性を得る為には球状であるのが望まし
い。The shape of the particles can be spherical, scale-like, rod-like, etc. to obtain smooth sliding properties, but in order to obtain particularly uneven sliding properties, spherical shapes are preferred. is desirable.
本発明の熱硬化性樹脂組成物においては、前述の熱硬化
性樹脂とパラ配向芳香族ポリアミド粒子との混合割合は
、重要な因子であり、熱硬化性樹脂100重量部に対し
て、パラ配向芳香族ポリアミド粒子を5〜300重量部
とすることが必要である。In the thermosetting resin composition of the present invention, the mixing ratio of the above-mentioned thermosetting resin and para-oriented aromatic polyamide particles is an important factor. It is necessary to use 5 to 300 parts by weight of aromatic polyamide particles.
パラ配向芳香族ポリアミド粒子の混合割合が、5重量部
未満では、その効果が小さく、摩擦係数、摩耗性共に不
充分で、高い摺動特性を得ることが出来ない。一方、3
00重量部以−トート、硬質のパラ配向芳香族ポリアミ
ド粒子自体が基材として作用し、摩擦係数が増大するた
め好ましくない。If the mixing ratio of the para-oriented aromatic polyamide particles is less than 5 parts by weight, the effect is small, the friction coefficient and abrasion properties are both insufficient, and high sliding characteristics cannot be obtained. On the other hand, 3
00 parts by weight or more is not preferable because the hard para-oriented aromatic polyamide particles themselves act as a base material and increase the coefficient of friction.
パラ配向芳香族ポリアミド粒子の好適な混合割合は5〜
200重量部であり、更に10〜100重量部であるの
が耐熱性、機械的特性及び摺動性のいずれの点からも最
も好ましい。The preferred mixing ratio of para-oriented aromatic polyamide particles is 5 to 5.
The amount is preferably 200 parts by weight, and more preferably 10 to 100 parts by weight from the viewpoint of heat resistance, mechanical properties, and sliding properties.
本発明の組成物とするために、熱硬化性樹脂とパラ配向
芳香族ポリアミド粒子とを上述の配合割合に混合するに
は、従来から公知の方法を利用すればよい。具体的には
、例えば熱硬化性樹脂の粉末と、バラ配向芳香族ポリア
ミ1粒子の所定量を、ヘンシェルミキサー、ボールミル
、タンブラ−ミキサー等々の混合機によって混合する方
法があげられる。A conventionally known method may be used to mix the thermosetting resin and para-oriented aromatic polyamide particles in the above-mentioned mixing ratio to form the composition of the present invention. Specifically, for example, there is a method of mixing a thermosetting resin powder and a predetermined amount of one particle of unevenly oriented aromatic polyamide using a mixer such as a Henschel mixer, a ball mill, a tumbler mixer, or the like.
本発明の組成物を用いて、例えば摺動材等に成形する方
法は特に限定されるものではないが、通常は、−■混合
粉体を圧縮することによって賦形し、ついて加熱加圧下
に硬化成形する圧縮成形法が採用される。また、場合に
よっては熱可塑性樹脂を混合し7、押出し成形等をする
ことも可能であり、使用I:I的に応じて適宜選択すれ
ばよい。The method of molding the composition of the present invention into, for example, a sliding material is not particularly limited, but usually -■ The mixed powder is shaped by compressing it, and then heated and pressurized. A compression molding method of hardening molding is used. Further, depending on the case, it is also possible to mix a thermoplastic resin 7 and perform extrusion molding, etc., and it may be selected as appropriate depending on the usage I:I.
本発明の熱硬化性樹脂組成物は、熱硬化性樹脂及びパラ
配向芳香族ポリアミ1−粒子のほかに、般に合成樹脂に
広く配合し得る添加剤、充填剤を、本発明の組成物の特
性・を低下させない範囲において適宜併用することが出
来る。このような添加剤としては、たとえば離型剤、f
1燃剤、耐候性改良剤等々が例示されるがこれらに限定
されるものではなく、従来から公知、公用の固体もしく
は液状の潤滑剤を併用することは勿論可能であり、四フ
フ化エチレン樹脂、グラフアイ1〜、フッ化黒鉛、タル
ク、窒化ホウ素、シリコーン系の樹脂又はオイル、その
他工業用潤滑剤等も使用目的に応して適宜選択使用する
ことができる。いずれも、この発明の熱硬化性樹脂組成
物の性能を損わない限り、中間製品もしくは最終製品に
おいて化学的もしくは物理的な処理によって性質改善の
ための変性が可能であることは勿論である。The thermosetting resin composition of the present invention contains, in addition to the thermosetting resin and the para-oriented aromatic polyamide particles, additives and fillers that can be widely incorporated into synthetic resins. They can be used in combination as appropriate within a range that does not reduce the properties. Such additives include, for example, a mold release agent, f
Examples include, but are not limited to, refractory agents, weather resistance improvers, etc., and it is of course possible to use conventionally known and publicly used solid or liquid lubricants, such as tetrafluoroethylene resin, Graphi 1~, fluorinated graphite, talc, boron nitride, silicone resin or oil, and other industrial lubricants can also be selected and used as appropriate depending on the purpose of use. In any case, it is of course possible to modify the intermediate or final product to improve its properties by chemical or physical treatment, as long as the performance of the thermosetting resin composition of the present invention is not impaired.
