JPH01221452A - Stabilized polyphenylene ether resin composition - Google Patents
Stabilized polyphenylene ether resin compositionInfo
- Publication number
- JPH01221452A JPH01221452A JP4454588A JP4454588A JPH01221452A JP H01221452 A JPH01221452 A JP H01221452A JP 4454588 A JP4454588 A JP 4454588A JP 4454588 A JP4454588 A JP 4454588A JP H01221452 A JPH01221452 A JP H01221452A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- ether resin
- acid dihydrazide
- formula
- alkyl group
- 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
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 24
- 239000011342 resin composition Substances 0.000 title claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 125000000732 arylene group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- -1 poly(2,6-dimethyl-1,4-phenylene) Polymers 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 7
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 7
- 239000004793 Polystyrene Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920002223 polystyrene Chemical group 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZNGSVRYVWHOWLX-KHFUBBAMSA-N (1r,2s)-2-(methylamino)-1-phenylpropan-1-ol;hydrate Chemical compound O.CN[C@@H](C)[C@H](O)C1=CC=CC=C1.CN[C@@H](C)[C@H](O)C1=CC=CC=C1 ZNGSVRYVWHOWLX-KHFUBBAMSA-N 0.000 description 1
- FVBBMPBYVZWAAI-UHFFFAOYSA-N 2-butyl-4-[1-(5-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C1=C(O)C(CCCC)=CC(C(CCC)C=2C(=CC(O)=C(CCCC)C=2)C)=C1C FVBBMPBYVZWAAI-UHFFFAOYSA-N 0.000 description 1
- HCILJBJJZALOAL-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 HCILJBJJZALOAL-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- JDCCCHBBXRQRGU-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile Chemical class N#CC=CC=CC1=CC=CC=C1 JDCCCHBBXRQRGU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 101001091203 Homo sapiens Peptidyl-prolyl cis-trans isomerase E Proteins 0.000 description 1
- 102100034844 Peptidyl-prolyl cis-trans isomerase E Human genes 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- LGYJSPMYALQHBL-UHFFFAOYSA-N pentanedihydrazide Chemical compound NNC(=O)CCCC(=O)NN LGYJSPMYALQHBL-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-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、ポリフェニレンエーテル樹脂組成物、特に熱
安定性と色調が改善されたポリフェニレンエーテル樹脂
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to polyphenylene ether resin compositions, particularly polyphenylene ether resin compositions with improved thermal stability and color tone.
ポリフェニレンエーテル樹脂は、機械的、電気的特性に
優れ且つ高い熱変形温度を有し、エンジニアリング樹脂
として用いられているか、熱安定性が低く、空気中で高
温に晒されると着色や脆化がおこり易く、また高温で成
形加工する場合にも着色等の問題があり、その優れた特
性にもか−わらず広範囲な利用を制限するところとなっ
ている。Polyphenylene ether resin has excellent mechanical and electrical properties and a high heat distortion temperature, and is used as an engineering resin or has low thermal stability, causing discoloration and embrittlement when exposed to high temperatures in the air. Furthermore, there are problems such as coloring when molding at high temperatures, which limits its widespread use despite its excellent properties.
このため従来種々の提案がなされているが、上述の欠点
を完全に克服するにいたっておらず、ために、もう−歩
の利用拡大かとさされているのか現状である。従来技術
の具体例としては、以下の提案がある。即ち、特定構造
のジカルボン酸シし１′ラジト置換体を安定剤とした組
成物（特開昭５１−２５２６５号公報）、有機ボスファ
イトまたはこれとヒドラジンや安息香酸との混合物を安
定剤として用いる組成物（特公昭５１−３３９３８号公
報）、硫化カドミニウムや硫化亜鉛等の無機硫化物また
はこれと有機ホスファイトを混合して用いた組成物（特
開昭４７−４３０３８号公報）等が提案されているが、
ポリフェニレンエーテル樹脂を成形加工して用いる場合
の前記問題は解決されていない。To this end, various proposals have been made in the past, but none have been able to completely overcome the above-mentioned drawbacks, and as a result, the current state of affairs is that the use of these devices is expected to be further expanded. As a specific example of the prior art, there are the following proposals. That is, compositions using a 1'-substituted dicarboxylic acid with a specific structure as a stabilizer (Japanese Unexamined Patent Application Publication No. 51-25265), organic bosphite or a mixture thereof with hydrazine or benzoic acid are used as a stabilizer. A composition using an inorganic sulfide such as cadmium sulfide or zinc sulfide or a mixture thereof with an organic phosphite (Japanese Patent Laid-Open No. 47-43038) has been proposed. Although,
The above-mentioned problem when molding and using polyphenylene ether resin has not been solved.
