JPS63286464A - Polyphenylene ether resin composition - Google Patents
Polyphenylene ether resin compositionInfo
- Publication number
- JPS63286464A JPS63286464A JP12006887A JP12006887A JPS63286464A JP S63286464 A JPS63286464 A JP S63286464A JP 12006887 A JP12006887 A JP 12006887A JP 12006887 A JP12006887 A JP 12006887A JP S63286464 A JPS63286464 A JP S63286464A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- molecular weight
- polyphenylene ether
- resin composition
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 20
- 239000011342 resin composition Substances 0.000 title claims description 18
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims abstract description 7
- 239000011256 inorganic filler Substances 0.000 claims abstract description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims abstract description 5
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 abstract description 13
- -1 poly(2,6-dimethyl-1,4- phenylene) Polymers 0.000 abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003365 glass fiber Substances 0.000 abstract description 4
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 239000004793 Polystyrene Substances 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 14
- 229920002223 polystyrene Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 8
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- CIRRFAQIWQFQSS-UHFFFAOYSA-N 6-ethyl-o-cresol Chemical compound CCC1=CC=CC(C)=C1O CIRRFAQIWQFQSS-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RLEWTHFVGOXXTN-UHFFFAOYSA-N 2,3-diethylphenol Chemical compound CCC1=CC=CC(O)=C1CC RLEWTHFVGOXXTN-UHFFFAOYSA-N 0.000 description 1
- HRQPPTDGMMGDKC-UHFFFAOYSA-N 2,3-dipropylphenol Chemical compound CCCC1=CC=CC(O)=C1CCC HRQPPTDGMMGDKC-UHFFFAOYSA-N 0.000 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- XRSWLVYCXFHDDB-UHFFFAOYSA-N 2-ethyl-3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1CC XRSWLVYCXFHDDB-UHFFFAOYSA-N 0.000 description 1
- XNCTZUPZTWUFNW-UHFFFAOYSA-N 2-methyl-3-propylphenol Chemical compound CCCC1=CC=CC(O)=C1C XNCTZUPZTWUFNW-UHFFFAOYSA-N 0.000 description 1
- NXSQQKKFGJHACS-UHFFFAOYSA-N 2-methyl-6-propylphenol Chemical compound CCCC1=CC=CC(C)=C1O NXSQQKKFGJHACS-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- IVFJPARIJHUGPZ-UHFFFAOYSA-N 3-ethyl-2-methylphenol Chemical compound CCC1=CC=CC(O)=C1C IVFJPARIJHUGPZ-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- BOLVXBAXRSJQMP-UHFFFAOYSA-N 5-ethyl-3-propyl-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound CCC1=C(O2)C(CCC)=CC2=C1 BOLVXBAXRSJQMP-UHFFFAOYSA-N 0.000 description 1
- NGSJNQJPYFYNJV-UHFFFAOYSA-N 5-methyl-2-propylphenol Chemical compound CCCC1=CC=C(C)C=C1O NGSJNQJPYFYNJV-UHFFFAOYSA-N 0.000 description 1
- PRYWLASFWHTGGI-UHFFFAOYSA-N CC1=CC=CC(O)=C1.CCC1=CC=CC=C1O Chemical compound CC1=CC=CC(O)=C1.CCC1=CC=CC=C1O PRYWLASFWHTGGI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- KFLXTWMGKAROOX-UHFFFAOYSA-N oxygen(2-) titanium(4+) triphenyl phosphate Chemical compound [O-2].[O-2].[Ti+4].P(=O)(OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 KFLXTWMGKAROOX-UHFFFAOYSA-N 0.000 description 1
- NKTOLZVEWDHZMU-UHFFFAOYSA-N p-cumyl phenol Natural products CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、成形加工性および耐候性に優れ、良好な表面
光沢を示し、且つ塗装性等二次加工性に優れたポリフェ
ニレンエーテル系樹脂組成物に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention provides a polyphenylene ether resin composition that has excellent moldability and weather resistance, exhibits good surface gloss, and has excellent secondary processability such as paintability. relating to things.
