JP5277517B2 - Method for producing polyamide-based conductive resin composition - Google Patents
Method for producing polyamide-based conductive resin composition Download PDFInfo
- Publication number
- JP5277517B2 JP5277517B2 JP2006084765A JP2006084765A JP5277517B2 JP 5277517 B2 JP5277517 B2 JP 5277517B2 JP 2006084765 A JP2006084765 A JP 2006084765A JP 2006084765 A JP2006084765 A JP 2006084765A JP 5277517 B2 JP5277517 B2 JP 5277517B2
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- polyamide
- carbon black
- ethylene
- resin composition
- 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.)
- Active
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229920002647 polyamide Polymers 0.000 title claims description 22
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 54
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 23
- 125000000524 functional group Chemical group 0.000 claims abstract description 22
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 17
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- 125000003368 amide group Chemical group 0.000 claims abstract description 5
- 239000004711 α-olefin Substances 0.000 claims description 20
- 238000004898 kneading Methods 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 2
- 235000021384 green leafy vegetables Nutrition 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 abstract description 19
- 239000000203 mixture Substances 0.000 abstract description 19
- 241000872198 Serjania polyphylla Species 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 235000019241 carbon black Nutrition 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000013329 compounding Methods 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002828 fuel tank Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 241000282320 Panthera leo Species 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229920006213 ethylene-alphaolefin copolymer Polymers 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- -1 oxadoline groups Chemical group 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- 101710082795 30S ribosomal protein S17, chloroplastic Proteins 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 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
- 239000006082 mold release agent Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリアミド樹脂と導電性カーボンブラックおよびオレフィン系の樹脂からなるポリアミド系導電性樹脂組成物の製造方法に関するものである。さらに詳しくは、本発明は、導電性に優れると共に優れた耐衝撃性と摺動性を併せもつ燃料タンク用キャップなどに使用するためのポリアミド系導電性樹脂組成物の製造方法に関するものである。 The present invention relates to a method for producing a polyamide-based conductive resin composition comprising a polyamide resin, conductive carbon black, and an olefin-based resin. More specifically, the present invention relates to a method for producing a polyamide-based conductive resin composition for use in a fuel tank cap having excellent conductivity and excellent impact resistance and slidability.
ポリアミド樹脂は、ガソリン等の有機溶剤やアルカリ液に対して優れた耐薬品性を示すと共に、流動性が高く、耐熱性、耐クリープ性に優れるため、自動車の外装材やエンジンルーム内部品として用いられている。また、さらにカーボンブラック等を配合して導電性を付与し、静電気の発生・帯電を抑制し、比較的短時間で放電可能な機能を持たせて、燃料タンク用キャップなどの自動車部品の給油系統部品として用いられている。
ポリアミド樹脂に導電性を付与するために、ポリアミド樹脂にカーボンブラックを配合することは良く知られているが、導電性を向上させるためにカーボンブラックの配合量を増やすと組成物の流動性や物性が著しく損なわれてしまう。そのため流動性や成形性を改良するため、ポリアミド樹脂にカーボンブラックと変性されたエチレン共重合体を配合することが提案されている（特許文献１参照）。
Polyamide resin has excellent chemical resistance against gasoline and other organic solvents and alkaline liquids, and has high fluidity, heat resistance, and creep resistance, so it is used as an exterior material for automobiles and parts in engine rooms. It has been. In addition, carbon black, etc. is added to provide conductivity, suppress the generation and charging of static electricity, and have a function that can be discharged in a relatively short time. It is used as a part.
It is well known to add carbon black to the polyamide resin in order to impart conductivity to the polyamide resin. However, increasing the amount of carbon black to improve the conductivity increases the fluidity and physical properties of the composition. Will be significantly impaired. Therefore, in order to improve fluidity and moldability, it has been proposed to blend a polyamide resin with carbon black and a modified ethylene copolymer (see Patent Document 1).
しかし、これらの方法では流動性や成形性は改良されるが、ポリアミド樹脂組成物の耐衝撃性の改良が十分でない。耐衝撃性が低いことから、ポリアミド樹脂組成物中に分散している変性されたエチレン共重合体の分散粒径が比較的大きな粒径で分散しているものと思われる。また柔らかい変性エチレン共重合体が大きな分散粒径でポリアミド樹脂組成物中に分散しているため、本来優れた摺動特性を持つポリアミド樹脂ではあるが、これらのポリアミド系樹脂組成物においては摺動特性が著しく損なわれてしまう。 However, these methods improve the fluidity and moldability, but the impact resistance of the polyamide resin composition is not sufficiently improved. Since the impact resistance is low, it is considered that the modified ethylene copolymer dispersed in the polyamide resin composition has a relatively large dispersed particle diameter. In addition, since soft modified ethylene copolymer is dispersed in a polyamide resin composition with a large dispersed particle size, it is originally a polyamide resin having excellent sliding characteristics. However, in these polyamide resin compositions, sliding is difficult. The characteristics are significantly impaired.
