JPH0292956A - Polyphenylene ether resin composition for expansion molding - Google Patents
Polyphenylene ether resin composition for expansion moldingInfo
- Publication number
- JPH0292956A JPH0292956A JP24393188A JP24393188A JPH0292956A JP H0292956 A JPH0292956 A JP H0292956A JP 24393188 A JP24393188 A JP 24393188A JP 24393188 A JP24393188 A JP 24393188A JP H0292956 A JPH0292956 A JP H0292956A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- resin composition
- group
- ether
- ether resin
- 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
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 36
- 239000011342 resin composition Substances 0.000 title claims abstract description 18
- 238000000465 moulding Methods 0.000 title description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000004088 foaming agent Substances 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 238000010097 foam moulding Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- -1 polyphenylene Polymers 0.000 abstract description 16
- 239000004156 Azodicarbonamide Substances 0.000 abstract description 5
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 abstract description 5
- 235000019399 azodicarbonamide Nutrition 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000004593 Epoxy Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 229920000265 Polyparaphenylene Polymers 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000021523 carboxylation Effects 0.000 description 3
- 238000006473 carboxylation reaction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 2
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 1
- IDCPFAYURAQKDZ-UHFFFAOYSA-N 1-nitroguanidine Chemical compound NC(=N)N[N+]([O-])=O IDCPFAYURAQKDZ-UHFFFAOYSA-N 0.000 description 1
- VVHFXJOCUKBZFS-UHFFFAOYSA-N 2-(chloromethyl)-2-methyloxirane Chemical compound ClCC1(C)CO1 VVHFXJOCUKBZFS-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- CMUOJBJRZUHRMU-UHFFFAOYSA-N nitrourea Chemical compound NC(=O)N[N+]([O-])=O CMUOJBJRZUHRMU-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 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
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing 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
- 239000001294 propane Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は発泡成形用樹脂組成物、特にアンモニアを発生
する発泡剤を使用する発泡成形用の樹脂組成物に関する
。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a resin composition for foam molding, and particularly to a resin composition for foam molding using a blowing agent that generates ammonia.
従来技術及び発明が解決しようとする課題発泡成形は、
優れた構造剛性が得られること、通常の射出成形で問題
となるヒケ、パリ、ソリ等が少なく成形品設計が容易で
あること、更には成形が容易であること等多くの利点を
もっている。Problems to be solved by the prior art and the invention Foam molding:
It has many advantages such as excellent structural rigidity, ease of molded product design with fewer sink marks, cracks, warpage, etc. that are problems in ordinary injection molding, and ease of molding.
このため、近年、事務機器用品のシャーシ、ハウジング
等に使用され、極めて有用である。Therefore, in recent years, it has been used for chassis, housings, etc. of office equipment, and is extremely useful.
発泡成形には、従来より公知の化学発泡剤を成形時に添
加し、射出成形又は押出成形を行う方法が一般に採られ
ている。化学発泡剤としては、アゾジカルボンアミド、
アゾイソブチロニトリル、Ｎ、Ｎ’−ジニトロソペンタ
メチレンテトラミン、トルエンスルホニルヒドラジド、
Ｐ、Ｐ’−オキシビス（ベンゼンスルホニルヒドラジド
）等の化合物が知られている。Foam molding generally involves adding a known chemical foaming agent during molding and performing injection molding or extrusion molding. Chemical blowing agents include azodicarbonamide,
Azoisobutyronitrile, N,N'-dinitrosopentamethylenetetramine, toluenesulfonylhydrazide,
Compounds such as P,P'-oxybis(benzenesulfonylhydrazide) are known.
