JP4725050B2 - Polyarylene sulfide composition - Google Patents
Polyarylene sulfide composition Download PDFInfo
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- JP4725050B2 JP4725050B2 JP2004225952A JP2004225952A JP4725050B2 JP 4725050 B2 JP4725050 B2 JP 4725050B2 JP 2004225952 A JP2004225952 A JP 2004225952A JP 2004225952 A JP2004225952 A JP 2004225952A JP 4725050 B2 JP4725050 B2 JP 4725050B2
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- epoxy resin
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ポリアリーレンスルフィド組成物に関するものであり、さらに詳しくは、機械的物性、耐熱性、成形加工性に優れ、かつエポキシ樹脂、ウレタン樹脂、シリコーン樹脂等に対する接着性をも改良したポリアリーレンスルフィド組成物に関するものである。 The present invention relates to a polyarylene sulfide composition. More specifically, the present invention relates to a polyarylene having excellent mechanical properties, heat resistance, molding processability, and improved adhesion to epoxy resins, urethane resins, silicone resins and the like. It relates to a sulfide composition.
ポリアリーレンスルフィド(以下、PASと略記することもある。)は、機械的強度、耐熱性、耐薬品性、成形加工性、寸法安定性に優れ、これら特性を利用して、電気・電子機器部品、自動車部品材料等として使用されている。 Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) is excellent in mechanical strength, heat resistance, chemical resistance, molding processability, and dimensional stability. It is used as a material for automobile parts.
そして、これら部品はその二次加工としてエポキシ樹脂、ウレタン樹脂、シリコーン樹脂等からなる部品材料と接着する場合が多々見られる。しかし、PAS材料の場合、接着剤によって得られる接合力は比較的小さいことが知られており、この際にこれらエポキシ樹脂、ウレタン樹脂、シリコーン樹脂等からなる部品材料とPASからなる部品材料との接着性が問題となることが多い。 In many cases, these parts are bonded to a part material made of epoxy resin, urethane resin, silicone resin or the like as the secondary processing. However, in the case of the PAS material, it is known that the bonding force obtained by the adhesive is relatively small. At this time, the component material composed of these epoxy resin, urethane resin, silicone resin, etc. and the component material composed of PAS Adhesion often becomes a problem.
そこで、このような部品材料の接着性を改良する方法として、成形品表面を機械的又は化学的に粗面化し、そのアンカー効果によって接着強度を向上させる方法が提案されており、該方法としては、例えば無水クロム酸と硫酸との混合液、フリーデル・クラフツ反応触媒を有機溶媒に溶解せしめた液(例えば、特許文献1参照。)、クロロスルホン酸とジクロロエタンとからなる処理剤(例えば、特許文献2参照。)、フィリップス石油社が開発したフッ酸系エッチング液等による表面処理法等が挙げられる。また、成形品表面をコロナ放電処理する方法も知られている。更に、PASにカルナバワックスを添加しエポキシ樹脂との接着性を改良する方法も提案されている(例えば、特許文献3参照。)。 Therefore, as a method for improving the adhesion of such component materials, a method has been proposed in which the surface of a molded article is roughened mechanically or chemically, and the adhesion strength is improved by the anchor effect. For example, a mixed solution of chromic anhydride and sulfuric acid, a solution obtained by dissolving a Friedel-Crafts reaction catalyst in an organic solvent (see, for example, Patent Document 1), a treating agent comprising chlorosulfonic acid and dichloroethane (for example, a patent) Reference 2), and surface treatment methods using hydrofluoric acid-based etching solutions developed by Philips Oil. A method of corona discharge treatment of the surface of a molded product is also known. Furthermore, a method for improving the adhesion with an epoxy resin by adding carnauba wax to PAS has also been proposed (see, for example, Patent Document 3).
しかし、特許文献1、特許文献2等に提案された方法は、人体に有毒な劇薬を使用する場合が多く、安全衛生上や廃水処理など環境上に課題を残す場合が多い。また、コロナ放電処理法には、特殊な設備を必要とすることが多く実用上に課題がある。更に、特許文献3に提案された方法では、PASの接着性改良に効果は見られるものの厳しい使用環境下における実用では充分とは言い難いレベルのものである。 However, the methods proposed in Patent Document 1, Patent Document 2, and the like often use powerful drugs that are toxic to the human body, and often leave environmental problems such as safety and hygiene and wastewater treatment. Also, the corona discharge treatment method often requires special equipment and has practical problems. Furthermore, although the method proposed in Patent Document 3 is effective in improving the adhesiveness of PAS, it is at a level that cannot be said to be sufficient for practical use in a severe use environment.
また、熱可塑性樹脂にエポキシ樹脂を配合した組成物として、特定のポリアリーレンスルフィド樹脂にエポキシ樹脂を配合した組成物が開示されている。しかし、その効果は溶融粘度を増加させるものであり接着性改良効果について何ら開示されていない(例えば、特許文献4参照。)。 Moreover, the composition which mix | blended the epoxy resin with specific polyarylene sulfide resin is disclosed as a composition which mix | blended the epoxy resin with the thermoplastic resin. However, the effect is to increase the melt viscosity, and there is no disclosure about the adhesive improvement effect (for example, see Patent Document 4).
加えて、ポリフェニレンスルフィドに無水マレイン酸変性エチレン系共重合体を配合した組成物が開示されている。しかし、その効果は耐衝撃性、靭性を改良するものであり接着性改良効果について何ら開示されていない(例えば、特許文献5、6参照。)。 In addition, a composition in which a maleic anhydride-modified ethylene copolymer is blended with polyphenylene sulfide is disclosed. However, the effect is to improve the impact resistance and toughness, and no adhesive improvement effect is disclosed (for example, see Patent Documents 5 and 6).
そこで、本発明は、機械的物性、耐熱性、成形加工性に優れ、かつエポキシ樹脂、ウレタン樹脂、シリコーン樹脂に対する接着性を改良したPAS組成物を提供するものである。 Therefore, the present invention provides a PAS composition that is excellent in mechanical properties, heat resistance, and moldability, and has improved adhesion to epoxy resins, urethane resins, and silicone resins.
本発明者らは上記課題に関し鋭意検討した結果、特定のPAS、ビスフェノールA型エポキシ樹脂、無水マレイン酸変性エチレン系共重合体及びカルナバワックスからなるPAS組成物が、機械的物性、耐熱性、成形加工性かつエポキシ樹脂、ウレタン樹脂、シリコーン樹脂に対する接着性に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies on the above problems, the present inventors have found that a PAS composition comprising a specific PAS, a bisphenol A type epoxy resin, a maleic anhydride-modified ethylene copolymer, and carnauba wax has mechanical properties, heat resistance, and molding. It has been found that it has excellent workability and adhesion to epoxy resins, urethane resins, and silicone resins, and has completed the present invention.
