JP4886385B2 - Molded product of methacrylic resin composition - Google Patents
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Description
本発明は、耐衝撃性を向上したメタクリル樹脂組成物の成形品に関するものである。 The present invention relates to a molded product of a methacrylic resin composition having improved impact resistance.
メタクリル樹脂（ポリメタクリル酸メチル：ＰＭＭＡ）は熱可塑性樹脂の中では硬度が最も高く、また酸やアルカリなどに対する耐薬品性にも優れるために、各種の成形品に広く使用されている。しかし、ＰＭＭＡは耐衝撃性が比較的低く、また割れた際の割れ面が鋭く尖ることがあるため、使用上の注意が必要である。 Methacrylic resin (polymethyl methacrylate: PMMA) has the highest hardness among thermoplastic resins and is excellent in chemical resistance against acids, alkalis, and the like, and is therefore widely used in various molded products. However, since PMMA has a relatively low impact resistance and the cracked surface may be sharp when it is cracked, it must be used with care.
そこで、ＰＭＭＡにアクリルゴムなどのゴムを配合して、ＰＭＭＡの耐衝撃性を上げることが行なわれている（例えば、特許文献１等参照）。
しかし、ＰＭＭＡにゴムを配合すると、ＰＭＭＡ単独の場合に比較して、強度や硬度が低下し、また温度による寸法変化が大きくなり、さらに耐薬品性が低下するという問題が生じるものであった。 However, when rubber is blended with PMMA, the strength and hardness are reduced as compared with the case of PMMA alone, the dimensional change due to temperature is increased, and the chemical resistance is further deteriorated.
本発明は上記の点に鑑みてなされたものであり、強度や硬度、寸法安定性、耐薬品性を低下させることなく、耐衝撃性を向上することができるメタクリル樹脂組成物の成形品を提供することを目的とするものである。 The present invention has been made in view of the above points, and provides a molded product of a methacrylic resin composition that can improve impact resistance without reducing strength, hardness, dimensional stability, and chemical resistance. It is intended to do.
本発明の請求項１に係るメタクリル樹脂組成物の成形品は、メタクリル樹脂に、四フッ化エチレン樹脂のみからなる微粉末樹脂フィラーを配合して成るメタクリル樹脂組成物を成形して成ることを特徴とするものである。 The molded product of the methacrylic resin composition according to claim 1 of the present invention is formed by molding a methacrylic resin composition formed by blending a methacrylic resin with a fine powder resin filler made of only tetrafluoroethylene resin. It is what.
この発明によれば、耐熱性及び耐薬品性が高く硬度が低い四フッ化エチレン樹脂のみからなる微粉末樹脂フィラーをメタクリル樹脂に配合することによって、強度や硬度、寸法安定性、耐薬品性を低下させることなく、耐衝撃性を向上することができるものである。 According to this invention, by blending a methacrylic resin with a fine powder resin filler consisting only of a tetrafluoroethylene resin having high heat resistance and chemical resistance and low hardness, strength, hardness, dimensional stability and chemical resistance can be improved. The impact resistance can be improved without lowering.
また、微粉末樹脂フィラーの平均粒径が５〜２５μｍであることを特徴とするものである。 Moreover , the average particle diameter of the fine powder resin filler is 5 to 25 μm.
この発明によれば、成形品の外観を損なうことなく、耐衝撃性を向上することができるものである。 According to this invention, impact resistance can be improved without impairing the appearance of the molded product.
また、微粉末樹脂フィラーの配合量が０．５〜５質量％であることを特徴とするものである。 Moreover , the compounding quantity of a fine powder resin filler is 0.5-5 mass%, It is characterized by the above-mentioned.
この発明によれば、曲げ強度を低下させることなく、耐衝撃性を向上することができるものである。 According to this invention, the impact resistance can be improved without lowering the bending strength.
本発明によれば、メタクリル樹脂に耐熱性及び耐薬品性が高く硬度が低い四フッ化エチレン樹脂のみからなる微粉末樹脂フィラーをメタクリル樹脂に配合することによって、強度や硬度、寸法安定性、耐薬品性、外観、曲げ強度を低下させることなく、耐衝撃性を向上することができるものである。 According to the present invention, strength, hardness, dimensional stability, resistance to methacrylic resin can be obtained by blending methacrylic resin with a finely divided resin filler made of only tetrafluoroethylene resin having high heat resistance and chemical resistance and low hardness. Impact resistance can be improved without reducing chemical properties , appearance, and bending strength .
