JP2009114331A - Filament-reinforced composite resin composition and molded article - Google Patents
Filament-reinforced composite resin composition and molded article Download PDFInfo
- Publication number
- JP2009114331A JP2009114331A JP2007289238A JP2007289238A JP2009114331A JP 2009114331 A JP2009114331 A JP 2009114331A JP 2007289238 A JP2007289238 A JP 2007289238A JP 2007289238 A JP2007289238 A JP 2007289238A JP 2009114331 A JP2009114331 A JP 2009114331A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- reinforced composite
- resin composition
- long fiber
- composite resin
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title abstract description 12
- 239000000805 composite resin Substances 0.000 title abstract description 5
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229910052623 talc Inorganic materials 0.000 claims abstract description 23
- 239000000454 talc Substances 0.000 claims abstract description 22
- 239000000835 fiber Substances 0.000 claims description 95
- 229920005672 polyolefin resin Polymers 0.000 claims description 31
- 239000011342 resin composition Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 17
- 238000000465 moulding Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 9
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000008188 pellet Substances 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- -1 propylene-ethylene Chemical group 0.000 description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- 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
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- HEBKCHPVOIAQTA-QWWZWVQMSA-N D-arabinitol Chemical compound OC[C@@H](O)C(O)[C@H](O)CO HEBKCHPVOIAQTA-QWWZWVQMSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 101000837308 Homo sapiens Testis-expressed protein 30 Proteins 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 102100028631 Testis-expressed protein 30 Human genes 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000013351 cheese Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、長繊維強化複合樹脂組成物および成形品に関し、詳しくは、長繊維の分散がよく、外観に優れ、剛性や耐衝撃性などの機械的強度に優れた、長繊維強化複合樹脂組成物、および、これから得られる成形品に関する。 TECHNICAL FIELD The present invention relates to a long fiber reinforced composite resin composition and a molded article. Specifically, the long fiber reinforced composite resin composition has excellent dispersion of long fibers, excellent appearance, and excellent mechanical strength such as rigidity and impact resistance. And a molded article obtained therefrom.
今日、様々な分野で樹脂製品に高い剛性が求められており、例えば、家電製品などの筐体、建材、自動車向け構造材などの用途では、物性バランスを取りながらより高い剛性を樹脂に付与する試みが多数なされている(特許文献1〜6)。その中の一つとして、樹脂にゴム成分とタルクを配合し、前者で耐衝撃性を、後者で剛性を付与する方法が知られている。この方法によれば、原料が比較的安価なため、製造される製品も安価であること、常温使用条件において延性破壊し得ること、平滑な成形品外観が得られること、等の利点がある。 Today, resin products are required to have high rigidity in various fields. For example, in applications such as housings for home appliances, building materials, and structural materials for automobiles, higher rigidity is imparted to the resin while balancing the physical properties. Many attempts have been made (Patent Documents 1 to 6). As one of them, a method is known in which a rubber component and talc are blended in a resin, and the former provides impact resistance and the latter provides rigidity. According to this method, since the raw material is relatively inexpensive, there are advantages that the manufactured product is inexpensive, can be ductile fractured under normal temperature use conditions, and can obtain a smooth molded product appearance.
しかしながら、通常、零下の低温使用条件において脆性破壊が起こること、ゴム成分の組成比が多量になることにより剛性などの物性バランスを取ることが困難であること、経時変化としてゴム成分や相溶化成分などが劣化したり分離したりすること、等の問題がある。 However, usually, brittle fracture occurs under low temperature usage conditions below zero, it is difficult to balance physical properties such as rigidity due to a large composition ratio of rubber components, and rubber components and compatibilizing components as time-dependent changes There are problems such as deterioration or separation.
そこで、低温使用条件でも延性破壊し得るように改良するため、ゴム成分を更に大量に配合する試みが多数なされているが、ゴム成分はマトリクス樹脂に比べて高価であり製造される製品の価格も高価になってしまうこと、剛性などの物性バランスを補うため更に大量にフィラー成分などを加えることにより成形加工時の流動性が著しく低下すること、等の別の問題が引き起こされる。 Therefore, many attempts have been made to add a larger amount of the rubber component in order to improve the ductile fracture under low temperature use conditions, but the rubber component is more expensive than the matrix resin and the price of the manufactured product is also high. Another problem is caused, such as being expensive, and adding a large amount of a filler component to compensate for the balance of physical properties such as rigidity, and thereby the fluidity at the time of molding is remarkably lowered.
本発明は、上記実情に鑑みなされたものであり、その目的は、長繊維の分散がよく、外観に優れ、剛性や耐衝撃性などの機械的強度に優れている、長繊維強化複合樹脂組成物、および、これから得られる成形品を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to provide a long fiber reinforced composite resin composition having good long fiber dispersion, excellent appearance, and excellent mechanical strength such as rigidity and impact resistance. It is in providing a molded article obtained from this.
すなわち、本発明の第1の要旨は、オレフィン系樹脂、有機長繊維、タルクを含有して成り、オレフィン系樹脂100重量部に対する、有機長繊維の割合が10〜200重量部、タルクの割合が10〜200重量部であることを特徴とする長繊維強化複合樹脂組成物に存し、本発明の第2の要旨は、上記の長繊維強化複合樹脂組成物を成形して成ることを特徴とする長繊維強化複合樹脂成形品に存する。 That is, the first gist of the present invention comprises an olefin resin, an organic long fiber, and talc, and the organic fiber has a ratio of 10 to 200 parts by weight and the ratio of talc to 100 parts by weight of the olefin resin. The present invention resides in a long fiber reinforced composite resin composition characterized by being 10 to 200 parts by weight, and the second gist of the present invention is characterized by forming the above long fiber reinforced composite resin composition. It exists in long fiber reinforced composite resin molded products.
