JPH01279959A - Highly heat-resistant thermoplastic resin composition - Google Patents
Highly heat-resistant thermoplastic resin compositionInfo
- Publication number
- JPH01279959A JPH01279959A JP10907788A JP10907788A JPH01279959A JP H01279959 A JPH01279959 A JP H01279959A JP 10907788 A JP10907788 A JP 10907788A JP 10907788 A JP10907788 A JP 10907788A JP H01279959 A JPH01279959 A JP H01279959A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- methacrylic
- resin composition
- maleimide
- copolymer
- 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 claims abstract description 12
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 7
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 125000005395 methacrylic acid group Chemical group 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 14
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000005060 rubber Substances 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 18
- -1 N-substituted maleimide Chemical class 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 11
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 2
- 125000000753 cycloalkyl group Chemical group 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000007423 decrease Effects 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- MKRBAPNEJMFMHU-UHFFFAOYSA-N 1-benzylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1CC1=CC=CC=C1 MKRBAPNEJMFMHU-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- HOLZCMFSCBLOLX-UHFFFAOYSA-N 1-octadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCN1C(=O)C=CC1=O HOLZCMFSCBLOLX-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000005907 alkyl ester 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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- CLNYHERYALISIR-UHFFFAOYSA-N nona-1,3-diene Chemical compound CCCCCC=CC=C CLNYHERYALISIR-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 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、耐熱性、成型加工性、耐衝撃性に優れた高耐
熱性熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a highly heat-resistant thermoplastic resin composition having excellent heat resistance, moldability, and impact resistance.
〈従来の技術〉
ポリフェニレンエーテルは、耐熱性、機械的及び電気的
特性に優れた樹脂であるが、耐衝撃性及び耐薬品性に劣
り、また、成型加工性と耐熱性を同時に付与することが
できない等の欠点がある。<Prior art> Polyphenylene ether is a resin with excellent heat resistance, mechanical and electrical properties, but it has poor impact resistance and chemical resistance, and it is difficult to impart moldability and heat resistance at the same time. There are drawbacks such as not being able to do so.
耐衝撃性を改良するため、ゴム変性したスチレン系の樹
脂をブレンドする方法が考えられるが、該方法を用いる
場合には、耐熱性が著しく低下するという欠点が生じる
ので好ましくない。前記欠点を解決するためにゴム状重
合体の存在下、スチレンとＮ−置換マレイミドとを共重
合させた共重合体をブレンドする方法が開示されている
（特開昭６２−１００５５１号公報）が、該方法を用い
ても耐熱性が低下すること、又成型加工性が劣る等の問
題点がある。In order to improve the impact resistance, a method of blending a rubber-modified styrene resin may be considered, but when using this method, there is a disadvantage that the heat resistance is significantly reduced, so it is not preferable. In order to solve the above-mentioned drawbacks, a method has been disclosed in which a copolymer of styrene and N-substituted maleimide is blended in the presence of a rubbery polymer (Japanese Patent Application Laid-open No. 100551/1983). Even if this method is used, there are problems such as a decrease in heat resistance and poor moldability.
〈発明が解決しようとする課題〉
本発明の目的は、ポリフェニレンエーテル組成物におい
て、耐熱性、成型加工性及び耐Ｗｆ撃性等の物性に優れ
、且つ前記物性のバランスの取れた高耐熱性熱可塑性樹
脂組成物を提供することにある。<Problems to be Solved by the Invention> The object of the present invention is to provide a polyphenylene ether composition with excellent physical properties such as heat resistance, moldability and Wf impact resistance, and with a well-balanced balance of the above physical properties. An object of the present invention is to provide a plastic resin composition.
〈課題を解決するための手段〉
本発明によれば、（ａ）ポリフェニレンエーテル１０〜
８０重量％と、（ｂ）メタアクリル系マレイミド共重合
体１０〜８０重量％と、（ｃ）スチレン系重合体５〜６
０重量％とを含むことを特徴とする高耐熱性熱可塑性樹
脂組成物が提供される。<Means for Solving the Problems> According to the present invention, (a) polyphenylene ether 10-
80% by weight, (b) 10 to 80% by weight of a methacrylic maleimide copolymer, and (c) 5 to 6% of a styrene polymer.
