JPS63152628A - Production of polyphenylene ether resin having excellent color tone - Google Patents
Production of polyphenylene ether resin having excellent color toneInfo
- Publication number
- JPS63152628A JPS63152628A JP29895986A JP29895986A JPS63152628A JP S63152628 A JPS63152628 A JP S63152628A JP 29895986 A JP29895986 A JP 29895986A JP 29895986 A JP29895986 A JP 29895986A JP S63152628 A JPS63152628 A JP S63152628A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- styrene
- color tone
- compound
- ether
- 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 32
- 239000011347 resin Substances 0.000 title claims abstract description 16
- 229920005989 resin Polymers 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 7
- 238000004898 kneading Methods 0.000 claims abstract description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 32
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 26
- -1 poly(2,6- dimethyl-1,4-phenylene) Polymers 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 7
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 2
- 241001082241 Lythrum hyssopifolia Species 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 229920001971 elastomer Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010559 graft polymerization reaction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- VOGVOLGCIBZOMR-UHFFFAOYSA-N 2-(5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-trien-3-yl)ethanol Chemical compound OCCC1=C(O2)C(C)=CC2=C1 VOGVOLGCIBZOMR-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-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
- GGZZISOUXJHYOY-UHFFFAOYSA-N 8-amino-4-hydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C(N)=CC=CC2=C1O GGZZISOUXJHYOY-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002431 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000007704 transition Effects 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
- 239000011345 viscous material Substances 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、色調の優れたポリフェニレンエーテル系樹脂
の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a polyphenylene ether resin with excellent color tone.
更に詳しくは、ポリフェニレンエーテル系樹脂を炭素−
炭素二重結合を有する化合物の存在下、ラジカル発生剤
無除加でポリフェニレンエーテルのガラス転移温度以上
で浴融混練する事七特徴とする色―改良法に閃するもの
である。More specifically, polyphenylene ether resin is carbon-
This invention is inspired by a color improvement method characterized by bath melt-kneading at a temperature higher than the glass transition temperature of polyphenylene ether without the addition of a radical generator in the presence of a compound having a carbon double bond.
（従来の技術）
ポリフェニレンエーテル系樹脂としては、ポリフェニレ
ンエーテルとゴム変性ポリスチレンとのブレンド物が広
く知られており、七の優れた熱的性質、機械的性質及び
電気的性質より、電気電子部品、事務機器などに広く使
用されている。(Prior Art) Blends of polyphenylene ether and rubber-modified polystyrene are widely known as polyphenylene ether resins, and due to their excellent thermal, mechanical, and electrical properties, they are suitable for electrical and electronic components, Widely used in office equipment, etc.
しかし、通常のポリフェニレンニーテルハ、ソれ自体の
色満が悪く、更に加熱による色調の悪化が犬ぎい。七の
結果ポリフェニレンエーテル系樹脂においては、鮮やか
な色や白糸着色が不可能であったり、又染顔料勿多負に
添加する事により、看色可北であっても、その結果、熱
的性質、＠械的性情が大幅に低下する等の問題ケ有して
いる。However, with ordinary polyphenylene nitrates, the color saturation itself is poor, and furthermore, the color tone deteriorates due to heating. As a result of (7), polyphenylene ether resins may not be able to produce bright colors or white thread coloring, and due to the negative addition of dyes and pigments, even if the color is good, the thermal properties may be poor. , @ There are problems such as a significant decrease in mechanical nature.
それ故、従来、ポリフェニレンエーテル系樹脂の色調改
良に関しては、次亜リン酸塩、亜すン酸エステル會添加
することが特公昭４２−１２５３０号公報、特公昭５１
−３３９３８号公報及び特公昭５１−４０５８９号公報
等に示されている。又次亜リン酸を用いる事も特開昭５
９−９８１６０号公報及び％開昭５９−９８１６１号公
報に示されている。Therefore, in order to improve the color tone of polyphenylene ether resins, it has been conventionally recommended to add hypophosphite or sulfite ester, as disclosed in Japanese Patent Publication Nos. 42-12530 and 51.
