JPH03182552A - Thermoplastic polyamide resin composition - Google Patents
Thermoplastic polyamide resin compositionInfo
- Publication number
- JPH03182552A JPH03182552A JP32338189A JP32338189A JPH03182552A JP H03182552 A JPH03182552 A JP H03182552A JP 32338189 A JP32338189 A JP 32338189A JP 32338189 A JP32338189 A JP 32338189A JP H03182552 A JPH03182552 A JP H03182552A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- polyamide resin
- group
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 7
- 229920006345 thermoplastic polyamide Polymers 0.000 title claims description 7
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 10
- -1 ketene dimer compound Chemical class 0.000 claims description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 238000004898 kneading Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 abstract description 24
- 229920002647 polyamide Polymers 0.000 abstract description 24
- 238000000465 moulding Methods 0.000 abstract description 11
- 229920002292 Nylon 6 Polymers 0.000 abstract description 4
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical group 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 4
- 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
- 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
- 150000004985 diamines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011191 terminal modification Methods 0.000 description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-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
- 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
- 229920001577 copolymer Polymers 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
- 239000000463 material Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 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
- QUBNFZFTFXTLKH-UHFFFAOYSA-N 2-aminododecanoic acid Chemical compound CCCCCCCCCCC(N)C(O)=O QUBNFZFTFXTLKH-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
- OZUBMBIDHPBIDL-UHFFFAOYSA-N 4-Propylcyclohexylamine Chemical compound CCCC1CCC(N)CC1 OZUBMBIDHPBIDL-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
- 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
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-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
- 125000001931 aliphatic group Chemical group 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
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 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
- 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 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
- 238000004519 manufacturing process Methods 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
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 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ケテンダイマー化合物を含み、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 ketene dimer compound and having excellent molding properties such as fluidity and high cycleability, and excellent 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、機械部
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 resin generally has excellent mechanical properties such as heat resistance, strength, rigidity, and impact resistance, as well as chemical resistance, and has good moldability, so it is used in automobile parts, electrical/electronic parts, and machinery. It is used in a wide range of applications including 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、本来酸形加工性の良好なポリ
アミド樹脂にも、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
拭みがいくっ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 the automobile, electrical, electronic, and mechanical parts mentioned above have progressed significantly, and with this, more advanced molding processing characteristics, such as good flowability and high cycle performance, are required of the resin material. Therefore, it has become necessary to further improve molding processability even for polyamide resins that originally have good acid form 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 effects have been recognized. 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. Examples include a method of obtaining polyamide, or a method of kneading and adding a specific alkyl monoepoxide to polyamide as shown in JP-A-61-207436.
〈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、短時間の熔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 in order to compensate for this, a special pressure reduction step is required in the latter half of the polymerization, which inevitably lowers 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, there are problems in that the reaction between the monoepoxide and the polyamide terminals is not completed during short-time melt-kneading, and the remaining monoepoxide compound bleeds out during heat treatment of the polyamide molded product. In other words, the current situation is that 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、十リアミドの末端
修飾用添加剤につき検討した結果、特定の有機ケテンダ
イマー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。Means for Solving the Problems In order to solve the above problems, the present inventors investigated additives for modifying the terminals of decalyamide and found that a specific organic ketene dimer compound reacts extremely efficiently with the terminals of polyamide. The inventors have discovered that a terminal-modified polyamide with excellent moldability can be obtained without problems such as bleed-out of residual materials, and has arrived at the present invention.
すなわち、本発明はポリアミド樹脂１００重量部および
下記一般式（Ｉ）で示される有機ケテンダイマー化合物
０．０１−１５重量部を混練してなる熱可塑性ポリアミ
ド樹脂組成物である。That is, the present invention is a thermoplastic polyamide resin composition prepared by kneading 100 parts by weight of a polyamide resin and 0.01-15 parts by weight of an organic ketene dimer compound represented by the following general formula (I).