これらの導電性と耐衝撃性を両立させる方法として、カーボンブラックの分散剤を配合する方法が提案されている（特許文献２参照）。しかし、流動性や吸水時寸法変化の抑制という点では不十分であり、またカーボンブラックの分散剤が成形加工時に金型を汚染する問題があった。
本発明は、上述の従来技術の現状に鑑み創案されたものであり、その目的は、ポリアミド樹脂にカーボンブラックを配合した導電性ポリアミド樹脂組成物において、組成およびその製造方法を特定化することにより高い導電性と衝撃強度、および優れた摺動特性を持つ成形品の提供を可能とするポリアミド樹脂組成物の製造方法を提供することにある。 The present invention was devised in view of the current state of the prior art described above, and its purpose is to specify a composition and a manufacturing method thereof in a conductive polyamide resin composition in which carbon black is blended with a polyamide resin. An object of the present invention is to provide a method for producing a polyamide resin composition that can provide a molded article having high conductivity, impact strength, and excellent sliding properties.
本発明者等は、上記課題を解決するために鋭意研究した結果、ポリアミド樹脂中に導電性カーボンブラックを分散させた後、更にポリアミド樹脂と反応しうる反応性官能基を有するエチレン−αオレフィン共重合体をポリアミド樹脂の中に微分散させ、かつ高密度ポリエチレンを配合する導電性樹脂組成物の製造方法によって上記課題を達成し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have dispersed conductive carbon black in a polyamide resin, and then have an ethylene-α olefin copolymer having a reactive functional group capable of reacting with the polyamide resin. The inventors have found that the above problems can be achieved by a method for producing a conductive resin composition in which a polymer is finely dispersed in a polyamide resin and high-density polyethylene is blended, and the present invention has been completed.
即ち、本発明は、（Ａ）ポリアミド樹脂９５〜４０質量％、（Ｂ）導電性カーボンブラック５〜３０質量％、（Ｃ）ポリアミド樹脂の末端基および／又は主鎖のアミド基と反応しうる反応性官能基を有するエチレン−αオレフィン共重合体１０〜４０質量％、および（Ｄ）高密度ポリエチレン樹脂１〜１０質量％を配合してなり、かつ２×１０ ２ Ω・ｃｍ以下の体積固有抵抗値を有するポリアミド系導電性樹脂組成物の製造方法において、（Ａ）ポリアミド樹脂および（Ｂ）導電性カーボンブラックを予め溶融混練し、次いで（Ｃ）エチレン−αオレフィン共重合体および（Ｄ）高密度ポリエチレン樹脂を更に溶融混練することを特徴とするポリアミド系導電性樹脂組成物の製造方法である。 That is, the present invention can react with (A) 95 to 40% by mass of polyamide resin, (B) 5 to 30% by mass of conductive carbon black, and (C) an end group and / or amide group of the main chain of the polyamide resin. ethylene -α-olefin copolymer 10 to 40 wt% having a reactive functional group, and (D) Ri greens by blending 1 to 10 mass% high density polyethylene resin, and 2 × less volume 10 2 Ω · cm In the method for producing a polyamide-based conductive resin composition having a specific resistance value , (A) polyamide resin and (B) conductive carbon black are previously melt-kneaded, and then (C) an ethylene-α-olefin copolymer and (D ) A process for producing a polyamide-based conductive resin composition, characterized by further melt-kneading a high-density polyethylene resin.
本発明の方法によって得られたポリアミド系導電性樹脂組成物はポリアミド樹脂にカーボンブラックを配合して導電性を付与すると共に成形性を改良し、優れた耐衝撃性や摺動特性を保持している。このような良好な特性を持つ導電性樹脂組成物は自動車の燃料系部品、例えば燃料タンクのキャップやストレーナー、フィルター、バルブ等の部品に使用することができ、産業界に寄与することが大である。 The polyamide-based conductive resin composition obtained by the method of the present invention imparts conductivity by blending carbon black with polyamide resin, improves moldability, and retains excellent impact resistance and sliding properties. Yes. The conductive resin composition having such good characteristics can be used for fuel system parts of automobiles, such as fuel tank caps, strainers, filters, valves and the like, and contributes greatly to the industry. is there.
