JPH02167364A - Resin composition - Google Patents
Resin compositionInfo
- Publication number
- JPH02167364A JPH02167364A JP11517289A JP11517289A JPH02167364A JP H02167364 A JPH02167364 A JP H02167364A JP 11517289 A JP11517289 A JP 11517289A JP 11517289 A JP11517289 A JP 11517289A JP H02167364 A JPH02167364 A JP H02167364A
- Authority
- JP
- Japan
- Prior art keywords
- polyamide
- resin composition
- resin
- terminal
- rubber
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 16
- 229920006380 polyphenylene oxide Polymers 0.000 claims abstract description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000005060 rubber Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 2
- 229920003052 natural elastomer Polymers 0.000 abstract description 2
- 229920001194 natural rubber Polymers 0.000 abstract description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 description 29
- 229920002647 polyamide Polymers 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- -1 poly(2,6-dimethyl-1,4-phenylene Chemical group 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 229920001955 polyphenylene ether Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical compound CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- LULCPJWUGUVEFU-UHFFFAOYSA-N Phthiocol Natural products C1=CC=C2C(=O)C(C)=C(O)C(=O)C2=C1 LULCPJWUGUVEFU-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000004615 ingredient 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 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
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリフェニレンオキサイド系樹脂とポリアミ
ド樹脂を含む樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition containing a polyphenylene oxide resin and a polyamide resin.
［従来の技術とその問題点］
ポリフェニレンオキサイドは、その浸れた機械的性質及
び電気的性質の故に成形材料用樹脂として有用であるが
、耐油性が不十分である。この点を改善するために、ポ
リフェニレンオキサイドと胴部性の良いポリアミドとを
混合することが知られている（例えば特開昭５６−１６
５２５ ）。しかし、ポリフェニレンオキサイドとポリ
アミドは互の相容性が悪いので、これらを混合した樹脂
組成物から成形した成形量において、両樹脂が本来有し
ている特性例えば良好な機械的特性が発揮されず、特に
耐衝撃性が悪いと言う問題がある。この問題を解決する
ために、ポリフェニレンオキサイドとポリアミドに不飽
和カルボン酸等を溶融混練する方法が知られている（特
開昭５６−２６９１３ ）。また、脂肪族ポリカルボン
酸等を加えることも知られている（特表昭６１−５０２
１９５＞。[Prior Art and its Problems] Polyphenylene oxide is useful as a resin for molding materials because of its strong mechanical and electrical properties, but its oil resistance is insufficient. In order to improve this point, it is known to mix polyphenylene oxide and polyamide with good body properties (for example, JP-A-56-16
525). However, since polyphenylene oxide and polyamide have poor compatibility with each other, the properties originally possessed by both resins, such as good mechanical properties, are not exhibited in the amount of molding made from a resin composition in which they are mixed. In particular, there is a problem of poor impact resistance. In order to solve this problem, a method is known in which polyphenylene oxide and polyamide are melt-kneaded with unsaturated carboxylic acid, etc. (Japanese Patent Laid-Open No. 56-26913). It is also known to add aliphatic polycarboxylic acids etc.
195>.
［発明の構成］
本発明者は、ポリフェニレンオキサイド系樹脂、ポリア
ミド樹脂、及び所望により更にゴム様物質を含む樹脂組
成物において、ポリアミドの末端アミノ基量が末端カル
ボキシル基量に比較して多いポリアミド樹脂を用いるこ
とによって、樹脂組成物から作られた成形量の機械的強
度、例えば耐衝撃性が相当に改善されることを見い出し
て本発明を完成した。[Structure of the Invention] In a resin composition containing a polyphenylene oxide resin, a polyamide resin, and optionally a rubber-like substance, the present inventor has developed a polyamide resin in which the amount of terminal amino groups in the polyamide is larger than the amount of terminal carboxyl groups. The present invention was completed based on the discovery that the mechanical strength, such as impact resistance, of a molded mass made from a resin composition can be considerably improved by using the resin composition.
