JPH02151654A - Thermoplastic polyamide resin composition - Google Patents
Thermoplastic polyamide resin compositionInfo
- Publication number
- JPH02151654A JPH02151654A JP30710188A JP30710188A JPH02151654A JP H02151654 A JPH02151654 A JP H02151654A JP 30710188 A JP30710188 A JP 30710188A JP 30710188 A JP30710188 A JP 30710188A JP H02151654 A JPH02151654 A JP H02151654A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide resin
- polyamide
- resin composition
- acid
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920006345 thermoplastic polyamide Polymers 0.000 title claims abstract description 9
- 239000011342 resin composition Substances 0.000 title claims description 8
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 11
- -1 monooxazoline compound Chemical class 0.000 claims description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 abstract description 14
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 abstract description 4
- 229920002292 Nylon 6 Polymers 0.000 abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- XGBNRVRKSGTHJT-UHFFFAOYSA-N 2-hexadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCC1=NCCO1 XGBNRVRKSGTHJT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 239000004952 Polyamide Substances 0.000 description 27
- 229920002647 polyamide Polymers 0.000 description 27
- 239000000203 mixture Substances 0.000 description 13
- 238000004898 kneading Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000011191 terminal modification Methods 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 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
- 150000003951 lactams Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-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
- RUVBPVSYYIKNRZ-UHFFFAOYSA-N 2-(2,2-dimethylpropyl)-4,5-dihydro-1,3-oxazole Chemical compound CC(C)(C)CC1=NCCO1 RUVBPVSYYIKNRZ-UHFFFAOYSA-N 0.000 description 1
- KMWZCMUULSFFBR-UHFFFAOYSA-N 2-(4-ethylphenyl)-4,5-dihydro-1,3-oxazole Chemical compound C1=CC(CC)=CC=C1C1=NCCO1 KMWZCMUULSFFBR-UHFFFAOYSA-N 0.000 description 1
- NYTUDOKVKPJSOI-UHFFFAOYSA-N 2-(4-methylphenyl)-4,5-dihydro-1,3-oxazole Chemical compound C1=CC(C)=CC=C1C1=NCCO1 NYTUDOKVKPJSOI-UHFFFAOYSA-N 0.000 description 1
- MQSWQEJNJKRFBN-UHFFFAOYSA-N 2-(4-tert-butylphenyl)-4,5-dihydro-1,3-oxazole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=NCCO1 MQSWQEJNJKRFBN-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- VERUITIRUQLVOC-UHFFFAOYSA-N 2-butyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCC1=NCCO1 VERUITIRUQLVOC-UHFFFAOYSA-N 0.000 description 1
- NUNKLRNANFBFIP-UHFFFAOYSA-N 2-decyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCC1=NCCO1 NUNKLRNANFBFIP-UHFFFAOYSA-N 0.000 description 1
- AHWWSAKLCQMNOS-UHFFFAOYSA-N 2-docosyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCCCCCC1=NCCO1 AHWWSAKLCQMNOS-UHFFFAOYSA-N 0.000 description 1
- OWWOMMRAJBVMAC-UHFFFAOYSA-N 2-dodecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCC1=NCCO1 OWWOMMRAJBVMAC-UHFFFAOYSA-N 0.000 description 1
- AADZRTSFCAMLBV-UHFFFAOYSA-N 2-hexyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCC1=NCCO1 AADZRTSFCAMLBV-UHFFFAOYSA-N 0.000 description 1
- ZWXOPTQPMFPVNA-UHFFFAOYSA-N 2-octadecyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCCCCCCCCCCCC1=NCCO1 ZWXOPTQPMFPVNA-UHFFFAOYSA-N 0.000 description 1
- LRTZAUAUUUURAF-UHFFFAOYSA-N 2-octyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCCCCC1=NCCO1 LRTZAUAUUUURAF-UHFFFAOYSA-N 0.000 description 1
- OEENXWLHBPUUFL-UHFFFAOYSA-N 2-pentyl-4,5-dihydro-1,3-oxazole Chemical compound CCCCCC1=NCCO1 OEENXWLHBPUUFL-UHFFFAOYSA-N 0.000 description 1
- ZXTHWIZHGLNEPG-UHFFFAOYSA-N 2-phenyl-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC=C1 ZXTHWIZHGLNEPG-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- KZCVKSAXYITLRA-UHFFFAOYSA-N C(C)C(CC=1OCCN=1)CCCC Chemical compound C(C)C(CC=1OCCN=1)CCCC KZCVKSAXYITLRA-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
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyamides (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は特定の有機モノオキサゾリン化合物を含み、流
動性、ハイサイクル性などの成形加工特性および耐水性
にすぐれた熱可塑性ポリアミド樹脂組成物に関するもの
である。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a thermoplastic polyamide resin composition containing a specific organic monooxazoline compound and having excellent molding properties such as fluidity and high cycleability, and water resistance. It is something.