本発明者等は、以上の問題を解決すべく、鋭意検討を行
った結果、本発明を為すにいたった。The inventors of the present invention conducted extensive studies to solve the above problems, and as a result, they came up with the present invention.
即ち本発明は、−数式
］（１
％式％
（但しＲ，、Ｒ３は水素、アルキル基またはアリール基
、Ｒ２はアルキレン基又はアリーレン基である。）
で示されるジカルホン酸ジヒドラジドと、−数式
（但しＲ４，、Ｉ７５は炭素原子１〜４のアルキル基、
Ｒ６は水素あるいは炭素原子１〜４のアルキル基、ｎは
０，１またば２である。）
て示される立体障害性フェノールとを含有するポリフェ
ニレンエーテル樹脂組成物である。本発明の特徴は、上
記二種の化合物を併用する事により、はじめて特異的に
、熱安定性と色調が大幅に改良される点にある。That is, the present invention provides a dicarphonic acid dihydrazide represented by the formula - (1% formula % (where R, R3 is hydrogen, an alkyl group or an aryl group, and R2 is an alkylene group or an arylene group); However, R4, I75 is an alkyl group having 1 to 4 carbon atoms,
R6 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is 0,1 or 2. ) This is a polyphenylene ether resin composition containing a sterically hindered phenol. The feature of the present invention is that the heat stability and color tone can be significantly improved specifically by using the above two types of compounds together.
以下本発明を詳述する。The present invention will be explained in detail below.
本発明のポリフェニレンエーテル樹脂としては、ポリフ
ェニレンエーテル樹脂（以下、ＰＰＥと略記する）その
もの、及び該ＰＩ）Ｅと混合して用いられるスチレン系
重合体樹脂との組成物であってもよい。The polyphenylene ether resin of the present invention may be a polyphenylene ether resin (hereinafter abbreviated as PPE) itself, or a composition of a styrene polymer resin mixed with the PI)E.
本発明にいうＰＰＥとは、下記−数式（１）（式中、Ｒ
７及びＲ８はそれぞれ炭素数１〜４のアルキル基又はハ
ロゲン原子を表わす。ｎは重合度を示す整数である。）
で表わされるものが用いうる。The PPE referred to in the present invention refers to the following formula (1) (in which R
7 and R8 each represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. n is an integer indicating the degree of polymerization. )
The following can be used.
この−数式（Ｉ）で示されるものの具体例としては、ポ
リ （２，６−シメチルー１，４−フェニレン）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 （２，６−ジエチル−１，４−フ
エニレン）エーテル、ポリ（２−エチル−６−ｎプロピ
ル−１，４−フェニレン）エーテル、ポリ（２，６−ジ
−ｎプロピル−１，４−フェニレン）エーテル、ポリ（
２−メチル−６−ｎブチル−１，４フエニレン）エーテ
ル、ポリ（２−エチル−６−イツプロビルー１゜４−フ
ェニレン）エーテル、ポリ（２−メチル−６−クロル−
１，４−フェニレン）エーテル、ポリ（２−メチル−６
−ヒドロキシエチル−１，４一フェニレン）エーテル、
ポリ（２−メチル−６−り四ロエチルー１．４−フェニ
レン）エーテル等のホモポリマーが挙げられる。Specific examples of this formula (I) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly( 2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(
2-Methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-itsuprobyl-1°4-phenylene) ether, poly(2-methyl-6-chloro-
1,4-phenylene)ether, poly(2-methyl-6)
-hydroxyethyl-1,4-phenylene)ether,
Examples include homopolymers such as poly(2-methyl-6-di-4loethyl-1,4-phenylene) ether.