以下、本発明を実施するための最良の形態を説明する。 Hereinafter, the best mode for carrying out the present invention will be described.
本発明は、メタクリル樹脂（ポリメタクリル酸メチル：ＰＭＭＡ）にＰＭＭＡより耐熱性及び耐薬品性が高く、且つＰＭＭＡより硬度が低い樹脂材料からなる微粉末フィラーを配合するようにしたものである。 In the present invention, a fine powder filler made of a resin material having higher heat resistance and chemical resistance than PMMA and lower hardness than PMMA is blended with methacrylic resin (polymethyl methacrylate: PMMA).
ＰＭＭＡに硬度が低く柔軟性を有する微粉末フィラーを配合することによって、応力を緩和し、またクラックの発生を分散させて、耐衝撃性を向上させることができるものである。このとき、微粉末フィラーがＰＭＭＡより溶融温度が低く、熱分解温度が低い場合、すなわちＰＭＭＡよりも耐熱性が低いと、成形時に形状を維持できないことや、ＰＭＭＡと分離したり、成形後に剥離したりするおそれがある。このため、微粉末フィラーとして、ＰＭＭＡより耐熱性が高いものを用いるものである。さらに、耐薬品性が低下することを防ぐために、ＰＭＭＡより耐薬品性が高いものを用いるものである。 By blending a fine powder filler with low hardness and flexibility into PMMA, the stress can be relieved and the occurrence of cracks can be dispersed to improve the impact resistance. At this time, if the fine powder filler has a melting temperature lower than that of PMMA and the thermal decomposition temperature is lower, that is, if the heat resistance is lower than that of PMMA, the shape cannot be maintained during molding, separated from PMMA, or peeled off after molding. There is a risk of For this reason, as the fine powder filler, one having higher heat resistance than PMMA is used. Furthermore, in order to prevent the chemical resistance from decreasing, a material having higher chemical resistance than PMMA is used.
本発明では、このような特性を有する微粉末フィラーとして、フッ素系樹脂からなるものを用いるものである。このフッ素系樹脂としては、四フッ化エチレン樹脂（ＰＴＦＥ）、四フッ化エチレン・パーフルオロアルコキシエチレン共重合樹脂（ＰＦＡ）、四フッ化エチレン・六フッ化ポリプロピレン共重合樹脂（ＦＥＰ）、四フッ化エチレン・エチレン共重合樹脂（ＥＴＦＥ）、ビニリデンフルオライド樹脂（ＰＶＦ）、クロロトリフルオロエチレン樹脂（ＰＣＴＦＥ）、エチレン・クロロトリフルオロエチレン樹脂（ＥＣＴＦＥ）などを挙げることができる。本発明では、四フッ化エチレン樹脂を用いる。 In the present invention, a fine powder filler having such characteristics is made of a fluororesin. Examples of the fluororesin include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkoxyethylene copolymer resin (PFA), tetrafluoroethylene / hexafluoropolypropylene copolymer resin (FEP), and tetrafluoroethylene resin. And ethylene-ethylene copolymer resin (ETFE), vinylidene fluoride resin (PVF), chlorotrifluoroethylene resin (PCTFE), and ethylene-chlorotrifluoroethylene resin (ECTFE). In the present invention, tetrafluoroethylene resin is used.
フッ素系樹脂は、ＰＭＭＡより硬度が低く柔軟性に富むものであり、例えばＰＭＭＡの曲げ弾性率は３ＧＰａであるのに対して、ＰＴＦＥの曲げ弾性率は０．５５ＧＰａ、ＰＦＡの曲げ弾性率は０．６６ＧＰａである。またフッ素系樹脂はＰＭＭＡより耐薬品性が高く、耐熱性も高い。例えばＰＭＭＡの溶融温度は２００℃程度であるが、ＰＴＦＥは耐熱温度が２５０℃以上であり、溶融温度は３００℃以上である。 The fluororesin has a lower hardness and a higher flexibility than PMMA. For example, the bending elastic modulus of PMMA is 3 GPa, whereas the bending elastic modulus of PTFE is 0.55 GPa and the bending elastic modulus of PFA is 0. .66 GPa. In addition, fluororesin has higher chemical resistance and higher heat resistance than PMMA. For example, the melting temperature of PMMA is about 200 ° C., but PTFE has a heat resistant temperature of 250 ° C. or higher, and the melting temperature is 300 ° C. or higher.
