JP4061695B2 - Thermoplastic resin composition and molded body - Google Patents

Description

で表される繰り返し単位を有する単独重合体、共重合体およびその混合物である。式中、Ａは原料の二価フェノールの残基である二価芳香族基である。このような芳香族ポリカーボネートを製造するために用いることのできる二価フェノールは、官能基として芳香族の炭素原子に直接結合している２つの水酸基を含有する単核または多核芳香族化合物である。二価フェノールの例としては、ビスフェノールＡ、ビス（４−ヒドロキシフェニル）メタン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、２，２−（３，５，３’，５’−テトラクロロ−４，４’−ヒドロキシフェニル）プロパン、２，２−（３，５，３’，５’−テトラブロモ−４，４’−ヒドロキシフェニル）プロパン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、ヒドロキノン、レゾルシノール、ビフェニル−４，４’−ジオール、などが挙げられるが、これらに限定されるものではない。
特に二価フェノールとしてビスフェノールＡを少なくとも３０ｍｏｌ％以上を用いるコポリカーボネートもしくはホモポリカーボネートであることが好ましい。
【０００９】
【化４】

で表される繰り返し単位を有する単独重合体、共重合体およびその混合物である。
式中、Ｅは原料の二価フェノールの残基である二価芳香族基である。このようなポリアリレート樹脂を製造するために用いることのできる二価フェノールの例としては、ビス（４−ヒドロキシフェニル）−メタン、ビス（４−ヒドロキシ−３−メチルフェニル）−メタン、ビス（４−ヒドロキシ−３，５−ジクロロフェニル）−メタン、ビス（４−ヒドロキシ−３，５−ジブロモフェニル）−メタン、ビス（４−ヒドロキシ３，５−ジフルオロフェニル）−メタン、ビス（４−ヒドロキシフェニル）−ケトン、ビス（４−ヒドロキシフェニル）−サルファイド、ビス（４−ヒドロキシフェニル）−サルホン、４，４−ジヒドロキレジフェニルエーテル、１，１−ビス（４−ヒドロキシフェニル）−エタン、２，２−ビス（４−ヒドロキシフェニル）−プロパン、２，２−ビス（ヒドロキシ−３−メチルフェニル）−ブロパン、２，２−ビス（４−ビドロキシ−３−クロロフェニル）−プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジクロロフェニル）−プロパン、２，２−ビス（４−ビドロキレナフチル）−プロパン、ビス（４−ヒドロキシフェニル−フェニルメタン、ビス（４−ヒドロキシフェニル）−ジフェニルメタン、ビス（４−ヒドロキシフェニル）−４−メチルフェニルメタン、１，１−ビス（４−ヒドロキシフェニル）−２，２，２−トリクロロエタン、ビス（４−ヒドロキシフェニル）−４−クロロフェニル）−メタン、１，１−ビス（４−ヒドロキシフェニル）−シクロヘキサン、ビス（４−ヒドロキシフェニル）−シタロヘキサシルメタン、４，４−ジヒドロキシジフェニル、２，２−ジヒドロキシジフェニル、２，６−ジヒドロキシテフタレンのようなジビドロキシナフタレン、ヒドロキノン、レゾルシノール、２，６−ジヒドロキシトルエン、２，６−ジヒドロキシクロロベンゼン、３，６−ジビドロキシトルエン、ニ価フェノールの誘導体とは具体釣には前記ニ価フエノールのアルキル、フェニルなどのジエステルである。またこれらの混合物を用いてもよい。
また、式中、Ｄは原料の芳香族ジカルボン酸の残基である二価芳香族基であって、その例としては前記の通りである。これらの中でも好ましいポリアリレート樹脂としては、二価フェノール成分を基準として少なくとも８０重量％の、好ましくは少なくとも９０重量％の２，２−ビス（４−ヒドロキシフェニル）−プロパンを含有し、芳香族ジカルボン酸単位としてテレフタル酸およびイソフタル酸を含有するものである。