すなわち、本発明は、
（Ａ）ポリフェニレンオキサイド系樹脂３０〜７０重量
部
（Ｂ）末端アミノ基量が末端カルボキシル基母に比較し
て多いポリアミド樹脂７０〜３０重量部（Ｃ）上記成分
（Ａ）及び（Ｂ）の合計１００重量部に対して０〜２０
重量部のゴム様物質
を含む樹脂組成物である。That is, the present invention comprises (A) 30 to 70 parts by weight of a polyphenylene oxide resin (B) 70 to 30 parts by weight of a polyamide resin in which the amount of terminal amino groups is larger than that of the terminal carboxyl group (C) The above component (A) and 0 to 20 parts by weight per 100 parts by weight of (B)
A resin composition containing parts by weight of a rubber-like material.
本発明において、末端アミノ基量が末端カルボキシル基
量に比べて多いポリアミドを用いることが大きな特徴で
ある。かかるポリアミドの使用により、後述するように
成形量の耐衝撃性が飛跳的に改善される。A major feature of the present invention is the use of a polyamide in which the amount of terminal amino groups is greater than the amount of terminal carboxyl groups. The use of such polyamide dramatically improves the impact resistance of the molded amount, as will be described later.
ここでポリフェニレンオキサイド系樹脂は、それ自体公
知であり、例えば一般式
〔式中Ｒ１，Ｒ２、Ｒ３並びにＲ４は水素、ハロゲン、
アルキル基、アルコキシ基、ハロゲン原子とフェニル環
との間に少くとも２個の炭素原子を有するハロアルキル
基及びハロアルコキシ基で第３級α−炭素を含まないも
のから選んだ一価置換基を示し、ｎは重合度を表す整数
である〕
で表される重合体の総称であって、上記一般式で表され
る重合体の一種単独であっても、二種以上が組合された
共重合体であってもよい。好ましい具体例ではＲ１及び
Ｒ２は炭素原子数１〜４のアルキル基であり、Ｒ３，Ｒ
４は水素もしくは炭素原子数１〜４のアルキル基である
。例えばポリ（２，６−シメチルー１，４−フェニレン
〉エーテル、ポリ（２，６−ジエチル−１，４−フエニ
レン〉エーテル、ポリ（２−メチル−６−エチル−１，
４−フエニレン）エーテル、ポリ（２−メチル−６−ブ
ロビルー１，４−フェニレン）エーテル、ポリ（２，Ｆ
ジプロピル−１，４−フェニレン）エーテル、ポリ（２
−エチル−６−ブロビルー１，４−フェニレン〉エーテ
ル等が挙げられる。Here, the polyphenylene oxide resin is known per se, and for example, the general formula [wherein R1, R2, R3 and R4 are hydrogen, halogen,
Indicates a monovalent substituent selected from alkyl groups, alkoxy groups, haloalkyl groups having at least two carbon atoms between the halogen atom and the phenyl ring, and haloalkoxy groups that do not contain a tertiary α-carbon. , n is an integer representing the degree of polymerization] is a general term for polymers represented by the above general formula, and is a copolymer that is a combination of two or more of the polymers represented by the above general formula. It may be. In a preferred embodiment, R1 and R2 are alkyl groups having 1 to 4 carbon atoms, and R3, R
4 is hydrogen or an alkyl group having 1 to 4 carbon atoms. For example, poly(2,6-dimethyl-1,4-phenylene>ether, poly(2,6-diethyl-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,
4-phenylene) ether, poly(2-methyl-6-broby-1,4-phenylene) ether, poly(2,F
dipropyl-1,4-phenylene) ether, poly(2
-ethyl-6-brobyl-1,4-phenylene>ether and the like.
特に好ましいポリフェニレンエーテル樹脂はポリ（２，
６−シメチルー１，４−フェニレン）エーテルである。A particularly preferred polyphenylene ether resin is poly(2,
6-dimethyl-1,4-phenylene) ether.