また、微粉末フィラーとしては、平均粒径が５〜２５μｍの範囲のものを用いる。平均粒径が５μｍ未満であると、取り扱い性が悪くなり、また均一混合も難しくなる。逆に平均粒径が２５μｍを超えると、粒子が粗くなるためにこれが成形品の表面に表れて外観を損なうおそれがある。 Moreover, as a fine powder filler, a thing with an average particle diameter of the range of 5-25 micrometers is used . When the average particle size is less than 5 μm, the handleability is deteriorated and uniform mixing becomes difficult. On the other hand, if the average particle size exceeds 25 μm, the particles become coarse, which may appear on the surface of the molded product and impair the appearance.
そして、ＰＭＭＡに上記の微粉末フィラーを配合し、これを混合・混練することによって、本発明のメタクリル樹脂を得ることができるものである。ここで微粉末フィラーの配合量は、０．５〜５質量％（ＰＭＭＡ１００質量部に対して０．５〜５質量部）の範囲である。微粉末フィラーの配合量が０．５質量％未満では、微粉末フィラーを配合することによる耐衝撃性向上の効果を十分に得ることができない。耐衝撃性向上の効果は微粉末フィラーの配合量が１質量％程度のときに最も高く、微粉末フィラーの配合量が５質量％を超えると曲げ強度の低下が大きくなるので、微粉末フィラーの配合量は５質量％以下であることが好ましい。 And the methacryl resin of this invention can be obtained by mix | blending said fine powder filler with PMMA, and mixing and kneading this. Here, the blending amount of the fine powder filler is in the range of 0.5 to 5% by mass (0.5 to 5 parts by mass with respect to 100 parts by mass of PMMA) . When the blending amount of the fine powder filler is less than 0.5% by mass, the effect of improving the impact resistance by blending the fine powder filler cannot be sufficiently obtained. The effect of improving the impact resistance is the highest when the blending amount of the fine powder filler is about 1% by mass, and when the blending amount of the fine powder filler exceeds 5% by mass, the bending strength decreases greatly. The blending amount is preferably 5% by mass or less.
上記のようにして得られた本発明のメタクリル樹脂組成物を、射出成形など任意の成形法で成形することによって、成形品を得ることができる。ここで、上記のようにＰＭＭＡに微粉末フィラーを混合・混練するときの温度、及び成形の際の温度は、ＰＭＭＡの溶融温度より高く、且つ微粉末フィラーの溶融温度より低い温度に設定されるものである。 A molded product can be obtained by molding the methacrylic resin composition of the present invention obtained as described above by any molding method such as injection molding. Here, as described above, the temperature at which the fine powder filler is mixed and kneaded with PMMA and the temperature at the time of molding are set to a temperature higher than the melting temperature of PMMA and lower than the melting temperature of the fine powder filler. Is.
そしてこの成形品において、ＰＭＭＡには、ＰＭＭＡより耐熱性及び耐薬品性が高く、硬度が低い微粉末フィラーが含有されているので、硬度が低く柔軟性の高い微粉末フィラーによって、成形品の耐衝撃性を高めることができるものである。また微粉末フィラーは硬度が低いが、成形品中にフィラーとして含有されているために、成形品の硬度や強度を大きく低下させるようなことはなく、しかも微粉末フィラーは耐熱性や耐薬品性が高いので、寸法安定性や耐薬品性を低下させることもないものである。 In this molded product, PMMA contains a fine powder filler that has higher heat resistance and chemical resistance than PMMA and has a low hardness. The impact property can be increased. Although the fine powder filler has low hardness, it does not significantly reduce the hardness and strength of the molded product because it is contained as a filler in the molded product, and the fine powder filler is heat and chemical resistant. Therefore, dimensional stability and chemical resistance are not deteriorated.
