JP2009091527A - Method of manufacturing oil-containing thermoplastic synthetic resin molding - Google Patents

Method of manufacturing oil-containing thermoplastic synthetic resin molding Download PDF

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JP2009091527A
JP2009091527A JP2007266198A JP2007266198A JP2009091527A JP 2009091527 A JP2009091527 A JP 2009091527A JP 2007266198 A JP2007266198 A JP 2007266198A JP 2007266198 A JP2007266198 A JP 2007266198A JP 2009091527 A JP2009091527 A JP 2009091527A
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carbon dioxide
thermoplastic synthetic
synthetic resin
oil
pressure vessel
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JP5329789B2 (en
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Takashi Yamamoto
隆司 山本
Toshihiko Sekine
敏彦 関根
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Oiles Industry Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To improve sliding characteristics such as friction coefficient and abrasion resistance without lowering mechanical characteristics in moldings such as a bearing formed from these thermoplastic synthetic resins, although the thermoplastic synthetic resins such as a polyacetal resin and a polyamide resin have superior mechanical characteristics, also are superior in friction abrasion characteristic, heat resistance, chemical resistance and electric characteristics, and widely utilized as engineering plastics for automobile parts and parts for electric or electronic products. <P>SOLUTION: The oil-containing thermoplastic resin molding is manufactured by arranging a molding 1 made of the thermoplastic synthetic resin in a high-pressure container 2 in contact with a lubricant oil 4, injecting a carbon dioxide gas 5 preliminarily pressurized at the normal temperature to it to be hermetically closed, and after bringing the carbon dioxide into supercritical state, maintaining this state for a prescribed time to impregnate the molding 1 with the supercritical carbon dioxide dissolved in the lubricant oil, then removing carbon dioxide gas from the molding. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、含油熱可塑性合成樹脂成形物の製造方法に関する。   The present invention relates to a method for producing an oil-containing thermoplastic synthetic resin molding.

ポリアセタール樹脂やポリアミド樹脂などの熱可塑性合成樹脂は、優れた機械的性質を有し、摩擦摩耗特性、耐熱性、耐薬品性および電気特性にも優れ、エンジニアリングプラスチックスとして自動車部品、電気・電子製品の部品として広く利用されている。ところで、これら熱可塑性合成樹脂からなる軸受などの成形物においては、機械的特性を低下させることなく、摩擦係数、耐摩耗性などの摺動特性を向上させる幾つかの提案がなされている。   Thermoplastic synthetic resins such as polyacetal resin and polyamide resin have excellent mechanical properties and excellent friction and wear characteristics, heat resistance, chemical resistance, and electrical characteristics. Automotive parts and electrical / electronic products as engineering plastics Widely used as a part of By the way, in a molded article such as a bearing made of these thermoplastic synthetic resins, several proposals have been made to improve sliding characteristics such as a coefficient of friction and wear resistance without deteriorating mechanical characteristics.

ポリアセタール又はポリアミドから成る熱可塑性合成樹脂を粉末状にし、これに潤滑油剤を混ぜて撹拌してその樹脂粉末表面に潤滑油剤を均一に附着させ、次いで、これを加熱シリンダーの成形原料供給部が冷却手段によって該合成樹脂の融点以下の低温に保たれ、シリンダーの他の部分が少なくとも該合成樹脂の融点以上の温度に保たれた造粒機によって溶融混練して粒状とし、これを成形原料として所要の形状に成形する軸受などの要滑部材の製造方法が提案されている（特許文献１所載）。   A thermoplastic synthetic resin made of polyacetal or polyamide is powdered, and a lubricant is mixed and stirred to uniformly attach the lubricant to the surface of the resin powder. By means of a granulator in which the other part of the cylinder is kept at a temperature not lower than the melting point of the synthetic resin, and at least the melting point of the synthetic resin is maintained. A method of manufacturing a sliding member such as a bearing that is molded into the shape of this is proposed (Patent Document 1).

また、平均分子量５０万以上を有する超高分子量のポリエチレンに潤滑油を混和したものを合成樹脂に添加し、成形する含油プラスチック組成物が提案されている（特許文献２所載）。
特公昭４６−４２２１７号公報 特公昭４７−２９３７４号公報 Further, an oil-containing plastic composition has been proposed in which an ultra-high molecular weight polyethylene having an average molecular weight of 500,000 or more and a lubricating oil mixed therein is added to a synthetic resin and molded (Patent Document 2).
Japanese Examined Patent Publication No. 46-42217 Japanese Patent Publication No. 47-29374

しかしながら、前記のポリアセタール樹脂組成物から成る摺動部材は、射出成形等の成形加工性に問題がある。特に、前述の特許文献１に開示された技術においては、成形機の各部の温度コントロールを必要とする等、通常の成形条件では満足し得る成形物が得られ難いと言う問題がある。また、特許文献２に開示された技術においては、合成樹脂に潤滑油の保持体としてポリエチレン樹脂を配合しているため、成形物としては機械的物性値を低下させたり、原料段階で潤滑油を混合するため成形性を低下させるなどの問題がある。さらに、成形前の段階で潤滑油を混合しているため、潤滑油の分解温度以上の融点を有する合成樹脂には適用し難いという問題もある。   However, the sliding member made of the polyacetal resin composition has a problem in molding processability such as injection molding. In particular, the technique disclosed in Patent Document 1 described above has a problem that it is difficult to obtain a molded product that is satisfactory under normal molding conditions, such as requiring temperature control of each part of the molding machine. In the technique disclosed in Patent Document 2, since a polyethylene resin is blended with a synthetic resin as a lubricating oil holding body, the mechanical properties of the molded product are reduced, or the lubricating oil is used at the raw material stage. There is a problem that the formability is lowered due to mixing. Furthermore, since the lubricating oil is mixed in the stage before molding, there is a problem that it is difficult to apply to a synthetic resin having a melting point higher than the decomposition temperature of the lubricating oil.

