JPH02206648A - New resin composition - Google Patents
New resin compositionInfo
- Publication number
- JPH02206648A JPH02206648A JP2660689A JP2660689A JPH02206648A JP H02206648 A JPH02206648 A JP H02206648A JP 2660689 A JP2660689 A JP 2660689A JP 2660689 A JP2660689 A JP 2660689A JP H02206648 A JPH02206648 A JP H02206648A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- modified
- anhydride
- unsaturated
- ppe
- 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 abstract description 14
- 150000008065 acid anhydrides Chemical group 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 17
- 229920001971 elastomer Polymers 0.000 claims abstract description 17
- 239000000806 elastomer Substances 0.000 claims abstract description 17
- -1 olefin compound Chemical class 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004711 α-olefin Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 32
- 150000007513 acids Chemical class 0.000 claims description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 16
- 238000002156 mixing Methods 0.000 abstract description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 8
- 229920001577 copolymer Polymers 0.000 abstract description 5
- 150000008064 anhydrides Chemical class 0.000 abstract description 2
- 229920006380 polyphenylene oxide Polymers 0.000 abstract 2
- 150000001993 dienes Chemical class 0.000 abstract 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000004677 Nylon Substances 0.000 description 11
- 229920001778 nylon Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 4
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical group O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- GWOWVOYJLHSRJJ-UHFFFAOYSA-L cadmium stearate Chemical compound [Cd+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GWOWVOYJLHSRJJ-UHFFFAOYSA-L 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical group OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、変性ポリフェニレンエーテル樹脂及びポリア
ミド樹脂と、ステアリン酸金属塩からなる耐衝撃性、流
動性、ウェルド強度、に侵れた樹脂組成物に関するもの
であり、種々の機械的性質、耐薬品性、耐熱性に優れて
お抄、自動車分野、OA機器分野、家電・雑貨分野等に
好適な材料を提供するものである。Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin composition comprising a modified polyphenylene ether resin, a polyamide resin, and a metal stearate, which has excellent impact resistance, fluidity, and weld strength. The material is excellent in various mechanical properties, chemical resistance, and heat resistance, and is suitable for paper making, automobile fields, office automation equipment fields, home appliances and miscellaneous goods fields, etc.
(従来技術及びその問題点)
ポリフェニレンエーテル樹脂は、熱的性質、機械的性質
、電気的性質等諸性質に優れているが、溶融加工温度が
高く、かつ流動性が低いために成形加工性に劣る欠点が
ある。又、酸、アルカリ等の無機系薬品に対しては強い
抵抗性を有するが、ある種の有機溶剤に対しては溶解、
膨潤等がおこり、耐溶剤性、耐油性の改善が強く求めら
れている。(Prior art and its problems) Although polyphenylene ether resin has excellent properties such as thermal properties, mechanical properties, and electrical properties, it has poor moldability due to its high melt processing temperature and low fluidity. There are some disadvantages. In addition, it has strong resistance to inorganic chemicals such as acids and alkalis, but does not dissolve or dissolve in certain organic solvents.
Swelling occurs, and there is a strong demand for improvements in solvent resistance and oil resistance.
この成形加工性と耐油性を共に改良する試みがいくつか
為されている。例えば、ポリフェニレンエーテルにポリ
アミドを20%l、I下の量配合する方法(特公昭45
−997号公報)、ポリフェニレンエーテルにポリアミ
ドを30〜95%の範囲で配合する方法(特公昭59−
41663号公報)などがある。ポリアミドを少量配合
した場合は、成形加工性がある程度改、停されるものの
、耐油性という面からすると充分な改善とはいい難く、
また、比較的配合量が多いと耐溶剤性は改良されるもの
の、靭性が無く脆い材料にしかならない。これは、本質
的にポリフェニレンエーテル樹脂とポリアミド樹脂との
相溶性が悪いことに起因している。このポリ?エニレン
エーテル樹脂(以下、PPEと略称する。)とポリアミ
ド樹脂(以下、PAと略称する。)の相溶性を高める方
法がいくつか提案されている。Several attempts have been made to improve both moldability and oil resistance. For example, a method in which polyphenylene ether is blended with polyamide in an amount of 20% l, below I (Japanese Patent Publication No. 45
-997), a method of blending polyamide with polyphenylene ether in a range of 30 to 95% (Japanese Patent Publication No. 1983-
41663). When a small amount of polyamide is blended, the molding processability is improved or stopped to some extent, but it is difficult to say that the improvement is sufficient from the perspective of oil resistance.
