JP2004307589A - Flame-retardant polyamide resin composition - Google Patents
Flame-retardant polyamide resin composition Download PDFInfo
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- JP2004307589A JP2004307589A JP2003100698A JP2003100698A JP2004307589A JP 2004307589 A JP2004307589 A JP 2004307589A JP 2003100698 A JP2003100698 A JP 2003100698A JP 2003100698 A JP2003100698 A JP 2003100698A JP 2004307589 A JP2004307589 A JP 2004307589A
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- 229920006122 polyamide resin Polymers 0.000 title claims abstract description 43
- 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 title claims abstract description 33
- 239000003063 flame retardant Substances 0.000 title claims abstract description 33
- 239000011342 resin composition Substances 0.000 title claims abstract description 25
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 34
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000012778 molding material Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- -1 fatty acid ester Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010128 melt processing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920006065 Leona® Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Images
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、物性の改良された難燃性ポリアミド樹脂組成物に関するものであり、さらに詳しくは難燃性、成形性に優れるとともに、機械的特性、特に、ヒンジ特性や引張り破断伸度が改良された難燃性ポリアミド樹脂組成物に関するものである。
【０００２】
【従来の技術】
ポリアミド樹脂は、機械的特性、電気特性、耐薬品性、成形加工性などに優れることを利用して自動車部品、電気・電子部品などの各種分野で使用されている。このうち電気・電子部品等のように高度の難燃性を要求される分野では難燃性ポリアミドが広く利用されていて、その中でメラミンシアヌレートを配合してなる難燃性ポリアミド樹脂は公知である（例えば、特許文献１、２参照）。
このようにメラミンシアヌレートを配合して難燃性を向上させる場合、メラミンシアヌレートのポリアミド樹脂に対する分散性は悪いため、かかる難燃剤を配合した難燃性ポリアミド樹脂は、難燃剤を配合しないものと比較して機械的特性が劣るという欠点を有している。したがって、特に高い材料信頼性が要求される自動車部品や電気・電子部品等の用途においては、ヒンジ特性などの機械的特性に関しての改善が望まれる。
【０００３】
一方、メラミンシアヌレートのポリアミド樹脂中での分散状態を向上させて機械的特性の低下を防ぐ方法として、ポリアミド樹脂とメラミンシアヌレートとを溶融混練したマスターバッチとポリアミド樹脂を溶融混練する手法（例えば、特許文献３参照。）が知られている。しかしながら、かかる方法では二段階の混練のためポリアミド樹脂中のメラミンシアヌレートが熱分解により、メラミンとシアヌール酸とに分解し昇華しやすくなる。この昇華したメラミン及びシアヌル酸の影響で成形加工時に成形品表面にシルバーが発生したり、金型表面を汚染しやすい。また、メラミンシアヌレートの分散性が十分とは言えず、成形品の表面に凸凹が発生したりウエルド部伸度が低いという欠点がある。
【０００４】
また、ポリアミドとメラミンシアヌレートに界面活性剤を配合したメラミンシアヌレートマスターバッチで、分散性を向上させる技術も開示されている。（例えば、特許文献４参照。）かかる方法でも二段階の混練のためポリアミド樹脂中のメラミンシアヌレートが熱分解により、メラミンとシアヌール酸とに分解し昇華しやすく、シルバーや金型汚染の原因となる。また、この技術により分散性は向上するが、高度なヒンジ特性を実現するには至らない。
【０００５】
【特許文献１】
特開昭５３−１２５４５９号公報
【特許文献２】
特開昭５３−３１７５９号公報
【特許文献３】
特開平０８−２４５８７５号公報
【特許文献４】
特開平１１−３０２５３６号公報
【０００６】
【発明が解決しようとする課題】