これらの化合物のうち、一般によく使用されるたとえば
アゾジカルボンアミドは分解した際に窒素と共にアンモ
ニアを発生する。このために、得られた成形品はアンモ
ニア臭がして不快であり、またアンモニアが成形品内に
組み込まれた金属を腐食するという問題がある。またプ
レートアウトと呼ばれる成形品表面への発泡剤残渣の析
出を生じ、塗装等の二次加工時に問題が生じる。このた
めアンモニアを除去するために、成形品を熱処理する等
の特別な工程が必要であった。このアンモニア除去のた
めの特別な工程を削除するために、樹脂組成中にカルボ
キシル基又は無水カルボン酸基を有する化合物（モノマ
ー、オリゴマー、ポリマー）を含有させる方法が提案さ
れている（特開昭６１−２３５４４０）。Among these compounds, commonly used azodicarbonamide, for example, generates ammonia along with nitrogen when decomposed. For this reason, the obtained molded product has an unpleasant odor of ammonia, and there is also the problem that ammonia corrodes the metal incorporated in the molded product. In addition, foaming agent residues are deposited on the surface of the molded product, which is called plate-out, which causes problems during secondary processing such as painting. Therefore, in order to remove ammonia, a special process such as heat treatment of the molded product was required. In order to eliminate this special step for removing ammonia, a method has been proposed in which a compound (monomer, oligomer, polymer) having a carboxyl group or carboxylic anhydride group is included in the resin composition (JP-A-61 -235440).
しかし、この方法は樹脂成分以外にカルボキシル基等を
有する化合物を添加するために、樹脂組成物の物性（例
えば耐熱性、強度等）に悪影響を及ぼすことがある。However, since this method adds a compound having a carboxyl group or the like in addition to the resin component, the physical properties (eg, heat resistance, strength, etc.) of the resin composition may be adversely affected.
一方、アンモニアの発生の無い発泡剤として、たとえば
、炭酸水素ナトリウム、バリウムカルボキシレート、５
−フェニルテトラゾール、あるいは、フレオンガス等も
検討されたが、取り扱い性、安全性、成形性等の面から
実用されるまでには致っていない。On the other hand, examples of foaming agents that do not generate ammonia include sodium hydrogen carbonate, barium carboxylate,
- Phenyltetrazole, Freon gas, etc. have been considered, but they have not been put to practical use due to handling, safety, moldability, etc. aspects.
従って、本発明は前記間踊点の解消されたアンモニアを
発生する発泡剤を用いる発泡成形用樹脂組成物を提供す
ることを目的とするものである。Therefore, it is an object of the present invention to provide a resin composition for foam molding that uses a foaming agent that generates ammonia in which the above-mentioned interstitial point has been eliminated.
課題を解決するための手段
本発明は、アンモニアを発生する発泡剤を用いる発泡成
形用のポリフェニレンエーテル系樹脂組成物において、
エポキシ基、カルボキシル基、及び酸無水物基の中の少
くとも１つの基を末端基として有するポリフェニレンエ
ーテル樹脂を含むことを特徴とする樹脂組成物である。Means for Solving the Problems The present invention provides a polyphenylene ether resin composition for foam molding using a foaming agent that generates ammonia.
This is a resin composition characterized by containing a polyphenylene ether resin having at least one group among an epoxy group, a carboxyl group, and an acid anhydride group as a terminal group.
本発明においては、ポリフェニレンエーテルの末端基が
エポキシ化、カルボキシル化、及び酸無水物化の中の少
くとも１つによって変性されている末端基変性ポリフェ
ニレンエーテルか使用される。In the present invention, a terminal group-modified polyphenylene ether in which the terminal group of the polyphenylene ether is modified by at least one of epoxidation, carboxylation, and acid anhydride conversion is used.
本発明において末端基が変性されるポリフェニレンエー
テルは、たとえば一般式（八）Ｒ４Ｒ１
Ｒ３Ｒ２
（式中Ｒ、Ｒ、Ｒ、並びにＲ４は水素、ハ０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は重合度を表わす整数で
ある）
で表わされる重合体の総称であって、上記一般式で表わ
される重合体の一種単独であっても、二種以上が組合わ
された共重合体であってもよい。In the present invention, the polyphenylene ether whose terminal group is modified has the general formula (8) R4R1 R3R2 (where R, R, R, and R4 are hydrogen, halogen, an alkyl group, an alkoxy group, a halogen atom, and a phenyl ring). represents a monovalent substituent selected from haloalkyl and haloalkoxy groups having at least 2 carbon atoms between them and containing no tertiary α-carbon, where n is an integer representing the degree of polymerization) It is a general term for polymers represented by the above general formula, and may be a single type of polymer represented by the above general formula or a copolymer in which two or more types are combined.
