JP5080718B2 - Polyamide resin composition - Google Patents
Polyamide resin composition Download PDFInfo
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- JP5080718B2 JP5080718B2 JP2004163959A JP2004163959A JP5080718B2 JP 5080718 B2 JP5080718 B2 JP 5080718B2 JP 2004163959 A JP2004163959 A JP 2004163959A JP 2004163959 A JP2004163959 A JP 2004163959A JP 5080718 B2 JP5080718 B2 JP 5080718B2
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- polyamide resin
- resin composition
- hinge structure
- polyamide
- molded product
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- 229920006122 polyamide resin Polymers 0.000 title claims description 55
- 239000011342 resin composition Substances 0.000 title claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 11
- 239000000194 fatty acid Substances 0.000 claims description 9
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 239000000047 product Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 12
- -1 enanthractam Chemical compound 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000008117 stearic acid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 3
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 3
- 229940063655 aluminum stearate Drugs 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 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
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-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
- UKWUOTZGXIZAJC-UHFFFAOYSA-N 4-nitrosalicylic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1O UKWUOTZGXIZAJC-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- VWPQCOZMXULHDM-UHFFFAOYSA-N 9-aminononanoic acid Chemical compound NCCCCCCCCC(O)=O VWPQCOZMXULHDM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- KMJRBSYFFVNPPK-UHFFFAOYSA-K aluminum;dodecanoate Chemical class [Al+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O KMJRBSYFFVNPPK-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 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
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000003763 resistance to breakage Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 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
- 239000001993 wax Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Description
本発明は、ポリアミド樹脂組成物に関する。さらに詳しくは、結束バンドまたはヒンジ構造部を有する成形品などの製造用に好適な、ポリアミド樹脂組成物に関するものである。 The present invention relates to a polyamide resin composition. More specifically, the present invention relates to a polyamide resin composition suitable for producing a molded article having a binding band or a hinge structure.
ポリアミド樹脂は、自動車、電気・電子分野の部品類をはじめとする種々の用途に使用されている。充填材やガラス繊維などが配合されていない未強化ポリアミド樹脂組成物の主用途としては、結束バンド（後記、図１および図２参照）、ヒンジ構造部を有する成形品（後記、図３および図４参照）、特に自動車、電気・電子分野で使用されるコネクターが挙げられる。 Polyamide resins are used in various applications including parts for automobiles and electrical / electronic fields. The main application of the unreinforced polyamide resin composition in which no filler, glass fiber, or the like is blended is a molded product having a binding band (see FIG. 1 and FIG. 2) and a hinge structure (see FIG. 3, FIG. 3 and FIG. 3). 4), and particularly connectors used in the automobile and electrical / electronic fields.
原料樹脂が剛直性の高いポリアミド樹脂であり、成形品が肉厚の薄い結束バンド部や、ヒンジ構造部を有する場合には、肉薄部を折り曲げ変形するときに折れ易いので、原料樹脂に吸水処理を施して柔軟化する工夫がなされてきた。しかし、吸水処理を施しても低温環境下で使用するときは柔軟性が不十分で、ヒンジ構造部などの薄い部分で折損するというトラブルが発生していた。 If the raw material resin is a polyamide resin with high rigidity and the molded product has a thin binding band part or hinge structure part, it is easy to bend when the thin part is bent and deformed. It has been devised to make it flexible. However, even when the water absorption treatment is performed, when used in a low temperature environment, the flexibility is insufficient, and there has been a problem that the thin portion such as the hinge structure breaks.
ヒンジ構造部などの薄い部分の折損防止のため、剛直性の高いポリアミド６・６、または難燃グレードなどの改良検討がなされてきた。原料樹脂に柔軟性を付与するため、剛直性の高いポリアミド樹脂に、柔軟性を付与する成分を共重合化させる方法、ポリオレフィン系樹脂や柔軟なポリアミド樹脂を配合する方法などが提案されている。 In order to prevent breakage of a thin portion such as a hinge structure portion, improvement studies have been made on polyamides 6 and 6 having high rigidity or a flame retardant grade. In order to impart flexibility to the raw material resin, a method of copolymerizing a component imparting flexibility with a highly rigid polyamide resin, a method of blending a polyolefin-based resin or a flexible polyamide resin, and the like have been proposed.