本発明の目的は、難燃性に優れるとともに、機械的特性、特に高度なヒンジ特性、引張り破断伸度が改良され、更には押出や成形等の溶融加工時での難燃剤の熱分解によるガス発生を低減させた難燃性ポリアミド樹脂組成物を提供することにある。
【０００７】
【課題を解決するための手段】
本発明者等は、鋭意研究を重ねた結果、共重合ポリアミド６６／６樹脂、ポリアミド６とポリマー重合時に同系中で合成したメラミンシアヌレートを含有する共重合ポリアミド６６／６樹脂からなる組成物がその目的を達しうることを見い出し、この知見に基づいて本発明を完成させるに至った。
すなわち、本発明は、共重合ポリアミド６６／６樹脂（Ａ）成分、ポリアミド６樹脂（Ｂ）成分およびメラミンシアヌレート含有共重合ポリアミド６６／６樹脂（Ｃ）成分からなる難燃性ポリアミド樹脂組成物であって、シアヌール酸とメラミンをポリアミド形成モノマー中に添加し、ポリアミド６６／６の重合およびメラミンシアヌレートの合成を同時に同系中で行って得た（Ｃ）成分であり、該樹脂組成物中のメラミンシアヌレートが０．１５〜１５重量％であることを特徴とする難燃性ポリアミド樹脂組成物、である。
【０００８】
以下、本発明を詳細に説明する。本発明において、共重合ポリアミド６６／６樹脂（Ａ）成分は、ポリアミド６６に比べて融点が低く、押出時や成形時の溶融加工温度も低くすることができるため、難燃剤の熱分解を抑えることができ、さらにポリアミド６に比べて引張強度や剛性などに優れるので、難燃剤のガス低減と物性の両者のバランスを持っている。そして、この共重合ポリアミド６６／６樹脂のポリアミド６ユニットが融点と難燃剤の分解の観点から５重量％以上であり、機械物性の観点から３０重量％以下である。より好ましくは、６〜２０重量％であり、更に好ましくは、７〜１５重量％である。
【０００９】
ポリアミド６樹脂（Ｂ）成分は、本願組成物のポリアミド６ユニット率を調整し、高度なヒンジ特性を発現するために必要である。（Ｂ）成分の量は特に規定しないが、該難燃性ポリアミド樹脂組成物のポリアミド成分のポリアミド６ユニット率が、ヒンジ特性の観点から１５重量％以上であり、機械特性の観点から７０重量％以下になるように（Ｂ）成分を添加する。より好ましくは、２０〜６０重量％、更に好ましくは、３０〜５０重量％である。
【００１０】
メラミンシアヌレート含有共重合ポリアミド６６／６樹脂（Ｃ）成分は、シアヌール酸とメラミンをポリアミド形成モノマー中に添加し、ポリアミド６６／６の重合及びメラミンシアヌレートの合成を同時に同系中で行って得たメラミンシアヌレート含有共重合ポリアミド６６／６樹脂である。
この共重合ポリアミド６６／６も、（Ａ）成分と同様な理由で、ポリアミド６ユニットが融点と難燃剤の分解の観点から５重量％以上、機械物性の観点から３０重量％以下である。より好ましくは、６〜２０重量％であり、更に好ましくは、７〜１５重量％である。
【００１１】
また、メラミンシアヌレート含有共重合ポリアミド６６／６樹脂（Ｃ）成分中のメラミンシアヌレート含有率は、難燃性の観点から（Ｃ）成分の３重量％以上、ヒンジ特性の観点から３０重量％以下である。より好ましくは、４〜２０重量％であり、更に好ましくは、５〜１５重量％である。
該難燃性ポリアミド樹脂組成物に占めるメラミンシアヌレートの割合は難燃性の観点から０．１５重量％以上、ヒンジ特性の観点から１５重量％以下である。
より好ましくは、０．５〜１２重量％であり、更に好ましくは、１〜１０重量％である
【００１２】
本願発明の組成物を得るには、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の三成分を均一混合することが必要であるが、この方法は特に限定はしないが、例えば、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の三成分をペレット状のまま、ブレンダー、ミキサー、ニューマーなどで混合したペレットブレンド物を得て、それを射出成形機、押出成形機、プレス成形機を用いて成形することができる。また、（Ａ）成分、（Ｂ）成分および（Ｃ）成分の三成分を押出機を用いて溶融混練後ペレタイズして、均一な組成のペレットを得て、それを射出成形機、押出成形機、プレス成形機を用いて成形することができる。好ましくは、後者の均一混練方法で一度押出機で溶融混練することにより、メラミンシアヌレートの分散性が向上し、より高度なヒンジ特性を発現できる。
【００１３】
なお、本発明の成形材料には所望に応じ、種々の添加剤、例えばポリアルキレンアルコール又は脂肪酸エステル等の難燃剤の分散剤、熱安定剤、紫外線吸収剤、酸化劣化防止剤、可塑剤、帯電防止剤、耐候性改良剤、滑剤、離形剤、充填剤、染料、顔料等の、他の添加剤や、他の樹脂ポリマーを本発明の目的を損なわない範囲において添加することができる。
【００１４】
【発明の実施の形態】
以下の実施例により本発明をさらに詳しく説明するが、本発明はこれに限定されるものではない。
なお、実施例及び比較例に用いた原材料及び測定方法を以下に示す。
［原材料］
（Ａ）成分 共重合ポリアミド６６／６樹脂
（Ａ−１）：製造例１の共重合ポリアミド６６／６樹脂
（共重合成分の重量比 ６６：６＝９０：１０ 融点＝２４５℃）
（Ｂ）成分 ポリアミド６樹脂
（Ｂ−１）：ポリアミド６樹脂 宇部興産（株）製 商品名 ＳＦ１０１３Ａ
【００１５】
（Ｃ）成分 メラミンシアヌレート含有ポリアミド樹脂
（Ｃ−１）：製造例２のメラミンシアヌレート含有共重合ポリアミド６６／６樹脂 （共重合成分の重量比 ６６：６＝９０：１０）（メラミンシアヌレート含有率＝１２重量％）
（Ｃ−２）：製造例３のメラミンシアヌレート含有ポリアミド６６（メラミンシアヌレート含有率＝３０重量％）
（その他）