好ましい具体例ではＲ及びＲ２は炭素原子数１〜４のア
ルキル基であり、Ｒ３，Ｒ４は水素もしくは炭素原子数
１〜４のアルキル基である。たとえばポリ（２，６−シ
メチルー１．４−フェニレン）エーテル、ポリ（２，６
−ジニチルー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−メチル−６−ブロビルー１．４−）ユニレ
ノ）エーテル、ポリ（２，６−ジプロビルー１．４−フ
ェニレン）エーテル、ポリ（２−エチル−６−プロピル
−１，４−フェニレン）エーテル、等が挙げられる。In a preferred embodiment, R and R2 are alkyl groups having 1 to 4 carbon atoms, and R3 and R4 are hydrogen or alkyl groups having 1 to 4 carbon atoms. For example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2,6-dimethyl-1,4-phenylene)
- dinityl-1,4-phenylene) ether, poly(2
-Methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-broby-1,4-)unileno) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly( 2-ethyl-6-propyl-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
ノールたとえば２，３．６− トリメチルフェノールを
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
グラフミル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、たと
えばスチレン、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得られる共重合体
である。Examples of the polyphenylene ether copolymer include copolymers containing a portion of alkyl trisubstituted phenol, such as 2,3,6-trimethylphenol, in the polyphenylene ether repeating units. Alternatively, a copolymer in which a styrene compound is grafted onto these polyphenylene ethers may be used. Styrene compound graphylated polyphenylene ether includes the above-mentioned polyphenylene ether, styrene compound such as styrene, α-methylstyrene, vinyltoluene,
It is a copolymer obtained by graft polymerization of chlorstyrene, etc.
本発明のために特に好ましいポリフェニレンエーテルの
群にはエーテル酸素原子に対し２つのオルソ位にＣ１〜
Ｃ４アルキル置換基を有するものを含む。この群の例に
は、
ポリ（２，６−シメチルー１．４−フェニレン）エーチ
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（２，６−ジプロビルー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
等があり、最も好ましいのはポリ（２，６−シメチルー
１，４−フェニレン）エーテルであって、式（８）
％式％
式（Ｃ）
４ Ｒ４
の末端基のうち少くとも１つを有するものである。A particularly preferred group of polyphenylene ethers for the present invention includes C1-
Including those with C4 alkyl substituents. Examples of this group include: Poly(2,6-dimethyl-1,4-phenylene)ethyl: Poly(2,6-diethyl-1,4-phenylene)ether: Poly(2-methyl-6-ethyl-1, 4-phenylene)
Ether: Poly(2,6-diprobyl-1,4-phenylene) ether: Poly(2-ethyl-6-brobyl-1,4-phenylene) ether, etc., and the most preferred is poly(2,6-dimethyl-1,4-phenylene) ether. 4-phenylene) ether having at least one terminal group of formula (8) % formula % formula (C) 4 R4 .
前記ポリフェニレンエーテルの末端基の、エポキシ化、
カルボキシル化、又は酸無水物化は公知の方法によって
行うことができる。Epoxidation of the terminal group of the polyphenylene ether,
Carboxylation or acid anhydride conversion can be performed by a known method.
末端基のエポキシ化については、たとえば特開昭６３−
１２５５２５号公報に記載されている。末端エポキシ化
ポリフェニレンエーテルは、ポリフェニレンエーテルと
エポキシ基をもつ物質とを加熱下に接触させることによ
って得ることができる。Regarding epoxidation of terminal groups, for example, JP-A-63-
It is described in No. 125525. The terminally epoxidized polyphenylene ether can be obtained by bringing polyphenylene ether and a substance having an epoxy group into contact under heating.
