JPH04117444A - Preparation of heat-resistant styrene resin composition - Google Patents
Preparation of heat-resistant styrene resin compositionInfo
- Publication number
- JPH04117444A JPH04117444A JP2236135A JP23613590A JPH04117444A JP H04117444 A JPH04117444 A JP H04117444A JP 2236135 A JP2236135 A JP 2236135A JP 23613590 A JP23613590 A JP 23613590A JP H04117444 A JPH04117444 A JP H04117444A
- Authority
- JP
- Japan
- Prior art keywords
- styrene resin
- resin
- polyphenylene ether
- weight
- composition
- 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011342 resin composition Substances 0.000 title claims description 20
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 4
- 229920001890 Novodur Polymers 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 abstract description 27
- 229920000642 polymer Polymers 0.000 abstract description 18
- -1 polyphenylene Polymers 0.000 abstract description 12
- 229920000265 Polyparaphenylene Polymers 0.000 abstract 1
- 230000000593 degrading effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 239000008188 pellet Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- CYLVUSZHVURAOY-UHFFFAOYSA-N 2,2-dibromoethenylbenzene Chemical compound BrC(Br)=CC1=CC=CC=C1 CYLVUSZHVURAOY-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-UHFFFAOYSA-N 2-bromoethenylbenzene Chemical compound BrC=CC1=CC=CC=C1 YMOONIIMQBGTDU-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
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl 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
- 230000003078 antioxidant effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 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
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 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
- 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
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 238000006116 polymerization reaction 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
- 238000011084 recovery Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
Landscapes
- Processing And Handling Of Plastics And Other Materials For Molding In General (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、耐熱性スチレン系樹脂組成物の製造方法に関
するものであり、詳しくは、スチレン系樹脂とポリフェ
ニレンエーテルとを含有する樹脂組成物であって、ポリ
フェニレンエーテルの未溶融ポリマー塊を実質的に含ま
ない、耐熱性スチレン系樹脂組成物の工業的有利な製造
方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 heat-resistant styrenic resin composition. The present invention relates to an industrially advantageous method for producing a heat-resistant styrenic resin composition that is substantially free of unmelted polymer lumps of polyphenylene ether.
ポリフェニレンエーテルは、耐熱性に優れ、また、基本
的には、スチレン系樹脂とあらゆる混合割合において完
全相溶することか知られている。Polyphenylene ether has excellent heat resistance and is basically known to be completely compatible with styrene resins at all mixing ratios.
従って、ポリフェニレンエーテルは、スチレン系樹脂の
主として耐熱性の向上を目的としてブレンド使用されて
きた。Therefore, polyphenylene ether has been used in blends with styrenic resins mainly for the purpose of improving heat resistance.
例えば、本発明者の一人は、先に、ポリスチレン系樹脂
シートの耐熱性を向上させたものとして一般用ポリスチ
レン５０〜９５重量％とポリフェニレンエーテル５０〜
５重量％から成る組成物より製せられる二軸延伸シート
を提案している（特開平２−５５１２２）。For example, one of the inventors of the present invention previously proposed a polystyrene-based resin sheet with 50 to 95% by weight of general polystyrene and 50 to 95% by weight of polyphenylene ether.
A biaxially oriented sheet made of a composition containing 5% by weight has been proposed (Japanese Patent Application Laid-Open No. 2-55122).
従来、スチレン系樹脂とポリフェニレンエーテルとをブ
レンドする方法としては、以下の方法で代表される機械
的混合法、溶液ブレンド法が知られている。Conventionally, as methods for blending styrene resin and polyphenylene ether, mechanical mixing methods and solution blending methods, typified by the following methods, are known.
（１）両者の樹脂粉体又はペレットを固体状態で混合し
、得られる混合物を直接射出成形あるいは押出成形して
成形品を得る方法。(1) A method of mixing both resin powders or pellets in a solid state and directly injection molding or extrusion molding the resulting mixture to obtain a molded product.
（２）両者の樹脂粉体又はペレットを混合し、溶融押出
機等の混線機を用いてペレット化した後、そのペレット
を射出成形あるいは押出成形して成形品を得る方法。(2) A method in which both resin powders or pellets are mixed, pelletized using a mixer such as a melt extruder, and then the pellets are injection molded or extruded to obtain a molded product.
（３）両者を共通溶媒に溶解して混合した後、両者の非
溶媒にて回収し、その回収組成物を直接射出成形あるい
は押出成形して成形品を得る方法。(3) A method of dissolving and mixing both in a common solvent, recovering both in a non-solvent, and directly injection molding or extrusion molding the recovered composition to obtain a molded article.