（ＭＣ−１）：メラミンシアヌレート 三菱化学（株）製商品名 ＭＣＡ−Ｃ１
（分散剤）：ポリエチレングリコールモノラウレート 花王（株）製 商品名 エマノーン１１１２
【００１６】
【製造例１】
ポリアミド６６に相当する結合ユニット９０重量％、ポリアミド６に相当する結合ユニット１０重量％を含む共重合ポリアミド６６／６を１８．８ｋｇ製造するのに必要な単量体水溶液を５０重量％のＡＨ塩（アジピン酸とヘキサメチレンジアミンの等モル塩）水溶液３９．２ｋｇとε−カプロラクタム１．９ｋｇとを８０リットルのオートクレーブ中に仕込みよく撹拌した。充分に窒素で置換した後、温度を室温から２２０℃まで昇温した。この際、オートクレーブ内の圧力は、ゲージ圧にして１８ｋｇ／ｃｍ２になるが、圧力が１８ｋｇ／ｃｍ２以上にならないように水を系外に除去しながら加熱を１時間続けた。その後、内温が２７０℃に達した時点で水を系外に除去しながら１時間かけて大気圧まで圧力を下げ、その後加熱を止め、下部ノズルからストランド状にポリマーを排出し、水冷後カッターで直径３ｍｍφ×３ｍｍ長の円柱状ペレットに切断し、共重合ポリアミド６６／６樹脂の粒状体を得た。（共重合成分の重量比 ６６：６＝９０：１０
融点＝２４５℃）
【００１７】
【製造例２】
ポリアミド６６に相当する結合ユニット９０重量％、ポリアミド６に相当する結合ユニット１０重量％を含む共重合ポリアミド６６／６を１８．８ｋｇ製造するのに必要な単量体水溶液を５０重量％のＡＨ塩（アジピン酸とヘキサメチレンジアミンの等モル塩）水溶液３９．２ｋｇとε−カプロラクタム１．９ｋｇとを混合して調整した。次に該単量体濃度を７０重量％まで８０リットルのオートクレーブ中で加熱濃縮した。次にメラミン１１８０ｇ（９．４モル）に水２ｋｇを加えてスラリー状にしたものとシアヌール酸１２２０ｇ（９．４モル）に水２ｋｇを加えてスラリー状にしたものをこのオートクレーブ中に注入し、直ちに撹拌しながら加熱し、温度と圧力を調整して約４時間４０分重合反応を行った後、内容物をストランド状に排出し、水冷後カッターで直径３ｍｍφ×３ｍｍ長の円柱状ペレットに切断し、メラミンシアヌレート含有共重合ポリアミド６６／６樹脂の粒状体を得た。得られた粒状体のメラミンシアヌレート含有率は１２重量％であった。
【００１８】
【製造例３】
ポリアミド６６樹脂（旭化成（株）製 レオナ１１００：融点２６０℃）とメラミンシアヌレート粉末（三菱化学（株）製 ＭＣＡ−Ｃ１）とを別々に供給できる重量フィーダーを用いてメラミンシアヌレートの含有量が３０重量％になるよう二軸押出機（東芝機械（株）製 ＴＥＭ３５）のホッパーから供給しながら、溶融混練後、ストランド状に押出し、水冷後カッターで直径３ｍｍφ×３ｍｍ長の円柱ペレットに切断し、メラミンシアヌレート含有ポリアミド６６の粒状体を得た。得られた粒状体のメラミンシアヌレート含有率は３０重量％であった。
【００１９】
なお、実施例に於ける諸特性の測定は次の様にして行った。
［測定方法］
（１）機械特性
射出成形機（日精工業（株）製：ＰＳ４０Ｅ シリンダー温度２７０℃、金型温度８０℃）を用いて、ＡＳＴＭ Ｄ６３８の引張成形片（厚さ３ｍｍ）、ＡＳＴＭ Ｄ７９０の曲げ試験片（厚さ３ｍｍ）を成形し、ＡＳＴＭ Ｄ６３８、ＡＳＴＭ Ｄ７９０に準拠した方法で引張試験、曲げ試験を実施し、引張強度、引張伸び、曲げ強度、曲げ弾性率を求めた。
【００２０】
（２）ヒンジ特性
射出成形機（日精工業（株）製：ＰＳ４０Ｅ シリンダー温度２７０℃、金型温度６０℃）を用いて、ヒンジ成形品（図１）を成形し、２３℃、５０％ＲＨ雰囲気下で自動繰り返しヒンジ試験機を用いて、ヒンジ部をほとんど１８０°まで折り曲げて、元の位置（０°）の位置に戻す動作を１回／秒の速度で繰り返し、何回折り曲げた段階で折れて破壊するかを測定した。２万回でも破壊しないものを合格とした。
【００２１】
（３）難燃性（特殊酸素指数）
射出成形機（東芝機械製：ＩＳ１５０）を用いて成形して、平板成形品（幅１３０ｍｍ×長さ１３０ｍｍ×厚さ１ｍｍ）得た。この成形品を６．５ｍｍ幅に切削して、幅６．５ｍｍ×長さ１３０ｍｍ×厚さ１ｍｍの棒状の試験片を得た。この試験片をＪＩＳ Ｋ７２０１−２に準じる装置と方法を用いて測定した。但し、着火時間（接炎時間）は１５秒以内にし、合否判定を接炎後の燃焼時間が４秒以上継続するか否かで判定し、４秒までに消える最大の酸素濃度を求めた。この値が大きいほど、難燃性が高い。ここでは２４％以上のものを合格とした。
【００２２】
（４）ガス発生量
二軸押出機（東芝機械（株）製 ＴＥＭ３５）を用いて、コンパウンドした際の紡口先から発生するガスを目視にて判断した。難燃剤が分解してガス発生量が多いときは不合格（×）、少ないときは合格（○）とした。
【００２３】
【実施例１】
共重合ポリアミド６６／６樹脂Ａ−１が６５．７重量％、ポリアミド６樹脂Ｂ−１が２１．９重量％、メラミンシアヌレート含有ポリアミド樹脂が共重合ポリアミド樹脂であるＣ−１が１２．４重量％からなるポリアミド組成物を得た。
原材料（即ち、押出機への投入速度の設定）はＡ−１が６５．７重量％、Ｂ−１が２１．９重量％、Ｃ−１が１２．４重量％となるように用意し、予めコーンブレンダーで混合した。上流側に１ヶ所（以下ｔｏｐ−Ｆと略記）と、押出機中央部並びにダイに近い下流側の２ヶ所に供給口を有する二軸押出機（東芝機械製：ＴＥＭ３５）の上流側のｔｏｐ−Ｆ以外の二箇所の供給口を塞いだ状態で、シリンダー設定温度２７０℃、スクリュー回転２００ｒｐｍ、吐出量３０ｋｇ／ｈｒの条件下で、予めブレンドしたものをｔｏｐ−Ｆから供給し、溶融混練してストランド状に取り出し、ストランドバス（水槽）で冷却後、カッターで造粒しポリアミド樹脂組成物ペレットを得た。このときのガス発生量は目視で少なかった。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
