JPH0545625B2 - - Google Patents
Info
- Publication number
- JPH0545625B2 JPH0545625B2 JP61148270A JP14827086A JPH0545625B2 JP H0545625 B2 JPH0545625 B2 JP H0545625B2 JP 61148270 A JP61148270 A JP 61148270A JP 14827086 A JP14827086 A JP 14827086A JP H0545625 B2 JPH0545625 B2 JP H0545625B2
- Authority
- JP
- Japan
- Prior art keywords
- aromatic polyester
- formula
- polyester resin
- mol
- repeating unit
- 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 - Fee Related
Links
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 229920001225 polyester resin Polymers 0.000 claims description 23
- 239000004645 polyester resin Substances 0.000 claims description 23
- 229920000515 polycarbonate Polymers 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 15
- 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 8
- 229920000728 polyester Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 5
- GDBUZIKSJGRBJP-UHFFFAOYSA-N 4-acetoxy benzoic acid Chemical compound CC(=O)OC1=CC=C(C(O)=O)C=C1 GDBUZIKSJGRBJP-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- -1 naphthoxy groups Chemical group 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical group C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910000634 wood's metal Inorganic materials 0.000 description 1
Description
［産業上の利用分野］
本発明は芳香族ポリエステル樹脂組成物に関
し、さらに詳しくは、可撓性および靱性に優れ、
例えば光フアイバーの被覆材として有用な芳香族
ポリエステル樹脂組成物に関する。
［従来の技術および発明が解決しようとする問題
点］
液晶を構成する芳香族ポリエステル樹脂は、線
膨張係数が低く、しかも高い弾性および強度を有
するため光フアイバーの被覆材をはじめとする各
種用途において注目されている。
ところが、この芳香族ポリエステル樹脂は、可
撓性および靱性の点で満足すべきものであるとは
言い難い。
かかる問題を解消するため、従来、芳香族ポリ
エステルおよびこれとは別の共重合成分よりなる
共重合体（特開昭60−186527号および同60−
245630号の各公報参照）、ならびに、芳香族ポリ
エステル樹脂に他成分を配合してなる芳香族ポリ
エステル樹脂組成物（特開昭57−25354号、同57
−40551号および同60−93407号の各公報参照）が
提案されている。
しかしながら、これらの共重合体や樹脂組成物
は可撓性および靱性の点である程度満足すべきも
のである反面、弾性率および強度が著しく低下し
てしまい、また、座屈やけば立ちが発生するとい
う問題がある。
本発明は、従来のかかる問題を解消し、高い弾
性率および強度を維持し、しかも、可撓性、靱性
に優れた芳香族ポリエステル樹脂組成物の提供を
目的とする。
［問題点を解決するための手段］
本発明者は上記目的を達成すべく、鋭意研究を
重ねた結果、特定の繰り返し単位を有し、特定の
対数粘度数を有する芳香族ポリエステルを第１の
必須成分とし、ポリカーボネートを第２の必須成
分として、両成分が所定の割合で配合されてなる
芳香族ポリエステル樹脂組成物が優れた効果を示
すことを見出して本発明を完成するに至つた。
すなわち、本発明の芳香族ポリエステル樹脂組
成物は、
(イ) 次式：
[Industrial Application Field] The present invention relates to an aromatic polyester resin composition, and more specifically, it has excellent flexibility and toughness,
The present invention relates to aromatic polyester resin compositions useful as coating materials for optical fibers, for example. [Prior art and problems to be solved by the invention] Aromatic polyester resins that constitute liquid crystals have a low linear expansion coefficient and high elasticity and strength, so they are used in various applications such as coating materials for optical fibers. Attention has been paid. However, it cannot be said that this aromatic polyester resin is satisfactory in terms of flexibility and toughness. In order to solve this problem, copolymers consisting of aromatic polyester and other copolymer components (JP-A-60-186527 and JP-A-186527) have been developed.
