JPH0314868B2 - - Google Patents
Info
- Publication number
- JPH0314868B2 JPH0314868B2 JP2043085A JP2043085A JPH0314868B2 JP H0314868 B2 JPH0314868 B2 JP H0314868B2 JP 2043085 A JP2043085 A JP 2043085A JP 2043085 A JP2043085 A JP 2043085A JP H0314868 B2 JPH0314868 B2 JP H0314868B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- acid
- parts
- glycol
- poly
- 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.)
- Expired
Links
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 49
- 229920000642 polymer Polymers 0.000 claims description 39
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 23
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 239000011342 resin composition Substances 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 8
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 8
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 7
- 239000000806 elastomer Substances 0.000 claims description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 5
- 150000003951 lactams Chemical class 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- -1 ω-aminocaprylic acid Chemical class 0.000 description 36
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- WIHMDCQAEONXND-UHFFFAOYSA-M butyl-hydroxy-oxotin Chemical compound CCCC[Sn](O)=O WIHMDCQAEONXND-UHFFFAOYSA-M 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 2
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- UQXNEWQGGVUVQA-UHFFFAOYSA-N 8-aminooctanoic acid Chemical compound NCCCCCCCC(O)=O UQXNEWQGGVUVQA-UHFFFAOYSA-N 0.000 description 1
- WXIOPKYMMKAUEP-UHFFFAOYSA-N C(CCCCCCCCC)(C(=O)O)C(=O)O.C(CCCCCCCCCCC(=O)O)(=O)O Chemical compound C(CCCCCCCCC)(C(=O)O)C(=O)O.C(CCCCCCCCCCC(=O)O)(=O)O WXIOPKYMMKAUEP-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- LHLUQDDQLCJCFU-UHFFFAOYSA-L disodium;1-sulfocyclohexa-3,5-diene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1(C([O-])=O)CC(C([O-])=O)=CC=C1 LHLUQDDQLCJCFU-UHFFFAOYSA-L 0.000 description 1
- 239000000975 dye Substances 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