オレフィン系樹脂、有機長繊維、タルクを含有する本発明の樹脂組性物は、有機長繊維が網目状に分散して補強していることと、有機長繊維とマトリクス樹脂との界面接着を弱くさせていることにより、従来公知の長繊維複合樹脂組性物では達成し得ない耐衝撃性などの機械的強度を得ることが出来る。 The resin composition of the present invention containing an olefin resin, organic long fibers, and talc weakens the interfacial adhesion between the organic long fibers and the matrix resin because the organic long fibers are dispersed and reinforced in a network. By doing so, it is possible to obtain mechanical strength such as impact resistance that cannot be achieved by a conventionally known long-fiber composite resin assembly.
また、本発明の樹脂組成物を成形して成る成形品は、タルクを含有することにより、有機長繊維の複合により得られる耐衝撃性を低下させることなく剛性を付与することが出来る。これにより、種々の製品用途毎に求められる、耐衝撃性や剛性などの物性バランスをそれぞれ損なうことなく容易に設計することが出来るようになり、ひいては長繊維複合樹脂組成物が適用できる用途範囲を格段に広めることが出来る。 Moreover, the molded product formed by shape | molding the resin composition of this invention can provide rigidity, without reducing the impact resistance obtained by the composite of organic long fiber by containing a talc. As a result, it becomes possible to easily design without impairing the balance of physical properties such as impact resistance and rigidity required for each of various product applications, and as a result, the range of applications in which the long fiber composite resin composition can be applied. It can be widely spread.
本発明で使用するオレフィン系樹脂としては、特に制限されず、各種のオレフィン系樹脂を使用することが出来る。例えば、エチレンの単独重合体、エチレンを主成分とした、プロピレン、1−ブテン等の他のα−オレフィン等の1種または2種以上との共重合体などのエチレン系樹脂;プロピレンの単独重合体、プロピレンを主成分とした、エチレン、1−ブテン等の他のα−オレフィン等の1種または2種以上との共重合体などのプロピレン系樹脂;1−ブテンの単独重合体、1−ブテンを主成分とした、エチレン、プロピレン等の他のα−オレフィン等の1種または2種以上との共重合体などのブテン系樹脂などが挙げられる。これらのオレフィン系樹脂は、単独重合体であっても、共重合体でもよく、また、ランダム共重合体であってもよいし、ブロック共重合体であってもよい。なお、上記の「主成分」とは、オレフィン系樹脂中の当該成分の含有量が通常50重量%以上、好ましくは60重量%以上であるものを指す。 The olefin resin used in the present invention is not particularly limited, and various olefin resins can be used. For example, ethylene-based resins such as ethylene homopolymers, copolymers of ethylene as a main component and one or more of other α-olefins such as propylene and 1-butene; A propylene-based resin such as a copolymer, a copolymer of propylene as a main component and one or more of other α-olefins such as ethylene and 1-butene; 1-butene homopolymer, 1- Examples include butene-based resins such as copolymers of butene as a main component and one or more of other α-olefins such as ethylene and propylene. These olefin-based resins may be homopolymers or copolymers, may be random copolymers, or may be block copolymers. In addition, said "main component" refers to that whose content of the said component in an olefin resin is 50 weight% or more normally, Preferably it is 60 weight% or more.
これらのうち、耐熱性に優れる点から、プロピレン系樹脂が好ましく、その具体例としては、プロピレンの単独重合体、プロピレンを主成分とするプロピレン−エチレンランダム共重合体樹脂、プロピレン−エチレンブロック共重合体樹脂などが挙げられる。なお、オレフィン系樹脂は2種以上を併用してもよい。オレフィン系樹脂の重合様式は、特に限定されないが、気相法または溶液法が好ましい。 Among these, a propylene resin is preferable from the viewpoint of excellent heat resistance. Specific examples thereof include a propylene homopolymer, a propylene-ethylene random copolymer resin mainly composed of propylene, and a propylene-ethylene block copolymer. Examples include coalesced resins. Two or more olefin resins may be used in combination. The polymerization mode of the olefin resin is not particularly limited, but a gas phase method or a solution method is preferable.
オレフィン系樹脂のメルトフローレート(JIS K7210に準拠し、温度230℃、荷重21.18Nで測定した値)は、通常0.05〜200g/10分、好ましくは0.1〜100g/10分である。メルトフローレートが0.05g/10分未満の場合は、成形加工性が低下し、得られる成形品の表面外観が不良になり易い傾向にあり、200g/10分を超える場合は、成形品の機械的強度と有機長繊維の分散が不良になり易い傾向にある。 The melt flow rate of the olefin resin (based on JIS K7210, measured at a temperature of 230 ° C. and a load of 21.18 N) is usually 0.05 to 200 g / 10 minutes, preferably 0.1 to 100 g / 10 minutes. is there. When the melt flow rate is less than 0.05 g / 10 minutes, the moldability tends to be deteriorated, and the surface appearance of the resulting molded product tends to be poor, and when it exceeds 200 g / 10 minutes, Mechanical strength and dispersion of organic long fibers tend to be poor.
本発明で使用する有機長繊維は、その表面に極性樹脂を付着させておくことが出来る。ここで、極性樹脂とは、非極性であるオレフィン系樹脂より極性の高い樹脂を指す。斯かる極性樹脂としては、例えば、不飽和ポリエステル、ビニルエステル樹脂、エポキシ樹脂(エポキシ化合物を含む)、フェノール(レゾール型)樹脂、ユリア・メラミン樹脂、ポリイミド、ウレタン樹脂、これらの共重合体、変性体などの熱硬化性樹脂が挙げられる。また、飽和ポリエステル、ポリアミド、アクリル系樹脂、これらの共重合体、変性体などの熱可塑性樹脂も挙げられる。極性樹脂としては、特に、取扱・加工性や力学特性の観点から、熱硬化性樹脂のエポキシ樹脂またはウレタン樹脂が好ましく、特にエポキシ樹脂が好ましい。エポキシ樹脂の具体例としては、次の化合物が挙げられる。 The organic long fiber used in the present invention can have a polar resin attached to its surface. Here, the polar resin refers to a resin having a higher polarity than a non-polar olefin resin. Examples of such polar resins include unsaturated polyesters, vinyl ester resins, epoxy resins (including epoxy compounds), phenol (resole type) resins, urea / melamine resins, polyimides, urethane resins, copolymers thereof, and modified And thermosetting resins such as body. Moreover, thermoplastic resins, such as saturated polyester, polyamide, acrylic resin, these copolymers, and a modified body, are also mentioned. As the polar resin, a thermosetting resin epoxy resin or urethane resin is particularly preferable from the viewpoint of handling / workability and mechanical properties, and an epoxy resin is particularly preferable. Specific examples of the epoxy resin include the following compounds.