ポリフェニレンエーテル樹脂（以下ｒＰＰＢ樹脂」と略
称する）は、耐熱性に優れ、機械的性質、電気的性質、
その他種々の性質に優れていることから、その特性を生
かしてエンジニアリングプラスチックとして各種用途に
実用化されている。このように％ＰＰＢ樹脂は耐熱性が
高いことが一つの大きな特徴であるが、反面、溶融粘度
が高いので成形加工性が悪く、さらに高温下において熱
酸化されやすいので、高温における成形加工によって本
来有する優れた性能が損われることが多い。Polyphenylene ether resin (rPPB resin) has excellent heat resistance, mechanical properties, electrical properties,
Since it has various other excellent properties, it has been put to practical use as an engineering plastic for various purposes by taking advantage of its properties. One of the major characteristics of %PPB resin is that it has high heat resistance, but on the other hand, it has poor moldability due to its high melt viscosity, and it is also prone to thermal oxidation at high temperatures, so it cannot be processed by molding at high temperatures. The excellent performance it possesses is often compromised.
そこで、ＰＰＥ樹脂の成形加工性を改善するために、例
えば米国特許第３，３８５，４５５号明細書には、ＰＰ
ＩＢ樹脂にポリスチレンな配合することが開示されてお
り、ポリスチレンとしてゴム変性ポリスチレンな用いる
ことによつて、成形加工性とともに耐衝撃性も改良され
ることが教示されている。しかし、それらの樹脂組成物
では、成形加工性や耐衝撃性は改良されるものの、表面
光沢、耐候性、二次加工性などの点で満足できない。さ
らに、成形加工性を改善する別の方法として、可塑剤あ
るいは滑剤を添加する方法も提案されている。しかし、
いずれの方法においても、成形加工性は改善されるもの
の、ＰＰＢ樹脂本来の特徴である耐熱性の低下、具体的
には熱変形温度の低下は避は難いのが実情である。Therefore, in order to improve the moldability of PPE resin, for example, US Patent No. 3,385,455 discloses that PPE resin
It is disclosed that polystyrene is blended with IB resin, and it is taught that by using rubber-modified polystyrene as the polystyrene, moldability and impact resistance are improved. However, although these resin compositions have improved moldability and impact resistance, they are not satisfactory in terms of surface gloss, weather resistance, secondary processability, and the like. Furthermore, as another method of improving moldability, a method of adding a plasticizer or a lubricant has also been proposed. but,
In either method, although moldability is improved, the reality is that it is difficult to avoid a decrease in heat resistance, specifically a decrease in heat distortion temperature, which is an inherent characteristic of PPB resin.
耐候性や表面光沢を改良するために、一般的には紫外線
吸収剤やシリコンオイル等を添加すればよいとされてい
るが、その効果は十分ではなく、また、表面光沢の改良
法として、ゴム変性ポリスチレン中のゴム粒径な小さく
することも提案されているが、この方法でも表面光沢の
改良はまだ不十分である。In order to improve weather resistance and surface gloss, it is generally considered that adding ultraviolet absorbers, silicone oil, etc. is sufficient, but the effect is not sufficient, and as a method for improving surface gloss, rubber It has also been proposed to reduce the rubber particle size in modified polystyrene, but even with this method the improvement in surface gloss is still insufficient.
さらに、無機充填剤や無機強化剤を配合したＰＰＭ樹脂
組成物では、表面光沢のみならず、塗装等の二次加工性
が悪いという間嘔点がある。Furthermore, PPM resin compositions containing inorganic fillers and inorganic reinforcing agents have drawbacks such as poor surface gloss and poor secondary processability such as painting.
本発明は、上述の如き従来技術の欠陥に鑑み、耐熱性の
低下を招くことなく良好な成形加工性を保持し、１つ耐
衝撃性、耐候性、表面光沢および塗装等の二次加工性に
すぐれたＰＰＢ樹脂組成物を得ることを目的とする。In view of the deficiencies of the prior art as described above, the present invention has been developed to maintain good moldability without causing a decrease in heat resistance, and to provide impact resistance, weather resistance, surface gloss, and secondary processability such as painting. The purpose of the present invention is to obtain a PPB resin composition with excellent properties.
上記目的を達成するべく、本発明者らが鋭意検討を進め
た結果、（ａ） Ｐ Ｐ Ｂ樹脂とｒｂｌビニル芳香族
炭化水素樹脂との混合物に（ｃ）オリゴビニル重合体と
（ａｌ無機充填剤を配合することによって、ＰＰＭ樹脂
本来の耐熱性が損なわれることなくＰＰＰ樹脂の成形加
工性が改良されるという特異な効果が達成されることを
見出した。さらには、当＃ＰＰＥ樹脂組成物では、耐候
性にも優れ、良好な表面光沢を示し、且つ塗装等の二次
加工性にも顕著に優れていることも明らかになった。本
発明のＰＰＥ樹脂組成物に見られる上記特徴は、従来技
術から予測できない特異な効果であり、実用上有用なＰ
ＰＥ樹脂成形材料を提供する。In order to achieve the above object, the present inventors conducted intensive studies and found that (a) a mixture of P P B resin and RBL vinyl aromatic hydrocarbon resin, (c) oligovinyl polymer and (al inorganic filling) It has been found that by blending the #PPE resin composition with this #PPE resin composition, the unique effect of improving the molding processability of the PPP resin without impairing the inherent heat resistance of the PPM resin can be achieved. It has also been revealed that the PPE resin composition of the present invention has excellent weather resistance, good surface gloss, and remarkable secondary processability such as painting.The above characteristics of the PPE resin composition of the present invention are , a unique effect that cannot be predicted from the conventional technology, and a practically useful P
We provide PE resin molding materials.
本発明の組成物において用いられるポリフェニレンエー
テル樹脂とは、一般式（ｒ）で示される単環式フェノー
ルの一種以上な重縮合して得られるポリフェニレンエー
テル；このポリフェニレンエーテルにビニル芳香族化合
物をグラフト（ここに、几ｌ は炭素数１〜３の低級ア
ルキル基そして、 ＦＬｚ および几３ は水素原子
または炭素数１〜３の低級アルキル基である。）重合し
て得られる根幹にポリフェニレンエーテルを有するグラ
フト共重合体を意味する。このポリフェニレンエーテル
は、単独重合体であっても共重合体であってもよい。The polyphenylene ether resin used in the composition of the present invention is a polyphenylene ether obtained by polycondensation of one or more monocyclic phenols represented by the general formula (r); a vinyl aromatic compound is grafted onto this polyphenylene ether ( Here, 几l is a lower alkyl group having 1 to 3 carbon atoms, and FLz and 几3 are hydrogen atoms or lower alkyl groups having 1 to 3 carbon atoms. means a copolymer. This polyphenylene ether may be a homopolymer or a copolymer.
前記一般式（Ｉ）で示される単環式フェノールとしては
、例えば％ ２．６−ジエチルフェノール。Examples of the monocyclic phenol represented by the general formula (I) include %2.6-diethylphenol.
２ 、６−９エチルフエノール、２．６−ジプロピルフ
ェノール、２−メチル−６−エチルフェノール、２−メ
チル−６−プロピルフェノール、２−エチル−６−ブロ
ピルフエ／−ル、０−クレゾール、２．３−ジメチルフ
ェノール、２゜３−ジエチルフェノール、２，３−ジプ
ロピルフェノール、２−メチル−３−エチルフェノール
、２−メチル−３−プロピルフェノール、２−エチル−
３−メチルフェノール、２−エチル−３−プロピルフェ
ノール、２−プロピル−５−メチルフェノール、２−７
’口ピル−３−エチルフェノール、２，３．６−）ジエ
チルフェノール、２，３．６−ドリエチルフエノール、
２゜３．６−１−ジプロピルフェノール、２．６−シメ
チルー３−エチル−フェノール、２．６−シメチルー５
−プロピルフェノール等が挙げられる。そして、これら
のフェノールの一種以上の重縮合により得られるポリフ
ェニレンエーテルと−しては、例えば、ポリ（２，６−
シメチルー１．４−フェニレン）エーテル、ポリ（２，
６−シエチルー１．４−フェニレン）エーテル、ホＩＪ
（２、６−ジプロビルー１．４−フェニレン）エーテ
ル、ｒｔ！ＩＪ（２−メチル−６−エチル−１，４−フ
エニレン）エーテル、ポリ（２−メチル−６−ブロビル
ー１，４−フェニレン）エーテル、＋ｔ！ＩＪ（２−エ
チル−６−プロピル−１，４−フェニレン）エーテル、
２．６−シメチルフエノール／２，３．６−）リメチル
フェノール共ｊＬ＆体、２ 、６−シメチルフエノール
／２，３．６−１リ工チルフエノール共重合体、２．６
−ジメチルフェノール／２ 、３ 、６−ドリメチルフ
エノール共重合体、２，６−ジプロピルフェノール／２
、５ 、６−ドリメチルフエノール共重合体、ポＩＪ
（２、６−シメチルー１゜４−フェニレン）エーテル
にスチレンをグラフト重合したグラフト共重合体、２，
６−シメチルフエノール／２，５．６−ドリメチルフエ
ノール共重合体にスチレンをグラフト重合したグラフト
共重合体等が挙げられる。特に、ポリ（２，６−シメチ
ルー１，４−フェニレン）エーテル、２，６−ジメチル
フェノール／２ 、３ 。2, 6-9 ethylphenol, 2.6-dipropylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol, 2-ethyl-6-bropylphenol, 0-cresol, 2 .3-dimethylphenol, 2゜3-diethylphenol, 2,3-dipropylphenol, 2-methyl-3-ethylphenol, 2-methyl-3-propylphenol, 2-ethylphenol
3-methylphenol, 2-ethyl-3-propylphenol, 2-propyl-5-methylphenol, 2-7
'mouth pill-3-ethylphenol, 2,3.6-)diethylphenol, 2,3.6-driethylphenol,
2゜3.6-1-dipropylphenol, 2.6-dimethyl-3-ethyl-phenol, 2.6-dimethyl-5
-propylphenol and the like. Examples of the polyphenylene ether obtained by polycondensation of one or more of these phenols include poly(2,6-
dimethyl-1,4-phenylene)ether, poly(2,
6-ethyl-1,4-phenylene) ether, HoIJ
(2,6-diprobyl-1,4-phenylene)ether, rt! IJ (2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, +t! IJ (2-ethyl-6-propyl-1,4-phenylene) ether,
2,6-dimethylphenol/2,3.6-)limethylphenol copolymer, 2,6-dimethylphenol/2,3.6-1-dimethylphenol copolymer, 2.6
-dimethylphenol/2,3,6-dimethylphenol copolymer, 2,6-dipropylphenol/2
, 5, 6-drimethylphenol copolymer, PoIJ
(2,6-dimethyl-1゜4-phenylene) Graft copolymer of styrene grafted to ether, 2,
Examples include a graft copolymer obtained by graft polymerizing styrene onto a 6-dimethylphenol/2,5.6-drimethylphenol copolymer. In particular, poly(2,6-dimethyl-1,4-phenylene)ether, 2,6-dimethylphenol/2,3.
６−ドリメチルフエノール共重合体および前二者にそれ
ぞれスチレンをグラフト重合したグラフト共重合体が本
発明に用いるＰＰＥ樹脂として好ましいものである。A 6-dolimethylphenol copolymer and a graft copolymer obtained by graft-polymerizing styrene onto each of the former two are preferred as the PPE resin used in the present invention.
次に、本発明の組成物において、ＰＰＢ樹脂と混合して
用いられるビニル芳香族炭化水素樹脂とは、下記一般式
（［１）で示される単量体構造単几４
（ここに、几４ は水素原子又は低級アルキル基、２は
ハロゲン原子又は低級アルキル基を示し、ｐは０または
１〜３の正の整数である。）位を、その重合体中に少な
くとも２５重量％以上有する樹脂であり、例えばポリス
チレン、ゴム変性ポリスチレン（耐衝撃性ポリスチレン
）、スチレン−ブタジェンコポリマー、スチレン−ブタ
ジェン−アクリロニトリルコポリマー、スチレンーナク
リル酸ゴムーアクリロニトリルコポリマー、スチレン−
α−メチルスチレンコポリマー、スチレン・ブタジェン
・ブロックコポリマー等が挙げられ、これらは２種以上
を混合して用いてもよい。なかでも、ゴム変性ポリスチ
レンは好適に用いられる。ビニル芳香族炭化水素樹脂は
、ＰＰＥ樹脂との合計量に対して９０重量％以下の割合
で混合するのが望ましく、９０重量％を超えるとＰＰＢ
樹脂を使用する特徴が発揮され得ない。Next, in the composition of the present invention, the vinyl aromatic hydrocarbon resin used in combination with the PPB resin has a monomer structure represented by the following general formula ([1)]. is a hydrogen atom or a lower alkyl group, 2 is a halogen atom or a lower alkyl group, and p is 0 or a positive integer of 1 to 3. Yes, such as polystyrene, rubber-modified polystyrene (high-impact polystyrene), styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, styrene-naacrylate rubber-acrylonitrile copolymer, styrene-butadiene copolymer,
Examples include α-methylstyrene copolymer and styrene-butadiene block copolymer, and two or more of these may be used as a mixture. Among them, rubber-modified polystyrene is preferably used. It is desirable to mix vinyl aromatic hydrocarbon resin at a ratio of 90% by weight or less based on the total amount of PPE resin, and if it exceeds 90% by weight, PPB
The characteristics of using resin cannot be exhibited.
次に、本発明の樹脂組成物において、用いられるオリゴ
ビニル重合体とは、低分子量のホモポリスチレンおよび
低分子量のスチレン−アクリロニトリル共重合体を指し
、これらは混合して用いられてもよい。これらのオリゴ
ビニル重合体は、数平均で５００〜６５０００の範囲の
分子量を持つ重合体であって、塊状重合、溶液重合、乳
化重合あるいは懸濁重合のいずれの方法で製造されても
よい。オリゴビニル重合体の配合量は、ＰＰＢ樹脂とビ
ニル芳香族炭化水素樹脂と当該オリゴビニル重合体との
合計量において０．３〜２０重量％の範囲を占める割合
で選定されればよい。０．３重量％より少ない割合の量
で用いられると、成形加工性゛、表面光沢および二次加
工性の改良効果は達成されず、他方、２０重量％を超え
る割合の量で用いられると、耐衝撃性および曲げ強度に
低下が見られ、好ましくない。Next, in the resin composition of the present invention, the oligovinyl polymer used refers to a low molecular weight homopolystyrene and a low molecular weight styrene-acrylonitrile copolymer, and these may be used in combination. These oligovinyl polymers have a number average molecular weight in the range of 500 to 65,000, and may be produced by any of bulk polymerization, solution polymerization, emulsion polymerization, or suspension polymerization. The amount of the oligovinyl polymer to be blended may be selected to be in the range of 0.3 to 20% by weight based on the total amount of the PPB resin, the vinyl aromatic hydrocarbon resin, and the oligovinyl polymer. If used in a proportion of less than 0.3% by weight, the effect of improving molding processability, surface gloss and fabrication properties will not be achieved, while if used in a proportion of more than 20% by weight, A decrease in impact resistance and bending strength is observed, which is not preferable.
本発明の樹脂組成物に配合される無機充填剤とは、金属
単体、金属化合物、炭素または黒鉛の粉末、フレークあ
るいは繊維をいい、金属化合物としては、酸化物、水酸
化物、硫酸塩、硫化物、けい酸塩、はう酸塩、チタン酸
塩などが挙げられる。さらに具体的には、ガラス繊維、
ガラス粉末、シリカ、タルク、アルミナ、マイカ、クレ
ー、ドーソナイト、モンモリロナイト、炭素繊維、六チ
タン酸カリウム繊維、酸化亜鉛、酸化カルシウム、炭酸
カルシウムなどが挙げられる。無機充填剤の配合量は、
本発明の樹脂組成物全量中７０を量％を超えない範囲で
選ばれればよく、７０重量％を超えると、成形加工性が
著しく不良となる。The inorganic filler blended into the resin composition of the present invention refers to an elemental metal, a metal compound, carbon or graphite powder, flakes, or fibers, and examples of the metal compound include oxides, hydroxides, sulfates, and sulfides. Examples include salts, silicates, balates, titanates, etc. More specifically, glass fiber,
Examples include glass powder, silica, talc, alumina, mica, clay, dawsonite, montmorillonite, carbon fiber, potassium hexatitanate fiber, zinc oxide, calcium oxide, and calcium carbonate. The amount of inorganic filler is
It may be selected within a range not exceeding 70% by weight in the total amount of the resin composition of the present invention, and if it exceeds 70% by weight, the molding processability will be extremely poor.
本発明の樹脂組成物には、所望に応じて、耐衝撃性付与
剤を添加してもよく、例えば、Ａ−Ｂ−ｘ型ブロック共
重合体エラストマー（ここで、Ａおよびにとは、ビニル
芳香族化合物が重合したブロックを、Ｂとは、共役ジエ
ン化合物が重合したブロックを意味し、ブロックＢは水
素添加されていてもよい。）を挙げることができる。An impact resistance imparting agent may be added to the resin composition of the present invention as desired, such as an A-B-x type block copolymer elastomer (here, A and Ni are B means a block polymerized with a conjugated diene compound, and block B may be hydrogenated.
本発明の樹脂組成物には、さらに公知の熱安定剤、光安
定剤、酸化防止剤、難燃剤、難燃助剤、顔料、滑剤、可
塑剤、有機充填剤等の各種添加剤を適宜添加することが
できる。これらは単独でも混合して用いても良く、本発
明の樹脂組成物の特長が損なわれない範囲の量で用いら
れねばならない。Various additives such as known heat stabilizers, light stabilizers, antioxidants, flame retardants, flame retardant aids, pigments, lubricants, plasticizers, and organic fillers are further added to the resin composition of the present invention. can do. These may be used alone or in combination, and must be used in amounts that do not impair the characteristics of the resin composition of the present invention.
本発明のＰＰＢ樹脂組成物を調製する方法としては、特
に制約はなく、たとえば、各成分をブレンダーで混合し
たのち押出機を用いて溶融、混練する方法などそれ自体
公知の方法を適宜選択して用いればよい。There are no particular restrictions on the method for preparing the PPB resin composition of the present invention, and methods known per se may be selected as appropriate, such as a method in which each component is mixed in a blender and then melted and kneaded using an extruder. Just use it.
以下、実施例および比較例によって本発明を具体的に説
明する。実施例中、特に断わりがない限り、部数および
％は重量基準である。Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. In the examples, unless otherwise specified, parts and percentages are based on weight.
実施例１〜４および比較段１〜４
２５℃、クロロホルム中で測定した固有粘度がｏ、ｓ５
ｄ／／ｇの２．６−シメチルフエノールと２．３．６−
ドリメチルフエノールとの共重合体（２，３，６−トＩ
Ｊメチルフエノールの含有賃は５モル％）とゴム変性ポ
リスチレン（ゲル含有率１６％、ポリスチレンマトリッ
クスの２５℃クロロホルム中の固有粘度０ 、９０ ｄ
／／９）と低分子量ホモポリスチレンとガラス繊維また
は炭素繊維とカーボンブラックとを、表−１に示す割合
で配合した。Examples 1 to 4 and comparative stages 1 to 4 Intrinsic viscosity measured in chloroform at 25°C is o, s5
d//g of 2.6-dimethylphenol and 2.3.6-
Copolymer with dolimethylphenol (2,3,6-tI
The content of J methylphenol is 5 mol%) and rubber-modified polystyrene (gel content 16%, the intrinsic viscosity of the polystyrene matrix in chloroform at 25°C is 0.90 d).
//9), low molecular weight homopolystyrene, glass fiber or carbon fiber, and carbon black in the proportions shown in Table 1.
先ず、ガラス繊維または炭素繊維を除いた成分をブレン
ダーで混合し、二軸押出機を用いて溶融、混練し、押出
してベレットを得た。次いで、得られたベレットとガラ
スＮＩＬ維または炭素繊維とをタンブラ−で混合し、得
られた混合物を一軸押出機で溶融、混練し、押出してペ
レット化した。First, the components except for glass fibers or carbon fibers were mixed in a blender, melted, kneaded, and extruded using a twin-screw extruder to obtain pellets. Next, the obtained pellets and glass NIL fibers or carbon fibers were mixed in a tumbler, and the obtained mixture was melted and kneaded in a single screw extruder, and extruded into pellets.
得られたベレットを射出成形機を用いて各種試験片に成
形した。The obtained pellets were molded into various test pieces using an injection molding machine.
ここで用いた低分子量のホモポリスチレンは、数平均分
子量が約５０００のオリゴスチレンである。The low molecular weight homopolystyrene used here is oligostyrene with a number average molecular weight of about 5,000.
得られた各試験片を用いて測定した諸性質は、表−１に
示す。表中、バーフローテストは、シリンダ一温度３０
０℃に設定した射出成形機を用いて射出圧力１００ Ｋ
ｆ／ｃｄ、射出率２０％の条件で、８０℃に設定した厚
み２％の金型に射出することＫよって行ない、射出時の
流動距離を測定した。The properties measured using each of the obtained test pieces are shown in Table-1. In the table, the bar flow test is performed at a cylinder temperature of 30
Injection pressure 100 K using an injection molding machine set at 0°C
Injection was performed by K into a mold with a thickness of 2% set at 80° C. under the conditions of f/cd and injection rate of 20%, and the flow distance during injection was measured.
比較のために１低分子量のホモポリスチレンな使用しな
い組成についても試験片を作成し、諸物性を測定した。For comparison, test pieces were also prepared for a composition in which low molecular weight homopolystyrene was not used, and various physical properties were measured.
結果を表−１に併記する。The results are also listed in Table-1.
表−１から判るように１本発明の低分子量のホモポリス
チレンを添加した組成物は、添加しない組成物に比較し
て、熱変形温度を低下させることなく、衝撃強度、表面
光沢度およびバーフロー値（成形性）がすぐれている。As can be seen from Table 1, the composition to which the low molecular weight homopolystyrene of the present invention is added can improve impact strength, surface gloss, and bar flow without lowering the heat distortion temperature, compared to the composition without the addition. Excellent value (formability).
さらに、成形品の塗装、印刷という二次加工性も良好で
あった。Furthermore, the secondary processability of painting and printing of molded products was also good.
実施例５〜８および比較例５〜８
実施例１〜４において低分子量のポリスチレンに代えて
低分子量のスチレン−アクリロニトリル共重合体を使用
する以外は、実施例１〜４を繰り返した。Examples 5-8 and Comparative Examples 5-8 Examples 1-4 were repeated except that low molecular weight styrene-acrylonitrile copolymer was used in place of low molecular weight polystyrene in Examples 1-4.
ここで用いた低分子量のスチレン−アクリロニトリル共
重合体は、数平均分子量約１００００のオリゴコポリマ
ーである。The low molecular weight styrene-acrylonitrile copolymer used here is an oligo copolymer with a number average molecular weight of about 10,000.
測定した諸物性は、表−２に示す。The measured physical properties are shown in Table-2.