Furthermore, if the amount is relatively large, the solvent resistance is improved, but the material lacks toughness and becomes brittle. This is essentially due to the poor compatibility between the polyphenylene ether resin and the polyamide resin. This poly? Several methods have been proposed to improve the compatibility between enylene ether resin (hereinafter abbreviated as PPE) and polyamide resin (hereinafter abbreviated as PA).
例えば、マレイン酸やマレイミド等の分子内に炭素−炭
素二重結合とカルボン酸基、酸無水物基、酸アミド基、
イミド基等の官能基を有する化合物を第三成分として配
合する方法(特開昭56−26913号公報)、スチレ
ン系化合物とα、β−不飽和ジカルボン酸との共重合体
を配合する方法(特公昭59−33614号公報)など
がある。無水マレイン酸やマレイミドを第三成分として
配合しても充分なる相溶性の改善は為し得ず、射出成形
のような高温、高速成形では、層状剥離、外観不良を呈
し、しかも充分なる靭性を有する材料が得がたい。また
、無水マレイン酸とスチレンの共重合体を配合する場合
には、耐熱性が低下する。For example, in molecules such as maleic acid and maleimide, carbon-carbon double bonds and carboxylic acid groups, acid anhydride groups, acid amide groups,
A method of blending a compound having a functional group such as an imide group as a third component (JP-A-56-26913), a method of blending a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid ( Japanese Patent Publication No. 59-33614). Even if maleic anhydride or maleimide is added as a third component, the compatibility cannot be sufficiently improved, and in high-temperature, high-speed molding such as injection molding, delamination and poor appearance occur, and moreover, sufficient toughness is not achieved. It is difficult to obtain materials that have Furthermore, when a copolymer of maleic anhydride and styrene is blended, heat resistance decreases.
PPEに酸無水物構造を有する1、2−置換オレフィン
化合物を無触媒下熱的に反応せしめた変性ポリ21ニレ
ンエーテル樹脂(以下、変性PPEと略称する)にPA
を配合すると、未変性のPPEとPAの配合の場合と異
な秒、広い組成!!!囲において靭性のある樹脂組成物
が得られることが知られている。(特開昭62−132
924)。PA is added to a modified poly-21 nylene ether resin (hereinafter abbreviated as modified PPE) obtained by thermally reacting a 1,2-substituted olefin compound having an acid anhydride structure with PPE (hereinafter referred to as modified PPE).
When blended with , the composition is different from that of unmodified PPE and PA, and the composition is wide! ! ! It is known that a resin composition with good toughness can be obtained when (Unexamined Japanese Patent Publication No. 62-132
924).
しかしながら、この樹脂組成物は、耐衝撃性の一つの測
定法である、ノツチ付アイゾツト衝撃強度において極め
て低い値しか得られない。However, this resin composition provides only an extremely low value in notched Izot impact strength, which is one method of measuring impact resistance.
アイゾツト衝撃強度の改良を間約として種々のエラスト
マーを添加することが試みられているが必ずしも充分と
は言えない。また、エラストマーを添加することにより
初期のアイゾツト衝撃強度は改良されるものの、高温雰
囲気環境ではアイゾツト衝撃強度が著しく低下したり、
更に射出成形時の熱安定性が悪いと言う欠点がある。Attempts have been made to add various elastomers to improve the Izod impact strength, but this is not always sufficient. In addition, although the initial Izot impact strength is improved by adding an elastomer, the Izot impact strength decreases significantly in a high-temperature atmosphere environment.
Furthermore, it has the disadvantage of poor thermal stability during injection molding.