このうち、好ましいものは、ポリ （２，６ジメチルー
１．４−フェニレン）エーテルである。Among these, poly(2,6 dimethyl-1,4-phenylene) ether is preferred.
また上記−数式で表わされる化学構造を主体としてなる
ポリフェニレンエーテル共重合体も使用可能である。そ
の具体例としては２．６−シメチルフエノールと２．３
．６−４リメチルフエノールの共重合体があげられる。Further, a polyphenylene ether copolymer mainly having the chemical structure represented by the above-mentioned formula can also be used. Specific examples include 2.6-dimethylphenol and 2.3
．． Examples include copolymers of 6-4-limethylphenol.
本発明で用いられるＰＰＥは、クロロポルム中３０°Ｃ
で測定したときの固有粘度が０．３５〜０．７ＦＭｅ／
ｇの範囲のものが好ましい。より好ましくは０．４０〜
０．７０み７ｇのものである。The PPE used in the present invention was prepared in chloroporm at 30°C.
Intrinsic viscosity when measured at 0.35-0.7FMe/
g range is preferred. More preferably 0.40~
It is 0.70 and weighs 7g.
このＰＰＥには、Ｒ７，Ｒ１１に低分子量のアミンやポ
リスチレンが結合していてもよく、またＰＰＥ主鎖の一
部にジフェノキノン等が結合しているもの等も対象とな
る。This PPE may have a low molecular weight amine or polystyrene bonded to R7 and R11, or may have a diphenoquinone or the like bonded to a part of the PPE main chain.
本発明ＰＰＩＥと混合して用いうるスチレン系重合体樹
脂としては、ポリスチレン、又はスチレンと他のビニル
化合物の少くとも一種との共重合体、及びそれらのゴム
変性重合体を含むものである。Styrenic polymer resins that can be used in combination with the PPIE of the present invention include polystyrene, copolymers of styrene and at least one other vinyl compound, and rubber-modified polymers thereof.
スチレンと他のビニル化合物の少なくとも１種との共重
合体の具体例としては、スチレン−アクリロニトリル共
重合体、スチレン−メタクリル酸メチル共重合体、スチ
レン−α−メチルスチレン共重合体、スチレン−無水マ
レイン酸共重合体等があげられる。また、ゴム変性重合
体としては、ゴム変成ポリスチレン（ＩＩＩＰＳ） 、
ゴム変成スチレン−アクリロニトリル共重合体（ＡＢＳ
）、ゴム変成スチレン−無水マレイン酸共重合体等があ
る。Specific examples of copolymers of styrene and at least one other vinyl compound include styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-α-methylstyrene copolymer, and styrene-anhydride copolymer. Examples include maleic acid copolymers. In addition, rubber-modified polymers include rubber-modified polystyrene (IIIPS),
Rubber modified styrene-acrylonitrile copolymer (ABS
), rubber-modified styrene-maleic anhydride copolymer, etc.
この内、特に好ましい重合体はポリスチレン（ＰＳ）及
びゴム変成ポリスチレン（ＩＩＩＰｓ）である。Among these, particularly preferred polymers are polystyrene (PS) and rubber-modified polystyrene (IIIPs).
ＰＰＥとスチレン系重合体のブレンド比率に関しては、
特に限定されずＰＰＥ９５〜１０重量部とスチレン系重
合体５〜９０重量部の範囲が好ましい。Regarding the blend ratio of PPE and styrenic polymer,
There is no particular limitation, but a range of 95 to 10 parts by weight of PPE and 5 to 90 parts by weight of styrene polymer is preferred.
本発明に用いる一般式
］］
％式％
（但しＲ，、Ｒ３は水素、アルキル基またはアリール基
、Ｒ２はアルキレン基又はアリーレン基である。）
で示されるジカルボン酸ジヒドラジドとしては、マロン
酸ジヒドラジド、コハク酸シヒト゛ラシド、グルタル酸
ジヒドラジド、アジピン酸ジヒドラジド、スヘリン酸ジ
ヒドラジド、アセライン酸ジヒドラジド、セハチン酸ジ
ヒドラジド、ドデカンニ酸ジヒドラジド、イソフタル酸
ジヒドラジド等である。The dicarboxylic acid dihydrazide represented by the general formula used in the present invention]]% formula % (wherein R,, R3 is hydrogen, an alkyl group or an aryl group, and R2 is an alkylene group or an arylene group) include malonic acid dihydrazide, These include succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sheric acid dihydrazide, acelaic acid dihydrazide, cehatic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and the like.
