JP5542733B2 - Resin molded body, vacuum cleaner piping and vacuum cleaner - Google Patents
Resin molded body, vacuum cleaner piping and vacuum cleaner Download PDFInfo
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Description
本発明は、中空フィラと、それを用いた樹脂成形体，樹脂成形体で構成される掃除機配管に関する。 The present invention relates to a hollow filler, a resin molded body using the hollow filler, and a vacuum cleaner pipe composed of the resin molded body.
一般に、家電製品には、鋼板やガラス，樹脂等から成る多くの家電用部品が使用されている。特に樹脂は他の材料に比較して安価でしかも軽量であるため、家電製品の部位に応じて使用される。中でもポリプロピレンを代表とするポリオレフィン樹脂は、耐薬品性に優れ、高強度であることから家電用部品として多用されている。 In general, many home appliance parts made of steel plate, glass, resin, and the like are used for home appliances. In particular, since resin is cheaper and lighter than other materials, it is used depending on the part of the home appliance. Among them, polyolefin resins typified by polypropylene are widely used as home appliance parts because of their excellent chemical resistance and high strength.
ポリオレフィン樹脂は比重が０.９程度と各種の樹脂の中でも軽量の部類に入る。また、さらに軽量化を図る際には樹脂中にガラスバルーンやシラスバルーンなどの内部に空気が入った中空のフィラを加えることでさらなる軽量化を図ることができる。（例えば、特許文献１参照）。 Polyolefin resins have a specific gravity of about 0.9 and are among the light weight of various resins. Further, when further reducing the weight, it is possible to further reduce the weight by adding a hollow filler in which air is contained in a resin such as a glass balloon or a shirasu balloon. (For example, refer to Patent Document 1).
しかしながら、例えば射出成型のように溶融状態にある樹脂材料に高圧が加わる手法で中空フィラを混合した樹脂材料を成型すると、中空フィラは破損を起こし易いと言う課題がある。破損した中空フィラは樹脂よりも重いガラスやセラミックスとして樹脂材料に含まれるため、軽量化を打ち消すと言う問題がある。 However, for example, when a resin material in which a hollow filler is mixed is molded by a technique in which a high pressure is applied to a molten resin material as in injection molding, there is a problem that the hollow filler is easily damaged. Since the damaged hollow filler is contained in the resin material as glass or ceramics heavier than the resin, there is a problem of negating the weight reduction.
そこで、中空フィラにシランカップリング処理によってフィラの滑り性を改善する方法が開示されている。（例えば、特許文献２参照）また、中空フィラ表面にゴムなど軟質の樹脂を被覆する方法が開示されている。（例えば、特許文献３参照）。 Therefore, a method for improving the slipperiness of the filler by silane coupling treatment to the hollow filler is disclosed. (For example, refer to Patent Document 2) In addition, a method of coating the hollow filler surface with a soft resin such as rubber is disclosed. (For example, refer to Patent Document 3).
しかしながら、シランカップリングによる方法では滑りは改善するが中空フィラ自体の耐圧性が改善される訳ではないため、破損の防止効果は限定的であった。また、単純な樹脂被覆では被覆する樹脂と中空フィラが結合しているわけではないため、被覆樹脂がマトリックスの熱可塑性樹脂中に分散して効果が不十分であった。 However, the silane coupling method improves slipping, but does not improve the pressure resistance of the hollow filler itself, so that the damage prevention effect is limited. In addition, since the resin to be coated and the hollow filler are not bonded with a simple resin coating, the coating resin is dispersed in the thermoplastic resin of the matrix and the effect is insufficient.
本発明の目的は、掃除機配管などの軽量化，高強度に有効な中空フィラと、それを用いた樹脂成形体を提供することにある。 An object of the present invention is to provide a hollow filler effective for weight reduction and high strength of a vacuum cleaner pipe and the like, and a resin molded body using the same.
本発明の中空フィラは、中空部材と、中空部材表面に被覆され、下記式で表される化合物を含む第一の層と、第一の層を覆い、第一の層と結合した変性ポリオレフィンを含む第二の層と、を備えることを特徴とする。 The hollow filler of the present invention comprises a hollow member, a first layer coated on the surface of the hollow member and containing a compound represented by the following formula, and a modified polyolefin that covers the first layer and is bonded to the first layer. And a second layer.
（式中、ｎは０以上の整数、Ｘはアミノ基またはエポキシ基、Ｙは塩素または−ＯＲ（Ｒは水素またはアルキル鎖）で示される化合物。）
(In the formula, n is an integer of 0 or more, X is an amino group or an epoxy group, Y is a compound represented by chlorine or -OR (R is hydrogen or an alkyl chain).)
