JP3665383B2 - Resin composition - Google Patents
Resin composition Download PDFInfo
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- JP3665383B2 JP3665383B2 JP11450995A JP11450995A JP3665383B2 JP 3665383 B2 JP3665383 B2 JP 3665383B2 JP 11450995 A JP11450995 A JP 11450995A JP 11450995 A JP11450995 A JP 11450995A JP 3665383 B2 JP3665383 B2 JP 3665383B2
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- resin
- thermoplastic
- aromatic polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
Description
【０００１】
【産業上の利用分野】
本発明は、引張強さおよび曲げ弾性などの機械的特性に優れた摺動性成形部品用途に好適な樹脂組成物、さらに詳しくは熱可塑性樹脂マトリックスに熱可塑性フェノール系樹脂および全芳香族ポリアミドの粒子または繊維を添加した樹脂組成物に関する。
【０００２】
【従来の技術】
ポリアミド等の熱可塑性樹脂またはフェノール等の熱硬化性樹脂の潤滑性や耐摩耗性などの摩擦特性を改善することを目的として、これらのマトリックス樹脂に芳香族ポリアミド粒子を添加した樹脂組成物が、国際公開ＷＯ０９３／０４３００号、特開平２−１６３１６３号公報、特開平２−１８５５６３号公報などに開示されている。また特開平４−２８３２６２号公報には、芳香族ポリアミド粒子表面に有機質部がグラフト的に付加された表面改質芳香族ポリアミド粒子をマトリックス樹脂に配合することが提案されている。
【０００３】
【発明が解決しようとする課題】
これらの熱可塑性樹脂への芳香族ポリアミド粒子の添加により、成形品の摺動性は改善されるものの、引張強さおよび曲げ弾性などの機械的特性が低下することが問題となっている。表面改質芳香族ポリアミド粒子の場合には、機械的特性の低下をある程度抑止することはできても、芳香族ポリアミド粒子の表面改質操作そのものが繁雑であり、必ずしも生産性の良好な方法ではない。
【０００４】
本発明は、引張強さおよび曲げ弾性などの機械的特性および摩擦特性に優れ、摺動部品の成形に好適な樹脂組成物を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは、芳香族ポリアミド粒子の添加による機械的特性の低下が、芳香族ポリアミド粒子とマトリックス樹脂との密着性に起因していることを突き止め、熱可塑性フェノール系樹脂の添加によりそれらの密着性を向上できることを見出し、本発明を完成した。
【０００６】
本発明は、熱可塑性フェノール系樹脂と相溶性または半相溶性を有する熱可塑性樹脂からなるマトリックス樹脂９９.８〜３０.０重量％、熱可塑性フェノール系樹脂０.１〜３０.０重量％、および全芳香族ポリアミドの粒子または繊維０．１〜４０.０重量％を含有することを特徴とする樹脂組成物である。
【０００７】
本発明において、熱可塑性フェノール系樹脂は、フェノール化合物とホルムアルデヒドとの重縮合物であり、特に酸触媒の存在下で重縮合して得られるオリゴマーおよびポリマーのいずれかを使用するのが好ましい。フェノール化合物としては、フェノール、クレゾール、ブチルフェノール、オクチルフェノールなどのアルキルフェノール類、ナフトール、レゾルシノール、ハイドロキノン、ヒドロキシ安息香酸などが挙げられる。またｐ−ビニルフェノールの重合体であるポリビニルフェノールも好適に使用することができる。
熱可塑性フェノール系樹脂として、数平均分子量が一般に１５０,０００まで、好ましくは２００〜１０,０００のものを使用する。
【０００８】
熱可塑性フェノール系樹脂の添加量が過少な場合には、全芳香族ポリアミドの粒子または繊維とマトリックス樹脂との密着性を改良するに至らず、また過剰に使用した場合には成形品の伸びが著しく低下するので好ましくない。熱可塑性フェノール系樹脂の好適な添加量は、全樹脂分を基準として０.１〜３０.０重量％である。