すなわち、ジグリシジルエーテル化合物では、エチレングリコールジグリシジルエーテル及びポリエチレングリコールジグリシジルエーテル類、プロピレングリコールジグリシジルエーテル及びポリプロピレングリコールジグリシジルエーテル類、1,4−ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、ポリテトラメチレングリコールジグリシジルエーテル、ポリアルキレングリコールジグリシジルエーテル類などが挙げられる。また、ポリグリシジルエーテル化合物では、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル類、ソルビトールポリグリシジルエーテル類、アラビトールポリグリシジルエーテル類、トリメチロールプロパンポリグリシジルエーテル類、ペンタエリスリトールポリグリシジルエーテル類、脂肪族多価アルコールのポリグリシジルエーテル類などが挙げられる。好ましくは、反応性の高いグリシジル基を有する脂肪族のポリグリシジルエーテル化合物である。更に好ましくは、ポリエチレングリコールジグリシジルエーテル類、ポリプロピレングリコールジグリシジルエーテル類、アルカンジオールジグリシジルエーテル類である。 That is, in the diglycidyl ether compound, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether , Polytetramethylene glycol diglycidyl ether, polyalkylene glycol diglycidyl ether, and the like. In addition, in the polyglycidyl ether compound, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, arabitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol poly Examples thereof include glycidyl ethers and polyglycidyl ethers of aliphatic polyhydric alcohols. Preferably, it is an aliphatic polyglycidyl ether compound having a highly reactive glycidyl group. More preferred are polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, and alkanediol diglycidyl ethers.
ところで、本発明において、前記のオレフィン系樹脂としては、例えば、無水マレイン酸で変性された酸変性オレフィン系樹脂などは除くのが好ましい。また、後述する有機長繊維においても酸変性オレフィン系樹脂で表面処理されたものを除くのが好ましい。更に、有機長繊維に付着させる上記の極性樹脂としても酸変性オレフィン系樹脂は除くのが好ましい。斯かる条件を満足することにより、マトリクス樹脂であるオレフィン系樹脂と有機長繊維との界面強度を一層弱くすることが出来、引張破断伸びや耐衝撃性を一層高めることが出来る。 By the way, in the present invention, as the olefin resin, for example, an acid-modified olefin resin modified with maleic anhydride is preferably excluded. Moreover, it is preferable to remove the organic long fiber described later from the surface treated with the acid-modified olefin resin. Furthermore, it is preferable to exclude the acid-modified olefin resin as the polar resin to be attached to the organic long fiber. By satisfying such conditions, the interfacial strength between the olefin resin as the matrix resin and the organic long fibers can be further reduced, and the tensile elongation at break and impact resistance can be further enhanced.
上記の酸変性オレフィン系樹脂としては、(A)オレフィンの単独重合体または2種以上のオレフィンの共重合体、例えば、ポリオレフィンに不飽和カルボン酸またはその誘導体をグラフト重合したもの、(B)ポリオレフィンの重合原料モノマーである1種または2種以上のオレフィンと1種または2種以上の不飽和カルボン酸またはその誘導体を共重合したもの、(C)上記(B)で得られたものに更に不飽和カルボン酸またはその誘導体をグラフト重合したもの等が挙げられる。 Examples of the acid-modified olefin resin include (A) an olefin homopolymer or a copolymer of two or more olefins, for example, a polyolefin obtained by graft polymerization of an unsaturated carboxylic acid or a derivative thereof, and (B) a polyolefin. A copolymer of one or more olefins and one or two or more unsaturated carboxylic acids or derivatives thereof, which is a polymerization raw material monomer of (C), and (C) those obtained in (B) above. Examples include those obtained by graft polymerization of saturated carboxylic acids or derivatives thereof.
有機長繊維としては、例えば、ポリエステル系繊維、ポリアミド系繊維、ポリウレタン系繊維、ポリアクリロニトリル系繊維、ケナフ、セルロース系繊維などが挙げられる。これらの有機長繊維は2種以上を併用してもよい。これらの中では、取扱・加工性や力学特性の観点から、ポリエステル系繊維またはポリアミド系繊維が好ましく、特に、ポリエチレンテレフタレート(PET)繊維(融点260℃、ガラス転移温度67℃)、ポリエチレンナフタレート(PEN)繊維(融点272℃、ガラス転移温度113℃)が好ましい。ポリエステル系繊維は、射出成形品中の分散が良く、繊維としての物性も高いため、良好な機械物性の射出成形品が得られる。 Examples of the organic long fibers include polyester fibers, polyamide fibers, polyurethane fibers, polyacrylonitrile fibers, kenaf, and cellulose fibers. These organic long fibers may be used in combination of two or more. Among these, polyester fiber or polyamide fiber is preferable from the viewpoint of handling / workability and mechanical properties, and in particular, polyethylene terephthalate (PET) fiber (melting point 260 ° C., glass transition temperature 67 ° C.), polyethylene naphthalate ( PEN) fibers (melting point 272 ° C., glass transition temperature 113 ° C.) are preferred. Since the polyester fiber is well dispersed in the injection molded product and has high physical properties as a fiber, an injection molded product having good mechanical properties can be obtained.
