JPS6242941B2 - - Google Patents
Info
- Publication number
- JPS6242941B2 JPS6242941B2 JP12919578A JP12919578A JPS6242941B2 JP S6242941 B2 JPS6242941 B2 JP S6242941B2 JP 12919578 A JP12919578 A JP 12919578A JP 12919578 A JP12919578 A JP 12919578A JP S6242941 B2 JPS6242941 B2 JP S6242941B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- polyester polycarbonate
- aromatic
- resin composition
- weight
- 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.)
- Expired
Links
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 229920000728 polyester Polymers 0.000 claims description 29
- 239000004417 polycarbonate Substances 0.000 claims description 23
- 229920000515 polycarbonate Polymers 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 12
- 150000001875 compounds Chemical group 0.000 claims description 8
- 239000004593 Epoxy Substances 0.000 claims description 6
- 229920005668 polycarbonate resin Polymers 0.000 claims description 6
- 239000004431 polycarbonate resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N terephthalic acid group Chemical group C(C1=CC=C(C(=O)O)C=C1)(=O)O KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 230000009477 glass transition Effects 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- WGMBWDBRVAKMOO-UHFFFAOYSA-L disodium;4-[2-(4-oxidophenyl)propan-2-yl]phenolate Chemical compound [Na+].[Na+].C=1C=C([O-])C=CC=1C(C)(C)C1=CC=C([O-])C=C1 WGMBWDBRVAKMOO-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical group OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱安定性および耐湿熱性が改善された
芳香族ポリエステルポリカーボネート樹脂組成物
に関するものである。
芳香族ポリエステルポリカーボネートは、同一
分子内にエステル結合とカーボネート結合を有す
る線状の樹脂であり、例えば、２，２―ビス（４
―ヒドロキシフエニル）プロパン（ビスフエノー
ルＡ）、テレフタロイルクロリドおよびホスゲン
を反応させることによつて製造され、すぐれた機
械的性質、耐候性、耐薬品性および透明性を有す
るものであることが知られている。（特開昭52―
128992）
しかしながら、このような芳香族ポリエステル
ポリカーボネートは軟化温度が高く溶融粘度も高
いため、成形加工に際しては高い温度を必要とす
るが、樹脂を高温にさらすことは、熱分解による
分子量の低下、着色あるいは成形品中の気泡の発
生などの不都合を招くので、これの改善が望まれ
ていた。
また、上記のような芳香族ポリエステルポリカ
ーボネートは、耐湿熱性、すなわち、スチームや
熱水との接触による脆化またはクラツクやクレー
ズの発生の点で十分満足し得るものではなかつ
た。
本発明者らは、上記した芳香族ポリエステルポ
リカーボネートの欠点を解決すべく鋭意研究の結
果、芳香族ポリエステルポリカーボネートに、エ
ポキシ化合物を配合するときは、芳香族ポリエス
テルポリカーボネートが本来有するすぐれた性質
を損うことなく、その熱安定性および耐湿熱性を
大巾に改善できることを知得して本発明を完成し
た。
すなわち本発明は、熱安定性および耐湿熱性の
改善された工業的価値の大きい芳香族ポリエステ
ルポリカーボネートを提供することを目的とする
ものであり、その要旨とするところは、一般式
（式中、Ｘは２価の基を示し、芳香核は置換基
を有していてもよい。）
で表わされる構造単位と、一般式
（式中、Ｘおよび芳香族は上と同一意義を有す
る。）
で表わされる構造単位とからなり、かつジヒドロ
キシジアリール化合物残基：テレフタル酸残基：
カーボネート結合のモル比が１：0.33〜0.75：
0.67〜0.25である芳香族ポリエステルポリカーボ
ネート100重量部に対し、エポキシ化合物を0.005
〜10重量部配合してなる芳香族ポリエステルポリ
カーボネート樹脂組成物である。
以下、本発明を詳細に説明する。
本発明で使用する芳香族ポリエステルポリカー
ボネートは、例えば、一般式
〔式中、Ｘは、
The present invention relates to an aromatic polyester polycarbonate resin composition with improved thermal stability and moist heat resistance. Aromatic polyester polycarbonate is a linear resin having an ester bond and a carbonate bond in the same molecule, for example, 2,2-bis(4
-Hydroxyphenyl)propane (bisphenol A), terephthaloyl chloride and phosgene, and has excellent mechanical properties, weather resistance, chemical resistance and transparency. Are known. (Unexamined Japanese Patent Publication 1973-