実施例
以下、実施例によって本発明を更に詳細にかつ具体的に
説明する。EXAMPLES Hereinafter, the present invention will be explained in more detail and concretely using examples.
摩擦摩耗性の評価
摩擦係数;銘木式摩擦摩耗試験機により面圧10kg/
c+fl、線速度60cm/秒、50時間、相手材34
5C無給油
で測定した。Evaluation of friction and wear properties Friction coefficient: surface pressure of 10 kg/
c+fl, linear velocity 60 cm/sec, 50 hours, mating material 34
Measured without 5C oil.
摩耗係数;銘木式摩擦摩耗試験機により面圧2kg/c
Ifl、線速度60cm/秒、50時間、相手材345
C無給油で測
定した。Wear coefficient: surface pressure 2kg/c by precious wood type friction and wear tester
Ifl, linear velocity 60 cm/sec, 50 hours, mating material 345
C Measured without oil.
参考例1
撹拌機を備えた重合器中のN−メチル−2−ピロリドン
250kgに塩化リチウム8.5 kg及びパラフェニ
レンジアミン10.8 kgを加えて溶解し、ついで粉
末状のテレフタル酸クロライド20.3 kgを一度に
投入して重合を行った。投入後約3分で撹拌が困難とな
ったので撹拌を停止し、そのまま30分間放置したのち
、チーズ状に固化した重合固化ドープを得た。Reference Example 1 8.5 kg of lithium chloride and 10.8 kg of paraphenylenediamine were added and dissolved in 250 kg of N-methyl-2-pyrrolidone in a polymerization vessel equipped with a stirrer, and then 20.5 kg of powdered terephthalic acid chloride was added. Polymerization was carried out by adding 3 kg at once. About 3 minutes after the addition, stirring became difficult, so stirring was stopped and the mixture was allowed to stand for 30 minutes, to obtain a polymerized and solidified dope that solidified into a cheese shape.
ついでこの重合固化ドープを水と共にヘンシェルミキサ
ー内に入れ、30分間撹拌し粉砕を行った。このヘンシ
エルミキザーには、器壁との間隔が5mmとなる位置に
竪型のブレードが備えつけである。粉砕操作を終了後、
内容物を取出しポリマ粒子を水洗し、ついで乾燥した。Next, this polymerized and solidified dope was put into a Henschel mixer together with water and stirred for 30 minutes to perform pulverization. This Henschel mixer is equipped with a vertical blade located at a distance of 5 mm from the vessel wall. After finishing the crushing operation,
The contents were taken out and the polymer particles were washed with water and then dried.
得られた乾燥粒子をウイレー型粉砕機に投入して粉砕を
行い、平均粒子径がそれぞれ37μm、84μmのポリ
パラフェニレンテレフタルアミl゛の粒子を得た。The obtained dry particles were placed in a Wiley-type pulverizer and pulverized to obtain particles of polyparaphenylene terephthalamyl having average particle diameters of 37 μm and 84 μm, respectively.
得られた粒子の対数粘度(ηinh = ff1n77
r/C。Logarithmic viscosity of the obtained particles (ηinh = ff1n77
r/C.
30°C0,2g/100cc、98%硫酸中で測定)
は4.78であった。Measured in 98% sulfuric acid at 30°C 0.2g/100cc)
was 4.78.
参考例2
参考例1と同様にしてメタフェニレンジアミン及びイソ
フタル酸クロライドとからポリメタフェニレンイソフタ
ルアミドの粒子(平均粒子径;78μm)を得た。Reference Example 2 Polymetaphenylene isophthalamide particles (average particle diameter: 78 μm) were obtained from metaphenylene diamine and isophthalic acid chloride in the same manner as in Reference Example 1.
実施例1〜4.比較例1及び2
ノボラック型フェノール樹脂として、三片東圧社製ミレ
ツクス2410粉末を用い、参考例1で得られたポリ−
パラフェニレンテレフタルアミド粉末と第1表に示され
る混合割合で混合し、ついで、金型温度180°C1硬
化時間45秒の条件で試験片を成形した。Examples 1-4. Comparative Examples 1 and 2 The poly-
It was mixed with paraphenylene terephthalamide powder at the mixing ratio shown in Table 1, and then a test piece was molded at a mold temperature of 180° C. and a curing time of 45 seconds.