（４）上記の（３）の方法で回収した組成物を押出機等
の混練機を用いてペレット化した後、そのペレットを射
出成形あるいは押出成形して成形品を得る方法。(4) A method of pelletizing the composition recovered by the method (3) above using a kneader such as an extruder, and then injection molding or extrusion molding the pellets to obtain a molded product.
しかしながら、元来、スチレン系樹脂とポリフェニレン
エーテルとは融解温度あるいは同一温度における溶融粘
度に大きな差があり、従って、上記の（１）又は（２）
の方法では、混練り効率が悪く、混練りの程度によって
はポリフェニレンエーテルの未溶融ポリマー塩が粒子状
に残存し、その結果、成形品の耐熱性や機械的強度にム
ラか生じ、著しい場合には、成形品の外観不良等を生じ
る。更に、延伸シートにおいては、延伸時のシート破断
やソート表面のブツ発生現象を惹起する。However, originally, styrene resins and polyphenylene ethers have a large difference in melting temperature or melt viscosity at the same temperature, so the above (1) or (2)
In this method, the kneading efficiency is poor, and depending on the degree of kneading, unmelted polymer salts of polyphenylene ether may remain in the form of particles, resulting in uneven heat resistance and mechanical strength of the molded product, and in severe cases. This results in poor appearance of the molded product. Furthermore, in stretched sheets, sheet breakage occurs during stretching, and bumps occur on the sorting surface.
ポリフェニレンエーテルの未溶融ポリマー塩をなくすた
めには、厳しい混−線条件下にて混合を行うことも考え
られるが、この場合には、低分子量物質が多量に生成し
て機械的性質を大巾に低下せしめたり、また、ゲル状重
合体（線状高分子が部分的に橋かけ結合したものであり
、溶媒により膨潤するが溶解することのない重合体をさ
す）が生成し、却って成形品の表面外観を悪（し、実用
上好ましくない。 一方、上記の（３）又は（４）の方
法では、粘度差の影響が顕著でなく混合が容易に行なわ
れるが、溶解装置や大量の溶剤および非溶剤の回収装置
を必要とする。また、ユーティリティの面からも経済的
でない。In order to eliminate the unmelted polymer salt of polyphenylene ether, it may be possible to perform mixing under severe crosstalk conditions, but in this case, a large amount of low molecular weight substances will be generated and the mechanical properties will be greatly affected. In addition, a gel-like polymer (a polymer made of partially cross-linked linear polymers that swells with a solvent but does not dissolve) may be formed, and the molded product may deteriorate. On the other hand, in methods (3) and (4) above, the influence of viscosity difference is not noticeable and mixing is easily carried out, but it requires a dissolving device and a large amount of solvent. It also requires non-solvent recovery equipment.It is also not economical from a utility standpoint.
本発明の目的は、スチレン系樹脂とポリフェニレンエー
テルとを含有し、両者に対するスチレン系樹脂の割合が
５０重量％を超え９５重量％以下の耐熱性スチレン系樹
脂組成物であって、ポリフェニレンエーテルの未溶融ポ
リマー塩やゲル状重合体を実質的に含まず、樹脂の諸性
質を低下せしめることのない゛組成物のための工業的有
利な製造方法を提供することにある。The object of the present invention is to provide a heat-resistant styrenic resin composition containing a styrene resin and a polyphenylene ether, in which the proportion of the styrene resin to both is more than 50% by weight and 95% by weight or less, wherein the composition contains a styrene resin and a polyphenylene ether. The object of the present invention is to provide an industrially advantageous manufacturing method for a composition that does not substantially contain molten polymer salts or gel polymers and does not deteriorate the properties of the resin.
本発明者等は、上記目的を達成すべ（鋭意検討を重ねた
結果、多量のポリフェニレンエーテルと少量のスチレン
系樹脂との溶融混合は、比較的容易であり、しかも、驚
くべきことに、斯くして得られた組成物とスチレン系樹
脂との溶融混合は、単なる機械的混合法で極めて良好に
行い得るとの知見を得た。To achieve the above object, the present inventors have found that it is relatively easy to melt-mix a large amount of polyphenylene ether and a small amount of styrene resin. It has been found that the composition obtained by the above method and the styrene resin can be melt-mixed very well by a simple mechanical mixing method.