【００１６】
本発明で用いられる芳香族ポリサルホン樹脂は、アリーレン単位、エーテル結合およびスルホン結合の三者が必須の構成単位であって、アリーレン単位がエーテルおよびスルホン結合とともに無秩序にまたは秩序正しく位置するポリアリーレン化合物として定義される。代表的な例としては次のような繰り返し単位を有するものがあげられるが、これに限定されるものではない。
【００１７】
【化１０】

［（ＩＩ）の化合物はランダム共重合体を含む。式中、Ｒ₁は炭素原子数１ないし６のアルキル基、炭素原子数３ないし１０のアルケニル基、フェニル基またはハロゲン原子を表し、ｐは０ないし４の正数である。ｍ、ｎは平均の繰り返し単位数を示しｍ、ｎは０．１から１００の正数である。同一または異なる核上の各Ｒ₁は相互に異なっていても良い。各ｐは相互に異なっていても良い。］
【００１８】
【化１１】

（この化合物はランダム共重合体を含む。式中、Ｒ₁は炭素原子数１ないし６のアルキル基、炭素原子数３ないし１０のアルケニル基、フェニル基またはハロゲン原子を表し、ｐは０ないし４の正数である。ｑ、ｍ、ｎは平均の繰り返し単位数を示し、ｑは１〜３の正数、ｍ、ｎは０．１〜１００の正数である。同一または異なる核上の各Ｒ₁は相互に異なっていても良い。各ｐは相互に異なっていても良い。）
本発明で用いられる芳香族ポリサルホン樹脂としては、（ＩＩ）または（ＩＩＩ）で表される繰り返し単位中の（ｍ／ｍ＋ｎ）は０．８以上であることが好ましい。また、（ＩＩＩ）の構造単位中のｑは１であることが好ましい。
これらの中でも（Ｉ）、（ＩＩ）の繰り返し構造単位を持つものが好ましく、さらに好ましくは（Ｉ）の繰り返し構造単位を持つものである。
また、その末端構造は、各々の樹脂の製法に従って決まるものであり、例えば、Ｃｌ、ＯＨ，ＯＲ（Ｒはアルキル基）などが挙げられるが、これらに限定されるものではない。
【００１９】
本発明で用いられる芳香族ポリサルホン樹脂は、含有するアルカリ金属の総量が３００ｐｐｍ以下のものであり、２５０ｐｐｍ以下のものがより好ましい。アルカリ金属の総量が３００ｐｐｍより多いものは、溶融混練の際にポリカーボネート樹脂の分解が生じて本来期待される物性が得られなかったり、分解に伴う粘度低下やガスの発生により射出成形や押出成形などの溶融成形加工が困難になるために好ましくない。芳香族ポリサルホン樹脂に含まれるアルカリ金属は、各々の樹脂の製法に従って決まるものであり、例えば、カリウム、ナトリウムなどが挙げられる。また、その総量が３００ｐｐｍ以下の芳香族ポリサルホン樹脂を得るための方法としては、重合反応を終結させた芳香族ポリサルホン樹脂の重合溶液、あるいは芳香族ポリサルホン樹脂を極性有機溶媒に溶解させた溶液と、芳香族ポリサルホン樹脂の貧溶媒、例えば、アセトン、メタノール、水およびそれらの混合物を混合することにより、アルカリ金属を低減させた芳香族ポリサルホン樹脂を析出させる、芳香族ポリサルホン樹脂を水あるいは酢酸水溶液などで洗浄する、含有するアルカリ金属の総量が３００ｐｐｍより多い芳香族ポリサルホン樹脂を含有するアルカリ金属の総量が３００ｐｐｍ以下のものとブレンドするなどがあげられるが、これらに限定されるものではない。
【００２０】
本発明に適用する熱可塑性樹脂組成物に配合されるポリカーボネート樹脂の配合量は、芳香族ポリサルホン樹脂およびポリカーボネート樹脂の全重量を基にして５〜５５重量％であることが好ましく、２５〜４５重量％であることがより好ましい。
【００２１】