ところで、本発明の樹脂組成物を、射出成形によって成形する場合、オレフィン系樹脂の融点以上の温度で成形するため、有機長繊維としては射出成形の際に溶融しないものを使用するのが好ましい。すなわち、オレフィン系樹脂の融点は、通常70〜170℃、成形温度(成形機の出口温度とする)は通常150〜210℃の範囲から選択される。有機長繊維の融点は、成形温度より、通常10℃以上、好ましくは20℃以上高いことが好ましい。従って、有機長繊維の融点は通常200℃以上の範囲から選択される。 By the way, when the resin composition of the present invention is molded by injection molding, it is preferable to use an organic long fiber that does not melt during injection molding because it is molded at a temperature equal to or higher than the melting point of the olefin resin. That is, the melting point of the olefin resin is usually selected from the range of 70 to 170 ° C., and the molding temperature (the outlet temperature of the molding machine) is usually selected from the range of 150 to 210 ° C. The melting point of the organic long fiber is preferably higher than the molding temperature by 10 ° C. or more, preferably 20 ° C. or more. Therefore, the melting point of the organic long fiber is usually selected from a range of 200 ° C. or higher.
また、有機長繊維の繊維径が太すぎると成形品のアイゾット衝撃強度が低下する。一方、繊維径が細すぎても何ら問題はなく、ナノサイズの繊維まで使用可能と思われ、成形品の用途によっては良好な結果をもたらす。このように繊維径が広範に亘るため、有機長繊維の使用本数は一義的に規定できない。しかしながら、繊維の束の断面積で考えると、通常は、ペレットの繊維と略直行する方向の断面積中5〜60%程度を有機長繊維の断面積が占める程の本数が好ましい。有機長繊維の単糸繊度は、通常1〜20dtex、好ましくは2〜15dtexである。また、有機長繊維の総繊度は、通常150〜3,000dtex、好ましくは250〜2000dtexである。さらに、有機長繊維のフィラメント数は、通常10〜1,000フィラメント、好ましくは50〜500フィラメントである。 Moreover, if the fiber diameter of the organic long fiber is too large, the Izod impact strength of the molded product is lowered. On the other hand, there is no problem even if the fiber diameter is too thin, and it seems that nano-sized fibers can be used, and good results are obtained depending on the application of the molded product. Thus, since the fiber diameter covers a wide range, the number of organic long fibers used cannot be uniquely defined. However, considering the cross-sectional area of the bundle of fibers, the number of the organic long fibers is preferably about 5 to 60% of the cross-sectional area in the direction substantially perpendicular to the pellet fibers. The single yarn fineness of the organic long fiber is usually 1 to 20 dtex, preferably 2 to 15 dtex. The total fineness of the organic long fibers is usually 150 to 3,000 dtex, preferably 250 to 2000 dtex. Furthermore, the number of filaments of the organic long fiber is usually 10 to 1,000 filaments, preferably 50 to 500 filaments.
有機長繊維に極性樹脂を付着させる方法としては、(A)有機長繊維を製造する工程においてチーズ状に巻き取る前に、オレフィン系樹脂と相溶または反応しない、極性のある化合物を付与する方法、(B)有機長繊維を一旦巻取った後に、オレフィン系樹脂と相溶または反応しない、極性のある化合物を有機長繊維に含浸付与し熱処理する方法が挙げられる。 As a method for attaching the polar resin to the organic long fiber, (A) a method of providing a polar compound that is not compatible with or reacts with the olefin-based resin before being wound into a cheese shape in the step of producing the organic long fiber. (B) After winding up the organic long fiber, a method of impregnating the organic long fiber with a polar compound that does not dissolve or react with the olefin-based resin and heat-treats it may be mentioned.
有機長繊維への極性樹脂の付着量は、通常0.01〜5重量%、好ましくは0.03〜3.5重量%である。極性樹脂の付着量が0.01重量%未満の場合は、有機長繊維とマトリクス樹脂の界面接着を弱くさせる効果が得にくく、また、成形中に繊維同士が絡み合うため、有機長繊維の分散が悪くなり、その結果、外観品位が低下する。一方、極性樹脂の付着量が5重量%を超える場合は、有機長繊維が硬くなりすぎるため、加工性が低下し、有機長繊維との複合化が困難になる。 The adhesion amount of the polar resin to the organic long fiber is usually 0.01 to 5% by weight, preferably 0.03 to 3.5% by weight. When the adhesion amount of the polar resin is less than 0.01% by weight, it is difficult to obtain the effect of weakening the interfacial adhesion between the organic long fibers and the matrix resin, and the fibers are entangled with each other during molding. As a result, appearance quality deteriorates. On the other hand, when the adhesion amount of the polar resin exceeds 5% by weight, the organic long fiber becomes too hard, so that the processability is lowered and it is difficult to combine with the organic long fiber.
本発明の樹脂組性物においてペレット中の有機長繊維の長さは、ペレットの長さに相当する。オレフィン系樹脂より成るペレット中に含有された有機長繊維の平均繊維長は、通常4〜50mm、好ましくは4〜20mm、更に好ましくは4〜10mmである。有機長繊維の平均繊維長が4mm未満の場合は耐衝撃性の向上効果が十分に得られず、一方、平均繊維長が50mmを超える場合は成形が困難になる。 In the resin composition of the present invention, the length of the organic long fiber in the pellet corresponds to the length of the pellet. The average fiber length of the organic long fibers contained in the pellet made of olefin resin is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the average fiber length of the organic long fibers is less than 4 mm, the effect of improving the impact resistance is not sufficiently obtained. On the other hand, when the average fiber length exceeds 50 mm, molding becomes difficult.