- 239000003063 flame retardant Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- XJRAOMZCVTUHFI-UHFFFAOYSA-N isocyanic acid;methane Chemical compound C.N=C=O.N=C=O XJRAOMZCVTUHFI-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
〔産業上の利用分野〕
本発明は耐摩耗性、成形加工性、柔軟性、機械
的性質のすぐれた樹脂組成物に関するものであ
る。
〔従来の技術〕
ポリマー主鎖中にポリアミド繰返し単位、ポリ
エーテル繰返し単位およびエステル結合を有する
ポリエーテルエステルアミドは公知である(米国
特許第3044987号明細書)。また、熱可塑性ポリウ
レタンエラストマーも公知である。
〔発明が解決しようとする問題点〕
ポリエーテルエステルアミドは軽量性、透明
性、低温耐衝撃性にすぐれ、また成形時にバリ、
ヒケ等が生じにくいため、各種成形用途に有望で
あるが、耐摩耗性にまだ改良の余地がある。たと
えばホース、コネクタ、電線被覆、スキーブーツ
などの用途では特に耐摩耗性が要求され、これら
の用途に対しては使用が制限されているのが現状
である。一方、熱可塑性ポリウレタンエラストマ
ーは弾性回復性、耐摩耗性、機械的強度がすぐれ
ているものの、熱安定性、耐加水分解性、成形加
工性などに劣るという問題がある。
本発明は上記問題を解決し、柔軟性、成形加工
性、耐摩耗性、機械的強度のすぐれた樹脂組成物
を提供することを目的とする。
〔問題点を解決するための手段〕
本発明の上記の目的は、炭素原子数6以上のア
ミノカルボン酸、ラクタム、及び炭素数6以上の
ジアミンとジカルボン酸の塩から選ばれる少なく
とも1種のポリアミド形成成分a、数平均分子量
300〜6000のポリ(アルキレンオキシド)グリコ
ールb、および炭素原子数4〜20のジカルボン酸
cから誘導されるポリエーテルエステルアミド
(重合体A)と熱可塑性ポリウレタンエラストマ
ー(重合体B)とからなる樹脂組成物であり、全
組成物に対して重合体Aが99〜1重量%、重合体
Bが1〜99重量%の割合で配合されている樹脂組
成物とすることによつて達成できる。
以下、本発明の構成、実施例および効果を詳し
く説明する。
本発明のポリエーテルエステルアミド(重合体
A)における炭素数が6以上のアミノカルボン酸
またはラクタムもしくは炭素数6以上のジアミン
とジカルボン酸の塩aとしては、ω−アミノカプ
ロン酸、ω−アミノエナント酸、ω−アミノカプ
リル酸、ω−アミノペラルゴン酸、ω−アミノカ
プリン酸、11−アミノウンデカン酸、12−アミノ
ドデカン酸等のアミノカルボン酸あるいはカプロ
ラクタム、エナントラクタム、カプリルラクタ
ム、ラウロラクタム等のラクタムおよびヘキサメ
チレンジアミン−アジピン酸塩、ヘキサメチレン
ジアミン−セバシン酸塩、ヘキサメチレンジアミ
ン−イソフタル酸塩、ウンデカメチレンジアミン
−アジピン酸塩、4,4′−ジアミノジシクロヘキ
シルメタン−ドデカンジ酸塩などのジアミン−ジ
カルボン酸の塩があるが、特に11−アミノウンデ
カン酸、12−アミノドデカン酸が好ましく、目的
と用途に応じてはこれらを併用して用いることも
できる。
また、ポリエーテルエステルアミドの融点を下
げたり、接着性を高めるなどの目的その他のアミ
ド形成性成分を共重合成分として用いることも少
量範囲なら許容される。
本発明のポリエーテルエステルアミド(重合体
A)におけるポリ(アルキレンオキシド)グリコ
ールbとしては、ポリエチレングリコール、ポリ
(1,2−および1,3−プロピレンオキシド)
グリコール、ポリ(テトラメチレンオキシド)グ
リコール、ポリ(ヘキサメチレンオキシド)グリ
コール、エチレンオキシドとプロピレンオキシド
のブロツク又はランダム共重合体、エチレンオキ
シドとテトラヒドロフランのブロツク又はランダ
ム共重合体などが挙げられ、就中耐熱性、耐水
性、機械的強度、弾性回復性など、すぐれたポリ
エーテルエステルアミドの物理的性質からポリ
(テトラメチレンオキシド)グリコールが好まし
く用いられる。ポリ(アルキレンオキシド)グリ
コールの数平均分子量は300〜6000の範囲で用い
うるが、重合時に粗大な相分離を起こさず、低温
特性や機械的性質がすぐれる分子量領域が選択さ
れ、この最適分子量領域はポリ(アルキレンオキ
シド)グリコールの種類によつて異なる。例え
ば、ポリエチレングリコールの場合300〜6000、
特に好ましくは1000〜4000が、ポリ(プロピレン
オキシド)グリコールの場合300〜5000、特に好
ましくは500〜3000が、またポリ(テトラメチレ
ンオキシド)グリコールの場合500〜3000、特に
好ましくは500〜2500の分子量領域のものが好ま
しく用いられる。
本発明のポリエーテルエステルアミド(重合体
A)における炭素数4〜20のジカルボン酸cとし
てはテレフタル酸、イソフタル酸、ナフタレン−
2,6−ジカルボン酸、ナフタレン−2,7−ジ
カルボン酸、ジフエニル−4,4′−ジカルボン