This is disclosed in Japanese Patent Publication No. 51-40589 and Japanese Patent Publication No. 51-40589. In addition, the use of hypophosphorous acid was also disclosed in 1973.
It is shown in Japanese Patent No. 9-98160 and Japanese Patent Publication No. 59-98161.
一方、ポリフェニレンエーテル存在下にスナレン等？ラ
ジカル発生剤を用いグラフト重合することにより、混合
特性、流動％性ケ改良することが特公昭５９１１６０５
号公報に示されている。On the other hand, Sunalene etc. in the presence of polyphenylene ether? Japanese Patent Publication No. 5911605 shows that mixing characteristics and fluidity can be improved by graft polymerization using a radical generator.
It is shown in the publication No.
（発明が解決しようとする問題点）
しかしこれら一連の添加剤によるポリフェニレンエーテ
ル系樹脂の色調改良効果は元号でなく、いずれも、この
樹脂の特徴である流動性？大幅に低下させ、七〇結米、
成形品の外観にも多大の悪影智會およぼ丁。又、衝撃強
さ熱安定性も低下するため署しく商品１ｉ１ｉｉ （１
！＋が横われるとの問題ゲ有している。また、ポリフェ
ニレンエーテル存在下にヌテレン等ｔラジカル発生剤を
用いクラフト１合することにより、混合物性、流動特性
を改良するため＋Ｃはスチレン等がポリフェニレンエー
テルにグラフト重合することが必要であり、七のためラ
ジカル発生剤の使用が不可欠であった。(Problems to be Solved by the Invention) However, the effect of improving the color tone of polyphenylene ether resin by these series of additives is not based on the original name, but rather on the fluidity which is the characteristic of this resin. Significantly reduced, 70 knots,
There are also many negative effects on the appearance of the molded product. In addition, the impact strength and thermal stability are also reduced, so the product 1i1ii (1
! I have a problem with + lying down. In addition, +C requires graft polymerization of styrene, etc. to polyphenylene ether in order to improve the mixture properties and flow characteristics by combining kraft with a t-radical generator such as nutelene in the presence of polyphenylene ether. Therefore, the use of radical generators was essential.
本発明者らに樹脂の色調改良の面より、恨討會進めた結
果、ラジカル発生剤自体が樹脂の色ル１改良に非常に恋
影響し、またデル状物質の生成等、品グー上好ましくな
い影９七与えることが判明した。As a result of discussions with the present inventors regarding the improvement of the color tone of the resin, it was found that the radical generator itself has a great effect on improving the color tone of the resin, and also causes the formation of delta-like substances, which is unfavorable in terms of quality. It turns out that it gives no shadow 97.
’！７’ｃ、衝撃補強用として含まれるジエン糸ゴム負
重合体の存在下でラジカル発生剤を併用するとゴムのケ
９ル化が促進され、衝撃強度の低下が起ることも判明し
た。'! 7'c, It has also been found that when a radical generator is used in combination with a diene thread rubber negative polymer included for impact reinforcement, the keration of the rubber is promoted, resulting in a decrease in impact strength.
本発明者らは色調改良に関して洩々の検討ケ進めた給米
、上す己の従来知られている技術とは全く異なる手法に
より、樹脂の特性全損うことなく、大幅に色調改良効果
る事七見い出し、本発明に達したものである。The present inventors have carried out extensive studies regarding color tone improvement, and by using a method completely different from conventionally known technology, we have achieved a significant color tone improvement effect without completely losing the properties of the resin. Seven things have led to the present invention.