本発明においては、必要に応じてガラス繊維、シリカアルミナ繊維、アルミナ繊維、炭素繊維、ホウ酸アルミニウムウィスカーなどの繊維状あるいは針状の補強剤、タルク、マイカ、クレー、ガラスビーズなどの無機充填剤、フッ素樹脂などや金属石鹸類などの離型改良材、染料、顔料などの着色剤、酸化防止剤、熱安定剤、紫外線吸収剤、帯電防止剤、界面活性剤などの通常の添加剤を１種以上添加することができる。また、少量の熱可塑性樹脂、たとえば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、ＡＢＳ樹脂、ポリスチレン、メタクリル樹脂、ポリアミド、ポリフェニレンスルフィド、ポリエーテルケトン、ポリフェニレンエーテルおよびその変成物、ポリエーテルイミドなど、少量の熱硬化性樹脂、たとえば、フェノール樹脂、エポキシ樹脂、シアネート樹脂、イソシアネート樹脂、ポリイミド樹脂などや、少量のゴム成分などの一種または二種以上を添加することもできる。本発明の樹脂組成物を得るための原材料の配合手段は特に限定されない。ポリカーボネート樹脂、芳香族ポリサルホン樹脂、必要に応じてガラス繊維などの補強材や無機充填材、離型改良剤、熱安定剤などをヘンシェルミキサー、タンブラー等を用いて混合した後、押出機を用いて溶融混練することが一般的である。そのときの溶融混練法としては、すべての原材料を一括して混合した後で押出機へフィードしてもかまわないし、必要に応じてガラス繊維などの補強材や無機充填材などの原材料を、樹脂を主体とする原材料とは別にフィードしてもかまわない。
【００２２】
本発明の熱可塑性樹脂組成物を用いて成形した成形体の作成方法は特に限定されない。樹脂を溶融し賦形、固化せしめる方法としては押出成形、射出成形、ブロー成形などが挙げられるが、この中では特に射出成形が好ましく用いられる。
また、押出成形された成形品を、切削やプレスによって加工しても良い。
本発明の熱可塑性樹脂組成物は、自動車、航空機等の部品、産業用機器、家電製品、食器や医療機器、ＯＡ、ＡＶ機器、電子、電子部品、たとえば、特に耐熱性が必要とされるＩＣトレーやＩＣソケットなどに好適に用いることができる。
【００２３】
【実施例】
以下、本発明の実施例を示すが、本発明はこれらに限定されるものではない。
なお、実施例中のアルカリ金属の総量、溶融粘度の測定は、次の方法で行った。
（１）アルカリ金属の総量：
対象となる芳香族ポリサルホン樹脂２ｇを電熱器、ガスバーナー、および５５０℃の電気炉で灰化させ、希塩酸に溶解して原子吸光光度計でアルカリ金属の量を定量した。
（２）溶融粘度：
対象となる組成物２．３ｇを１２０℃で８時間乾燥させた後、高化式フローテスター（島津製作所製 ＣＦＴ−５００）を用いて、３５０℃、荷重５０ｋｇ、ダイ径１ｍｍ、ダイ長１０ｍｍで溶融粘度を測定した。
【００２４】
参考例１
攪拌機、窒素導入管、温度計、先端に受け器を付したコンデンサーとを備えた０．５ＬのＳＵＳ３１６Ｌ製フラスコ内に、４，４’−ヒドロキシジフェニルサルホン １００．１１ｇ、４，４’−ジクロロジフェニルサルホン １１９．００ｇ、およびジフェニルサルホン １９６．００ｇを仕込み、フラスコ内に窒素ガスを流通させながら１８０℃まで昇温し、単量体を溶融させた。その後、無水炭酸カリウム ５７．５０ｇを添加し、引き続いて２９０℃まで徐々に昇温し、そのまま３時間反応させた。反応液を取り出して室温まで冷却固化させ、小型粉砕機（協立理工社製）ＳＫＭ１０Ｒにより最大粒径が１ｍｍ以下になるまで粉砕した。
【００２５】
参考例２
３Ｌフラスコに参考例１で得た反応混合物１５０ｇと４０℃の温水１Ｌを加え錨型攪拌翼で３時間攪拌し、重合体とジフェニルサルホンの粉状混合物を濾取した。その後、３Ｌフラスコにアセトン１２００ｍｌ、メタノール８００ｍｌ、および水１００ｍｌを混合した溶媒とその粉状体を仕込み、錨型攪拌翼で３時間攪拌し、この操作を溶媒を入れ替えて３回繰り返した後、２Ｌの水で２回洗浄し１５０℃の熱風循環オーブンで８時間乾燥して約６０ｇの重合体を得た。この重合体に含まれるアルカリ金属の量を上記の方法で測定したところ、カリウムが５５０ｐｐｍであり、その他のアルカリ金属は１０ｐｐｍ以下であった。
【００２６】
比較例１