【０００９】
本発明において、マトリックス樹脂は、フェノール系樹脂と相溶性または半相溶性の熱可塑性樹脂である。ここに、相溶性または半相溶性は、マトリックス樹脂とフェノール系樹脂とを溶融混練した溶融物の透明性、示差走査熱量測定（ＤＳＣ）によるガラス転移温度（Ｔｇ）または融解温度（ＭＰ）の移動、動的粘弾性測定（ＤＭＡ）による散逸率（ｔａｎδ）のピークの温度位置の変化などにより判断する。具体的には、マトリックス樹脂と熱可塑性フェノール系樹脂との混合溶融物が透明または半透明であれば、相溶性または半相溶性であると判断し、またマトリックス樹脂に熱可塑性フェノール系樹脂を混合してＤＳＣで測定したガラス転移温度（Ｔｇ）または融解温度（ＭＰ）のピークがマトリックス樹脂単独のＤＳＣ測定値から移動すれば相溶性または半相溶性と判断し、またマトリックス樹脂単独の場合と混合物とのＤＭＡで測定した散逸率（ｔａｎδ）のピークの温度位置に変化があれば相溶性または半相溶性と判断する。
【００１０】
これらの熱可塑性樹脂は、エステル、ニトリル、アミド、ケトン、エーテル、スルフィド、スルホン、カーボネート、ウレタンなどの官能基を有する熱可塑性樹脂、たとえばスチレン−アクリロニトリル共重合体樹脂（ＳＡＮ）、メチルメタクリレート樹脂（ＰＭＭＡ）、ポリカプロラクトン樹脂（ＰＣＬ）、スチレン−無水マレイン酸共重合体樹脂（Ｓ／ＭＡｎｈ）、イミド化メチルメタクリレート樹脂（ｉｍｍ−ＭＭＡ）、ポリカーボネート樹脂（ＰＣ）、ポリアリレート樹脂（ＰＡＲ）、ポリスルホン樹脂、ポリフェニレンオキサイド（ＰＰＯ）、半芳香族ポリアミド樹脂（６Ｔ／６Ｉ）、ポリアミド樹脂（６ナイロン、６１２ナイロン）、ポリエチレンテレフタレート樹脂（ＰＥＴ）、ポリブチレンテレフタレート樹脂（ＰＢＴ）、液晶高分子樹脂（ＬＣＰ）、ポリフェニレンスルフィド樹脂（ＰＰＳ）、ポリアセタール樹脂（ＰＯＭ）、ポリエーテルケトンケトン樹脂（ＰＥＫＫ）等である。
【００１１】
マトリックス樹脂の添加量は、全樹脂分を基準として９９.８〜３０.０重量％である。
【００１２】
本発明において、全芳香族ポリアミドは、次式の繰り返し単位から本質的になるポリマーである。
【００１３】
−ＮＨ−Ａｒ1−ＮＨ−ＣＯ−Ａｒ2−ＣＯ−
ここに、Ａｒ1およびＡｒ2は、二価の芳香族基であり、同一であってもまた異なっていてもよい。パラ系全芳香族ポリアミド、詳しくはＡｒ1およびＡｒ2が同一または異なる二価のパラ配向芳香族基であるパラ配向芳香族ポリカーボンアミドが好ましい。パラ配向芳香族基とは、１，４−フェニレン、４,４’−ビフェニレン、２,６−ナフタレン、１,５−ナフタレンを含む置換または未置換の芳香族基を意味する。好適な置換基として、クロロ、低級アルキルおよびメトキシ基を例示することができる。また、パラ配向全芳香族ポリアミドは、同一の芳香族に酸およびアミン官能基が共存するコモノマーの少量を含む２以上のパラ配向コモノマーのパラ配向共重合体を含む。
【００１４】
本発明において、好適に使用される全芳香族ポリアミドは、８０モル％以上がパラフェニレンジアミンである芳香族ジアミンと、８０モル％以上がテレフタロイルハライドである芳香族二酸ハロゲン化物とを、アミド溶媒中で、好ましくは６０℃以下の温度で重合させることにより得られる。好ましいアミド溶媒として、Ｎ−メチルピロリドン、ジメチルアセトアミドおよびアルカリ金属ハロゲン化物を含有するテトラメチルユリアを挙げることができる。
【００１５】
本発明において、最も好適な全芳香族ポリアミドは、ポリ−ｐ−フェニレンテレフタルアミドである。
【００１６】
本発明において使用される全芳香族ポリアミド繊維は、直径が３０ミクロン以下であり、また粒子は粒径が５００ミクロン以下である。好ましくは、全芳香族ポリアミドの粒子を使用するが、粒径が過大であると成形品の機械的特性が低下し、熱可塑性フェノール系樹脂を添加してもそれを防止できない。全芳香族ポリアミド粒子の粒径は、１〜５０ミクロンが好ましい。
【００１７】
全芳香族ポリアミドの粒子または繊維の添加量が過少な場合は、期待する摺動性の改善効果が得られず、また過剰な場合には機械的特性が低下するので好ましくない。好ましい全芳香族ポリアミドの粒子または繊維の添加量は、全樹脂分基準で０．１〜４０重量％である。
【００１８】