本発明は、上記の新規な知見に基すいて完成されたもの
であり、その要旨は、スチレン系樹脂とポリフェニレン
エーテルとを含有し、両者に対するスチレン系樹脂の割
合が５０重量％を超え９５重量％以下の耐熱性スチレン
系樹脂組成物の製造方法あって、先ず、スチレン系樹脂
とポリフェニレンエーテルとを含有し、両者に対するス
チレン系樹脂の割合が５〜５０重量％の混合物を、溶融
混練機を用い、３００〜３４０°Ｃの温度条件下、１０
５ｅｃ−’以上の剪断速度を与えつつ混練して均一な樹
脂組成物となし、次いで、この樹脂組成物にスチレン系
樹脂を混合して均一に溶融混練することを特徴とする耐
熱性スチレン系樹脂組成物の製造方法に存する。The present invention has been completed based on the above-mentioned new findings, and its gist is that the present invention contains a styrene resin and a polyphenylene ether, and the proportion of the styrene resin to both exceeds 50% by weight and is 95% by weight. % or less, first, a mixture containing a styrene resin and polyphenylene ether in which the ratio of the styrene resin to both is 5 to 50% by weight is melt-kneaded using a melt-kneading machine. 10 at a temperature of 300 to 340°C.
A heat-resistant styrenic resin characterized by kneading a uniform resin composition while applying a shear rate of 5 ec-' or more, and then mixing a styrene resin with this resin composition and uniformly melting and kneading the resin composition. The invention consists in a method for producing a composition.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用されるスチレン系樹脂は、ビニル芳香族化
合物の単独重合体、ビニル芳香族化合物およびこれとラ
ジカル共重合可能な単量体の１種または２種以上からな
る共重合体である。The styrenic resin used in the present invention is a homopolymer of a vinyl aromatic compound, or a copolymer consisting of one or more of a vinyl aromatic compound and a monomer radically copolymerizable with the vinyl aromatic compound.
上記の共重合可能な単量体としては、例えばαメチルス
チレン、ビニルトルエン、ビニルキシレン、モノクロル
スチレン、ジクロルスチレン、モノブロムスチレン、ジ
ブロムスチレン等のスチレン誘導体、メチルメタクリレ
ート、エチルメタクリレート等のメタクリル酸エステル
、メチルアクリレート、ブチルアクリレート等のアクリ
ル酸エステル、アクリロニトリル、メタクリレートリル
等の不飽和ニトリル化合物、無水マレイン酸、無水イタ
コン酸等の不飽和酸無水物、アクリル酸、メタクリル酸
等の不飽和酸等が挙げられる。Examples of the above-mentioned copolymerizable monomers include styrene derivatives such as α-methylstyrene, vinyltoluene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, and dibromostyrene, and methacrylates such as methyl methacrylate and ethyl methacrylate. Acid esters, acrylic esters such as methyl acrylate and butyl acrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylate, unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride, and unsaturated acids such as acrylic acid and methacrylic acid. etc.
本発明のスチレン系樹脂のうち好ましい樹脂は、ポリス
チレン、スチレン−アクリロニトリル共重合体、スチレ
ン−メチルメタクリレート共重合体、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、スチレン−アクリル酸共重合体等のスチレン含有
樹脂が挙げられる。Preferred resins among the styrene resins of the present invention are polystyrene, styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-α-methylstyrene copolymer, styrene-maleic anhydride copolymer, and styrene-maleic anhydride copolymer. Examples include styrene-containing resins such as acrylic acid copolymers.
本発明で使用されるポリフェニレンエーテルは、下記一
般式で表わされるものである。The polyphenylene ether used in the present invention is represented by the following general formula.
（式中、
及びＲ２
はそれぞれ炭素数１〜４の
アルキル素又はハロゲン原子を表わし、ｎは重合度を示
す整数で６０〜２５０である）
上記のポリフェニレンエーテルの具体例としては、ポリ
（２，６−シメチルフエニレンー１．４−エーテル）、
ポリ（２，６−ジクロルフェニレンー１゜４−エーテル
）、ポリ（２−メチル−６−ｎ−ブチルフェニレン−１
，４−エーテル）、ポリ（２−メチル−６−ブロムフェ
ニレン−１，４−エーテル）、ポリ（２−メチル−６−
クロルフェニレン−１，４−エーテル）、ポリ（２，６
−シクロルフエニレンー１，４−エーテル）、ポリ（２
，６−ジーｎ−プロピルフェニレン−１，４−エーテル
）等が挙げられる。(In the formula, and R2 each represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n is an integer indicating the degree of polymerization and is 60 to 250.) Specific examples of the above polyphenylene ether include poly(2, 6-dimethylphenylene-1,4-ether),
Poly(2,6-dichlorophenylene-1゜4-ether), poly(2-methyl-6-n-butylphenylene-1)
, 4-ether), poly(2-methyl-6-bromphenylene-1,4-ether), poly(2-methyl-6-
chlorophenylene-1,4-ether), poly(2,6
-cyclophenylene-1,4-ether), poly(2
, 6-di-n-propylphenylene-1,4-ether), and the like.