245630), as well as aromatic polyester resin compositions made by blending aromatic polyester resin with other components (Japanese Patent Application Laid-open Nos. 57-25354 and 57)
-40551 and 60-93407) have been proposed. However, while these copolymers and resin compositions are satisfactory to some extent in terms of flexibility and toughness, they have a significant decrease in elastic modulus and strength, and also cause buckling and fuzzing. There's a problem. The present invention aims to solve these conventional problems and provide an aromatic polyester resin composition that maintains high elastic modulus and strength and has excellent flexibility and toughness. [Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted intensive research and found that an aromatic polyester having a specific repeating unit and a specific logarithmic viscosity is used as a first material. The inventors have completed the present invention by discovering that an aromatic polyester resin composition in which polycarbonate is an essential component and polycarbonate is a second essential component, and both components are blended in a predetermined ratio exhibits excellent effects. That is, the aromatic polyester resin composition of the present invention has the following formula:
【式】 (1)
（式中、R1は水素原子、塩素原子または炭素
数１〜４のアルキル基もしくはアルコキシ基を表
わす）
で示される繰返し単位（Ａ）９〜42モル％、
次式：−０（−CH2−CH2）−oＯ− (2)
（式中、ｎは１〜20の整数を表わす）
で示される繰返し単位（Ｂ）９〜42モル％、およ
び
次式：
（式中、R2は上記R1と同じ意味を表わす）
で示される繰返し単位（Ｃ）16〜82モル％を含有
し、かつ、対数粘度数が0.8以上である芳香族ポ
リエステル樹脂98〜94.5重量％、並びに
(ロ) ポリカーボネート２〜5.5重量％からなるこ
とを特徴とする。
本発明の芳香族ポリエステル樹脂組成物は上記
(イ)で示される第１の必須成分と上記(ロ)で示される
第２の必須成分とからなる。
まず、第１の必須成分である芳香族ポリエステ
ル樹脂を構成する繰返し単位（Ａ）〜（Ｃ）につ
いて説明する。
繰返し単位（Ａ）は式（１）で示されるもの
で、R1としては上に列挙したものであればよい
が、なかでも水素原子、塩素原子、フッ素原子、
メチル基、エチル基、メトキシ基、エトキシ基、
フエノキシ基、ナフトキシ基は好適である。繰返
し単位（Ｂ）は式（２）で示されるが、式中ｎは
１〜20の整数であり、好ましくは１〜４の整数で
ある。また、繰返し単位（Ｃ）は式（３）で示さ
れ、R2としては上記したR1と同様、上に列挙し
たものであればよいが、R1と同様、とくに、水
素原子、塩素原子、フッ素原子、メチル基、エチ
ル基、メトキシ基、フエノキシ基、ナフトキシ基
は好ましい。これらの繰返し単位（Ａ）、（Ｂ）お
よび（Ｃ）のもっとも好適な組み合せは、
[Formula] (1) (wherein R 1 represents a hydrogen atom, a chlorine atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms) 9 to 42 mol% of the repeating unit (A) represented by the following formula: -0( -CH2- CH2) -oO- ( 2 ) (in the formula, n represents an integer of 1 to 20) 9 to 42 mol% of the repeating unit (B), and the following formula: (In the formula, R 2 has the same meaning as R 1 above.) Aromatic polyester resin 98 to 94.5 containing 16 to 82 mol% of the repeating unit (C) represented by the formula and having a logarithmic viscosity of 0.8 or more % by weight, and (b) 2 to 5.5% by weight of polycarbonate. The aromatic polyester resin composition of the present invention is as described above.