以下に本発明を具体的に説明する。
本発明の（Ａ）ポリアミド樹脂とは、分子中に酸アミド結合（−ＣＯＮＨ−）を有するものであり、具体的には、ε−カプロラクタム、６−アミノカプロン酸、ω−エナントラクタム、７−アミノヘプタン酸、１１−アミノウンデカン酸、９−アミノノナン酸、α−ピロリドン、α−ピペリジンなどから得られる重合体または共重合体もしくはこれらのブレンド物、ヘキサメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、メタキシリレンジアミンなどのジアミンとテレフタール酸、イソフタール酸、アジピン酸、セバシン酸などのジカルボン酸とを重縮合して得られる重合体または共重合体もしくはこれらのブレンド物等を例示することができるが、これらに限定されるものではない。
The present invention will be specifically described below.
The (A) polyamide resin of the present invention has an acid amide bond (—CONH—) in the molecule, and specifically includes ε-caprolactam, 6-aminocaproic acid, ω-enantolactam, 7-amino. Polymers or copolymers obtained from heptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidine and the like, hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, Examples include polymers or copolymers obtained by polycondensation of diamines such as dodecamethylenediamine and metaxylylenediamine and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, and sebacic acid, or blends thereof. However, it is not limited to these.
これらのポリアミド樹脂の数平均分子量は７０００〜３００００のものが好ましく用いられる。数平均分子量が７０００未満ではタフネスが低下し、また３００００を越えると流動性が低下して好ましくない。（Ａ）ポリアミド樹脂の配合量は９５〜４０質量％、より好ましくは９０〜５０質量％である。ポリアミド樹脂が４０質量％以下になるとポリアミド系導電性樹脂組成物からなる成形品の微細構造においてポリアミド樹脂が連続相となるべきモルフォロジー構造が不安定になり好ましくない。 These polyamide resins preferably have a number average molecular weight of 7,000 to 30,000. If the number average molecular weight is less than 7000, the toughness is lowered, and if it exceeds 30,000, the fluidity is lowered. (A) The compounding quantity of a polyamide resin is 95-40 mass%, More preferably, it is 90-50 mass%. When the polyamide resin is 40% by mass or less, the morphology structure in which the polyamide resin should be a continuous phase becomes unstable in the microstructure of the molded article made of the polyamide-based conductive resin composition, which is not preferable.
本発明の（Ｂ）導電性カーボンブラックとしては特に制限されるものではなく、ケッチェンブラック、アセチレンブラック、ファーネスブラックおよびチャンネルブラック等を使用することができる。これらの中ではケッチェンブラックが少ない配合量で優れた導電性を発揮するため特に好ましい。（Ｂ）導電性カーボンブラックの配合量は目的とする導電性の度合いにもよるが、３０〜５質量％が好適である。 The conductive carbon black (B) of the present invention is not particularly limited, and ketjen black, acetylene black, furnace black, channel black, and the like can be used. Among these, ketjen black is particularly preferable because it exhibits excellent conductivity with a small blending amount. (B) Although the compounding quantity of electroconductive carbon black is based also on the electroconductive degree made into the objective, 30-5 mass% is suitable.
これらの導電性カーボンブラックはポリアミド系導電性樹脂組成物の連続相を形成するポリアミド樹脂中に配合量の８０質量％以上分散することが必要である。そのためには混練工程が極めて重要であると共にカーボンブラックの粒子表面に存在するカルボキシル基や水酸基等の官能基も重要である。混錬工程で十分練ることによりカーボンブラックの表面の官能基が作用してポリアミド樹脂との親和性が増大し、ポリアミド樹脂の連続相に分散しやすくなる。本発明では、混錬条件やカーボンブラックの表面にある官能基濃度等は特に限定するものではなく、ポリアミド系導電性樹脂組成物の成形品においてカーボンブラックの配合量の８０質量％以上が連続相であるポリアミド樹脂中に分散するような組成物の製造法が重要である。このようなカーボンブラックの分散によって体積固有抵抗が１×１０１１Ω・ｃｍ以下の優れた導電性を持つ組成物が得られると共に、衝撃強度や耐磨耗性等の物性値も良好となる。 These conductive carbon blacks need to be dispersed in an amount of 80% by mass or more of the blending amount in the polyamide resin forming the continuous phase of the polyamide-based conductive resin composition. For this purpose, the kneading step is extremely important, and functional groups such as carboxyl groups and hydroxyl groups existing on the surface of the carbon black particles are also important. By sufficiently kneading in the kneading process, the functional group on the surface of the carbon black acts to increase the affinity with the polyamide resin, and it becomes easy to disperse in the continuous phase of the polyamide resin. In the present invention, the kneading conditions and the functional group concentration on the surface of the carbon black are not particularly limited. In the molded product of the polyamide-based conductive resin composition, 80% by mass or more of the blending amount of the carbon black is a continuous phase. It is important to prepare a composition that can be dispersed in the polyamide resin. By such dispersion of carbon black, a composition having excellent conductivity with a volume resistivity of 1 × 10 11 Ω · cm or less can be obtained, and physical properties such as impact strength and wear resistance can be improved.