本発明で使用するタルクの平均粒径は、通常15μm以下、好ましくは12mμ以下、更に好ましくは10μm以下であり、その下限は通常0.5μmである。平均粒径が15μmを超える場合は製品の耐衝撃性が低下する傾向がある。また、平均粒径が0.5μmの場合は、タルク自体が高価となり、更に、組成物の流動性が著しく低下する。ここでいう平均粒径は液相沈降式光透過法で測定し、粒度累積分布曲線から読み取った累積量50重量%の粒径値である。なお、上記の様な平均粒径のタルクは、一般に乾式粉砕後に乾式分級して製造される。 The average particle diameter of talc used in the present invention is usually 15 μm or less, preferably 12 μm or less, more preferably 10 μm or less, and its lower limit is usually 0.5 μm. When the average particle size exceeds 15 μm, the impact resistance of the product tends to decrease. When the average particle size is 0.5 μm, talc itself is expensive, and the fluidity of the composition is significantly reduced. The average particle size referred to here is a particle size value measured by a liquid phase precipitation type light transmission method and having a cumulative amount of 50% by weight read from a cumulative particle size distribution curve. The talc having an average particle diameter as described above is generally produced by dry classification after dry pulverization.
タルクの比表面積は、通常1.5m2/g以上、好ましくは2.0m2/g以上、更に好ましくは3.0m2/g以上であり、その上限は通常20m2/gである。比表面積が1.5m2/g未満の場合は、製品の耐衝撃性が不足する傾向がある。また、比表面積が20m2/gを超える場合は、タルク自体が高価となり、しかも、組成物の流動性が低下する傾向にある。ここでいう比表面積は空気透過法により測定した値である。 The specific surface area of talc is usually 1.5 m 2 / g or more, preferably 2.0 m 2 / g or more, more preferably 3.0 m 2 / g or more, and the upper limit is usually 20 m 2 / g. When the specific surface area is less than 1.5 m 2 / g, the impact resistance of the product tends to be insufficient. On the other hand, when the specific surface area exceeds 20 m 2 / g, talc itself is expensive, and the fluidity of the composition tends to decrease. The specific surface area here is a value measured by an air permeation method.
本発明の樹脂組成物は、オレフィン系樹脂、有機長繊維、タルクを含有する。そして、オレフィン系樹脂100重量部に対する割合として、有機長繊維の割合は、10〜200重量部、好ましくは20〜180重量部であり、タルクの割合は、10〜200重量部、好ましくは20〜180重量部である。有機長繊維の割合が上記の範囲未満の場合は、補強効果が不十分となる傾向にあり、上記の範囲より多い場合は、成形が困難になり成形品外観も悪くなる傾向にある。一方、タルクの割合が上記の範囲より少ない場合は、所望の剛性を付与できない傾向にあり、上記の範囲より多い場合は、流動性が著しく低下し成形が困難になり成形品外観も悪くなる傾向にあり、また、比重が重くなる傾向にある。 The resin composition of the present invention contains an olefin resin, organic long fibers, and talc. And as a ratio with respect to 100 weight part of olefin resin, the ratio of an organic long fiber is 10-200 weight part, Preferably it is 20-180 weight part, The ratio of talc is 10-200 weight part, Preferably it is 20- 180 parts by weight. When the ratio of the organic long fibers is less than the above range, the reinforcing effect tends to be insufficient, and when it is more than the above range, molding tends to be difficult and the appearance of the molded product tends to deteriorate. On the other hand, when the ratio of talc is less than the above range, the desired rigidity tends not to be imparted, and when it is more than the above range, the fluidity is remarkably lowered and the molding becomes difficult and the appearance of the molded product tends to be poor In addition, the specific gravity tends to increase.
本発明の樹脂組成物(ペレット)は、連続した有機長繊維をクロスヘッドダイを通して引きながら溶融樹脂で含浸する方法(引き抜き成形法)により得られる。例えば、オレフィン系樹脂に必要に応じて樹脂添加剤を加え、有機長繊維をクロスヘッドダイに通して引き抜きながら、オレフィン系樹脂を押出機から溶融状態でクロスヘッドダイに供給し、有機長繊維にオレフィン系樹脂を含浸被覆させ、溶融含浸物を加熱し、冷却後、引き抜き方向と直角に切断して得られる。この方法によれば、有機長繊維の損傷を起こすことなく、得られるペレットの長さ方向に有機長繊維が同一長さで平行配列している樹脂組成物(ペレット)が得られる。 The resin composition (pellet) of the present invention is obtained by a method (pulling molding method) in which continuous organic long fibers are impregnated with a molten resin while being drawn through a crosshead die. For example, if necessary, a resin additive is added to the olefin resin, and the olefin resin is supplied from the extruder to the crosshead die in a molten state while being drawn through the crosshead die. It is obtained by impregnating and coating an olefin-based resin, heating the melt-impregnated material, cooling, and cutting it at right angles to the drawing direction. According to this method, a resin composition (pellet) in which organic long fibers are arranged in parallel with the same length in the length direction of the obtained pellet can be obtained without causing damage to the organic long fibers.
引き抜き成形法は、基本的には、連続した強化用繊維束を引き抜きながら樹脂を含浸する方法である。そして、その態様として、クロスヘッドの中に繊維束を通しながら押出機などからクロスヘッドに樹脂を供給して含浸する方法の他、樹脂のエマルジョン、サスペンジョン又は溶液を入れた含浸浴の中に繊維束を通して含浸する方法、樹脂の粉末を繊維束に吹きつけるか又は粉末を入れた槽の中に繊維束を通して繊維に樹脂粉末を付着させた後に樹脂を溶融して含浸する方法などが知られており、本発明では何れの態様も利用できる。特に好ましいのはクロスヘッド方法である。また、これらの引き抜き成形法における樹脂の含浸操作は1段で行うのが一般的であるが、2段以上に分けてもよく、更に、含浸方法を異にして行ってもよい。 The pultrusion method is basically a method of impregnating a resin while drawing a continuous reinforcing fiber bundle. In addition to the method of supplying and impregnating the resin to the crosshead from an extruder or the like while passing the fiber bundle through the crosshead, as an aspect thereof, the fiber is contained in an impregnation bath containing a resin emulsion, suspension or solution. There are known methods of impregnating through bundles, methods of spraying resin powder onto fiber bundles, or attaching resin powder to fibers through fiber bundles in a tank containing the powder, and then melting and impregnating the resin. Therefore, any aspect can be used in the present invention. Particularly preferred is the crosshead method. Further, the resin impregnation operation in these pultrusion methods is generally performed in one stage, but it may be divided into two or more stages, and may be performed by different impregnation methods.