またポリフェニレンエーテル共重合体としては上記ポリ
フェニレンエーテル繰返し単位中にアルキル三置換フェ
ノール例えば２，３．６−ドリメチルフエノールを一部
含有する共重合体を挙げることができる。またこれらの
ポリフェニレンエーテルに、スチレン系化合物がグラフ
トした共重合体であってもよい。スチレン系化合物グラ
フト化ポリフェニレンエーテルとしては上記ポリフェニ
レンエーテルに、スチレン系化合物として、例えばスヂ
レン、α−メチルスチレン、ビニルトルエン、クロルス
チレン等をグラフト重合して１ｑられる共重合体である
。Examples of the polyphenylene ether copolymer include copolymers containing a portion of alkyl trisubstituted phenol, such as 2,3,6-dolimethylphenol, in the polyphenylene ether repeating unit. Alternatively, a copolymer in which a styrene compound is grafted onto these polyphenylene ethers may be used. The styrene-based compound-grafted polyphenylene ether is a copolymer obtained by graft-polymerizing a styrene-based compound such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, etc. to the above-mentioned polyphenylene ether.
ポリアミド樹脂自体は公知のものであり、例えばナイロ
ン−４、ナイロン−６、ナイロン−６，６、ナイロン−
１２、ナイロン−６，１０等が挙げられるが、これらに
限定されない。本発明において必須なことは、ポリアミ
ドの末端アミノ基量が末端カルボキシル基量に比較して
多いことである。このようなポリアミドは、ポリアミド
の重合の際に例えばカルボキシル基と反応する基を持つ
化合物例えばジアミノを余分に添加することによって得
ることができる。あるいは、ポリアミドの重合の後に、
例えばカルボキシル基と反応する基を有する化合物と反
応させることによっても１９ることかできる。Polyamide resin itself is known, such as nylon-4, nylon-6, nylon-6,6, nylon-
12, nylon-6,10, etc., but are not limited to these. What is essential in the present invention is that the amount of terminal amino groups in the polyamide is greater than the amount of terminal carboxyl groups. Such a polyamide can be obtained by adding an extra compound having a group that reacts with a carboxyl group, such as diamino, during the polymerization of the polyamide. Alternatively, after polymerization of polyamide,
For example, this can also be achieved by reacting with a compound having a group that reacts with a carboxyl group.
本発明において、ポリアミドの末端アミノ基対末端カル
ボキシル基の当量比（以下、末端基比という）が１より
大きいことが重要である。これによって、意外にも、機
械的強度が著しく改善され、比較的表面外観の優れた成
形品を与える樹脂組成物が１ｑられる。In the present invention, it is important that the equivalent ratio of terminal amino groups to terminal carboxyl groups (hereinafter referred to as terminal group ratio) of the polyamide is greater than 1. As a result, surprisingly, a resin composition with significantly improved mechanical strength and a molded article with a relatively excellent surface appearance can be produced.
通常、ポリアミド樹脂は末Ｄａ基比が１ないしはそれ以
下である。割出成型用のポリアミドにおいて、溶融粘度
を適当に調節するために重合成分に末端封止剤を加える
ことが行われているが、そのようなポリアミドの末端基
比は１より小さい。本発明に従い末端基比が１より大き
いポリアミドを用いると、末端基比が１以下のポリアミ
ドを用いた場合に比べて成形品の機械的強度が飛躍的に
良くなる。ポリアミドの末端基比の違いによってこのよ
うな顕著な違いが起ることは驚きである。末端基比は、
１．０１以上、好ましくは１．１以上、より好ましくは
１．３以上である。Usually, the polyamide resin has a terminal Da group ratio of 1 or less. In polyamides for index molding, a terminal capping agent is added to the polymerization component in order to appropriately control the melt viscosity, but the terminal group ratio of such polyamides is less than 1. When a polyamide with an end group ratio of more than 1 is used according to the present invention, the mechanical strength of the molded article is dramatically improved compared to a case where a polyamide with an end group ratio of 1 or less is used. It is surprising that such a significant difference occurs due to the difference in the end group ratio of polyamide. The end group ratio is
It is 1.01 or more, preferably 1.1 or more, more preferably 1.3 or more.