本発明の（Ｃ）ポリアミド樹脂の末端基および／または主鎖のアミド基と反応しうる官能基を有するエチレン−αオレフィン共重合体としては、エチレン／プロピレン共重合体、エチレン／プロピレン／ジエン共重合体、エチレン／ブテン−１共重合体、エチレン／オクテン−１共重合体、エチレン／ヘキセン−１共重合体、エチレン／４メチルペンテン−１共重合体、エチレン／環状オレフィン共重合体等を挙げることができるが、これらに限定されるものではない。（Ｃ）エチレン−αオレフィン共重合体の配合量は１０〜４０質量％が好ましい。配合量が１０質量％未満ではポリアミド系導電性樹脂組成物の衝撃強度が低くなる。また４０質量％を越えると組成物の弾性率や強度が著しく低くなり、更に耐摩耗性も悪くなり好ましくない。 Examples of the ethylene-α-olefin copolymer having a functional group capable of reacting with the terminal group of the polyamide resin (C) and / or the main chain amide group of the present invention include ethylene / propylene copolymer, ethylene / propylene / diene copolymer. Polymers, ethylene / butene-1 copolymers, ethylene / octene-1 copolymers, ethylene / hexene-1 copolymers, ethylene / 4 methylpentene-1 copolymers, ethylene / cyclic olefin copolymers, etc. It can be mentioned, but is not limited to these. (C) As for the compounding quantity of an ethylene-alpha olefin copolymer, 10-40 mass% is preferable. When the blending amount is less than 10% by mass, the impact strength of the polyamide-based conductive resin composition becomes low. On the other hand, if it exceeds 40% by mass, the elastic modulus and strength of the composition are remarkably lowered, and the wear resistance is also deteriorated.
本発明の（Ｃ）エチレン−αオレフィン共重合体におけるポリアミド樹脂の末端基および／または主鎖のアミド基と反応しうる官能基とはポリアミド樹脂の末端基であるアミノ基、カルボキシル基および主鎖のアミド基と反応しうる基であり、具体的にはカルボン酸基、酸無水物基、エポキシ基、オキサドリン基、アミノ基、イソシアネート基等が例示されるが、これらの中では酸無水物基が最も反応性に優れているので好ましい。また官能基の量は当然のことであるが、多い方がポリアミド樹脂との反応が進み、エチレン−αオレフィン共重合体はポリアミド樹脂の連続相の中でより微細な粒径で分散し、組成物の耐衝撃性も向上する。これらの官能基を有するエチレン−αオレフィン共重合体の製造法は共重合体を製造する工程で上記の官能基を持つ化合物を反応させる方法や共重合体のペレットと官能基を持つ化合物等を混合し、押出機等で混錬して反応させる方法等があるが、これらに限定されるものではない。 The functional group capable of reacting with the terminal group of the polyamide resin and / or the amide group of the main chain in the (C) ethylene-α-olefin copolymer of the present invention is the amino group, carboxyl group and main chain which are the terminal groups of the polyamide resin. Examples of these groups include carboxylic acid groups, acid anhydride groups, epoxy groups, oxadoline groups, amino groups, and isocyanate groups, among which acid anhydride groups are exemplified. Is preferable because it has the most excellent reactivity. The amount of functional groups is natural, but the larger the reaction, the more the reaction with the polyamide resin proceeds, and the ethylene-α-olefin copolymer is dispersed with a finer particle size in the continuous phase of the polyamide resin. Improves impact resistance of objects. The method for producing an ethylene-α-olefin copolymer having these functional groups includes a method of reacting a compound having the above functional group in a step of producing the copolymer, a copolymer pellet and a compound having a functional group, etc. Although there is a method of mixing and kneading with an extruder or the like, the method is not limited thereto.
本発明における（Ｄ）高密度ポリエチレンとは密度で０．９６以上のポリエチレンであり、その他の限定はない。（Ｄ）高密度ポリエチレンの配合量は１〜１０質量％が好ましい。配合量が１質量％未満では摩耗性の改良効果が少なく、また１０質量％を越えると組成物の強度や耐衝撃性を悪くするため好ましくない。本発明のポリアミド系導電性樹脂組成物ではポリアミド樹脂中に分散しているエチレン−αオレフィン共重合体と高密度ポリエチレンとは同類のオレフィン系樹脂で親和性が良いため、組成物中での分散性は良好であり、高結晶性の高密度ポリエチレンが微分散しているポリアミド系導電性樹脂組成物は優れた摺動性を発揮し、テーパー摩耗値が２５ｍｇ以下となる。 The (D) high density polyethylene in the present invention is polyethylene having a density of 0.96 or more, and there is no other limitation. (D) As for the compounding quantity of a high density polyethylene, 1-10 mass% is preferable. If the blending amount is less than 1% by mass, the effect of improving the wear resistance is small. In the polyamide-based conductive resin composition of the present invention, the ethylene-α olefin copolymer and high-density polyethylene dispersed in the polyamide resin are similar olefin-based resins and have good affinity. The polyamide-based conductive resin composition in which highly crystalline high-density polyethylene is finely dispersed exhibits excellent slidability and has a taper wear value of 25 mg or less.