又−数式
（但しＲａ、Ｒ５は炭素原子１〜４のアルキル基、Ｒ６
は水素あるいは炭素原子１〜４のアルキル基、ｎは０．
１または２である。）
で示される立体障害性フェノールとしては、Ｎ、Ｎ′−
ビス（３−（３，５−ジーも一ブチルー４−ヒドロキシ
ヘンゾイル）〕ヒドラジン、Ｎ、Ｎ′−ビス（３−（３
，５−ジーＬ−ブチルー４−ヒドロキシフェニル）エチ
オニル〕ヒドラジン、Ｎ、Ｎ ′−ビス［３−（３，５
−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオ
ニル］ヒドラジン等である。両者の使用量としては、ポ
リフェニレンエーテル樹脂に対し０．０１〜１重量％、
好ましくは、０．０２〜０．５重量％である。- Numerical formula (where Ra, R5 is an alkyl group having 1 to 4 carbon atoms, R6
is hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is 0.
1 or 2. ) The sterically hindered phenol represented by N, N'-
bis(3-(3,5-di-butyl-4-hydroxyhenzoyl))]hydrazine, N,N'-bis(3-(3
,5-di-L-butyl-4-hydroxyphenyl)ethionyl]hydrazine, N,N'-bis[3-(3,5
-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine, and the like. The amount of both used is 0.01 to 1% by weight based on the polyphenylene ether resin.
Preferably it is 0.02 to 0.5% by weight.
本発明の組成物の製造においては、特に厳密な条件は必
要とせず、公知の任意の方法を採りうる。The production of the composition of the present invention does not require particularly strict conditions, and any known method may be used.
例えばヘンシェルミキサー等で混合し、押出機でペレッ
ト化する方法が簡便で都合がよい。For example, a method of mixing with a Henschel mixer or the like and pelletizing with an extruder is simple and convenient.
本発明の組成物を種々の用途に使用する場合に、単独で
の使用の他、この組成物の特性を害わない範囲で他のポ
リマーを配合しても用いられる。その具体例としてはポ
リオレフィン、ポリアミド、ポリブタジェン、スチレン
−ブタジェン系ブロック共重合体及びその水素添加物等
が挙けられる。When the composition of the present invention is used for various purposes, it may be used alone or may be blended with other polymers as long as the properties of the composition are not impaired. Specific examples include polyolefins, polyamides, polybutadiene, styrene-butadiene block copolymers, and hydrogenated products thereof.
更にはガラス繊維、カーボン繊維、カーボンブラックそ
の他の無機系充填剤、可塑剤、難燃剤、安定剤等の添加
も可能である。Furthermore, it is also possible to add glass fibers, carbon fibers, carbon black and other inorganic fillers, plasticizers, flame retardants, stabilizers, and the like.
本発明の安定化されたポリフェニレンエーテル樹脂組成
物は、従来から知られている安定剤を用いて得られるポ
リフェニレンエーテル樹脂組成物に比べて、熱安定性に
優れ、特に空気中、長期高温下での物性及び色調の変化
が非常に少い。その結果、従来品と比べ、より広い用途
への展開が可能となった。The stabilized polyphenylene ether resin composition of the present invention has excellent thermal stability compared to polyphenylene ether resin compositions obtained using conventionally known stabilizers. There are very few changes in physical properties and color tone. As a result, it has become possible to develop it into a wider range of applications than conventional products.
（実施例］
以下、本発明を実施例により詳細に説明するが、本発明
はこれらに限定されるものではない。(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.