次に、本発明を実施例によって具体的に説明する。 Next, the present invention will be specifically described with reference to examples.
（参考例１，実施例２〜４，参考例５，実施例６〜７）
ＰＭＭＡとして、三菱レイヨン（株）製の「アクリペットＶＨ００１」を用いた。またＰＴＦＥの微粉末フィラーとして、平均粒径２５μｍの（株）サンプラテック製「サンプラＰＴＦＥパウダーＷＥＢ９３１３１」、平均粒径１０μｍの（株）サンプラテック製「サンプラＰＴＦＥパウダーＷＥＢ９３１３２」、平均粒径６μｍの（株）サンプラテック製「サンプラＰＴＦＥパウダーＷＥＢ９３１３３」を用いた。
( Reference Example 1, Examples 2-4, Reference Example 5, Examples 6-7)
As PMMA, “Acrypet VH001” manufactured by Mitsubishi Rayon Co., Ltd. was used. Further, as a fine powder filler of PTFE, “Sampler PTFE Powder WEB93131” manufactured by Sampratec Co., Ltd. having an average particle diameter of 25 μm, “Sampler PTFE Powder WEB93132” manufactured by Samplertech Co., Ltd. having an average particle diameter of 10 μm, and Co., Ltd. having an average particle diameter of 6 μm. “Sampler PTFE Powder WEB93133” manufactured by Sampler Tech was used.
そしてＰＭＭＡにＰＴＦＥの微粉末フィラーを表１の配合量で配合し、二軸ニーダーを用いてシリンダー温度３００℃の温度条件で加熱混合し、冷却後、粉砕することによって、メタクリル樹脂組成物の成形用ペレットを調製した。 Then, a fine powder filler of PTFE is blended with PMMA in the blending amount shown in Table 1, heated and mixed at a cylinder temperature of 300 ° C. using a biaxial kneader, cooled, and pulverized to form a methacrylic resin composition. Pellets were prepared.
このように調製した成形用ペレットを、射出成形機を用いて、シリンダー温度２４５℃の温度条件で射出成形することによって、試験用の成形品を得た。 The molding pellets thus prepared were injection-molded using an injection molding machine at a cylinder temperature of 245 ° C. to obtain a test molded product.
（比較例１）
ＰＭＭＡとして、三菱レイヨン（株）製の「アクリペットＶＨ００１」をそのまま用い、上記と同様にして射出成形することによって、試験用の成形品を得た。
(Comparative Example 1)
As the PMMA, “Acrypet VH001” manufactured by Mitsubishi Rayon Co., Ltd. was used as it was, and a molded product for test was obtained by injection molding in the same manner as described above.
（比較例２）
ＰＭＭＡとして、三菱レイヨン（株）製の「アクリペットＩＲ Ｄ３０ ００１」（ゴムを添加した耐衝撃グレード）をそのまま用い、上記と同様にして射出成形することによって、試験用の成形品を得た。
(Comparative Example 2)
As PMMA, “Acrypet IR D30 001” (impact resistant grade added with rubber) manufactured by Mitsubishi Rayon Co., Ltd. was used as it was, and a molded product for test was obtained by injection molding in the same manner as described above.
上記の参考例１，実施例２〜４，参考例５，実施例６〜７及び比較例１〜２で得た試験用成形品について、鉛筆硬度（ＪＩＳ Ｋ ５４００）、曲げ強度（ＪＩＳ Ｋ ７１７１）、シャルピー衝撃強度（ＪＩＳ Ｋ ７１１１）、線膨張係数（ＡＳＴＭ Ｄ６９６）を測定した。結果を表１に示す。 About the molded article for a test obtained in the above Reference Example 1, Examples 2 to 4, Reference Example 5, Examples 6 to 7 and Comparative Examples 1 to 2, pencil hardness (JIS K 5400), bending strength (JIS K 7171) ), Charpy impact strength (JIS K 7111), and linear expansion coefficient (ASTM D696). The results are shown in Table 1.