芳香族ポリカーボネート樹脂（住友ダウ（株）製 ＣＡＲＩＢＲＥ ２００−３）２６ｇと参考例２で得た芳香族ポリサルホン樹脂３９ｇを混合して１２０℃で８時間乾燥させた後、３４０℃に設定した２軸溶融混練機（（株）東洋精機製作所製、ラボプラストミル２０Ｒ２００）に仕込み、１５０ｒｐｍで混練を行った。５分経過した時点で約３ｇの樹脂組成物を抜き出し、引き続き１０分間混練を続けた後、全量を回収した。それぞれの樹脂組成物は上記の方法で溶融粘度を測定した。
【００２７】
参考例３
３Ｌフラスコに参考例１で得た反応混合物１５０ｇと８０℃の温水１Ｌを加え錨型攪拌翼で３時間攪拌し、重合体とジフェニルサルホンの粉状混合物を濾取した。この温水による洗浄操作を３回繰り返した。続いて５Ｌフラスコにアセトン１７００ｍｌ、メタノール１１００ｍｌおよび水１４０ｍｌを混合した溶媒とその粉状混合物を仕込み、錨型攪拌翼で３時間攪拌し、この操作を溶媒を入れ替えて３回繰り返した後、２Ｌの水で２回洗浄し１５０℃の熱風循環オーブンで８時間乾燥し、約６０ｇの重合体を得た。この重合体に含まれるアルカリ金属の量を上記の方法で測定したところ、カリウムが２４０ｐｐｍであり、その他のアルカリ金属は１０ｐｐｍ以下であった。
【００２８】
実施例１
参考例３で得た芳香族ポリサルホン樹脂を用いる他は、比較例１と同様にして混練および溶融粘度の測定をおこなった。
両者の溶融粘度を表１に示す。混練初期は比較例１、実施例１ともどもほとんど等しい溶融粘度であるが、１５分間溶融混練を行った後の溶融粘度は、実施例１の溶融粘度には変化がないが、比較例１の溶融粘度は著しく低下する。このことから、芳香族ポリエステル系樹脂とアルカリ金属の総量が３００ｐｐｍより多い芳香族ポリサルホン系樹脂からなる組成物は、溶融時に粘度低下を生じるため安定した溶融成形加工が困難であることがわかる。一方、芳香族ポリエステル系樹脂とアルカリ金属の総量が３００ｐｐｍ以下である芳香族ポリサルホン系樹脂からなる組成物は、溶融しても粘度低下を生じないため安定して溶融成形加工を行えることがわかる。
【００２９】
【表１】

【発明の効果】
本発明の熱可塑性樹脂組成物および成形体は、耐熱性や機械的物性に優れ、溶融成形加工が容易である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic resin composition excellent in mechanical properties, heat resistance, moldability, appearance of a molded product, and the like, and a molded article molded using the same.
[0002]
[Prior art]
For the purpose of improving the chemical resistance of aromatic polyester resins and improving the impact resistance of aromatic polysulfone resins and the fluidity during molding, mixing aromatic polyester resins and aromatic polysulfone resins Various thermoplastic resin compositions are disclosed.
For example, Japanese Patent Publication No. 45-39181 discloses that chemical resistance and thermal stress embrittlement are improved by mixing an aromatic polysulfone resin and an aromatic polycarbonate resin as compared with each resin. ing.