本発明において、（＾）ポリフエニレンオキザイド系樹
脂と（Ｂ）末端アミノ基量が末端カルボキシル基量に比
較して多いポリアミド樹脂は、各々３０〜７０重量部及
び７０〜３０重量部の範囲で配合される。In the present invention, (^) polyphenylene oxide-based resin and (B) polyamide resin in which the amount of terminal amino groups is larger than the amount of terminal carboxyl groups are in the range of 30 to 70 parts by weight and 70 to 30 parts by weight, respectively. It is blended with.
成分（Ｂ）がこれより多くなると成分（Ａ）自体の望ま
しい性質が実現されにくく、他方、これより少なくなる
と成分（Ｂ）を加える目的つより耐油性の改善が達成さ
れにくくなる。If the amount of component (B) is more than this, it is difficult to achieve the desired properties of component (A) itself, and on the other hand, if it is less than this, it is difficult to achieve the improvement in oil resistance that is the purpose of adding component (B).
本発明の樹脂組成物は、成形品の耐衝撃強度の一＋ｉの
向上のために、必要によりゴム様物質（Ｃ）を含むこと
ができる。The resin composition of the present invention may contain a rubber-like substance (C), if necessary, in order to improve the impact strength of the molded article (1+i).
ゴム様物質は、室温で弾性体である天然みよび合成の重
合体材料である。その具体例としては、天然ゴム、ブタ
ジェン重合体、ブタジェン−スチレン共重合体（ランダ
ム共重合体、ブロック共重合体、グラフト共重合体等、
全て含まれる。）、イソプレン重合体、クロロブタジェ
ン重合体、ブタジェン−アクリロニトリル共重合体、イ
ソブチレン重合体、イソブチレン−ブタジェン共重合体
、イソブチレン−イソプレン共重合体、アクリル酸エス
テル重合体、エチレン−プロピレン共重合体、エチレン
−プロピレン−ジエン共重合体、チオコールゴム、多硫
化ゴム、ポリウレタンゴム、ポリエーテルゴム（例えば
、ポリプロピレンオキシド等）、エビクロレオヒドリン
ゴム等が挙げられる。Rubber-like materials are natural and synthetic polymeric materials that are elastic at room temperature. Specific examples include natural rubber, butadiene polymer, butadiene-styrene copolymer (random copolymer, block copolymer, graft copolymer, etc.)
All included. ), isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic acid ester polymer, ethylene-propylene copolymer, Examples include ethylene-propylene-diene copolymer, thiocol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxide, etc.), and chlororeohydrin rubber.
これらのゴム様物質は、いかなる製造法（例えば、乳化
重合、溶液重合）、いかなる触ｔＳ＜例えば過酸化物、
トリアルキルアルミニウム、ハロゲン化リチウム、ニッ
ケル系触媒）で作られたものでもよい。更に、各種の架
橋度を有するもの、各種の割合のミクロ構造を有するも
の（例えば、シス構造、トランス構造、ビニル基等）あ
るいは、各種の平均ゴム粒径を有するものも使われる。These rubber-like materials can be produced by any method of preparation (e.g. emulsion polymerization, solution polymerization), by any treatment (e.g. peroxides,
Trialkylaluminum, lithium halide, nickel-based catalysts) may also be used. Further, rubber particles having various degrees of crosslinking, microstructures in various proportions (for example, cis structure, trans structure, vinyl group, etc.), or rubber particles having various average particle diameters may also be used.