It consists of the first essential component shown in (a) and the second essential component shown in (b) above. First, the repeating units (A) to (C) constituting the aromatic polyester resin, which is the first essential component, will be explained. The repeating unit (A) is represented by formula (1), and R 1 may be any of those listed above, among which hydrogen atom, chlorine atom, fluorine atom,
Methyl group, ethyl group, methoxy group, ethoxy group,
Phenoxy and naphthoxy groups are preferred. The repeating unit (B) is represented by the formula (2), where n is an integer of 1 to 20, preferably an integer of 1 to 4. Further, the repeating unit (C) is represented by the formula (3), and R 2 may be any of those listed above, like R 1 above, but like R 1 , hydrogen atoms, chlorine atoms, etc. , a fluorine atom, a methyl group, an ethyl group, a methoxy group, a phenoxy group, and a naphthoxy group. The most preferred combination of these repeating units (A), (B) and (C) is
【式】、−０−CH2−CH2−０− および[Formula], -0-CH 2 -CH 2 -0- and
【式】である。
また、各繰返し単位（Ａ）、（Ｂ）および（Ｃ）
の含有量はそれぞれ９〜42モル％、９〜42モル％
および16〜82モル％で、かつ合計で100モル％と
なるように設定する。このうち、とくに重要なも
のは繰返し単位（Ｃ）の含有量であつて、これが
16モル％未満である場合には、該芳香族ポリエス
テルが液晶を形成せず、逆に82モル％を超えると
液晶は形成するものの、成形性が低下するので好
ましくない。さらに、この芳香族ポリエステル
は、このものを例えばフエノールとテトラクロロ
エタンの混合溶液（体積比３：２）100mlに0.5g
溶解せしめて得られる溶液について30℃で測定し
た対数粘度数が0.80以上、好ましくは0.85以上で
あることが必要である。なお、かかる芳香族ポリ
エステルは、通常の方法を適用して調製しても、
また、市販品、例えばイーストマンコダツク社製
のX7Gなどを使用してもよい。
ついで、第２の必須成分であるポリカーボネー
トは、
下記式：
(4)
（ここで、Ｚは単結合または炭素数１〜８のア
ルキレン、炭素数２〜８のアルキリデン、炭素数
５〜15のシクロアルキレン、SO2、SO、Ｏ、CO
または
基を意味し、Ｒは水素、塩素もしくは臭素原子ま
たは１〜８個の炭素原子を有する飽和アルキル基
を意味し、ｍは０〜４の数を示す。）
で表わされる構造単位を有する重合体である。
このポリカーボネート樹脂は溶剤法、すなわち
塩化メチレン等の溶剤中で公知の酸受容体、分子
量調製材の存在下、二価フエノールとホスゲンの
ようなカーボネート前駆体との反応または二価フ
エノールとジフエニルカーボネートのようなカー
ボネート前駆体とのエステル交換反応によつて製
造することができる。
ここで、好適に使用し得る二価フエノールとし
てはビスフエノール類があり、特に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）が好ましい。また、ビスフエノールＡ
の一部または全部を他の二価フエノールで置換し
たものであつてもよい。ビスフエノールＡ以外の
二価フエノールとしては、例えばハイドロキノ
ン、４，4′−ジヒドロキシジフエニル、ビス（４
−ヒドロキシフエニル）アルカン、ビス（４−ヒ
ドロキシフエニル）シクロアルカン、ビス（４−
ヒドロキシフエニル）スルフイド、ビス（４−ヒ
ドロキシフエニル）スルホキシド、ビス（４−ヒ
ドロキシフエニル）エーテルのような化合物また
はビス（３，５−ジブロモ−４−ヒドロキシフエ
ニル）プロパン、ビス（３，５−ジクロロ−４−
ヒドロキシフエニル）プロパンのようなハロゲン