Provided is a highly heat-resistant thermoplastic resin composition containing 0% by weight.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明に用いるポリフェニレンエーテル（ａ）は、下記
一般式（Ｉ）
（式中、Ｒユ及びＲ２は炭素数１〜８のアルキル基を示
し、Ｒ１及びＲ４は水素原子又は炭素数１〜８のアルキ
ル基を示す、、）にて表わされるフェノール化合物の少
なくとも１種を例えば第１銅塩、第三アミン等の触媒系
の存在下、ｒａ素で酸化カップリング重合する方法等に
より製造することができる。この際、前記Ｒ工乃至Ｒ４
の炭素数が９以上の場合は、製造が困難となるため好ま
しくない。また得られるポリフェニレンエーテル（ａ）
の分子量は、極限粘度〔η〕 （クロロホルム中３０℃
）０．２〜１ａ／ｇであることが望ましい。前記ポリフ
ェニレンエーテル（ａ）の配合割合は、樹脂組成物にお
いて、１０〜８０重量％であり、好ましくは２０〜６０
重量％であることが望ましく、１０重量％未満では耐熱
性に劣り、８０重量％を超えると充分な耐衝撃性及び加
工性が得られないので使用できない。The polyphenylene ether (a) used in the present invention has the following general formula (I) (wherein R and R2 represent an alkyl group having 1 to 8 carbon atoms, and R1 and R4 are hydrogen atoms or carbon atoms having 1 to 8 carbon atoms. It can be produced by a method such as oxidative coupling polymerization of at least one phenol compound represented by , ) representing an alkyl group with ra element in the presence of a catalyst system such as a cuprous salt or a tertiary amine. can. At this time, the R process to R4
If the number of carbon atoms is 9 or more, it is not preferable because manufacturing becomes difficult. Also obtained polyphenylene ether (a)
The molecular weight is the intrinsic viscosity [η] (at 30°C in chloroform)
) It is desirable that it is 0.2 to 1a/g. The blending ratio of the polyphenylene ether (a) in the resin composition is 10 to 80% by weight, preferably 20 to 60% by weight.
If it is less than 10% by weight, the heat resistance will be poor, and if it exceeds 80% by weight, sufficient impact resistance and processability will not be obtained, so it cannot be used.
本発明に用いるメタアクリル系マレイミド共重合体（ｂ
）としては、例えばＮ−Ｈ換マレイミドとアクリル酸エ
ステル及び／又はメタクリル酸エステルの共重合体を好
ましく挙げることができる。Methacrylic maleimide copolymer (b) used in the present invention
), for example, a copolymer of N--H converted maleimide and an acrylic ester and/or a methacrylic ester can be preferably mentioned.
前記共重合体（ｂ）の好ましい成分であるＮ−１換１マ
レイミドは１例えば下記一般式（ＩＩ）で表わすことが
でき、
式中Ｒ工及びＲ２は、水素原子、ハロゲン原子又はメチ
ル基を示し、Ｒ３は炭素数１〜１８の無置換又はハロゲ
ン置換の直鎖アルキル基、分枝アルキル基、シクロアル
キル基又はアラルキル基を表わす。この際Ｒ１の炭素数
が１８を超えると製造が困難となるので好ましくない。N-1 substituted 1-maleimide, which is a preferred component of the copolymer (b), can be represented by, for example, the following general formula (II), where R and R2 represent a hydrogen atom, a halogen atom, or a methyl group. and R3 represents an unsubstituted or halogen-substituted straight-chain alkyl group, branched alkyl group, cycloalkyl group, or aralkyl group having 1 to 18 carbon atoms. In this case, it is not preferable that the number of carbon atoms in R1 exceeds 18 because manufacturing becomes difficult.
前記一般式（ＩＩ）により示されるＮ−置換マレイミド
としては１例えばマレイミド、Ｎ−メチルマレイミド、
Ｎ−エチルマレイミド、Ｎ−イソプロピルマレイミド、
Ｎ−ブチルマレイミド、Ｎ−シクロへキシルマレイミド
、Ｎ−ラウリルマレイミド、Ｎ−ステアリルマレイミド
、Ｎ−フェニルマレイミド、Ｎ−。Examples of the N-substituted maleimide represented by the general formula (II) include maleimide, N-methylmaleimide,
N-ethylmaleimide, N-isopropylmaleimide,
N-butylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-stearylmaleimide, N-phenylmaleimide, N-.