即ち、本発明は、直径1mm、長さ2mmのダイスを装着した高化式フローテスターにて、測定温度315℃、荷重10kgの条件下で測定した溶融粘度が200〜30000ポイズであるPAS60〜98.3重量%、エポキシ当量が450〜2300、かつ融点が50〜135℃であるビスフェノールA型エポキシ樹脂0.5〜20重量%、無水マレイン酸変性エチレン系共重合体1〜30重量%及びカルナバワックス0.2〜10重量%からなることを特徴とするPAS組成物に関するものである。 That is, the present invention is a PAS 60 to 98 having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. 0.5 wt% to 20 wt% bisphenol A type epoxy resin having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135 ° C, 1 to 30 wt% of maleic anhydride-modified ethylene copolymer, and carnauba The present invention relates to a PAS composition comprising 0.2 to 10% by weight of a wax.
以下に、本発明を詳細に説明する。 The present invention is described in detail below.
本発明のPAS組成物は、直径1mm、長さ2mmのダイスを装着した高化式フローテスターにて、測定温度315℃、荷重10kgの条件下で測定した溶融粘度が200〜30000ポイズであるポリアリーレンスルフィド60〜98.3重量%、エポキシ当量が450〜2300、かつ融点が50〜135℃であるビスフェノールA型エポキシ樹脂0.5〜20重量%、無水マレイン酸変性エチレン系共重合体1〜30重量%及びカルナバワックス0.2〜10重量%からなるPAS組成物である。 The PAS composition of the present invention is a polysiloxane having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. Arylene sulfide 60 to 98.3% by weight, epoxy equivalent 450 to 2300, melting point 50 to 135 ° C. bisphenol A type epoxy resin 0.5 to 20% by weight, maleic anhydride modified ethylene copolymer 1 to 1 A PAS composition comprising 30% by weight and 0.2-10% by weight of carnauba wax.
本発明に用いられるPASは、直径1mm、長さ2mmのダイスを装着した高化式フローテスターにて、測定温度315℃、荷重10kgの条件下で測定した溶融粘度が200〜30000ポイズであるPASであり、該PASとしては、例えば下記一般式(1)〜(8)に示されるp−フェニレンスルフィド単位、m−フェニレンスルフィド単位、o−フェニレンスルフィド単位、フェニレンスルフィドスルフォン単位、フェニレンスルフィドケトン単位、フェニレンスルフィドエーテル単位、ビフェニルスルフィド単位、置換基含有フェニレンスルフィド単位からなる単独重合体又は共重合体を挙げることができ、これら単独重合体又は共重合体の具体的例示としては、ポリ(p−フェニレンスルフィド)、ポリフェニレンスルフィドスルフォン、ポリフェニレンスルフィドケトン、ポリフェニレンスルフィドエーテル、アミノ基置換ポリ(p−フェニレンスルフィド)、アミノ基置換ポリフェニレンスルフィドスルフォン、アミノ基置換ポリフェニレンスルフィドケトン、アミノ基置換ポリフェニレンスルフィドエーテル、ヒドロキシル基置換ポリ(p−フェニレンスルフィド)、ヒドロキシル基置換ポリフェニレンスルフィドスルフォン、ヒドロキシル基置換ポリフェニレンスルフィドケトン、ヒドロキシル基置換ポリフェニレンスルフィドエーテル、カルボキシル基置換ポリ(p−フェニレンスルフィド)、カルボキシル基置換ポリフェニレンスルフィドスルフォン、カルボキシル基置換ポリフェニレンスルフィドケトン、カルボキシル基置換ポリフェニレンスルフィドエーテル等が挙げられ、その中でも、特に耐熱性、接着性に優れたPAS組成物となることから、ポリ(p−フェニレンスルフィド)、アミノ基置換ポリ(p−フェニレンスルフィド)であることが好ましい。 The PAS used in the present invention is a PAS having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. Examples of the PAS include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units represented by the following general formulas (1) to (8), A homopolymer or copolymer comprising a phenylene sulfide ether unit, a biphenyl sulfide unit, and a substituent-containing phenylene sulfide unit can be exemplified. Specific examples of these homopolymers or copolymers include poly (p-phenylene). Sulfide), polyphenylene sulfide Phon, polyphenylene sulfide ketone, polyphenylene sulfide ether, amino group substituted poly (p-phenylene sulfide), amino group substituted polyphenylene sulfide sulfone, amino group substituted polyphenylene sulfide ketone, amino group substituted polyphenylene sulfide ether, hydroxyl group substituted poly (p-phenylene) Sulfide), hydroxyl group substituted polyphenylene sulfide sulfone, hydroxyl group substituted polyphenylene sulfide ketone, hydroxyl group substituted polyphenylene sulfide ether, carboxyl group substituted poly (p-phenylene sulfide), carboxyl group substituted polyphenylene sulfide sulfone, carboxyl group substituted polyphenylene sulfide ketone, carboxyl Group-substituted polyphenylene sulfide Ether and the like, and among them, particularly heat resistance, since the PAS composition excellent in adhesion, poly (p- phenylene sulfide) is preferably an amino group substituted poly (p- phenylene sulfide).
また、本発明に用いられるPASは、直鎖状であっても、重合時にトリハロゲン以上のポリハロゲン化合物を少量添加して若干の架橋又は分岐構造を導入したものであっても、前処理として窒素などの非酸化性の不活性ガス中で加熱処理を施したものであってもかまわない。また、直鎖状PASを酸素存在下高温で加熱硬化して得られる熱硬化型PASでもよい。さらにこれらの構造の混合物であってもかまわない。 Further, the PAS used in the present invention may be linear, or may be prepared by adding a small amount of a trihalogen or higher polyhalogen compound during polymerization to introduce a slight cross-linked or branched structure. The heat treatment may be performed in a non-oxidizing inert gas such as nitrogen. Moreover, thermosetting PAS obtained by heat-curing linear PAS at high temperature in the presence of oxygen may be used. Further, it may be a mixture of these structures.
これらPASの中でも、特に靱性、ウエルド強度が向上したPAS組成物となることから、直径1mm、長さ2mmのダイスを装着した高化式フローテスターにて、測定温度315℃、荷重10kgの条件下で測定した溶融粘度が200ポイズ以上、好ましくは300ポイズ以上の溶融粘度を有する直鎖状PASを酸素存在下高温で加熱硬化して得られる熱硬化型PASが好ましい。 Among these PAS, since it becomes a PAS composition with improved toughness and weld strength in particular, with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, the measurement temperature is 315 ° C. and the load is 10 kg. A thermosetting PAS obtained by heat-curing a linear PAS having a melt viscosity of 200 poise or more, preferably 300 poise or more at a high temperature in the presence of oxygen, is preferred.
また、該PASは、加熱硬化前又は後に脱イオン処理(酸洗浄や熱水洗浄など)、あるいはアセトン、メチルアルコールなどの有機溶媒による洗浄処理を行うことによってイオン、オリゴマーなどの不純物を低減させたものであってもよい。 In addition, the PAS reduces impurities such as ions and oligomers by performing deionization treatment (acid washing, hot water washing, etc.) before or after heat curing, or washing treatment with an organic solvent such as acetone or methyl alcohol. It may be a thing.