〈従来の技術〉
ポリアミド樹脂は一般に耐熱性や強度、剛性、耐衝撃性
などの機械的性質、耐薬品性に優れ、かつ、成形加工性
も良好なことから自動車部品、電気・電子部品、a械部
品、フィラメント、フィルムなど広範な用途に使用され
ている。<Conventional technology> Polyamide resins generally have excellent mechanical properties such as heat resistance, strength, rigidity, and impact resistance, as well as chemical resistance, and have good moldability, so they are used for automobile parts, electrical/electronic parts, a It is used in a wide range of applications, including mechanical parts, filaments, and films.
近年、上記自動車、電気、電子、機械部品の小型化、精
密化が著しく進行し、これに伴い材料樹脂にはより高度
な成形加工特性、すなわち、良流動性、ハイサイクル性
が要求されるようになり、本来成形加工性の良好なポリ
アミドm脂にも、さらに、成形加工性の向上が必要とな
ってきた。このような要求に対しポリアミド樹脂の分子
末端を適宜修飾することにより、問題を解決せんとする
試みがいくつかなされており、ある程度の効果が認めら
れている。たとえば特開昭61−163935号公報や
特開昭62−10136号公報に示されているように有
機モノアミン、または、有機モノカルボン酸の存在下に
ポリアミドの重合を行い末端に炭化水素基を有するポリ
アミドを得る方法、あるいは特開昭61−207436
号公報に示されているように特定のアルキルモノエポキ
シドをポリアミドに混練添加する方法などを例として挙
げることができる。In recent years, the miniaturization and precision of automobile, electric, electronic, and mechanical parts have progressed significantly, and with this, more advanced molding properties, such as good flowability and high cycle performance, are required of resin materials. Therefore, it has become necessary to further improve the molding processability of polyamide resins, which originally have good molding processability. In response to these demands, several attempts have been made to solve the problem by appropriately modifying the molecular terminals of polyamide resins, and some success has been observed. For example, as shown in JP-A-61-163935 and JP-A-62-10136, polyamide is polymerized in the presence of an organic monoamine or an organic monocarboxylic acid to form a hydrocarbon group at the end. Method for obtaining polyamide or JP-A-61-207436
Examples include a method of kneading and adding a specific alkyl monoepoxide to polyamide as shown in the above publication.
〈発明が解決しようとする課題〉
しかし、上記従来技術には次のような問題点がある。す
なわち、特開昭61−163935号公報や特開昭62
−10136号公報に示されるような有機モノアミン、
または、有機モノカルボン酸の存在下にポリアミド重合
する場合に重合時間が著しく長くなり、これを補うため
には重合後半に特殊な減圧工程を要することになり、製
造効率の低下が避けられない、また、特開昭61−20
7436号公報に示されるポリアミドと特定のアルキル
モノエポキシドを用いる場合、ポリアミドとモノエポキ
シドを溶融混練するという効率的な方法で組成物が得ら
れる利点はあるが、アルキルモノエポキシドの反応性が
十分でないために、短時間の溶融混練時にはモノエポキ
シドとポリアミド末端との反応が完結せず、残存するモ
ノエポキシド化合物がポリアミド成形品の熱処理時にブ
リードアウトしてくるなどの問題点がある。つまり−高
効率かつ成形加工性向上効果の高いポリアミド末端修飾
方法はまだ得られていないのが現状である。<Problems to be Solved by the Invention> However, the above prior art has the following problems. That is, JP-A-61-163935 and JP-A-62
- Organic monoamines as shown in Publication No. 10136,
Alternatively, when polyamide is polymerized in the presence of an organic monocarboxylic acid, the polymerization time becomes significantly longer, and to compensate for this, a special pressure reduction step is required in the latter half of the polymerization, which inevitably reduces production efficiency. Also, JP-A-61-20
When using the polyamide shown in Publication No. 7436 and a specific alkyl monoepoxide, there is an advantage that the composition can be obtained by an efficient method of melt-kneading the polyamide and the monoepoxide, but the reactivity of the alkyl monoepoxide is not sufficient. Therefore, during short-time melt-kneading, the reaction between the monoepoxide and the polyamide ends is not completed, and the remaining monoepoxide compound bleeds out during heat treatment of the polyamide molded product. In other words, at present, a method for modifying polyamide terminals that is highly efficient and highly effective in improving molding processability has not yet been obtained.