酸、ジフエノキシエタンジカルボン酸、3−スル
ホイソフタル酸ナトリウムのごとき芳香族ジカル
ボン酸、1,4−シクロヘキサンジカルボン酸、
1,2−シクロヘキサンジカルボン酸、ジシクロ
ヘキシル−4,4′−ジカルボン酸のごとき脂環族
ジカルボン酸、およびコハク酸、シユウ酸、アジ
ピン酸、セバシン酸、ドデカンジ酸(デカンジカ
ルボン酸)のごとき脂肪酸ジカルボン酸を挙げる
ことができる。特にテレフタル酸、イソフタル
酸、1,4−シクロヘキサンジカルボン酸、セバ
シン酸、ドデカンジ酸のようなジカルボン酸が重
合性、色調およびポリマの物理的性質の点から好
ましく用いられる。
本発明の効果が就中最も顕著に示されるために
は、ポリエーテルエステルアミド(重合体A)中
のポリ(アルキレンオキシド)グリコールbの共
重合量として5〜90重量%が好ましい。共重合量
が5重量%未満では柔軟性、弾性回復性が失わ
れ、逆に90重量%を越えると高温特性、機械的性
質が十分でない。
ポリエーテルエステルアミド(重合体A)の重
合方法は特に限定されず、公知の方法を利用する
ことができる。たとえば、アミノカルボン酸また
はラクタムaとジカルボン酸cを反応させて両末
端がカルボン酸基のポリアミドプレポリマをつく
り、これにポリ(アルキレンオキシド)グリコー
ルbを真空下に反応させる方法、あるいは上記
a,b,cの化合物を反応槽に仕込み、水の存在
下または不存在下に高温で加熱反応させることに
よりカルボン酸末端のポリアミドプレポリマを生
成させ、その後、常圧または減圧下で重合を進め
る方法が知られている。また、上記a,b,cの
化合物を同時に反応槽に仕込み、溶融重合したの
ち、高真空下で一挙に重合をすすめる方法もあ
り、むしろこの方法がポリマの着色も少なく好ま
しい。
本発明の熱可塑性ポリウレタンエラストマー
(重合体B)としては、分子量700〜8000のポリエ
チレングリコール、ポリ(1,2−および1,3
−プロピレンオキシド)グリコール、ポリ(テト
ラメチレンオキシド)グリコールのようなポリ
(アルキレンオキシド)グリコール類あるいはポ
リエチレンアジペート、ポリテトラメチレンセバ
ケート、ポリカプロラクトンのような脂肪族ポリ
エステルグリコールに、トリレンジイソシアネー
ト、ジフエニルメタンジイソシアネートのような
芳香族ジイソシアネートを反応させた末端にイソ
シアネート基を有するプレポリマーを水、エチレ
ングリコールのようなグリコールあるいはヒドラ
ジン、エチレンジアミン、プロピレンジアミンの
ようなジアミンなどで鎖延長して得られる共重合
体が使用され得る。その例として、分子量1000〜
3000のポリ(テトラメチレンオキシド)グリコー
ルまたはポリエチレンアジペートに過剰モルのジ
フエニルメタンジイソシアネートを反応させ、ヒ
ドラジンによつて鎖延長した重合体が挙げられ
る。
本発明において、ポリエーテルエステルアミド
(重合体A)と、熱可塑性ポリウレタンエラスト
マー(重合体B)との配合比は、全組成物に対し
てAが99〜1重量%、好ましくは95〜5重量%、
さらに好ましくは80〜20重量%、Bが1〜99重量
%、好ましくは5〜95重量%、さらに好ましくは
20〜80重量%となるようにする必要がある。Bが
1重量%未満では本発明の耐摩耗性が十分でな
く、また99重量%を越えると成形加工性が損われ
るので好ましくない。
本発明において、ポリエーテルエステルアミド
と熱可塑性ポリウレタンエラストマーの相溶性が
きわめて良好なことが特徴であり、通常の非相溶
系のポリマーブレンドでは本発明の効果を得るこ
とはできない。さらに、驚くべきことには、本発
明の樹脂組成物の破断強度が各成分ポリマーの破
断強度値の算術平均を上回つており、このことか
らも相溶性のよさがうかがえる。
本発明の樹脂組成物は溶融混練されていること
が好ましく、溶融混練の方法は公知の方法を用い
ることができる。例えばバンバリーミキサー、ゴ
ムロール機、一軸もしくは二軸の押出機などを用
い、通常100〜300℃の温度で溶融混練して樹脂組
成物とすることができる。
また、本発明の樹脂組成物には公知の酸化防止
剤、熱分解防止剤、紫外線吸収剤、耐加水分解改
良剤、着色剤(顔料、染料)、帯電防止剤、導電
剤、難燃剤、補強剤、充填剤、滑剤、核剤、離型
剤、可塑剤、接着助剤、粘着剤などを任意に含有
せしめることができる。
〔実施例〕
実施例 1〜9
実施例中、特にことわらない限り、部数は重量
部を意味する。
(1) 重合体Aの製造
● 重合体(A−1)の重合
ω−アミノドデカン酸81.9部、ドデカンジ酸
6.8部、および数平均分子量650のポリ(テトラメ
チレンオキシド)グリコール19.3部を“イルガノ
ツクス”1098 0.5部(酸化防止剤)とともにヘリ
カルリボン撹拌翼を備えた反応容器に仕込み、窒
素パージして260℃で1時間加熱撹拌して均質透
明溶液とした後、三酸化アンチモン触媒0.015部、
モノブチルモノヒドロキシスズオキシド触媒