また、共重合体は、ランダム共重合体、ブロック共重合
体、グラフト共重合体等、各種の共重合体はいずれも本
発明のゴム様物質として用いることができる。更には、
これらのゴム様物質を作るに際し、他のオレフィン類、
ジエン類、芳香族ビニル化合物、アクリル酸、アクリル
酸エステル、メタアクリル酸エステル等の単量体との共
重合も可能である。それらの共重合の方法は、ランダム
共重合、ブロック共重合、グラフト共重合等、いずれの
手法も可能である。これらの単量体の具体例としては、
例えば、エチレン、プロピレン、スチレン、クロロスチ
レン、α−メチルスチレン、ブタジェン、イソプレン、
クロロブタジェン、ブテン、イソブチレン、アクリル酸
メチル、アクリル酸、アクリル酸エチル、アクリル酸ブ
チル、メタアクリアル酸メチル、アクリロニトリル等が
挙げられる。更に、ゴム様物質の部分変成したものも用
いることができ、例えばヒドロキシまたはカルボキシ−
末端変成ポリブタジェン、部分水添スチレン−ブタジェ
ンブロック共重合体等が挙げられる。Further, any of various copolymers such as random copolymers, block copolymers, and graft copolymers can be used as the rubber-like material of the present invention. Furthermore,
In making these rubber-like substances, other olefins,
Copolymerization with monomers such as dienes, aromatic vinyl compounds, acrylic acid, acrylic esters, and methacrylic esters is also possible. Any method such as random copolymerization, block copolymerization, graft copolymerization, etc. can be used for their copolymerization. Specific examples of these monomers include:
For example, ethylene, propylene, styrene, chlorostyrene, α-methylstyrene, butadiene, isoprene,
Examples include chlorobutadiene, butene, isobutylene, methyl acrylate, acrylic acid, ethyl acrylate, butyl acrylate, methyl methacrylate, and acrylonitrile. Furthermore, partially modified rubber-like substances can also be used, such as hydroxy or carboxy-
Examples include terminal-modified polybutadiene, partially hydrogenated styrene-butadiene block copolymer, and the like.
ゴム様物質（Ｃ）は、成分（Ａ）及び（Ｂ）の合計１０
０重量部に対して０〜２０重量部加えられる。この成分
（Ｃ）は、成形品の耐衝撃性の改善のために加えられる
。この成分（Ｃ）を含まない組成物も可能である。本発
明において、成分（Ｃ）を含まない組成物から作った成
形品では、耐衝撃性の改善は相対的に小さいが、表面外
観の改善が顕著である。Rubber-like substance (C) consists of components (A) and (B) in total of 10
0 to 20 parts by weight are added to 0 parts by weight. This component (C) is added to improve the impact resistance of the molded article. Compositions that do not contain this component (C) are also possible. In the present invention, in molded articles made from compositions that do not contain component (C), the improvement in impact resistance is relatively small, but the improvement in surface appearance is remarkable.
上記した各成分（Ａ）〜（Ｃ）は、任意の順に慣用の方
法で配合し、加熱溶融して射出溶融することができる。The above-mentioned components (A) to (C) can be blended in any order by a conventional method, heated and melted, and then injection-melted.
本発明の組成物に更に他の潰用の成分、例えばガラスＩ
維、炭素繊維、カーボンブラック、シリカ、二酸化チタ
ン等の充填剤、可塑剤、難燃剤、顔料、染料等を添加す
ることができる。The compositions of the invention may further include other crushing ingredients, such as glass I.
Fillers such as carbon fiber, carbon fiber, carbon black, silica, titanium dioxide, plasticizers, flame retardants, pigments, dyes, etc. can be added.
以下、本発明を実施例により説明する。The present invention will be explained below using examples.
［実施例］
実施例１、比較例１．〜２
成分（Ａ）としてポリ（２，６−シメチルー１，４−フ
ェニレン〉エーテルを用いた。成分（Ｂ）ポリアミドと
しては、各種の末端基比を持つナイロン−６を用いた。[Example] Example 1, Comparative Example 1. ~2 Poly(2,6-dimethyl-1,4-phenylene)ether was used as component (A). Nylon-6 having various end group ratios was used as component (B) polyamide.
実施例で用いたポリアミドは、８．４ ＸＩＯ’モル／
ｇの末端アミノ基、１．８ Ｘ１０’モル／９の末端カ
ルボキシル基を持つポリアミド（分子量１３．０００）
と、４．６ ＸＩＯ’モル／ｇの末端アミノ基、７、Ｏ
ＸＩＯ’モル／ｇの末端カルボキシル基を持つポリアミ
ド（分子ｆ！ １３，０００ ＞を配合して作った。The polyamide used in the example had 8.4 XIO'mol/
Polyamide with terminal amino groups of g and terminal carboxyl groups of 1.8 x 10'mol/9 (molecular weight 13.000)
and 4.6 XIO' mol/g of terminal amino groups, 7, O
It was made by blending a polyamide (molecule f! 13,000>) with terminal carboxyl groups of XIO' mol/g.