また、結束バンドの低温折損性の改善を目的として、変性ポリオレフィンを添加した樹脂組成物（特許文献１参照）、ヨウ化カリウムを添加した樹脂組成物（特許文献２参照）、好ましくはポリアミド６・６とポリアミド６の混合物に、滑剤と結晶核剤とを配合したポリアミド樹脂組成物（特許文献３参照）などが提案されている。 In addition, for the purpose of improving the low-temperature breakability of the binding band, a resin composition to which modified polyolefin is added (see Patent Document 1), a resin composition to which potassium iodide is added (see Patent Document 2), preferably polyamide 6 · A polyamide resin composition in which a lubricant and a crystal nucleating agent are blended in a mixture of 6 and polyamide 6 (see Patent Document 3) has been proposed.
また、結束バンド部や、ヒンジ構造部を有する成形品は、ヒンジ構造部と成形品の他の部分との間に肉厚差があるので、成形品製造時に成形品を金型から離型する際にトラブル（離型性不良）が発生することがある。このような離型性不良の改良は、これまで縷々試みられてきた。例えば、ステアリン酸バリウム、ラウリン酸バリウム、ステアリン酸アルミニウムよりなる群より選ばれた一種以上の化合物を配合した樹脂組成物とする方法、炭索数１０〜２０の脂肪族カルボン酸の塩、および炭素数２２以上の脂肪族カルボン酸、またはその誘導体を配合した樹脂組成物とする方法のほか、粒径が１０μ以下の窒化ホウ素の粉末と、炭素数１５以上の脂肪族カルボン酸の誘導体とを配合したポリアミド樹脂組成物（特許文献４参照）。さらに分子末端に炭素数６〜２２の炭化水素基を有するポリアミド樹脂（特許文献５参照）、などが提案されている。
本発明は、上記従来の諸欠点を解決するために、鋭意検討の結果完成したものである。すなわち、本発明の目的は、製造時の離型性に優れて折損が発生し難い結束バンド、または、ヒンジ構造部を有する成形品の製造に好適なポリアミド樹脂組成物を提供することにある。 The present invention has been completed as a result of intensive studies in order to solve the above-described conventional drawbacks. That is, an object of the present invention is to provide a polyamide resin composition suitable for the production of a bundling band that is excellent in releasability during production and hardly breaks or a molded product having a hinge structure.
上記課題を解決するために、本発明では、ポリアミド樹脂に、炭素数１２〜２２の脂肪族カルボン酸のアルミニウム塩が配合されてなるポリアミド樹脂組成物において、ポリアミド樹脂が、末端に炭素数６〜２２の炭化水素基を有し、この炭化水素基の数が前記ポリアミド樹脂の全末端基の４０〜１００％であることを特徴とする、ポリアミド樹脂組成物を提供する。 In order to solve the above problems, in the present invention, in a polyamide resin composition in which an aluminum salt of an aliphatic carboxylic acid having 12 to 22 carbon atoms is blended with a polyamide resin, the polyamide resin has 6 to 6 carbon atoms at the terminal. There is provided a polyamide resin composition having 22 hydrocarbon groups, wherein the number of hydrocarbon groups is 40 to 100% of the total terminal groups of the polyamide resin.
本発明は以下に詳細に説明するとおりであり、次のような特別に有利な効果を奏し、その産業上の利用価値は極めて大である。
１．本発明に係るポリアミド樹脂組成物は、肉薄部を有する結束バンド、ヒンジ構造部を有する成形品などの製造時離型性に優れて折損が発生し難い。
２．本発明に係るポリアミド樹脂組成物から得られる、結束バンド、ヒンジ構造部を有する成形品は、薄肉部が優れた低温折損防止効果を発揮する。
３．本発明に係るポリアミド樹脂組成物から得られる、結束バンド、ヒンジ構造部を有する成形品は、自動車、電気・電子分野で使用される製品の品質を安定+化させ、部品の高機能化に寄与する。
The present invention is as described in detail below, and has the following particularly advantageous effects, and its industrial utility value is extremely large.
1. The polyamide resin composition according to the present invention is excellent in releasability during production of a binding band having a thin portion, a molded product having a hinge structure portion, and the like, and hardly breaks.