Ｏ
１
Ｒ’−Ｃ−Ｃ
（Ｉ）
ＲｔＣＨ露 Ｃ−Ｏ
（ここでＲ１，Ｒ２は炭素数３〜３０の炭化水素基を表
わし、Ｒ１，Ｒｅは同じであっても翼なっていてもよい
。）
本発明で用いられる有機ケテンダイマー化合物とは炭素
数３〜３０、好ましくは７〜２６の炭化水素基をもつ有
機ケテンダイマー化合物であり、下記構造式で表わされ
るものである。O 1 R'-C-C (I) RtCH Dew C-O (Here, R1 and R2 represent a hydrocarbon group having 3 to 30 carbon atoms, and R1 and Re may be the same or form a wing. ) The organic ketene dimer compound used in the present invention is an organic ketene dimer compound having a hydrocarbon group having 3 to 30 carbon atoms, preferably 7 to 26 carbon atoms, and is represented by the following structural formula.
）（０
１
Ｒ’−Ｃ−Ｃ
（Ｉ）
ＲｔＣＨ−Ｃ−０
（ここでＲ１，Ｒ２は炭素数３〜３０の炭化水素基を表
わし、Ｒ１，Ｒ２は同じであっても翼なっていてもよい
。〉
式（Ｉ）中の置換基Ｒ１，Ｒ２は直鎖または側鎖を有す
る脂肪族炭化水素基または芳香族環を含む炭化水素基で
あり、具体例としては、プロピル基、Ｉ−プロピル基、
ｎ−ブチル基、 １−ブチル基。)(0 1 R'-C-C (I) RtCH-C-0 (Here, R1 and R2 represent a hydrocarbon group having 3 to 30 carbon atoms, and even if R1 and R2 are the same, they form a wing. Substituents R1 and R2 in formula (I) are an aliphatic hydrocarbon group having a straight chain or a side chain, or a hydrocarbon group containing an aromatic ring, and specific examples include a propyl group, I- propyl group,
n-butyl group, 1-butyl group.
ｎ−ペンチル基、ネオペンチル基、ｎ−ヘキシル基、ｎ
−ヘプチル基、ｎ−オクチル基、２−エチルフェニル基
、ｎ−デシル基、 ｉ−デシル基、ラウリル基、ミスチ
ル基、パルミチル基、ステアリル基、オレイル基、ベヘ
ニル基、ヘキンルデンル基、フェニル基、９−メチルフ
ェニルＬ ｐ−エチルフェニル基、ｐ−ｔ−ブチルフ
ェニル基などを挙げることができる。n-pentyl group, neopentyl group, n-hexyl group, n
-heptyl group, n-octyl group, 2-ethylphenyl group, n-decyl group, i-decyl group, lauryl group, mystyl group, palmityl group, stearyl group, oleyl group, behenyl group, hequineldenyl group, phenyl group, 9 -Methylphenyl L Examples include p-ethylphenyl group and pt-butylphenyl group.
本発明で用いる有機ケテンダイマー化合物の添加量は十
リアミド樹脂１００重量部に対して０゜０１〜１５重量
部である。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、離形性など
の酸形加工性改良効果が十分でないので好ましくない。The amount of the organic ketene dimer compound used in the present invention is 0.01 to 15 parts by weight per 100 parts by weight of the decalyamide resin. Preferably 0. It is 1 to 12 parts by weight. If the amount added is less than 0.01 part by weight, the effect of improving acid form processability such as fluidity and mold releasability will not be sufficient, which is not preferable.
一方、添加量が１５重量部を越えると溶融成形時の発心
あるいは成形品の耐熱性低下などの問題を生じるので好
ましく ない。On the other hand, if the amount added exceeds 15 parts by weight, problems such as centering during melt molding or a decrease in heat resistance of the molded product are undesirable.
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、＋２−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−） 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−キシリレンジアミン
、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へ牛
サン、ビス−ｐ−アミノシクロヘキシルメタン、ビス−
ｐ−アミノシクロヘキシルプロパン、インホロンジアミ
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 +2-aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2. 2. 4-/2. 2.
4-) Li-methylhexamethylene diamine, 5-
Methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-
Diamines such as p-aminocyclohexylpropane and inphorondiamine, adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1°3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid , naphthalene dicarboxylic acid, dimer acid, and other dicarboxylic acids.
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）、ポリヘ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ジアミン（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 diamine (nylon 610), and polyundecaneamide (nylon 11).
, polydodecaneamide (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 are no particular restrictions on the degree of polymerization of the polyamide used here, and the relative viscosity of a 1% sulfuric acid solution at 25°C is usually 1. Any value within the range of 5 to 5.0 can be used.