Japanese Patent Publication No. 49-13855 discloses that a composition comprising an aromatic polysulfone resin and an aromatic polycarbonate resin is superior in heat distortion resistance as compared to an ABS resin.
JP-A-54-28361 discloses that a composition comprising an aromatic polycarbonate resin having a weight average molecular weight of more than 60,000 and an aromatic polysulfone resin has improved chemical resistance and deflection temperature under load compared to each resin. It is disclosed.
JP-A-60-51739 discloses that a composition comprising an aromatic polysulfone resin having a specific structure and an aromatic polycarbonate resin has excellent mechanical properties and improved chemical resistance. .
However, in these compositions, the aromatic polyester-based resin such as aromatic polycarbonate resin is decomposed during the production by melt-kneading, so that the originally expected physical properties cannot be obtained, the viscosity is reduced due to the decomposition, the gas Occurrence of defects such as difficulty in melt molding such as injection molding and extrusion molding.
[0003]
[Problems to be solved by the invention]
An object of this invention is to provide the stabilization method of the melt viscosity of the thermoplastic resin composition which is excellent in heat resistance and is easy for a melt molding process.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have selected the aromatic polysulfone resin in which the total amount of alkali metals is not more than a specific value, and the above object is achieved by forming a composition with a polycarbonate resin. As a result, the present invention has been reached. That is, the present invention comprises a thermoplastic resin composition comprising a polycarbonate resin and an aromatic polysulfone resin, wherein the total amount of alkali metal atoms (hereinafter simply referred to as alkali metal) contained in the aromatic polysulfone resin is 300 ppm or less. The present invention relates to a method for stabilizing the melt viscosity of a product.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The polycarbonate resin used in the present invention is a general formula,
[0006]
[Chemical 2]

Homopolymers, copolymers and mixtures thereof having a repeating unit represented by the formula: In the formula, A is a divalent aromatic group which is a residue of the raw material dihydric phenol. The dihydric phenol that can be used to produce such an aromatic polycarbonate is a mononuclear or polynuclear aromatic compound containing two hydroxyl groups directly bonded to an aromatic carbon atom as a functional group. Examples of dihydric phenols include bisphenol A, bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2- (3,5,3 ′, 5 '-Tetrachloro-4,4'-hydroxyphenyl) propane, 2,2- (3,5,3', 5'-tetrabromo-4,4'-hydroxyphenyl) propane, 1,1-bis (4- Hydroxyphenyl) cyclohexane, hydroquinone, resorcinol, biphenyl-4,4′-diol, and the like, but are not limited thereto.
Particularly preferred is a copolycarbonate or homopolycarbonate using at least 30 mol% of bisphenol A as a dihydric phenol.
[0009]
[Formula 4]

Homopolymers, copolymers and mixtures thereof having a repeating unit represented by the formula:
In the formula, E is a divalent aromatic group which is a residue of the raw material dihydric phenol. Examples of dihydric phenols that can be used to produce such polyarylate resins include bis (4-hydroxyphenyl) -methane, bis (4-hydroxy-3-methylphenyl) -methane, bis (4 -Hydroxy-3,5-dichlorophenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl) -methane, bis (4-hydroxy3,5-difluorophenyl) -methane, bis (4-hydroxyphenyl) Ketone, bis (4-hydroxyphenyl) -sulfide, bis (4-hydroxyphenyl) -sulfone, 4,4-dihydroxyphenyl ether, 1,1-bis (4-hydroxyphenyl) -ethane, 2,2-bis (4-Hydroxyphenyl) -propane, 2,2-bis (hydroxy-3-methylphenyl) -Bropan, 2,2-bis (4-bidoxy-3-chlorophenyl) -propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2-bis (4-bidoxylennaphthyl) ) -Propane, bis (4-hydroxyphenyl-phenylmethane, bis (4-hydroxyphenyl) -diphenylmethane, bis (4-hydroxyphenyl) -4-methylphenylmethane, 1,1-bis (4-hydroxyphenyl)- 2,2,2-trichloroethane, bis (4-hydroxyphenyl) -4-chlorophenyl) -methane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, bis (4-hydroxyphenyl) -cytalohexyl methane 4,4-dihydroxydiphenyl, 2,2-dihydroxydiphenyl, 2,6-di Specific examples of dividroxynaphthalene such as droxytephthalene, hydroquinone, resorcinol, 2,6-dihydroxytoluene, 2,6-dihydroxychlorobenzene, 3,6-dividroxytoluene, and dihydric phenol derivatives Divalent phenol diesters such as alkyl and phenyl. A mixture of these may also be used.