2. A molded product having a binding band and a hinge structure part obtained from the polyamide resin composition according to the present invention exhibits a low-temperature breakage preventing effect with an excellent thin part.
3. The molded product having a binding band and a hinge structure obtained from the polyamide resin composition according to the present invention stabilizes the quality of products used in the automobile and electrical / electronic fields, and contributes to higher functionality of parts. To do.
以下、本発明につき詳細に説明する。
本発明に係る樹脂組成物を構成するポリアミド樹脂は、３員環以上のラクタム、重合可能なω−アミノ酸、二塩基酸とジアミンなどの重縮合によって得られるポリアミド類を言う。具体的には、ε−カプロラクタム、アミノカプロン酸、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−ピベリドンなどの重合体、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、テレフタル酸、イソフタル酸、アジピン酸、セバチン酸、ドデカン二塩基酸、グルタール酸などのジカルボン酸とを重縮合させて得られる重合体、または、これらの共重合体、例えば、ポリアミド４、６、７、８、１１、１２、６・６、６・９、６・１０、６・１１、６・１２、６Ｔ、６／６・６、６／１２、６／６Ｔなどが挙げられる。ここで「・」は単量体の組合せを意味し、「／」は共重合体を意味する。この中で特にポリアミド６、ポリアミド６・６またはこれらの共重合体が好ましく、とりわけポリアミド６が好ましい。ポリアミド樹脂の好ましい粘度数は、ＩＳＯ ３０７に準拠して測定した値で９０〜１９０ｍｌ／ｇの範囲であり、特に好ましいのは９９〜１３８ｍｌ／ｇの範囲である。
Hereinafter, the present invention will be described in detail.
The polyamide resin constituting the resin composition according to the present invention refers to polyamides obtained by polycondensation of a lactam having three or more members, a polymerizable ω-amino acid, a dibasic acid and a diamine. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piberidone, hexamethylenediamine, nonamethylene Obtained by polycondensation of diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, and metaxylylenediamine with dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, and glutaric acid. Polymers, or copolymers thereof, such as
上記原料ポリアミド樹脂は、末端に炭素数６〜２２の炭化水素基を有し、この炭化水素基の数が前記ポリアミド樹脂の全末端基の４０〜１００％であるポリアミド樹脂である。このようなポリアミド系樹脂は、炭素数７〜２３のモノカルボン酸類と、炭素数６〜２２のモノアミン類、および／または、炭素数２〜２２のジアミン類、あるいは、炭素数６〜２２のモノアミン類と炭素数３〜２４のジカルボン酸類とを組合せて存在させ、重合して得られる末端が封止されたポリアミド樹脂である。これらの末端基封止剤の組合せとしては、ステアリン酸とオクタデシルアミン、ステアリン酸とヘキサメチレンジアミン、ステアリン酸とアジピン酸とステアリルアミンなどの組合せが好ましい。全末端基中の炭素数６〜２２の炭化水素基の比率は５０％以上が好ましく、より好ましいのは７０％以上である。 The raw material polyamide resin is a polyamide resin having a hydrocarbon group having 6 to 22 carbon atoms at the terminal, and the number of hydrocarbon groups is 40 to 100% of the total terminal groups of the polyamide resin. Such polyamide resins include monocarboxylic acids having 7 to 23 carbon atoms, monoamines having 6 to 22 carbon atoms, and / or diamines having 2 to 22 carbon atoms, or monoamines having 6 to 22 carbon atoms. It is a polyamide resin having a terminal end sealed obtained by polymerizing it and a dicarboxylic acid having 3 to 24 carbon atoms in combination. As a combination of these end group blocking agents, a combination of stearic acid and octadecylamine, stearic acid and hexamethylenediamine, stearic acid, adipic acid and stearylamine is preferable. The ratio of the hydrocarbon group having 6 to 22 carbon atoms in all terminal groups is preferably 50% or more, more preferably 70% or more.