本発明の熱可塑性十リアミド樹脂組成物のＩＩ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輪の押出機、バンバリーミキサ
−ニーダ−ミキシングロールなど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１パーに投入して溶融成形す
る方法などが簡便で適している。The method II for producing the thermoplastic decalyamide 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-screw or two-wheel extruder, a Banbury mixer-kneader, etc. A method of kneading at 200 to 350° C. using a commonly known melt mixer such as a mixing roll, or a method of melt molding by putting the mixer as it is into a molding machine hopper is simple and suitable.
本発明の熱可塑性ポリアミド樹ＪＩｔ紹酸物は添加した
有機ケテンダイマーの一部はポリアミド樹脂の末端基と
反応しているが残部があり、全体として組成物となって
いるものである。In the thermoplastic polyamide JIt shoic acid product of the present invention, a part of the added organic ketene dimer reacts with the terminal group of the polyamide resin, but the remainder remains, and the composition is made as a whole.
本発明の熱可塑性組成物にはその特性を損なわない限り
において混線時、成形時に他の添加剤たとえば顔料、染
料、補強剤、充ｌＩ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 composition of the present invention may contain other additives such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, lubricants, 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緒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. The properties in the Examples and Comparative Examples were measured by the following method.
（Ｉ）ポリアミドの相対粘度：ＪＩＳ Ｋ−６８Ｏ
〈２〉末端修飾率： 添加剤導入前後のポリアミドのカ
ルボキンル末端基量をベンジルアルコール溶媒中１１５
ＯＮ ＮａＯＨで滴定定量し修飾率を算出した。(I) Relative viscosity of polyamide: JIS K-68O <2> Terminal modification rate: The amount of carboquine terminal groups of polyamide before and after introduction of additives was 115% in benzyl alcohol solvent.
The modification rate was calculated by titration with ON NaOH.
（３）？Ｉｔ勤性： シリンダー温度をポリアミドの融
点＋３０℃に設定した射出成形機を用い５００Ｋｇ ／
ｃ ｍ ２の射出圧力で８０℃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、流動性の巨資とした。(3)? Workability: 500Kg /
Thickness 1 mm set at 80 °C with injection pressure of cm 2
Injection molding was performed in a spiral mold, and the flow length was measured to determine the flowability.
（４〉離形性：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十３０
℃の７リンダ一温度、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
の離形不良が発生するまでの連続ショート数を記録して
雌形性の目安とした。(4> Mold release property: A box-shaped molded product with a length of 70 mm, a width of 60 mm, and a height of 40 mm is
Continuous molding was performed under the conditions of 7 cylinder temperature of ℃ and injection/cooling time = 10/10 seconds, and the number of consecutive shorts until mold release failure such as deformation due to ejector pins occurred was recorded to determine the female moldability. It was used as a guideline.
実施例１
相対粘度２．７０のナイロン６ペレフト１００重量部と
下記一般式（＋）式で示されるＯ
Ｉ
Ｃｌ＠５ｓｓ−Ｃ−Ｃ
（Ｉ）
Ｃ＋ａＨｓｒ ＣＨ＝ Ｃ−０
２−ヘキサデシル−３−エイコセン−３−オリド２、ｏ
ｆｃｌｌ＋をヘンンエルミキサーで混合し、得られた混
合物を３０ｍｍφ単軸押出機のホフバーに供給し、２５
０℃の混線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”Ｃ／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プリン
ダー温度２５０℃、金型！１度８０℃で流動性および離
形性を評価が判明した。Example 1 100 parts by weight of nylon 6 pellets having a relative viscosity of 2.70 and O I Cl@5ss-C-C (I) C+aHsr CH= C-0 2-hexadecyl-3- represented by the following general formula (+) eicosene-3-olide 2,o
fcll+ was mixed in a Hennel mixer, and the resulting mixture was fed to a Hofbar of a 30 mmφ single-screw extruder.
The mixture was kneaded and pelletized at a mixing temperature of 0°C. After vacuum drying the nylon 6 composition obtained here at 80"C for 16 hours, the terminal modification rate was measured and the fluidity and release properties were measured using an injection molding machine at a printer temperature of 250°C and a mold temperature of 80°C. The shape was evaluated.
したところ第１表に示す結果が得られ、ここで得られた
ポリアミド組成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。As a result, the results shown in Table 1 were obtained, and it was found that the polyamide composition obtained here was effectively end-blocked, had excellent fluidity and mold releasability, and had extremely high practical value. .