本発明は、上記実情に鑑みなされたものであり、その目的とするところは、機械的性質を低下させることなく、摩擦係数、耐摩耗性などの摺動特性を改善することができる含油熱可塑性合成樹脂成形物の製造方法を提供することにある。   The present invention has been made in view of the above circumstances, and its object is to provide an oil-containing thermoplastic capable of improving sliding characteristics such as a coefficient of friction and wear resistance without deteriorating mechanical properties. It is providing the manufacturing method of a synthetic resin molding.

本発明の含油熱可塑性合成樹脂成形物の製造方法は、（ａ）熱可塑性合成樹脂からなる成形物を、高圧容器内において潤滑油と接触させるか、又は接触させることなく該高圧容器内に配置する工程と、（ｂ）該高圧容器内に、常温において予め加圧された二酸化炭素を注入し、密閉する工程と、（ｃ）該高圧容器内で二酸化炭素を加熱して該二酸化炭素に気化膨張にともなう圧力上昇を生じせしめ、該二酸化炭素を臨界温度（３１．１℃）以上の温度を有しかつ臨界圧力（７．３８Ｍｐａ）以上の圧力を有する領域にある超臨界状態、あるいは温度が臨界温度未満でかつ圧力が臨界圧力以上を有する領域にある亜臨界状態にする工程と、（ｄ）超臨界状態あるいは亜臨界状態を所定時間保持せしめ、潤滑油に溶解した超臨界状態あるいは亜臨界状態の二酸化炭素を該成形物中に含浸させる工程と、（ｅ）潤滑油に溶解した超臨界あるいは亜臨界状態の二酸化炭素が含浸された成形物を、所定温度で該成形物中から二酸化炭素を除去する工程とからなる。   The method for producing an oil-containing thermoplastic synthetic resin molding according to the present invention comprises: (a) a molded article made of a thermoplastic synthetic resin is placed in a high-pressure vessel without being brought into contact with or in contact with lubricating oil in the high-pressure vessel. And (b) injecting pre-pressurized carbon dioxide at room temperature into the high-pressure vessel and sealing, and (c) heating the carbon dioxide in the high-pressure vessel to vaporize the carbon dioxide. Causing a pressure increase with expansion, and the carbon dioxide is in a supercritical state in a region having a temperature higher than the critical temperature (31.1 ° C.) and higher than the critical pressure (7.38 Mpa), or A subcritical state in which the pressure is lower than the critical temperature and the pressure is higher than the critical pressure; and (d) a supercritical state or a subcritical state dissolved in the lubricating oil by holding the supercritical state or the subcritical state for a predetermined time. A step of impregnating the molded product with carbon dioxide in a state; and (e) a molded product impregnated with supercritical or subcritical carbon dioxide dissolved in a lubricating oil from the molded product at a predetermined temperature. The process of removing.

本発明の含油熱可塑性合成樹脂成形物の製造方法によれば、高圧容器内に常温（２３℃）において予め加圧（６Ｍｐａ程度）された状態で注入された二酸化炭素は、臨界温度（３１．１℃）以上の温度を有しかつ臨界圧力（７．３８Ｍｐａ）以上の圧力を有する領域にある液体状の超臨界状態、あるいは臨界温度未満の温度を有しかつ臨界圧力以上の圧力を有する領域にある亜臨界状態になることにより潤滑油に溶解し、超臨界あるいは亜臨界状態を所定時間保持することにより潤滑油に溶解した超臨界あるいは亜臨界状態の二酸化炭素は成形物中に含浸される。そして、潤滑油に溶解した超臨界あるいは亜臨界状態の二酸化炭素が含浸された成形物を、所定温度で該成形物中から二酸化炭素を除去することにより、該成形物中に潤滑油のみが含浸された含油熱可塑性合成樹脂成形物が得られる。   According to the method for producing an oil-containing thermoplastic synthetic resin molding of the present invention, carbon dioxide injected into a high-pressure container in a state of being pressurized (about 6 Mpa) at room temperature (23 ° C.) in advance is a critical temperature (31. A liquid supercritical state in a region having a temperature equal to or higher than 1 ° C. and having a pressure equal to or higher than a critical pressure (7.38 Mpa), or a region having a temperature lower than the critical temperature and a pressure higher than the critical pressure. The supercritical or subcritical carbon dioxide dissolved in the lubricating oil is impregnated in the molding by maintaining the supercritical or subcritical state for a predetermined time. . The molded product impregnated with supercritical or subcritical carbon dioxide dissolved in lubricating oil is then impregnated with only lubricating oil in the molded product by removing carbon dioxide from the molded product at a predetermined temperature. An oil-containing thermoplastic synthetic resin molded product is obtained.