上記ポリアミド樹脂には、炭素数１２〜２２の脂肪族カルボン酸のアルミニウム塩を配合する。脂肪族カルボン酸のアルミニウム塩の中で好ましいのは、ステアリン酸アルミニウム、ラウリン酸アルミニウムである。脂肪族カルボン酸のアルミニウム塩の配合量は、ポリアミド樹脂組成物の０．０１〜１重量％の範囲とする。配合量が０．０１重量％未満であると、成形品薄肉部の低温折損性の改良効果が発揮されないし、配合量が１重量％より多いと、機械的性質が低下し、低温折損性も低下する。上記範囲で好ましいのは、０．０３〜０.７重量％であり、とりわけ好ましいのは０．０５〜０．５重量％である。 The polyamide resin is blended with an aluminum salt of an aliphatic carboxylic acid having 12 to 22 carbon atoms. Among the aluminum salts of aliphatic carboxylic acids, aluminum stearate and aluminum laurate are preferred. The amount of the aliphatic carboxylic acid aluminum salt is in the range of 0.01 to 1% by weight of the polyamide resin composition. If the blending amount is less than 0.01% by weight, the effect of improving the low-temperature breakability of the thin part of the molded product will not be exhibited. descend. In the above range, 0.03 to 0.7% by weight is preferable, and 0.05 to 0.5% by weight is particularly preferable.
脂肪族カルボン酸アルミニウム塩の離型性の改良効果を補足するために、上記ポリアミド樹脂に、他の離型剤を０．００５〜０．５重量％、より好ましくは０．０１〜０．２重量％の範囲で配合することができる。他の離型剤としては、パラフィンワックス、ポリエチレンワックス、脂肪酸類、脂肪酸エステル類、ビス脂肪酸アミド類などであり、ポリアミドとの相溶性の観点から肪酸アミド類が特に好ましい。ビス脂肪酸アミド類の具体例としては、エチレンビスステアリン酸アミド、メチレンビスステアリン酸アミドが挙げられる。 In order to supplement the effect of improving the release property of the aliphatic carboxylic acid aluminum salt, another release agent is added to the polyamide resin in an amount of 0.005 to 0.5% by weight, more preferably 0.01 to 0.2%. It can mix | blend in the range of weight%. Other mold release agents include paraffin wax, polyethylene wax, fatty acids, fatty acid esters, bisfatty acid amides, and the like, and fatty acid amides are particularly preferred from the viewpoint of compatibility with polyamide. Specific examples of the bis fatty acid amides include ethylene bis stearic acid amide and methylene bis stearic acid amide.
また、上記ポリアミド樹脂組成物には、本発明の目的を損なわない範囲で、他種の樹脂や各種樹脂添加剤を、配合することができる。他の樹脂としては、ポリオレフィン系樹脂、変性ポリオレフィン系樹脂、ポリエステル系樹脂、ポリエステルエラストマー、ポリアミドエラストマー、ポリスチレン系樹脂などが挙げられる。樹脂添加剤としては、ヒンダードフェノ一ル類などの安定剤、ハロゲン化銅化合物などの耐熱性改良剤、シアヌル酸メラミンなどの難燃剤、顔料、染料、帯電防止剤などが挙げられる。しかし、結晶化を促進する核剤や無機充填剤は、特別な目的がない限り配合しない。このような著しい結晶化促進効果があり配合するのに好ましくない核剤や無機充填材としては、タルク、ワラストナイト、カオリン、焼成カオリン、マイカ、ゼオオライト、ボロンナイトライドなどが挙げられる。 In addition, other types of resins and various resin additives can be blended with the polyamide resin composition as long as the object of the present invention is not impaired. Examples of other resins include polyolefin resins, modified polyolefin resins, polyester resins, polyester elastomers, polyamide elastomers, and polystyrene resins. Examples of the resin additive include stabilizers such as hindered phenols, heat resistance improvers such as copper halide compounds, flame retardants such as melamine cyanurate, pigments, dyes, and antistatic agents. However, nucleating agents and inorganic fillers that promote crystallization are not blended unless there is a special purpose. Examples of such nucleating agents and inorganic fillers that have a remarkable crystallization promoting effect and are not preferable for blending include talc, wollastonite, kaolin, calcined kaolin, mica, zeolite, and boron nitride.