In the formula, D is a divalent aromatic group which is a residue of the starting aromatic dicarboxylic acid, and examples thereof are as described above. Among these, preferred polyarylate resins include at least 80% by weight, preferably at least 90% by weight of 2,2-bis (4-hydroxyphenyl) -propane, based on the dihydric phenol component, and aromatic dicarboxylic acids. It contains terephthalic acid and isophthalic acid as acid units.
[0016]
The aromatic polysulfone resin used in the present invention is an essential structural unit consisting of an arylene unit, an ether bond, and a sulfone bond, and the arylene unit is a polyarylene compound that is randomly or orderly located together with an ether and a sulfone bond. Defined. Representative examples include those having the following repeating units, but are not limited thereto.
[0017]
[Chemical Formula 10]

[The compound of (II) contains a random copolymer. In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a phenyl group, or a halogen atom, and p is a positive number from 0 to 4. m and n represent the average number of repeating units, and m and n are positive numbers from 0.1 to 100. Each R ₁ on the same or different nucleus may be different from each other. Each p may be different from each other. ]
[0018]
Embedded image

(This compound includes a random copolymer. In the formula, R ₁ represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, a phenyl group or a halogen atom, and p represents 0 to 4). Q, m, and n represent the average number of repeating units, q is a positive number of 1 to 3, and m and n are positive numbers of 0.1 to 100. On the same or different nuclei Each R ₁ may be different from each other, and each p may be different from each other.)
As the aromatic polysulfone resin used in the present invention, (m / m + n) in the repeating unit represented by (II) or (III) is preferably 0.8 or more. Further, q in the structural unit of (III) is preferably 1.
Among these, those having the repeating structural units (I) and (II) are preferable, and those having the repeating structural unit (I) are more preferable.
Moreover, the terminal structure is determined according to the manufacturing method of each resin, for example, Cl, OH, OR (R is an alkyl group) etc., However, It is not limited to these.
[0019]
The aromatic polysulfone resin used in the present invention has a total alkali metal content of 300 ppm or less, and more preferably 250 ppm or less. When the total amount of alkali metal is more than 300 ppm, the polycarbonate resin is decomposed during melt-kneading and the originally expected physical properties cannot be obtained, or the viscosity is reduced due to decomposition or the generation of gas causes injection molding or extrusion molding. This is not preferable because the melt molding process becomes difficult. The alkali metal contained in the aromatic polysulfone resin is determined according to the production method of each resin, and examples thereof include potassium and sodium. Moreover, as a method for obtaining an aromatic polysulfone resin having a total amount of 300 ppm or less, a polymerization solution of an aromatic polysulfone resin in which a polymerization reaction is terminated, or a solution in which an aromatic polysulfone resin is dissolved in a polar organic solvent, By mixing an aromatic polysulfone resin with a poor solvent, for example, acetone, methanol, water and a mixture thereof, the aromatic polysulfone resin with reduced alkali metal is precipitated. Examples include, but are not limited to, washing, blending with a total amount of alkali metal containing 300 ppm or less of an aromatic polysulfone resin containing an aromatic polysulfone resin with a total amount of alkali metal greater than 300 ppm.
[0020]
The blending amount of the polycarbonate resin blended in the thermoplastic resin composition applied to the present invention is preferably 5 to 55% by weight based on the total weight of the aromatic polysulfone resin and the polycarbonate resin , and is 25 to 45% by weight. % Is more preferable.