また、前記一般式で表わされる化学構造を主体として成
るポリフェニレンエーテル共重合体も使用可能である。Furthermore, a polyphenylene ether copolymer mainly composed of the chemical structure represented by the above general formula can also be used.
そして、その具体例としては２，６−ジ置換フェノール
と２，４−ジ置換フェノールとの共重合体、２，６−ジ
置換フェノールと２．３．６−トリ置換フェノールとの
共重合体、２，６−シメチルフエノールと２−置換フェ
ノール、３−置換フェノールまたは４−置換フェノール
との共重合体などが挙げられる。Specific examples include copolymers of 2,6-disubstituted phenol and 2,4-disubstituted phenol, and copolymers of 2,6-disubstituted phenol and 2,3,6-trisubstituted phenol. , a copolymer of 2,6-dimethylphenol and a 2-substituted phenol, a 3-substituted phenol, or a 4-substituted phenol.
本発明で使用されるポリフェニレンエーテルは、得られ
る樹脂組成物の強度および成形性の観点から、その固有
粘度（クロロホルム、２５°Ｃ測定）か０．２〜１ｄｌ
／ｇの範囲のもの、好ましくは０．３〜０．７ ｄｉ／
ｇの範囲のものが使用される。The polyphenylene ether used in the present invention has an intrinsic viscosity (chloroform, measured at 25°C) of 0.2 to 1 dl from the viewpoint of the strength and moldability of the resulting resin composition.
/g, preferably 0.3 to 0.7 di/
g range is used.
本発明の特徴は、スチレン系樹脂とポリフェニレンエー
テルとの溶融混合を特定割合の二段階に分けて行なうこ
とにより、両者に対するスチレン系樹脂の割合が５０重
量％を超える耐熱性スチレン系樹脂組成物を製造する点
にある。A feature of the present invention is that the styrene resin and polyphenylene ether are melt-mixed in two stages at specific ratios, thereby producing a heat-resistant styrenic resin composition in which the ratio of the styrene resin to both is more than 50% by weight. It's about manufacturing.
先ず、本発明においては、前混合として、スチレン系樹
脂とポリフェニレンエーテルとに対するスチレン系樹脂
の割合が５〜５０重量％、好ましくは、５〜３０重量％
の組成物（予備組成物）を得る。First, in the present invention, as a premix, the ratio of the styrene resin to the styrene resin and polyphenylene ether is 5 to 50% by weight, preferably 5 to 30% by weight.
A composition (preliminary composition) is obtained.
上記の前混合において、スチレン系樹脂の割合が５重量
％未満の場合（ポリフェニレンエーテルの割合が９５重
量％を超える場合）は、次の後混合において、予備組成
物とスチレン系樹脂との溶融混合特性が悪くなり、また
、スチレン系樹脂の割合が５０重量％を超える場合は、
前混合における混合効率が低下し、ポリフェニレンエー
テルの未溶融ポリマー塩が残存するようになる。In the above premixing, if the proportion of styrene resin is less than 5% by weight (if the proportion of polyphenylene ether exceeds 95% by weight), in the next postmixing, the precomposition and styrene resin are melt-mixed. If the properties deteriorate or the proportion of styrene resin exceeds 50% by weight,
The mixing efficiency in premixing is reduced, and unmelted polymer salts of polyphenylene ether remain.
上記の予備組成物は、所定の混合物を溶融混練機を用い
、３００〜３４０°Ｃの温度条件下、１０ＳｅＣ−’以
上の剪断速度を与えつつ混練することにより、均一な組
成物として容易に得られる。The above precomposition can be easily obtained as a uniform composition by kneading the predetermined mixture using a melt kneader at a temperature of 300 to 340°C while applying a shear rate of 10 SeC-' or more. It will be done.