【００２４】
【実施例２】
共重合ポリアミド６６／６樹脂Ａ−１が４３．８重量％、ポリアミド６樹脂Ｂ−１が４３．８重量％、メラミンシアヌレート含有ポリアミド樹脂が共重合ポリアミド樹脂であるＣ−１が１２．４重量％からなるポリアミド組成物を得た。このときのガス発生量は目視で少なかった。
以下、実施例１と同様にしてポリアミド樹脂組成物ペレットを得た。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
【００２５】
【比較例１】
共重合ポリアミド６６／６樹脂Ａ−１が８７．６重量％、メラミンシアヌレート含有ポリアミド樹脂が共重合ポリアミド樹脂であるＣ−１が１２．４重量％からなるポリアミド組成物を得た。
以下、実施例１と同様にしてポリアミド樹脂組成物ペレットを得た。このときのガス発生量は目視で少なかった。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
【００２６】
【比較例２】
共重合ポリアミド６６／６樹脂Ａ−１が７３．０重量％、ポリアミド６樹脂Ｂ−１が２１．９重量％、メラミンシアヌレート含有ポリアミド樹脂がポリアミド６６樹脂であるＣ−２が５．１重量％からなるポリアミド組成物を得た。
以下、実施例１と同様にしてポリアミド樹脂組成物ペレットを得た。このときのガス発生量は目視で少なかった。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
【００２７】
【比較例３】
共重合ポリアミド６６／６樹脂Ａ−１が９８．４重量％、メラミンシアヌレートＭＣ−１が１．５重量％、分散剤が０．１重量％からなるポリアミド組成物を得た。
以下、ブレンドする際に樹脂ペレット（Ａ−１）と分散剤を先に混合して、その後にメラミンシアヌレートＭＣ−１を混合する、二工程を経て行ったこと以外は、実施例１と同様にしてポリアミド樹脂組成物ペレットを得た。このときのガス発生量は目視で少なかった。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
【００２８】
【比較例４】
共重合ポリアミド６６／６樹脂Ａ−１が７６．５重量％、ポリアミド６樹脂Ｂ−１が２１．９重量％、メラミンシアヌレートＭＣ−１が１．５重量％、分散剤が０．１重量％からなるポリアミド組成物を得た。
以下、ブレンドする際に樹脂ペレット（Ａ−１とＢ−１）と分散剤を先に混合して、その後にメラミンシアヌレートＭＣ−１を混合する、二工程を経て行ったこと以外は、実施例１と同様にしてポリアミド樹脂組成物ペレットを得た。このときのガス発生量は目視で少なかった。
得られたペレットを前記した測定方法にて機械特性、ヒンジ特性、難燃性を調べた。その結果を表１に示す。
表１の実施例１、２と比較例１〜４から分かるように、共重合ポリアミド６６／６樹脂、ポリアミド６とポリマー重合時に同系中で重合したメラミンシアヌレートを含有する共重合ポリアミド６６／６樹脂からなる組成物が、難燃剤の熱分解によるガス発生を低減させ、機械特性はほとんど低下させず、難燃性、ヒンジ特性の著しい向上させることができた。
【００２９】
【表１】
【発明の効果】
本発明の組成物は、難燃性ポリアミド樹脂材料であり、ポリアミド樹脂が本来有する機械的特性、耐薬品性、良成形性、電気特性等を損なうことなく、押出や成形時の加熱による難燃剤の分解ガスの発生を抑え、難燃性、ヒンジ特性を向上させることができ、家電部品、電子部品、自動車部品等の用途に好適に用いることが出来る。
【図面の簡単な説明】
【図１】本発明の実施例で用いたヒンジ特性を評価する成形品の模式図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a flame-retardant polyamide resin composition having improved physical properties, more specifically, flame retardancy, excellent moldability, and improved mechanical properties, particularly, hinge properties and tensile elongation at break. And a flame-retardant polyamide resin composition.
[0002]
[Prior art]
Polyamide resins are used in various fields such as automobile parts and electric / electronic parts, utilizing their excellent mechanical properties, electrical properties, chemical resistance, moldability and the like. Among these, flame-retardant polyamides are widely used in fields requiring a high degree of flame retardancy, such as electric and electronic parts. Among them, flame-retardant polyamide resins containing melamine cyanurate are known. (For example, see Patent Documents 1 and 2).