本発明のポリアミド系導電性樹脂組成物には上述した（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）の成分の他に、通常のポリアミド系樹脂組成物に用いられる耐候性改良材である銅酸化物および／又はハロゲン化アルカリ金属、光または熱安定剤としてフェノール系酸化防止剤やリン系酸化防止剤、離型剤、結晶核剤、滑剤、顔料、染料等を配合しても良い。 In addition to the components (A), (B), (C) and (D) described above, the polyamide-based conductive resin composition of the present invention is a weather resistance improving material used in ordinary polyamide-based resin compositions. Certain copper oxides and / or alkali metal halides, phenolic antioxidants, phosphorus antioxidants, mold release agents, crystal nucleating agents, lubricants, pigments, dyes, etc. may be blended as light or heat stabilizers. .
本発明のポリアミド系導電性樹脂組成物を得るための製造方法で最も重要な点は導電性カーボンブラックをあらかじめ連続相となるポリアミド樹脂中に分散させることにある。その理由は組成物で効率の良い導電性が得られることと導電性カーボンブラックの粒子表面にある官能基と（Ｃ）官能基を付与したエチレン−αオレフィン共重合体とが溶融混錬中に反応し、エチレン−αオレフィン共重合体に付与した官能基が失活ことを阻止する点にある。特に後者の反応が起こると、ポリアミド樹脂と（Ｃ）エチレン−αオレフィン共重合体の反応が著しく抑えられ、（Ｃ）エチレン−αオレフィン共重合体がポリアミド樹脂中で微細な分散ができなくなり、耐衝撃性や耐摩耗性が著しく悪くなる。 The most important point in the production method for obtaining the polyamide-based conductive resin composition of the present invention is that conductive carbon black is dispersed in advance in a polyamide resin that becomes a continuous phase. The reason is that the composition can provide efficient conductivity, and the functional group on the particle surface of the conductive carbon black and (C) the ethylene-α olefin copolymer to which the functional group is added are melt kneaded. It exists in the point which reacts and the functional group provided to the ethylene-alpha olefin copolymer prevents that it deactivates. In particular, when the latter reaction occurs, the reaction between the polyamide resin and the (C) ethylene-α olefin copolymer is remarkably suppressed, and the (C) ethylene-α olefin copolymer cannot be finely dispersed in the polyamide resin. Impact resistance and wear resistance are significantly deteriorated.
本発明のポリアミド系導電性樹脂組成物の具体的な製造方法は、溶融混錬機、（例えば二軸押出機、加圧ニーダー、単軸押出機、溶融反応釜等）で、（Ａ）ポリアミド樹脂と（Ｂ）導電性カーボンブラックを混合および溶融混錬し、ポリアミド樹脂中に導電性カーボンブラックを均一に分散させた後、次に（Ｃ）官能基を持つエチレン−αオレフィン共重合体、（Ｄ）高密度ポリエチレンおよび必要に応じて他の添加剤を配合して更に溶融混錬する。このような二段階の溶融混錬することにより、本発明のポリアミド系導電性樹脂組成物が得られる。本発明では上述の二回に分けて溶融混錬する二段階溶融混錬法に限定されるもではない。例えば中間部に供給口があるベント式の二軸押出機では主供給部であるホッパーに（Ａ）ポリアミド樹脂と（Ｂ）導電性カーボンブラックを投入・溶融混錬し、二軸押出機の中間部の供給口であるベント口から（Ｃ）官能基を持つエチレン−αオレフィン共重合体と（Ｄ）高密度ポリエチレン等を投入・溶融混錬することにより、一連の連続した溶融混錬によって本発明の組成物を製造することができる。これらの具体的な製造法はここに記載した方法に限定されるものではなく、前述したように導電性カーボンブラックがポリアミド樹脂中に微分散するような製造法であれば他の製造方法を用いて本発明の組成物を製造することができる。 A specific method for producing the polyamide-based conductive resin composition of the present invention is a melt kneader (for example, a twin screw extruder, a pressure kneader, a single screw extruder, a melt reaction kettle, etc.), and (A) polyamide After the resin and (B) conductive carbon black are mixed and melt-kneaded to uniformly disperse the conductive carbon black in the polyamide resin, (C) an ethylene-α olefin copolymer having a functional group, (D) High density polyethylene and other additives as necessary are blended and further melt kneaded. The polyamide-based conductive resin composition of the present invention can be obtained by such two-stage melt kneading. The present invention is not limited to the above-described two-stage melt kneading method in which the melt kneading is performed twice. For example, in a vent type twin-screw extruder with a supply port in the middle part, (A) polyamide resin and (B) conductive carbon black are charged into the hopper, which is the main supply part, and melted and kneaded, so (C) An ethylene-α olefin copolymer having a functional group and (D) high-density polyethylene are charged and melt-kneaded from the vent port, which is the supply port of the section, so that a series of continuous melt-kneading is performed. Inventive compositions can be produced. These specific production methods are not limited to the methods described herein, and other production methods can be used as long as the conductive carbon black is finely dispersed in the polyamide resin as described above. Thus, the composition of the present invention can be produced.