本発明によれば、化学結合によって固定された第二の層によって中空フィラの破損を防ぎ、ポリオレフィン樹脂と該中空フィラを含む樹脂成型体を軽量化することができる。さらに、ポリオレフィン樹脂と中空フィラの密着性が改善されるため、破壊時の中空部材表面における界面剥離を抑制し、その結果として樹脂成型体の強度を改善できる。 According to the present invention, the hollow filler can be prevented from being damaged by the second layer fixed by chemical bonding, and the resin molded body including the polyolefin resin and the hollow filler can be reduced in weight. Furthermore, since the adhesion between the polyolefin resin and the hollow filler is improved, interfacial peeling on the surface of the hollow member at the time of destruction can be suppressed, and as a result, the strength of the resin molded body can be improved.
以下に、本発明の実施形態について適宜図面を参照しながら詳細に説明する。ここでは、まず、掃除機配管などに使用する樹脂成型体について説明した後に、樹脂成型体に使用する中空フィラについて説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. Here, after first describing the resin molded body used for the vacuum cleaner piping, the hollow filler used for the resin molded body will be described.
（家電製品及び樹脂成型体）
図２は図１に示す掃除機Ｌの一部をなす掃除機配管１であり、樹脂成型体１００からなる。掃除機Ｌにおいて吸口２と掃除機本体３を繋ぐ配管として機能する。この配管は、空気・ゴミを通す円筒形状である。
(Household appliances and resin moldings)
FIG. 2 shows a vacuum cleaner pipe 1 that forms part of the vacuum cleaner L shown in FIG. In the vacuum cleaner L, it functions as piping connecting the suction mouth 2 and the vacuum cleaner body 3. This pipe has a cylindrical shape that allows air and dust to pass through.
樹脂成型体１００は図３に示すように中空フィラ１０１とポリオレフィン樹脂１０２からなる。 As shown in FIG. 3, the resin molded body 100 includes a hollow filler 101 and a polyolefin resin 102.
このポリオレフィン樹脂１０２としては、ポリプロピレン，ポリエチレン，シクロオレフィンポリマー及びこれらを含む共重合体などが代表例として挙げられる。 Typical examples of the polyolefin resin 102 include polypropylene, polyethylene, cycloolefin polymers, and copolymers containing these.
図４に示す中空フィラ１０１の中空部材１０４としては、内部に真空もしくは気体層１０３を有する無機中空粒子類を用いることができる。このような中空フィラの中空部材１０４としては、ガラスバルーン，シラスバルーン，セライト，中空ガラス繊維などがある。これらの粒子のうち、好ましい直径は１マイクロメートル以上１ミリメートル以下である。この範囲以下の大きさでは一般に比重（真比重）が大きくなるために成型体重量の軽量化効果が得がたい。また、この範囲以上の大きさでは成型体表面に目視で判別可能である明確な凹凸が生じるなど意匠性に課題が生じる。また、これらの粒子の真比重は０.０１以上１.０以下が好ましい。０.０１未満の比重では中空フィラ１０１としての強度が低く成型には適さず、１.０以上ではポリオレフィン樹脂１０２に対して比重が高くなるために比重の低減効果が得られなくなる。 As the hollow member 104 of the hollow filler 101 shown in FIG. 4, inorganic hollow particles having a vacuum or a gas layer 103 inside can be used. Examples of the hollow member 104 of the hollow filler include glass balloons, shirasu balloons, celite, and hollow glass fibers. Among these particles, the preferred diameter is 1 micrometer or more and 1 millimeter or less. If the size is less than this range, the specific gravity (true specific gravity) generally increases, so it is difficult to obtain the effect of reducing the weight of the molded body. In addition, when the size is larger than this range, there is a problem in design properties such as clear irregularities that can be visually discerned on the surface of the molded body. The true specific gravity of these particles is preferably 0.01 or more and 1.0 or less. If the specific gravity is less than 0.01, the strength as the hollow filler 101 is low and is not suitable for molding. If the specific gravity is 1.0 or more, the specific gravity is higher than that of the polyolefin resin 102, so that the effect of reducing the specific gravity cannot be obtained.