128992) However, such aromatic polyester polycarbonates have a high softening temperature and high melt viscosity, so they require high temperatures during molding, but exposing the resin to high temperatures can cause a decrease in molecular weight and discoloration due to thermal decomposition. Alternatively, this may lead to problems such as the generation of air bubbles in the molded product, so there has been a desire to improve this problem. Furthermore, the above-mentioned aromatic polyester polycarbonates are not sufficiently satisfactory in terms of heat and humidity resistance, that is, embrittlement or generation of cracks or crazes due to contact with steam or hot water. As a result of intensive research to solve the above-mentioned drawbacks of aromatic polyester polycarbonate, the present inventors have found that when blending an epoxy compound with aromatic polyester polycarbonate, the excellent properties inherent to aromatic polyester polycarbonate are impaired. The present invention was completed based on the knowledge that the thermal stability and heat-and-moisture resistance could be greatly improved without any problems. That is, the purpose of the present invention is to provide an aromatic polyester polycarbonate having improved thermal stability and moist heat resistance and having great industrial value. (In the formula, X represents a divalent group, and the aromatic nucleus may have a substituent.) A structural unit represented by the general formula (In the formula, X and aromatic group have the same meanings as above.) Consisting of a structural unit represented by the following, and a dihydroxydiaryl compound residue: a terephthalic acid residue:
The molar ratio of carbonate bonds is 1:0.33-0.75:
0.005 parts by weight of an epoxy compound for 100 parts by weight of aromatic polyester polycarbonate with a molecular weight of 0.67 to 0.25
This is an aromatic polyester polycarbonate resin composition containing ~10 parts by weight. The present invention will be explained in detail below. The aromatic polyester polycarbonate used in the present invention has, for example, the general formula [In the formula, X is
テレフタロイルクロリドの３％塩化メチレン溶
液、ビスフエノールＡを５％水酸化ナトリウム水
溶液に溶解して調製したビスフエノールＡナトリ
ウム塩13％の水溶液および２％トリエチルアミン
水溶液を、それぞれ44.2Kg／hr、15.9Kg／hrおよ
び0.2Kg／hrの流量で、内径30mm、長さ1.5ｍのガ
ラス球充填塔に供給し、該塔の供給口から0.75ｍ
の位置からホスゲン0.75Kg／hrを吹込んで反応を
行い、エステル結合を有し、末端にクロロホーメ
ート基を有するオリゴマーを製造した。
反応混合物を分液して得た上記オリゴマーの塩
化メチレン溶液44.0Kg／hr、上記と同じビスフエ
ノールＡナトリウム塩の13％水溶液17.6Kg／hr、
25％水酸化ナトリウム水溶液1.1Kg／hr、２％ト
リエチルアミンの水溶液0.67Kg／hrおよびｐ―タ
ーシヤリ―ブチルフエノール27ｇ／hrを、撹拌槽
に供給し、平均滞留時間が２時間となるようにし
て重縮合反応を行つた。
反応混合物を分液して得たポリマーの塩化メチ
レン溶液を、水、塩酸水溶液、次いで水で洗浄し
た後、塩化メチレンを蒸発させて、〔η〕が0.75
でビスフエノールＡ残基：テレフタル酸残基：カ
ーボネート結合のモル比が１：0.46：0.54の芳香
族ポリエステルポリカーボネートを得た。
＜全芳香族ポリエステルの製造例＞
テレフタル酸ジクロリドとイソフタル酸ジクロ
リドの１：１混合物の塩化メチレン溶液と、ビス
フエノールＡのアルカリ水溶液とを界面重合法に
より重合させて〔η〕が0.63の全芳香族ポリエス
テルを得た。
＜芳香族ポリカーボネートの製造例＞
ビスフエノールＡのアルカリ水溶液とホスゲン
とを塩化メチレンの存在下界面重合法により重合
させて〔η〕0.61の芳香族ポリカーボネートを得
た。
＜全芳香族ポリエステルと芳香族ポリカーボネー
トの混合物の製造例＞
上記両樹脂を同重量混合して得た混合物。
実施例１〜２および比較例１
上記製造例により製造した芳香族ポリエステル
ポリカーボネートのフレーク100部に、下記表１
に示すエポキシ化合物の25％塩化メチレン溶液２
部（エポキシ化合物として0.5部）を添加してよ
く混合し、塩化メチレンを蒸発させ、更に真空乾
燥器で十分乾燥した。
このフレークを、射出成形機（日精樹脂(株)製
TS―100型）およびASTMで規定する試験片成形
用金型を用いて、樹脂温度330℃、金型温度140℃
で成形を行つた。
成形前後の芳香族ポリエステルポリカーボネー
トの〔η〕、成形品の色調および成形品の耐湿熱
性は下記表１に示す通りであつた。
なお、比較のためエポキシ化合物を配合しなか
つた場合の結果を併記する。
A 3% methylene chloride solution of terephthaloyl chloride, a 13% aqueous solution of bisphenol A sodium salt prepared by dissolving bisphenol A in a 5% aqueous sodium hydroxide solution, and a 2% aqueous triethylamine solution were mixed at 44.2 Kg/hr and 15.9 kg/hr, respectively. Kg/hr and 0.2 Kg/hr flow rate to a glass bulb packed tower with an inner diameter of 30 mm and a length of 1.5 m, and 0.75 m from the supply port of the tower.