本発明の含油熱可塑性合成樹脂成形物の製造方法において、熱可塑性合成樹脂成形物は、高圧容器内において該圧力容器内に設けられた支持体の上に配置されていると共に該圧力容器内に貯留された潤滑油中に浸漬されている態様が採られる。   In the method for producing an oil-containing thermoplastic synthetic resin molded product of the present invention, the thermoplastic synthetic resin molded product is disposed on a support provided in the pressure vessel in the high-pressure vessel, and in the pressure vessel. The aspect immersed in the stored lubricating oil is taken.

また、本発明の含油熱可塑性合成樹脂成形物の製造方法において、熱可塑性合成樹脂成形物は、高圧容器内において該圧力容器内に設けられた支持体の上に配置されていると共に該成形物の表面に潤滑油が塗布されている態様でもよく、さらに熱可塑性合成樹脂成形物は、高圧容器内において該高圧容器内に貯留された潤滑油と接触することなく該圧力容器内に設けられた支持体の上に配置されている態様でもよい。特に、高圧容器内に設けられた支持体の上に配置されていると共に該成形物の表面に潤滑油が塗布されている態様においては、熱可塑性合成樹脂成形物への潤滑油の含浸量を高めることができる。   In the method for producing an oil-containing thermoplastic synthetic resin molded product of the present invention, the thermoplastic synthetic resin molded product is disposed on a support provided in the pressure vessel in the high-pressure vessel and the molded product. The surface may be coated with lubricating oil, and the thermoplastic synthetic resin molded article is provided in the pressure vessel without contacting the lubricating oil stored in the high pressure vessel in the high pressure vessel. The aspect arrange | positioned on a support body may be sufficient. In particular, in an embodiment in which a lubricating oil is applied to the surface of the molded product and disposed on a support provided in a high-pressure vessel, the amount of lubricating oil impregnated into the thermoplastic synthetic resin molded product is reduced. Can be increased.

本発明の含油熱可塑性合成樹脂成形物の製造方法において、高圧容器内の温度は、二酸化炭素を臨界温度以上の温度を有しかつ臨界圧力以上の圧力を有する領域にある超臨界状態で使用する場合は、臨界温度以上の３５〜１２０℃に設定されるのが好ましく、また高圧容器内の圧力は、臨界圧力以上の８．５〜２５ＭＰａに設定されるのが好ましい。また、二酸化炭素を臨界温度未満の温度を有しかつ臨界圧力以上の圧力を有する領域にある亜臨界状態で使用する場合は、高圧容器内の温度は、臨界温度未満であって、高圧容器内の圧力は、臨界圧力以上の８．５〜２５ＭＰａに設定される。そして、そして、高圧容器内での超臨界状態での保持時間は、５〜１２０時間に設定されるのが好ましい。   In the method for producing an oil-containing thermoplastic synthetic resin molding of the present invention, the temperature in the high-pressure vessel is such that carbon dioxide is used in a supercritical state in a region having a temperature higher than the critical temperature and a pressure higher than the critical pressure. In this case, it is preferably set to 35 to 120 ° C. above the critical temperature, and the pressure in the high-pressure vessel is preferably set to 8.5 to 25 MPa above the critical pressure. When carbon dioxide is used in a subcritical state in a region having a temperature lower than the critical temperature and a pressure higher than the critical pressure, the temperature in the high-pressure vessel is lower than the critical temperature, The pressure is set to 8.5 to 25 MPa which is equal to or higher than the critical pressure. And it is preferable that the holding time in the supercritical state in the high-pressure vessel is set to 5 to 120 hours.

本発明の含油熱可塑性合成樹脂成形物の製造方法において、熱可塑性合成樹脂の成形物は、ポリアセタール樹脂、ポリアミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレン樹脂、ポリフェニレンサルファイド樹脂のいずれかからなる。   In the method for producing an oil-containing thermoplastic synthetic resin molding of the present invention, the thermoplastic synthetic resin molding is any one of a polyacetal resin, a polyamide resin, a polyether ether ketone resin, a polyethylene terephthalate resin, a polyethylene resin, and a polyphenylene sulfide resin. Become.

本発明によれば、潤滑油の分解温度以上の融点を有する合成樹脂に対しても機械的性質を低下させることなく、摩擦係数、耐摩耗性などの摺動特性を改善することができる含油熱可塑性合成樹脂成形物の製造方法を提供することができる。   According to the present invention, oil-impregnated heat that can improve sliding characteristics such as a coefficient of friction and wear resistance without deteriorating mechanical properties even for a synthetic resin having a melting point equal to or higher than the decomposition temperature of the lubricating oil. A method for producing a plastic synthetic resin molded product can be provided.

以下、本発明の含油熱可塑性合成樹脂成形物の製造方法について詳細に説明する。   Hereafter, the manufacturing method of the oil-containing thermoplastic synthetic resin molding of this invention is demonstrated in detail.