−クロルフェニルマレイミド、Ｎ−ｏ−メチルフェニル
マレイミド、Ｎ−ベンジルマレイミド等を好ましく挙げ
ることができ、単独又は２種以上を混合して用いること
ができる。前記Ｎ−ｆｆ１ｆ換マレイミドのメタアクリ
ル系マレイミド共重合体（ｂ）中における配合割合は、
１０〜８ｏ重量％であることが好ましく、特に２０〜７
０重量％であることが望ましい。前記Ｎ−ｆｆ換マレイ
ミドの配合割合が、１０重量％未満では耐熱性が低下し
、８０重量％を超えると成形加工性が低下するので好ま
しくない、また前記メタアクリル系マレイミド共重合体
（ｂ）の好ましい他の成分であるアクリル酸エステル及
び／又はメタクリル酸エステルは、耐熱性、成形加工性
及び耐衝撃性の物性バランスを保持するために、メタク
リル酸エステルを含有させることが必要であり、好まし
くは少なくとも５０重量％以上のメタクリル酸メチルを
含有することが望ましい。前記アクリル酸エステル又は
メタクリル酸エステルの単量体としては、メタクリル酸
メチルを含有するアクリル酸エステル及びメタクリル酸
エステルが挙げられ、特に炭素数１〜１８のアルキルエ
ステルから選択することができ、具体的には、メチルア
クリレート、エチルアクリレート、ブチルアクリレート
、ラウリルアクリレート、エチルメタクリレート、ブチ
ルメタクリレート、２−エチルへキシルメタクリレート
、ステアリルメタクリレート等を好ましく挙げることが
できる。前記アクリル酸エステル及び／又はメタクリル
酸エステルのメタアクリル系マレイミド共重合体（ｂ）
中における配合割合は、９０〜２０重量％であることが
好ましく、特に８０〜３０重量％であることが望ましい
。この際９０重量％を超えると、耐熱性が低下し、また
２０重量％未満では成形加工性が低下するので好ましく
ない。Preferred examples include -chlorophenylmaleimide, N-o-methylphenylmaleimide, N-benzylmaleimide, and the like, which can be used alone or in combination of two or more. The blending ratio of the N-ff1f-converted maleimide in the methacrylic maleimide copolymer (b) is:
It is preferably 10 to 8% by weight, especially 20 to 7% by weight.
Preferably, it is 0% by weight. If the blending ratio of the N-ff converted maleimide is less than 10% by weight, the heat resistance will decrease, and if it exceeds 80% by weight, the molding processability will decrease, which is not preferable, and the methacrylic maleimide copolymer (b) Acrylic ester and/or methacrylic ester, which are other preferred components of It is desirable to contain at least 50% by weight of methyl methacrylate. Examples of the acrylic ester or methacrylic ester monomer include acrylic esters and methacrylic esters containing methyl methacrylate, and can be particularly selected from alkyl esters having 1 to 18 carbon atoms. Preferred examples include methyl acrylate, ethyl acrylate, butyl acrylate, lauryl acrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate. Methacrylic maleimide copolymer (b) of the acrylic ester and/or methacrylic ester
The blending ratio therein is preferably 90 to 20% by weight, particularly preferably 80 to 30% by weight. In this case, if it exceeds 90% by weight, heat resistance will decrease, and if it is less than 20% by weight, moldability will decrease, which is not preferable.
本発明に用いる前記メタアクリル系マレイミド共重合体
（ｂ）を製造するには、例えば、前記Ｎ−置換マレイミ
ドと前記アクリル酸エステル及び／又はメタクリル酸エ
ステルとを公知の塊状重合、溶液重合、懸濁重合又は乳
化重合等により共重合することができる。In order to produce the methacrylic maleimide copolymer (b) used in the present invention, for example, the N-substituted maleimide and the acrylic ester and/or methacrylic ester may be polymerized by known bulk polymerization, solution polymerization, suspension polymerization, etc. Copolymerization can be carried out by turbidity polymerization, emulsion polymerization, or the like.
更に前記メタアクリル系マレイミド共重合体（ｂ）は、
ゴムとのポリマーとして使用することも可能である。こ
こでゴムとのポリマーとは、前記メタクリル系マレイミ
ド共重合体鎖がゴムを構成するポリマー鎖とグラフトし
た高分子Ｊｉｔ造を有するものであると考えられる。本
発明に用いる前記ゴムとしては、例えば、ポリブタジェ
ン、ポリイソプレン、スチレン−ブタジェン共重合体、
ニトリルゴム等のジエン系ゴム、エチレン−プロピレン
共重合体、エチレン−エチルアクリレート共重合体、エ
チレン−グリシジルメタクリレート共重合体、エチレン
−酢酸ビニル共重合体、エチレン−プロピレン−ジエン
共重合体、アクリルゴム等の非ジエン系ゴム等を使用す
ることができる。前記ゴムの配合割合はメタクリル系マ
レイミド共重合体中に、０〜５０重量％の範囲であるこ
とが好ましく、５０重量％を超えると耐熱性が低下する
ので好ましくない。前記メタクリル系マレイミド共重合
体（ｂ）とゴムとのポリマーを製造するには、ゴムとメ
タアクリル系マレイミド共重合体（ｂ）を構成する七ツ
マ−とを混合し、公知の塊状重合、溶液重合、懸濁重合
又は乳化重合等にょリモノマーをゴムポリマーに重合さ
せることにより製造することができる。Furthermore, the methacrylic maleimide copolymer (b) is
It is also possible to use it as a polymer with rubber. Here, the polymer with rubber is considered to have a polymer JIT structure in which the methacrylic maleimide copolymer chain is grafted with the polymer chain constituting the rubber. Examples of the rubber used in the present invention include polybutadiene, polyisoprene, styrene-butadiene copolymer,
Diene rubber such as nitrile rubber, ethylene-propylene copolymer, ethylene-ethyl acrylate copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene-diene copolymer, acrylic rubber Non-diene rubbers such as, etc. can be used. The blending ratio of the rubber in the methacrylic maleimide copolymer is preferably in the range of 0 to 50% by weight, and if it exceeds 50% by weight, heat resistance decreases, which is not preferable. In order to produce a polymer of the methacrylic maleimide copolymer (b) and rubber, the rubber and the hexamer constituting the methacrylic maleimide copolymer (b) are mixed and subjected to known bulk polymerization and solution polymerization. It can be produced by polymerizing a rubber polymer with a rubber monomer, such as polymerization, suspension polymerization, or emulsion polymerization.
本発明に用いる前記各成分を含むメタアクリル系マレイ
ミド共重合体（ｂ）の配合割合は、樹脂組成物において
、１０〜８０重量％であり、好ましくは２０〜６０重量
％であることが望ましい。この際、１０重量％未満では
耐熱性が不充分である。The blending ratio of the methacrylic maleimide copolymer (b) containing the above-mentioned components used in the present invention is 10 to 80% by weight, preferably 20 to 60% by weight in the resin composition. At this time, if it is less than 10% by weight, heat resistance is insufficient.
また８０重量％超えると成型加工性が悪くなり。Moreover, when it exceeds 80% by weight, moldability deteriorates.
ポリフェニレンの含有量も相対的に少なくなるので物性
が悪くなる。Since the content of polyphenylene is also relatively small, the physical properties deteriorate.
本発明において、スチレン系重合体（Ｃ）は、前記ポリ
フェニレンエーテル（ａ）とメタアクリル系マレイミド
共重合体（ｂ）との相溶性等を向上させることが可能な
成分であり、具体的には１例えばスチレンの単独重合体
又は３０重量％以下の共重合成分を含むスチレン系重合
体等を好ましく挙げることができる。前記共重合成分と
しては１例えばメチルスチレン、クロルスチレン、ジク
ロルスチレン、α−メチルスチレン等のスチレン系単量
体又はシアン化ビニル単量体等を好ましく挙げることが
できる。前記スチレン系重合体（ｃ）の配合割合は、樹
脂組成物において、５〜６ｏ重量％であり、好ましくは
１０〜５ｏ重量％であることが望ましい。配合割合が５
重量％未満では、樹脂組成物にする際に、前記ポリフェ
ニレンエーテル（ａ）とメタアクリル系マレイミド共重
合体（ｂ）との相溶性が低下し、且つ成形加工性も低下
するので使用できない、また６０重量％を超える場合に
は、耐熱性が低下するので使用できない。In the present invention, the styrene polymer (C) is a component that can improve the compatibility between the polyphenylene ether (a) and the methacrylic maleimide copolymer (b), and specifically, 1. For example, a styrene homopolymer or a styrene polymer containing 30% by weight or less of a copolymer component can be preferably mentioned. Preferred examples of the copolymerization component include styrenic monomers such as methylstyrene, chlorostyrene, dichlorostyrene, and α-methylstyrene, and vinyl cyanide monomers. The blending ratio of the styrene polymer (c) in the resin composition is 5 to 60% by weight, preferably 10 to 50% by weight. The blending ratio is 5
If the amount is less than % by weight, the compatibility between the polyphenylene ether (a) and the methacrylic maleimide copolymer (b) will decrease when forming a resin composition, and the moldability will also decrease, so it cannot be used. If it exceeds 60% by weight, it cannot be used because the heat resistance decreases.