以下に実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例に何ら制限されるものではない。
また以下の実施例、比較例において示した各特性、物性値は下記の試験方法で測定した。試験片は射出成形機（東芝機械（株）製、ＩＳ８０）により下記条件にて成形した。
樹脂温度：２７５℃
金型温度：４０℃
射出圧力：５０Ｋｇ／ｃｍ２
射出時間：１秒
保圧力：６０Ｋｇ／ｃｍ２
保持時間：６秒
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.
In addition, each characteristic and physical property value shown in the following examples and comparative examples were measured by the following test methods. The test piece was molded under the following conditions by an injection molding machine (Toshiba Machine Co., Ltd., IS80).
Resin temperature: 275 ° C
Mold temperature: 40 ℃
Injection pressure: 50 kg / cm 2
Injection time: 1 second Holding pressure: 60 Kg / cm 2
Holding time: 6 seconds
１．体積固有抵抗； 射出成形で得た１００ｍｍ×１００ｍｍ厚さ２ｍｍのプレートのゲートに対し直角な両端に端子を接続し、デジタルマルチメーター（アドバンテスト（株）製、ＴＲ−６８４３）で測定した。
なお測定試験片は７０℃で１２時間、真空乾燥した後、２０℃、５０％ＲＨの雰囲気で２４時間シーズニングしてから測定した。
２．アイゾット衝撃強度； ＡＳＴＭ Ｄ２５６（ノッチ有り）に準拠して測定した。
３．テーパー摩耗； ＪＩＳ Ｋ ７２０４（磨耗輪ＣＳ１７、荷重１０００ｇ、回転数１０００回転）に準拠して測定した。
1. Volume specific resistance: Terminals were connected to both ends perpendicular to the gate of a 100 mm × 100 mm 2 mm thick plate obtained by injection molding, and measurement was performed with a digital multimeter (manufactured by Advantest Co., Ltd., TR-6843).
The measurement specimen was vacuum-dried at 70 ° C. for 12 hours and then seasoned in an atmosphere of 20 ° C. and 50% RH for 24 hours.
2. Izod impact strength; measured in accordance with ASTM D256 (notched).
3. Tapered wear: Measured according to JIS K 7204 (wear wheel CS17, load 1000 g, rotation speed 1000 rotations).
実施例および比較例に用いた組成物の原材料は下記のような材料を使用した。
（Ａ）；東洋紡ナイロンＴ−８４０（東洋紡績（株）製、ナイロン６、相対粘度２．２）
（Ｂ）カーボンブラックは次の二種類を使った。
Ｂ−１；ファーネスカーボン Ｃ１００（ライオン（株）製）
Ｂ−２；ケッチェンカーボンＥＣ（ライオン（株）製）
（Ｃ）変性エチレン−αオレフィン共重合体はいずれも無水マレイン酸変性したもので次の二種類を使用した。
Ｃ−１；タフマー（Ｒ）ＭＨ５０１０（三井化学（株）製）
Ｃ−２；タフマー（Ｒ）ＭＨ５０２０（三井化学（株）製）
（Ｄ）高密度ポリエチレンは次の材料を使用した。
Ｄ；高密度ポリエチレンＭＭＥ００１（三井化学（株）製）
The raw materials of the compositions used in the examples and comparative examples were as follows.
(A): Toyobo Nylon T-840 (Toyobo Co., Ltd., nylon 6, relative viscosity 2.2)
(B) The following two types of carbon black were used.
B-1; Furnace Carbon C100 (manufactured by Lion Corporation)
B-2; Ketjen Carbon EC (manufactured by Lion Corporation)
(C) The modified ethylene-α olefin copolymer was modified with maleic anhydride, and the following two types were used.
C-1; Tuffmer (R) MH5010 (manufactured by Mitsui Chemicals, Inc.)