図４に示す中空フィラ１０１の中空部材１０４の表面には第二の層１０６との化学結合を得るために第一の層１０５が形成される。この第一の層１０５は中空部材１０４の化学気相処理法，プラズマ気相処理法，紫外線照射法などによって中空部材１０４の表面を直接改質することでも得られるが、ガラスバルーンやシラスバルーンなどの中空部材を用いる場合にはシランカップリング剤，アルミネート，チタネート系表面処理剤など、より好ましくはシランカップリング剤を被覆することで形成される。各手法で第一の層１０５に導入する官能基としてはアミノ基，エポキシ基，カルボキシル基，無水酸基，アクリル基，メタクリル基，ビニル基，イソシアネート基などがあり、特に第二の層１０６に酸変性ポリオレフィンを用いる場合にはアミノ基やエポキシ基が好適である。 A first layer 105 is formed on the surface of the hollow member 104 of the hollow filler 101 shown in FIG. 4 in order to obtain a chemical bond with the second layer 106. The first layer 105 can also be obtained by directly modifying the surface of the hollow member 104 by a chemical vapor treatment method, a plasma vapor treatment method, an ultraviolet irradiation method or the like of the hollow member 104, but a glass balloon, a shirasu balloon, etc. When the hollow member is used, it is formed by coating a silane coupling agent, aluminate, titanate surface treatment agent, or the like, more preferably a silane coupling agent. The functional groups introduced into the first layer 105 by each method include amino groups, epoxy groups, carboxyl groups, hydroxyl groups-free, acrylic groups, methacryl groups, vinyl groups, isocyanate groups, and the like. When a modified polyolefin is used, an amino group or an epoxy group is preferable.
図４に示す中空フィラ１０１の第二の層１０６にはポリオレフィン樹脂１０２と親和性が高く、第一の層１０５との化学結合を得られる官能基を導入した変性ポリオレフィン樹脂が用いられる。例えばこのような官能基の導入方法としてはランダム重合，ブロック重合，グラフト重合などが挙げられる。導入される官能基には無水マレイン酸などの無水酸基，アミノ基，エポキシ基，水酸基，カルボキシル基，アクリル基，メタクリル基，ビニル基，イソシアネート基などがあり、先に示した第一の層１０５に合わせて選択する。特に無水マレイン酸の無水酸基を導入した無水マレイン酸変性ポリオレフィンを第二の層として用いるのが本構成では最も好ましく、それに合わせて第一の層１０５にはアミノ基，エポキシ基を用いるのが好適である。 As the second layer 106 of the hollow filler 101 shown in FIG. 4, a modified polyolefin resin having a functional group capable of obtaining a chemical bond with the first layer 105 having high affinity with the polyolefin resin 102 is used. For example, such functional group introduction methods include random polymerization, block polymerization, and graft polymerization. The functional groups to be introduced include hydroxyl-free groups such as maleic anhydride, amino groups, epoxy groups, hydroxyl groups, carboxyl groups, acrylic groups, methacryl groups, vinyl groups, isocyanate groups, etc., and the first layer 105 shown above. Select according to. In particular, it is most preferable to use a maleic anhydride-modified polyolefin into which a maleic anhydride-free hydroxyl group has been introduced as the second layer, and it is preferable to use an amino group or an epoxy group for the first layer 105 accordingly. It is.
中空フィラ１０１の形成方法を図５に示す。まず、中空フィラ１０１の中空部材１０４の表面に先に示した手法によって第一の層１０５を形成する（図５（ｂ））。さらに変性ポリオレフィン樹脂の溶液と中空部材１０４を混合することによって第一の層１０５と化学結合を形成した第二の層１０６を得る（図５（ｃ））。変性ポリオレフィン樹脂に溶解する溶剤としては２−ブタノン，ジメチルアセトアミド，トルエン，キシレン，酢酸メチル，酢酸エチル，酢酸ブチル，アセトン，メタノール，エタノール，２−プロパノール，ｎ−ブタノール，２−メチルプロパノール，４−ヒドロキシ−４−メチル−２−ペンタノン，エチレングリコール，メチルセロソルブ，エチルセロソルブ，ブチルセロソルブなどの有機溶剤から１以上を選択する。これらは中空フィラへの第二の層１０６の形成後にろ過や熱処理などの手法で除去することが好ましい。また、第二の層１０６と第一の層１０５の化学結合を促進するために、混合後に熱処理，光照射，電子線照射などを施しても良い。また、第二の層１０６の分量は中空部材１０４の１００重量部に対して１重量部から１０００重量部とすることが好ましい。この範囲以下では被覆量が不足して所定の効果が得られず、この範囲以上では中空フィラ１０１の比重が大きくなるために軽量化の効果が損なわれる課題が生じる。 A method for forming the hollow filler 101 is shown in FIG. First, the first layer 105 is formed on the surface of the hollow member 104 of the hollow filler 101 by the method described above (FIG. 5B). Furthermore, the solution of the modified polyolefin resin and the hollow member 104 are mixed to obtain the second layer 106 in which a chemical bond is formed with the first layer 105 (FIG. 5C). Solvents soluble in the modified polyolefin resin include 2-butanone, dimethylacetamide, toluene, xylene, methyl acetate, ethyl acetate, butyl acetate, acetone, methanol, ethanol, 2-propanol, n-butanol, 2-methylpropanol, 4- One or more organic solvents such as hydroxy-4-methyl-2-pentanone, ethylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve are selected. These are preferably removed by a technique such as filtration or heat treatment after the formation of the second layer 106 on the hollow filler. In order to promote chemical bonding between the second layer 106 and the first layer 105, heat treatment, light irradiation, electron beam irradiation, or the like may be performed after mixing. The amount of the second layer 106 is preferably 1 part by weight to 1000 parts by weight with respect to 100 parts by weight of the hollow member 104. Below this range, the coating amount is insufficient, and a predetermined effect cannot be obtained. Above this range, the specific gravity of the hollow filler 101 increases, so that the effect of reducing the weight arises.