本発明の高耐熱性熱可塑性樹脂組成物を調製するには、
前記ポリフェニレンエーテル（ａ）、メタアクリル系マ
レイミド共重合体（ｂ）及びスチレン系重合体（Ｃ）を
１例えばバンバリーミキサ−、ニーダ−等の混合機器に
より混合し、次いで押出機等により溶融混合した後ペレ
ット化する方法等により！ｌ！ｉｓすることができる。To prepare the highly heat resistant thermoplastic resin composition of the present invention,
The polyphenylene ether (a), the methacrylic maleimide copolymer (b), and the styrene polymer (C) were mixed using a mixing device such as a Banbury mixer or a kneader, and then melt-mixed using an extruder or the like. Depending on the method of pelletizing afterwards! l! is possible.
また本発明の高耐熱性熱可塑性樹脂組成物に、通常用い
られる公知の酸化防止剤、紫外線吸収剤、滑剤、難燃剤
、帯電防止剤、フィラー類等を配合することも可能であ
る。It is also possible to blend commonly used antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, fillers, etc. into the highly heat-resistant thermoplastic resin composition of the present invention.
〈発明の効果〉
本発明の高耐熱性熱可塑性樹脂組成物は、従来のポリフ
ェニレンエーテル組成物に比して、耐熱性、成型加工性
及び耐衝撃性等の各物性に優れ、しかもこれらの物性バ
ランスが整っているので、自動車用部品、電気部品、ハ
ウジング材料等に利用することが可能である。<Effects of the Invention> The highly heat-resistant thermoplastic resin composition of the present invention is superior to conventional polyphenylene ether compositions in physical properties such as heat resistance, moldability, and impact resistance. Since it is well balanced, it can be used for automobile parts, electrical parts, housing materials, etc.
〈実施例〉
以下製造例、実施例により更に詳細に説明するが１本発
明はこれらに限定されるものではない。<Examples> The present invention will be explained in more detail with reference to production examples and examples, but the present invention is not limited thereto.
゛ １．ポリフェニレンエーテルの ゛撹拌器、冷却
コイル及び酸素吹込み管を供えたステンレス製反応容器
内を窒素ガスでＭ換した。゛ 1. The inside of a stainless steel reaction vessel equipped with a stirrer, a cooling coil, and an oxygen blowing tube for polyphenylene ether was replaced with nitrogen gas.
次いで臭化第二銅１０７ｇ、ジ−ｎ−ブチルアミン２２
２０ｇ及びトルエン１００Ｑに溶解させた２、６−キシ
レノール１７．５ｋｇを添加した。撹拌下に、反応系内
に酸素を吹込み２時間重合させた０重合温度は、３０℃
に保つよう冷却コイル中に冷水を通した。その後トルエ
ンを２０Ｑ添加し、エチレンジアミン四酢酸二ナトリウ
ム４３０ｇを水に溶解した２０％水溶液を添加して反応
を停止させた。Next, 107 g of cupric bromide, 22 g of di-n-butylamine
20 g and 17.5 kg of 2,6-xylenol dissolved in 100Q of toluene were added. While stirring, oxygen was blown into the reaction system and polymerization was carried out for 2 hours. The polymerization temperature was 30°C.