C-2: Tuffmer (R) MH5020 (manufactured by Mitsui Chemicals, Inc.)
(D) The following materials were used for the high density polyethylene.
D: High density polyethylene MME001 (Mitsui Chemicals, Inc.)
（実施例１、２および比較例１〜３）
実施例１、２および比較例２、３の製造法は、一段練り工程で表１の組成割合で各原料を計量ブレンドし、シリンダー温度２６０℃に設定した二軸押出機（池貝鉄工（株）製、ＰＣＭ３０）で溶融混練してペレットとした。次にこのペレットと二段練り工程で表１の組成割合で各原料を計量ブレンドし、一段練り工程と同様に２６０℃に設定した二軸押出機で溶融混錬し、ポリアミド系導電性樹脂組成物を得た。一方、比較例１では一段練り工程を経ずに二段練り工程のみで表１の組成割合で全部の原料成分を計量ブレンドし、前記と同様に２６０℃に設定した二軸押出機で溶融混錬を行いポリアミド系導電性樹脂組成物を得た。
(Examples 1 and 2 and Comparative Examples 1 to 3)
In the production methods of Examples 1 and 2 and Comparative Examples 2 and 3, each raw material was metered and blended at a composition ratio shown in Table 1 in a one-step kneading process, and a cylinder temperature was set to 260 ° C. Manufactured by PCM30) and kneaded into pellets. Next, the raw materials are weighed and blended at the composition ratio shown in Table 1 in this pellet and the two-stage kneading process, and melt-kneaded in a twin-screw extruder set at 260 ° C. in the same manner as in the first-stage kneading process. I got a thing. On the other hand, in Comparative Example 1, all the raw material components were metered and blended at the composition ratio shown in Table 1 only in the two-stage kneading process without going through the one-stage kneading process, and melt-mixed with a twin-screw extruder set at 260 ° C. as described above. Refined to obtain a polyamide-based conductive resin composition.
実施例１および２では一段練り工程でポリアミド樹脂とカーボンブラックとを溶融混錬し、連続相となるポリアミド樹脂中にカーボンブラックを分散し、その後二段練り工程で変性エチレン−αオレフィン共重合体と高密度ポリエチレンを溶融混練した。このような製造方法で製造された組成物では導電性と共に高い衝撃強度および優れたテーパー摩耗値が得られている。 In Examples 1 and 2, polyamide resin and carbon black are melt-kneaded in a one-stage kneading process, carbon black is dispersed in a polyamide resin that becomes a continuous phase, and then a modified ethylene-α-olefin copolymer in a two-stage kneading process. And high-density polyethylene were melt-kneaded. In the composition produced by such a production method, high impact strength and excellent taper wear value are obtained together with conductivity.
一方、比較例１において全組成成分を同時にブレンド溶融混錬した。特に注目すべき点は実施例１と比較例１は同一組成であるが、アイゾット衝撃強度やテーパー摩耗値が大きく異なることである。比較例１では全成分を同時に混合し、溶融混練したため（Ｂ）導電性カーボンブラックの粒子表面にある官能基と官能基を付与した（Ｃ）エチレン−αオレフィン共重合体とが溶融混錬中に反応し、エチレン−αオレフィン共重合体に付与した官能基の活性が失われたため本来反応すべきポリアミド樹脂との反応割合が減少することにより、組成物の衝撃強度や摩耗性が著しく悪化したものと推定される。
また、比較例２では（Ｄ）高密度ポリエチレンが配合されていないため、テーパー摩耗値が著しく低下する。比較例３では官能基を持つ（Ｃ）エチレン−αオレフィン共重合体の配合量を少なくすると、当然のことながら組成物の衝撃強度が低下する。
On the other hand, in Comparative Example 1, all the composition components were blended and kneaded simultaneously. Of particular note is that Example 1 and Comparative Example 1 have the same composition, but the Izod impact strength and the taper wear value differ greatly. In Comparative Example 1, all the components were mixed at the same time and melt kneaded, so (B) the functional group on the particle surface of the conductive carbon black and the functional group (C) the ethylene-α-olefin copolymer were melt kneaded. Since the activity of the functional group imparted to the ethylene-α-olefin copolymer is lost, the reaction rate with the polyamide resin that should be reacted is reduced, so that the impact strength and wear resistance of the composition are remarkably deteriorated. Estimated.
In Comparative Example 2, since (D) high-density polyethylene is not blended, the taper wear value is remarkably lowered. In Comparative Example 3, when the blending amount of the (C) ethylene-α olefin copolymer having a functional group is decreased, the impact strength of the composition is naturally reduced.