そこで本発明は、効率良く成形加工特性の改良を達成し
得る熱可塑性ポリアミド樹脂組成物の取得を課題とする
。Therefore, an object of the present invention is to obtain a thermoplastic polyamide resin composition that can efficiently improve molding properties.
く課題を解決するための手段〉
本発明者らは上記課題を解決すべく、ポリアミドの末端
修飾用添加剤につき検討した結果、特定の有機モノオキ
サゾリン化合物がポリアミド末端と極めて効率的に反応
し、残存物のブリードアウトなどの問題もなく成形加工
性のすぐれた末端変性ポリアミドを与えることを見出し
本発明に到達した。すなわち1本発明はポリアミド樹脂
100重量部および下記一般式(I)で示される有機モ
ノオキサゾリン化合物0.01〜15重量部よりなる熱
可塑性ポリアミド樹脂組成物、である。Means for Solving the Problems In order to solve the above problems, the present inventors investigated additives for modifying the ends of polyamides, and found that a specific organic monooxazoline compound reacts extremely efficiently with the ends of polyamides. The inventors have discovered that it is possible to provide a terminally modified polyamide with excellent moldability without problems such as bleed-out of residual materials, and have arrived at the present invention. That is, one aspect of the present invention is a thermoplastic polyamide resin composition comprising 100 parts by weight of a polyamide resin and 0.01 to 15 parts by weight of an organic monooxazoline compound represented by the following general formula (I).
\0−CH。\0-CH.
(ここでRは炭素数4〜20の炭化水素基を表わす、)
本発明で用いられる有機モノすキサゾリン化合物とは炭
素数4〜20、好ましくは7〜20の炭化水素基をもつ
モノオキサゾリン化合物であり、基本となる炭化水素基
は直鎖、または、側鎧、または、芳香族を含むことがで
きる。具体例としてはn−ブチルオキサゾリン、l−ブ
チルオキサゾリン、n−ペンチルオキサゾリン、ネオペ
ンチルオキサゾリン、n−へキシルオキサゾリン、n−
へブチルオキサゾリン、n−オクチルオキサゾリン、2
−エチルへキシルオキサゾリン、n−デシルオキサゾリ
ン、l−デシルオキサゾリン、ラウリルオキサゾリン、
ミスチルオキサゾリン、セチルオキサゾリン、ステアリ
ルオキサゾリン、オレイルオキサゾリン、ベヘニルオキ
サゾリン、ヘキシルデシルオキサゾリン、フェニルオキ
サゾリン、p−メチルフェニルオキサゾリン、p−エチ
ルフェニルオキサゾリン、p−t−ブチルフェニルオキ
サゾリンなどを挙げることができる。(Here, R represents a hydrocarbon group having 4 to 20 carbon atoms.) The organic monoxazoline compound used in the present invention is a monooxazoline compound having a hydrocarbon group having 4 to 20 carbon atoms, preferably 7 to 20 carbon atoms. and the basic hydrocarbon group can be straight chain, sidearm, or aromatic. Specific examples include n-butyloxazoline, l-butyloxazoline, n-pentyloxazoline, neopentyloxazoline, n-hexyloxazoline, n-
Hebutyloxazoline, n-octyloxazoline, 2
-ethylhexyloxazoline, n-decyloxazoline, l-decyloxazoline, lauryloxazoline,
Examples include mystyloxazoline, cetyloxazoline, stearyloxazoline, oleyloxazoline, behenyloxazoline, hexyldecyloxazoline, phenyloxazoline, p-methylphenyloxazoline, p-ethylphenyloxazoline, and p-t-butylphenyloxazoline.
本発明で用いる有機モノオキサゾリン化合物の添加量は
ポリアミド樹脂100重量部に対して0゜01〜15重
量部、好ましくは0.1〜12重量部である。添加量が
0.01重量部に満たないと流動性、鍵形性などの成形
加工性改良効果が十分でないので好ましくない、一方、
添加量が15重量部を越えると溶融成形時の発泡あるい
は成形品の耐熱性低下などの問題が生じるので好ましく
ない。The amount of the organic monooxazoline compound used in the present invention is 0.01 to 15 parts by weight, preferably 0.1 to 12 parts by weight, per 100 parts by weight of the polyamide resin. If the amount added is less than 0.01 part by weight, the effect of improving moldability such as fluidity and key shape is not sufficient, so it is not preferable.