なお、オレフィン系樹脂に必要に応じて他の熱可塑性樹脂やゴムの1種または2種以上を補助的に少量併用することも可能である。また、目的に応じ、所望の特性を付与するため、一般に熱可塑性樹脂に添加される公知の物質、例えば、酸化防止剤、耐熱安定剤、紫外線吸収剤などの安定剤、帯電防止剤、難燃剤、難燃助剤、着色剤(染料や顔料)、潤滑剤、可塑剤、結晶化促進剤、結晶核剤などを更に配合することも可能である。 In addition, it is also possible to supplementarily use a small amount of one or more other thermoplastic resins and rubbers as needed in combination with the olefin resin. In addition, in order to impart desired properties according to the purpose, known substances generally added to thermoplastic resins, for example, stabilizers such as antioxidants, heat stabilizers, UV absorbers, antistatic agents, flame retardants, etc. In addition, flame retardant aids, colorants (dyes and pigments), lubricants, plasticizers, crystallization accelerators, crystal nucleating agents, and the like can be further blended.
上記の含浸操作は、通常150〜300℃、好ましくは170〜260℃、更に好ましくは190〜230℃で行われる。また、上記の含浸物は上記の温度で加熱される。加熱温度が低すぎる場合は含浸が不十分になり、高すぎる場合はオレフィン系樹脂の分解が起こる。 The above impregnation operation is usually performed at 150 to 300 ° C, preferably 170 to 260 ° C, more preferably 190 to 230 ° C. The impregnated material is heated at the above temperature. When the heating temperature is too low, the impregnation is insufficient, and when it is too high, the olefin resin is decomposed.
溶融含浸物は、加熱反応後、押出されてストランドとなり、切断可能な温度まで冷却され、カッターで切断されてペレットとされる。ペレットの形状としては、円柱状、角柱状、板状、さいころ状などが挙げられる。このようにして得られたペレットでは、有機長繊維が実質的に同じ長さで且つ各繊維の方向が押し出された方向(すなわちペレットの長さ方向)に揃っている。また、上記のペレットは、種類や濃度の異なる2種類以上の有機長繊維を使用したもの、オレフィン系樹脂の混合物を使用したものでもよい。なお、本発明において、「ペレット」は、上記の狭義のペレットの他に、ストランド状、シート状、平板状なども含む広義の意味で使用される。 The melt impregnated product is extruded to a strand after the heating reaction, cooled to a temperature capable of being cut, and cut by a cutter into pellets. Examples of the shape of the pellet include a columnar shape, a prismatic shape, a plate shape, and a die shape. In the pellet thus obtained, the organic long fibers have substantially the same length, and the direction of each fiber is aligned in the extruded direction (that is, the length direction of the pellet). In addition, the above pellets may be those using two or more types of organic long fibers having different types and concentrations, and those using a mixture of olefinic resins. In the present invention, “pellet” is used in a broad sense including strand shape, sheet shape, flat plate shape and the like in addition to the above-mentioned narrowly defined pellets.
本発明の樹脂組成物から成るペレットの寸法は、有機長繊維の長さとなり、通常4〜50mm、好ましくは4〜20mm、更に好ましくは4〜10mmである。ペレット中の有機長繊維の長さが短すぎる場合は複合材料としての所望の機械的強度が得られず、一方、長すぎる場合はペレットの射出成形機などへの供給が困難となる。 The size of the pellet made of the resin composition of the present invention is the length of the organic long fiber, and is usually 4 to 50 mm, preferably 4 to 20 mm, and more preferably 4 to 10 mm. When the length of the organic long fiber in the pellet is too short, the desired mechanical strength as a composite material cannot be obtained. On the other hand, when the length is too long, it becomes difficult to supply the pellet to an injection molding machine or the like.
上記の様にして得られたペレットは、単独で又は他の熱可塑性樹脂、好ましくはオレフィン系樹脂と同じタイプの樹脂で希釈し、射出成形などの原料として使用される。希釈する樹脂の種類および比率は、所望の成形品の物性値により定められる。本発明の樹脂組成物(ペレット)を使用し、射出成形により得られた成形品は、有機長繊維の射出成形時に折損が少なく、有機長繊維が均一に分散している。本発明の樹脂組成物から得られる成形品は、外観に優れ、剛性や耐衝撃性などの機械的強度に優れたものであって、車両、建築・土木、機械部品、電子部品などに極めて有用である。 The pellets obtained as described above are used alone or diluted with another thermoplastic resin, preferably the same type of resin as the olefin resin, and used as a raw material for injection molding or the like. The kind and ratio of the resin to be diluted are determined by the physical property values of the desired molded product. A molded product obtained by injection molding using the resin composition (pellet) of the present invention has little breakage during the injection molding of organic long fibers, and the organic long fibers are uniformly dispersed. The molded product obtained from the resin composition of the present invention has excellent appearance and mechanical strength such as rigidity and impact resistance, and is extremely useful for vehicles, construction / civil engineering, mechanical parts, electronic parts, etc. It is.
なお、本発明においては、前記のように、オレフィン系樹脂、有機長繊維、タルクを含有する樹脂組成物(ペレット)を製造した後に成形して成形品とする他に、オレフィン系樹脂と有機長繊維を含有する樹脂組成物(ペレットA)と、オレフィン系樹脂とタルクを含有する樹脂組成物(ペレットB)を製造した後にペレットAとBとを混合して成形してもよい。すなわち、成形品とした際に本発明の樹脂組成物が完成されていればよい。また、本発明の樹脂組成物(ペレット)は、前述の引き抜き成形法の他、有機長繊維の切断の心配がないため、必要成分の混練処理によって組成物化する方法を採用することも可能である。 In the present invention, as described above, in addition to the production of a resin composition (pellet) containing an olefin resin, organic long fibers, and talc, the molded product is formed into a molded product. After manufacturing the resin composition (pellet A) containing a fiber and the resin composition (pellet B) containing an olefin resin and talc, the pellets A and B may be mixed and molded. That is, it is sufficient that the resin composition of the present invention is completed when it is formed into a molded product. Moreover, since the resin composition (pellet) of the present invention has no fear of cutting organic long fibers in addition to the above-described pultrusion molding method, a method of forming a composition by kneading necessary components can also be employed. .