本発明の含油熱可塑性合成樹脂成形物の製造方法は、（ａ）熱可塑性合成樹脂からなる成形物を、高圧容器内において潤滑油と接触させるか、又は接触させることなく該高圧容器内に配置する工程と、（ｂ）該高圧容器内に、常温において予め加圧された二酸化炭素を注入し、密閉する工程と、（ｃ）該高圧容器内で二酸化炭素を加熱して該二酸化炭素に気化膨張にともなう圧力上昇を生じせしめ、該二酸化炭素を臨界温度（３１．１℃）以上の温度を有しかつ臨界圧力（７．３８Ｍｐａ）以上の圧力を有する領域にある超臨界状態、あるいは温度が臨界温度未満でかつ圧力が臨界圧力以上を有する領域にある亜臨界状態にする工程と、（ｄ）超臨界状態あるいは亜臨界状態を所定時間保持せしめ、潤滑油に溶解した超臨界状態あるいは亜臨界状態の二酸化炭素を該成形物中に含浸させる工程と、（ｅ）潤滑油に溶解した超臨界あるいは亜臨界状態の二酸化炭素が含浸された成形物を、所定温度で該成形物中から二酸化炭素を除去する工程とからなるものである。   The method for producing an oil-containing thermoplastic synthetic resin molding according to the present invention comprises: (a) a molded article made of a thermoplastic synthetic resin is placed in a high-pressure vessel without being brought into contact with or in contact with lubricating oil in the high-pressure vessel. And (b) injecting pre-pressurized carbon dioxide at room temperature into the high-pressure vessel and sealing, and (c) heating the carbon dioxide in the high-pressure vessel to vaporize the carbon dioxide. Causing a pressure increase with expansion, and the carbon dioxide is in a supercritical state in a region having a temperature higher than the critical temperature (31.1 ° C.) and higher than the critical pressure (7.38 Mpa), or A subcritical state in which the pressure is lower than the critical temperature and the pressure is higher than the critical pressure; and (d) a supercritical state or a subcritical state dissolved in the lubricating oil by holding the supercritical state or the subcritical state for a predetermined time. A step of impregnating the molded product with carbon dioxide in a state; and (e) a molded product impregnated with supercritical or subcritical carbon dioxide dissolved in a lubricating oil from the molded product at a predetermined temperature. The process which removes.

図１乃至図３は、熱可塑性合成樹脂からなる成形物を、高圧容器内において潤滑油と接触させるか、又は接触させることなく該高圧容器内に配置する態様を示すものであり、図１は、熱可塑性合成樹脂製成形物１が高圧容器２内において、該高圧容器２内に設けられた支持体３としての金属メッシュの上に配置されていると共に該高圧容器２内に貯留された潤滑油４中に浸漬されている態様を示す。また図２は、熱可塑性合成樹脂製成形物１が高圧容器２内において、該高圧容器２内に設けられた支持体３としての金属メッシュの上に配置されていると共に該成形物の表面に潤滑油４が塗布されている態様を示し、図３は、熱可塑性合成樹脂製成形物１が高圧容器２内において、該高圧容器２内に貯留された潤滑油４と接触することなく該高圧容器２内に設けられた支持体３としての金属メッシュの上に配置されている態様を示す。   FIG. 1 to FIG. 3 show a mode in which a molded product made of a thermoplastic synthetic resin is placed in a high-pressure vessel without or in contact with a lubricating oil in the high-pressure vessel. The molded product 1 made of a thermoplastic synthetic resin is disposed in a high-pressure vessel 2 on a metal mesh as a support 3 provided in the high-pressure vessel 2 and is stored in the high-pressure vessel 2. The aspect immersed in the oil 4 is shown. Further, FIG. 2 shows that a thermoplastic synthetic resin molded product 1 is disposed in a high-pressure vessel 2 on a metal mesh as a support 3 provided in the high-pressure vessel 2 and on the surface of the molded product. FIG. 3 shows an embodiment in which the lubricating oil 4 is applied, and FIG. 3 shows that the molded article 1 made of a thermoplastic synthetic resin is not in contact with the lubricating oil 4 stored in the high-pressure vessel 2 in the high-pressure vessel 2. The aspect arrange | positioned on the metal mesh as the support body 3 provided in the container 2 is shown.

このように熱可塑性合成樹脂製成形物１が高圧容器２内に配置された状態で、該高圧容器２内に室温（２３℃）で予め６ＭＰａ程度の圧力に加圧した二酸化炭素５を注入し密閉する。この二酸化炭素５の高圧容器２内への注入により、図１に示す態様では潤滑油４の層の上に二酸化炭素５が層状に形成され、二酸化炭素５と潤滑油４の層とは完全に分離されている。また図２に示す態様では、二酸化炭素５が熱可塑性合成樹脂製成形物１と該成形物１の表面に塗布された潤滑油４の層を覆っている。さらに図３に示す態様では、二酸化炭素５が潤滑油４の層の上に熱可塑性合成樹脂製成形物１を覆って層状に形成され、二酸化炭素５と潤滑油４の層とは完全に分離されている。   With the thermoplastic synthetic resin molding 1 thus placed in the high-pressure vessel 2, carbon dioxide 5 that has been pressurized to a pressure of about 6 MPa in advance at room temperature (23 ° C.) is injected into the high-pressure vessel 2. Seal. By injecting the carbon dioxide 5 into the high-pressure vessel 2, the carbon dioxide 5 is formed on the lubricating oil 4 layer in the form shown in FIG. 1, and the carbon dioxide 5 and the lubricating oil 4 layer are completely separated. It is separated. In the embodiment shown in FIG. 2, carbon dioxide 5 covers the thermoplastic synthetic resin molded product 1 and the layer of lubricating oil 4 applied to the surface of the molded product 1. Further, in the embodiment shown in FIG. 3, carbon dioxide 5 is formed on the lubricating oil 4 layer so as to cover the thermoplastic synthetic resin molding 1, and the carbon dioxide 5 and the lubricating oil 4 layer are completely separated. Has been.

二酸化炭素５が注入された高圧容器２を、二酸化炭素の臨界温度（３１．１℃）以上の温度、好ましくは３５〜１２０℃の温度に加熱する。   The high-pressure vessel 2 into which the carbon dioxide 5 has been injected is heated to a temperature not lower than the critical temperature (31.1 ° C.) of carbon dioxide, preferably 35 to 120 ° C.