0.015部、リン酸0.005部(着色防止剤)を添加
し、減圧プログラムに従つて1時間で1mmHg以
下の重合条件にもたらした。この条件にて2.5時
間反応せしめると粘稠な無色透明の溶融ポリマー
が得られ、このポリマーをガツトとして水中に吐
出すると結晶化して白化した。得られたポリエー
テルエステルアミド(A−1)は、オルトクロロ
フエノール中25℃、0.5%濃度で測定した相対粘
度(ηr)が1.81であり、DSCによる結晶融点は
167℃であつた。
● 重合体(A−2)の重合
ω−アミノドデカン酸49.1部、テレフタル酸
7.9部、数平均分子量が1020のポリ(テトラメチ
レンオキシド)グリコール48.8部、“イルガノツ
クス”1098 0.5部、三酸化アンチモン0.015部、
モノブチルモノヒドロキシスズオキシド0.015部、
およびリン酸0.005部からポリマー(A−1)と
同様の条件で重合し、相対粘度1.93、融点154℃
のポリエーテルエステルアミド(A−2)を得
た。
● 重合体(A−3)の重合
ω−アミノドデカン酸27.3部、テレフタル酸
5.7部、数平均分子量が2060のポリ(テトラメチ
レンオキシド)グリコール70.5部、“イルガノツ
クス”1098 0.5部、三酸化アンチモン0.015部、
モノブチルモノヒドロキシスズオキシド0.015部、
およびリン酸0.005部からポリマー(A−1)と
同様の条件で重合し、相対粘度1.92、融点145℃
のポリエーテルエステルアミド(A−3)を得
た。
(2) 重合体Bの製造
● 重合体(B−1)の製造
ジフエニルメタンジイソシアネート41.6部およ
び数平均分子量1400のポリ(エチレンアジペー
ト)グリコール50.9部を混合加熱し、末端にイソ
シアネート基を有するプレポリマーを得た。この
プレポリマーに鎖延長剤としてエチレンジアミン
7.5部を加え、加熱反応させることにより、MI=
5.3(200℃、2160g荷重)の重合体(B−1)を
得た。
● 重合体(B−2)の製造
ジフエニルメタンジイソシアネート36.4部、数
平均分子量1900のポリ(テトラメチレンオキシ
ド)グリコール53.0部、およびブタンジオール
10.6部から重合体(B−1)と同様に重合し、
MI=2.5(200℃、2160g荷重)の重合体(B−
2)を得た。
● 重合体(B−3)の製造
ジフエニルメタンジイソシアネート46.8部、数
平均分子量1000のポリ(ε−カプロラクトン)
40.0部およびブタンジオール13.2部から重合体
(B−1)と同様に重合し、MI=1.9(200℃、
2160g荷重)の重合体(B−3)を得た。
(3) 組成物の製造と物性測定
ポリエーテルエステルアミドブロツク共重合体
(A−1),(A−2)および(A−3)に、表に
示すポリウレタンを混合し、200℃に加熱された
30mmφの押出機で溶融混練した後ペレツト化し
た。得られたペレツトを5ozの射出能力を有する
射出成形機を使用して200℃の成形温度で、また
金型温度は40℃でJIS2号引張試験片を成形した。
引張特性はASTM D−638に、またテーバー
摩耗量はASTM D−1044(CS−17Wheel)に従
い測定した。成形サイクルは良好な成形品を得る
ための保圧時間+冷却時間とした。その結果を表
に示す。
比較例 1〜6
ポリエーテルエステルアミド(A−1),(A−
2)および(A−3)、ポリウレタン(B−1),
(B−2)および(B−3)について実施例1〜
9と同様にJIS2号引張試験片を成形し、引張特
性、テーバー摩耗性、成形サイクルを求めた。そ
の結果を表に示す。
[Industrial Application Field] The present invention relates to a resin composition having excellent wear resistance, moldability, flexibility, and mechanical properties. [Prior Art] Polyetherester amides having polyamide repeating units, polyether repeating units and ester bonds in the polymer main chain are known (US Pat. No. 3,044,987). Thermoplastic polyurethane elastomers are also known. [Problems to be solved by the invention] Polyether ester amide has excellent lightness, transparency, and low-temperature impact resistance, and also does not cause burrs or burrs during molding.