本発明の中空フィラ１０１には、第一の層１０５と第二の層１０６の化学結合を促進する反応促進剤，熱安定性を高める酸化防止剤を第二の層１０６に予め添加することで適宜加えることができる。上記反応促進剤としては、第一の層１０５と第二の層１０６の材質に応じて適切に選択されるが、第一の層にアミノ基を含み、第二の層に無水マレイン酸変性ポリオレフィンを含む場合にはトリエチルアミンなどのアミン類を用いることが好ましく、第一の層にエポキシ基を含み、第二の層に無水マレイン酸変性ポリオレフィンを含む場合にはイミダゾール類を用いると良い。また、フェノール類などの酸化防止剤は中空フィラ１０１上の第二の層１０６の熱分解を防ぐことができるために第二の層１０６に加えることが好ましい。 In the hollow filler 101 of the present invention, a reaction accelerator that promotes chemical bonding between the first layer 105 and the second layer 106 and an antioxidant that enhances thermal stability are added to the second layer 106 in advance. It can be added as appropriate. The reaction accelerator is appropriately selected according to the materials of the first layer 105 and the second layer 106. The first layer contains an amino group, and the second layer is a maleic anhydride-modified polyolefin. Is preferably used, and an amine such as triethylamine is preferably used. When the first layer contains an epoxy group and the second layer contains maleic anhydride-modified polyolefin, imidazoles may be used. Further, an antioxidant such as phenols is preferably added to the second layer 106 because it can prevent thermal decomposition of the second layer 106 on the hollow filler 101.
中空フィラ１０１はポリオレフィン樹脂１０２と混合することで樹脂成型体１００とする。その混合方法としては熱混練法，プレス成型法，射出成型法などの樹脂成型に常用されるプロセスを用いることができる。また、中空フィラ１０１とポリオレフィン樹脂１０２の混合と、樹脂成型体１００を得る成型工程を別に行っても良いし、押出成型や射出成型のように成型装置内に中空フィラ１０１とポリオレフィン樹脂１０２を投入して混合と成型を同時に行っても良い。 The hollow filler 101 is mixed with the polyolefin resin 102 to form a resin molded body 100. As the mixing method, a process commonly used for resin molding, such as a thermal kneading method, a press molding method, and an injection molding method, can be used. Further, the mixing of the hollow filler 101 and the polyolefin resin 102 and the molding process for obtaining the resin molded body 100 may be performed separately, or the hollow filler 101 and the polyolefin resin 102 are put into a molding apparatus like extrusion molding or injection molding. Then, mixing and molding may be performed simultaneously.
本発明の樹脂成型体には中空フィラ１０１，ポリオレフィン樹脂１０２の他に対候剤，着色顔料，可塑剤，中空フィラ１０１以外の固形フィラを含んでも良い。 In addition to the hollow filler 101 and the polyolefin resin 102, the resin molding of the present invention may contain a weathering agent, a coloring pigment, a plasticizer, and a solid filler other than the hollow filler 101.
本実施形態によれば、従来の樹脂成型体（例えば、特許文献１から３参照）で得られた樹脂成型体と比較して、成型時の中空フィラ１０１の破損を抑制し、ポリオレフィン樹脂１０２と中空フィラ１０１の密着性を改善できる。このために、軽量性と強度に優れた中空フィラ１０１を含む樹脂成型体１００からなる掃除機配管１（家電用部品）、及びこの掃除機配管１を使用した掃除機Ｌ（家電製品）を得ることができる。ここで樹脂成型体の強度についてはＪＩＳ−Ｋ７１６２に準拠して行われる引張試験法において測定される引張強度が１４ＭＰａ以上であると掃除機配管１として要求される強度を満足することができ、好適である。 According to this embodiment, compared with a resin molded body obtained with a conventional resin molded body (for example, see Patent Documents 1 to 3), the hollow filler 101 is prevented from being damaged during molding, and the polyolefin resin 102 The adhesion of the hollow filler 101 can be improved. For this reason, the vacuum cleaner pipe 1 (parts for household appliances) which consists of the resin molding 100 containing the hollow filler 101 excellent in light weight and intensity | strength, and the vacuum cleaner L (home appliances) using this vacuum cleaner pipe 1 are obtained. be able to. Here, the strength of the resin molded body can satisfy the strength required as the vacuum cleaner pipe 1 when the tensile strength measured by the tensile test method performed in accordance with JIS-K7162 is 14 MPa or more, and is preferable. It is.