本発明に係るポリアミド樹脂組成物を調製する方法としては、（１）原料ポリアミド樹脂と炭素数１２〜２２の脂肪族カルボン酸アルミニウム塩とを所定量秤量し、要すれば、他の樹脂、樹脂添加剤などを追加配合し、ブレンダーなどで混合し、ドライブレンド物とする方法、（２）炭素数１２〜２２の脂肪族カルボン酸アルミニウム塩が多く配合されたマスターバッチを調整し、このマスターバッチを原料ポリアミド樹脂にドライブレンドする方法、または、（３）上記（１）または（２）のドライブレンド物を押出機などの溶融混練機によって溶融してペレット化する方法、などによればよい。ドライブレンド物またはペレットは、射出成形法によって目的の結束バンド（後記、図１および図２参照）や、ヒンジ構造部を有する成形品（後記、図３および図４参照）などを製造する際の原料樹脂材料として使用できる。 As a method for preparing the polyamide resin composition according to the present invention, (1) a predetermined amount of a raw material polyamide resin and an aliphatic carboxylic acid aluminum salt having 12 to 22 carbon atoms are weighed and, if necessary, other resins and resins. A method of adding additional additives, etc., and mixing with a blender to make a dry blend, (2) preparing a masterbatch containing a large number of aliphatic carboxylic acid aluminum salts having 12 to 22 carbon atoms, this masterbatch Or a method of dry blending the raw material polyamide resin into a raw material polyamide resin, or (3) a method of melting and pelletizing the dry blend of (1) or (2) with a melt kneader such as an extruder. The dry blended product or pellet is produced by producing an intended binding band (see below, FIG. 1 and FIG. 2), a molded product having a hinge structure (see below, FIG. 3 and FIG. 4), etc. by an injection molding method. It can be used as a raw material resin material.
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越えない限り、以下の記載例に制限されるものではない EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to the following description examples, unless the summary is exceeded.
実施例および比較例で使用した成分の種類と特性は、以下のとおりである。
１．ポリアミド樹脂：
（１）ＰＡ−１：ポリアミド６であって、全末端基の８５％がステアリン酸とオクタデシルアミンを導入することによって封止され、粘度数１１８ｍｌ／ｇのものである。
（２）ＰＡ−２：ポリアミド６であって、全末端基の４０％が酢酸を導入して封止され、粘度数１１８ｍｌ／ｇのものである。
The types and characteristics of the components used in the examples and comparative examples are as follows.
1. Polyamide resin:
(1) PA-1: Polyamide 6 wherein 85% of all end groups are sealed by introducing stearic acid and octadecylamine, and have a viscosity number of 118 ml / g.
(2) PA-2: Polyamide 6, in which 40% of all end groups are sealed by introducing acetic acid and have a viscosity number of 118 ml / g.
２．脂肪酸金属塩または滑剤
（３）Ａｌ：ステアリン酸アルミニウム（日本油脂社製）である。
（４）Ｃａ：ステアリン酸カルシウム（日本油脂社製）である。
（５）Ｂａ：ステアリン酸バリウム（日本油脂社製）である。
（６）Ｍｇ：ステアリン酸マグネシウム（日本油脂社製）である。
（７）ＥＢＳ：チレンビスステアリン酸アミド（花王社製）である。
2. Fatty acid metal salt or lubricant (3) Al: Aluminum stearate (manufactured by NOF Corporation).
(4) Ca: calcium stearate (manufactured by NOF Corporation).
(5) Ba: Barium stearate (manufactured by NOF Corporation).
(6) Mg: Magnesium stearate (manufactured by NOF Corporation).
(7) EBS: Tylene bis stearamide (manufactured by Kao Corporation).
実施例および比較例における樹脂組成物と成形品の評価試験は、以下に記載のとおりである。
（ａ）離型試験：射出成形機（日精樹脂工業社製、形式：ＰＳ４０）を使用して、図１および図２に示した構造を有する結束バンドと、図３および図４に示した構造を有する成形品を、以下に記載の方法で１２０ショット連続して成形して成形品を得た。得られた成形品について、結束バンドの肉薄部（図１参照）またはヒンジ構造部（図３参照）の折損、割れなどの離型トラブル発生の有無を目視観察して評価する方法である。離型トラブルの発生が認められなかったものを○、認められたものを×と判定し、評価結果を表−２に示した。
Evaluation tests of resin compositions and molded products in Examples and Comparative Examples are as described below.