エポキシ基をもつ化合物としては、片末端がハロゲン化
物であるエポキシ化合物か又は両末端エポキシ化合物で
ある。具体的には、好ましい片末端エポキシ化物にはエ
ピクロルヒドリン、２−メチルエピクロルヒドリン等が
あり、好ましい両末端エポキシ化物には２，２−ビス（
４−グリシジルフェニルエーテル）プロパン、エポキシ
樹脂等がある。ポリフェニレンエーテル同志のブロック
化を抑制する点より、片末端エポキシ化物が特に好まし
い。The compound having an epoxy group is an epoxy compound having a halide at one end or an epoxy compound having both ends. Specifically, preferred epoxidized products at one end include epichlorohydrin, 2-methylepichlorohydrin, etc., and preferred epoxidized products at both ends include 2,2-bis(
4-glycidyl phenyl ether) propane, epoxy resins, etc. From the viewpoint of suppressing blocking of polyphenylene ethers, one end epoxidized product is particularly preferable.
末端基のカルボキシル化及び酸無水物化については、た
とえば特表昭６２−５００４５６号公報に記載されてい
る。末端カルボキシル化又は酸無水物化ポリフェニレン
エーテルは、カルボキシル基又は酸無水物基をもつ酸ク
ロライド、たとえばトリメリット酸無水物クロライドと
ポリフェニレンエーテルとを反応させることによって得
られる。Carboxylation and acid anhydride conversion of terminal groups are described, for example, in Japanese Patent Publication No. 1983-500456. The terminally carboxylated or acid anhydride polyphenylene ether is obtained by reacting an acid chloride having a carboxyl group or an acid anhydride group, such as trimellitic anhydride chloride, with a polyphenylene ether.
本発明において用いるポリフェニレンエーテルは、必ず
しもそのすべてが末端基を変性したものである必要はな
く、本発明の樹脂組成物は末端基未変性のポリフェニレ
ンエーテルを含むことができる。ただし、末端基変性ポ
リフェニレンエーテルが少くともアンモニア臭を抑制す
るために十分な量、例えば１０重量％以上、好ましくは
２０重量％以上含まれることが必要である。The polyphenylene ether used in the present invention does not necessarily all have modified terminal groups, and the resin composition of the present invention can contain polyphenylene ether with unmodified terminal groups. However, it is necessary that the terminal group-modified polyphenylene ether be contained in an amount sufficient to suppress at least ammonia odor, for example, 10% by weight or more, preferably 20% by weight or more.
本発明の樹脂組成物はポリフェニレンエーテルと相溶性
の良い種々の樹脂を含むことができるが、たとえばスチ
レン系樹脂が好ましい。スチレン系樹脂は、一般式：
（式中、Ｒは水素原子、低級アルキル基、又はハロゲン
原子であり、Ｚはビニル基、水素原子、塩素原子及び低
級アルキル基から選択された同−又は異なる基であり、
そしてＰはＯ〜５の整数である）
を有する化合物から誘導された骨格を少くとも２５重量
％有するものが好ましい。具体的には、ポリスチレンホ
モポリマー、ゴム改質ポリスチレン、及びスチレン−ア
クリロニトリルコポリマー、スチレノーアクリロニトリ
ルーブタジエンコポリマー等のスチレン含有コポリマー
を挙げることができる。The resin composition of the present invention can contain various resins that are compatible with polyphenylene ether, but styrene resins are preferred, for example. The styrenic resin has the general formula: and
and P is an integer from 0 to 5). Specific examples include polystyrene homopolymers, rubber-modified polystyrene, and styrene-containing copolymers such as styrene-acrylonitrile copolymers and styrene-acrylonitrile-butadiene copolymers.