以上、本発明の実施形態について説明したが、本発明は前記実施形態に限定されず、種々の形態で実施することができる。実施形態では、中空フィラ１０１を含む樹脂成型体１００からなる掃除機配管１、及びこの掃除機配管１を使用した掃除機Ｌについて説明したが、本発明が適用される家電製品及び家電用塗装部品はこれに限定されるものではない。少なくとも樹脂製の家電用塗装部品，具体的には、洗濯機，冷蔵庫，炊飯器，エアーコンディショナー，空気清浄機等の家電製品に使用される家電用塗装部品に適用することができる。本発明は、前記した掃除機Ｌのほか、軽量で断熱性に優れたプラスチック部品が望まれる洗濯機，乾燥機，冷蔵庫等の家電製品及びその他の家電用塗装部品に適用されることが好ましい。 As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, It can implement with a various form. In the embodiment, the vacuum cleaner pipe 1 including the resin molded body 100 including the hollow filler 101 and the vacuum cleaner L using the vacuum cleaner pipe 1 have been described. However, home appliances and home appliance coating parts to which the present invention is applied. Is not limited to this. It can be applied to at least resin-made paint parts for home appliances, specifically, home-use paint parts used for home appliances such as washing machines, refrigerators, rice cookers, air conditioners, and air purifiers. In addition to the cleaner L described above, the present invention is preferably applied to household appliances such as washing machines, dryers, refrigerators, and other coating parts for household appliances in which lightweight and excellent plastic parts are desired.
〔実施例〕
次に、実施例を説明する。
〔Example〕
Next, examples will be described.
（実施例１，２および比較例１，２）
本実施例では掃除機配管１を射出成形法により作製した。マトリックスとなる熱可塑性樹脂１０１には、ポリプロピレン（サンアロマー社製、商品名ＰＭ９７０Ｗ）を使用した。
(Examples 1 and 2 and Comparative Examples 1 and 2)
In this example, the vacuum cleaner pipe 1 was produced by an injection molding method. Polypropylene (manufactured by Sun Allomer, trade name: PM970W) was used for the thermoplastic resin 101 serving as a matrix.
中空フィラ１０２は表１に示す組成１，２，比較組成１，２に示す組成で調整した。ガラスバルーン（住友スリーエム、グラスバブルス Ｓ４２ＸＨＳ、真比重０.４２），シランカップリング剤（信越シリコーン、ＫＢＭ６０３：Ｎ−２−(アミノエチル)−３−アミノプロピルトリメトキシシラン、ＫＢＭ４０３：３−グリシドキシプロピルトリメトキシシラン），無水マレイン酸変性ポリオレフィン（日本製紙ケミカル、商品名アウローレン（登録商標）２００Ｓ），タフテックＨ１０３１（旭化成ケミカルズ、水添スチレンブタジエンゴム）、及びトリエチルアミン（和光純薬工業），イミダゾール２Ｅ４ＭＺ（四国化成工業），フェノール系酸化防止剤（エーピーアイコーポレーション、商品名ヨシノックス（登録商標）ＢＢ）を表１に示す配合量で含むものを使用した。 The hollow filler 102 was prepared using the compositions 1 and 2 shown in Table 1 and the compositions shown in Comparative compositions 1 and 2. Glass balloon (Sumitomo 3M, Glass Bubbles S42XHS, true specific gravity 0.42), Silane coupling agent (Shin-Etsu Silicone, KBM603: N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, KBM403: 3-glycid Xylpropyltrimethoxysilane), maleic anhydride modified polyolefin (Nippon Paper Chemicals, trade name Auroren (registered trademark) 200S), Tuftec H1031 (Asahi Kasei Chemicals, hydrogenated styrene butadiene rubber), and triethylamine (Wako Pure Chemical Industries, Ltd.), A compound containing imidazole 2E4MZ (Shikoku Kasei Kogyo Co., Ltd.) and a phenolic antioxidant (AP Corporation, trade name Yoshinox (registered trademark) BB) in the amounts shown in Table 1 was used.