表１にみられるように、平均粒径６〜２５μｍのＰＴＦＥの微粉末フィラーを０．５〜５質量％の範囲で配合した各実施例のものは、無配合のＰＭＭＡの比較例１よりもシャルピー衝撃強度が向上し、耐衝撃グレードＰＭＭＡの比較例２と同等のシャルピー衝撃強度が得られることが確認される。一方、各実施例の鉛筆硬度、曲げ強度、線膨張係数は比較例１と同等であり、硬度、強度、寸法安定性が低下していないことが確認される。 As can be seen in Table 1, those of each Example in which a fine powder filler of PTFE having an average particle diameter of 6 to 25 μm was blended in the range of 0.5 to 5% by mass is more than Comparative Example 1 of PMMA without blending. It is confirmed that the Charpy impact strength is improved and the Charpy impact strength equivalent to that of Comparative Example 2 of impact resistant grade PMMA is obtained. On the other hand, the pencil hardness, bending strength, and linear expansion coefficient of each example are equivalent to those of Comparative Example 1, and it is confirmed that the hardness, strength, and dimensional stability are not lowered.
また実施例２，４，６にみられるように、ＰＴＦＥの微粉末フィラーの平均粒径が６μｍ、１０μｍ、２５μｍのいずれでもほぼ同等の結果が得られたが、平均粒径が５μｍ未満では取り扱いが難しく、平均粒径が２５μｍ超では粒子の粗さによる成形品の外観の問題があるので、微粉末フィラーの平均粒径は５〜２５μｍの範囲が好ましいことが確認される。 In addition, as seen in Examples 2, 4 and 6, almost the same results were obtained when the average particle size of the PTFE fine powder filler was 6 μm, 10 μm or 25 μm, but the average particle size was less than 5 μm. When the average particle size exceeds 25 μm, there is a problem of the appearance of the molded product due to the roughness of the particles. Therefore, it is confirmed that the average particle size of the fine powder filler is preferably in the range of 5 to 25 μm.
また参考例１，実施例２〜４，参考例５にみられるように、ＰＴＦＥの微粉末フィラーの配合量が１質量％のときにシャルピー衝撃強度の向上はピークであり、これより少ない場合も多い場合も向上の効果は低くなる傾向にあり、５質量％の配合のときは曲げ強度の低下がみられるので、微粉末フィラーの配合量は０．５〜５質量％の範囲が好ましいことが確認される。 Further, as seen in Reference Examples 1, Examples 2 to 4, and Reference Example 5, when the blending amount of the fine powder filler of PTFE is 1% by mass, the improvement in Charpy impact strength is a peak, and there are cases where the amount is less than this. In many cases, the improvement effect tends to be low, and when the blending amount is 5% by mass, a decrease in bending strength is observed. It is confirmed.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2006177334A JP4886385B2 (en) | 2006-06-27 | 2006-06-27 | Molded product of methacrylic resin composition |
| EP07767389.5A EP2036948B1 (en) | 2006-06-27 | 2007-06-22 | Methacrylic resin composition and molded article thereof |
| KR1020097001429A KR101170034B1 (en) | 2006-06-27 | 2007-06-22 | Methacrylic resin composition and molded article thereof |
| CN2007800246546A CN101479338B (en) | 2006-06-27 | 2007-06-22 | Methacrylic resin composition and molded article thereof |
| PCT/JP2007/062577 WO2008001684A1 (en) | 2006-06-27 | 2007-06-22 | Methacrylic resin composition and molded article thereof |
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| JP2009057577A (en) * | 2008-12-15 | 2009-03-19 | Panasonic Electric Works Co Ltd | Methacrylic resin composition, method for manufacturing molded article of methacrylic resin composition, and molded article of methacrylic resin composition |
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| JPWO2014104223A1 (en) * | 2012-12-27 | 2017-01-19 | 旭硝子株式会社 | POLYMER COMPOSITION, MOLDED BODY THEREOF, AND SOLAR CELL BACK SHEET |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009057577A (en) * | 2008-12-15 | 2009-03-19 | Panasonic Electric Works Co Ltd | Methacrylic resin composition, method for manufacturing molded article of methacrylic resin composition, and molded article of methacrylic resin composition |
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| Publication number | Publication date |
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| CN101479338B (en) | 2012-05-30 |
| JP2008007574A (en) | 2008-01-17 |
| CN101479338A (en) | 2009-07-08 |
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