混線温度が３００℃未満の場合は、ポリフェニレンエー
テルの未溶融ポリマー塩が残存する傾向を示し、成形品
の外観を損なうので好ましくない。If the crosstalk temperature is less than 300° C., unmelted polymer salt of polyphenylene ether tends to remain, which is undesirable because it impairs the appearance of the molded product.
一方、混線温度が３４０°Ｃを超える場合は、ゲル状重
合体を生成する傾向を示し、同様に成形品の外観を損な
う。On the other hand, if the crosstalk temperature exceeds 340°C, there is a tendency to produce a gel-like polymer, which similarly impairs the appearance of the molded product.
また、与えられる剪断速度が１０ ｓｅｃ’−’に達し
ない状態で溶融混練した場合には、混練り効率が低いた
めにポリフェニレンエーテルの未溶融ポリマー塩が残存
することが避けられず、本発明の目的は達成できない。Furthermore, if melt-kneading is carried out at a shear rate that does not reach 10 sec'-', unmelted polymer salt of polyphenylene ether will inevitably remain due to low kneading efficiency. The purpose cannot be achieved.
また、逆に、剪断速度が太きすぎる場合は、低分子量物
質が多量生成して機械的性質を大巾に低下せしめたり、
また、ゲル状重合体が生成し、成形品の外観を損なうこ
とがあるので、剪断速度は、通常２５０ｓｅｃ’以下に
抑えるのが好ましい。On the other hand, if the shear rate is too high, a large amount of low-molecular-weight substances will be produced, which will greatly reduce the mechanical properties.
Further, since a gel-like polymer may be generated and the appearance of the molded article may be impaired, it is preferable that the shearing rate is normally kept to 250 sec' or less.
前混合は、上記の各条件を満たし得る方法であれば如何
なる方法によってもよく、バッチ方式、連続方式のいず
れの方法も使用できるが、生産性を高めるためには連続
方式が好ましい。その具体例としては、押出機、インタ
ーナルミキサー、ニーダ−等による方法が挙げられる。The premixing may be carried out by any method as long as it satisfies each of the above conditions, and either a batch method or a continuous method can be used, but a continuous method is preferred in order to improve productivity. Specific examples thereof include methods using an extruder, an internal mixer, a kneader, and the like.
次に、本発明においては、後混合として、上記の予備組
成物とスチレン系樹脂とを溶融混合し、スチレン系樹脂
の割合が５０重量％を超え９５重量％以下の耐熱性スチ
レン系樹脂組成物（最終組成物）を得る。この後混合は
、通常に用いられる加熱溶融混合方法に従って容易に行
うことができる。Next, in the present invention, as post-mixing, the above precomposition and styrene resin are melt-mixed to form a heat-resistant styrenic resin composition in which the proportion of styrene resin is more than 50% by weight and not more than 95% by weight. (Final composition) is obtained. This post-mixing can be easily carried out according to a commonly used heating melt mixing method.
上記の最終組成物において、スチレン系樹脂の割合は、
最終組成物の物性に応じて上記範囲から適宜選択される
が、予備組成物とスチレン系樹脂との混練性の観点から
、予備組成物における割合と最終組成物における割合と
か極端に違わないことが好ましい。In the above final composition, the proportion of styrenic resin is
The proportion in the preliminary composition and the proportion in the final composition should not be extremely different from the viewpoint of kneading properties between the preliminary composition and the styrene resin, although they are appropriately selected from the above range depending on the physical properties of the final composition. preferable.
また、前混合と後混合とにおけるスチレン系樹脂の種類
は、同一でも異なってもよい。Further, the types of styrene resins used in the pre-mixing and the post-mixing may be the same or different.
なお、前混合または後混合においては、公知の酸化防止
剤などの安定化剤を添加することもできる。In addition, in the pre-mixing or post-mixing, a stabilizer such as a known antioxidant can also be added.
また、本発明の効果を損なわない限り、必要に応じ、他
の相溶性樹脂を添加することもできる。Further, other compatible resins may be added as necessary, as long as the effects of the present invention are not impaired.
以下、本発明を実施例に基づき更に詳細に説明するが、
本発明はその要旨を越えない限り、以下の例に限定され
るものではない。Hereinafter, the present invention will be explained in more detail based on Examples.