実施例１，２及び比較例１〜３
ＰＰＥとしてクロロホルム中、３０°Ｃで測定した固有
粘度が０．５５ｄｌ／ｇのポリ−（２，６ジメチルー１
，４フエニレン）エーテル５５重量部とゴム補強ポリス
チレン（旭化成■製、スタイロン４９２） ４５重量部
、トリフェニルホスフェート３．０重量部、トリデシル
ホスファイｌ−１，０重量部からなる組成物に、ジカル
ボン酸ジヒドラジドとして、イソフタル酸ジヒドラジド
を、又立体障害性フェノールとして、Ｎ、Ｎ’−ビス［
３−３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル
）プロピオニル〕ヒドラジンを表−１に示す量添加して
、Ｎ２下ヘンシエルミキサーで十分混合した。Examples 1 and 2 and Comparative Examples 1 to 3 Poly-(2,6 dimethyl-1
, 4 phenylene) ether, 45 parts by weight of rubber-reinforced polystyrene (manufactured by Asahi Kasei ■, Styron 492), 3.0 parts by weight of triphenyl phosphate, and 1.0 parts by weight of tridecylphosphite, Isophthalic acid dihydrazide is used as the dicarboxylic acid dihydrazide, and N,N'-bis[
3-3,5-di-t-butyl-4-hydroxyphenyl)propionyl]hydrazine was added in the amount shown in Table 1, and thoroughly mixed in a Henschel mixer under N2.
このものを、３０ｎｕｎφ２軸押出機でＮ２雰囲気中３
００°Ｃにて押出し、ペレット化した。このペレットを
５オンスの射出成形機で２９０°Ｃにて、厚さ１／８″
の短冊状試験片を作成した。得られた試験片を、空気循
環式オーブン中１１０°Ｃで任意時間熱エージングした
後取り出してアイゾツト衝撃強さを測定した。熱エージ
ング前のアイゾツト衝撃強さに対しての保持率を求め、
その結果を表−１に示す。又熱エージングによる試験片
の色調の変化に関しても目視により比較した。This product was processed in a N2 atmosphere using a 30nunφ twin-screw extruder.
It was extruded and pelletized at 00°C. The pellets were molded in a 5 oz injection molding machine at 290°C to a thickness of 1/8".
A strip-shaped test piece was prepared. The obtained test piece was heat aged at 110°C for an arbitrary period of time in an air circulating oven, and then taken out and the Izod impact strength was measured. Calculate the retention rate for the Izotz impact strength before heat aging,
The results are shown in Table-1. Changes in color tone of the test pieces due to heat aging were also visually compared.
実施例３
実施例２の組成中、イソフタル酸ジヒドラジドをアジピ
ン酸ジヒドラジドに変える以下は、実施例２と全く同一
条件下で評価を実施した。その結果を表−２に示す。Example 3 Evaluation was carried out under exactly the same conditions as in Example 2 except that isophthalic acid dihydrazide in the composition of Example 2 was changed to adipic acid dihydrazide. The results are shown in Table-2.
表−２ 実施例４ 実施例２の組成中、Ｎ、Ｎ′−ビス（３−（３’。Table-2 Example 4 In the composition of Example 2, N,N'-bis(3-(3'.
５−ジーも一ブチルー４−ヒドロキシフェニル）プロピ
オニル〕ヒドラジンをＮ、Ｎ′−ビス〔３−（３，５−
ジ−ｔ−ブチル−４−ヒドロキシベンゾイル）〕ヒドラ
ジンに変える以外は、実施例２と全く同一条件下で評価
を実施した。5-Di-monobutyl-4-hydroxyphenyl)propionyl]hydrazine is converted to N,N'-bis[3-(3,5-
Evaluation was carried out under exactly the same conditions as in Example 2, except that hydrazine (di-t-butyl-4-hydroxybenzoyl) was used.
その結果を表−３に示す。The results are shown in Table-3.
＝１３＝
表−３
比較例４
立体障害性フェノールとして、−＋ｙ的な４，４′−ブ
チリデン−ビス−（３−メチル−６−Ｌ−ブチルフェノ
ール）とイソフタル酸ジヒドラジドを各々０．２重量％
用いる以外は、実施例２と全く同一条件下で評価を実施
した。その結果を表−４に示す。=13= Table-3 Comparative Example 4 As sterically hindered phenol, -+y-like 4,4'-butylidene-bis-(3-methyl-6-L-butylphenol) and isophthalic acid dihydrazide were each used in an amount of 0.2% by weight.