When the flame retardancy is improved by blending melamine cyanurate in this way, the dispersibility of the melamine cyanurate in the polyamide resin is poor. Therefore, the flame retardant polyamide resin blended with such a flame retardant does not contain the flame retardant. Has the disadvantage that the mechanical properties are inferior to those of Therefore, in applications such as automobile parts and electric / electronic parts that require particularly high material reliability, improvements in mechanical properties such as hinge properties are desired.
[0003]
On the other hand, as a method of improving the dispersion state of melamine cyanurate in a polyamide resin to prevent a decrease in mechanical properties, a method of melt-kneading a polyamide resin and a master batch obtained by melt-kneading a polyamide resin and melamine cyanurate (for example, And Patent Document 3) are known. However, in such a method, melamine cyanurate in the polyamide resin is decomposed into melamine and cyanuric acid by thermal decomposition due to the two-stage kneading, and is easily sublimated. Under the influence of the sublimated melamine and cyanuric acid, silver is generated on the surface of the molded product during molding and the surface of the mold is easily contaminated. In addition, the dispersibility of melamine cyanurate cannot be said to be sufficient, and there are disadvantages in that irregularities are generated on the surface of the molded product and the weld portion has low elongation.
[0004]
Also disclosed is a technique for improving the dispersibility of a melamine cyanurate masterbatch obtained by mixing a surfactant with polyamide and melamine cyanurate. (For example, refer to Patent Document 4.) Even in such a method, melamine cyanurate in the polyamide resin is decomposed into melamine and cyanuric acid by thermal decomposition due to two-stage kneading and easily sublimates, causing silver and mold contamination. Become. Further, although the dispersibility is improved by this technique, it is not possible to realize a high hinge characteristic.
[0005]
[Patent Document 1]
JP-A-53-125559 [Patent Document 2]
JP-A-53-31759 [Patent Document 3]
JP 08-245875 A [Patent Document 4]
JP-A-11-302536
[Problems to be solved by the invention]
The object of the present invention is to improve the flame retardancy, improve the mechanical properties, especially the high hinge properties, the tensile elongation at break, and further improve the gas by the thermal decomposition of the flame retardant during melt processing such as extrusion and molding. An object of the present invention is to provide a flame-retardant polyamide resin composition with reduced generation.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies and found that a composition comprising a copolyamide 66/6 resin and a copolyamide 66/6 resin containing melamine cyanurate synthesized in the same system at the time of polymer polymerization with polyamide 6 was obtained. The inventors have found that the object can be achieved, and have completed the present invention based on this finding.
That is, the present invention provides a flame-retardant polyamide resin composition comprising a copolymerized polyamide 66/6 resin (A) component, a polyamide 6 resin (B) component and a melamine cyanurate-containing copolymerized polyamide 66/6 resin (C) component. A component (C) obtained by adding cyanuric acid and melamine to a polyamide-forming monomer and simultaneously performing polymerization of polyamide 66/6 and synthesis of melamine cyanurate in the same system; Wherein the melamine cyanurate is 0.15 to 15% by weight.
[0008]
Hereinafter, the present invention will be described in detail. In the present invention, the copolymerized polyamide 66/6 resin (A) component has a lower melting point than the polyamide 66, and can lower the melt processing temperature during extrusion and molding, thereby suppressing the thermal decomposition of the flame retardant. Since it is excellent in tensile strength and rigidity as compared with polyamide 6, it has a balance between both gas reduction of the flame retardant and physical properties. The polyamide 6 unit of the copolymerized polyamide 66/6 resin is at least 5% by weight from the viewpoint of melting point and decomposition of the flame retardant, and is at most 30% by weight from the viewpoint of mechanical properties. More preferably, it is 6 to 20% by weight, still more preferably 7 to 15% by weight.
[0009]
The polyamide 6 resin (B) component is necessary to adjust the polyamide 6 unit ratio of the composition of the present invention and to exhibit high hinge characteristics. Although the amount of the component (B) is not particularly limited, the polyamide 6 unit ratio of the polyamide component of the flame-retardant polyamide resin composition is 15% by weight or more from the viewpoint of hinge characteristics, and 70% by weight from the viewpoint of mechanical characteristics. The component (B) is added so as to be as follows. More preferably, it is 20 to 60% by weight, still more preferably 30 to 50% by weight.
[0010]
Melamine cyanurate-containing copolymerized polyamide 66/6 resin (C) component is obtained by adding cyanuric acid and melamine to a polyamide-forming monomer and simultaneously performing polymerization of polyamide 66/6 and synthesis of melamine cyanurate in the same system. Melamine cyanurate-containing copolymerized polyamide 66/6 resin.
For the same reason as the component (A), this copolymer polyamide 66/6 has a polyamide 6 unit content of 5% by weight or more from the viewpoint of melting point and decomposition of the flame retardant, and 30% by weight or less from the viewpoint of mechanical properties. More preferably, it is 6 to 20% by weight, still more preferably 7 to 15% by weight.
[0011]
Melamine cyanurate-containing copolymerized polyamide 66/6 The melamine cyanurate content in the component (C) is 3% by weight or more of the component (C) from the viewpoint of flame retardancy and 30% by weight from the viewpoint of hinge characteristics. It is as follows. More preferably, it is 4 to 20% by weight, still more preferably 5 to 15% by weight.
