JP2878977B2 - Sliding resin composition - Google Patents
Sliding resin compositionInfo
- Publication number
- JP2878977B2 JP2878977B2 JP6319170A JP31917094A JP2878977B2 JP 2878977 B2 JP2878977 B2 JP 2878977B2 JP 6319170 A JP6319170 A JP 6319170A JP 31917094 A JP31917094 A JP 31917094A JP 2878977 B2 JP2878977 B2 JP 2878977B2
- Authority
- JP
- Japan
- Prior art keywords
- ptfe
- weight
- pps
- molecular weight
- resin composition
- 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.)
- Expired - Lifetime
Links
Description
【０００１】[0001]
【産業上の利用分野】この発明は、耐熱性、耐摩擦摩耗
特性に優れ、安定した耐摩擦摩耗特性を有する射出成形
可能な摺動用樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for sliding which is excellent in heat resistance and friction and wear resistance and has stable friction and wear resistance and which can be injection molded.
【０００２】[0002]
【従来の技術】ポリフェニレンサルフアイド（以下、Ｐ
ＰＳと記す）は耐熱性、耐薬品性に優れた熱可塑性樹脂
として知られており、多くの産業分野に使用されてい
る。しかしこのＰＰＳは自己潤滑性に乏しいため、摺動
用材料として使用する場合には別途潤滑材等を添加して
潤滑性を付与しなければならない。そこでＰＰＳに黒
鉛、四弗化エチレン樹脂（以下、ＰＴＦＥと記す）、芳
香族ポリアミド等の固体潤滑材あるいはガラス繊維、カ
ーボン繊維、芳香族ポリアミド繊維等の補強繊維を充填
した樹脂組成物が提案されている。特に自己潤滑性に優
れたＰＴＦＥを添加、混合して成形した樹脂組成物は、
その優れた耐熱性、耐摩擦摩耗特性から摺動用材料とし
て好適である。2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as P
PS) is known as a thermoplastic resin having excellent heat resistance and chemical resistance, and is used in many industrial fields. However, since this PPS has poor self-lubricating properties, when used as a sliding material, it is necessary to add a lubricant or the like separately to impart lubricating properties. Therefore, a resin composition in which PPS is filled with a solid lubricant such as graphite, tetrafluoroethylene resin (hereinafter referred to as PTFE), aromatic polyamide, or a reinforcing fiber such as glass fiber, carbon fiber, or aromatic polyamide fiber has been proposed. ing. Particularly, a resin composition molded by adding and mixing PTFE having excellent self-lubricating properties is:
It is suitable as a sliding material because of its excellent heat resistance and friction and wear resistance.
【０００３】[0003]
【発明が解決しようとする課題】通常、ＰＰＳに各種充
填材を添加する場合、ベースのＰＰＳには300 ℃での溶
融粘度が 1,500〜3,000 poise であるＰＰＳが使用され
る。このＰＰＳとＰＴＦＥを混練り、混合するには、単
軸あるいは二軸押出機等が使用されるが、ＰＰＳとＰＴ
ＦＥの相溶性がよくないことから、均一な分散状態に混
合することが難しく、その結果優れた摩擦摩耗特性を有
した材料であっても、分散状態の不均一により定常的に
安定した特性が得られないことがあった。即ち、ＰＰＳ
とＰＴＦＥの分散が不均一な部分が摺動面に現れると異
常摩耗を生じ、場合によってはその発熱により摺動材自
体が溶融するという不具合があった。Generally, when various fillers are added to PPS, PPS having a melt viscosity at 300 ° C. of 1,500 to 3,000 poise is used as the base PPS. In order to knead and mix the PPS and PTFE, a single-screw or twin-screw extruder is used.
Due to the poor compatibility of FE, it is difficult to mix into a uniform dispersion state. As a result, even if the material has excellent friction and wear characteristics, a stable and stable characteristic due to the uneven dispersion state is obtained. Sometimes it was not possible. That is, PPS
When a portion where the dispersion of PTFE and PTFE is not uniform appears on the sliding surface, abnormal wear occurs, and in some cases, the sliding material itself is melted by the heat generated.
【０００４】[0004]
【課題を解決するための手段】この発明の摺動用樹脂組
成物は、上記問題点を解決するためになされたもので、
ベースとなるＰＰＳとして300 ℃での溶融粘度が 400〜
800 poise であるポリフェニレンサルフアイドを50〜90
重量％、ＰＴＦＥとして乳化重合法により製造されその
分子量が 5,000〜600,000 である低分子量の四弗化エチ
レン樹脂粉末を10〜50重量％配合することを特徴とす
る。ここで用いられるＰＰＳは、一般式SUMMARY OF THE INVENTION The sliding resin composition of the present invention has been made to solve the above problems.
Melt viscosity at 300 ℃ is 400 ~
Add 800 poise of polyphenylene sulfide to 50-90
% By weight, and 10 to 50% by weight of a low molecular weight ethylene tetrafluoride resin powder having a molecular weight of 5,000 to 600,000 produced by an emulsion polymerization method as PTFE. The PPS used here is a general formula
【０００５】[0005]
【化１】 で示される合成樹脂であり、特に300 ℃での溶融粘度が
400〜800 poise であるものが好適である。一般式にお
けるｎはその溶融粘度に対応する繰返し単位数を表す。
これよりも溶融粘度が高いＰＰＳでは、低分子量のＰＴ
ＦＥを混合しても良好に分散しない。Embedded image The melt viscosity at 300 ° C is particularly
Those having a poise of 400-800 poise are preferred. N in the general formula represents the number of repeating units corresponding to the melt viscosity.
In the case of PPS having a higher melt viscosity, a low molecular weight PT
Even if FE is mixed, it does not disperse well.
【０００６】またこの発明における低分子量のＰＴＦＥ
は、重合法、放射線分解法、熱分解法等によって製造さ
れる低分子量ＰＴＦＥのうち、乳化重合法で製造される
分子量 5,000〜600,000 のＰＴＦＥであり、この低分子
量ＰＴＦＥを10〜50重量％配合することが好適である。
この場合、高分子量のＰＴＦＥを放射線あるいは熱等で
その高分子鎖を切断することにより得られる低分子量Ｐ
ＴＦＥでは、ＰＰＳとの分散性が悪く、混合時あるいは
成形時に低分子量ＰＴＦＥが凝集し、均一な分散状態の
成形体が得られない。一方、本発明の乳化重合法で製造
される低分子量ＰＴＦＥでは、ＰＰＳとの混合時や成形
時にこのような凝集が起こらず、均一な分散状態の成形
体が得られる。さらに、放射線分解法により製造された
低分子量ＰＴＦＥと乳化重合法により製造された低分子
量ＰＴＦＥの分散性の違いについて以下詳しく説明す
る。The low molecular weight PTFE of the present invention
Is PTFE having a molecular weight of 5,000 to 600,000 produced by an emulsion polymerization method among low molecular weight PTFE produced by a polymerization method, a radiolysis method, a thermal decomposition method, etc., and 10 to 50% by weight of the low molecular weight PTFE is blended. It is preferred to do so.
In this case, a low molecular weight P obtained by cutting a high molecular weight PTFE with a radiation or heat to break the high molecular chain thereof.
TFE has poor dispersibility with PPS, and low-molecular-weight PTFE agglomerates during mixing or molding, and a molded article in a uniform dispersed state cannot be obtained. On the other hand, with the low-molecular-weight PTFE produced by the emulsion polymerization method of the present invention, such agglomeration does not occur at the time of mixing with PPS or molding, and a molded article in a uniform dispersed state can be obtained. Further, the difference in dispersibility between the low molecular weight PTFE manufactured by the radiolysis method and the low molecular weight PTFE manufactured by the emulsion polymerization method will be described in detail below.