本発明の樹脂組成物において、ポリフェニレンエーテル
（末端基変性及び末端基未変性のポリフェニレンエーテ
ル）とポリスチレン系樹脂は使用の目的に応じて任意の
割合で配合することができる。In the resin composition of the present invention, polyphenylene ether (terminally modified and unmodified polyphenylene ether) and polystyrene resin can be blended in any proportion depending on the purpose of use.
アンモニアを発生する発泡剤としては、アゾジカルボン
アミド、重炭酸アンモニウム、ジニトロソペンタメチレ
ンテトラミン、ニトロウレア、ヒドラゾジカルボンアミ
ド、ニトログアニジン、トリヒドラジノトリアゾオキザ
リルヒドラジド、り−トルエンスルホンセミ力ルバジド
、ｐ−メチルウレタンベンゼンスルホニルヒドラジド、
２．４−）ルエンジスルホンヒドラジド等が知られてお
り、これらのいずれもが本発明の樹脂組成物の発泡成形
に使用することができる。Foaming agents that generate ammonia include azodicarbonamide, ammonium bicarbonate, dinitrosopentamethylenetetramine, nitrourea, hydrazodicarbonamide, nitroguanidine, trihydrazinotriazooxalylhydrazide, tri-toluenesulfone semihydrabazide, p-methylurethane benzenesulfonyl hydrazide,
2.4-) Luene disulfone hydrazide and the like are known, and any of these can be used for foam molding of the resin composition of the present invention.
本発明の樹脂組成物にはその物性を損なわない限りにお
いて樹脂の混合時、成形時に添加剤、たとえば顔料、染
料、補強剤、充填剤、耐熱剤、酸化劣化防止剤、耐候剤
、滑剤、離形剤、難燃剤、帯電防止剤等を添加すること
ができる。The resin composition of the present invention may contain additives such as pigments, dyes, reinforcing agents, fillers, heat resistant agents, oxidative deterioration inhibitors, weathering agents, lubricants, and release agents during resin mixing and molding, as long as the physical properties are not impaired. Excipients, flame retardants, antistatic agents, etc. can be added.
以下、実施例により本発明をより具体的に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例
（１） 末端基にエポキシ基を有するポリフェニレン
エーテルの製造
乾燥したフラスコに固有粘度０．４６ （クロロホルム
中３０℃で測定）のポリフェニレンエーテル１００重量
部をエピクロルヒドリン１５００重量部に溶解させた。Example (1) Production of polyphenylene ether having an epoxy group at the end group In a dry flask, 100 parts by weight of polyphenylene ether having an intrinsic viscosity of 0.46 (measured in chloroform at 30°C) was dissolved in 1500 parts by weight of epichlorohydrin.
次に、３３．３％苛性ソーダ溶液１５重量部を加え、撹
拌しながら１００℃まで加熱し、この温度で４時間反応
させた。温度が室温付近になるまで冷却した後、添加し
たエピクロルヒドリンの２倍容酋のメタノールを添加し
ポリマーを析出させた。Next, 15 parts by weight of 33.3% caustic soda solution was added, heated to 100° C. with stirring, and reacted at this temperature for 4 hours. After the mixture was cooled to around room temperature, methanol was added in an amount twice the volume of epichlorohydrin added to precipitate a polymer.
ポリマーを濾別してメタノール、水、メタノールの順で
洗浄した後、１５０℃で８時間減圧下で乾燥し、末端基
にエポキシ基を有するポリフェニレンエーテルを得た。The polymer was filtered and washed with methanol, water, and methanol in this order, and then dried under reduced pressure at 150° C. for 8 hours to obtain polyphenylene ether having an epoxy group at the terminal group.