本発明のPAS組成物を構成するPASの配合量は60〜98.3重量%であり、特に機械的物性、耐熱性、接着性に優れるPAS組成物となることから75〜95重量%であることが好ましい。ここで、PASの配合量が60重量%未満である場合、得られるPAS組成物は耐熱性、成形加工性、機械的物性に劣るものとなる。一方、98.3重量%を越える場合、得られるPAS組成物は、接着性に劣るものとなる。 The blending amount of PAS constituting the PAS composition of the present invention is 60 to 98.3% by weight, and particularly 75 to 95% by weight because it becomes a PAS composition having excellent mechanical properties, heat resistance and adhesiveness. It is preferable. Here, when the blending amount of PAS is less than 60% by weight, the obtained PAS composition is inferior in heat resistance, molding processability, and mechanical properties. On the other hand, when it exceeds 98.3% by weight, the obtained PAS composition is inferior in adhesiveness.
本発明に用いられるエポキシ樹脂は、エポキシ当量が450〜2300で、かつ融点が50〜135℃のビスフェノールA型エポキシ樹脂であり、その中でもエポキシ当量が700〜2100で、かつ融点が80〜131℃のビスフェノールA型エポキシ樹脂が好ましく、その性状としては、エポキシ基を2個以上含む固体状のビスフェノールA型エポキシ樹脂が用いられ、ビスフェノールA型エポキシ樹脂以外のエポキシ樹脂である場合、得られるPAS組成物は接着性に劣るものとなる。 The epoxy resin used in the present invention is a bisphenol A type epoxy resin having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135 ° C. Among them, an epoxy equivalent of 700 to 2100 and a melting point of 80 to 131 ° C. The bisphenol A type epoxy resin is preferable, and as its properties, a solid bisphenol A type epoxy resin containing two or more epoxy groups is used, and when it is an epoxy resin other than the bisphenol A type epoxy resin, the resulting PAS composition Things are inferior in adhesion.
ここで、エポキシ当量が450未満のビスフェノールA型エポキシ樹脂である場合、得られるPAS組成物を成形品とする際に金型汚染性が著しく悪化したり、成形品の外観が劣ったものとなる。一方、エポキシ当量が2300を越えるビスフェノールA型エポキシ樹脂である場合、得られるPAS組成物の接着強度の改善効果にバラツキが発生し、扱い難いものとなる。また、融点が50℃未満のビスフェノールA型エポキシ樹脂である場合、得られるPAS組成物を成形品とする際に金型汚染性が著しく悪化したり、成形品の外観が劣ったものとなる。一方、融点が135℃を越えるビスフェノールA型エポキシ樹脂である場合、得られるPAS組成物の接着強度の改善効果にバラツキが発生し、扱い難いものとなる。 Here, in the case of a bisphenol A type epoxy resin having an epoxy equivalent of less than 450, when the obtained PAS composition is used as a molded product, the mold contamination is remarkably deteriorated or the appearance of the molded product is inferior. . On the other hand, when the epoxy equivalent is a bisphenol A type epoxy resin exceeding 2300, the effect of improving the adhesive strength of the resulting PAS composition varies, making it difficult to handle. Further, in the case of a bisphenol A type epoxy resin having a melting point of less than 50 ° C., when the obtained PAS composition is formed into a molded product, the mold contamination is remarkably deteriorated or the appearance of the molded product is inferior. On the other hand, in the case of a bisphenol A type epoxy resin having a melting point exceeding 135 ° C., the effect of improving the adhesive strength of the obtained PAS composition varies, making it difficult to handle.
本発明のPAS組成物を構成するビスフェノールA型エポキシ樹脂の配合量は、0.5〜20重量%であり、特に機械的物性、耐熱性、接着性に優れるPAS組成物となることから1〜15重量%であることが好ましい。ここで、ビスフェノールA型エポキシ樹脂の配合量が0.5重量%未満である場合、得られるPAS組成物の接着性改良効果が発現しない。一方、ビスフェノールA型エポキシ樹脂の配合量が20重量%を越える場合、得られるPAS組成物の成形加工性が著しく低下する。 The blending amount of the bisphenol A type epoxy resin constituting the PAS composition of the present invention is 0.5 to 20% by weight, and in particular, it becomes a PAS composition having excellent mechanical properties, heat resistance and adhesiveness. It is preferably 15% by weight. Here, when the blending amount of the bisphenol A type epoxy resin is less than 0.5% by weight, the effect of improving the adhesiveness of the obtained PAS composition does not appear. On the other hand, when the blending amount of the bisphenol A type epoxy resin exceeds 20% by weight, the molding processability of the obtained PAS composition is remarkably lowered.
本発明に使用される無水マレイン酸変性エチレン系共重合体としては、如何なる無水マレイン酸変性エチレン系共重合体をも用いることが可能であり、例えば無水マレイン酸変性ポリエチレン重合体、無水マレイン酸変性ポリプロピレン重合体、無水マレイン酸−エチレン−アクリル酸エステル共重合体等の共重合体;エチレンあるいはエチレン−プロピレン共重合体に無水マレイン酸がグラフトした共重合体等を用いることができる。これらの中でも、接着性に優れるPAS組成物となることから、メルトフローレート[測定方法はJIS K6730(1980年)準拠]が10g/10分以下である無水マレイン酸変性エチレン系共重合体であることが好ましい。 As the maleic anhydride-modified ethylene copolymer used in the present invention, any maleic anhydride-modified ethylene copolymer can be used. For example, maleic anhydride-modified polyethylene polymer, maleic anhydride-modified A copolymer such as a polypropylene polymer or a maleic anhydride-ethylene-acrylic acid ester copolymer; a copolymer obtained by grafting maleic anhydride on an ethylene or ethylene-propylene copolymer, or the like can be used. Among these, since it becomes a PAS composition having excellent adhesiveness, it is a maleic anhydride-modified ethylene copolymer having a melt flow rate [measurement method conforming to JIS K6730 (1980)] of 10 g / 10 min or less. It is preferable.
次に、本発明に使用される無水マレイン酸変性エチレン系共重合体の配合量は1〜30重量%であり、PAS組成物を成形する際にガス発生が抑えられることから好ましくは3〜20重量%である。配合量が1重量%未満ではPAS組成物が接着性に劣り、30重量%を越えるとPAS組成物を成形する際にガスの発生が著しい。 Next, the blending amount of the maleic anhydride-modified ethylene copolymer used in the present invention is 1 to 30% by weight, and preferably 3 to 20 because gas generation is suppressed when the PAS composition is molded. % By weight. If the blending amount is less than 1% by weight, the PAS composition is inferior in adhesiveness, and if it exceeds 30% by weight, gas generation is remarkable when the PAS composition is molded.
本発明のPAS組成物は、カルナバワックスを0.2〜10重量%配合するものである。ここで、カルナバワックスの配合量が0.2重量部未満である場合、得られるPAS組成物を成形品とした際の成形品表面外観性が著しく低下したものとなる。一方、カルナバワックスが10重量%を越える場合、成形加工時にこれら成分が金型汚染等を引き起こす問題が発生しやすい。該カルナバワックスとしては、一般的な市販品を用いることができる。 The PAS composition of the present invention contains 0.2 to 10% by weight of carnauba wax. Here, when the compounding amount of the carnauba wax is less than 0.2 parts by weight, the surface appearance of the molded product when the obtained PAS composition is used as a molded product is significantly reduced. On the other hand, when the carnauba wax exceeds 10% by weight, a problem that these components cause mold contamination or the like during molding is likely to occur. As the carnauba wax, a general commercial product can be used.