[0021]
In the present invention, fiber fillers such as glass fibers, silica alumina fibers, alumina fibers, carbon fibers, and aluminum borate whiskers, as well as inorganic fillers such as talc, mica, clay, and glass beads, if necessary. Normal additives such as mold release improvers such as fluororesins and metal soaps, colorants such as dyes and pigments, antioxidants, heat stabilizers, UV absorbers, antistatic agents and surfactants More than seeds can be added. In addition, a small amount of thermoplastic resin such as polyethylene, polypropylene, polyvinyl chloride, ABS resin, polystyrene, methacrylic resin, polyamide, polyphenylene sulfide, polyether ketone, polyphenylene ether and its modified products, polyetherimide, etc. A curable resin such as a phenol resin, an epoxy resin, a cyanate resin, an isocyanate resin, a polyimide resin, or a small amount of a rubber component may be added. The raw material compounding means for obtaining the resin composition of the present invention is not particularly limited. After mixing polycarbonate resin, aromatic polysulfone resin, if necessary, reinforcing materials such as glass fiber, inorganic filler, mold release improver, heat stabilizer, etc. using a Henschel mixer, tumbler, etc., using an extruder It is common to melt-knead. As the melt-kneading method at that time, all raw materials may be mixed and fed to an extruder, and if necessary, raw materials such as reinforcing materials such as glass fibers and inorganic fillers may be used as resins. It is also possible to feed it separately from the raw material mainly composed of.
[0022]
The production method of the molded object shape | molded using the thermoplastic resin composition of this invention is not specifically limited. Examples of methods for melting and shaping and solidifying the resin include extrusion molding, injection molding, blow molding and the like, and among these, injection molding is particularly preferably used.
Further, the extruded product may be processed by cutting or pressing.
The thermoplastic resin composition of the present invention is used for parts such as automobiles and aircraft, industrial equipment, home appliances, tableware and medical equipment, OA, AV equipment, electronics, and electronic parts, for example, ICs that particularly require heat resistance. It can be suitably used for trays and IC sockets.
[0023]
【Example】
Examples of the present invention will be described below, but the present invention is not limited thereto.
The total amount of alkali metals and the melt viscosity in the examples were measured by the following method.
(1) Total amount of alkali metal:
The target aromatic polysulfone resin (2 g) was incinerated with an electric heater, a gas burner, and an electric furnace at 550 ° C., dissolved in diluted hydrochloric acid, and the amount of alkali metal was quantified with an atomic absorption photometer.
(2) Melt viscosity:
After 2.3 g of the target composition was dried at 120 ° C. for 8 hours, using a Koka flow tester (CFT-500 manufactured by Shimadzu Corporation) at 350 ° C., a load of 50 kg, a die diameter of 1 mm, and a die length of 10 mm. The melt viscosity was measured.
[0024]
Reference example 1
In a 0.5 L SUS316L flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a condenser with a receiver at the tip, 100.11 g of 4,4′-hydroxydiphenylsulfone, 4,4′-dichloro 119.00 g of diphenylsulfone and 196.00 g of diphenylsulfone were charged, and the temperature was raised to 180 ° C. while flowing nitrogen gas through the flask to melt the monomer. Thereafter, 57.50 g of anhydrous potassium carbonate was added, and then the temperature was gradually raised to 290 ° C. and reacted for 3 hours. The reaction solution was taken out, cooled and solidified to room temperature, and pulverized with a small pulverizer (manufactured by Kyoritsu Riko Co., Ltd.) SKM10R until the maximum particle size became 1 mm or less.
[0025]
Reference example 2
150 g of the reaction mixture obtained in Reference Example 1 and 1 L of 40 ° C. warm water were added to a 3 L flask, and the mixture was stirred with a vertical stirring blade for 3 hours, and a powdery mixture of the polymer and diphenylsulfone was collected by filtration. Thereafter, a solvent in which 1200 ml of acetone, 800 ml of methanol, and 100 ml of water were mixed in a 3 L flask and its powder were stirred and stirred with a vertical stirring blade for 3 hours. This operation was repeated 3 times with the solvent changed, and then 2 L The product was washed twice with water and dried in a hot air circulating oven at 150 ° C. for 8 hours to obtain about 60 g of a polymer. When the amount of alkali metal contained in this polymer was measured by the above method, potassium was 550 ppm and other alkali metals were 10 ppm or less.