【０００７】放射線分解法により製造された低分子量Ｐ
ＴＦＥは高分子量のＰＴＦＥを放射線により分解し、粉
砕などによって製造されるため加工工程において静電気
を帯びた状態になっている。このようなＰＴＦＥ粉末を
ＰＰＳと溶融混合すると、この静電気のためＰＴＦＥが
凝集し、ＰＰＳとＰＴＦＥの分散が悪くなる。またある
程度良好に分散したコンパウンドが得られたとしても、
このコンパウンドを射出成形機に投入して成形しようと
する場合、成形機内で再度加熱溶融した時にＰＴＦＥが
再凝集し、結果的に得られた成形品のＰＰＳとＰＴＦＥ
の分散状態が不均一となり、安定した性能を有する製品
が得られない。Low molecular weight P produced by radiolysis
Since TFE is produced by decomposing high-molecular-weight PTFE by radiation and pulverizing it, it is charged with static electricity in the processing step. When such PTFE powder is melt-mixed with PPS, PTFE aggregates due to the static electricity, and the dispersion of PPS and PTFE deteriorates. Also, even if a somewhat well-dispersed compound is obtained,
When this compound is put into an injection molding machine and molding is to be performed, the PTFE is re-agglomerated when heated and melted again in the molding machine, and the PPS and PTFE of the resulting molded product are obtained.
Becomes uneven, and a product having stable performance cannot be obtained.
【０００８】一方、乳化重合法により製造された低分子
量ＰＴＦＥは、高分子量のＰＴＦＥを低分子量化したも
のではなく、通常の乳化重合法で重合する時に低い重合
度で反応を停止させて製造したものであるから、基本的
に静電気を帯びていない。このため乳化重合法で製造さ
れた低分子量ＰＴＦＥは、凝集しにくく分散性がよい。
また乳化重合法で製造された低分子量ＰＴＦＥは、溶融
混合時のせん断力により容易に分子鎖が伸び、これがＰ
ＰＳとからみあって分散され、さらに成形機内で再溶融
した場合でもそのからみあいが維持されるので、良好な
分散状態を持った成形体が得られる。このように乳化重
合法により製造された低分子量ＰＴＦＥを用いることに
より均一な分散状態が得られるが、その配合量が50重量
％を超えると著しく成形性が損なわれ、また10重量％よ
り少ないと十分な摩擦摩耗特性の向上に効果が現れな
い。On the other hand, the low-molecular-weight PTFE produced by the emulsion polymerization method is not the one obtained by reducing the molecular weight of the high-molecular-weight PTFE, but is produced by stopping the reaction at a low degree of polymerization when polymerizing by the ordinary emulsion polymerization method. It is basically not charged with static electricity. For this reason, the low molecular weight PTFE produced by the emulsion polymerization method is hard to aggregate and has good dispersibility.
In addition, the low molecular weight PTFE produced by the emulsion polymerization method easily expands the molecular chain due to the shear force at the time of melt mixing.
It is dispersed entangled with the PS, and even when remelted in the molding machine, the entanglement is maintained, so that a molded article having a good dispersion state can be obtained. A uniform dispersion state can be obtained by using the low-molecular-weight PTFE manufactured by the emulsion polymerization method as described above. No effect is exhibited in sufficiently improving the friction and wear characteristics.
【０００９】このＰＰＳ及び低分子量ＰＴＦＥを混合分
散する方法については、特に限定するものではなく、通
常広く用いられている方法、たとえば両材料をヘンシェ
ルミキサー、ボールミル等の混合機により適宜乾式混合
した後、溶融押出機、ニーダー等で溶融混合する方法を
利用すればよい。The method of mixing and dispersing the PPS and the low-molecular-weight PTFE is not particularly limited, and a method generally used widely, for example, after dry-mixing both materials appropriately by a mixer such as a Henschel mixer or a ball mill, A method of melt mixing with a melt extruder, a kneader or the like may be used.
【００１０】[0010]
【実施例】以下、この発明を実施例に基づいて説明す
る。DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.