本発明者らは、この変性PPE、PA、及びエラストマ
ーから成る樹脂組成物の耐衝撃性、耐熱性、射出成形時
の熱安定性を改善すべく鋭意検討した結果、PPEを特
定のエラストマーの共存下に酸無水物構造を有する1、
2−置換オレフィン化合物と溶融状態で反応せしめた変
性PPEとPAを混合することによハ、上記の欠点が著
しく改良されることを見い出し先に特許出願した。The present inventors have conducted intensive studies to improve the impact resistance, heat resistance, and thermal stability during injection molding of resin compositions made of modified PPE, PA, and elastomers. 1, which has an acid anhydride structure below;
They discovered that the above-mentioned drawbacks can be significantly improved by mixing PA with modified PPE reacted with a 2-substituted olefin compound in the molten state, and filed a patent application.
即ち特定のエラストマーとして、水素添加A−B−A型
ブロック共重合弾性体(ここで、Aはビニル芳香族炭化
水素の重合体ブロックをBは共役ジエン系炭化水素化合
物の重合体ブロックを意味する)及び又は、不飽和酸無
水物及び不飽和酸から選ばれた少なくとも一種で変性さ
れたエチレン−α−オレフィン系共重合体を用いるとア
イゾツト衝撃強度が著しく改善されるのである。That is, as a specific elastomer, a hydrogenated A-B-A type block copolymer elastomer (where A means a polymer block of a vinyl aromatic hydrocarbon and B means a polymer block of a conjugated diene hydrocarbon compound) ) and/or an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids, the Izod impact strength is significantly improved.
(発明が解決しようとする問題点)
然しなからこれらの組成物はアイゾツト衝撃強度は優れ
ているが面衝撃強度は必ずしも充分ではない。又大型成
形を行う場合に要求される流動性、ウェルド強度につい
ても満足できるものではない。(Problems to be Solved by the Invention) However, although these compositions have excellent isot impact strength, their surface impact strength is not necessarily sufficient. Furthermore, the fluidity and weld strength required for large-scale molding are not satisfactory.
即ちアイゾツト衝撃強度、面衝撃強度、流動性、及びウ
ェルド強度に優れた材料が強く要望されているのである
。That is, there is a strong demand for materials with excellent isot impact strength, surface impact strength, fluidity, and weld strength.
(問題点を解決するための手段)
本発明者らはこのPPE、PA及びエラストマーからな
る樹脂組成物の上記欠点を改善すべく鋭意検討した結果
、更にステアリン酸金属塩を添加することによって面衝
撃強度、流動性、ウェルド強度が著しく改善されること
を見い出し本発明を完成したものである。(Means for Solving the Problems) As a result of intensive studies by the present inventors to improve the above-mentioned drawbacks of the resin composition made of PPE, PA, and elastomer, the inventors found that by further adding a stearic acid metal salt, surface impact The present invention was completed by discovering that strength, fluidity, and weld strength were significantly improved.
即ち、本発明は、
■ 変性ポリフェニレンエーテル樹脂
(b) ポリアミド樹脂
(c) ステアリン酸金属塩
からなる組成物でありでここで(2)成分は一般式(式
中、R1は炭素数1〜3の低級アルキル基、R2、Rs
は水素原子又は炭素数1〜3の低級アルキル基である。That is, the present invention is a composition consisting of (1) a modified polyphenylene ether resin (b), a polyamide resin (c), and a stearic acid metal salt, where the component (2) is represented by the general formula (wherein R1 has 1 to 3 carbon atoms). lower alkyl group, R2, Rs
is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms.
)
で表わされる構造単位を主鎖に持つポリフェニレンエー
テル樹脂を水素添加A−B−A型ブロック共重合弾性体
(ここで、Aはビニル芳香族炭化水素の重合ブロックを
、ぢは共役ジエン系炭化水素化合物の重合体ブロックを
意味する)及び又は、不飽和酸無水物及び不飽和酸から
選ばれた少なくとも一種で変性されたエチレン−α−オ
レフィン系共重合体の共存下に酸無水物構造を有する1
、2−置換オレフィン化合物と溶融状態で反応せしめて
得られる変性ポリフェニレンエーテル樹脂であることを
特徴とする熱可塑性樹脂組成物である。) Hydrogenated A-B-A type block copolymer elastomer of polyphenylene ether resin having a structural unit represented by (meaning a polymer block of a hydrogen compound) and/or an acid anhydride structure in the coexistence of an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. have 1
, a thermoplastic resin composition characterized in that it is a modified polyphenylene ether resin obtained by reacting it with a 2-substituted olefin compound in a molten state.