（問題点上解決するための手段〕
即ち、不発９３はポリフェニレンエーテル糸Ｎ 合体を
炭素−炭素二重結合を有する化合物の存在下で、ラジカ
ル発生剤無碓加の状凹で、ポリフェニレンエーテルのガ
ラス転移飄度以上で浴融混練することより成る色調の非
常に浚れたポリフェニレンエーテル系樹脂を製造する方
法である。(Means for solving the problem) In other words, in the misfire 93, the polyphenylene ether thread N is combined in the presence of a compound having a carbon-carbon double bond, and the polyphenylene ether glass is formed without a radical generator. This is a method for producing a polyphenylene ether resin with a very fine color tone, which involves melt-kneading in a bath at a temperature above transition temperature.
本発明にいうポリフェニレンエーテル系７１体とは、下
記一般式ｔｌ＋
（式中、Ｒ□及びＲ２は七れぞれ炭素数１〜４のアルキ
ル基又はハロゲン原子に！わす。ｎは１合艮會示す整数
である。）で表わされるものと、スチレン共重合体とよ
りなるものであり、一般式（１１で示されるものの具体
例としては、ボ’Ｊ （２、６−ヅメナル−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−ジエテ
ルー１，４−フェニレン）エーテル、ボＩＪ （２−エ
テル−６−ｎプロピル−１，４−）ユニしン）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
−フェニレン）エーテル、ポリ（２−エチル−６−イソ
プロビル−１，４−フエニレン）エーテル、ポリ（２−
ノナルー６−クロル−１゜４−フェニレン）エーテル、
？ ’） （２−メチル−６−ヒドロキシエチル−１，
４−フェニレン）エーテル、ボＩＪ （２−ノナルー６
−クロロエテル−１，４−フェニレン）エーテル等のホ
モポリマーが挙げらｎる。また上記一般式で表わされる
化学搗造會主体としてなるポリフェニレンエーテル共１
合体も便用可能である。七の具体例としては２．６−ジ
メナルフエノールと２．５．６−ドリメテルフエノール
の共重合体があげられ心。The polyphenylene ether system 71 referred to in the present invention is defined by the following general formula tl+ (wherein, R□ and R2 each represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. ) and a styrene copolymer. Specific examples of those represented by the general formula (11) include Bo'J (2,6-dumenal-1,4- phenylene)ether, poly(2-methyl-6-ethyl-
1,4-phenylene) ether, poly(2,6-diether-1,4-phenylene) ether, BoIJ (2-ether-6-npropyl-1,4-)unisine) 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-isopropyl-1,4-phenylene) ether, poly(2-
nonal-6-chloro-1°4-phenylene) ether,
? ') (2-methyl-6-hydroxyethyl-1,
4-phenylene) ether, BoIJ (2-nonal-6
Examples include homopolymers such as -chloroether-1,4-phenylene) ether. In addition, polyphenylene ether which is the main body of the chemical formula represented by the above general formula 1
Combination is also possible. A specific example of 7 is a copolymer of 2,6-dimenalphenol and 2,5,6-drimetherphenol.
ぼた、スナＶン糸１合体としては、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ｆ １１＝Ｅ Ｂ−合体を百〇も
のである。スチレンと他のビニル化＠物の少なくと１種
との共１合体の具体例とじては、スチレン−アクリロニ
トリル共Ｎ合’ｆ４−、スｆレンーメタクリル酸メナル
共１合体、スチレン−α−メチルステレン共１合体、ス
チレン−無水マレイン酸共重合体等があげられる。テた
、ゴム変成１合体としては、ゴム変成ポリスチレン（Ｈ
工ｐｓ ）、ゴム変成スチレン−アクリロニトリル共１
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。The 100% polystyrene, or a copolymer of styrene and at least one other vinyl compound, and a rubber f 11 =E B-combination thereof are used as the 100% polystyrene or a copolymer of styrene and at least one other vinyl compound. Specific examples of comonomers of styrene and at least one other vinylated compound include styrene-acrylonitrile co-N-bond 'f4-, styrene-menal methacrylate co-monolith, styrene-α- Examples include methylsterene copolymer, styrene-maleic anhydride copolymer, and the like. The rubber modified polystyrene (H
PS), rubber modified styrene-acrylonitrile 1
There are rubber-modified styrene-maleic anhydride copolymers, etc.
ポリフェニレンエーテルとスチレン基Ｎ 合体の割合に
関しては特に限定を要しないが、ステンン糸１合体は、
実用上ポリフェニレンエーテル１００〜２５Ｎ量％に対
しＯ〜７５重振％の範囲から選はれる。Although there is no particular limitation on the ratio of polyphenylene ether and styrene group N, one styrene thread combination is as follows:
Practically speaking, it is selected from the range of 0 to 75% by weight per 100 to 25% of polyphenylene ether.
本発明に用いられる、炭素−炭素二重結合を有する化合
物としては、下記一般式（Ｉｌ）Ｈ２Ｃ−Ｃ−Ｒ３ｆｉ
１
（式中Ｒ３に水素、炭素原子数１〜４の低紗アルキル基
またはハロゲンを示し、Ｒ４はフェニル基、炭素原子数
１〜４の低級アルキル化フェニル基及び七のハロゲン置
換体、カルボン酸の炭素原子数Ｉ ５８（７）フルキル
エステル、ニトリル基を示す。）を有するものであり、
具体例としては、スチレン、α−メチルスチレン、０−
メチルスチレン、Ｍ−メチルスチレン、Ｐ−メチルスチ
レン、Ｐ−ｍ三級ブチルスチレン及びごれらのハロケ１
ン直挨体があげられる。七の他の例としては、メタクリ
ル酸メチル、メタクリル酪エナル、メタクリル酸プロピ
ル、メタクリル酸ブチル、メタクリル酸ヘキシル、メタ
クリル酸オクチル及び′これらのハロゲン瓢挾体があげ
られる。アクリル酸メナル、アクリル醇エナル、アクリ
ル酸ブナル、アクリル酸２−エチルヘキシル等も用いう
る。七の他アクリロニトリル、メタクリロニトリル類も
用いることができる。ごれらの中で好ヱしいものとして
は、スチレン、α−メチルスチレン及びメタクリル酸メ
チルであり、最も好ましいものにスチレンである。The compound having a carbon-carbon double bond used in the present invention has the following general formula (Il) H2C-C-R3fi
1 (In the formula, R3 represents hydrogen, a lower alkyl group having 1 to 4 carbon atoms, or a halogen, and R4 represents a phenyl group, a lower alkylated phenyl group having 1 to 4 carbon atoms, a halogen substituted compound of 7, and a carboxylic acid having a carbon atom number I of 58 (7) indicating a furkyl ester, a nitrile group),
Specific examples include styrene, α-methylstyrene, 0-
Methyl styrene, M-methyl styrene, P-methyl styrene, P-m tertiary butyl styrene and gorera haloke 1
Examples include direct dust. Other examples of methacrylate include methyl methacrylate, methacrylbutyenal, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate and their halogenated forms. Menal acrylate, enal acrylate, bunal acrylate, 2-ethylhexyl acrylate, etc. can also be used. In addition to 7, acrylonitrile and methacrylonitrile can also be used. Preferred among these are styrene, α-methylstyrene and methyl methacrylate, with styrene being the most preferred.
ごの炭素−炭素二重結合を有する化合物のへ加量として
は、ポリフェニレンエーテル系重合体１００ｉ：ｆｔ部
に対し０．５〜３０’ｉｌｋ童部、より好ましくは１〜
２５重ｔｈ［ｓである。The amount of addition of the compound having a carbon-carbon double bond is from 0.5 to 30 parts, more preferably from 1 to 30 parts per 100 parts of the polyphenylene ether polymer.
25 times th[s.