Since it does not easily cause sink marks, it is promising for various molding applications, but there is still room for improvement in wear resistance. For example, abrasion resistance is particularly required in applications such as hoses, connectors, wire sheaths, and ski boots, and currently, their use in these applications is restricted. On the other hand, although thermoplastic polyurethane elastomers have excellent elastic recovery properties, abrasion resistance, and mechanical strength, they have problems in that they are inferior in thermal stability, hydrolysis resistance, moldability, and the like. The object of the present invention is to solve the above problems and provide a resin composition with excellent flexibility, moldability, abrasion resistance, and mechanical strength. [Means for Solving the Problems] The above object of the present invention is to provide at least one polyamide selected from aminocarboxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms. Forming component a, number average molecular weight
A resin consisting of a polyether ester amide (polymer A) derived from a poly(alkylene oxide) glycol b having 300 to 6000 carbon atoms and a dicarboxylic acid c having 4 to 20 carbon atoms, and a thermoplastic polyurethane elastomer (polymer B) This can be achieved by creating a resin composition in which polymer A is blended in an amount of 99 to 1% by weight and polymer B is blended in a proportion of 1 to 99% by weight based on the total composition. Hereinafter, the configuration, embodiments, and effects of the present invention will be explained in detail. Examples of the aminocarboxylic acid or lactam having 6 or more carbon atoms or the diamine and dicarboxylic acid salt a having 6 or more carbon atoms in the polyether ester amide (polymer A) of the present invention include ω-aminocaproic acid, ω-aminoenanthic acid, , aminocarboxylic acids such as ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, or lactams such as caprolactam, enantholactam, capryllactam, laurolactam, and Diamine-dicarboxes such as hexamethylenediamine-adipate, hexamethylenediamine-sebacate, hexamethylenediamine-isophthalate, undecamethylenediamine-adipate, 4,4'-diaminodicyclohexylmethane-dodecanedioate, etc. Although there are acid salts, 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferred, and these may be used in combination depending on the purpose and use. It is also permissible to use a small amount of other amide-forming components as copolymerization components for purposes such as lowering the melting point of polyether ester amide or increasing adhesiveness. Poly(alkylene oxide) glycol b in the polyether ester amide (polymer A) of the present invention includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide)
Examples include glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, among others, heat resistance, Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as water resistance, mechanical strength, and elastic recovery. The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 300 to 6000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature properties and mechanical properties is selected, and this optimum molecular weight range is selected. varies depending on the type of poly(alkylene oxide) glycol. For example, 300 to 6000 for polyethylene glycol;
The molecular weight is particularly preferably 1000 to 4000, in the case of poly(propylene oxide) glycol 300 to 5000, particularly preferably 500 to 3000, and in the case of poly(tetramethylene oxide) glycol 500 to 3000, particularly preferably 500 to 2500. Areas are preferably used. The dicarboxylic acid c having 4 to 20 carbon atoms in the polyether ester amide (polymer A) of the present invention is terephthalic acid, isophthalic acid, naphthalene-
Aromatic dicarboxylic acids such as 2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, 1,4- cyclohexanedicarboxylic acid,
Alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and fatty acid dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid, and dodecanedioic acid (decanedicarboxylic acid). can be mentioned. In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, and dodecanedioic acid are preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. In order for the effects of the present invention to be exhibited most notably, the copolymerization amount of poly(alkylene oxide) glycol b in the polyether ester amide (polymer A) is preferably 5 to 90% by weight. If the copolymerization amount is less than 5% by weight, flexibility and elastic recovery properties will be lost, and if it exceeds 90% by weight, high temperature properties and mechanical properties will be insufficient. The method for polymerizing polyether ester amide (polymer A) is not particularly limited, and any known method can be used. For example, there is a method in which an aminocarboxylic acid or lactam a and a dicarboxylic acid c are reacted to produce a polyamide prepolymer having carboxylic acid groups at both ends, and this is reacted with poly(alkylene oxide) glycol b under vacuum, or the method described in a. A method in which a carboxylic acid-terminated polyamide prepolymer is produced by charging the compounds b and c into a reaction tank and carrying out a heating reaction at high temperature in the presence or absence of water, and then proceeding with polymerization under normal pressure or reduced pressure. It has been known. There is also a method in which the above compounds a, b, and c are simultaneously charged into a reaction tank, melt-polymerized, and then polymerized all at once under high vacuum; this method is preferable since it causes less coloring of the polymer. The thermoplastic polyurethane elastomer (polymer B) of the present invention includes polyethylene glycol, poly(1,2- and 1,3-