化ビスフエノール類をあげることができる。これ
ら二価フエノールは二価フエノールのホモポリマ
ーまたは２種以上のコポリマー若しくはブレンド
物であつてもよい。更に、本発明で用いるポリカ
ーボネート樹脂は多官能性芳香族化合物を二価フ
エノールおよび／またはカーボネート前駆体と反
応させた熱化塑性ランダム分岐ポリカーボネート
であつてもよい。
本発明に用いるポリカーボネート樹脂は、機械
的強度および成形性の点からして、その粘度平均
分子量は10000〜50000のものが好ましく、特に
18000〜35000のものは好適である。
本発明の芳香族ポリエステル樹脂組成物は、前
述した第１および第２の必須成分を混合して得ら
れるものである。このとき、第１の必須成分であ
る芳香族ポリエステルの配合量を98〜94.5重量
％、第２の必須成分であるポリカーボネートの配
合量を２〜5.5重量％とし、合計で100重量％とす
る必要がある。第１の必須成分が98重量％を超え
る場合、すなわち、第２の必須成分が２重量％未
満であると得られた樹脂組成物に座屈、けば立ち
などが発生し、一方、第１の必須成分が94.5重量
％未満である場合、すなわち、第２の必須成分が
5.5重量％を超えると、樹脂組成物の強度および
弾性率が低下してしまうので好ましくない。
このような本発明の芳香族ポリエステル樹脂組
成物は、各成分を上述の配合量で配合したのち、
混合混練することによつて容易に製造することが
できる。この混練工程には、乾混法、融混併用
法、多段溶融混合法、単純溶融混合法などを適用
することができ、必要に応じて、一軸押出機、二
軸混練機、コニーダー、バンバリミキサー、ヘン
シエルミキサーなどを使用することができる。
［実施例］
調製例１ （ポリエステル樹脂の調製）
ポリエチレンテレフタレート（対数粘度数
0.68）80gおよびｐ−アセトキシ安息香酸（上野
製薬(株)製）を無水酢酸で再結晶して得られた高純
度のｐ−アセトキシ安息香酸112gを攪拌機つき
の短い蒸留塔および窒素入口を備えた内容積500
mlのフラスコに仕込んだ。このフラスコ内を真空
にし、窒素ガスで３回パージしたのち、275℃に
保持されたウツドメタル浴中に入れた。ついで、
275℃においてフラスコの内容物を攪拌すると、
フラスコから酢酸が徐々に留出し、約40分後には
低溶融粘度のポリエステルフラグメントが得られ
た。しかるのち、温度275℃、0.2〜0.3mmHgの真
空下で５時間攪拌することにより、白色透明で高
溶融粘度の芳香族ポリエステル樹脂Ｘを得た。
この芳香族ポリエステル樹脂Ｘの組成は、繰返
し単位（Ａ）［テレフタレート成分］が29モル％、
繰返し単位（Ｂ）［エチレングリコール成分］が
29モル％、繰返し単位（Ｃ）［ｐ−アセトキシ安
息香酸成分］が42モル％であつた。また、対数粘
度数は0.90であつた。
調製例２ （ポリエステル樹脂の調製）
ｐ−アセトキシ安息香酸を再結晶せしめなかつ
たことを除いては、上記調製例１と同様にしてポ
リエステル樹脂Ｙを得た。このポリステル樹脂Ｙ
の繰返し単位の組成は調製例１で得られたものと
同じであり、また、対数粘度数は0.75であつた。
実施例１〜７および比較例１〜８
芳香族ポリエステル樹脂として、上記調製例１
および２で得られたもの（ＸおよびＹ）およびイ
−ストマンコダツク社製X7G（対数粘度数0.62）
Ｚの３種を使用し、これに、ポリカーボネートを
表示の割合で配合し、二軸混練機を使用して270
℃において溶融混練したのちペレツト化した。
なお、ポリカーボネートとしては、下記に示す
ものを使用した。
ポリカーボネート：ポリエステルポリカーボネ
ート［タフロンA2200（出光石油化学(株)製）］
ついで、溶融紡糸機（日本レオロジー(株)製）を
使用して、上記により得られたペレツトから直径
0.4mmおよび１mmの２種類のフアイバーを作製し
た。このときの条件は、成形温度270℃、剪断速
度70sec-1ダイス径2φ、Ｌ／Ｄ＝20にそれぞれ設
定した。
このようにして得られた各樹脂組成物につき、
下記の各評価試験を行なつて、結果を表中に示し
た。
(1) 機械的強度
直径0.4mmのフアイバーを引張り試験機［(株)島
津製作所製、DCS−2000］にかけ、温度23℃、
引張速度５mm／分、チヤツク間距離100mmの条件
で、引張強度および引張弾性率を測定した。
(2) 靱性
同じく直径0.4mmのフアイバーを使用し、JIS
Ｌ 1013に準拠して、靱性の指標となる結節強度
および引掛強度を求めた。
(3) 座屈およびけば立ち
直径１mmのフアイバーを使用し、このフアイバ
ーを直径５mmの鉄心に巻回したのち、もとに戻
し、まつすぐにしたフアイバーの表面を目視する
ことにより圧縮による剪断変形の有無および表面
のけば立ちの有無を評価した。[Formula]. In addition, each repeating unit (A), (B) and (C)
The content of is 9-42 mol% and 9-42 mol%, respectively.