The proportion of melamine cyanurate in the flame-retardant polyamide resin composition is 0.15% by weight or more from the viewpoint of flame retardancy and 15% by weight or less from the viewpoint of hinge characteristics.
More preferably, it is 0.5 to 12% by weight, still more preferably 1 to 10% by weight.
In order to obtain the composition of the present invention, it is necessary to uniformly mix the three components (A), (B) and (C). This method is not particularly limited. A pellet blend obtained by mixing the three components A), (B) and (C) with a blender, a mixer, a Newmer, etc., in the form of a pellet, and injecting it into an injection molding machine, an extrusion molding machine, and press molding. It can be formed using a machine. Further, the three components (A), (B) and (C) are melt-kneaded using an extruder and then pelletized to obtain pellets having a uniform composition, which are then injected into an injection molding machine or an extrusion molding machine. Can be formed using a press forming machine. Preferably, the dispersibility of melamine cyanurate is improved by melt-kneading once with an extruder by the latter uniform kneading method, and higher hinge characteristics can be exhibited.
[0013]
In the molding material of the present invention, if necessary, various additives such as a dispersant for a flame retardant such as a polyalkylene alcohol or a fatty acid ester, a heat stabilizer, an ultraviolet absorber, an antioxidant, a plasticizer, Other additives such as an inhibitor, a weather resistance improver, a lubricant, a release agent, a filler, a dye, a pigment, and the like, and other resin polymers can be added as long as the object of the present invention is not impaired.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In addition, the raw materials and measuring methods used in the examples and comparative examples are shown below.
[raw materials]
(A) Component Copolyamide 66/6 resin (A-1): Copolyamide 66/6 resin of Production Example 1 (weight ratio of copolymer components 66: 6 = 90: 10, melting point = 245 ° C.)
(B) Component Polyamide 6 resin (B-1): Polyamide 6 resin Product name SF1013A manufactured by Ube Industries, Ltd.
[0015]
(C) Component Melamine cyanurate-containing polyamide resin (C-1): melamine cyanurate-containing copolymer polyamide 66/6 resin of Production Example 2 (weight ratio of copolymer components 66: 6 = 90: 10) (melamine cyanurate) (Content = 12% by weight)
(C-2): Melamine cyanurate-containing polyamide 66 of Production Example 3 (melamine cyanurate content = 30% by weight)
(Other)
(MC-1): Melamine cyanurate MCA-C1 manufactured by Mitsubishi Chemical Corporation
(Dispersant): Polyethylene glycol monolaurate (trade name) manufactured by Kao Corporation Emanon 1112
[0016]
[Production Example 1]
50% by weight of an aqueous monomer solution required for producing 18.8 kg of copolymerized polyamide 66/6 containing 90% by weight of a binding unit corresponding to polyamide 66 and 10% by weight of a binding unit corresponding to polyamide 6 (Equimolar salt of adipic acid and hexamethylenediamine) 39.2 kg of an aqueous solution and 1.9 kg of ε-caprolactam were charged into an 80 liter autoclave and stirred well. After the atmosphere was sufficiently replaced with nitrogen, the temperature was raised from room temperature to 220 ° C. At this time, the pressure in the autoclave became 18 kg / cm 2 in gauge pressure, but heating was continued for 1 hour while removing water from the system so that the pressure did not become 18 kg / cm 2 or more. Then, when the internal temperature reached 270 ° C, the pressure was lowered to atmospheric pressure over 1 hour while removing water from the system, then heating was stopped, the polymer was discharged in a strand form from the lower nozzle, and then cooled with water, Was cut into cylindrical pellets having a diameter of 3 mmφ and a length of 3 mm to obtain granules of copolymerized polyamide 66/6 resin. (Weight ratio of copolymer components 66: 6 = 90: 10)
(Melting point = 245 ° C)
[0017]
[Production Example 2]
50% by weight of an aqueous monomer solution required for producing 18.8 kg of copolymerized polyamide 66/6 containing 90% by weight of a binding unit corresponding to polyamide 66 and 10% by weight of a binding unit corresponding to polyamide 6 (Equimolar salt of adipic acid and hexamethylenediamine) An aqueous solution (39.2 kg) and ε-caprolactam (1.9 kg) were mixed and adjusted. Next, the concentration of the monomer was heated and concentrated to 70% by weight in an 80-liter autoclave. Next, a slurry obtained by adding 2 kg of water to 1180 g (9.4 mol) of melamine and a slurry obtained by adding 2 kg of water to 1220 g (9.4 mol) of cyanuric acid were injected into the autoclave. Immediately with stirring and heating, the temperature and pressure are adjusted and the polymerization reaction is carried out for about 4 hours and 40 minutes. The contents are discharged into strands, and after cooling with water, cut into
[0018]
[Production Example 3]
The content of melamine cyanurate is determined using a weight feeder that can separately supply polyamide 66 resin (Leona 1100, manufactured by Asahi Kasei Corporation: melting point: 260 ° C.) and melamine cyanurate powder (MCA-C1, manufactured by Mitsubishi Chemical Corporation). While being supplied from a hopper of a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.), the mixture is melt-kneaded, extruded into strands, water-cooled, and then cut into cylindrical pellets having a diameter of 3 mm and a length of 3 mm using a cutter. Thus, a granular material of melamine cyanurate-containing polyamide 66 was obtained. The melamine cyanurate content of the obtained granules was 30% by weight.