A reaction was carried out by blowing 0.75 Kg/hr of phosgene from the position, and an oligomer having an ester bond and a chloroformate group at the end was produced. A methylene chloride solution of the above oligomer obtained by separating the reaction mixture 44.0 Kg/hr, a 13% aqueous solution of the same bisphenol A sodium salt as above 17.6 Kg/hr,
25% sodium hydroxide aqueous solution 1.1Kg/hr, 2% triethylamine aqueous solution 0.67Kg/hr and p-tert-butylphenol 27g/hr were fed into a stirring tank, and the mixture was heated so that the average residence time was 2 hours. A condensation reaction was carried out. The methylene chloride solution of the polymer obtained by separating the reaction mixture was washed with water, an aqueous hydrochloric acid solution, and then water, and the methylene chloride was evaporated until [η] was 0.75.
An aromatic polyester polycarbonate having a bisphenol A residue: terephthalic acid residue: carbonate bond molar ratio of 1:0.46:0.54 was obtained. <Production example of fully aromatic polyester> A methylene chloride solution of a 1:1 mixture of terephthalic acid dichloride and isophthalic acid dichloride and an alkaline aqueous solution of bisphenol A are polymerized by an interfacial polymerization method to obtain a fully aromatic polyester with [η] of 0.63. A group polyester was obtained. <Production Example of Aromatic Polycarbonate> An aqueous alkaline solution of bisphenol A and phosgene were polymerized by interfacial polymerization in the presence of methylene chloride to obtain an aromatic polycarbonate with [η] 0.61. <Production example of mixture of wholly aromatic polyester and aromatic polycarbonate> A mixture obtained by mixing the above-mentioned resins in the same weight. Examples 1 to 2 and Comparative Example 1 100 parts of the aromatic polyester polycarbonate flakes produced according to the above production example were added to the following table 1.
25% methylene chloride solution of the epoxy compound shown in 2
(0.5 parts as an epoxy compound) was added, mixed well, methylene chloride was evaporated, and the mixture was thoroughly dried in a vacuum dryer. The flakes were molded using an injection molding machine (manufactured by Nissei Plastics Co., Ltd.).
TS-100 type) and a test piece mold specified by ASTM, the resin temperature was 330℃ and the mold temperature was 140℃.
I did the molding. The [η] of the aromatic polyester polycarbonate before and after molding, the color tone of the molded product, and the heat and humidity resistance of the molded product were as shown in Table 1 below. For comparison, the results obtained when no epoxy compound was added are also shown.
【表】【table】
【表】
実施例３、及び比較例２〜８
〔η〕が0.80でビスフエノールＡ残基：テレフ
タル酸残基：カーボネート結合のモル比が１：
0.38：0.62の芳香族ポリエステルポリカーボネー
トのフレーク100部を用い、実施例１におけると
同様にして、ビスフエノールＡグリシジルエーテ
ル0.5部配合したの（実施例３）を乾燥した。こ
のフレークを、射出成形機（日精樹脂(株)製TS―
100型）およびASTMで規定する試験片成形用金
型を用いて、樹脂温度370℃、金型温度140℃で射
出成形を行つた。
また比較のため前記製造例で製造した全芳香族
ポリエステル、芳香族ポリカーボネート及びその
混合物を用いた場合の結果を併せて示す（比較例
２〜８）。なお芳香族ポリカーボネートの場合に
は金型温度を100℃に変更した。[Table] Example 3 and Comparative Examples 2 to 8 [η] is 0.80 and the molar ratio of bisphenol A residue: terephthalic acid residue: carbonate bond is 1:
Using 100 parts of aromatic polyester polycarbonate flakes of 0.38:0.62, 0.5 part of bisphenol A glycidyl ether was blended in the same manner as in Example 1 (Example 3) and dried. The flakes were molded using an injection molding machine (TS-- manufactured by Nissei Plastics Co., Ltd.)