不発９３を実施するにあた９、ポリフェニレンエーテル
と炭素−炭素二重結合七頁する化合物と？充分俗融混練
する必要があり、七のためポリフエニレンエーテルのガ
ラス転移温度以上で混線丁ゐ事が必要である。ガラス転
移温度未満でにポリフェニレンエーテルと炭素−炭素二
重結合を有する化合物との接触が充分進まないためと思
われ、その結果、色調改良効果はほとんど表われず、炭
素−炭素二重結合を有する１ヒ金物の残留物が増加しｈ
ｘしくない、一方、溶融混練り温良の上限に関してはポ
リフェニレンエーテルの***定性の面より ３２０ ’
Ｃ以下で実施するのが好ましい。In carrying out Misfire 93, what is the compound that contains polyphenylene ether and a carbon-carbon double bond? It is necessary to thoroughly melt and knead the mixture, and for this reason, it is necessary to mix the wires at a temperature higher than the glass transition temperature of polyphenylene ether. This seems to be because the contact between polyphenylene ether and the compound having a carbon-carbon double bond does not proceed sufficiently below the glass transition temperature, and as a result, the color tone improvement effect is hardly visible, and the compound having a carbon-carbon double bond 1) Residues of hardware increase
On the other hand, regarding the upper limit of melt-kneading temperature, it is 320'
It is preferable to carry out at C or less.
なおポリフェニレンエーテルのガラス転移温度は代表的
なポリ（２，６−ヅメナル−１，４−フエニレン）エー
テルでは２０９°Ｃの僅か知られている０本発明で溶融
混練りする方法としては、浴＃！粘性体會取り扱い得る
方法であれば如何なる方法であっても艮いカニ、作業性
、混練Ｖ効果、生産性葡閏慮すれは押出機、特に２軸押
出恢での実施が好ましい、なお、炭素−炭素二重結合ｔ
゛有する化合物の分散ケよくするために予倫混名として
ヘンシェルミキサーを用いて行うのが好ヱしい。The glass transition temperature of polyphenylene ether is only 209°C for typical poly(2,6-dumenal-1,4-phenylene) ether. ! Any method can be used as long as it can handle a viscous material, but it is preferable to use an extruder, especially a twin-screw extruder, considering the efficiency, workability, kneading V effect, and productivity. -carbon double bond t
In order to improve the dispersion of the compound, it is preferable to use a Henschel mixer for mixing.
本さし明ケ実方するに際し、色ａｌ＝、改良ケ阻害しな
い物乍」であるならば路−加削、例えはＥｉＪ塑剤、ｂ
科、難燃剤、補強剤（ガラスＭ維、ガラスピーズ等）、
安定剤等ｋｔ４≦加することは可能である。更に他のポ
リマー例えはポリブタジェン、ブタジェン−スチレン共
１−合体及びそれらの水素添〃口物、ポリオレフィン、
ポリアミド等を加える手も川口しである。When carrying out the actual presentation, if the color is ``al=, a material that does not impede improvement,'' then road-machining, for example, EiJ plastic, b
family, flame retardants, reinforcing agents (glass M fiber, glass beads, etc.),
It is possible to add a stabilizer or the like with kt4≦. Further examples of other polymers include polybutadiene, butadiene-styrene comonomers and hydrogenated products thereof, polyolefins,
Kawaguchi also added materials such as polyamide.
（実施例）
以下、不発明を実施例により評細に説明するが、不発Ｂ
Ａはごれらに限定されるものではない。(Example) Hereinafter, non-invention will be explained in detail using examples.
A is not limited to Gorera.
実施例１〜７及び比較例１
ポリ（２，６−ジメテルー１，４−フェニレン）エーテ
ル（３０°Ｃクロロホルム中で両足した固有キろ度がＣ
１−５７”ｔ／９ ） ６０京に都と、小すスナレン（
旭化厄（株）装、商品名ニスタイロン６８５）Ａ Ｏ＠
ｉＲｔＪとのフ゛レンド吻に、スチレンｗ 下ｓａの
表−１に示す一際加し、ヘンシェルミキサー１よく撹拌
混合した。これら配合物ｔろ０妬φペント付２軸押出機
で２９０°Ｃのム友で浴融混枕し、ペレット化し、５オ
ンス射出奴骸ｂｋ用い２シ［’Ｊ ’Ｑで５ Ｄ Ｘ
９ ［３Ｘ ２ ＃Ｉｎ＋のカラーナソ７′？成堰した
。Examples 1 to 7 and Comparative Example 1 Poly(2,6-dimether-1,4-phenylene) ether (both intrinsic kirosities in chloroform at 30°C are C)
1-57”t/9) 60 Kyoto and the small Suna Ren (
Asahi Kayaku Co., Ltd., product name Nistyron 685) A O@
Styrene w as shown in Table 1 below was added to the iRtJ fraternity, and the mixture was thoroughly stirred using a Henschel mixer 1. These blends were mixed in a bath at 290°C in a twin-screw extruder equipped with a t0 x φ pent, pelletized, and made into pellets using a 5 oz.