本発明の樹脂組成物には、前記成分以外にマトリックス樹脂に通常添加配合される各種添加剤、たとえば安定剤、核剤、帯電防止剤、難燃剤、着色剤、潤滑剤などを添加してもよい。またガラス繊維、無機粉末、タルクなどの充填剤を添加することもできる。
【００１９】
本発明の樹脂組成物の製造には、公知の方法を採用することができる。たとえば、各成分を押出機などの成形機内で混練する方法、ニーダーなどで機械的に混練する方法、各成分を適当な良溶媒中で同時に混合するか、またはそれぞれを個別に溶解して混合した後、溶媒を除去する方法、さらにはこれらの二以上を組合わせた方法などが挙げられる。
【００２０】
【作用】
本発明において、熱可塑性フェノール系樹脂は、マトリックス樹脂と相溶性または半相溶性であり、マトリックス樹脂に摺動性を付与するために添加される全芳香族ポリアミドの粒子または繊維とマトリックス樹脂との密着性を向上させる。したがって、熱可塑性フェノール系樹脂を全芳香族ポリアミドの粒子または繊維と共にマトリックス樹脂に添加することにより、全芳香族ポリアミドの粒子または繊維がマトリックス樹脂中に均一に分散し、摺動性を低下させることなく成形品の機械的特性を向上させる作用を奏する。
【００２１】
【実施例】
例１ 熱可塑性フェノール系樹脂とマトリックス樹脂との相溶性
ノボラック樹脂と各種マトリックス樹脂との溶融混合物の透明性の観察、またはＤＳＣによるガラス移転温度（Ｔｇ）もしくは融解温度（ＭＰ）の移動、またはＤＭＡによるガラス移転温度（ｔａｎδ）のピークの温度位置の変化を測定し、各マトリックス樹脂とノボラック樹脂との相溶性または半相溶性を判断した。熱可塑性フェノール系樹脂と相溶性または半相溶性を有する熱可塑性樹脂を表１に示す。
【００２２】
【表１】
例２ 機械的特性の測定
各成分を二軸押出機（東芝製ＴＥＭ３５）を用いて溶融混練し、水冷後、各種組成のペレットを製造した。得られたペレットを用いてＡＳＴＭ Ｄ６３８に準拠した１３mm×１３０mm×３.２mmの試験片を成形した。
得られた試験片を用いて、下記の機械的特性を測定した。
引張強さ ＡＳＴＭ Ｄ６３８に準拠
伸び ＡＳＴＭ Ｄ６３８に準拠
曲げ弾性率 ＡＳＴＭ Ｄ７９０に準拠
衝撃強さ(ノッチ付きアイゾット) ＡＳＴＭ Ｄ２５６に準拠
製造したペレットの組成および機械的特性の測定結果を表２〜４に示す。
【００２４】
【表２】
実施例のいずれにおいても、引張強さおよび曲げ弾性率が向上する。また実施例４および６よりＫＥＶＬＡＲの含有量を多くすると引張強さは低下するが、曲げ弾性率は向上することがわかる。
【００２６】
【表３】
マトリックス樹脂としてポリフェニレンスルフィドを使用した場合も、ポリブチレンテレフタレートを使用した場合と同様に、引張り強さおよび曲げ弾性率が向上する。
【００２８】
【表４】
マトリックス樹脂としてナイロン６６を用いた場合も、ＰＢＴおよびＰＰＳを用いた場合と同様に引張り強さおよび曲げ弾性率が向上する。また実施例１３および１５よりＫＥＶＬＡＲの粒径が小さいほうが、引張り強さの向上が著しく伸びおよび衝撃強さの低下が小さい。
【００３０】
【発明の効果】
本発明においては、熱可塑性フェノール系樹脂を全芳香族ポリアミドの粒子または繊維と共にマトリックス樹脂に添加したことにより、得られた成形品の摺動性が損なわれることなく機械的特性が向上する。[0001]
[Industrial application fields]
The present invention relates to a resin composition suitable for use in slidable molded parts having excellent mechanical properties such as tensile strength and flexural elasticity, and more specifically, a thermoplastic phenolic resin and wholly aromatic polyamide are added to a thermoplastic resin matrix. The present invention relates to a resin composition to which particles or fibers are added.