比較のために、オリゴコポリマーを使用しない組成につ
いての結果を表−２に併記する。For comparison, the results for compositions that do not use oligo copolymers are also shown in Table 2.
実施例９〜１５および比較例９
実施例１で用いたＰＰＰ樹脂およびゴム変性ポリスチレ
ンとポリスチレン・ポリブタジェン・ポリスチレンブロ
ック共重合体エラストマー（ポリスチレン部分とポリブ
タジェン部分との重量比が３０／７０であり、２５％ト
ルエン溶液のブルックフィールドモデルＲＶＴ粘度計を
用いて２５℃で測定した結果が４０００ ｃｐｓ）と低
分子量ホモポリスチレンとトリフェニルホスフェート酸
化チタンとを、それぞれ表−３に示す割合で用い、ブレ
ンダーで混合した。得られた混合物を二軸押出機で溶融
し、混練し、押出してペレット化した。得られたベレッ
トを射出成形機を用いて各種試験片に成形した。Examples 9 to 15 and Comparative Example 9 The PPP resin and rubber-modified polystyrene used in Example 1 and the polystyrene/polybutadiene/polystyrene block copolymer elastomer (the weight ratio of the polystyrene part to the polybutadiene part was 30/70, and 25 % toluene solution at 25°C using a Brookfield model RVT viscometer), low molecular weight homopolystyrene and triphenylphosphate titanium oxide were used in the proportions shown in Table 3, and mixed in a blender. did. The resulting mixture was melted, kneaded, and extruded into pellets using a twin-screw extruder. The obtained pellets were molded into various test pieces using an injection molding machine.
ここで用いられた低分子量ホモポリスチレンの種類は、
それぞれの数平均分子量が、人では約ｓ、ｏｏｏ、Ｂで
は約１５，０００セしてＣでは約５０，０００であった
。The type of low molecular weight homopolystyrene used here is
The respective number average molecular weights were approximately s, ooo for human, approximately 15,000 for B, and approximately 50,000 for C.
各種試験片を用いて測定した諸物性は、表−６に示す。Various physical properties measured using various test pieces are shown in Table-6.
比較のために、低分子量ホモポリスチレンな使用しない
組成についての結果を表−３に併記する。For comparison, Table 3 also shows the results for a composition in which low molecular weight homopolystyrene was not used.
実施例および比較例の結果から明らかなごとく、オリゴ
ビニル重合体の使用によって、熱変形温度を低下させる
ことなく、流動性、機械的性質および表面光沢度が向上
していることが判る。As is clear from the results of Examples and Comparative Examples, it can be seen that the use of the oligovinyl polymer improves fluidity, mechanical properties, and surface gloss without lowering the heat distortion temperature.
Claims (1)
量スチレン−アクリロニトリル共重合体であるオリゴビ
ニル重合体、および （ｄ）無機充填剤 を含有してなるポリフェニレンエーテル系樹脂組成物 ２、オリゴビニル重合体が５００〜６５０００の範囲の
数平均分子量を有している特許請求の範囲第１項記載の
樹脂組成物[Claims] 1. (a) polyphenylene ether resin, (b) vinyl aromatic hydrocarbon resin, (c) oligovinyl polymer that is low molecular weight homopolystyrene and/or low molecular weight styrene-acrylonitrile copolymer; and (d) polyphenylene ether resin composition 2 containing an inorganic filler, the resin composition according to claim 1, wherein the oligovinyl polymer has a number average molecular weight in the range of 500 to 65,000. thing
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12006887A JPS63286464A (en) | 1987-05-19 | 1987-05-19 | Polyphenylene ether resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12006887A JPS63286464A (en) | 1987-05-19 | 1987-05-19 | Polyphenylene ether resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63286464A true JPS63286464A (en) | 1988-11-24 |
Family
ID=14777095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12006887A Pending JPS63286464A (en) | 1987-05-19 | 1987-05-19 | Polyphenylene ether resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63286464A (en) |
-
1987
- 1987-05-19 JP JP12006887A patent/JPS63286464A/en active Pending
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