成分（Ｃ）としてはＳＢＳ （スチレン−ブタジェン−
スチレンブロック共重合体（シェル社製カリフレックス
ＴＲｌｌ０Ｉ） ）を用いた。Component (C) is SBS (styrene-butadiene-
A styrene block copolymer (Califlex TRll0I manufactured by Shell) was used.
上記各成分を配合した配合物を減圧ベント付き二軸押出
機で２９０°Ｃの温度で押出してペレットを先ず作った
。このペレットを、シリンダー温度２８０℃、射出圧力
１．２００ Ｋ’ｊ／ ｃｒｉ、金型温度８０’Ｃに設
定した射出成形機により成形品を作った。First, pellets were made by extruding a blend of the above components at a temperature of 290°C using a twin screw extruder equipped with a vacuum vent. A molded article was made from the pellets using an injection molding machine set at a cylinder temperature of 280°C, an injection pressure of 1.200 K'j/cri, and a mold temperature of 80'C.
成形品の評価として、ＪＩＳ Ｋ ７１１０に準阻する
アイゾツトインパクトテスト（１／８″ノツチ付）を行
った。成形品の外観は肉眼で観察した。To evaluate the molded product, an Izot impact test (with a 1/8 inch notch) was conducted in accordance with JIS K 7110. The appearance of the molded product was observed with the naked eye.
ポリアミドの末端基比を種々変えた実施例の結果を表１
に示す。Table 1 shows the results of examples in which the end group ratio of polyamide was varied.
Shown below.
表中、ＰＰＯは成分（Ａ＞、ＰＡは成分（Ｂ）を指す。In the table, PPO refers to component (A>) and PA refers to component (B).
表１より、ポリアミドの末端基当量比（Ｎ １−１２／
ＣＯＯ目）が１より大きいと耐衝撃性が顕著に改善さ
れることが判る。表面外観も比較例に比べて実施例のも
のは明らかに良好であった。From Table 1, the terminal group equivalent ratio of polyamide (N 1-12/
It can be seen that when COO) is larger than 1, the impact resistance is significantly improved. The surface appearance of the Example was also clearly better than that of the Comparative Example.
比較例３
上記で用いたポリアミドはポリフェニレンオキサイドに
比べて低粘度であるので、ポリアミド中でのポリフェニ
レンオキサイドの分散が元来良くない。Comparative Example 3 Since the polyamide used above has a lower viscosity than polyphenylene oxide, the dispersion of polyphenylene oxide in the polyamide is inherently poor.
次に、ポリアミドの分子量を高くし、但し、末端基当量
比は１より小さいままとして実験を行った。用いたナイ
ロン−６の性質は次の通りである。Next, experiments were conducted in which the molecular weight of the polyamide was increased, but the end group equivalent ratio remained below 1. The properties of the nylon-6 used are as follows.
分子量 ３０．０００
末端基当量比 ０．９４
他は実施例１と同様にして成形品を作った。アイゾツト
衝撃値は、僅か２．３Ｋｌ・ｃｍ ／ ｃｍであった。Molecular weight: 30.000 End group equivalent ratio: 0.94 A molded article was produced in the same manner as in Example 1 except for the following. The Izod impact value was only 2.3 Kl·cm/cm.