[0002]
[Prior art]
For the purpose of improving friction properties such as lubricity and abrasion resistance of thermoplastic resins such as polyamide or thermosetting resins such as phenol, resin compositions in which aromatic polyamide particles are added to these matrix resins, It is disclosed in International Publication WO093 / 04300, Japanese Patent Laid-Open No. 2-163163, Japanese Patent Laid-Open No. 2-185563, and the like. Japanese Laid-Open Patent Publication No. 4-283262 proposes that surface-modified aromatic polyamide particles having an organic part graft added to the surface of the aromatic polyamide particles are blended in the matrix resin.
[0003]
[Problems to be solved by the invention]
Although addition of aromatic polyamide particles to these thermoplastic resins improves the slidability of the molded product, it has a problem that mechanical properties such as tensile strength and bending elasticity are lowered. In the case of surface-modified aromatic polyamide particles, even though the deterioration of mechanical properties can be suppressed to some extent, the surface modification operation itself of aromatic polyamide particles is complicated, and it is not always possible to use a method with good productivity. Absent.
[0004]
An object of the present invention is to provide a resin composition which is excellent in mechanical properties such as tensile strength and flexural elasticity and friction properties, and suitable for molding of sliding parts.
[0005]
[Means for Solving the Problems]
The present inventors have found out that the deterioration of the mechanical properties due to the addition of the aromatic polyamide particles is due to the adhesion between the aromatic polyamide particles and the matrix resin, and the addition of the thermoplastic phenol-based resin makes them The inventors have found that the adhesion can be improved and completed the present invention.
[0006]
The present invention comprises 99.8 to 30.0% by weight of a matrix resin composed of a thermoplastic resin compatible or semi-compatible with a thermoplastic phenolic resin, 0.1 to 30.0% by weight of a thermoplastic phenolic resin, And 0.1 to 40.0% by weight of fully aromatic polyamide particles or fibers.
[0007]
In the present invention, the thermoplastic phenol resin is a polycondensate of a phenol compound and formaldehyde, and it is particularly preferable to use any one of an oligomer and a polymer obtained by polycondensation in the presence of an acid catalyst. Examples of the phenol compound include alkylphenols such as phenol, cresol, butylphenol, and octylphenol, naphthol, resorcinol, hydroquinone, and hydroxybenzoic acid. Moreover, polyvinylphenol which is a polymer of p-vinylphenol can also be used suitably.
As the thermoplastic phenolic resin, those having a number average molecular weight of generally up to 150,000, preferably 200 to 10,000 are used.
[0008]
If the amount of thermoplastic phenol resin added is too small, the adhesion between the particles or fibers of the wholly aromatic polyamide and the matrix resin will not be improved, and if used excessively, the elongation of the molded product will not increase. Since it falls remarkably, it is not preferable. A suitable addition amount of the thermoplastic phenol-based resin is 0.1 to 30.0% by weight based on the total resin content.
[0009]
In the present invention, the matrix resin is a thermoplastic resin that is compatible or semi-compatible with the phenolic resin. Here, compatibility or semi-compatibility means transparency of a melt obtained by melt-kneading a matrix resin and a phenol resin, movement of glass transition temperature (Tg) or melting temperature (MP) by differential scanning calorimetry (DSC). Judgment is based on the change in temperature position of the peak of the dissipation factor (tan δ) by dynamic viscoelasticity measurement (DMA). Specifically, if the mixed melt of the matrix resin and the thermoplastic phenolic resin is transparent or translucent, it is determined that it is compatible or semi-compatible, and the thermoplastic resin is mixed with the matrix resin. If the peak of the glass transition temperature (Tg) or melting temperature (MP) measured by DSC moves from the DSC measurement value of the matrix resin alone, it is judged as compatible or semi-compatible. If there is a change in the temperature position of the peak of the dissipation factor (tan δ) measured by DMA, it is judged as compatible or semi-compatible.
[0010]
These thermoplastic resins include thermoplastic resins having a functional group such as ester, nitrile, amide, ketone, ether, sulfide, sulfone, carbonate, urethane, such as styrene-acrylonitrile copolymer resin (SAN), methyl methacrylate resin ( PMMA), polycaprolactone resin (PCL), styrene-maleic anhydride copolymer resin (S / MANh), imidized methyl methacrylate resin (imm-MMA), polycarbonate resin (PC), polyarylate resin (PAR), polysulfone Resin, polyphenylene oxide (PPO), semi-aromatic polyamide resin (6T / 6I), polyamide resin (6 nylon, 612 nylon), polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), Crystal polymer resin (LCP), polyphenylene sulfide resin (PPS), a polyacetal resin (POM), polyether ketone ketone resin (PEKK) and the like.