（２） 末端基に酸無水物基を有するポリフェニレン
エーテルの製造
固有粘度０．４６のポリフェニレンエーテル１００重量
部をトルエン５００重量部に溶解させた。次に、トリメ
リット酸無水物酸クロライド３重量部を添加した後、攪
拌しながら１００℃まで昇温し、ジメチル−ｎ−ブチル
アミン６重量部を加えて２時間反応させた。次に、（１
）と同様に洗浄、乾燥して末端基に酸無水物基を有する
ポリフェニレンエーテルを得た。(2) Production of polyphenylene ether having an acid anhydride group at the terminal group 100 parts by weight of polyphenylene ether having an intrinsic viscosity of 0.46 was dissolved in 500 parts by weight of toluene. Next, after adding 3 parts by weight of trimellitic anhydride acid chloride, the temperature was raised to 100° C. with stirring, and 6 parts by weight of dimethyl-n-butylamine was added, and the mixture was reacted for 2 hours. Next, (1
) was washed and dried in the same manner as in ) to obtain polyphenylene ether having an acid anhydride group at the terminal group.
実施例１〜２及び比較例１〜２
表１に示す割合の組成成分を５０ａｍの２軸押用機を用
いて混練し、ペレットを作成した。得られたペレット１
００重量部に対して０．３重量部のアゾジカルボンアミ
ドをブレンドして発泡成形を行った。Examples 1 and 2 and Comparative Examples 1 and 2 Composition components in the proportions shown in Table 1 were kneaded using a 50 am twin screw press to create pellets. Obtained pellet 1
Foam molding was performed by blending 0.3 parts by weight of azodicarbonamide with respect to 00 parts by weight.
得られた成形品について次の試験を行った。The following tests were conducted on the obtained molded product.
アンモニア臭の有無：臭覚による評価
プレートアウトの有無二目視による評価熱変形温度 ：
ＡＳＴＭ Ｄ６４８
（４，８に９／ Ｃ／／１荷重）
得られた結果は表１に示す通りである。Presence or absence of ammonia odor: evaluation by sense of smell Evaluation of presence or absence of plate out by second sight Heat distortion temperature:
ASTM D648 (4,8 to 9/C//1 load) The results obtained are shown in Table 1.
本発明の樹脂組成物（実施例１及び２）は比較例２に見
られるような熱変形温度の低下を来たすことなしにアン
モニア臭が全（抑制されている。In the resin compositions of the present invention (Examples 1 and 2), the ammonia odor was completely suppressed without causing a decrease in heat distortion temperature as seen in Comparative Example 2.
出 願 人Out wish Man
Claims (1)
ポリフェニレンエーテル系樹脂組成物において、エポキ
シ基、カルボキシル基、及び酸無水物基の中の少くとも
１つの基を末端基として有するポリフェニレンエーテル
樹脂を含むことを特徴とする樹脂組成物。1. In a polyphenylene ether resin composition for foam molding using a foaming agent that generates ammonia, a polyphenylene ether resin having at least one group among an epoxy group, a carboxyl group, and an acid anhydride group as a terminal group is used. A resin composition comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24393188A JPH0292956A (en) | 1988-09-30 | 1988-09-30 | Polyphenylene ether resin composition for expansion molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24393188A JPH0292956A (en) | 1988-09-30 | 1988-09-30 | Polyphenylene ether resin composition for expansion molding |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0292956A true JPH0292956A (en) | 1990-04-03 |
Family
ID=17111156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24393188A Pending JPH0292956A (en) | 1988-09-30 | 1988-09-30 | Polyphenylene ether resin composition for expansion molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0292956A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480244A2 (en) * | 1990-10-04 | 1992-04-15 | General Electric Company | Methods for reducing odor in polyphenylene ether resins |
| US8704430B2 (en) | 2006-08-09 | 2014-04-22 | Continental Automotive Gmbh | Piezoceramic multilayer actuator with high reliability |
-
1988
- 1988-09-30 JP JP24393188A patent/JPH0292956A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0480244A2 (en) * | 1990-10-04 | 1992-04-15 | General Electric Company | Methods for reducing odor in polyphenylene ether resins |
| US8704430B2 (en) | 2006-08-09 | 2014-04-22 | Continental Automotive Gmbh | Piezoceramic multilayer actuator with high reliability |
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