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り以下の実施例により限定されるものではない。以下の諸例で使用した材料および評価方法は以下に示すとおりである。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by a following example, unless the summary is exceeded. The materials and evaluation methods used in the following examples are as shown below.
成分(a):ポリプロピレン〔日本ポリプロ(株)製「ノバテックBC10AHA」、メルトフローレート100g/10分(230℃、21.2N荷重)〕 Ingredient (a): Polypropylene ["Novatec BC10AHA" manufactured by Nippon Polypro Co., Ltd., melt flow rate 100 g / 10 min (230 ° C., 21.2 N load)]
成分(b):エポキシ樹脂としてポリグリシジルエーテル系エポキシ樹脂を付着させた、PET長繊維〔帝人ファイバー(株)製「P903AL BHT1670T250」、平均繊維径24μm、エポキシ樹脂付着量=0.2重量%〕 Component (b): PET long fiber (“P903AL BHT1670T250” manufactured by Teijin Fibers Ltd., average fiber diameter: 24 μm, epoxy resin adhesion amount = 0.2% by weight) with a polyglycidyl ether epoxy resin attached as an epoxy resin
成分(c):タルク〔日本タルク(株)製「K−1」、平均粒径7.4μm、比表面積7.0m2/g〕 Component (c): Talc [“K-1” manufactured by Nippon Talc Co., Ltd., average particle size of 7.4 μm, specific surface area of 7.0 m 2 / g]
ガラス長繊維強化ポリプロピレン〔日本ポリプロ(株)製「ファンクスターLR23C」、ガラス含量30重量%〕(比較用材料として使用) Long glass fiber reinforced polypropylene [Nippon Polypro Co., Ltd. "Funkster LR23C", glass content 30% by weight] (used as a comparative material)
(1)最大曲げ応力および曲げ弾性率:
成形により得られた厚み4mm×幅10mm×長さ80mmのバーについて、JIS−K7171に準拠して下記条件で測定を行った。試験速度は2mm/min、支点間距離は64mmとした。
(1) Maximum bending stress and flexural modulus:
A bar having a thickness of 4 mm, a width of 10 mm, and a length of 80 mm obtained by molding was measured in accordance with JIS-K7171 under the following conditions. The test speed was 2 mm / min, and the distance between fulcrums was 64 mm.
(2)アイゾット衝撃強度:
成形により得られた厚み4mm×幅12.7mm×長さ63.5mmのバーについて、JIS−K7110に準拠して下記条件で測定を行った。ノッチ加工の回転数は400rpm、ノッチ加工の送り速度は120mm/min、ハンマー容量は5.5J、測定温度は23℃と−40℃とした。
(2) Izod impact strength:
A bar having a thickness of 4 mm, a width of 12.7 mm, and a length of 63.5 mm obtained by molding was measured according to JIS-K7110 under the following conditions. The rotation speed of notch processing was 400 rpm, the feed speed of notch processing was 120 mm / min, the hammer capacity was 5.5 J, and the measurement temperatures were 23 ° C. and −40 ° C.
(3)引張破断強度および引張破断伸び:
成形により得られた厚み3.2mm×幅10mmのダンベル型バーについて、JIS−K7161に準拠して試験速度50mm/minで測定を行った。
(3) Tensile breaking strength and tensile breaking elongation:
A dumbbell bar having a thickness of 3.2 mm and a width of 10 mm obtained by molding was measured at a test speed of 50 mm / min in accordance with JIS-K7161.
(4)外観:
成形により得られた100mm×100mm×厚さ3mmの平板の表面を目視にて観察し、以下の基準で評価した。
(4) Appearance:
The surface of a flat plate of 100 mm × 100 mm × thickness 3 mm obtained by molding was visually observed and evaluated according to the following criteria.
○:繊維分散が良好で、開繊していない繊維の束が殆ど無く、平板表面も平滑である。
△:開繊していない繊維の束が少し見られるか又は平板表面に少し凸凹がある。
×:開繊していない繊維の束が多数見られ、平板表面が荒れている。
○: The fiber dispersion is good, there is almost no bundle of unopened fibers, and the flat plate surface is smooth.
(Triangle | delta): The bundle | flux of the fiber which is not opened is seen for a while, or a flat surface has a little unevenness.
X: Many bundles of unopened fibers are seen, and the flat plate surface is rough.
実施例1〜4及び比較例1〜6:
ポリプロピレンとPET長繊維成分とタルクとを表1に示す配合で使用し、引き抜き成形を行い、長繊維強化ポリオレフィン樹脂ペレットを製造した。製造装置としては、クロスヘッドダイを有する二軸押出機(日本製鋼所(株)製「TEX30」、L/D=42、シリンダー径30mm、シリンダー温度:190〜220℃、クロスダイヘッド温度:220℃)を使用した。なお、ペレット長は8mmとなるように調節した。次いで、得られた長繊維含有ポリオレフィン系樹脂ペレットを、射出成形機に供し、シリンダー温度210℃、金型温度70℃、背圧10kg/cm2、スクリュー回転数50rpmにて、平板およびバーを成形した。評価結果を表1及び表2に示す。
Examples 1-4 and Comparative Examples 1-6:
Polypropylene, PET long fiber components and talc were used in the composition shown in Table 1, and pultrusion molding was performed to produce long fiber reinforced polyolefin resin pellets. As a manufacturing apparatus, a twin screw extruder having a crosshead die (“TEX30” manufactured by Nippon Steel Works Co., Ltd., L / D = 42, cylinder diameter 30 mm, cylinder temperature: 190 to 220 ° C., cross die head temperature: 220 ° C. )It was used. The pellet length was adjusted to 8 mm. Next, the obtained long fiber-containing polyolefin resin pellets were subjected to an injection molding machine, and flat plates and bars were molded at a cylinder temperature of 210 ° C., a mold temperature of 70 ° C., a back pressure of 10 kg / cm 2 , and a screw rotation speed of 50 rpm. did. The evaluation results are shown in Tables 1 and 2.