本発明のPAS組成物は、特に機械的強度に優れたものとなることからPAS100重量部に対し、さらに繊維状充填材及び/又は無機充填材10〜200重量部を配合してなるものが好ましい。 Since the PAS composition of the present invention is particularly excellent in mechanical strength, it is preferable to further blend 10 to 200 parts by weight of a fibrous filler and / or an inorganic filler with respect to 100 parts by weight of PAS. .
該繊維状充填材としては、例えばガラス繊維、炭素繊維、グラファイト化繊維、ウイスカー、金属繊維、無機系繊維、有機系繊維、鉱物系繊維等が挙げられる。 Examples of the fibrous filler include glass fiber, carbon fiber, graphitized fiber, whisker, metal fiber, inorganic fiber, organic fiber, and mineral fiber.
そして、ガラス繊維の具体的例示としては、平均繊維径が6〜14μmのチョップドストランド、ミルドファイバー、ロービング等のガラス繊維;ニッケル、銅等金属コートしたガラス繊維;シラン繊維;アルミノ珪酸塩ガラス繊維;中空ガラス繊維;ノンホーローガラス繊維等が挙げられる。 As specific examples of glass fibers, glass fibers such as chopped strands, milled fibers, and rovings having an average fiber diameter of 6 to 14 μm; glass fibers coated with metal such as nickel and copper; silane fibers; aluminosilicate glass fibers; Hollow glass fiber; non-hollow glass fiber and the like.
炭素繊維の具体的例示としては、ポリアクリロニトリルを原料とするPAN系炭素繊維、ピッチを原料とするピッチ系炭素繊維等が挙げられる。 Specific examples of the carbon fiber include PAN-based carbon fiber using polyacrylonitrile as a raw material, pitch-based carbon fiber using pitch as a raw material, and the like.
無機系繊維の具体的例示としては、ロックウール、ジルコニア、アルミナシリカ、チタン酸バリウム、炭化珪素、アルミナ、シリカ、高炉スラグ等の各種無機系繊維が挙げられる。 Specific examples of the inorganic fiber include various inorganic fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag, and the like.
鉱物系繊維の具体的例示としては、アスベスト、ワラステナイト、マグネシウムオキシサルフェート等が挙げられる。 Specific examples of mineral fibers include asbestos, wollastonite, magnesium oxysulfate, and the like.
有機系繊維の具体的例示としては、全芳香族ポリアミド繊維、フェノール樹脂繊維、全芳香族ポリエステル繊維等が挙げられる。 Specific examples of organic fibers include wholly aromatic polyamide fibers, phenol resin fibers, wholly aromatic polyester fibers, and the like.
ウイスカーの具体的例示としては、窒化珪素ウイスカー、塩基性硫酸マグネシウムウイスカー、チタン酸バリウムウイスカー、チタン酸カリウムウイスカー、炭化珪素ウイスカー、ボロンウイスカー、酸化亜鉛ウイスカー等が挙げられる。 Specific examples of the whisker include silicon nitride whisker, basic magnesium sulfate whisker, barium titanate whisker, potassium titanate whisker, silicon carbide whisker, boron whisker, and zinc oxide whisker.
また、該無機充填材とは、板状、粉粒状の無機物であり、例えば炭酸カルシウム、炭酸リチウム、炭酸マグネシウム、炭酸亜鉛、マイカ、シリカ、タルク、クレイ、硫酸カルシウム、カオリン、ワラステナイト、ゼオライト、ガラスパウダー、アルミナ、酸化珪素、酸化マグネシウム、酸化ジルコニウム、酸化鉄、酸化スズ、珪酸マグネシウム、珪酸カルシウム、リン酸カルシウム、リン酸マグネシウム、黒鉛、カーボンブラック、ガラスパウダー、ガラスバルーン、ガラスフレーク、ハイドロタルサイト等が挙げられる。これらの無機充填材は2種以上を併用することも可能であり、必要によりエポキシ系化合物、イソシアネート系化合物、シラン系化合物、チタネート系化合物等の官能性化合物又はポリマーで、予め表面処理したものを用いてもよい。 The inorganic filler is a plate-like, powder-like inorganic substance such as calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, Glass powder, alumina, silicon oxide, magnesium oxide, zirconium oxide, iron oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, graphite, carbon black, glass powder, glass balloon, glass flake, hydrotalcite, etc. Is mentioned. These inorganic fillers can be used in combination of two or more, and if necessary, a surface treated with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound as necessary. It may be used.
本発明において場合によっては用いることのできる繊維状充填材及び/又は無機充填材は、シランカップリング剤、チタネート系カップリング剤で処理したものあることが好ましく、特にアミノアルコキシルシラン又はエポキシアルコキシルシランで表面処理されたものであることが好ましい。また、繊維状充填材は、場合によって前記表面処理を行った後、ハンドリング性を良くするためにガラス繊維の束をエポキシ樹脂及び/又はウレタン樹脂で収束処理を施したものであってもよい。 The fibrous filler and / or inorganic filler that can be used in some cases in the present invention is preferably treated with a silane coupling agent or a titanate coupling agent, particularly aminoalkoxylsilane or epoxyalkoxylsilane. It is preferable that it is surface-treated. In addition, the fibrous filler may be obtained by subjecting a bundle of glass fibers to a convergence treatment with an epoxy resin and / or a urethane resin in order to improve handling properties after performing the surface treatment in some cases.
さらに、本発明のPAS組成物は、本発明の効果を損なわない範囲で、ポリアルキレンオキサイドオリゴマー系化合物、チオエーテル系化合物、エステル系化合物、有機リン化合物などの可塑剤;酸化防止剤;熱安定剤;滑剤;紫外線防止剤;着色剤;結晶核剤;発泡剤などの通常の添加剤を1種以上添加することも可能である。 Furthermore, the PAS composition of the present invention is a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organophosphorus compound, an antioxidant, and a heat stabilizer, as long as the effects of the present invention are not impaired. One or more usual additives such as a lubricant, an ultraviolet ray preventive agent, a coloring agent, a crystal nucleating agent, and a foaming agent may be added.
また、本発明のPAS組成物は、本発明の目的を逸脱しない範囲で、各種熱硬化性樹脂、熱可塑性樹脂、例えばシアン酸エステル樹脂、ポリイミド、シリコーン樹脂、ポリオレフィン、ポリエステル、ポリアミド、ポリフェニレンオキサイド、ポリカーボネート、ポリスルホン、ポリエーテルイミド、ポリエーテルスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリアミドイミド、ポリアミド系エラストマー、ポリオレフィン系エラストマー、ポリエステル系エラストマー、ポリアルキレンオキサイド等を1種以上混合して使用することができる。 Further, the PAS composition of the present invention can be used in various thermosetting resins and thermoplastic resins, for example, cyanate ester resin, polyimide, silicone resin, polyolefin, polyester, polyamide, polyphenylene oxide, without departing from the object of the present invention. Use a mixture of one or more of polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, polyamide elastomer, polyolefin elastomer, polyester elastomer, polyalkylene oxide, etc. Can do.