比較例１
２−へ半すデシルー３−エイコセンー３−オリドの代わ
りにドデセン−１−オキシドを用いた以外は実施＄１１
１と全く同様に混線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 Implementation $11 except that dodecene-1-oxide was used in place of 2-hemisdecyl-3-eicosene-3-olide.
When crosstalk and injection molding were carried out in exactly the same manner as in 1,
The results are shown in Table 1, and the composition obtained here has a low terminal modification rate and contains unreacted dodecene-1-
The properties were poor, with 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〈発明の効果〉
本発明のようにポリアミド樹脂に特定の有機ケテンダイ
マーを添加することにより、ポリアミドの末端が極めて
効率よく修飾され、流動性、離形性などの成形加工特性
の優れたポリアミド組成物が得られる。All of the compositions obtained here have been efficiently terminal-modified and have excellent moldability with good flowability and mold release properties. <Effects of the Invention> By adding a specific organic ketene dimer to a polyamide resin, the ends of the polyamide are modified extremely efficiently, and a polyamide composition with excellent molding properties such as fluidity and mold release properties can be obtained.
Claims (1)
で示される有機ケテンダイマー化合物０．０１〜１５重
量部を混練して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＾１、Ｒ＾２は炭素数３〜３０の炭化水素基
を表わし、Ｒ＾１、Ｒ＾２は同じであっても異なってい
てもよい。）[Claims] 100 parts by weight of polyamide resin and the following general formula (I)
A thermoplastic polyamide resin composition prepared by kneading 0.01 to 15 parts by weight of an organic ketene dimer compound represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (Here, R^1 and R^2 represent hydrocarbon groups with 3 to 30 carbon atoms, and R^1 and R^2 may be the same but different. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32338189A JPH03182552A (en) | 1989-12-12 | 1989-12-12 | Thermoplastic polyamide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32338189A JPH03182552A (en) | 1989-12-12 | 1989-12-12 | Thermoplastic polyamide resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03182552A true JPH03182552A (en) | 1991-08-08 |
Family
ID=18154117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32338189A Pending JPH03182552A (en) | 1989-12-12 | 1989-12-12 | Thermoplastic polyamide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03182552A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266166A (en) * | 1988-04-18 | 1989-10-24 | Kao Corp | Synthetic resin composition |
-
1989
- 1989-12-12 JP JP32338189A patent/JPH03182552A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266166A (en) * | 1988-04-18 | 1989-10-24 | Kao Corp | Synthetic resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS62127339A (en) | Resin composition | |
| WO2010014791A1 (en) | Heat resistant thermoplastic articles including polyhydroxy polymers | |
| JP2011012283A (en) | Composition including partially aromatic polyamide | |
| NL8400038A (en) | POLYMER MIXTURE, CONTAINING A POLYPHENYLENE ETHER AND A POLYAMIDE. | |
| JP7280146B2 (en) | Polyamide composition, method for producing the same, and molded article | |
| JPH0247154A (en) | Thermoplastic resin composition of improved heat resistance | |
| JPH05209123A (en) | Nonreinforced polyamide molding material | |
| JPH02105821A (en) | Thermoplastic polyamide composition | |
| JP6843698B2 (en) | Polyamide composition and molded product | |
| JPS62270654A (en) | Polyphenylene ether/polyamide composition and its production | |
| JP5637772B2 (en) | Polyamide welded molded product | |
| JPH03182552A (en) | Thermoplastic polyamide resin composition | |
| JP2011068876A (en) | Polyamide composition and molded product | |
| JPH0747636B2 (en) | Thermoplastic polyamide resin composition | |
| JP2016509121A (en) | Reinforced polyphthalamide / poly (phenylene ether) composition | |
| JPS6088066A (en) | Polyamide resin composition | |
| JP6042110B2 (en) | Copolyamide | |
| JPH05320501A (en) | Polyamide resin composition | |
| JP2640368B2 (en) | Polyamide resin composition | |
| JPH0463864A (en) | Resin composition | |
| JPH0827378A (en) | Production of polyamide molding | |
| JPS63241063A (en) | Resin composition | |
| JP2022156219A (en) | Polyamide composition, electric component and method for improving heat aging resistance, flowability and ion migration resistance of electric component | |
| JP3358496B2 (en) | Thermoplastic resin composition | |
| JPH04183747A (en) | Polyphenylene ether composition |