The evaluation was carried out under exactly the same conditions as in Example 2 except for the use of the following. The results are shown in Table 4.
表−４ 特許出願人 旭化成工業株式会社 ＝ １４−Table-4 Patent applicant: Asahi Kasei Industries, Ltd. = 14-
Claims (1)
ル基、Ｒ＿２はアルキレン基又はアリーレン基である。 ） で示されるジカルボン酸ジヒドラジドと、 一般式 ▲数式、化学式、表等があります▼ （但しＲ＿４、Ｒ＿５は炭素原子１〜４のアルキル基、
Ｒ＿６は水素あるいは炭素原子１〜４のアルキル基ｎは
０、１または２である。） で示される立体障害性フェノールとを含有するポリフェ
ニレンエーテル樹脂組成物[Claims] A dicarboxylic acid dihydrazide represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 and R_3 are hydrogen, an alkyl group or an aryl group, and R_2 is an alkylene group or an arylene group.) , General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_4 and R_5 are alkyl groups with 1 to 4 carbon atoms,
R_6 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and n is 0, 1 or 2. ) A polyphenylene ether resin composition containing a sterically hindered phenol represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044545A JP2670445B2 (en) | 1988-02-29 | 1988-02-29 | Stabilized polyphenylene ether resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63044545A JP2670445B2 (en) | 1988-02-29 | 1988-02-29 | Stabilized polyphenylene ether resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01221452A true JPH01221452A (en) | 1989-09-04 |
| JP2670445B2 JP2670445B2 (en) | 1997-10-29 |
Family
ID=12694473
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63044545A Expired - Lifetime JP2670445B2 (en) | 1988-02-29 | 1988-02-29 | Stabilized polyphenylene ether resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2670445B2 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49112868A (en) * | 1973-02-28 | 1974-10-28 | ||
| JPS503086A (en) * | 1973-05-14 | 1975-01-13 | ||
| JPS5056383A (en) * | 1973-09-20 | 1975-05-17 | ||
| JPS5114885A (en) * | 1974-07-30 | 1976-02-05 | Adeka Argus Chemical Co Ltd | JUKIZAIR YOSOSEI BUTSU |
| DE3118616A1 (en) * | 1981-05-11 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | Thermoplastic moulding compositions |
| JPS62501215A (en) * | 1984-12-20 | 1987-05-14 | ゼネラル・エレクトリック・カンパニイ | Oxalyl dihydrazide as a deterioration stabilizer for modified PPO |
| JPS62288655A (en) * | 1986-06-06 | 1987-12-15 | Sumitomo Naugatuck Co Ltd | Stabilized heat-resistant resin composition compounded with colorant |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3118618C2 (en) | 1981-05-11 | 1983-02-10 | AOA Apparatebau Gauting GmbH, 8035 Gauting | Method and circuit for measuring the time interval between first and second, in particular aperiodic, signals |
-
1988
- 1988-02-29 JP JP63044545A patent/JP2670445B2/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49112868A (en) * | 1973-02-28 | 1974-10-28 | ||
| JPS503086A (en) * | 1973-05-14 | 1975-01-13 | ||
| JPS5056383A (en) * | 1973-09-20 | 1975-05-17 | ||
| JPS5114885A (en) * | 1974-07-30 | 1976-02-05 | Adeka Argus Chemical Co Ltd | JUKIZAIR YOSOSEI BUTSU |
| DE3118616A1 (en) * | 1981-05-11 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | Thermoplastic moulding compositions |
| JPS62501215A (en) * | 1984-12-20 | 1987-05-14 | ゼネラル・エレクトリック・カンパニイ | Oxalyl dihydrazide as a deterioration stabilizer for modified PPO |
| JPS62288655A (en) * | 1986-06-06 | 1987-12-15 | Sumitomo Naugatuck Co Ltd | Stabilized heat-resistant resin composition compounded with colorant |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2670445B2 (en) | 1997-10-29 |
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