本発明のPAS組成物の製造方法としては、従来から使用されている加熱溶融混練方法を用いることができる。例えば、単軸又は二軸押出機、ニーダー、ミル、ブラベンダーなどによる加熱溶融混練方法が挙げられ、特に混練能力に優れた二軸押出機による溶融混練方法が好ましい。また、この際の混練温度は特に限定されるものではなく、通常280〜370℃の中から任意に選ぶことができる。原料の混合順序にも特に制限はなく、全ての原材料を配合した後上記の方法により溶融混練する方法;原材料の一部を配合した後で上記の方法により溶融混練し、さらに残りの原材料を配合し溶融混練する方法;原材料の一部を配合後単軸あるいは二軸の押出機により溶融混練中にサイドフィーダーを用いて残りの原材料を混合する方法など、いずれの方法を用いてもよい。また、小量添加成分については、他の成分を上記の方法などで混練しペレット化した後、成形前に添加することで使用してもよい。 As a method for producing the PAS composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-370 degreeC. The mixing order of the raw materials is not particularly limited, and all the raw materials are mixed and then melt kneaded by the above method; after a part of the raw materials are mixed, melt kneaded by the above method and the remaining raw materials are further mixed Melting and kneading method: Any method may be used, such as a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. Moreover, about a small amount addition component, after kneading | mixing and pelletizing another component by said method etc., you may use it by adding before shaping | molding.
本発明により得られるPAS組成物は、耐薬品性、成形加工性、寸法安定性などの特性を保持し、良好な機械的強度及び耐熱性を有し、エポキシ樹脂、ウレタン樹脂、シリコーン樹脂に対する接着性が良好な特徴を有する。さらに、得られたPAS組成物は、射出成形機、押出成形機、圧縮成形機などを用いて任意の形状に成形することができる。このようにして得られた成形品としては、リレーケース、バリコンケース、コンデンサーケース、パワーモジュールケース、インテリジェントパワーモジュールケース、エンジンコントロールユニットケース、点火装置ケース、ランプハウジング等の各種ケースとすることができ、電気・電子機器部材、自動車部材、OA機器部材などに幅広く使用できる。 The PAS composition obtained by the present invention retains properties such as chemical resistance, molding processability and dimensional stability, has good mechanical strength and heat resistance, and adheres to epoxy resins, urethane resins and silicone resins. It has the characteristic that the property is good. Furthermore, the obtained PAS composition can be formed into an arbitrary shape using an injection molding machine, an extrusion molding machine, a compression molding machine or the like. The molded products thus obtained can be various cases such as relay cases, variable capacitor cases, condenser cases, power module cases, intelligent power module cases, engine control unit cases, ignition device cases, lamp housings, etc. It can be widely used for electrical / electronic equipment members, automobile parts, office equipment parts, and the like.
本発明によれば、耐薬品性、成形加工性、寸法安定性などの特性を保持し、良好な機械的強度及び耐熱性をも合わせ有し、エポキシ樹脂、ウレタン樹脂、シリコーン樹脂に対する接着性が良好なPAS組成物が得られるため、その工業的価値は高い。 According to the present invention, it retains characteristics such as chemical resistance, molding processability and dimensional stability, and also has good mechanical strength and heat resistance, and has adhesion to epoxy resin, urethane resin and silicone resin. Since a good PAS composition is obtained, its industrial value is high.
以下に本発明を実施例によって具体的に説明するが、本発明はこれら実施例によりなんら制限されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
なお、実施例に用いたPAS、PAS組成物は、以下の方法により評価・測定した。 The PAS and PAS composition used in the examples were evaluated and measured by the following methods.
〜接着強度の測定〜
実施例により得られたPAS組成物をASTM1号引張試験片に成形し、該試験片を2つに切断しバリを取った後、アセトンで表面を洗浄し、接着面積1.3cm2にて、二液型エポキシ接着剤(長瀬産業(株)製;主剤:XNR5002(商品名)/硬化剤:XNH5002(商品名)=100/90(重量部))を塗布し、バインダークリップ(ライオン(株)製、商品名No.155)にて固定後、100℃、1時間硬化し、更に150℃、3時間にて硬化を行い、接着強度測定試験片を調製した。
~ Measurement of adhesive strength ~
The PAS composition obtained in the example was molded into ASTM No. 1 tensile test piece, the test piece was cut into two pieces and deburred, and then the surface was washed with acetone, with an adhesion area of 1.3 cm 2 , A two-pack type epoxy adhesive (manufactured by Nagase Sangyo Co., Ltd .; main agent: XNR5002 (trade name) / curing agent: XNH5002 (trade name) = 100/90 (parts by weight)) was applied, and a binder clip (Lion Corporation) was applied. Manufactured, product name No. 155), cured at 100 ° C. for 1 hour, and further cured at 150 ° C. for 3 hours to prepare an adhesive strength measurement test piece.
得られた接着強度測定試験片は、23℃、50RH%の環境下24時間放置し、その後、バインダークリップをはずし低速引張試験機(島津製作所製:商品名オートグラフAG−5000B)により、50mm/分の引張速度で引張剪断接着強度の試験を行い、その結果を接着強度とした。 The obtained test specimen for measuring the adhesive strength was allowed to stand in an environment of 23 ° C. and 50 RH% for 24 hours, and then the binder clip was removed, and a low speed tensile tester (manufactured by Shimadzu Corporation: trade name Autograph AG-5000B) The tensile shear bond strength test was conducted at a tensile rate of minutes, and the result was taken as the bond strength.
〜金型汚染性の評価〜
実施例により得られたPAS組成物をASTM1号引張試験片に成形し、該引張試験片を50ショット成形した後の成形金型の汚染性を目視により観察した。
~ Evaluation of mold contamination ~
The PAS composition obtained in the examples was molded into ASTM No. 1 tensile test pieces, and the contamination of the molding die after 50 shots of the tensile test pieces were visually observed.
評価基準を以下に示す。
○:金型表面への付着物なし。
×:金型表面に褐色の付着物有り。
The evaluation criteria are shown below.
○: No deposit on the mold surface.
X: Brown adhesion on the mold surface.
〜成形品表面外観の評価〜
実施例により得られたPAS組成物をASTM1号引張試験片に成形し、その表面を目視により観察した。
-Evaluation of appearance of molded product surface-
The PAS composition obtained in the examples was molded into ASTM No. 1 tensile test pieces, and the surface thereof was visually observed.
評価基準を以下に示す。
○:表面が平滑であり良好である。
×:表面にざらつきが発生又は成形不可である。
The evaluation criteria are shown below.
○: The surface is smooth and good.
X: Roughness is generated on the surface or molding is impossible.