ここで、ＫＢＭ６０３は、下記式において、ｎ＝６，Ｘ＝アミノ基，Ｙ＝−ＯＣＨ3で表される化合物である。また、ＫＢＭ４０３は、下記式において、ｎ＝５，Ｘ＝エポキシ基，Ｙ＝−ＯＣＨ3で表される化合物である。 Here, KBM603 is a compound represented by the following formula: n = 6, X = amino group, Y = —OCH 3 . KBM403 is a compound represented by the following formula: n = 5, X = epoxy group, Y = —OCH 3 .
いずれの掃除機配管１も中空フィラ１０１への第一の層１０５の形成，第二の層１０６の形成，中空フィラ１０２と熱可塑性樹脂１０１の混合・成型の３つの工程で形成される。 Each of the vacuum cleaner pipes 1 is formed by three processes of forming the first layer 105 on the hollow filler 101, forming the second layer 106, and mixing and molding the hollow filler 102 and the thermoplastic resin 101.
まず、表１に示す各シランカップリング剤をトルエン４０重量部に溶解した処理液に、中空フィラの中空部材１０４（ガラスバルーン）を室温（２５℃）にて４時間浸漬、攪拌することで中空部材１０４に第一の層１０５を被覆した。処理後に真空ろ過で処理液を分離除去し、１００℃の防爆乾燥炉で３０分の熱処理を施すことで残存した処理液を除去すると共に、第一の層１０５と中空フィラの中空部材１０４との化学結合を形成した。 First, a hollow filler 104 (glass balloon) is immersed in a treatment solution obtained by dissolving each silane coupling agent shown in Table 1 in 40 parts by weight of toluene at room temperature (25 ° C.) for 4 hours, and then hollowed. The member 104 was coated with the first layer 105. After the treatment, the treatment liquid is separated and removed by vacuum filtration, and the remaining treatment liquid is removed by performing a heat treatment for 30 minutes in an explosion-proof drying furnace at 100 ° C., and the first layer 105 and the hollow member 104 of the hollow filler are removed. A chemical bond was formed.
次に、実施例１，２、および比較例２における中空フィラへの第二の層１０６の形成には被覆樹脂（アウローレン２００Ｓ、若しくはタフテックＨ１０３１），反応を促進するためのトリエチルアミンあるいはイミダゾール、さらに酸化防止剤をトルエンに溶解した溶液と、前記のシランカップリング処理後の中空フィラ１０２を３０分混合して攪拌した。攪拌後の混合液を十分な排気雰囲気において室温で２時間乾燥した後に１００℃の防爆乾燥炉で３０分の熱処理を施すことで残存した処理液を除去すると共に、第一の層１０５と中空フィラの第二の層１０６との化学結合を形成し、中空フィラ１０１とした。なお、比較例１については第二の層１０６を形成しなかった。 Next, in the formation of the second layer 106 on the hollow filler in Examples 1 and 2 and Comparative Example 2, a coating resin (Aurolen 200S or Tuftec H1031), triethylamine or imidazole for promoting the reaction, A solution obtained by dissolving the antioxidant in toluene and the hollow filler 102 after the silane coupling treatment were mixed for 30 minutes and stirred. The mixed liquid after stirring is dried at room temperature in a sufficiently exhausted atmosphere for 2 hours and then subjected to a heat treatment for 30 minutes in an explosion-proof drying furnace at 100 ° C. to remove the remaining processing liquid, and the first layer 105 and the hollow filler A chemical bond was formed with the second layer 106 to form a hollow filler 101. In Comparative Example 1, the second layer 106 was not formed.
そして、各実施例，比較例において得られた中空フィラ１０１とポリオレフィン樹脂１０２（ポリプロピレン）を射出成型機（射出温度：２４０℃、射出圧力：２５ＭＰａ）によって成型することで、それぞれの組成の円筒状の掃除機配管１（長さ５００mm，直径５０mm，厚み３mm）を得た。得られた試験片に対してアルキメデス法によって比重を測定した。 Then, the hollow filler 101 and the polyolefin resin 102 (polypropylene) obtained in each of the examples and comparative examples are molded by an injection molding machine (injection temperature: 240 ° C., injection pressure: 25 MPa), so that each composition has a cylindrical shape. Vacuum pipe 1 (length 500 mm, diameter 50 mm, thickness 3 mm) was obtained. Specific gravity was measured by the Archimedes method with respect to the obtained test piece.
（実施例３，４および比較例３，４）
本実施例では、樹脂成型体１００を射出成形法により作製した。マトリックスとなる熱可塑性樹脂１０１はポリプロピレン（サンアロマー社製、商品名ＰＭ９７０Ｗ）である。実施例３，４および比較例３，４において用いた中空フィラ１０２の組成と製法は実施例１，２，比較例１，２と同一である。本検討では得られた中空フィラ１０１とポリオレフィン樹脂１０２の混合物を射出成型機（射出温度：２４０℃、射出圧力：２５ＭＰａ）によって成型することで、一辺１０mm，厚み０.５mmの板状の樹脂成型体１００（試験片）を得た。得られた試験片に対してレーザフラッシュ法（Ｎｅｔｚｓｃｈ社、ＬＦＡ４４７型）によって熱拡散率，ＤＳＣ法（ティー・エイ・インスツルメント社、Ｑ２００）によって比熱を測定し、実施例１，２，比較例１，２において求めた比重から熱伝導率を算出した。
(Examples 3 and 4 and Comparative Examples 3 and 4)
In this example, the resin molded body 100 was produced by an injection molding method. The thermoplastic resin 101 serving as a matrix is polypropylene (trade name: PM970W, manufactured by Sun Allomer Co., Ltd.). The composition and manufacturing method of the hollow filler 102 used in Examples 3 and 4 and Comparative Examples 3 and 4 are the same as those in Examples 1 and 2 and Comparative Examples 1 and 2. In this study, the resulting mixture of hollow filler 101 and polyolefin resin 102 is molded by an injection molding machine (injection temperature: 240 ° C., injection pressure: 25 MPa), thereby forming a plate-shaped resin molding with a side of 10 mm and a thickness of 0.5 mm. A body 100 (test piece) was obtained. For the obtained specimens, the thermal diffusivity was measured by the laser flash method (Netzsch, LFA447 type) and the specific heat was measured by the DSC method (TA Instruments, Q200). The thermal conductivity was calculated from the specific gravity obtained in Examples 1 and 2.
（実施例５，６および比較例５，６）
本実施例では、樹脂成型体１００を射出成形法により作製した。マトリックスとなる熱可塑性樹脂１０１はポリプロピレン（サンアロマー社製、商品名ＰＭ９７０Ｗ）である。実施例５，６および比較例５，６において用いた中空フィラ１０２の組成と製法は実施例１，２，比較例１，２と同一である。本検討では得られた中空フィラ１０１とポリオレフィン樹脂１０２の混合物を射出成型機（射出温度：２４０℃、射出圧力：２５ＭＰａ）によって長さ１００mm，幅２０mm，厚み４mmのダンベル型の樹脂成型体１００（ＪＩＳ−Ｋ７１３９ Ａ１型試験片）を得た。得られた試験片に対してＪＩＳ−Ｋ７１６２に準拠して行われる引張試験法によって引張強度を求めた。また、引張試験後の破断面を走査電子顕微鏡（日立 Ｓ−４８００形）によって観察し、破断面に露出したガラスバルーンの表面に対してエネルギー分散型Ｘ線分析装置（堀場製作所 ＥＸ−３５０形）によって元素分析を行うことで炭素元素の分量を評価し、ガラスバルーン表面に残存した樹脂被覆量を比較した。
(Examples 5 and 6 and Comparative Examples 5 and 6)
In this example, the resin molded body 100 was produced by an injection molding method. The thermoplastic resin 101 serving as a matrix is polypropylene (trade name: PM970W, manufactured by Sun Allomer Co., Ltd.). The composition and manufacturing method of the hollow filler 102 used in Examples 5 and 6 and Comparative Examples 5 and 6 are the same as those in Examples 1 and 2 and Comparative Examples 1 and 2. In this study, the obtained mixture of the hollow filler 101 and the polyolefin resin 102 was injected into a dumbbell-shaped resin molding 100 (length: 100 mm, width: 20 mm, thickness: 4 mm) by an injection molding machine (injection temperature: 240 ° C., injection pressure: 25 MPa). JIS-K7139 A1 type test piece) was obtained. The tensile strength was calculated | required with respect to the obtained test piece with the tension test method performed based on JIS-K7162. The fracture surface after the tensile test was observed with a scanning electron microscope (Hitachi S-4800 type), and an energy dispersive X-ray analyzer (Horiba EX-350 type) was applied to the surface of the glass balloon exposed on the fracture surface. The amount of the carbon element was evaluated by performing elemental analysis, and the resin coating amount remaining on the glass balloon surface was compared.
以上の実施例１から６，比較例１から６についてそれぞれの項目において示した方法にて、比重，熱伝導率，引張強度とラスバルーン表面における炭素の質量濃度を測定した。その結果をそれぞれの組成に対して整理した結果を表２に示す。 Specific gravity, thermal conductivity, tensile strength, and mass concentration of carbon on the surface of the lath balloon were measured by the methods shown in the respective items for Examples 1 to 6 and Comparative Examples 1 to 6. Table 2 shows the result of arranging the results for each composition.
（評価結果）
実施例１，３（組成１）及び実施例２，４の（組成２）の樹脂組成物は、表１に示すように、比較例１，３（比較組成１）及び比較例２，４の（比較組成２）に示した樹脂組成物よりも比重が低減され、熱伝導率が低くなることが確認された。また、機械強度においても実施例５（組成１），実施例６（組成２）においては比較例５（比較組成１），比較例６（比較組成２）に比較すると、中空フィラの第一層(ガラスバルーン)表面における樹脂の界面剥離を防ぐことによって引張強度が改善されることが確認された。ＥＤＸで測定した炭素の質量濃度比較においては、実施例５（組成１），実施例６（組成２）においては、比較例５（比較組成１），比較例６（比較組成２）に対してガラスバルーン表面の炭素の質量濃度が高くなっており、ガラスバルーン表面により多い分量の被覆樹脂が残存していることが示された。
(Evaluation results)
As shown in Table 1, the resin compositions of Examples 1 and 3 (Composition 1) and Examples 2 and 4 (Composition 2) are those of Comparative Examples 1 and 3 (Comparative Composition 1) and Comparative Examples 2 and 4, respectively. It was confirmed that the specific gravity was reduced and the thermal conductivity was lower than that of the resin composition shown in (Comparative composition 2). Moreover, also in mechanical strength, in Example 5 (Composition 1), Example 6 (Composition 2), compared with Comparative Example 5 (Comparative Composition 1) and Comparative Example 6 (Comparative Composition 2), the first layer of the hollow filler (Glass balloon) It was confirmed that the tensile strength was improved by preventing interfacial peeling of the resin on the surface. In the mass concentration comparison of carbon measured by EDX, in Example 5 (Composition 1) and Example 6 (Composition 2), compared to Comparative Example 5 (Comparative Composition 1) and Comparative Example 6 (Comparative Composition 2). The mass concentration of carbon on the glass balloon surface was increased, indicating that a larger amount of coating resin remained on the glass balloon surface.
以上のように、本発明に係る中空フィラと熱可塑性樹脂から得られる樹脂組成物によって比重が低く、熱伝導率が軽減され、強度に優れた樹脂成型体が得られることが確認された。本実施例で開示する樹脂成型体からなる掃除機配管は軽量で必要な強度を有しており、掃除機の軽量化に寄与できる。 As described above, it was confirmed that the resin composition obtained from the hollow filler and the thermoplastic resin according to the present invention has a low specific gravity, a reduced thermal conductivity, and a resin molded article having excellent strength. The vacuum cleaner piping made of the resin molded body disclosed in the present embodiment is lightweight and has the necessary strength, and can contribute to weight reduction of the vacuum cleaner.
また、同じ材質の部材を洗濯機，乾燥機，冷蔵庫のプラスチック部品に適用することで、プラスチック部品の断熱化に寄与し、それぞれの製品において熱効率の改善に寄与できる。 In addition, by applying the same material to plastic parts of washing machines, dryers and refrigerators, it contributes to heat insulation of plastic parts and can contribute to improvement of thermal efficiency in each product.
１ 掃除機配管
２ 吸口
３ 掃除機本体
１００ 樹脂成型体
１０１ 中空フィラ
１０２ 熱可塑性樹脂
１０３ 真空もしくは気体層
１０４ 中空部材
１０５ （中空フィラの）第一の層
１０６ （中空フィラの）第二の層
Ｌ 掃除機
DESCRIPTION OF SYMBOLS 1 Vacuum cleaner piping 2 Suction port 3 Vacuum cleaner main body 100 Resin molding 101 Hollow filler 102 Thermoplastic resin 103 Vacuum or gas layer 104 Hollow member 105 First layer 106 (of hollow filler) Second layer L (of hollow filler) Vacuum cleaner
Claims (7)
中空部材表面に被覆され、下記式で表される化合物を含む第一の層と、
第一の層を覆い、第一の層と結合した無水マレイン酸変性ポリオレフィン樹脂を含む第二の層と、を備える中空フィラが、前記無水マレイン酸変性ポリオレフィン樹脂と異なるポリオレフィン樹脂中に分散していることを特徴とする樹脂成形体。
A first layer coated on the surface of the hollow member and containing a compound represented by the following formula:
Covering the first layer, the second layer comprising a first layer and bound maleic anhydride-modified polyolefin resin, an empty filler in which Ru provided with, dispersed in different polyolefin resin and the maleic anhydride-modified polyolefin resin A resin molded body characterized by being made .
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