(A) Mold release test: Using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., model: PS40), a binding band having the structure shown in FIGS. 1 and 2 and the structure shown in FIGS. 3 and 4 A molded product having a shape was obtained by continuously molding 120 shots by the method described below. The obtained molded product is evaluated by visually observing the occurrence of mold release troubles such as breakage and cracking of the thin portion (see FIG. 1) or the hinge structure portion (see FIG. 3) of the binding band. The case where the occurrence of the release trouble was not recognized was judged as ◯, the case where the trouble was found was judged as ×, and the evaluation results are shown in Table 2.
なお、図１は実施例、比較例で製造した結束バンドの側面略図であり、図２は平面略図である。図３は、結束バンドの低温折損性試験の実施状態を説明する際の側面略図であり、図４は実施例、比較例で製造したヒンジ構造部を有する成形品の略図であり、図５は図４に示した成形品のヒンジ構造部の拡大略図であり、図６はヒンジ構造部の低温折損性の実施状態を説明する際の側面略図である。図１ないし図３において、１は結束バンド、２はバンド部、３はバンド部挿入穴、４は突起、５は結束部であり、図４ないし図５において、６は成形品、７は厚さが０．４ｍｍのフィルムによって構成されているヒンジ構造部である。 1 is a schematic side view of a binding band manufactured in Examples and Comparative Examples, and FIG. 2 is a schematic plan view. FIG. 3 is a schematic side view for explaining an implementation state of a low-temperature breakability test for a binding band, FIG. 4 is a schematic diagram of a molded product having a hinge structure manufactured in Examples and Comparative Examples, and FIG. FIG. 6 is an enlarged schematic view of the hinge structure portion of the molded product shown in FIG. 4, and FIG. 1 to 3, 1 is a binding band, 2 is a band part, 3 is a band part insertion hole, 4 is a protrusion, 5 is a binding part, in FIGS. 4 to 5, 6 is a molded product, and 7 is a thickness. It is a hinge structure part comprised with a 0.4 mm film.
（ｂ）低温折損性（バンド）：上記（ａ）に記載の方法で製造された図１および図２に示した結束バンドを、−２５℃の恒温槽内で８時間以上放置した後、図３に側面略図として示したように、バンド部２をバンド挿入穴３に通し、バンド挿入穴３を片手で保持しながら、バンド部２の先端を図３の矢印方向に強く引っ張り、結束バンド１への割れ発生の有無を目視観察する方法である。試験は２０本の結束バンドについて行い、割れが認められた数を表−２に示す。結束バンド１の割れは、ほとんど結束部５に発生する。
(B) Low temperature breakability (band): After the binding band shown in FIG. 1 and FIG. 2 manufactured by the method described in (a) above is left in a thermostatic bath at −25 ° C. for 8 hours or more, 3, the
（ｃ）低温折損性（ヒンジ）：図３および図４に示したヒンジ構造部を有する成形品（絶乾品）２０個を、−３５℃雰囲気下で８時間以上放置した後、図４に点線で示したように、角度９０度の一回折り曲げ、ヒンジ構造部の折損の有無を目視観察する方法である。２０個の成形品の中で、ヒンジ構造部に割れが認められた数を表−２に示す。 (C) Low temperature breakage (hinge): After 20 pieces of molded products (absolutely dried products) having the hinge structure shown in FIGS. 3 and 4 were left in an atmosphere of −35 ° C. for 8 hours or longer, FIG. As indicated by the dotted line, this is a method of visually observing whether the hinge structure part is bent once or bent at an angle of 90 degrees. Table 20 shows the number of cracks observed in the hinge structure portion among the 20 molded products.