[0026]
Comparative Example 1
A biaxial shaft set at 340 ° C. after mixing 26 g of aromatic polycarbonate resin (CARIBRE 200-3 manufactured by Sumitomo Dow Co., Ltd.) and 39 g of aromatic polysulfone resin obtained in Reference Example 2 and drying at 120 ° C. for 8 hours. A melt kneader (Toyo Seiki Seisakusho, Lab Plast Mill 20R200) was charged and kneaded at 150 rpm. When 5 minutes had passed, about 3 g of the resin composition was extracted, and after kneading was continued for 10 minutes, the entire amount was recovered. Each resin composition was measured for melt viscosity by the method described above.
[0027]
Reference example 3
150 g of the reaction mixture obtained in Reference Example 1 and 1 L of warm water at 80 ° C. were added to a 3 L flask, and the mixture was stirred with a vertical stirring blade for 3 hours, and a powdery mixture of the polymer and diphenylsulfone was collected by filtration. This washing operation with warm water was repeated three times. Subsequently, a solvent in which 1700 ml of acetone, 1100 ml of methanol and 140 ml of water were mixed in a 5 L flask and a powdered mixture thereof were charged and stirred for 3 hours with a vertical stirring blade. It was washed twice with water and dried in a hot air circulating oven at 150 ° C. for 8 hours to obtain about 60 g of polymer. When the amount of alkali metal contained in this polymer was measured by the above method, potassium was 240 ppm, and other alkali metals were 10 ppm or less.
[0028]
Example 1
Kneading and measurement of melt viscosity were performed in the same manner as in Comparative Example 1 except that the aromatic polysulfone resin obtained in Reference Example 3 was used.
Both melt viscosities are shown in Table 1. Although the melt viscosity at the initial stage of kneading is almost the same in both Comparative Example 1 and Example 1, the melt viscosity after 15 minutes of melt-kneading does not change the melt viscosity of Example 1, but the melt of Comparative Example 1 The viscosity is significantly reduced. This indicates that a composition comprising an aromatic polyester resin and an aromatic polysulfone resin in which the total amount of the aromatic polyester resin and the alkali metal is more than 300 ppm causes a decrease in viscosity at the time of melting, so that stable melt molding is difficult. On the other hand, it can be seen that a composition comprising an aromatic polyester resin and an aromatic polysulfone resin in which the total amount of the aromatic polyester resin and the alkali metal is 300 ppm or less does not cause a decrease in viscosity even when melted, and thus can be stably melt-molded.
[0029]
[Table 1]

【The invention's effect】
The thermoplastic resin composition and molded article of the present invention are excellent in heat resistance and mechanical properties, and are easy to be melt molded.

Claims (4)

In the production of a thermoplastic resin composition comprising a polycarbonate resin and an aromatic polysulfone resin, an aromatic polysulfone resin obtained through a step of obtaining an aromatic polysulfone resin having a total amount of alkali metal atoms of 300 ppm or less is blended as a raw material A method for stabilizing the melt viscosity of a thermoplastic resin composition. The thermoplastic resin composition is a resin composition comprising a polycarbonate resin 5 to 55 wt% and an aromatic polysulfone resin 95-45 wt%, the method for stabilizing a melt viscosity of claim 1 the thermoplastic resin composition. The method for stabilizing the melt viscosity of a thermoplastic resin composition according to claim 1 or 2, wherein the polycarbonate resin is a copolycarbonate or a homopolycarbonate using at least 30 mol% of bisphenol A. Aromatic polysulfone resin is the following formula

The method for stabilizing the melt viscosity of a thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a repeating unit represented by the formula: 80 mol% or more.