[0011]
The addition amount of the matrix resin is 99.8 to 30.0% by weight based on the total resin content.
[0012]
In the present invention, the wholly aromatic polyamide is a polymer consisting essentially of repeating units of the following formula.
[0013]
—NH—Ar 1 —NH—CO—Ar 2 —CO—
Here, Ar 1 and Ar 2 are divalent aromatic groups, which may be the same or different. Para-type wholly aromatic polyamides, specifically, para-oriented aromatic polycarbonates in which Ar 1 and Ar 2 are the same or different divalent para-oriented aromatic groups are preferred. The para-oriented aromatic group means a substituted or unsubstituted aromatic group including 1,4-phenylene, 4,4′-biphenylene, 2,6-naphthalene, and 1,5-naphthalene. Examples of suitable substituents include chloro, lower alkyl, and methoxy groups. Also, the para-oriented wholly aromatic polyamide includes a para-oriented copolymer of two or more para-oriented comonomers containing a small amount of a comonomer in which acid and amine functional groups coexist in the same aromatic.
[0014]
In the present invention, the wholly aromatic polyamide preferably used includes an aromatic diamine in which 80 mol% or more is paraphenylenediamine and an aromatic diacid halide in which 80 mol% or more is terephthaloyl halide. It can be obtained by polymerization in an amide solvent, preferably at a temperature of 60 ° C. or lower. Preferred amide solvents include tetramethyl urea containing N-methylpyrrolidone, dimethylacetamide and alkali metal halide.
[0015]
In the present invention, the most preferred wholly aromatic polyamide is poly-p-phenylene terephthalamide.
[0016]
The wholly aromatic polyamide fiber used in the present invention has a diameter of 30 microns or less, and the particles have a particle size of 500 microns or less. Preferably, particles of wholly aromatic polyamide are used. However, if the particle size is excessively large, the mechanical properties of the molded product are deteriorated and cannot be prevented even if a thermoplastic phenol resin is added. The particle size of the wholly aromatic polyamide particles is preferably 1 to 50 microns.
[0017]
When the amount of the fully aromatic polyamide particles or fibers is too small, the expected effect of improving the slidability cannot be obtained, and when it is excessive, the mechanical properties are deteriorated. The preferred amount of particles or fibers of wholly aromatic polyamide is 0.1 to 40% by weight based on the total resin content.
[0018]
In addition to the above components, various additives that are usually added to the matrix resin, such as stabilizers, nucleating agents, antistatic agents, flame retardants, colorants, lubricants, and the like may be added to the resin composition of the present invention. Good. Moreover, fillers, such as glass fiber, inorganic powder, and talc, can also be added.
[0019]
A well-known method is employable for manufacture of the resin composition of this invention. For example, a method of kneading each component in a molding machine such as an extruder, a method of kneading mechanically with a kneader, etc., mixing each component at the same time in an appropriate good solvent, or mixing each component separately Thereafter, a method of removing the solvent, a method of combining two or more of these, and the like can be mentioned.
[0020]
[Action]
In the present invention, the thermoplastic phenol-based resin is compatible or semi-compatible with the matrix resin, and is composed of a wholly aromatic polyamide particles or fibers added to impart slidability to the matrix resin and the matrix resin. Improve adhesion. Therefore, by adding the thermoplastic phenolic resin to the matrix resin together with the particles or fibers of the wholly aromatic polyamide, the particles or fibers of the wholly aromatic polyamide are uniformly dispersed in the matrix resin, thereby reducing the slidability. The mechanical properties of the molded product are improved.
[0021]
【Example】
Example 1 Compatibility of thermoplastic phenolic resin and matrix resin Observation of transparency of molten mixture of novolak resin and various matrix resins, movement of glass transition temperature (Tg) or melting temperature (MP) by DSC, or DMA The change in the temperature position of the peak of the glass transition temperature (tan δ) due to was measured, and the compatibility or semi-compatibility between each matrix resin and novolak resin was judged. Table 1 shows thermoplastic resins having compatibility or semi-compatibility with the thermoplastic phenolic resin.
[0022]
[Table 1]
Example 2 Measurement of mechanical properties Each component was melt-kneaded using a twin-screw extruder (TEM35 manufactured by Toshiba), and after cooling with water, pellets having various compositions were produced. A test piece of 13 mm × 130 mm × 3.2 mm conforming to ASTM D638 was molded using the obtained pellet.