If the amount added exceeds 15 parts by weight, problems such as foaming during melt molding or a decrease in heat resistance of the molded product may occur, which is not preferable.
本発明で用いられるポリアミド樹脂はアミノ酸、ラクタ
ム、あるいはジアミンとジカルボン酸を主たる構成成分
とするポリアミドである。構成成分の具体例を挙げると
ε−カプロラクタム、エナントラクタム、ω−ラウロラ
クタムなどのラクタム、ε−アミノカプロン酸、11−
アミノウンデカン酸、12−アミノドデカン酸などのア
ミノ酸、テトラメチレンジアミン、ヘキサメチレンジア
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、2.2.4−/2.2.4−トリメチルへキサメ
チレンジアミン、5−メチルノナメチレンジアミン、m
−−1rシリレンジアミン、P−キシリレンジアミン、
1,3−ビスアミノメチルシクロヘキサン、1.4−ビ
スアミノメチルシクロヘキサン、ビス−p−アミノシク
ロへキシルメタン、ビス−p−アミノシクロヘキシルプ
ロパン、イソホロンジアミンなどのジアミン、アジピン
酸、スペリン酸、アゼライン酸、セバシン酸、ドデカン
二酸、1.4−シクロヘキサンジカルボン酸、1゜3−
シクロヘキサンジカルボン酸、テレフタル酸、イソフタ
ル酸、ナフタレンジカルボン酸、ダイマー酸などのジカ
ルボン酸がある。The polyamide resin used in the present invention is a polyamide whose main components are an amino acid, a lactam, or a diamine and a dicarboxylic acid. Specific examples of constituent components include lactams such as ε-caprolactam, enantlactam, and ω-laurolactam, ε-aminocaproic acid, and 11-
Amino acids such as aminoundecanoic acid and 12-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2.2.4-/2.2.4-trimethylhexamethylenediamine, 5 -Methylnonamethylenediamine, m
--1r silylene diamine, P-xylylene diamine,
Diamines such as 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, isophoronediamine, adipic acid, speric acid, azelaic acid, Sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1゜3-
There are dicarboxylic acids such as cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, and dimer acid.
これらの構成成分は単独あるいは二種以上の混合物の形
で重合に供され、そうして得られるポリアミドホモポリ
マ、コポリマいずれも本発明で用いることができる。These components are subjected to polymerization either alone or in the form of a mixture of two or more, and both the polyamide homopolymer and copolymer thus obtained can be used in the present invention.
特に本発明で有用に用いられるポリアミドはポリカプロ
アミド(ナイロン6)、ポリへキサメチレンアジパミド
(ナイロン66)、ポリへキサメチレンアジパミド(ナ
イロン610)、ポリウンデカンアミド(ナイロン11
)、ポリドデカンアミド(ナイロン12)、そしてこれ
らポリアミドの共重合体および混合物である。Polyamides particularly useful in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene adipamide (nylon 610), and polyundecane amide (nylon 11).
), polydodecanamide (nylon 12), and copolymers and mixtures of these polyamides.
ここで用いられるポリアミドの重合度については特に制
限がなく、通常1%硫酸溶液の25℃における相対粘度
が1.5〜5.0の範囲内にあるものを任意に用いるこ
とができる。There is no particular restriction on the degree of polymerization of the polyamide used here, and any polyamide having a relative viscosity of 1% sulfuric acid solution at 25° C. within the range of 1.5 to 5.0 can be used.
本発明の熱可塑性ポリアミド樹脂組成物の製造法は特に
制限されないが、ポリアミド樹脂と添加剤をヘンシェル
ミキサー リボンブレンダーなどでトライブレンドした
混合物を単軸または二軸の押出機、バンバリーミキサ−
、ニーダ−、ミキシングロールなと通常公知の溶融混合
機を用いて200〜350℃で混練する方式あるいは上
記混合機をそのまま成形機ホッパーに投入して溶融成形
する方法などがfilで適している。The method for producing the thermoplastic polyamide resin composition of the present invention is not particularly limited, but a mixture obtained by tri-blending the polyamide resin and additives using a Henschel mixer, ribbon blender, etc., is prepared using a single- or twin-screw extruder, a Banbury mixer, etc.
A method of kneading at 200 to 350° C. using a commonly known melt mixer such as a kneader or a mixing roll, or a method of melt molding by putting the mixer as it is into a molding machine hopper is suitable for the fil.