実施例および比較例から明らかなように、本発明の製造法で製造されたポリアミド系導電性樹脂組成物は優れた導電性と高い衝撃強度や優れたテーバー磨耗値を持つことができる。 As is apparent from the examples and comparative examples, the polyamide-based conductive resin composition produced by the production method of the present invention can have excellent conductivity, high impact strength, and excellent Taber abrasion value.
本発明による製造方法によって製造されたポリアミド系樹脂組成物は、優れた導電性を有すると共に優れた耐衝撃性や摺動特性を保持している。このような良好な特性を持つ導電性樹脂組成物は自動車の燃料系部品、例えば燃料タンクのキャップやストレーナー、フィルター、バルブ等の部品として幅広い分野で使用することができ、産業界に寄与することが大である。 The polyamide-based resin composition produced by the production method according to the present invention has excellent conductivity and excellent impact resistance and sliding properties. Conductive resin compositions with such good properties can be used in a wide range of fields as automotive fuel system parts, such as fuel tank caps, strainers, filters, valves, etc., and contribute to the industry. Is big.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006084765A JP5277517B2 (en) | 2004-09-29 | 2006-03-27 | Method for producing polyamide-based conductive resin composition |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004283833 | 2004-09-29 | ||
| JP2004283834 | 2004-09-29 | ||
| JP2004283833 | 2004-09-29 | ||
| JP2004283834 | 2004-09-29 | ||
| JP2004286478 | 2004-09-30 | ||
| JP2004286478 | 2004-09-30 | ||
| JP2006084765A JP5277517B2 (en) | 2004-09-29 | 2006-03-27 | Method for producing polyamide-based conductive resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005269554A Division JP4889987B2 (en) | 2004-09-29 | 2005-09-16 | Fuel tank cap |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006206916A JP2006206916A (en) | 2006-08-10 |
| JP5277517B2 true JP5277517B2 (en) | 2013-08-28 |
Family
ID=36964093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006084765A Active JP5277517B2 (en) | 2004-09-29 | 2006-03-27 | Method for producing polyamide-based conductive resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5277517B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7056557B2 (en) * | 2017-02-07 | 2022-04-19 | 東洋紡株式会社 | Conductive polyamide resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329179A (en) * | 2000-05-24 | 2001-11-27 | Lion Corp | Method for producing electrically conductive resin composition |
| JP2003064255A (en) * | 2001-08-23 | 2003-03-05 | Mitsubishi Engineering Plastics Corp | Thermoplastic resin composition |
| JP4195285B2 (en) * | 2002-12-27 | 2008-12-10 | 大倉工業株式会社 | Polyamide-based electrophotographic member |
-
2006
- 2006-03-27 JP JP2006084765A patent/JP5277517B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006206916A (en) | 2006-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103328574B (en) | Resin combination and comprise its products formed | |
| KR101174303B1 (en) | Polyamide molding materials with an improved flowability, the production thereof and its use | |
| US20110027512A1 (en) | Conductive polyamide composite composition and fuel transport tube using the same | |
| US4755552A (en) | Impact-resistant polyamide molding compounds | |
| JPH04300956A (en) | Antistatic resin composition | |
| WO2006035619A1 (en) | Conductive polyamide resin composition, method for producing same and fuel tank cap composed of same | |
| KR101282710B1 (en) | Poly amide based resin composition | |
| WO1997044395A1 (en) | Aromatic polyamide resin composition having excellent balance of toughness and stiffness | |
| JP2005054087A (en) | Conductive polyamide resin composition | |
| JP3467518B2 (en) | Conductive resin composition and molded article for automotive parts | |
| JP2007502358A (en) | Articles made from a polyamide resin composition with improved fluid permeation barrier properties | |
| JP5277517B2 (en) | Method for producing polyamide-based conductive resin composition | |
| JP4889987B2 (en) | Fuel tank cap | |
| JP5277516B2 (en) | Polyamide-based conductive resin composition | |
| JPWO2018147250A1 (en) | Conductive polyamide resin composition | |
| JP2002322366A (en) | Conductive thermoplastic resin composition | |
| JP3456501B2 (en) | Polyamide resin composition | |
| JPH06313045A (en) | Production of reinforced polyamide resin composition | |
| WO2018147315A1 (en) | Conductive polyamide resin composition | |
| KR100591449B1 (en) | Polyamide / Polyethylene Compound Blend Resin Compositions | |
| JP2008019372A (en) | Conductive thermoplastic resin composition and production method | |
| JP3331639B2 (en) | Polytetramethylene adipamide resin composition | |
| JP3387219B2 (en) | Resin composition | |
| JP7197056B1 (en) | Polyphenylene sulfide resin composition, molded article and method for producing molded article | |
| JPH08259809A (en) | Polyamide resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20060410 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080903 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20110603 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120608 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120806 |
|
| 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: 20130423 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130506 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5277517 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| 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 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313111 |
|
| 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 |