高圧容器２を加熱することにより、該高圧容器２内に注入された二酸化炭素５は、気化膨張にともなう圧力上昇を生じ、該二酸化炭素５の臨界圧力（７．３８ＭＰａ）以上の圧力において、該二酸化炭素５は、上記臨界温度以上の温度を有しかつ臨界圧力以上の圧力を有する領域にある超臨界二酸化炭素となる。   By heating the high-pressure vessel 2, the carbon dioxide 5 injected into the high-pressure vessel 2 generates a pressure increase due to vaporization and expansion, and at a pressure equal to or higher than the critical pressure (7.38 MPa) of the carbon dioxide 5 The carbon dioxide 5 becomes supercritical carbon dioxide in a region having a temperature equal to or higher than the critical temperature and having a pressure equal to or higher than the critical pressure.

高圧容器５内の圧力としては、臨界圧力以上の圧力、好ましくは８．５〜２５ＭＰａの圧力となるよう適宜排気しながら調整する。   The pressure in the high-pressure vessel 5 is adjusted while appropriately evacuating so that the pressure is higher than the critical pressure, preferably 8.5 to 25 MPa.

高圧容器２内において、超臨界二酸化炭素は臨界状態で所定時間保持される。保持時間としては、５〜２５時間（ｈｒ）の範囲が好ましい。   In the high-pressure vessel 2, supercritical carbon dioxide is held in a critical state for a predetermined time. The holding time is preferably in the range of 5 to 25 hours (hr).

高圧容器２内において、臨界状態で保持された超臨界二酸化炭素は、潤滑油４に溶解すると共に熱可塑性合成樹脂製成形物１中に含浸される。この成形物１中に含浸された潤滑油４は、超臨界二酸化炭素を含んでいるので、該成形物１を、所定の温度、例えば１２０℃の温度に加熱された容器内に静置することにより、該成形物１中から超臨界二酸化炭素が気化して除去され、成形物１中に潤滑油４のみが含浸された含油熱可塑性合成樹脂製成形物１とされる。   In the high-pressure vessel 2, supercritical carbon dioxide held in a critical state is dissolved in the lubricating oil 4 and impregnated in the thermoplastic synthetic resin molding 1. Since the lubricating oil 4 impregnated in the molding 1 contains supercritical carbon dioxide, the molding 1 is allowed to stand in a container heated to a predetermined temperature, for example, 120 ° C. Thus, supercritical carbon dioxide is vaporized and removed from the molded product 1, and the molded product 1 is made of an oil-containing thermoplastic synthetic resin in which only the lubricating oil 4 is impregnated in the molded product 1.

図４は、高圧容器２内で、熱可塑性合成樹脂成形物としてポリアセタール樹脂成形物１を用いて、前記図１乃至３に示す態様、すなわち該成形物を潤滑油中に完全に浸漬させる態様（ａ）（図１）、該成形物の表面に潤滑油を塗布する態様（ｂ）（図２）、該成形物を潤滑油と接触させない態様（ｃ）（図３）について、超臨界二酸化炭素の条件を、圧力２５ＭＰａ、温度１２０℃、保持時間２５ｈｒに設定し、該成形物の質量変化率（％）、換言すれば該成形物中への潤滑油及び該潤滑油に溶解した超臨界状態の二酸化炭素の含浸率（％）について試験した結果を示すグラフである。潤滑油としては、シリコーン油（３０００ｍｍ２／ｓ＠２５℃）を使用した。なお、態様（ｄ）は、比較のために該成形物を潤滑油（シリコーン油）中に、温度１２０℃、保持時間２５ｈｒの条件で浸漬したものである。 FIG. 4 shows the embodiment shown in FIGS. 1 to 3 using the polyacetal resin molded product 1 as a thermoplastic synthetic resin molded product in the high-pressure vessel 2, that is, a mode in which the molded product is completely immersed in lubricating oil ( Supercritical carbon dioxide for a) (FIG. 1), embodiment (b) (FIG. 2) in which lubricating oil is applied to the surface of the molding, and embodiment (c) (FIG. 3) in which the molding is not contacted with lubricating oil Are set to a pressure of 25 MPa, a temperature of 120 ° C., and a holding time of 25 hours, and the mass change rate (%) of the molded product, in other words, the lubricating oil in the molded product and the supercritical state dissolved in the lubricating oil It is a graph which shows the result tested about the impregnation rate (%) of the carbon dioxide. Silicone oil (3000 mm 2 / s @ 25 ° C.) was used as the lubricating oil. In the embodiment (d), the molded product is immersed in a lubricating oil (silicone oil) at a temperature of 120 ° C. and a holding time of 25 hours for comparison.

試験結果から、態様（ａ）乃至態様（ｃ）のポリアセタール樹脂成形物１には、３．６〜５．２％の質量変化が認められることから、潤滑油及び該潤滑油に溶解した超臨界状態の二酸化炭素が分散含有されていることが分かる。特に態様（ｂ）のポリアセタール樹脂成形物１について、ＥＤＸ分析（Energy Dispersive X-ray Fluorescence Spectrometer）を実施し、シリコーン油中に含まれる珪素（Ｓｉ）についてマッピングした結果を図５に示す。該成形物のほぼ全面的に均一にＳｉが分散されていることが確認できることから、シリコーン油が含浸されているものと判断される。   From the test results, the mass change of 3.6 to 5.2% is recognized in the polyacetal resin molded product 1 of the embodiment (a) to the embodiment (c). It can be seen that the carbon dioxide in a state is dispersedly contained. In particular, the polyacetal resin molded product 1 of the embodiment (b) is subjected to EDX analysis (Energy Dispersive X-ray Fluorescence Spectrometer), and the result of mapping silicon (Si) contained in the silicone oil is shown in FIG. Since it can be confirmed that Si is uniformly dispersed on almost the entire surface of the molded product, it is determined that the silicone oil is impregnated.

なお、以上においては超臨界状態の二酸化炭素についての説明であったが、熱可塑性合成樹脂成形物１が高圧容器２内に配置された状態で、該高圧容器２内に室温で予め６ＭＰａの圧力に加圧した二酸化炭素５を注入し、密閉したのち、二酸化炭素を二酸化炭素の臨界温度未満の温度で、かつ該二酸化炭素５の臨界圧力以上の圧力に保持することにより臨界温度未満の温度を有しかつ臨界圧力以上の圧力を有する領域にある亜臨界二酸化炭素としてもよい。   In the above description, carbon dioxide in the supercritical state has been described. However, in the state where the thermoplastic synthetic resin molded article 1 is disposed in the high-pressure vessel 2, the pressure in the high-pressure vessel 2 is 6 MPa in advance at room temperature. After injecting and sealing the pressurized carbon dioxide 5, the carbon dioxide is kept at a temperature below the critical temperature of carbon dioxide and at a pressure higher than the critical pressure of the carbon dioxide 5 to reduce the temperature below the critical temperature. It is good also as subcritical carbon dioxide in the area | region which has and has a pressure more than critical pressure.

この亜臨界二酸化炭素においても、上記した超臨界二酸化炭素と同様、熱可塑性合成樹脂製成形物中に潤滑油を含浸させることができる。   This subcritical carbon dioxide can also be impregnated with a lubricating oil in a molded product made of a thermoplastic synthetic resin, similarly to the supercritical carbon dioxide described above.

熱可塑性合成樹脂は、上記したポリアセタール樹脂の他にポリアミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレン樹脂、ポリフェニレンサルファイド樹脂が使用されて好適であり、これらの熱可塑性合成樹脂を射出成形あるいは押出成形によって熱可塑性合成樹脂成形物が作製される。   As the thermoplastic synthetic resin, a polyamide resin, a polyether ether ketone resin, a polyethylene terephthalate resin, a polyethylene resin, and a polyphenylene sulfide resin are preferably used in addition to the above-mentioned polyacetal resin. A thermoplastic synthetic resin molding is produced by extrusion molding.

本発明で用いられる潤滑油としては、スピンドル油、エンジン油、タービン油、ダイナモ油、冷凍機油、シリンダー油、ギヤ油等などの鉱油、鯨油、ヒマシ油、ホホバ油等の動・植物油、ポリグリコール、ポリフェニルエーテル、シルコーン油等の合成油が挙げられる。   The lubricating oil used in the present invention includes mineral oil such as spindle oil, engine oil, turbine oil, dynamo oil, refrigeration oil, cylinder oil, gear oil, etc., animal and vegetable oils such as whale oil, castor oil, jojoba oil, polyglycol And synthetic oils such as polyphenyl ether and silcorn oil.

このようにして得られた含油熱可塑性合成樹脂成形物は、滑り板、軸受ブッシュなどの摺動部材として使用される。   The oil-containing thermoplastic synthetic resin molding thus obtained is used as a sliding member such as a sliding plate and a bearing bush.

以下、本発明を実施例により詳細に説明するが、本発明は、その要旨を超えない限り、以下の実施例に限定されるものではない。   EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a following example, unless the summary is exceeded.

実施例
熱可塑性合成樹脂としてポリアセタール樹脂を使用し、これを射出成形により一辺が２０ｍｍ、厚さ５ｍｍの方形状成形物（試験片）を準備した。 Example A polyacetal resin was used as a thermoplastic synthetic resin, and a rectangular molded product (test piece) having a side of 20 mm and a thickness of 5 mm was prepared by injection molding.

この方形状成形物を高圧容器内に、該高圧容器内に設けられた保持体としての金属メッシュ（金網）の上に配置すると共に該成形物の表面に潤滑油を塗布した（図２参照）。潤滑油として、２５℃の温度で６８ｍＰａ・ｓの動粘度を示す冷凍機油を使用した。   This rectangular shaped product was placed in a high-pressure vessel on a metal mesh (metal net) as a holding body provided in the high-pressure vessel, and lubricating oil was applied to the surface of the molded product (see FIG. 2). As the lubricating oil, a refrigerating machine oil having a kinematic viscosity of 68 mPa · s at a temperature of 25 ° C. was used.

高圧容器内に室温（２３℃）で予め６ＭＰａの圧力に加圧された二酸化炭素を注入し、密閉した。ついで、高圧容器をヒーターによって、二酸化炭素の臨界温度以上の１５０℃の温度に加熱した。該高圧容器を加熱することにより、該高圧容器内に注入された二酸化炭素に気化膨張に伴う圧力上昇を生じせしめ、該二酸化炭素を臨界温度以上の温度を有しかつ臨界圧力以上の２５Ｍｐａの圧力を有する領域にある超臨界二酸化炭素とした。   Carbon dioxide previously pressurized to a pressure of 6 MPa at room temperature (23 ° C.) was injected into the high-pressure vessel and sealed. Next, the high-pressure vessel was heated by a heater to a temperature of 150 ° C. above the critical temperature of carbon dioxide. By heating the high-pressure vessel, the carbon dioxide injected into the high-pressure vessel is caused to increase in pressure due to vaporization and expansion, and the carbon dioxide has a pressure higher than the critical temperature and a pressure of 25 Mpa higher than the critical pressure. Supercritical carbon dioxide in the region having

この超臨界二酸化炭素を超臨界状態で２５ｈｒ保持し、該超臨界二酸化炭素を成形物の表面に塗布された潤滑油に溶解させると共に潤滑油に溶解した超臨界二酸化炭素を成形物中に含浸させた。   The supercritical carbon dioxide is maintained in a supercritical state for 25 hours, and the supercritical carbon dioxide is dissolved in the lubricating oil applied to the surface of the molded product, and the supercritical carbon dioxide dissolved in the lubricating oil is impregnated in the molded product. It was.

ついで、高圧容器内の温度を室温まで冷却したのち高圧容器内の圧力を減圧し、該高圧容器から成形物を取出した。この成形物を１２０℃の温度に保持した容器内で静置して、該成形物中に含浸された二酸化炭素を気化除去した。二酸化炭素を除去した後の成形物中の潤滑油の含浸量は、０．３重量％であった。   Next, after the temperature in the high-pressure vessel was cooled to room temperature, the pressure in the high-pressure vessel was reduced, and the molded product was taken out from the high-pressure vessel. The molded product was allowed to stand in a container maintained at a temperature of 120 ° C. to vaporize and remove carbon dioxide impregnated in the molded product. The amount of the lubricating oil impregnated in the molded product after removing carbon dioxide was 0.3% by weight.

比較例１
実施例と同様のポリアセタール樹脂を使用し、これを射出成形により一辺が２０ｍｍ、厚さ５ｍｍの方形状成形物（試験片）を準備した。この成形物を１２０℃の温度に加熱した冷凍機油を貯留した容器中に２５ｈｒ浸漬したのち取出し、この成形物を比較例１とした。 Comparative Example 1
The same polyacetal resin as in the examples was used, and a rectangular molded product (test piece) having a side of 20 mm and a thickness of 5 mm was prepared by injection molding. This molded product was taken out after being immersed in a container storing refrigerating machine oil heated to a temperature of 120 ° C. for 25 hours, and this molded product was used as Comparative Example 1.

比較例２
実施例と同様のポリアセタール樹脂を使用し、これを射出成形により一辺が２０ｍｍ、厚さ５ｍｍの方形状成形物（試験片）を準備し、この成形物を比較例２とした。 Comparative Example 2
A polyacetal resin similar to that of the example was used, and a rectangular molded product (test piece) having a side of 20 mm and a thickness of 5 mm was prepared by injection molding.

上記した実施例、比較例１及び比較例２の成形物について、表１に示す試験条件で摩擦係数を試験した。   The molded products of the above-described Examples, Comparative Example 1 and Comparative Example 2 were tested for friction coefficient under the test conditions shown in Table 1.

（表１）
荷重（面圧） ０．９８ＭＰａ
すべり速度 ０．１７ｍ／ｓｅｃ
試験時間 １２０ｈｒ
相手材材質 ＳＵＳ３１６
潤滑 無潤滑
運動形態 スラスト試験 (Table 1)
Load (surface pressure) 0.98 MPa
Sliding speed 0.17m / sec
Test time 120hr
Mating material SUS316
Lubrication Non-lubrication Motion form Thrust test

上記した条件での摩擦係数を測定した試験結果を図６に示す。試験結果から、実施例の含油成形物は、試験時間を通して安定した摩擦係数を示したのに対し、比較例１及び比較例２の成形物は、試験時間の経過とともに摩擦係数が増加する傾向を示していることがわかる。   The test results of measuring the friction coefficient under the above conditions are shown in FIG. From the test results, the oil-impregnated moldings of the examples showed a stable friction coefficient throughout the test time, whereas the moldings of Comparative Example 1 and Comparative Example 2 showed a tendency that the friction coefficient increased with the lapse of the test time. You can see that

以上のように、本発明の含油熱可塑性合成樹脂成形物の製造方法は、潤滑油の分解温度以上の融点を有する合成樹脂に対しても機械的性質を低下させることなく含油処理を行うことができ、得られた含油熱可塑性合成樹脂成形物は摺動特性を改善することができる。   As described above, the method for producing an oil-containing thermoplastic synthetic resin molding of the present invention can perform an oil-impregnating treatment on a synthetic resin having a melting point equal to or higher than the decomposition temperature of the lubricating oil without deteriorating mechanical properties. The obtained oil-containing thermoplastic synthetic resin molding can improve the sliding characteristics.

本発明の含油熱可塑性合成樹脂成形物の製造方法における高圧容器内の態様を示す説明図である。It is explanatory drawing which shows the aspect in the high pressure container in the manufacturing method of the oil-containing thermoplastic synthetic resin molding of this invention. 本発明の含油熱可塑性合成樹脂成形物の製造方法における高圧容器内の他の態様を示す説明図である。It is explanatory drawing which shows the other aspect in the high pressure container in the manufacturing method of the oil-containing thermoplastic synthetic resin molding of this invention. 本発明の含油熱可塑性合成樹脂成形物の製造方法における高圧容器内の他の態様を示す説明図である。It is explanatory drawing which shows the other aspect in the high pressure container in the manufacturing method of the oil-containing thermoplastic synthetic resin molding of this invention. 図１乃至図３に示す態様について、試験した試験結果を示すグラフである。It is a graph which shows the test result which tested about the aspect shown in FIG. 態様（ｂ）のポリアセタール樹脂成形物についてのＥＤＸ分析によるシリコーン油中に含まれる珪素（Ｓｉ）についてマッピングした結果を示す分析写真である。It is an analysis photograph which shows the result mapped about the silicon (Si) contained in the silicone oil by the EDX analysis about the polyacetal resin molding of the aspect (b). スラスト試験結果を示すグラフである。It is a graph which shows a thrust test result.

符号の説明Explanation of symbols

１ 熱可塑性合成樹脂製成形物
２ 高圧容器
３ 保持体
４ 潤滑油
５ 二酸化炭素ガス DESCRIPTION OF SYMBOLS 1 Molded product made of thermoplastic synthetic resin 2 High-pressure vessel 3 Holding body 4 Lubricating oil 5 Carbon dioxide gas

Claims (5)

（ａ）熱可塑性合成樹脂からなる成形物を、高圧容器内において潤滑油と接触させるか、又は接触させることなく該高圧容器内に配置する工程と、
（ｂ）該高圧容器内に、常温において予め加圧された二酸化炭素ガスを注入し、密閉する工程と、
（ｃ）該高圧容器内で二酸化炭素を加熱して該二酸化炭素に気化膨張にともなう圧力上昇を生じせしめ、該二酸化炭素を臨界温度（３１．１℃）以上の温度を有しかつ臨界圧力（７．３８Ｍｐａ）以上の圧力を有する領域にある超臨界状態、あるいは温度が臨界温度未満でかつ圧力が臨界圧力以上を有する領域にある亜臨界状態にする工程と、
（ｄ）超臨界状態あるいは亜臨界状態を所定時間保持せしめ、潤滑油に溶解した超臨界状態あるいは亜臨界状態の二酸化炭素を該成形物中に含浸させる工程と、
（ｅ）潤滑油に溶解した超臨界あるいは亜臨界状態の二酸化炭素が含浸された成形物を、所定温度で該成形物中から二酸化炭素ガスを除去する工程と、
からなる含油熱可塑性合成樹脂成形物の製造方法。 (A) a step of placing a molded product made of a thermoplastic synthetic resin in the high-pressure vessel without bringing it into contact with or in contact with the lubricating oil in the high-pressure vessel;
(B) injecting and sealing carbon dioxide gas pre-pressurized at room temperature into the high-pressure vessel;
(C) heating carbon dioxide in the high-pressure vessel to cause the carbon dioxide to increase in pressure due to vaporization and expansion, so that the carbon dioxide has a temperature equal to or higher than the critical temperature (31.1 ° C.) and has a critical pressure ( 7. A supercritical state in a region having a pressure equal to or higher than 7.38 Mpa), or a subcritical state in a region where the temperature is lower than the critical temperature and the pressure is higher than the critical pressure;
(D) maintaining the supercritical state or subcritical state for a predetermined time and impregnating the molded product with carbon dioxide in the supercritical state or subcritical state dissolved in the lubricating oil;
(E) removing a carbon dioxide gas from the molded product impregnated with supercritical or subcritical carbon dioxide dissolved in a lubricating oil at a predetermined temperature;
A method for producing an oil-containing thermoplastic synthetic resin molded article. 前記成形物は、前記高圧容器内に貯留された潤滑油に浸漬されている請求項１に記載の含油熱可塑性合成樹脂成形物の製造方法。   The method for producing an oil-containing thermoplastic synthetic resin molded product according to claim 1, wherein the molded product is immersed in a lubricating oil stored in the high-pressure vessel. 前記成形物は、前記高圧容器内に設けられた保持体の上に配置されていると共に該成形物の表面に潤滑油が塗布されている請求項１に記載の含油熱可塑性合成樹脂成形物の製造方法。   2. The oil-containing thermoplastic synthetic resin molded article according to claim 1, wherein the molded article is disposed on a holding body provided in the high-pressure vessel, and a lubricating oil is applied to a surface of the molded article. Production method. 前記成形物は、前記高圧容器内に貯留された潤滑油と接触することなく圧力容器内に設けられた保持体の上に配置されている請求項１に記載の含油熱可塑性合成樹脂成形物の製造方法。   2. The oil-containing thermoplastic synthetic resin molded article according to claim 1, wherein the molded article is disposed on a holding body provided in the pressure vessel without contacting the lubricating oil stored in the high-pressure vessel. Production method. 前記熱可塑性合成樹脂からなる成形物は、ポリアセタール樹脂、ポリアミド樹脂、ポリエーテルエーテルケトン樹脂、ポリエチレンテレフタレート樹脂、ポリエチレン樹脂、ポリフェニレンサルファイド樹脂のいずれかからなる請求項１から４のいずれか一項に記載の含油熱可塑性合成樹脂成形物の製造方法。   The molded article made of the thermoplastic synthetic resin is made of any one of a polyacetal resin, a polyamide resin, a polyether ether ketone resin, a polyethylene terephthalate resin, a polyethylene resin, and a polyphenylene sulfide resin. Of producing an oil-containing thermoplastic synthetic resin molding.
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