9 [3X 2 #In+ color naso 7'? It was completed.
この物の色論評１四結果で表−１に示す。なお、色調は
デジタル迎１色色燈計Ｘ機（ガス試験機）にて測定した
白色ｋ （Ｗ （Ｌａｋ） ） ）の値を用いた。Table 1 shows the results of color evaluation of this product. As for the color tone, the value of white k (W (Lak) )) measured with a digital one-color color light meter X machine (gas tester) was used.
Ｗ （Ｌａｂ ）の値が太さい程、ａ（脂の色調が明る
く且つ色が薄くなっている事を示す。The thicker the value of W (Lab), the brighter and lighter the color tone of a (fat).
表−１
この結果よりスチレン’ｋ Ｏ，５ｍ蓋部〜３［］重量
部の範囲で重加したものの色調が非常に改良される”Ｊ
−７ＪＸ明らかである。特にスチレン１〜２５ｉｉ３１
品の範囲が色調改良に顕著な効果を示す。Table 1 From these results, the color tone of styrene added in the range of 5 m lid part to 3 parts by weight is greatly improved.
-7JX is obvious. Especially styrene 1-25ii31
A range of products show remarkable effects on color tone improvement.
実施例８〜１０
色調改良としてスチレンに変えてα−メチルススナレ、
メタクリルレメチル及びアクリル臓２−エチルヘキシル
を各１０重量部使用する以外は、実施例４と同じ条件下
で実験を進め、表−２の結果を得た。Examples 8 to 10 As a color improvement, α-methylsugar was used instead of styrene,
The experiment was carried out under the same conditions as in Example 4, except that 10 parts by weight each of methacryl lemethyl and acrylic 2-ethylhexyl were used, and the results shown in Table 2 were obtained.
衣−２
この結果より、α−メチルスチレン、メタクリルＩ４ン
メテル、アクリル酸２−エチルヘキシルも色調改良に効
果を示す事が明らかである。Clothing-2 From these results, it is clear that α-methylstyrene, methacrylic acid, and 2-ethylhexyl acrylate are also effective in improving color tone.
実施例１１及び比較例２％６
ポリ（２，６−ジメテルー１，４−フェニレン）エーテ
ル（６０℃クロロホルム中で測定した固有粘度が肌５５
ｄｔ／Ｆ！ ） ５５″ｊｊＬ量部とゴム補強ポリス
チレン（脂化ｆｆ（株）規、商品名；スタイロンＡ９２
）４５Ｎ童部、トリフェニルホスフェート４１門部、オ
クタデシル−ろ−（３，５−ジターシャＩＪ−フチルー
４−ヒドロキシフェニル）フロビオネート（イルガノッ
クス１０７６）０．５ｔａ！都からなる組成物に、スチ
レン上９１覧都几え、２９０−Ｃ″′ｃｆ＆心混練し、
待られたポリマー會実施例１〜７と１６１様に評価した
。比軟としてヌテレンケ加えずに浴θ混珠したケース（
比較例２）及びスチレン９ Ｔｆｉ ｋ 部にラジカル
発午創として通常艮〈知られているシータ−シャリ−ブ
チルパーオキサイド１．０重Ｒ都２ Ｉｆ＋川した糸（
比軟例６）についてもあわセで評価した。Example 11 and Comparative Example 2%6 Poly(2,6-dimether-1,4-phenylene) ether (intrinsic viscosity measured in chloroform at 60°C is 55%)
dt/F! ) 55″jjL quantity part and rubber reinforced polystyrene (Fuka ff Co., Ltd. regulations, product name: Styron A92
) 45N Dobe, triphenyl phosphate 41 phylum, octadecyl-ro-(3,5-ditasha IJ-phthyl-4-hydroxyphenyl) flobionate (Irganox 1076) 0.5ta! A composition consisting of 290-C'''cf &290-C'''cf& heart is kneaded on styrene.