本発明の熱可塑性ポリアミド樹脂組成物にはその特性を
損なわない限りにおいて混練時、成形時に他の添加剤た
とえば顔料、染料、補強剤、充填剤、耐熱剤、酸化劣化
防止剤、耐候剤、滑剤、離形剤、結晶核剤、可塑剤、難
燃剤、帯電防止剤などを添加導入することができる。The thermoplastic polyamide resin composition of the present invention may contain other additives during kneading and molding, such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, and lubricants, as long as they do not impair its properties. , a mold release agent, a crystal nucleating agent, a plasticizer, a flame retardant, an antistatic agent, etc. can be added and introduced.
本発明の熱可塑性ポリアミド樹脂組成物は流動性、離形
性にすぐれており、主として射出成形によって製造され
る。自動車部品、電気・電子部品、機械部品などに好適
に使用される。The thermoplastic polyamide resin composition of the present invention has excellent fluidity and mold releasability, and is mainly manufactured by injection molding. Suitable for use in automobile parts, electrical/electronic parts, mechanical parts, etc.
〈実施例〉
以下に実施例を示し本発明をさらに詳しく説明する。な
お、実施例および比較例中の諸特性は次の方法で測定し
た。<Example> The present invention will be explained in more detail by showing examples below. In addition, various properties in Examples and Comparative Examples were measured by the following methods.
(1)ポリアミドの相対粘度:JIS K−68(2
)末端修飾率:添加剤導入前後のポリアミドのカルボキ
シル末端基量をベンジルアルコール溶媒中115ON
NaOHで滴定定量し修飾率を算出した。(1) Relative viscosity of polyamide: JIS K-68 (2
) Terminal modification rate: The amount of carboxyl terminal groups of polyamide before and after introduction of additives was adjusted to 115ON in benzyl alcohol solvent.
The modification rate was calculated by titration with NaOH.
(3)流動性ニジリンダ−温度をポリアミドの融点+3
0℃に設定した射出成形機を用い500Kg/cdの射
出圧力で80゛Cに設定した厚さ1mmのスパイラル金
型に射出成形を行い、その流動長を測定し、流動性の目
安とした。(3) Fluidity temperature - melting point of polyamide + 3
Using an injection molding machine set at 0°C, injection molding was performed at an injection pressure of 500 kg/cd into a 1 mm thick spiral mold set at 80°C, and the flow length was measured, which was used as a measure of fluidity.
(4)離形性二縦70mm、横60mm、高さ40mm
の箱形形状の成形品をポリアミドの融点+30℃のシリ
ンダー温度、射出/冷却時間=10/10秒の条件下で
連続成形を行い、突き出しピンによる変形などの鍵形不
良が発生するまでの連続ショツト数を記録して離形性の
目安とした。(4) Mold release property 2 Length 70mm, Width 60mm, Height 40mm
A box-shaped molded product is continuously molded under the conditions of a cylinder temperature of polyamide melting point + 30°C, injection/cooling time = 10/10 seconds, and molding continues until key shape defects such as deformation due to ejector pins occur. The number of shots was recorded and used as a measure of mold releasability.
実施例1
相対粘度2.70のナイロン6ペレット100重量部と
バルミチルオキサゾリン2.0重量部をヘンシェルミキ
サーで混合し、得られた混合物を30mmφ単軸押出機
のホッパーに供給し、250℃の混練温度で混練しベレ
ット化した。ここで得られたナイロン6組成物を80℃
/16時間真空乾燥した後、末端修飾率の測定および射
出成形機を用いてシリンダー温度250℃、金型温度8
0℃で流動性および離形性を評価したところ第1表に示
す結果が得られ、ここで得られたポリアミド組放物は効
率よく末端が封鎖され、すぐれた流動性、離形性を有す
る極めて実用価値の高いものであることが判明した。Example 1 100 parts by weight of nylon 6 pellets with a relative viscosity of 2.70 and 2.0 parts by weight of valmityl oxazoline were mixed in a Henschel mixer, the resulting mixture was supplied to the hopper of a 30 mmφ single screw extruder, and the mixture was heated at 250°C. The mixture was kneaded at a kneading temperature to form pellets. The nylon 6 composition obtained here was heated at 80°C.
/ After vacuum drying for 16 hours, the terminal modification rate was measured and the cylinder temperature was 250°C and the mold temperature was 8°C using an injection molding machine.