The present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例１
固有粘度０．５２ｄｌ／ｇ （２５°Ｃ、クロロホルム
）のポリ（２，６−シメチルー１，４−）ユニレン）エ
ーテル７０重量部と重量平均分子量が２．８ Ｘ ］、
０ ’のポリスチレン３０重量部から成る樹脂混合物
に、フェノール系酸化防止剤（チバガイギ製イルガノッ
クス１０７６）０．５重量部を配合し、ヘンシェルミキ
サーを用いて充分混合した。Example 1 70 parts by weight of poly(2,6-dimethyl-1,4-)unilene)ether with an intrinsic viscosity of 0.52 dl/g (25°C, chloroform) and a weight average molecular weight of 2.8
0.5 parts by weight of a phenolic antioxidant (Irganox 1076 manufactured by Ciba-Geigi Co., Ltd.) was added to a resin mixture consisting of 30 parts by weight of 0' polystyrene, and thoroughly mixed using a Henschel mixer.
得られた混合物を４０ｍｍφベント付２軸押出機で溶融
混線下に押出してペレット化した。溶融温度は３２０°
Ｃ１剪断速度は５０ ｓｅｃ ’とした。The resulting mixture was extruded into pellets using a 40 mmφ vented twin-screw extruder under melt mixing. Melting temperature is 320°
The C1 shear rate was 50 sec'.
次いで、得られた混合物ペレット３６重量部に最初に使
用したのと同じポリスチレン６４重量部を加え、同じ４
０ｍｍφベント付２軸押出機で押出してペレット化し、
ポリフェニレンエーテル含量が２５重量％の耐熱性スチ
レン系樹脂組成物を得た。溶融温度は２８０℃、剪断速
度は２０ｓｅｃ−であった。Next, 64 parts by weight of the same polystyrene used initially was added to 36 parts by weight of the resulting mixture pellets, and the same 4 parts by weight of polystyrene was added.
Pelletize by extruding with a 0mmφ vented twin-screw extruder,
A heat-resistant styrenic resin composition containing 25% by weight of polyphenylene ether was obtained. The melting temperature was 280°C and the shear rate was 20 sec.
次いで、得られた組成物を４０ｍｍφベント付単軸押出
機（シリンダー温度２５０°Ｃ）にて溶融混練しつつ、
Ｔ−グイ（グイ温度２６０℃）よりシート状に押出した
後、冷却ロールにて冷却し、厚さ約０．９ｍｍの未延伸
シートを作成した。Next, while melt-kneading the obtained composition in a 40 mmφ vented single screw extruder (cylinder temperature 250°C),
After extruding into a sheet from T-Goui (Goui temperature: 260°C), it was cooled with a cooling roll to create an unstretched sheet with a thickness of about 0.9 mm.
次に、テスト延伸機を用い、上記の未延伸シートを１６
０℃の温度条件下で２軸方向へそれぞれ２．５倍に延伸
し、厚さ０．１５ｍｍの良好な透明性を有する２軸延伸
シートを得た。Next, using a test stretching machine, the above unstretched sheet was
The film was stretched 2.5 times in each biaxial direction under a temperature condition of 0° C. to obtain a biaxially stretched sheet having a thickness of 0.15 mm and good transparency.
上記の未延伸シート及び２軸延伸シートの表面外観評価
（ブツあるいはハードスポット現象の検査）を行ない、
その結果を表−１に示した。The above unstretched sheets and biaxially stretched sheets were evaluated for their surface appearance (inspection of bumps or hard spots),
The results are shown in Table-1.
実施例２
実施例１ににおいて、前混合におけるポリフェニレンエ
ーテルとポリスチレンの割合を重量部で５０１５０に変
更した以外は、実施例１と同様にして、ポリフェニレン
エーテル含量が２５重量％の耐熱性スチレン系樹脂組成
物を得た。Example 2 A heat-resistant styrenic resin with a polyphenylene ether content of 25% by weight was prepared in the same manner as in Example 1, except that the ratio of polyphenylene ether and polystyrene in the pre-mixing was changed to 50150 parts by weight. A composition was obtained.
次いで、実施例１と同様にして、上記の組成物から未延
伸シート及び２軸延伸シートを得た。Then, in the same manner as in Example 1, an unstretched sheet and a biaxially stretched sheet were obtained from the above composition.
上記各シートの表面外観の評価を行い、その結果を表−
１に示した。The surface appearance of each of the above sheets was evaluated and the results are shown in the table below.
Shown in 1.
実施例３
実施例１ににおいて、前混合における剪断速度を１５
ｓｅｃ”−’に変更し、また、後混合の押出温度を２６
０℃、剪断速度を８５ｅｃ−’に変更した以外は、実施
例１と同様にして、ポリフェニレンエーテル含量が２５
重量％の耐熱性スチレン系樹脂組放物を得た。Example 3 In Example 1, the shear rate in premixing was changed to 15
sec"-', and the post-mixing extrusion temperature was changed to 26".