〜ヒートサイクル試験〜
得られたケース(100mm×100mm×高さ30mm、肉厚1.5mm)に、二液型エポキシ接着剤(長瀬産業(株)製;主剤:XNR5002(商品名)/硬化剤:XNH5002(商品名)=100/90(重量部))を充填し硬化した。次に、該エポキシ接着剤を充填したケースを−40℃で1時間保持を行い、その後150℃まで昇温し1時間保持を行い再度−40℃まで冷却する工程を1サイクルとしたヒートサイクルを2000サイクル繰り返すヒートサイクル試験を行った。試験後、PAS組成物製ケースとエポキシ接着剤の界面の観察を行った。
~ Heat cycle test ~
In the obtained case (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm), a two-component epoxy adhesive (manufactured by Nagase Sangyo Co., Ltd .; main agent: XNR5002 (trade name) / curing agent: XNH5002 (trade name) ) = 100/90 (parts by weight)) and cured. Next, a heat cycle in which the case filled with the epoxy adhesive is held at −40 ° C. for 1 hour, then heated to 150 ° C., held for 1 hour, and cooled to −40 ° C. again is taken as one cycle. A heat cycle test was repeated 2000 times. After the test, the interface between the PAS composition case and the epoxy adhesive was observed.
評価基準を以下に示す。
○:PAS組成物製ケースとエポキシ接着剤の界面にクラックなし。
×:PAS組成物製ケースとエポキシ接着剤の界面にクラック発生。
The evaluation criteria are shown below.
○: No crack at the interface between the case made of the PAS composition and the epoxy adhesive.
X: Cracks occurred at the interface between the case made of the PAS composition and the epoxy adhesive.
〜PASの溶融粘度測定〜
直径1mm、長さ2mmのダイスを装着した高化式フローテスター(島津製作所製、商品名CFT−500)にて、測定温度315℃、荷重10kgの条件下で溶融粘度の測定を行った。
~ Measurement of melt viscosity of PAS ~
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg with a Koka type flow tester (manufactured by Shimadzu Corporation, trade name CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm.
合成例1(ポリ(p−フェニレンスルフィド)の合成)
攪拌機を装備する15リットルオートクレーブに、Na2S・2.9H2O1866g及びN−メチル−2−ピロリドン5lを仕込み、窒素気流下攪拌しながら徐々に205℃まで昇温して、407gの水を留去した。この系を140℃まで冷却した後、p−ジクロロベンゼン2150gとN−メチル−2−ピロリドン1500gを添加し、窒素気流下に系を封入した。この系を2時間かけて225℃に昇温し、225℃にて2時間重合させた後、30分かけて250℃に昇温し、さらに250℃にて3.0時間重合を行った。重合終了後、室温まで冷却しポリマーを遠心分離機により単離した。温水でポリマーを繰り返し洗浄し100℃で一昼夜乾燥することによりポリ(p−フェニレンスルフィド)(以下、PPS(1)と記す。)を得た。
Synthesis Example 1 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na 2 S · 2.9H 2 O and 5 l of N-methyl-2-pyrrolidone, gradually heated to 205 ° C. with stirring under a nitrogen stream, and 407 g of water was added. Distilled off. After cooling this system to 140 ° C., 2150 g of p-dichlorobenzene and 1500 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3.0 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried overnight at 100 ° C. to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (1)).
得られたPPS(1)の溶融粘度は、280ポイズであった。 The melt viscosity of the obtained PPS (1) was 280 poise.
合成例2(ポリ(p−フェニレンスルフィド)の合成)
合成例1で得られたPPS(1)を、さらに空気雰囲気下250℃で10時間硬化を行いポリ(p−フェニレンスルフィド)(以下、PPS(2)と記す。)を得た。
Synthesis Example 2 (Synthesis of poly (p-phenylene sulfide))
The PPS (1) obtained in Synthesis Example 1 was further cured at 250 ° C. for 10 hours in an air atmosphere to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (2)).
得られたPPS(2)の溶融粘度は、28000ポイズであった。 The obtained PPS (2) had a melt viscosity of 28,000 poise.
合成例3(ポリ(p−フェニレンスルフィド)の合成)
攪拌機を装備する15リットルオートクレーブに、N−メチル−2−ピロリドン3.5l及びNa2S・5.0H2O2400gを仕込み、窒素気流下約2時間かけて撹拌しながら徐々に205℃まで昇温して、水を970g留出させた。140℃まで冷却した後、p−ジクロロベンゼン1990gとN−メチル−2−ピロリドン1.2lを加えて、250℃に昇温し、250℃で3時間重合させて、スラリーを得た。次に、オートクレーブにn−デカン2100gを注入し、250℃に昇温し、5時間重合させた。重合終了後、室温まで冷却しポリマーを遠心分離機により単離した。温水でポリマーを繰り返し洗浄し100℃で一昼夜乾燥することによりポリ(p−フェニレンスルフィド)(以下、PPS(3)と記す。)を得た。得られたPPS(3)の溶融粘度は、1600ポイズであった。
Synthesis Example 3 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer is charged with 3.5 l of N-methyl-2-pyrrolidone and 2400 g of Na 2 S · 5.0H 2 O, and gradually heated to 205 ° C. with stirring over about 2 hours under a nitrogen stream. 970 g of water was distilled off. After cooling to 140 ° C., 1990 g of p-dichlorobenzene and 1.2 l of N-methyl-2-pyrrolidone were added, the temperature was raised to 250 ° C., and polymerization was performed at 250 ° C. for 3 hours to obtain a slurry. Next, 2100 g of n-decane was poured into the autoclave, heated to 250 ° C. and polymerized for 5 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried at 100 ° C. for a whole day and night to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (3)). The melt viscosity of the obtained PPS (3) was 1600 poise.
合成例4(ポリ(p−フェニレンスルフィド)の合成)
攪拌機を装備する15リットルオートクレーブに、Na2S・2.9H2O1866g及びN−メチル−2−ピロリドン5lを仕込み、窒素気流下攪拌しながら徐々に205℃まで昇温して、407gの水を留去した。この系を140℃まで冷却した後、p−ジクロロベンゼン2280gとN−メチル−2−ピロリドン1500gを添加し、窒素気流下に系を封入した。この系を2時間かけて225℃に昇温し、225℃にて2時間重合させた後、30分かけて250℃に昇温し、さらに250℃にて2.0時間重合を行った。重合終了後、室温まで冷却しポリマーを遠心分離機により単離した。温水でポリマーを繰り返し洗浄し100℃で一昼夜乾燥することによりポリ(p−フェニレンスルフィド)(以下、PPS(4)と記す。)
得られたPPS(4)の溶融粘度は、110ポイズであった。
Synthesis Example 4 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na 2 S · 2.9H 2 O and 5 l of N-methyl-2-pyrrolidone, gradually heated to 205 ° C. with stirring under a nitrogen stream, and 407 g of water was added. Distilled off. After cooling the system to 140 ° C., 2280 g of p-dichlorobenzene and 1500 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 2.0 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. Poly (p-phenylene sulfide) (hereinafter referred to as PPS (4)) is obtained by repeatedly washing the polymer with warm water and drying at 100 ° C. overnight.
The resulting PPS (4) had a melt viscosity of 110 poise.
合成例5(ポリ(p−フェニレンスルフィド)の合成)
合成例4で得られたPPS(4)を、さらに空気雰囲気下250℃で12時間硬化を行いポリ(p−フェニレンスルフィド)(以下、PPS(5)と記す。)を得た。
Synthesis Example 5 (Synthesis of poly (p-phenylene sulfide))
The PPS (4) obtained in Synthesis Example 4 was further cured at 250 ° C. for 12 hours in an air atmosphere to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (5)).