and 16 to 82 mol%, and the total amount is set to 100 mol%. Of these, the most important is the content of repeating units (C), which
If it is less than 16 mol %, the aromatic polyester will not form liquid crystals, and if it exceeds 82 mol %, liquid crystals will be formed, but the moldability will deteriorate, which is not preferable. Furthermore, for example, 0.5 g of this aromatic polyester is added to 100 ml of a mixed solution of phenol and tetrachloroethane (volume ratio 3:2).
It is necessary that the logarithmic viscosity number of the solution obtained by dissolving it measured at 30° C. is 0.80 or more, preferably 0.85 or more. In addition, even if such aromatic polyester is prepared by applying a normal method,
Alternatively, commercially available products such as X7G manufactured by Eastman Kodak Co., Ltd. may also be used. Next, the second essential component, polycarbonate, has the following formula: (4) (Here, Z is a single bond or alkylene having 1 to 8 carbon atoms, alkylidene having 2 to 8 carbon atoms, cycloalkylene having 5 to 15 carbon atoms, SO 2 , SO, O, CO
or R means a hydrogen, chlorine or bromine atom or a saturated alkyl group having 1 to 8 carbon atoms, and m represents a number from 0 to 4. ) It is a polymer having a structural unit represented by: This polycarbonate resin is produced by a solvent process, i.e., by reaction of dihydric phenol with a carbonate precursor such as phosgene or by reaction of dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of known acid acceptors and molecular weight modifiers. It can be produced by a transesterification reaction with a carbonate precursor such as. Here, as dihydric phenols that can be suitably used, there are bisphenols, and 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred. In addition, bisphenol A
may be partially or entirely replaced with other dihydric phenols. Examples of divalent phenols other than bisphenol A include hydroquinone, 4,4'-dihydroxydiphenyl, bis(4
-hydroxyphenyl)alkane, bis(4-hydroxyphenyl)cycloalkane, bis(4-
Compounds such as hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether or bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(3, 5-dichloro-4-
Examples include halogenated bisphenols such as hydroxyphenyl)propane. These dihydric phenols may be homopolymers or copolymers or blends of two or more dihydric phenols. Furthermore, the polycarbonate resin used in the present invention may be a thermoplastic randomly branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and/or a carbonate precursor. From the viewpoint of mechanical strength and moldability, the polycarbonate resin used in the present invention preferably has a viscosity average molecular weight of 10,000 to 50,000, particularly
18,000 to 35,000 is suitable. The aromatic polyester resin composition of the present invention is obtained by mixing the first and second essential components described above. At this time, the amount of aromatic polyester, which is the first essential component, must be 98 to 94.5% by weight, and the amount of polycarbonate, which is the second essential component, must be 2 to 5.5% by weight, for a total of 100% by weight. There is. When the first essential component exceeds 98% by weight, that is, when the second essential component is less than 2% by weight, buckling, fuzzing, etc. occur in the resulting resin composition; If the essential component of is less than 94.5% by weight, i.e. the second essential component is
If it exceeds 5.5% by weight, the strength and elastic modulus of the resin composition will decrease, which is not preferable. Such an aromatic polyester resin composition of the present invention is prepared by blending each component in the above-mentioned amounts, and then