The long-awaited polymer society Examples 1 to 7 and 161 were evaluated. A case in which bath θ beads were mixed without adding Nuterenke as a ratio (
Comparative Example 2) and styrene 9 Tfi k part as a radical generation wound (known as theta-shari-butyl peroxide 1.0 heavy R 2 If + river yarn)
Comparative softness example 6) was also evaluated by foaming.
物性評価の結米會表−５に示す。Table 5 shows the results of physical property evaluation.
（以下余ｆ３）
これらの結果より、実施例１１に色調が非常に優れ、し
かもなお、？！Ｉ注面でも優れたものが得られる事が明
らかである。比較例２では色調が非常に劣る。比較例６
では色調は比較例２よりは改良されるが、アイゾツト衝
撃強さの低下が檄しく、表面元沢も低下する。(Hereinafter, remainder f3) From these results, Example 11 has a very good color tone, and yet... ! It is clear that excellent results can be obtained even on the I-injection surface. In Comparative Example 2, the color tone is very poor. Comparative example 6
In this case, the color tone is improved compared to Comparative Example 2, but the drop in the isot impact strength is deplorable, and the surface roughness is also reduced.
なお、実施例１１と比較例２のｍ酸物１００Ｍ訊部に自
着色剤の酸化チタンを各々２．５Ｎ墓部、５１食部及び
１０重賃部加えたのち、４Ｑｉｉφ単軸押出機で２９０
’Ｃで造粒し、この物の白色度ケ演（１走した。七の結
果を表−４に示す。In addition, after adding titanium oxide as an autocoloring agent to 100M parts of the m-acid of Example 11 and Comparative Example 2, 2.5N parts, 51 parts and 10 parts, respectively, 290 parts of titanium oxide was added using a 4Qiiφ single-screw extruder.
The results were shown in Table 4.
表−４
これより実施例１１のＭ酸物では着色剤が通常品と比較
し半減し得る事が明らかであり、看色性が著しく改良さ
れる。Table 4 From this, it is clear that in the M acid of Example 11, the amount of coloring agent can be reduced by half compared to the ordinary product, and the color visibility is significantly improved.
Claims (1)
を有する化合物の存在下、ラジカル発生剤無添加の状態
で、ポリフェニレンエーテルのガラス転移温度以上の温
度で溶融混練することを特徴とする色調の優れたポリフ
ェニレンエーテル系樹脂の製造法A polyphenylene ether polymer with excellent color tone is produced by melt-kneading the polyphenylene ether polymer at a temperature higher than the glass transition temperature of the polyphenylene ether in the presence of a compound having a carbon-carbon double bond and without the addition of a radical generator. Manufacturing method of polyphenylene ether resin
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29895986A JPS63152628A (en) | 1986-12-17 | 1986-12-17 | Production of polyphenylene ether resin having excellent color tone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29895986A JPS63152628A (en) | 1986-12-17 | 1986-12-17 | Production of polyphenylene ether resin having excellent color tone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63152628A true JPS63152628A (en) | 1988-06-25 |
| JPH0551614B2 JPH0551614B2 (en) | 1993-08-03 |
Family
ID=17866397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29895986A Granted JPS63152628A (en) | 1986-12-17 | 1986-12-17 | Production of polyphenylene ether resin having excellent color tone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63152628A (en) |
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