Injection molding was performed at a resin temperature of 370°C and a mold temperature of 140°C using a test piece mold specified by ASTM. For comparison, the results obtained using the fully aromatic polyester, aromatic polycarbonate, and mixture thereof produced in the above production examples are also shown (Comparative Examples 2 to 8). In the case of aromatic polycarbonate, the mold temperature was changed to 100°C.
【表】【table】
Claims (1)
を有していてもよい。） で表わされる構造単位と、一般式 （式中、Ｘおよび芳香核は上記と同一意義を有
する。） で表わされる構造単位とからなり、かつジヒドロ
キシジアリール化合物残基：テレフタル酸残基：
カーボネート結合のモル比が１：0.33〜0.75：
0.67〜0.25である芳香族ポリエステルポリカーボ
ネート100重量部に対し、エポキシ化合物を0.005
〜10重量％配合してなる芳香族ポリエステルポリ
カーボネート樹脂組成物。 ２ 芳香族ポリエステルポリカーボネートの固有
粘度が0.4〜1.5である特許請求の範囲第１項記載
の芳香核ポリエステルポリカーボネート樹脂組成
物。 ３ 芳香族ポリエステルポリカーボネートのガラ
ス転移点が、160〜190℃である特許請求の範囲第
１項記載の芳香族ポリエステルポリカーボネート
樹脂組成物。 ４ 芳香族ポリエステルポリカーボネートの末端
カルボキシル基が10μ当量／ｇ樹脂以下である特
許請求の範囲第１項記載の芳香族ポリエステルポ
リカーボネート樹脂組成物。[Claims] 1. General formula (In the formula, X represents a divalent group, and the aromatic nucleus may have a substituent.) A structural unit represented by the following and the general formula (In the formula, X and the aromatic nucleus have the same meanings as above.) Consisting of a structural unit represented by: dihydroxydiaryl compound residue: terephthalic acid residue:
The molar ratio of carbonate bonds is 1:0.33-0.75:
0.005 parts by weight of an epoxy compound for 100 parts by weight of aromatic polyester polycarbonate with a molecular weight of 0.67 to 0.25
An aromatic polyester polycarbonate resin composition containing ~10% by weight. 2. The aromatic core polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has an intrinsic viscosity of 0.4 to 1.5. 3. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has a glass transition point of 160 to 190°C. 4. The aromatic polyester polycarbonate resin composition according to claim 1, wherein the aromatic polyester polycarbonate has a terminal carboxyl group of 10 μ equivalent/g resin or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12919578A JPS5556151A (en) | 1978-10-20 | 1978-10-20 | Aromatic polyester polycarbonate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12919578A JPS5556151A (en) | 1978-10-20 | 1978-10-20 | Aromatic polyester polycarbonate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5556151A JPS5556151A (en) | 1980-04-24 |
| JPS6242941B2 true JPS6242941B2 (en) | 1987-09-10 |
Family
ID=15003485
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12919578A Granted JPS5556151A (en) | 1978-10-20 | 1978-10-20 | Aromatic polyester polycarbonate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5556151A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5796567A (en) * | 1980-12-09 | 1982-06-15 | Nec Corp | Manufacture of semiconductor device |
| US4348500A (en) * | 1980-12-24 | 1982-09-07 | Union Carbide Corporation | Polyarylate compositions having improved hydrolytic stability |
| JPS60262851A (en) * | 1984-06-08 | 1985-12-26 | Unitika Ltd | Resin composition |
| US4894401A (en) * | 1986-12-22 | 1990-01-16 | General Electric Company | Color stabilized irradiated polycarbonate compositions |
| US20080118729A1 (en) * | 2006-11-16 | 2008-05-22 | General Electric Company | Thermoplastic composition, method of making, and articles formed therefrom |
-
1978
- 1978-10-20 JP JP12919578A patent/JPS5556151A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5556151A (en) | 1980-04-24 |
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