It can be easily produced by mixing and kneading. For this kneading process, dry mixing method, combined melt mixing method, multi-stage melt mixing method, simple melt mixing method, etc. can be applied. , Henschel mixer, etc. can be used. [Example] Preparation Example 1 (Preparation of polyester resin) Polyethylene terephthalate (logarithmic viscosity
0.68) 80g and 112g of high-purity p-acetoxybenzoic acid obtained by recrystallizing p-acetoxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.) with acetic anhydride into a short distillation column with a stirrer and a nitrogen inlet. Product 500
ml flask. The inside of this flask was evacuated and purged with nitrogen gas three times, and then placed in a wood metal bath maintained at 275°C. Then,
When the contents of the flask are stirred at 275°C,
Acetic acid gradually distilled out of the flask, and after about 40 minutes, polyester fragments with low melt viscosity were obtained. Thereafter, the mixture was stirred for 5 hours at a temperature of 275° C. under a vacuum of 0.2 to 0.3 mmHg to obtain a white transparent aromatic polyester resin X having a high melt viscosity. The composition of this aromatic polyester resin X is that the repeating unit (A) [terephthalate component] is 29 mol%,
Repeating unit (B) [ethylene glycol component]
29 mol%, and the repeating unit (C) [p-acetoxybenzoic acid component] was 42 mol%. Further, the logarithmic viscosity number was 0.90. Preparation Example 2 (Preparation of Polyester Resin) Polyester resin Y was obtained in the same manner as in Preparation Example 1 above, except that p-acetoxybenzoic acid was not recrystallized. This polyester resin Y
The composition of the repeating unit was the same as that obtained in Preparation Example 1, and the logarithmic viscosity number was 0.75. Examples 1 to 7 and Comparative Examples 1 to 8 As the aromatic polyester resin, the above Preparation Example 1
and those obtained in 2 (X and Y) and Eastman Kodak X7G (logarithmic viscosity number 0.62)
Using three kinds of
The mixture was melt-kneaded at ℃ and then pelletized. In addition, as the polycarbonate, those shown below were used. Polycarbonate: Polyester polycarbonate [Taflon A2200 (manufactured by Idemitsu Petrochemical Co., Ltd.)] Then, using a melt spinning machine (manufactured by Nippon Rheology Co., Ltd.), the diameter was
Two types of fibers, 0.4 mm and 1 mm, were produced. The conditions at this time were set to a molding temperature of 270°C, a shear rate of 70 sec -1 , a die diameter of 2φ, and L/D = 20. For each resin composition obtained in this way,
The following evaluation tests were conducted and the results are shown in the table. (1) Mechanical strength A fiber with a diameter of 0.4 mm was subjected to a tensile tester [manufactured by Shimadzu Corporation, DCS-2000] at a temperature of 23℃.
The tensile strength and tensile modulus were measured at a tensile speed of 5 mm/min and a chuck distance of 100 mm. (2) Toughness Similarly, using fibers with a diameter of 0.4 mm, JIS
Knot strength and hook strength, which are indicators of toughness, were determined in accordance with L 1013. (3) Buckling and fuzzing Using a fiber with a diameter of 1 mm, wind this fiber around a core with a diameter of 5 mm, return it to its original shape, and visually observe the surface of the straightened fiber to determine the shear due to compression. The presence or absence of deformation and the presence or absence of fuzz on the surface were evaluated.
【表】
［発明の効果］
以上の説明から明らかなように、本発明の芳香
族ポリエステル樹脂組成物は、充分に高い弾性率
および強度を有すると同時に、靱性も極めて高
く、また、座屈、けば立ちなどが防止され可撓性
に優れたものである。したがつて、例えば光フア
イバーの被覆材としてその工業的価値は極めて大
である。[Table] [Effects of the Invention] As is clear from the above description, the aromatic polyester resin composition of the present invention has sufficiently high elastic modulus and strength, and at the same time has extremely high toughness, and is resistant to buckling and It prevents fuzzing and has excellent flexibility. Therefore, its industrial value is extremely great, for example, as a coating material for optical fibers.