- Poly(alkylene oxide) glycols such as propylene oxide) glycol, poly(tetramethylene oxide) glycol, or aliphatic polyester glycols such as polyethylene adipate, polytetramethylene sebacate, polycaprolactone, tolylene diisocyanate, diphenyl A copolymer obtained by reacting an aromatic diisocyanate such as methane diisocyanate and extending the chain of a prepolymer having an isocyanate group at the end with water, a glycol such as ethylene glycol, or a diamine such as hydrazine, ethylene diamine, and propylene diamine. Coalescing may be used. As an example, molecular weight 1000~
3000 poly(tetramethylene oxide) glycol or polyethylene adipate is reacted with an excess mole of diphenylmethane diisocyanate, and the chain is extended with hydrazine. In the present invention, the blending ratio of polyether ester amide (polymer A) and thermoplastic polyurethane elastomer (polymer B) is such that A is 99 to 1% by weight, preferably 95 to 5% by weight based on the total composition. %,
More preferably 80 to 20% by weight, B 1 to 99% by weight, preferably 5 to 95% by weight, even more preferably
It is necessary to adjust the content to 20 to 80% by weight. If B is less than 1% by weight, the wear resistance of the present invention will not be sufficient, and if it exceeds 99% by weight, moldability will be impaired, which is not preferable. The present invention is characterized by extremely good compatibility between the polyether ester amide and the thermoplastic polyurethane elastomer, and the effects of the present invention cannot be obtained with ordinary incompatible polymer blends. Furthermore, surprisingly, the breaking strength of the resin composition of the present invention exceeds the arithmetic mean of the breaking strength values of each component polymer, which also indicates good compatibility. The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading using a Banbury mixer, a rubber roll machine, a single-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C. The resin composition of the present invention also includes known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (pigments, dyes), antistatic agents, conductive agents, flame retardants, and reinforcing agents. Agents, fillers, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, etc. can be optionally contained. [Examples] Examples 1 to 9 In the examples, unless otherwise specified, parts mean parts by weight. (1) Production of polymer A ● Polymerization of polymer (A-1) ω-aminododecanoic acid 81.9 parts, dodecanedioic acid
6.8 parts of poly(tetramethylene oxide) glycol and 19.3 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 650 were charged together with 0.5 parts of "Irganox" 1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated at 260°C. After heating and stirring for 1 hour to obtain a homogeneous transparent solution, 0.015 parts of antimony trioxide catalyst,
Monobutyl monohydroxytin oxide catalyst
0.015 parts of phosphoric acid and 0.005 parts of phosphoric acid (anticoloring agent) were added, and the polymerization conditions were brought to 1 mmHg or less in 1 hour according to a vacuum program. When reacted under these conditions for 2.5 hours, a viscous, colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) had a relative viscosity (ηr) of 1.81 when measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point by DSC of
It was 167℃. ● Polymerization of polymer (A-2) 49.1 parts of ω-aminododecanoic acid, terephthalic acid
7.9 parts, 48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 parts of phosphoric acid under the same conditions as polymer (A-1), relative viscosity 1.93, melting point 154℃
A polyether ester amide (A-2) was obtained. ● Polymerization of polymer (A-3) ω-aminododecanoic acid 27.3 parts, terephthalic acid
5.7 parts, 70.5 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 2060, 0.5 parts of "Irganox" 1098, 0.015 parts of antimony trioxide,
0.015 parts of monobutyl monohydroxytin oxide,
Polymerized from 0.005 parts of phosphoric acid under the same conditions as Polymer (A-1), with a relative viscosity of 1.92 and a melting point of 145°C.
A polyether ester amide (A-3) was obtained. (2) Production of Polymer B ● Production of Polymer (B-1) 41.6 parts of diphenylmethane diisocyanate and 50.9 parts of poly(ethylene adipate) glycol with a number average molecular weight of 1400 are mixed and heated to form a polymer having an isocyanate group at the end. A polymer was obtained. Ethylenediamine is added to this prepolymer as a chain extender.