[0019]
In addition, the measurement of various characteristics in the examples was performed as follows.
[Measuring method]
(1) Mechanical properties Using an injection molding machine (manufactured by Nissei Industry Co., Ltd .: PS40E cylinder temperature 270 ° C, mold temperature 80 ° C), a tensile molded piece (
[0020]
(2) Hinge characteristics Using an injection molding machine (manufactured by Nissei Industry Co., Ltd .: PS40E, cylinder temperature: 270 ° C, mold temperature: 60 ° C), a hinge molded product (Fig. 1) is molded, and the temperature is 23 ° C, 50% RH atmosphere. Using an automatic repetitive hinge tester below, bend the hinge part almost to 180 ° and return it to its original position (0 °) at a rate of once / second. It was measured whether it was destroyed. Those that did not break even 20,000 times were accepted.
[0021]
(3) Flame retardancy (special oxygen index)
Molding was performed using an injection molding machine (manufactured by Toshiba Machine Co., IS150) to obtain a flat molded product (width 130 mm × length 130 mm × thickness 1 mm). This molded product was cut into a width of 6.5 mm to obtain a rod-shaped test piece having a width of 6.5 mm, a length of 130 mm and a thickness of 1 mm. This test piece was measured using an apparatus and a method according to JIS K7201-2. However, the ignition time (flame contact time) was set within 15 seconds, and the pass / fail judgment was made based on whether the combustion time after the flame contact continued for 4 seconds or more, and the maximum oxygen concentration that disappeared by 4 seconds was obtained. The greater the value, the higher the flame retardancy. In this case, 24% or more was regarded as a pass.
[0022]
(4) Gas Generation A gas generated from the spinning tip when compounded was visually determined using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.). When the flame retardant was decomposed and the amount of generated gas was large, it was rejected (x), and when it was small, it was passed (o).
[0023]
Embodiment 1
The copolymerized polyamide 66/6 resin A-1 has 65.7% by weight, the polyamide 6 resin B-1 has 21.9% by weight, and the melamine cyanurate-containing polyamide resin has a copolymerized polyamide resin C-1 of 12.4%. % By weight of a polyamide composition was obtained.
Raw materials (that is, setting of the feeding speed to the extruder) were prepared so that A-1 was 65.7% by weight, B-1 was 21.9% by weight, and C-1 was 12.4% by weight, It was mixed in a corn blender in advance. The top-end of a twin-screw extruder (manufactured by Toshiba Machinery: TEM35) having a supply port at one location on the upstream side (hereinafter abbreviated as top-F) and two locations on the downstream side near the center of the extruder and the die. With the two supply ports other than F closed, the pre-blended product is supplied from top-F under the conditions of a cylinder set temperature of 270 ° C., a screw rotation of 200 rpm, and a discharge rate of 30 kg / hr, and melt-kneaded. It was taken out in a strand shape, cooled in a strand bath (water tank), and then granulated with a cutter to obtain a polyamide resin composition pellet. The amount of gas generated at this time was small visually.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
[0024]
Embodiment 2
The copolymerized polyamide 66/6 resin A-1 is 43.8% by weight, the polyamide 6 resin B-1 is 43.8% by weight, and the melamine cyanurate-containing polyamide resin is a copolymerized polyamide resin, C-1 is 12.4%. % By weight of a polyamide composition was obtained. The amount of gas generated at this time was small visually.
Thereafter, a polyamide resin composition pellet was obtained in the same manner as in Example 1.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
[0025]
[Comparative Example 1]
A polyamide composition was obtained in which the copolymer polyamide 66/6 resin A-1 was 87.6% by weight and the melamine cyanurate-containing polyamide resin was 12.4% by weight of the copolymerized polyamide resin C-1.
Thereafter, a polyamide resin composition pellet was obtained in the same manner as in Example 1. The amount of gas generated at this time was small visually.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
[0026]
[Comparative Example 2]
The copolymerized polyamide 66/6 resin A-1 is 73.0% by weight, the polyamide 6 resin B-1 is 21.9% by weight, and the melamine cyanurate-containing polyamide resin is polyamide 66 resin, C-2 is 5.1% by weight. % Of a polyamide composition.
Thereafter, a polyamide resin composition pellet was obtained in the same manner as in Example 1. The amount of gas generated at this time was small visually.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
[0027]
[Comparative Example 3]
A polyamide composition comprising 98.4% by weight of copolymerized polyamide 66/6 resin A-1, 1.5% by weight of melamine cyanurate MC-1 and 0.1% by weight of a dispersant was obtained.
Hereinafter, the same as Example 1 except that the resin pellets (A-1) and the dispersant were mixed first, and then the melamine cyanurate MC-1 was mixed. Thus, a polyamide resin composition pellet was obtained. The amount of gas generated at this time was small visually.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
[0028]
[Comparative Example 4]
76.5% by weight of copolymerized polyamide 66/6 resin A-1, 21.9% by weight of polyamide 6 resin B-1, 1.5% by weight of melamine cyanurate MC-1, and 0.1% by weight of dispersant % Of a polyamide composition.