得られたPPS(5)の溶融粘度は、36000ポイズであった。 The melt viscosity of the obtained PPS (5) was 36000 poise.
実施例1
合成例3で得られたPPS(3)92.0重量%、ビスフェノールA型エポキシ樹脂(大日本インキ化学工業(株)製、商品名エピクロン7050;エポキシ当量2000、融点125℃)(以下、エポキシ樹脂(1)と記す。)2.0重量%、無水マレイン酸変性エチレン系共重合体(アトフィナジャパン社製、商品名ボンダイン AX−8390[メルトフローレート:7g/10分])(以下、無水マレイン酸変性エチレン系共重合体(1)と記す。)5.5重量%及びカルナバワックス(関東化学(株)製)0.5重量%をあらかじめヘンシェルミキサー(三井三池化工機(株)製、HENSCHEL FD20D/K)にて均一に混合した。その後、スクリュー径37mmφの二軸押出機(東芝機械(株)製、商品名TEM―35B−102B)を用い、シリンダー温度300℃で溶融混練してペレット化したポリ(p−フェニレンスルフィド)組成物(以下、PPS組成物と記す。)を得、得られたPPS組成物を175℃で5時間乾燥した。
Example 1
PPS (3) 92.0% by weight obtained in Synthesis Example 3, bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron 7050; epoxy equivalent 2000, melting point 125 ° C.) (hereinafter referred to as epoxy) Resin (1).) 2.0% by weight, maleic anhydride-modified ethylene copolymer (manufactured by Atofina Japan, trade name Bondine AX-8390 [melt flow rate: 7 g / 10 min]) (hereinafter, Maleic anhydride-modified ethylene-based copolymer (1)) 5.5% by weight and carnauba wax (manufactured by Kanto Chemical Co., Ltd.) 0.5% by weight were previously prepared by Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.). , HENSCHEL FD20D / K). Then, using a twin screw extruder (trade name TEM-35B-102B, manufactured by Toshiba Machine Co., Ltd.) having a screw diameter of 37 mmφ, the poly (p-phenylene sulfide) composition was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. (Hereinafter referred to as a PPS composition) was obtained, and the obtained PPS composition was dried at 175 ° C. for 5 hours.
そして、得られたPPS組成物をシリンダー温度310℃、金型温度140℃に設定した射出成形機(住友重機械工業製、商品名SE75S)によりを試験片に成形し、接着強度、金型汚染性、成形品表面外観の評価を行った。その結果を表1に示す。 The obtained PPS composition was molded into a test piece by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name SE75S) set at a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. And the appearance of the molded product surface were evaluated. The results are shown in Table 1.
また、得られたPPS組成物をケース(100mm×100mm×高さ30mm、肉厚1.5mm)用金型を装着し、シリンダー温度310℃、金型温度140℃に設定した射出成形機(住友重機械工業製、商品名SE75S)によりケースに成形し、ヒートサイクル試験を行った。その結果を表1に示す。 In addition, the obtained PPS composition was mounted on a mold for a case (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm), and an injection molding machine (Sumitomo) set to a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. The product was molded into a case by a heavy machinery industry, trade name SE75S) and subjected to a heat cycle test. The results are shown in Table 1.
実施例2
PPS(3)92.0重量%の代わりに合成例2で得られたPPS(2)85.5重量%、エポキシ樹脂(1)2.0重量%の代わりに4.0重量%、無水マレイン酸変性エチレン系共重合体(1)5.5重量%の代わりに10.0重量%とし、さらにPPS(2)100重量部に対し、繊維径10μm、繊維長3mmのガラス繊維(日本板ガラス(株)製 チョップドストランド:RES03−TP91)28重量部を二軸押出機のサイドフィーダーから供給した以外は、実施例1と同様の方法により、PPS組成物、試験片、PPS製ケースを得、それらの評価を行った。その結果を表1に示す。
Example 2
PPS (3) 82.0 wt% obtained in Synthesis Example 2 instead of 92.0 wt%, Epoxy resin (1) 4.0 wt% instead of 2.0 wt%, anhydrous maleic Instead of 5.5% by weight of acid-modified ethylene copolymer (1), 10.0% by weight, and further for 100 parts by weight of PPS (2), a glass fiber having a fiber diameter of 10 μm and a fiber length of 3 mm (Japanese plate glass ( Co., Ltd. Chopped Strand: RES03-TP91) A PPS composition, a test piece, and a PPS case were obtained in the same manner as in Example 1 except that 28 parts by weight were supplied from the side feeder of the twin screw extruder. Was evaluated. The results are shown in Table 1.
実施例3
PPS(2)85.5重量%の代わりに合成例3で得られたPPS(3)64.0重量%、エポキシ樹脂(1)4.0重量%の代わりに5.0重量%、無水マレイン酸変性エチレン系共重合体(1)10.0重量%の代わりに無水マレイン酸変性エチレン系共重合体(アトフィナジャパン社製、商品名ボンダイン TX−8030[メルトフローレート:3g/10分])(以下、無水マレイン酸変性エチレン系共重合体(2)と記す。)28.0重量%、カルナバワックス0.5重量%の代わりに3.0重量%、ガラス繊維28重量部の代わりに80重量部とし、さらにPPS(3)100重量部に対し炭酸カルシウム(白石カルシウム(株)製、商品名ホワイトンP−30)19.0重量部とした以外は、実施例2と同様の方法により、PPS組成物、試験片、PPS製ケースを得、それらの評価を行った。その結果を表1に示す。
Example 3
PPS (2) instead of 85.5 wt% PPS (3) obtained in Synthesis Example 3 64.0 wt%, epoxy resin (1) 5.0 wt% instead of 4.0 wt% anhydrous maleic anhydride Acid-modified ethylene copolymer (1) Instead of 10.0% by weight, maleic anhydride-modified ethylene copolymer (manufactured by Atofina Japan, trade name Bondine TX-8030 [melt flow rate: 3 g / 10 min] ) (Hereinafter referred to as maleic anhydride-modified ethylene copolymer (2)) 28.0 wt%, carnauba wax 0.5 wt% instead of 3.0 wt%, glass fiber 28 wt% instead of 80 parts by weight and the same method as in Example 2 except that 19.0 parts by weight of calcium carbonate (product name: Whiten P-30, manufactured by Shiraishi Calcium Co., Ltd.) is added to 100 parts by weight of PPS (3). P A PS composition, a test piece, and a case made of PPS were obtained and evaluated. The results are shown in Table 1.