この試験片を用いて、摩擦摩耗試験を行なって得た結果
を第1表に示した。Using this test piece, a friction and wear test was conducted and the results obtained are shown in Table 1.
比較のため、ポリ−パラフェニレンテレフタルアミド粉
末を含まない成形試験片を同様にして作成し、合わせて
評価を行なった。その結果を第1表に並記したが、これ
ら比較例に対して本発明の成形品は、摩擦性、摩耗性い
ずれの点においても優れたものであることが証明された
。For comparison, a molded test piece containing no poly-paraphenylene terephthalamide powder was prepared in the same manner and evaluated. The results are listed in Table 1, and it was proven that the molded product of the present invention was superior to these comparative examples in terms of both friction and abrasion properties.
冒
実施例5
熱硬化性樹脂として、Rhone Poulenc社製
Kerimid ’1000の粉末125grと、参考
例1で得られた平均粒子径84μmのポリ−バラフェニ
レンテレフタルアミド粉末37.5grを混合した。得
られた混合粉体を金型に充填し、300 kg/c+f
l。Example 5 As a thermosetting resin, 125 gr of Kerimid '1000 powder manufactured by Rhone Poulenc and 37.5 gr of the poly-bula phenylene terephthalamide powder having an average particle diameter of 84 μm obtained in Reference Example 1 were mixed. The obtained mixed powder is filled into a mold and 300 kg/c+f
l.
230°C×15分間加熱硬化させて、摩擦摩耗性評価
のための試験片を成形し評価を行なった。この試験片の
摩擦係数は0.17 、摩耗係数はく0.1XIO−1
゜cnl/kg −c+nであり極めて優れた摩擦摩耗
特性を有するものであった。It was heated and cured at 230°C for 15 minutes to form a test piece for evaluation of friction and abrasion properties. The friction coefficient of this test piece is 0.17, and the wear coefficient is 0.1XIO-1.
°cnl/kg -c+n, and had extremely excellent friction and wear characteristics.
以上の説明ならびに実施例により明らかな如(、熱硬化
性樹脂に、パラ配向芳香族ポリアミド粒子を配合するこ
とによって、特に高速領域での摺動特性が著しく改善さ
れ、さらに長時間安定な摺動特性が得られる。その結果
、従来困難とされて来た高速領域での軸受等摺動材の樹
脂化が可能となり、軽量化と共に経済性の点においても
多大な効果を有するものである。As is clear from the above explanation and examples (by blending para-oriented aromatic polyamide particles into a thermosetting resin, the sliding properties, especially in the high-speed range, are significantly improved, and the sliding properties are stable for a long time. As a result, it becomes possible to use resin for sliding materials such as bearings in high-speed ranges, which has been considered difficult in the past, and has great effects in terms of weight reduction and economic efficiency.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
族ポリアミド粒子5〜300重量部を配合してなること
を特徴とする熱硬化性樹脂組成物(1) A thermosetting resin composition comprising 5 to 300 parts by weight of para-oriented aromatic polyamide particles per 100 parts by weight of the thermosetting resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP469189A JPH02185563A (en) | 1989-01-13 | 1989-01-13 | Thermosetting resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP469189A JPH02185563A (en) | 1989-01-13 | 1989-01-13 | Thermosetting resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02185563A true JPH02185563A (en) | 1990-07-19 |
Family
ID=11590915
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP469189A Pending JPH02185563A (en) | 1989-01-13 | 1989-01-13 | Thermosetting resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02185563A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2857015A1 (en) * | 2003-07-01 | 2005-01-07 | Tld | Polyurea elastomer for production of heavy-duty flooring or sealing elements, obtained by reacting polyisocyanate with a mixture of aramid powder and amines |
JP2005120128A (en) * | 2003-10-14 | 2005-05-12 | Teijin Techno Products Ltd | Thermosetting resin composition having excellent thermal dimensional stability |
-
1989
- 1989-01-13 JP JP469189A patent/JPH02185563A/en active Pending
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2857015A1 (en) * | 2003-07-01 | 2005-01-07 | Tld | Polyurea elastomer for production of heavy-duty flooring or sealing elements, obtained by reacting polyisocyanate with a mixture of aramid powder and amines |
JP2005120128A (en) * | 2003-10-14 | 2005-05-12 | Teijin Techno Products Ltd | Thermosetting resin composition having excellent thermal dimensional stability |
JP4505205B2 (en) * | 2003-10-14 | 2010-07-21 | 帝人テクノプロダクツ株式会社 | Thermosetting resin composition with excellent thermal dimensional stability |
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