【００１１】実施例１ 300 ℃での溶融粘度が600 poise であるＰＰＳ（（株）
トープレン製Ｔ−２）60重量％と乳化重合法により製造
される分子量400,000 のＰＴＦＥ（三井デュポンフロロ
ケミカル（株）製ＭＰ１５００−Ｊ）40重量％をヘンシ
ェルミキサーで乾式混合後、溶融押出機で溶融、混合
し、造粒してペレットを作製した。このペレットを樹脂
温度320 ℃、射出圧力2,000 kg／cm2 、金型温度140 ℃
の射出条件下で外径30mm、内径16mm、高さ35mmの円筒状
試験片を成形した。この試験片をジャーナル式摩擦摩耗
試験機にて、摺動速度80cm／sec 、荷重2.5 kg／cm2 、
相手軸ＳＵＳ３０４（研磨仕上げ）という条件で、200
時間摺動試験を行った。その結果を表１に示した。Example 1 A PPS having a melt viscosity at 300 ° C. of 600 poise (manufactured by
After dry-mixing 60% by weight of T-Toplen manufactured by Topren and 40% by weight of PTFE (MP1500-J, manufactured by DuPont Mitsui Fluorochemicals Co., Ltd.) having a molecular weight of 400,000 produced by an emulsion polymerization method, the mixture is dry-mixed with a Henschel mixer and then melted with a melt extruder. , Mixed and granulated to produce pellets. The pellets are heated at a resin temperature of 320 ° C, an injection pressure of 2,000 kg / cm 2 and a mold temperature of 140 ° C.
A cylindrical test piece having an outer diameter of 30 mm, an inner diameter of 16 mm, and a height of 35 mm was formed under the injection conditions described above. The test piece was subjected to a sliding speed test of 80 cm / sec, a load of 2.5 kg / cm 2 ,
Under the condition that the mating shaft is SUS304 (polished), 200
A time sliding test was performed. The results are shown in Table 1.
【００１２】実施例２〜４ 実施例１のＰＰＳ及びＰＴＦＥの配合量を表１の実施例
２〜４に示したように変えた他は、実施例１と同様な作
製方法、摩擦摩耗試験方法で行った実施例である。その
結果を表１に示した。Examples 2 to 4 The same preparation method and friction and wear test method as in Example 1 except that the amounts of PPS and PTFE in Example 1 were changed as shown in Examples 2 to 4 in Table 1. This is the embodiment performed in the above. The results are shown in Table 1.
【００１３】比較例１ 300 ℃での溶融粘度が600 poise であるＰＰＳ（（株）
トープレン製Ｔ−２）60重量％と放射線分解法により製
造された分子量400,000 のＰＴＦＥ（三井デュポンフロ
ロケミカル（株）製ＭＰ１３００）40重量％を実施例１
と同様の方法で混合し、作製した試験片を用いて同様な
摺動試験を行った。その結果を表１に示した。Comparative Example 1 A PPS having a melt viscosity at 300 ° C. of 600 poise (Co., Ltd.)
Example 1 60% by weight of T-2 manufactured by Toprene and 40% by weight of PTFE (MP1300 manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.) having a molecular weight of 400,000 produced by radiolysis.
The same sliding test was performed using the test pieces prepared by mixing and producing in the same manner. The results are shown in Table 1.
【００１４】 比較例２ ３００℃での溶融粘度が２，０００ｐｏｉｓｅであるＰ
ＰＳ（（株）トープレン製Ｔ−４）６０重量％と乳化重
合法により製造された分子量４００，０００のＰＴＦＥ
（三井デュポンフロロケミカル（株）製ＭＰ１５００−
Ｊ）４０重量％を実施例１と同様の方法で混合し、作製
した試験片を用いて同様な方法で摺動試験を行なった。
その結果を表１に示した。Comparative Example 2 P having a melt viscosity at 300 ° C. of 2,000 poise
PS (T-4 manufactured by Topren Co., Ltd.) 60% by weight and emulsified weight
PTFE with a molecular weight of 400,000 produced by a legal process
(Mitsui DuPont Fluorochemical Co., Ltd. MP1500-
J) 40% by weight was mixed in the same manner as in Example 1, and a sliding test was carried out in the same manner using the prepared test pieces.
The results are shown in Table 1.