A polyphenylene ether content of 25 was carried out in the same manner as in Example 1, except that the temperature was 0°C and the shear rate was changed to 85 ec-'.
A heat-resistant styrenic resin composition of % by weight was obtained.
次いで、実施例１と同様にして、上記の組成物から未延
伸シート及び２軸延伸シートを得た。Then, in the same manner as in Example 1, an unstretched sheet and a biaxially stretched sheet were obtained from the above composition.
上記各シートの表面外観の評価を行い、その結果を表−
１に示した。The surface appearance of each of the above sheets was evaluated and the results are shown in the table below.
Shown in 1.
比較例Ｉ
実施例１において、前混合における混練温度を２８０°
Ｃに変更した以外は、実施例１と同様にして、ポリフェ
ニレンエーテル含量が２５重量％の耐熱性スチレン系樹
脂組成物を得た。Comparative Example I In Example 1, the kneading temperature in pre-mixing was set to 280°.
A heat-resistant styrenic resin composition having a polyphenylene ether content of 25% by weight was obtained in the same manner as in Example 1 except that C was used.
次いで、実施例１と同様にして、上記の組成物から未延
伸シート及び２軸延伸シートを得た。Then, in the same manner as in Example 1, an unstretched sheet and a biaxially stretched sheet were obtained from the above composition.
上記各シートの表面外観の評価を行い、その結果を表−
１に示した。The surface appearance of each of the above sheets was evaluated and the results are shown in the table below.
Shown in 1.
比較例２
実施例１において、前混合における混線条件を３００°
Ｃ１剪断速度を８５ｅｃ−’に変更した以外は、実施例
１と同様にして、ポリフェニレンエーテル含量が２５重
量％の耐熱性スチレン系樹脂組成物を得た。Comparative Example 2 In Example 1, the crosstalk condition in pre-mixing was set to 300°.
A heat-resistant styrenic resin composition having a polyphenylene ether content of 25% by weight was obtained in the same manner as in Example 1 except that the C1 shear rate was changed to 85 ec-'.
次いで、実施例１と同様にして、上記の組成物から未延
伸シート及び２軸延伸シートを得た。Then, in the same manner as in Example 1, an unstretched sheet and a biaxially stretched sheet were obtained from the above composition.
上記各シートの表面外観の評価を行い、その結果を表−
１に示した。The surface appearance of each of the above sheets was evaluated and the results are shown in the table below.
Shown in 1.
比較例３
実施例１において、前混合におけるポリフェニレンエー
テルとポリスチレンの混合割合を重量部で２５／７５に
変更し、後混合を省いた以外は、実施例１と同様にして
、ポリフェニレンエーテル含量が２５重量％の耐熱性ス
チレン系樹脂組成物を得た。Comparative Example 3 The same procedure as in Example 1 was carried out, except that the mixing ratio of polyphenylene ether and polystyrene in the pre-mixing was changed to 25/75 in parts by weight, and the post-mixing was omitted. A heat-resistant styrenic resin composition of % by weight was obtained.
次いで、実施例１と同様にして、上記の組成物から未延
伸シート及び２軸延伸シートを得た。Then, in the same manner as in Example 1, an unstretched sheet and a biaxially stretched sheet were obtained from the above composition.
上記各シートの表面外観の評価を行い、その結果を表−
１に示した。The surface appearance of each of the above sheets was evaluated and the results are shown in the table below.
Shown in 1.
表−１から次のことが明らかである。The following is clear from Table-1.
すなわち、最終組成物中に残存するポリフェニレンエー
テルの未溶融ポリマー塊による、成形品に対する外観不
良は、２軸延伸シートにした場合により顕著に現れる。That is, the poor appearance of the molded product due to unmelted polymer lumps of polyphenylene ether remaining in the final composition becomes more noticeable when the molded product is made into a biaxially stretched sheet.
そして、本発明（実施例１〜３）によれば、成形品の外
観不良は発生しておらず、従って、最終組成物中にはポ
リフェニレンエーテルの未溶融ポリマー塊は実質的に含
まれていない。これに対し比較例１〜３においては、未
延伸シート及び２軸延伸シートのいずれにおいても、外
観不良を生じており、ポリフェニレンエーテルの未溶融
ポリマーが残存している。According to the present invention (Examples 1 to 3), no defective appearance of the molded product occurs, and therefore, the final composition does not substantially contain unmelted polymer lumps of polyphenylene ether. . On the other hand, in Comparative Examples 1 to 3, both the unstretched sheet and the biaxially stretched sheet had poor appearance, and unmelted polyphenylene ether polymer remained.