ここで本発明の樹脂組成物に用いられるポリフェニレン
エーテル樹脂(P P E) +t、 一般式(式中、
R1は炭素数1〜3の低級アルキル基、R2、R3は水
素原子又は炭素数1〜3の低級アルキル基である。)
で表わされる構造単位を主鎖にもつ重合体であって、ホ
モポリマーであってもコポリマーであってもよく、具体
的には、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(2,6−ジプロビルー
1.4−)ユニレン)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−6−6−プロピル、−1、4−フェニレン)
エーテル等があげられるが、特に、ポリ(2#6−シメ
チルー1.4−フェニレン)エーテル、2#6−シメチ
ルフエノール/2,3.6−)リメチルフェノール共重
合体が好ましい。又PPEと反応させる、酸無水物構造
を有する1、2−置換オレフィン化合物としては、例え
ば、無水マレイン酸、無水イタコン酸、無水シトラコン
酸等があげられ、特に無水マレイン酸が好ましい。Here, the polyphenylene ether resin (P P E) +t used in the resin composition of the present invention, general formula (in the formula,
R1 is a lower alkyl group having 1 to 3 carbon atoms, and R2 and R3 are a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) A polymer having a structural unit represented by Ether, poly(2,6-diethyl-1,4
-phenylene) ether, poly(2,6-diprobyl-1,4-)unilene) ether, poly(2-methyl-6)
-ethyl-1,4-phenylene)ether, poly(2
-methyl-6-6-propyl, -1,4-phenylene)
Among them, poly(2#6-dimethyl-1,4-phenylene)ether and 2#6-dimethylphenol/2,3.6-)limethylphenol copolymer are particularly preferred. Examples of the 1,2-substituted olefin compound having an acid anhydride structure to be reacted with PPE include maleic anhydride, itaconic anhydride, citraconic anhydride, and maleic anhydride is particularly preferred.
次に本発明の樹脂組成物に用いられる水素添加ブロック
共重合弾性体は、A−B−A型の構造をしてお9、At
dよびBはそれぞれ重合体ブロックを示し、中心ブロッ
クBは、共役ジエン系炭化水素化合物、通常はブタジェ
ンの重合体から成や水素添加する前はポリブタジェンブ
ロックであるが、水素添加することにより、ポリブタジ
ェン中の二重結合が飽和炭化水素に転化されているブロ
ックであゆ、末端ブロックAはビニル芳香族炭化水素の
重合体ブロックを示し、好適にはポリスチレンからなる
ブロックである。Next, the hydrogenated block copolymer elastomer used in the resin composition of the present invention has an A-B-A structure.
d and B each indicate a polymer block, and the central block B is composed of a conjugated diene hydrocarbon compound, usually a polymer of butadiene, and is a polybutadiene block before hydrogenation, but by hydrogenation. , a block in which the double bonds in polybutadiene are converted into saturated hydrocarbons, and the terminal block A represents a polymer block of vinyl aromatic hydrocarbon, preferably a block consisting of polystyrene.
末端ブロックAの分子量は、4,000〜115.00
0、好ましくは、5.000〜15゜000、中心ブロ
ックBの分子量は、20,000〜450.000、好
ましくは、25,000〜ioo、oooであることが
望ましい。The molecular weight of terminal block A is 4,000 to 115.00
The molecular weight of the central block B is preferably 20,000 to 450.000, preferably 25,000 to ioo, ooo.
かかる水素添加ブロック共重合弾性体は、容易に市場で
入手でき、たとえばシェル化学より「クレイトン G1
650J、「クレイトン G1651J、「クレイトン
G1657J等の商品名及びグレード名で市販されて
いる。Such hydrogenated block copolymer elastomer is easily available on the market, for example, "Krayton G1" from Shell Chemical Co., Ltd.
650J, "Krayton G1651J,""Klayton G1657J, etc." are commercially available under trade names and grade names.
また、本発明の樹脂組成物において水素添加ブロック共
重合弾性体と組み合わせて使用されるエラストマー成分
は、不飽和酸無水物および不飽和酸から選ばれた少なく
とも一種で変性されたエチレン−α−オレフィン系共重
合体であ抄、この中で特に好ましいのはエチレン−α−
オレフィン系共重合体に不飽和酸又は不飽和酸無水物が
共重合、特にグラフト重合した重合体である。Furthermore, the elastomer component used in combination with the hydrogenated block copolymer elastomer in the resin composition of the present invention is an ethylene-α-olefin modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. Among these copolymers, ethylene-α- is particularly preferred.
It is a polymer in which an unsaturated acid or an unsaturated acid anhydride is copolymerized, particularly graft polymerized, to an olefin copolymer.
ここで使用されるα−オレフィンは、炭素数3〜20個
を有する不飽和炭化水素化合物であり、具体例としては
プロピレン、ペテン−1、ベアf7−1.ヘキセン−1
、ヘフf 7−1.4−メチルブテン−1,4−メチル
ペンテン−1等が挙げられるが、特に好ましくはプロピ
レンである。エチレンとα−オレフィンの配合比は90
:10〜10:90が好ましい。The α-olefin used here is an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples include propylene, petene-1, bare f7-1. hexene-1
, Hoef f 7-1,4-methylbutene-1,4-methylpentene-1, etc., but propylene is particularly preferred. The blending ratio of ethylene and α-olefin is 90
:10 to 10:90 is preferable.
また不飽和酸無水物及び不飽和酸としては、無水マレイ
ン酸、無水イタコン酸、クロロ無水マレイン酸、無水シ
トラコン酸、ブテニル無水コハク酸、テトラヒドロ無水
フタル酸等及びこれらの酸があゆ、特に好ましい不飽和
酸無水物または酸は無水マレイン酸またはマレイン酸で
ある。これらの不飽和酸無水物または酸は一種又は二種
以上で使用される。エチレン−α−オレフィン系共重合
体と不飽和酸無水物又は不飽和酸との反応は、過酸化物
の存在下に、エチレン−α−オレフィン系共重合体と不
飽和酸無水物又は不飽和酸を混合し、押出機、ミキサー
等で100〜250℃で1〜10分混練することによっ
て行うが、この場合、不飽和酸無水物又は不飽和酸0量
は、エチレン−α−オレフィン系共重合体に対して0.
1〜5重量%が好ましい。Examples of unsaturated acid anhydrides and unsaturated acids include maleic anhydride, itaconic anhydride, chloromaleic anhydride, citraconic anhydride, butenylsuccinic anhydride, tetrahydrophthalic anhydride, and these acids, and particularly preferred unsaturated acids include The saturated acid anhydride or acid is maleic anhydride or maleic acid. These unsaturated acid anhydrides or acids may be used alone or in combination of two or more. The reaction between the ethylene-α-olefin copolymer and the unsaturated acid anhydride or unsaturated acid is carried out in the presence of a peroxide. This is carried out by mixing acids and kneading them for 1 to 10 minutes at 100 to 250°C using an extruder, mixer, etc. In this case, the amount of unsaturated acid anhydride or unsaturated acid is 0. 0 for polymers.
1 to 5% by weight is preferred.
かかるエラストマーは容易に市場で入手でき、例えば、
ニクソン化学株より「エクセロールVA1803J、三
井石油化学口より「タフマー MP−06104等の
商品名及びグレード名で市販されている。Such elastomers are readily available on the market, e.g.
It is commercially available under trade names and grade names such as Excelol VA1803J from Nixon Chemical Co., Ltd. and Tafmer MP-06104 from Mitsui Petrochemical Company.
PPEの亥性に要する酸無水物構造を有する1、2−置
換オレフィン化合物の量は、PPE100重量部に対し
て0.01〜10重量%、好ましくは0.1〜3!を量
%、特に好ましくは001〜2重量%の範囲の量である
。これより少量では、PPEとPAの相溶性の改善効果
が小さく、靭性のある組成物が得難いし、この範囲より
も多く使用すると、PPE粒子の分散径が大きくなる等
の不具合があり、更に耐熱性の低下や外観不良等好まし
からざる現象が惹起する。The amount of the 1,2-substituted olefin compound having an acid anhydride structure required to increase the repellency of PPE is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, based on 100 parts by weight of PPE. % by weight, particularly preferably in the range from 0.001 to 2% by weight. If the amount is less than this, the effect of improving the compatibility of PPE and PA will be small and it will be difficult to obtain a composition with good toughness.If the amount is used more than this range, there will be problems such as the dispersion diameter of the PPE particles becoming large, and there will be problems such as heat resistance. Undesirable phenomena such as a decrease in quality and poor appearance occur.
又、PPEの変性の際に共存せしめる水素添加ブロック
共重合弾性体と不飽和酸無水物および不飽和酸から選ば
れた少なくとも一種で変性されたエチレン−α−オレフ
ィン系共重合体はそれぞれ単独又は合量で、PPE
100重量部に対して2〜40重量%、好ましくは5〜
30重量%、特に好ましくは、10〜20重量%の範囲
であり、これより少ないと衝撃強度の改良が不十分で、
この範囲よ口多くすると機械的強度の低下が生じる。In addition, the hydrogenated block copolymer elastomer and the ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids, which are allowed to coexist during the modification of PPE, may be used alone or together. In total, PPE
2 to 40% by weight, preferably 5 to 40% by weight based on 100 parts by weight
The content is 30% by weight, particularly preferably in the range of 10 to 20% by weight, and if it is less than this, the improvement in impact strength is insufficient.
If the thickness is increased beyond this range, the mechanical strength will decrease.
この水素添加ブロック共重合弾性体と変性エチレン−α
−オレフィン系共重合体はそれぞれ単独又は併用して使
用しつるが、併用の場合この両者の含量中に変性エチレ
ン−α−オレフィン系共重合体が30〜70重量%存在
するのが組成物の物性上好ましい。This hydrogenated block copolymer elastomer and modified ethylene-α
- The olefin copolymers can be used alone or in combination, but when used in combination, the modified ethylene-α-olefin copolymer should be present in the composition in an amount of 30 to 70% by weight. Preferred in terms of physical properties.
PPEと水素添加ブロック共重合弾性体、および又は不
飽和酸無水物詔よび不飽和酸から選ばれた少なくとも一
種で変性されたエチレン−α−オレフィン系共重合体の
泥合物と酸無水物構造を有する1、2−置換オレフィン
化合物との反応は、加熱溶融混練することにより得られ
るが、混練にはニーグー、バンバリーミキサ−押出機等
が用いられるが操作性等から押出機を用いるのが好まし
い。An acid anhydride structure and a mixture of PPE and a hydrogenated block copolymer elastomer, and/or an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. The reaction with a 1,2-substituted olefin compound having 1,2-substituted olefin can be obtained by heating, melting, and kneading, and a Niegoo, Banbury mixer, extruder, etc. is used for kneading, but it is preferable to use an extruder from the viewpoint of operability etc. .
本発明の樹脂組成物に用いられるポリアミド樹脂(P
A)は、主鎖に −Go−NH−結合を有する重合体で
あって、例えば、4−ナイロン、4.6−ナイロン、6
−ナイロン、6.6−ナイロン、12−ナイロン、11
−ナイロン%6110−ナイロン、MXD−ナイロンな
どがあげられる。Polyamide resin (P) used in the resin composition of the present invention
A) is a polymer having a -Go-NH- bond in the main chain, such as 4-nylon, 4.6-nylon, 6-nylon, etc.
-nylon, 6.6-nylon, 12-nylon, 11
-Nylon%6110-nylon, MXD-nylon, etc.
変性PPEとPAの配合割合は、広い範囲で選択するこ
とができるが、好ましくは、変性PPE/PA−0,1
〜5の範囲、特に好ましくは、0.3〜3の範囲である
。この範囲よ9小さい組成物ではPPEの優れた耐水性
、寸法安定性等が損なわれるし、大きい組成物では耐油
性、成形性等の改善効果が充分でない。The blending ratio of modified PPE and PA can be selected within a wide range, but preferably modified PPE/PA-0,1
-5, particularly preferably 0.3-3. If the composition is smaller than this range by 9, the excellent water resistance, dimensional stability, etc. of PPE will be impaired, and if the composition is larger than this range, the effect of improving oil resistance, moldability, etc. will not be sufficient.
次に本発明の樹脂組成物に用いられるステアリン酸の金
属塩としてはステアリン酸カルシウム、ステアリン酸マ
グネシウム、ステアリン酸カドミウム、ステアリン酸部
、ステアリン酸鉛、ステアリン酸亜鉛、ステアリン酸バ
リウム、ステアリン酸カドミウム、ステアリン酸ナトリ
ウム等があり、特にステアリン酸カルシウム、ステアリ
ン酸バリウムが好ましい。ステアリン酸の金属塩の配合
量は変性PPEとPAの組成物に対し0.1〜10重量
%、好ましくは0.3〜5重量%、特に好ましくは0.
5〜3重量%である。この範囲より小さい場合には流動
性、ウェルド強度の改善が不充分であり、一方この範囲
より大きいと引張伸びとアイゾツト衝撃強度が低下し更
に外観が悪くなる。Next, the metal salts of stearic acid used in the resin composition of the present invention include calcium stearate, magnesium stearate, cadmium stearate, stearic acid moiety, lead stearate, zinc stearate, barium stearate, cadmium stearate, and stearate. Among them, calcium stearate and barium stearate are particularly preferred. The amount of the metal salt of stearic acid to be blended is 0.1 to 10% by weight, preferably 0.3 to 5% by weight, particularly preferably 0.1 to 10% by weight, based on the composition of modified PPE and PA.
It is 5 to 3% by weight. If it is smaller than this range, the improvement in fluidity and weld strength will be insufficient, while if it is larger than this range, the tensile elongation and isot impact strength will decrease and the appearance will deteriorate.
本発明の樹脂組成物には、所望tこ応じて、ガラス繊維
、炭素繊維などの繊維強化材料を配合することができる
。さらには、高分子材料に一般に用いられる各種添加剤
、例えば、安定剤、顔染料、離型剤、滑剤、充填剤など
を適宜配合することができる。The resin composition of the present invention can be blended with fiber reinforcing materials such as glass fibers and carbon fibers depending on the desired amount. Furthermore, various additives commonly used for polymeric materials, such as stabilizers, facial dyes, mold release agents, lubricants, fillers, etc., can be appropriately blended.
(実施例)
以下、実施例及び比較例によって本発明を具体的に示す
が、実施例中部数は重量基準で表されている。(Examples) Hereinafter, the present invention will be specifically illustrated by Examples and Comparative Examples, and the numbers in the examples are expressed on a weight basis.
実施例 1〜5
25℃クロロホルム中で測定した固有粘度が0.50d
l/17であるポリ(2,6−シメチルー1.4−)ユ
ニレン)エーテル粉末、無水マレイン酸、クレイトンG
1651 (シェル化学製)、エクセロールVA18
03(エクソン化学抄製)を表1に示す割合で配合し、
スーパーミキサーにて3分間混合した後、2軸押出機(
池貝鉄工!!! PCM−30)を使用して290℃
にて溶融混練し押し出しを行って変性PPHのペレット
を得た。得られた変性PPEと6−ナイロン(東し■製
、アミランCMIO07,0M1017)、6.6−ナ
イロン(東し抄製アミランCM3007)及びステアリ
ン酸金属塩を表1に示す割合で混合し2軸押出浅を使用
して280℃で溶融混合して得られたペレットを射出成
形によ抄各種試験片を成形した。この試験片を用いて測
定した各種物性値を表1に示した。Examples 1 to 5 Intrinsic viscosity measured in chloroform at 25°C is 0.50 d
l/17 poly(2,6-dimethyl-1,4-)unilene)ether powder, maleic anhydride, Kraton G
1651 (Shell Chemical), Excelol VA18
03 (manufactured by Exxon Kagakusho) in the proportions shown in Table 1,
After mixing for 3 minutes in a super mixer, use a twin screw extruder (
Ikegai Iron Works! ! ! 290℃ using PCM-30)
The mixture was melt-kneaded and extruded to obtain modified PPH pellets. The obtained modified PPE was mixed with 6-nylon (Amilan CMIO07,0M1017, manufactured by Toshisho Corporation), 6.6-nylon (Amilan CM3007, manufactured by Toshisho Corporation), and stearic acid metal salt in the proportions shown in Table 1, and then mixed with two screws. The pellets obtained by melt-mixing at 280°C using an extruder were molded into various test pieces by injection molding. Table 1 shows various physical property values measured using this test piece.
に行った結果を表1に示した。The results are shown in Table 1.
実施例 6
ガラス繊維(旭ファイバーグラスn製、JAFT−2A
)で補強した場合について表1に示した組成物について
実施例1と同様に行った結果を表1に示した。Example 6 Glass fiber (manufactured by Asahi Fiberglass n, JAFT-2A
) The compositions shown in Table 1 were tested in the same manner as in Example 1, and the results are shown in Table 1.
比較例 4
ガラス環m(旭ファイバーグラス■製、JAFT−2A
)で補強した場合について表1に示した組成物について
比較例1と同様に行った結果を表1に示した。Comparative example 4 Glass ring m (manufactured by Asahi Fiberglass ■, JAFT-2A
) The compositions shown in Table 1 were tested in the same manner as in Comparative Example 1, and the results are shown in Table 1.
比較例 1〜3
ステアリン酸金属塩を使用しない場合について表1に示
した組成物について実施例1と同様(発明の効果)
実施例、比較例から明らかなように本発明の組成物は衝
撃強度、流動性、ウェルド強度に優れてお抄従来法では
得られない特性を示している。Comparative Examples 1 to 3 Same as Example 1 for the compositions shown in Table 1 when metal stearate is not used (effects of the invention) As is clear from the Examples and Comparative Examples, the compositions of the present invention have low impact strength. It exhibits excellent fluidity and weld strength, properties that cannot be obtained by conventional papermaking methods.
Claims (1)
2、R_3は水素原子又は炭素数1〜3の低級アルキル
基である。) で表わされる構造単位を主鎖に持つポリフェニレンエー
テル樹脂を水素添加A−B−A型ブロック共重合弾性体
(ここで、Aはビニル芳香族炭化水素の重合体ブロック
をBは共役ジエン系炭化水素化合物の重合体ブロックを
意味する)及び又は、不飽和酸無水物及び不飽和酸から
選ばれた少なくとも一種で変性されたエチレン−α−オ
レフィン系共重合体の共存下に酸無水物構造を有する1
,2−置換オレフィン化合物と溶融状態で反応せしめて
得られる変性ポリフェニレンエーテル樹脂と、 (b)ポリアミド樹脂 (c)ステアリン酸金属塩 からなる樹脂組成物。[Claims] (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 is a lower alkyl group having 1 to 3 carbon atoms, R_
2, R_3 is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms. ) Hydrogenated A-B-A type block copolymer elastomer of polyphenylene ether resin having a structural unit represented by (meaning a polymer block of a hydrogen compound) and/or an acid anhydride structure in the coexistence of an ethylene-α-olefin copolymer modified with at least one selected from unsaturated acid anhydrides and unsaturated acids. have 1
, a modified polyphenylene ether resin obtained by reacting it with a 2-substituted olefin compound in a molten state, (b) a polyamide resin, and (c) a stearic acid metal salt.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2660689A JPH02206648A (en) | 1989-02-07 | 1989-02-07 | New resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2660689A JPH02206648A (en) | 1989-02-07 | 1989-02-07 | New resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH02206648A true JPH02206648A (en) | 1990-08-16 |
Family
ID=12198164
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2660689A Pending JPH02206648A (en) | 1989-02-07 | 1989-02-07 | New resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH02206648A (en) |
-
1989
- 1989-02-07 JP JP2660689A patent/JPH02206648A/en active Pending
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