［実施例１〜実施例２、比較例１〜比較例７］
ポリアミド系樹脂、脂肪酸金属塩およびその他の添加剤を、表−１に掲げた割合で秤量し、ブレンダーで混合した。得られたドライブレンド物を原料とし、図１および図２に示した結束バンド１と、図４および図５に示したヒンジ構造部を有する成形品６を、射出成形機（日精樹脂工業社製、型式：ＰＳ４０）によって、樹脂温度２５０℃、射出時間３秒、冷却時間７秒、全サイクル１０秒の条件で、１２０シヨット以上連続成形した。得られた結束バンド１とヒンジ構造部を有する成形品６につき、上記の評価方法に準拠して、成形品製造時の離型性と、成形品の低温時折損性を評価した。評価結果を、表−２に示す。
[Example 1 to Example 2, Comparative Example 1 to Comparative Example 7]
Polyamide resin, fatty acid metal salt and other additives were weighed in the proportions listed in Table 1 and mixed with a blender. Using the obtained dry blend as a raw material, a molded product 6 having a
表−１および表−２より、つぎのことが明らかになる。
１．本発明に係るポリアミド樹脂組成物は、結束バンド、ヒンジ構造部を有する成形品製造時の離型性に優れて折損が発生し難い（実施例１〜実施例２参照）。
２．本発明に係るポリアミド樹脂組成物から得られる、結束バンド、ヒンジ構造部を有する成形品の薄肉部は、優れた低温折損防止効果を発揮する（実施例１〜実施例２参照）。
３．これに対してポリアミド樹脂が請求項１の要件を満たすものであっても、炭素数６〜２２の脂肪族カルボン酸のアルミニウム塩を配合しないものは、離型性および低温折損防止性の双方が劣る（比較例１参照）。
４．ポリアミド樹脂が請求項１の要件を満たしても、満たさなくても、炭素数６〜２２の脂肪族カルボン酸のアルミニウム塩を配合しないものは、離型性および低温折損防止性の双方が劣る（比較例２、比較例３参照）。
５．これに対してポリアミド樹脂が、請求項１の要件を満たすものであっても、炭素数６〜２２の脂肪族カルボン酸のアルミニウム塩以外の脂肪酸金属塩または滑剤を配合したものは、離型性は改良されるが低温折損防止性が劣る（比較例４〜比較例７参照）。
The following becomes clear from Table-1 and Table-2.
1. The polyamide resin composition according to the present invention is excellent in releasability at the time of producing a molded product having a binding band and a hinge structure, and hardly breaks (see Examples 1 to 2).
2. The thin-walled part of the molded article having a binding band and a hinge structure part obtained from the polyamide resin composition according to the present invention exhibits an excellent low-temperature breakage preventing effect (see Examples 1 to 2).
3. On the other hand, even if the polyamide resin satisfies the requirements of
4). Even if the polyamide resin satisfies the requirement of
5. On the other hand, even if the polyamide resin satisfies the requirements of
本発明に係る成形品は、優れた薄肉部の低温折れ防止効果を有しているので、自動車、電気電子分野に使用される結束バンドや、ヒンジ構造部を有する成形品として使用され、その品質に対する信頼性向上が図られる。 Since the molded product according to the present invention has an excellent effect of preventing the low temperature breakage of the thin-walled portion, it is used as a molded product having a binding band and a hinge structure portion used in the automobile and electric / electronic fields, and its quality. The reliability is improved.
１：結束バンド
２：バンド部
３：バンド部挿入穴
４：突起
５：結束部
６：成形品
７：ヒンジ構造部
1: Bundling band 2: Band part 3: Band part insertion hole 4: Projection 5: Bundling part 6: Molded product 7: Hinge structure part
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| JP2004163959A Expired - Lifetime JP5080718B2 (en) | 2004-06-02 | 2004-06-02 | Polyamide resin composition |
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| JP2010095291A (en) * | 2008-10-16 | 2010-04-30 | Hellermann Tyton Co Ltd | Manufacturing method of fastening band which comprises polymer alloy containing polyamide resin and polyolefin resin and fastening band |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS58157856A (en) * | 1982-03-16 | 1983-09-20 | Asahi Chem Ind Co Ltd | Polyamide resin composition |
| JPS6032845A (en) * | 1983-08-01 | 1985-02-20 | Asahi Chem Ind Co Ltd | Polyamide composition |
| JPS61163935A (en) * | 1985-01-14 | 1986-07-24 | Mitsubishi Chem Ind Ltd | Polyamide resin and production thereof |
| JP3380008B2 (en) * | 1993-09-13 | 2003-02-24 | 旭化成株式会社 | Polyamide resin composition |
| JPH10204290A (en) * | 1997-01-23 | 1998-08-04 | Unitika Ltd | Binding band made of resin |
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