Cold water was passed through the cooling coil to maintain the temperature. Thereafter, 20Q of toluene was added, and a 20% aqueous solution in which 430 g of disodium ethylenediaminetetraacetate was dissolved in water was added to stop the reaction.
次に重合体溶液相を取り出し、該溶液相にメタノールを
ゆっくり添加しスラリー状にした。濾別して得られた粉
末を温風乾燥して重合体（Ａ）を得た。Next, the polymer solution phase was taken out, and methanol was slowly added to the solution phase to form a slurry. The powder obtained by filtration was dried with hot air to obtain a polymer (A).
゛ ２．メタアクリル′マレイミド 八 〇 ゛表
１にそれぞれ示したモノマー組成、重合条件によって重
合体Ｂ−１，Ｂ−２，Ｂ−３，Ｂ−４表１ （註）
懸濁重合によりポリスチレン（分子量約８００００）及
びアクリロニトリルを２３重量％含むスチレン−アクリ
ロニトリル共重合体（Ｃ）（分子量約７００００）を調
製した。゛ 2. Polymer B-1, B-2, B-3, B-4 according to the monomer composition and polymerization conditions shown in Table 1 Table 1 (Note) Polystyrene (molecular weight approximately 80,000 ) and a styrene-acrylonitrile copolymer (C) (molecular weight approximately 70,000) containing 23% by weight of acrylonitrile.
１〜９ び比 １〜３
表２に示す割合の組成で、各重合体を二軸混練押出機を
用いて２６０〜３００℃の温度範囲で押出しペレタイズ
した後、乾燥し射出成形機を用いて２４０〜２８０℃で
試験片を作成した。該試験片を以下の試験方法により各
種物性を測定した。1 to 9 and ratio 1 to 3 With the composition shown in Table 2, each polymer was extruded and pelletized using a twin-screw kneading extruder at a temperature range of 260 to 300°C, then dried and pelletized using an injection molding machine. Test pieces were prepared at 240 to 280°C. Various physical properties of the test piece were measured using the following test methods.
結果を表２に示す。The results are shown in Table 2.
（１）耐熱性
ＡＳＴＭ Ｄ６４８に従って、厚さ０．２５インチ、
２６４ｐｓｉで熱変形温度を測定した。(1) Heat Resistance 0.25 inch thick according to ASTM D648;
Heat distortion temperature was measured at 264 psi.
（２）耐衝撃性
ＡＳＴＭ Ｄ２５６に従い、厚さ０．２５インチ、「
ノツチあり」で測定した。(2) Impact resistance per ASTM D256, 0.25 inch thick;
Measured with "notched".
（３）成形加工性 ＪＩＳ Ｋ７２１０に従い、温度２８０℃。(3) Molding processability According to JIS K7210, temperature 280℃.
荷重１０ｋｇでメルトフローレート（ＭＦＲ。Melt flow rate (MFR) with a load of 10 kg.
ｇ／１０分）を測定した。g/10 minutes) was measured.
Claims (1)
、（ｂ）メタアクリル系マレイミド共重合体１０〜８０
重量％と、（ｃ）スチレン系重合体５〜６０重量％とを
含むことを特徴とする高耐熱性熱可塑性樹脂組成物。 ２）前記メタアクリル系マレイミド共重合体がゴムとの
ポリマーであることを特徴とする特許請求の範囲第１項
に記載の高耐熱性熱可塑性樹脂組成物。[Claims] 1) (a) 10 to 80% by weight of polyphenylene ether, and (b) 10 to 80% by weight of methacrylic maleimide copolymer
% by weight, and (c) 5 to 60% by weight of a styrenic polymer. 2) The highly heat-resistant thermoplastic resin composition according to claim 1, wherein the methacrylic maleimide copolymer is a polymer with rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10907788A JPH01279959A (en) | 1988-05-06 | 1988-05-06 | Highly heat-resistant thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10907788A JPH01279959A (en) | 1988-05-06 | 1988-05-06 | Highly heat-resistant thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01279959A true JPH01279959A (en) | 1989-11-10 |
Family
ID=14501022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10907788A Pending JPH01279959A (en) | 1988-05-06 | 1988-05-06 | Highly heat-resistant thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01279959A (en) |
-
1988
- 1988-05-06 JP JP10907788A patent/JPH01279959A/en active Pending
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