【００１５】比較例３，４ 実施例１のＰＰＳ及びＰＴＦＥの配合量を本発明の好ま
しい範囲から外した他は、実施例１と同様な作製方法、
摩擦摩耗試験方法で行った例である。その結果を表１に
示した。Comparative Examples 3 and 4 The same manufacturing method as in Example 1 except that the amounts of PPS and PTFE in Example 1 were excluded from the preferred range of the present invention,
It is an example performed by a friction and wear test method. The results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】[0017]
【発明の効果】以上述べたように、本発明によれば、耐
熱性、耐摩耗性に優れ、安定した摩擦摩耗特性を有する
摺動用樹脂組成物を得ることができる。また組成物は相
手軸が軟質材料例えば真鍮、ステンレス、アルミニウム
等であっても使用可能である。さらに本発明による樹脂
組成物は、ＰＰＳをベースとしているため射出成形が可
能であり、低コストの摺動材が製作可能となる。As described above, according to the present invention, a sliding resin composition having excellent heat resistance and wear resistance and having stable friction and wear characteristics can be obtained. The composition can be used even if the mating shaft is made of a soft material such as brass, stainless steel, aluminum or the like. Furthermore, since the resin composition according to the present invention is based on PPS, injection molding is possible, and a low-cost sliding material can be manufactured.
フロントページの続き (72)発明者 穴沢慶確 東京都中央区築地４−１−１東燃化学株 式会社内 (72)発明者 三川直浩 神奈川県川崎市川崎区千鳥町３−１ (56)参考文献 特開 平３−292366（ＪＰ，Ａ) 特開 平５−306371（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 81/02 C08L 27/18 Continuing on the front page (72) Inventor Keishou Anawazawa 4-1-1 Tsukiji, Chuo-ku, Tokyo Tonen Chemical Co., Ltd. (72) Inventor Naohiro Mikawa 3-1 Chidoricho, Kawasaki-ku, Kawasaki-shi, Kanagawa (56) Reference Reference JP-A-3-292366 (JP, A) JP-A-5-306371 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 81/02 C08L 27/18
Claims (2)
であるポリフェニレンサルフアイド50〜90重量％と、乳
化重合法により製造されその分子量が 5,000〜600,000
である低分子量の四弗化エチレン樹脂粉末10〜50重量％
から成ることを特徴とする摺動用樹脂組成物。1. A melt viscosity at 300 ° C. of 400 to 800 poise.
50 to 90% by weight of polyphenylene sulfide and a molecular weight of 5,000 to 600,000 produced by an emulsion polymerization method.
Low molecular weight ethylene tetrafluoride resin powder of 10 to 50% by weight
A sliding resin composition comprising:
量％である請求項１記載の摺動用樹脂組成物。2. The sliding resin composition according to claim 1, wherein the content of the ethylene tetrafluoride resin powder is 30 to 50% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6319170A JP2878977B2 (en) | 1994-11-29 | 1994-11-29 | Sliding resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6319170A JP2878977B2 (en) | 1994-11-29 | 1994-11-29 | Sliding resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08151497A JPH08151497A (en) | 1996-06-11 |
| JP2878977B2 true JP2878977B2 (en) | 1999-04-05 |
Family
ID=18107214
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6319170A Expired - Lifetime JP2878977B2 (en) | 1994-11-29 | 1994-11-29 | Sliding resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2878977B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998021277A1 (en) * | 1996-11-14 | 1998-05-22 | Asahi Glass Company | Polymer alloy of ethylene/tetrafluoroethylene copolymer |
| JP4668375B2 (en) * | 1999-08-19 | 2011-04-13 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Low melt viscosity polytetrafluoroethylene composition |
| DE102007038929B4 (en) * | 2007-08-13 | 2010-01-14 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Polyphenylene sulfide (per) fluoropolymer materials and processes for their preparation and use |
| DE102009018636A1 (en) | 2009-04-17 | 2010-10-21 | Elringklinger Ag | Polymer compound and components made using the compound |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03292366A (en) * | 1990-04-10 | 1991-12-24 | Nippon Seiko Kk | Wear-resistant resin composition |
| JPH05306371A (en) * | 1992-04-30 | 1993-11-19 | Ntn Corp | Resin composition for gear |
-
1994
- 1994-11-29 JP JP6319170A patent/JP2878977B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08151497A (en) | 1996-06-11 |
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