表1及び表2より、本発明によれば、外観に優れ、剛性や耐衝撃性などの機械的強度に優れた成形品が得られることが分かる。 From Tables 1 and 2, it can be seen that according to the present invention, a molded product having excellent appearance and excellent mechanical strength such as rigidity and impact resistance can be obtained.
Claims (10)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007289238A JP5238938B2 (en) | 2007-11-07 | 2007-11-07 | Long fiber reinforced composite resin composition and molded product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007289238A JP5238938B2 (en) | 2007-11-07 | 2007-11-07 | Long fiber reinforced composite resin composition and molded product |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2009114331A true JP2009114331A (en) | 2009-05-28 |
JP5238938B2 JP5238938B2 (en) | 2013-07-17 |
Family
ID=40781826
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2007289238A Active JP5238938B2 (en) | 2007-11-07 | 2007-11-07 | Long fiber reinforced composite resin composition and molded product |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5238938B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009132772A (en) * | 2007-11-29 | 2009-06-18 | Mitsubishi Chemicals Corp | Composition for automobile interior part |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021126772A (en) | 2020-02-10 | 2021-09-02 | 富士フイルムビジネスイノベーション株式会社 | Filament for three-dimensional modeling, three-dimensional model, three-dimensional modeling method, and three-dimensional modeling device |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01158044A (en) * | 1987-09-18 | 1989-06-21 | Yvan Landler | Composite material and its production |
JPH02124956A (en) * | 1988-11-02 | 1990-05-14 | Mitsubishi Corp | Production of composite material composition |
JPH06228376A (en) * | 1993-02-08 | 1994-08-16 | Idemitsu Petrochem Co Ltd | Polyolefin resin composition |
JPH06306216A (en) * | 1993-04-27 | 1994-11-01 | Idemitsu Petrochem Co Ltd | Polyolefinic resin composition |
JP2007224209A (en) * | 2006-02-24 | 2007-09-06 | Mitsubishi Chemicals Corp | Conductive thermoplastic resin molded article |
-
2007
- 2007-11-07 JP JP2007289238A patent/JP5238938B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01158044A (en) * | 1987-09-18 | 1989-06-21 | Yvan Landler | Composite material and its production |
JPH02124956A (en) * | 1988-11-02 | 1990-05-14 | Mitsubishi Corp | Production of composite material composition |
JPH06228376A (en) * | 1993-02-08 | 1994-08-16 | Idemitsu Petrochem Co Ltd | Polyolefin resin composition |
JPH06306216A (en) * | 1993-04-27 | 1994-11-01 | Idemitsu Petrochem Co Ltd | Polyolefinic resin composition |
JP2007224209A (en) * | 2006-02-24 | 2007-09-06 | Mitsubishi Chemicals Corp | Conductive thermoplastic resin molded article |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009132772A (en) * | 2007-11-29 | 2009-06-18 | Mitsubishi Chemicals Corp | Composition for automobile interior part |
Also Published As
Publication number | Publication date |
---|---|
JP5238938B2 (en) | 2013-07-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5238939B2 (en) | Long fiber reinforced composite resin composition and molded product | |
JP5676080B2 (en) | Organic fiber reinforced composite resin composition and organic fiber reinforced composite resin molded product | |
JP3073988B1 (en) | Manufacturing method of organic fiber reinforced resin pellets | |
EP2219839B1 (en) | Process for producing long glass fibre-reinforced thermoplastic compositions | |
US20060261509A1 (en) | Method for making fiber reinforced polypropylene composites | |
JP2001261844A (en) | Fiber-reinforced thermoplastic resin pellet and its preparation method | |
JP2011063029A (en) | Method for producing heat-treated carbon filament-reinforced resin pellet | |
CN104822736A (en) | Pellet mixture, carbon fiber-reinforced polypropylene resin composition, molded body, and method for producing pellet mixture | |
JP2010121108A (en) | Filament-reinforced composite resin composition and molded article | |
JP2009013331A (en) | Filament-reinforced composite resin composition and molded article | |
JP5560034B2 (en) | Lightweight automotive interior parts | |
JP5211658B2 (en) | Composition for automotive interior parts | |
JP4648052B2 (en) | Heat treated carbon long fiber reinforced resin pellets | |
JP5238938B2 (en) | Long fiber reinforced composite resin composition and molded product | |
JP2009242616A (en) | Resin injection-molded article and its molding method | |
JP7198287B2 (en) | Long fiber reinforced propylene resin composition and long fiber reinforced molded article | |
JP2007112041A (en) | Carbon filament reinforced resin molded article and its manufacturing method | |
JP2015183140A (en) | Fiber reinforced polypropylene resin material | |
JP2009013330A (en) | Filament-reinforced composite resin composition and molded article | |
JP2005040996A (en) | Organic fibre reinforced resin pellet, its manufacturing method and resin molded product | |
JP2002060502A (en) | Fiber-reinforced thermoplastic resin pellet and method for producing the same | |
WO2017056958A1 (en) | Propylene-resin-adhered fiber bundle | |
JP5161731B2 (en) | Aliphatic polyester resin pellets and molded articles obtained by molding them | |
JP2008150414A (en) | Lightweight fiber-reinforced resin composition excellent in impact resistance and molded article comprising the same | |
JP5226595B2 (en) | Aliphatic polyester resin composition and molded article obtained by molding them |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20100701 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20111116 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111122 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120120 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120221 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120417 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121002 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130122 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20130215 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130215 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20130218 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160412 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5238938 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |