JPS6343428B2 - - Google Patents
Info
- Publication number
- JPS6343428B2 JPS6343428B2 JP54039982A JP3998279A JPS6343428B2 JP S6343428 B2 JPS6343428 B2 JP S6343428B2 JP 54039982 A JP54039982 A JP 54039982A JP 3998279 A JP3998279 A JP 3998279A JP S6343428 B2 JPS6343428 B2 JP S6343428B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- resin composition
- polyester polycarbonate
- formula
- polycarbonate
- 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 18
- 229920000728 polyester Polymers 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 13
- 239000004417 polycarbonate Substances 0.000 claims description 13
- 229920005668 polycarbonate resin Polymers 0.000 claims description 6
- 239000004431 polycarbonate resin Substances 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 5
- 230000009477 glass transition Effects 0.000 claims description 3
- 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 3
- 238000012696 Interfacial polycondensation Methods 0.000 claims description 2
- 150000001875 compounds Chemical group 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 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 7
- 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
- 239000000243 solution Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 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
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Description
本発明は機械的および化学的性質のすぐれた樹
脂組成物に関するものである。詳しくは、成形
性、耐衝撃性が改善され耐熱性の優れた芳香族ポ
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、成形性が悪い欠点がある。例えば、射出
成形によつて成形品を製造する場合、高い成形温
度、金型温度および射出圧力を必要とするが、高
い温度を採用することはポリマーの熱劣化の原因
となり、高い射出圧力を採用することは製品の歪
の原因となる等の不都合があり、しかもコスト高
となるので、その成形性の改善が望まれていた。
本発明者らは、上記した芳香族ポリエステルボ
リカーボネートの欠点を改良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ポリ
カーボネート樹脂を配合するときは、その成形性
を大巾に改善することが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、成形性および耐衝撃性の改
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および芳香核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１：0.33〜0.49：
0.67〜0.51であり、ガラス転移点が170〜185℃で
あり、界面重縮合により得られた芳香族ポリエス
テルポリカーボネート100重量部に対し、ポリカ
ーボネート樹脂１〜60重量部を配合してなる熱変
形温度が162℃（以上で成形性および耐衝撃性の
優れた樹脂組成物である。
以下、本発明を詳明に説明する。
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 a resin composition with excellent mechanical and chemical properties. Specifically, the present invention relates to an aromatic polyester polycarbonate resin composition that has improved moldability, impact resistance, and excellent 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) is produced by reacting terephthaloyl chloride and phosgene and is known to have excellent mechanical properties, weather resistance, chemical resistance and transparency. It is being (Unexamined Japanese Patent Publication No. 52-
128992) However, such aromatic polyester polycarbonates have a high softening temperature and high melt viscosity, so they have the disadvantage of poor moldability. For example, when manufacturing molded products by injection molding, high molding temperature, mold temperature, and injection pressure are required, but high temperatures cause thermal deterioration of the polymer, so high injection pressure is necessary. Since doing so has disadvantages such as causing distortion of the product and also increases costs, it has been desired to improve the moldability. As a result of intensive research to improve the above-mentioned drawbacks of aromatic polyester polycarbonate, the present inventors have found that when a polycarbonate resin is blended with aromatic polyester polycarbonate, its moldability can be greatly improved. After learning this, the present invention was completed. That is, an object of the present invention is to provide an aromatic polyester polycarbonate having improved moldability and impact 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 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 1:0.33-0.49:
0.67 to 0.51, the glass transition point is 170 to 185°C, and the heat distortion temperature is obtained by blending 1 to 60 parts by weight of polycarbonate resin to 100 parts by weight of aromatic polyester polycarbonate obtained by interfacial polycondensation. 162°C (or higher, it is a resin composition with excellent moldability and impact resistance. The present invention will be explained in detail below. The aromatic polyester polycarbonate used in the present invention is, for example, (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、及び
ガラス転移点が180℃の芳香族ポリエステルポリ
カーボネートを得た。
実施例１〜２および比較例１〜２
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粉末100部に対し、下記表１
に示す量の平均分子量2.3万のポリカーボネート
樹脂（三菱化成(株)製、ノバレツクス7025A）を混
合し、押出機を用いて300℃で溶融混合し、押出
してペレツト化した。
これらのペレツトを、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射出成形した。その際の成
形温度、金型温度および射出圧力は下記表１に示
す値が必要であつた。
かくして得られた試験片の機械的性質および熱
変形温度は下記表１に示す通りであつた。
なお、比較のためポリカーボネート樹脂を使用
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 performed. 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 and a glass transition point of 180°C was obtained. Examples 1 to 2 and Comparative Examples 1 to 2 The following Table 1 was applied to 100 parts of the aromatic polyester polycarbonate powder produced in the above production example.
Polycarbonate resin (manufactured by Mitsubishi Kasei Corporation, Novarex 7025A) having an average molecular weight of 23,000 in the amount shown was mixed, melt-mixed at 300°C using an extruder, and extruded into pellets. These pellets are processed into an injection molding machine (Nissei Plastics Co., Ltd.).
The specimens were injection molded using a mold for molding specimens specified by ASTM. The molding temperature, mold temperature and injection pressure at that time required the values shown in Table 1 below. The mechanical properties and heat distortion temperature of the test piece thus obtained were as shown in Table 1 below. For comparison, the results obtained when no polycarbonate resin was used are also shown.
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１：0.33〜0.49：
0.67〜0.51であり、ガラス転移点が170〜185℃で
あり、界面重縮合により得られた芳香族ポリエス
テルポリカーボネート100重量部に対し、ポリカ
ーボネート樹脂１〜60重量部を配合してなる熱変
形温度が162℃以上で成形性および耐衝撃性の優
れた樹脂組成物。 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
の樹脂組成物。 ３ 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 1:0.33-0.49:
0.67 to 0.51, the glass transition point is 170 to 185°C, and the heat distortion temperature is obtained by blending 1 to 60 parts by weight of polycarbonate resin to 100 parts by weight of aromatic polyester polycarbonate obtained by interfacial polycondensation. A resin composition with excellent moldability and impact resistance at temperatures above 162°C. 2. The resin composition according to claim 1, wherein the aromatic polyester polycarbonate has an intrinsic viscosity of 0.4 to 1.5. 3. The 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 |
|---|---|---|---|
| JP3998279A JPS55133445A (en) | 1979-04-03 | 1979-04-03 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3998279A JPS55133445A (en) | 1979-04-03 | 1979-04-03 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55133445A JPS55133445A (en) | 1980-10-17 |
| JPS6343428B2 true JPS6343428B2 (en) | 1988-08-30 |
Family
ID=12568146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3998279A Granted JPS55133445A (en) | 1979-04-03 | 1979-04-03 | Resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55133445A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0090014B1 (en) * | 1981-09-30 | 1986-10-01 | The Dow Chemical Company | Blends of a polyesterpolycarbonate copolymer or terpolymer and a polycarbonate resin |
| US4469850A (en) * | 1982-11-05 | 1984-09-04 | General Electric Company | Compositions |
| US4504634A (en) * | 1982-12-27 | 1985-03-12 | General Electric Company | Copolyester-carbonate blends exhibiting improved processability |
| US4704432A (en) * | 1983-05-09 | 1987-11-03 | The Dow Chemical Company | Blends of polyestercarbonate with 4-methyl-1-pentene polymers |
| US4548991A (en) * | 1983-05-09 | 1985-10-22 | The Dow Chemical Company | Blends of polycarbonate or polyestercarbonate with 4-methyl-1-pentene polymers |
| EP0152825B1 (en) * | 1984-02-10 | 1989-05-17 | General Electric Company | Use of a polymer blend for producing medical devices with improved resistance to yellowing under ionizing radiation |
| US4833217A (en) * | 1984-12-14 | 1989-05-23 | Kuraray Co., Ltd. | Polycarbonate resin composition |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558248A (en) * | 1978-10-24 | 1980-04-30 | Toray Ind Inc | Aromatic copolyester composition |
| JPS55131048A (en) * | 1979-04-02 | 1980-10-11 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
-
1979
- 1979-04-03 JP JP3998279A patent/JPS55133445A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5558248A (en) * | 1978-10-24 | 1980-04-30 | Toray Ind Inc | Aromatic copolyester composition |
| JPS55131048A (en) * | 1979-04-02 | 1980-10-11 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55133445A (en) | 1980-10-17 |
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