実施例4
PPS(3)64.0重量%の代わりに合成例1で得られたPPS(1)71.0重量%、エポキシ樹脂(1)5.0重量%の代わりにビスフェノールA型エポキシ樹脂(大日本インキ化学工業(株)製、商品名エピクロン3050;エポキシ当量780、融点95℃)(以下、エポキシ樹脂(2)と記す。)18重量%、無水マレイン酸変性エチレン系共重合体(2)28.0重量%の代わりに4.0重量%、カルナバワックス3.0重量%の代わりに7.0重量%とし、PPS(1)100重量部に対し、ガラス繊維80.0重量部の代わりに86.0重量部、炭酸カルシウム19.0重量部の代わりに37.0重量部とした以外は、実施例3と同様の方法により、PPS組成物を得、試験片、PPS製ケースを得、それらの評価を行った。その結果を表1に示す。
Example 4
Instead of PPS (3) 64.0 wt%, PPS (1) 71.0 wt% obtained in Synthesis Example 1 and epoxy resin (1) 5.0 wt% instead of bisphenol A type epoxy resin (Dainippon Ink Chemical Industries, Ltd., trade name: Epicron 3050; epoxy equivalent 780, melting point 95 ° C.) (hereinafter referred to as epoxy resin (2)) 18% by weight, maleic anhydride-modified ethylene copolymer (2) 28 4.0 wt% instead of 0.0 wt%, 7.0 wt% instead of 3.0 wt% carnauba wax, and 100 wt% PPS (1) instead of 80.0 wt% glass fiber PPS composition was obtained in the same manner as in Example 3 except that 86.0 parts by weight and 37.0 parts by weight instead of 19.0 parts by weight of calcium carbonate were obtained, and a test piece, a PPS case was obtained. Perform those evaluations . The results are shown in Table 1.
比較例1
PPS(3)92.0重量%の代わりに合成例1で得られたPPS(1)100重量%とし、エポキシ樹脂(1)、無水マレイン酸変性エチレン系共重合体(1)及びカルナバワックスを用いなかった以外は、実施例1と同様の方法により、試験片、PPS製ケースを得、それらの評価を行った。その結果を表2に示す。
Comparative Example 1
Instead of 92.0% by weight of PPS (3), 100% by weight of PPS (1) obtained in Synthesis Example 1 was used. Epoxy resin (1), maleic anhydride-modified ethylene copolymer (1) and carnauba wax were used. A test piece and a PPS case were obtained and evaluated in the same manner as in Example 1 except that they were not used. The results are shown in Table 2.
得られたPPSは接着強度が低く、試験片は表面外観が劣り、さらにPPS製ケースはヒートサイクル性に劣るものであった。 The obtained PPS had low adhesive strength, the test piece was inferior in surface appearance, and the PPS case was inferior in heat cycleability.
比較例2
PPS(3)92.0重量%の代わりに合成例1で得られたPPS(1)97.5重量%とし、無水マレイン酸変性エチレン系共重合体(1)を用いなかった以外は、実施例1と同様の方法により、PPS組成物、試験片、PPS組成物製ケースを得、それらの評価を行った。その結果を表2に示す。
Comparative Example 2
Except that PPS (3) was 97.5 wt% instead of PPS (3) 92.0 wt%, maleic anhydride-modified ethylene copolymer (1) was not used. By the same method as in Example 1, a PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.
得られたPPS組成物は接着強度が低く、PPS組成物製ケースはヒートサイクル性に劣るものであった。 The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.
比較例3
PPS(3)92.0重量%の代わりに合成例1で得られたPPS(1)94.0重量%とし、エポキシ樹脂(1)を用いなかった以外は、実施例1と同様の方法により、PPS組成物、試験片、PPS組成物製ケースを得、それらの評価を行った。その結果を表2に示す。
Comparative Example 3
In the same manner as in Example 1 except that 94.0% by weight of PPS (3) was replaced by 94.0% by weight of PPS (1) obtained in Synthesis Example 1 and no epoxy resin (1) was used. A PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.
得られたPPS組成物は接着強度が低く、PPS組成物製ケースはヒートサイクル性に劣るものであった。 The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.
比較例4
PPS(3)92.0重量%の代わりに合成例5で得られたPPS(5)96.0重量%、無水マレイン酸変性エチレン共重合体(1)5.5重量%の代わりに2.0重量%とし、カルナバワックスを用いなかった以外は、実施例1と同様の方法により、PPS組成物、試験片を得、それらの評価を行った。なお、PPS組成物製ケースは成形することが出来なかった。その結果を表2に示す。
Comparative Example 4
Instead of 92.0% by weight of PPS (3), 96.0% by weight of PPS (5) obtained in Synthesis Example 5, and 2. 5% by weight of maleic anhydride-modified ethylene copolymer (1) A PPS composition and a test piece were obtained and evaluated in the same manner as in Example 1 except that the content was 0% by weight and no carnauba wax was used. The case made of the PPS composition could not be molded. The results are shown in Table 2.
得られたPPS組成物は接着強度が低く、試験片は表面外観が劣るものであった。 The obtained PPS composition had low adhesive strength, and the test piece was inferior in surface appearance.
比較例5
PPS(3)92.0重量%の代わりに合成例1で得られたPPS(1)92.0重量%、エポキシ樹脂(1)2.0重量%の代わりにクレゾールノボラック型エポキシ樹脂(3)(大日本インキ化学工業(株)製、商品名エピクロンN−695;エポキシ当量230、融点95℃)(以下、エポキシ樹脂(3)と記す。)2.0重量%とし、実施例1と同様の方法により、PPS組成物、試験片、PPS組成物製ケースを得、それらの評価を行った。その結果を表2に示す。
Comparative Example 5
Instead of 92.0% by weight of PPS (3), 92.0% by weight of PPS (1) obtained in Synthesis Example 1, and cresol novolac type epoxy resin (3) instead of 2.0% by weight of epoxy resin (1) (Dainippon Ink & Chemicals, Inc., trade name: Epicron N-695; epoxy equivalent 230, melting point 95 ° C.) (hereinafter referred to as epoxy resin (3)) 2.0% by weight, as in Example 1 By the method, a PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.
得られたPPS組成物は接着強度が低く、PPS組成物製ケースはヒートサイクル性に劣るものであった。 The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.
比較例6
PPS(1)92.0重量%の代わりに68.0重量%、エポキシ樹脂(3)2.0重量%の代わりにビスフェノールA型エポキシ樹脂(大日本インキ化学工業(株)製、商品名エピクロン855;エポキシ当量185、室温(25℃)で液体)(以下、エポキシ樹脂(4)と記す。)3.5重量%、無水マレイン酸変性エチレン共重合体(1)5.5重量%の代わりに28.0重量%とし、比較例5と同様の方法により、PPS組成物、試験片、PPS組成物製ケースを得、それらの評価を行った。その結果を表2に示す。
Comparative Example 6
PPS (1) 68.0 wt% instead of 92.0 wt%, epoxy resin (3) 2.0 wt% instead of bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron) 855; epoxy equivalent 185, liquid at room temperature (25 ° C.) (hereinafter referred to as epoxy resin (4)) 3.5 wt%, maleic anhydride modified ethylene copolymer (1) instead of 5.5 wt% The PPS composition, the test piece, and the case made of the PPS composition were obtained in the same manner as in Comparative Example 5 and evaluated. The results are shown in Table 2.
得られたPPS組成物は接着強度が低く、金型汚染性が激しく、さらにPPS組成物製ケースはヒートサイクル性に劣るものであった。 The obtained PPS composition had low adhesive strength and severe mold contamination, and the PPS composition case was inferior in heat cycleability.
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JPH0264159A (en) * | 1988-08-30 | 1990-03-05 | Dainippon Ink & Chem Inc | Polyphenylene sulfide resin composition |
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