Using the obtained test piece, the following mechanical properties were measured.
Tensile strength Elongation according to ASTM D638 Flexural modulus according to ASTM D638 Impact strength according to ASTM D790 (Izod with notch) Table 2-4 shows the measurement results of the composition and mechanical properties of pellets manufactured according to ASTM D256 .
[0024]
[Table 2]
In any of the examples, the tensile strength and the flexural modulus are improved. It can also be seen that increasing the KEVLAR content from Examples 4 and 6 decreases the tensile strength but improves the flexural modulus.
[0026]
[Table 3]
When polyphenylene sulfide is used as the matrix resin, the tensile strength and the flexural modulus are improved as in the case of using polybutylene terephthalate.
[0028]
[Table 4]
When nylon 66 is used as the matrix resin, the tensile strength and the flexural modulus are improved as in the case of using PBT and PPS. In addition, the smaller the KEVLAR particle size than in Examples 13 and 15, the remarkably improved tensile strength and the smaller the decrease in impact strength.
[0030]
【The invention's effect】
In the present invention, by adding the thermoplastic phenol resin to the matrix resin together with the particles or fibers of the wholly aromatic polyamide, the mechanical properties are improved without impairing the slidability of the obtained molded product.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11450995A JP3665383B2 (en) | 1995-05-12 | 1995-05-12 | Resin composition |
| PCT/US1996/006825 WO1996035742A1 (en) | 1995-05-12 | 1996-05-13 | All-aromatic polyamide particles or fibers containing resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11450995A JP3665383B2 (en) | 1995-05-12 | 1995-05-12 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08302212A JPH08302212A (en) | 1996-11-19 |
| JP3665383B2 true JP3665383B2 (en) | 2005-06-29 |
Family
ID=14639546
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11450995A Expired - Fee Related JP3665383B2 (en) | 1995-05-12 | 1995-05-12 | Resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3665383B2 (en) |
| WO (1) | WO1996035742A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY120047A (en) * | 1997-06-30 | 2005-08-30 | Kisco Ltd | Polyamide resin composition |
| JP2002293979A (en) | 2001-03-30 | 2002-10-09 | Sumitomo Chem Co Ltd | Porous para-oriented aromatic polyamide film, its prepreg and substrate using prepreg and used for printed circuit |
| JP4852932B2 (en) * | 2005-08-24 | 2012-01-11 | 住友ベークライト株式会社 | Phenol resin molding material and method for producing the same |
| US20070060712A1 (en) * | 2005-09-15 | 2007-03-15 | General Electric Company | Thermoplastic composition with improved wear properties and method for making thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3230441C2 (en) * | 1982-08-16 | 1994-12-15 | Borg Warner | Dry, asbestos-free friction material and / or friction elements and a process for their preparation |
| DE3925791A1 (en) * | 1989-08-04 | 1991-02-07 | Bayer Ag | FLAME-RETARDED, NON-DRIPING POLYAMIDE MOLDS |
| DE3925792A1 (en) * | 1989-08-04 | 1991-02-07 | Bayer Ag | FLAME-RETARDED, NON-DRIPING POLYAMIDE MOLDS |
| DE3934710A1 (en) * | 1989-10-18 | 1991-04-25 | Bayer Ag | IMPROVED METHOD FOR PRODUCING SEMI-FINISHED PRODUCTS / COMPOSITES |
| DE4002605A1 (en) * | 1990-01-30 | 1991-09-26 | Bayer Ag | POLYAMIDE MOLDS |
| DE4100316A1 (en) * | 1991-01-08 | 1992-07-09 | Bayer Ag | COLOR-STABILIZED POLYAMIDE MOLDS |
| DE4123041A1 (en) * | 1991-07-12 | 1993-01-14 | Bayer Ag | THERMOPLASTIC POLYCARBONATE MOLDINGS WITH FLAME-RESISTANT PROPERTIES |
| MX9204769A (en) * | 1991-08-20 | 1993-02-01 | Du Pont | COMPOSITE MATERIAL FOR PACKAGING AND PROCESS FOR ITS MANUFACTURE. |
-
1995
- 1995-05-12 JP JP11450995A patent/JP3665383B2/en not_active Expired - Fee Related
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1996
- 1996-05-13 WO PCT/US1996/006825 patent/WO1996035742A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08302212A (en) | 1996-11-19 |
| WO1996035742A1 (en) | 1996-11-14 |
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