（以下、余白）
〔発明の効果〕
以上説明した本発明によれば、スチレン系樹脂とポリフ
ェニレンエーテルとを含有して成り、ポリフェニレンエ
ーテルの未溶融ポリマー塊を実質的に含まない、耐熱性
スチレン系樹脂組成物の工業的有利な製造方法が提供さ
れる。(Hereinafter, blank spaces) [Effects of the Invention] According to the present invention described above, a heat-resistant styrenic resin containing a styrene resin and a polyphenylene ether and substantially free of unmelted polymer lumps of the polyphenylene ether is produced. An industrially advantageous method for producing a resin composition is provided.
出願人 三菱化成ポリチック株式会社 代理人 弁理士 岡 １）数 彦Applicant: Mitsubishi Kasei Polytech Co., Ltd. Agent: Patent Attorney Oka 1) Kazuhiko
Claims (1)
有し、両者に対するスチレン系樹脂の割合が５０重量％
を超え９５重量％以下の耐熱性スチレン系樹脂組成物の
製造方法あって、先ず、スチレン系樹脂とポリフェニレ
ンエーテルとを含有し、両者に対するスチレン系樹脂の
割合が５〜５０重量％の混合物を、溶融混練機を用い、
３００〜３４０℃の温度条件下、１０ｓｅｃ＾−＾１以
上の剪断速度を与えつつ混練して均一な樹脂組成物とな
し、次いで、この樹脂組成物にスチレン系樹脂を混合し
て均一に溶融混練することを特徴とする耐熱性スチレン
系樹脂組成物の製造方法。(1) Contains styrene resin and polyphenylene ether, the ratio of styrene resin to both is 50% by weight
There is a method for producing a heat-resistant styrenic resin composition of more than 95% by weight or less, first, a mixture containing a styrene resin and a polyphenylene ether in which the ratio of the styrenic resin to both is 5 to 50% by weight, Using a melt kneader,
A uniform resin composition is obtained by kneading under a temperature condition of 300 to 340°C while applying a shear rate of 10 sec^-^1 or more, and then a styrene resin is mixed with this resin composition and uniformly melted and kneaded. A method for producing a heat-resistant styrenic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2236135A JPH04117444A (en) | 1990-09-06 | 1990-09-06 | Preparation of heat-resistant styrene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2236135A JPH04117444A (en) | 1990-09-06 | 1990-09-06 | Preparation of heat-resistant styrene resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04117444A true JPH04117444A (en) | 1992-04-17 |
Family
ID=16996281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2236135A Pending JPH04117444A (en) | 1990-09-06 | 1990-09-06 | Preparation of heat-resistant styrene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04117444A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133379A (en) * | 1997-02-18 | 2000-10-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing a resin composition |
| EP1169391A1 (en) | 1999-04-02 | 2002-01-09 | General Electric Company | Process for preparing polyphenylene ether thermoplastic resin compositions and articles made therefrom |
| US7544728B2 (en) | 2006-04-19 | 2009-06-09 | Asahi Kasei Chemicals Corporation | Production process of polyphenylene ether composition |
| US7736565B2 (en) | 2005-05-11 | 2010-06-15 | Asahi Kasei Chemicals Corporation | Process for producing PPE resin composition |
-
1990
- 1990-09-06 JP JP2236135A patent/JPH04117444A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6133379A (en) * | 1997-02-18 | 2000-10-17 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing a resin composition |
| EP1169391A1 (en) | 1999-04-02 | 2002-01-09 | General Electric Company | Process for preparing polyphenylene ether thermoplastic resin compositions and articles made therefrom |
| JP2002541295A (en) * | 1999-04-02 | 2002-12-03 | ゼネラル・エレクトリック・カンパニイ | Method for producing polyphenylene ether thermoplastic resin composition and product made from the composition |
| US7736565B2 (en) | 2005-05-11 | 2010-06-15 | Asahi Kasei Chemicals Corporation | Process for producing PPE resin composition |
| US7544728B2 (en) | 2006-04-19 | 2009-06-09 | Asahi Kasei Chemicals Corporation | Production process of polyphenylene ether composition |
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