以上の結論として、ポリアミドの末端基当量比が従来通
り１より小さいままでは、ポリアミドの分子量を高く設
定することによってポリフェニレンオキサイドの分散を
良くしても、耐衝撃性を改善することはできない。それ
に対し、末＠基当量比が１より大きいポリアミドを用い
た場合には、たとえそのポリアミドの分子量が大きくな
く、粘度が低いものであっても、耐衝撃性に優れ、比較
的表面外観の良い成形量を得ることができる。As a conclusion from the above, if the terminal group equivalent ratio of the polyamide remains smaller than 1 as before, the impact resistance cannot be improved even if the dispersion of polyphenylene oxide is improved by setting the molecular weight of the polyamide high. On the other hand, when a polyamide with a terminal @ group equivalent ratio of more than 1 is used, even if the polyamide does not have a large molecular weight or a low viscosity, it has excellent impact resistance and a relatively good surface appearance. The amount of molding can be obtained.
Claims (1)
重量部 （Ｂ）末端アミノ基量が末端カルボキシル基量より多い
ポリアミド樹脂７０〜３０重量部 （Ｃ）上記成分（Ａ）及び（Ｂ）の合計１００重量部に
対して０〜２０重量部のゴム様物質 を含む樹脂組成物。 ２、成分（Ｂ）の末端アミノ基対末端カルボキシル基の
当量比が１．０１以上である特許請求の範囲第１項記載
の樹脂組成物。 ３、成分（Ｂ）の末端アミノ基対末端カルボキシル基の
当量比が１．１以上である特許請求の範囲第２項記載の
樹脂組成物。 ４、成分（Ｂ）の末端アミノ基対末端カルボキシル基の
当量比が１．３以上である特許請求の範囲第３項記載の
樹脂組成物。[Claims] 1. (A) Polyphenylene oxide resin 30-70
Part by weight (B) 70 to 30 parts by weight of a polyamide resin in which the amount of terminal amino groups is greater than the amount of terminal carboxyl groups (C) 0 to 20 parts by weight of rubber based on a total of 100 parts by weight of the above components (A) and (B) A resin composition containing a similar substance. 2. The resin composition according to claim 1, wherein component (B) has an equivalent ratio of terminal amino groups to terminal carboxyl groups of 1.01 or more. 3. The resin composition according to claim 2, wherein the equivalent ratio of terminal amino groups to terminal carboxyl groups in component (B) is 1.1 or more. 4. The resin composition according to claim 3, wherein component (B) has an equivalent ratio of terminal amino groups to terminal carboxyl groups of 1.3 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115172A JPH0830144B2 (en) | 1989-05-10 | 1989-05-10 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1115172A JPH0830144B2 (en) | 1989-05-10 | 1989-05-10 | Resin composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61078383A Division JPH0692535B2 (en) | 1986-03-07 | 1986-04-07 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02167364A true JPH02167364A (en) | 1990-06-27 |
| JPH0830144B2 JPH0830144B2 (en) | 1996-03-27 |
Family
ID=14656130
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1115172A Expired - Lifetime JPH0830144B2 (en) | 1989-05-10 | 1989-05-10 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830144B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524601A (en) * | 1998-09-08 | 2002-08-06 | ゼネラル・エレクトリック・カンパニイ | Incompatible polyphenylene ether-polyamide composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57200447A (en) * | 1981-06-03 | 1982-12-08 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether resin composition |
| JPS5918756A (en) * | 1982-07-21 | 1984-01-31 | Ube Ind Ltd | Polyamide composition |
| WO1985005372A1 (en) * | 1984-05-21 | 1985-12-05 | General Electric Company | Modified polyphenylene ether-polyamide compositions and process |
-
1989
- 1989-05-10 JP JP1115172A patent/JPH0830144B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57200447A (en) * | 1981-06-03 | 1982-12-08 | Mitsubishi Petrochem Co Ltd | Polyphenylene ether resin composition |
| JPS5918756A (en) * | 1982-07-21 | 1984-01-31 | Ube Ind Ltd | Polyamide composition |
| WO1985005372A1 (en) * | 1984-05-21 | 1985-12-05 | General Electric Company | Modified polyphenylene ether-polyamide compositions and process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002524601A (en) * | 1998-09-08 | 2002-08-06 | ゼネラル・エレクトリック・カンパニイ | Incompatible polyphenylene ether-polyamide composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0830144B2 (en) | 1996-03-27 |
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