When the fluidity and mold releasability were evaluated at 0°C, the results shown in Table 1 were obtained, and the polyamide assembly obtained here had the terminals effectively blocked and had excellent fluidity and mold releasability. It turned out to be of extremely high practical value.
比較例1
パルミチルオキサゾリンの代わりにドデセン−1−オキ
シドを用いた以外は実施例1と全く同様に混練および射
出成形を実施したところ、結果は第1表に示すとおりで
あり、ここで得られた組成物は末端修飾率が低く、しか
も未反応のドデセン−1−オキシドが金型表面を汚染す
るなど特性の劣るものであった。Comparative Example 1 Kneading and injection molding were carried out in exactly the same manner as in Example 1 except that dodecene-1-oxide was used instead of palmityloxazoline. The results are shown in Table 1. The composition had a low terminal modification rate and had poor properties such as unreacted dodecene-1-oxide contaminating the mold surface.
実施例2〜5
ポリアミドの種類、添加剤の種類および添加量を変えて
実施例1と同様の操作でポリアミド組成物を得、それら
の特性を測定し、結果を第1表にまとめて示した。Examples 2 to 5 Polyamide compositions were obtained in the same manner as in Example 1 by changing the type of polyamide, the type and amount of additives, and their properties were measured, and the results are summarized in Table 1. .
ここで得られた組成物はいずれも効率的な末端修飾がな
されており、流動性、離形性が良好な極めてすぐれた成
形加工性を有するものであることが判明した。It has been found that all of the compositions obtained here have been efficiently terminal-modified and have excellent moldability with good flowability and mold releasability.
〈発明の効果〉
本発明の目的は流動性、離形性などの成形加工性のすぐ
れた変性ポリアミド組成物を高効率で得ることである0
本発明のようにポリアミド樹脂に特定の有機モノオキサ
ゾリンを添加することにより、極めて効率よく末端修飾
された成形加工特性のすぐれたポリアミド組成物が得ら
れるようになっな。<Effects of the Invention> The purpose of the present invention is to obtain with high efficiency a modified polyamide composition having excellent molding processability such as fluidity and mold releasability.
By adding a specific organic monooxazoline to a polyamide resin as in the present invention, it becomes possible to obtain a polyamide composition that is extremely efficiently terminal-modified and has excellent molding properties.
Claims (1)
で示される有機モノオキサゾリン化合物0.01〜15
重量部よりなる熱可塑性ポリアミド樹脂組成物。 ▲数式、化学式、表等があります▼( I ) (ここでRは炭素数4〜20の炭化水素基を表わす。)[Claims] 100 parts by weight of polyamide resin and the following general formula (I)
Organic monooxazoline compound represented by 0.01 to 15
A thermoplastic polyamide resin composition consisting of parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, R represents a hydrocarbon group having 4 to 20 carbon atoms.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63307101A JPH0747636B2 (en) | 1988-12-05 | 1988-12-05 | Thermoplastic polyamide resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP63307101A JPH0747636B2 (en) | 1988-12-05 | 1988-12-05 | Thermoplastic polyamide resin composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH02151654A true JPH02151654A (en) | 1990-06-11 |
JPH0747636B2 JPH0747636B2 (en) | 1995-05-24 |
Family
ID=17965041
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP63307101A Expired - Lifetime JPH0747636B2 (en) | 1988-12-05 | 1988-12-05 | Thermoplastic polyamide resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0747636B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015511239A (en) * | 2012-02-17 | 2015-04-16 | エピテック グループ エッセ.エッレ.エッレ. | Compositions and methods for modulating amidases specific for N-acylethanolamines used in the treatment of inflammatory diseases |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0228216A (en) * | 1988-07-15 | 1990-01-30 | Kuraray Co Ltd | Production of modified polyamide(imide) |
-
1988
- 1988-12-05 JP JP63307101A patent/JPH0747636B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0228216A (en) * | 1988-07-15 | 1990-01-30 | Kuraray Co Ltd | Production of modified polyamide(imide) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015511239A (en) * | 2012-02-17 | 2015-04-16 | エピテック グループ エッセ.エッレ.エッレ. | Compositions and methods for modulating amidases specific for N-acylethanolamines used in the treatment of inflammatory diseases |
AU2012327209B2 (en) * | 2012-02-17 | 2016-05-19 | Epitech Group S.P.A. | Compositions and methods for the modulation of specific amidases for N-acylethanolamines for use in the therapy of inflammatory diseases |
Also Published As
Publication number | Publication date |
---|---|
JPH0747636B2 (en) | 1995-05-24 |
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