By adding 7.5 parts and heating reaction, MI=
A polymer (B-1) of 5.3 (200° C., 2160 g load) was obtained. ● Production of polymer (B-2) 36.4 parts of diphenylmethane diisocyanate, 53.0 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1900, and butanediol.
Polymerize from 10.6 parts in the same manner as polymer (B-1),
Polymer (B-
2) was obtained. ● Production of polymer (B-3) 46.8 parts of diphenylmethane diisocyanate, poly(ε-caprolactone) with a number average molecular weight of 1000.
Polymerize from 40.0 parts and 13.2 parts of butanediol in the same manner as polymer (B-1), MI=1.9 (200℃,
A polymer (B-3) with a weight of 2160 g was obtained. (3) Production of composition and measurement of physical properties The polyurethane shown in the table was mixed with the polyether ester amide block copolymers (A-1), (A-2) and (A-3), and the mixture was heated to 200°C. Ta
The mixture was melt-kneaded using a 30 mmφ extruder and then pelletized. The obtained pellets were molded into JIS No. 2 tensile test pieces using an injection molding machine having a 5 oz injection capacity at a molding temperature of 200°C and a mold temperature of 40°C. Tensile properties were measured according to ASTM D-638, and Taber wear was measured according to ASTM D-1044 (CS-17Wheel). The molding cycle was a holding time + cooling time to obtain a good molded product. The results are shown in the table. Comparative Examples 1 to 6 Polyether ester amide (A-1), (A-
2) and (A-3), polyurethane (B-1),
Examples 1 to (B-2) and (B-3)
JIS No. 2 tensile test pieces were molded in the same manner as in 9, and the tensile properties, Taber abrasion resistance, and molding cycles were determined. The results are shown in the table.
【表】【table】
【表】
* 配合比は重量部を示す。
<発明の効果>
実施例1〜9にみられるように、本発明の樹脂
組成物は柔軟性、成形加工性、耐摩耗性、機械的
強度にすぐれている。[Table] *Blending ratios indicate parts by weight.
<Effects of the Invention> As seen in Examples 1 to 9, the resin composition of the present invention has excellent flexibility, moldability, abrasion resistance, and mechanical strength.
Claims (1)
タム、及び炭素数6以上のジアミンとジカルボン
酸の塩から選ばれる少なくとも1種のポリアミド
形成成分a、数平均分子量300〜6000のポリ(ア
ルキレンオキシド)グリコールb、および炭素原
子数4〜20のジカルボン酸cから誘導されたポリ
エーテルエステルアミド(重合体A)と熱可塑性
ポリウレタンエラストマー(重合体B)とからな
る樹脂組成物であつて、全組成物に対して重合体
Aが99〜1重量%、重合体Bが1〜99重量%の割
合で配合されていることを特徴とする樹脂組成
物。1 At least one polyamide-forming component a selected from aminocarboxylic acids having 6 or more carbon atoms, lactams, and salts of diamines and dicarboxylic acids having 6 or more carbon atoms, poly(alkylene oxide) glycol having a number average molecular weight of 300 to 6000 b, and a polyether ester amide (polymer A) derived from a dicarboxylic acid having 4 to 20 carbon atoms (c) and a thermoplastic polyurethane elastomer (polymer B), the resin composition comprising: A resin composition characterized in that Polymer A is blended in a proportion of 99 to 1% by weight, and Polymer B is blended in a proportion of 1 to 99% by weight.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2043085A JPS61179257A (en) | 1985-02-05 | 1985-02-05 | Resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2043085A JPS61179257A (en) | 1985-02-05 | 1985-02-05 | Resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61179257A JPS61179257A (en) | 1986-08-11 |
JPH0314868B2 true JPH0314868B2 (en) | 1991-02-27 |
Family
ID=12026821
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2043085A Granted JPS61179257A (en) | 1985-02-05 | 1985-02-05 | Resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61179257A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69112661T2 (en) * | 1990-02-13 | 1996-04-18 | Atochem Elf Sa | Process for modifying thermoplastic polyurethanes by extrusion, and modifiers used in this process. |
JP5393036B2 (en) * | 2008-02-14 | 2014-01-22 | 花王株式会社 | Thermoplastic resin composition |
-
1985
- 1985-02-05 JP JP2043085A patent/JPS61179257A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS61179257A (en) | 1986-08-11 |
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