Hereinafter, except that the resin pellets (A-1 and B-1) and the dispersant were mixed first and then melamine cyanurate MC-1 was mixed, the blending was performed in two steps. A polyamide resin composition pellet was obtained in the same manner as in Example 1. The amount of gas generated at this time was small visually.
The obtained pellets were examined for mechanical properties, hinge properties, and flame retardancy by the above-described measuring methods. Table 1 shows the results.
As can be seen from Examples 1 and 2 and Comparative Examples 1 to 4 in Table 1, copolymerized polyamide 66/6 resin, copolymerized polyamide 66/6 containing melamine cyanurate polymerized in the same system during polymer polymerization with polyamide 6 The resin composition reduced gas generation due to the thermal decomposition of the flame retardant, and did not substantially reduce the mechanical properties, and could significantly improve the flame retardancy and hinge properties.
[0029]
[Table 1]
【The invention's effect】
The composition of the present invention is a flame-retardant polyamide resin material, without impairing the inherent mechanical properties of the polyamide resin, chemical resistance, good moldability, electrical properties, etc., and a flame retardant by heating during extrusion or molding. It can suppress the generation of decomposition gas, improve flame retardancy and hinge characteristics, and can be suitably used for applications such as home electric parts, electronic parts, and automobile parts.
[Brief description of the drawings]
FIG. 1 is a schematic view of a molded product for evaluating hinge characteristics used in an example of the present invention.
Claims (7)
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| JP2003100698A JP4361753B2 (en) | 2003-04-03 | 2003-04-03 | Method for producing flame retardant polyamide resin composition |
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| JP2003100698A JP4361753B2 (en) | 2003-04-03 | 2003-04-03 | Method for producing flame retardant polyamide resin composition |
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| JP4361753B2 JP4361753B2 (en) | 2009-11-11 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073715A (en) * | 2013-01-17 | 2013-05-01 | 湖南工业大学 | Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6 |
| JP2017025307A (en) * | 2015-07-24 | 2017-02-02 | 旭化成株式会社 | Polyamide resin composition and molded body |
| JP2017197646A (en) * | 2016-04-27 | 2017-11-02 | 旭化成株式会社 | Polyamide resin composition and molded body |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5560525A (en) * | 1978-10-28 | 1980-05-07 | Asahi Chem Ind Co Ltd | Preparation of flame-retardant polyamide composition |
| JPS56106924A (en) * | 1980-01-31 | 1981-08-25 | Asahi Chem Ind Co Ltd | Preparation of flame-retardant polyamide |
| JPS56110725A (en) * | 1980-02-06 | 1981-09-02 | Asahi Chem Ind Co Ltd | Preparation of melamine cyanurate-containing polyamide composition |
| JPS56127620A (en) * | 1980-02-19 | 1981-10-06 | Asahi Chem Ind Co Ltd | Preparation of polyamide composition containing melamine cyanurate |
| JPS56127619A (en) * | 1980-02-19 | 1981-10-06 | Asahi Chem Ind Co Ltd | Preparation of polyamide composition containing melamine cyanurate |
| JPH1112461A (en) * | 1997-06-27 | 1999-01-19 | Mitsubishi Eng Plast Kk | Polyamide resin composition |
| JPH1126060A (en) * | 1997-06-30 | 1999-01-29 | Mitsubishi Eng Plast Kk | Connector with polyamide resin hinge |
| JPH11302533A (en) * | 1998-04-16 | 1999-11-02 | Showa Denko Kk | Molded product of flame-retardant polyamide resin |
-
2003
- 2003-04-03 JP JP2003100698A patent/JP4361753B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5560525A (en) * | 1978-10-28 | 1980-05-07 | Asahi Chem Ind Co Ltd | Preparation of flame-retardant polyamide composition |
| JPS56106924A (en) * | 1980-01-31 | 1981-08-25 | Asahi Chem Ind Co Ltd | Preparation of flame-retardant polyamide |
| JPS56110725A (en) * | 1980-02-06 | 1981-09-02 | Asahi Chem Ind Co Ltd | Preparation of melamine cyanurate-containing polyamide composition |
| JPS56127620A (en) * | 1980-02-19 | 1981-10-06 | Asahi Chem Ind Co Ltd | Preparation of polyamide composition containing melamine cyanurate |
| JPS56127619A (en) * | 1980-02-19 | 1981-10-06 | Asahi Chem Ind Co Ltd | Preparation of polyamide composition containing melamine cyanurate |
| JPH1112461A (en) * | 1997-06-27 | 1999-01-19 | Mitsubishi Eng Plast Kk | Polyamide resin composition |
| JPH1126060A (en) * | 1997-06-30 | 1999-01-29 | Mitsubishi Eng Plast Kk | Connector with polyamide resin hinge |
| JPH11302533A (en) * | 1998-04-16 | 1999-11-02 | Showa Denko Kk | Molded product of flame-retardant polyamide resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073715A (en) * | 2013-01-17 | 2013-05-01 | 湖南工业大学 | Preparation method of composite material for inorganic modified melamine chlorinated isocyanurate flame-retardant nylon 6 |
| JP2017025307A (en) * | 2015-07-24 | 2017-02-02 | 旭化成株式会社 | Polyamide resin composition and molded body |
| JP2017197646A (en) * | 2016-04-27 | 2017-11-02 | 旭化成株式会社 | Polyamide resin composition and molded body |
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| JP4361753B2 (en) | 2009-11-11 |
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