Claims (1)
数１〜４のアルキル基もしくはアルコキシ基を表
わす） で示される繰返し単位（Ａ）９〜42モル％、 次式：−０（−CH2−CH2）−oＯ− (2) （式中、ｎは１〜20の整数を表わす） で示される繰返し単位（Ｂ）９〜42モル％、およ
び次式： （式中、R2は上記R1と同じ意味を表わす） で示される繰返し単位（Ｃ）16〜82モル％を含有
し、かつ、対数粘度数が0.8以上である芳香族ポ
リエステル樹脂98〜94.5重量％、並びに (ロ) ポリカーボネート２〜5.5重量％ からなることを特徴とする芳香族ポリエステル樹
脂組成物。[Claims] 1 (a) The following formula: (In the formula, R 1 represents a hydrogen atom, a chlorine atom, or an alkyl group or an alkoxy group having 1 to 4 carbon atoms.) 9 to 42 mol% of the repeating unit (A) represented by the following formula: -0(-CH 2 -CH2 ) -oO- (2) (in the formula, n represents an integer of 1 to 20) 9 to 42 mol% of the repeating unit (B), and the following formula: (In the formula, R 2 has the same meaning as R 1 above.) Aromatic polyester resin 98 to 94.5 containing 16 to 82 mol% of the repeating unit (C) represented by the formula and having a logarithmic viscosity of 0.8 or more % by weight, and (b) 2 to 5.5% by weight of polycarbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61148270A JPS636046A (en) | 1986-06-26 | 1986-06-26 | Aromatic polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61148270A JPS636046A (en) | 1986-06-26 | 1986-06-26 | Aromatic polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS636046A JPS636046A (en) | 1988-01-12 |
| JPH0545625B2 true JPH0545625B2 (en) | 1993-07-09 |
Family
ID=15449010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61148270A Granted JPS636046A (en) | 1986-06-26 | 1986-06-26 | Aromatic polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS636046A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3831873A1 (en) * | 1988-09-20 | 1990-03-29 | Basf Ag | BLENDS OF THERMOTROPEN POLYMERS WITH POLYESTERS AND POLYCARBONATE |
| US5242981A (en) * | 1989-01-26 | 1993-09-07 | Kawasaki Steel Corporation | Resin composition |
| CN103937409B (en) * | 2014-03-20 | 2016-08-10 | 常熟市方塔涂料化工有限公司 | High abrasion leather dope and preparation method thereof |
| JP7237524B2 (en) * | 2018-10-31 | 2023-03-13 | Ｅｎｅｏｓ株式会社 | A resin composition capable of alleviating anisotropy by melting, and a resin molded article made of the resin composition |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5740551A (en) * | 1980-07-03 | 1982-03-06 | Celanese Corp | Composition of polycarbonate and fully aromatic polyester |
| JPS58201850A (en) * | 1982-05-03 | 1983-11-24 | バイエル・アクチエンゲゼルシヤフト | Mixture of mesomorphous polycondensate and partially crystal thermoplast, manufacture and use |
| JPS6046225A (en) * | 1983-08-25 | 1985-03-13 | Sumitomo Chem Co Ltd | Preparation of aromatic polyester film |
| JPS6093406A (en) * | 1983-10-28 | 1985-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS6093407A (en) * | 1983-10-28 | 1985-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS60190449A (en) * | 1981-12-15 | 1985-09-27 | ヘキスト・セラニーズ・コーポレーション | Blend of polyalkylene terephthalate and high molecular weight fully aromatic polyester and manufacture |
| JPS6114616A (en) * | 1984-06-29 | 1986-01-22 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS6259662A (en) * | 1985-09-10 | 1987-03-16 | Idemitsu Petrochem Co Ltd | Aromatic polyester resin composition |
-
1986
- 1986-06-26 JP JP61148270A patent/JPS636046A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5740551A (en) * | 1980-07-03 | 1982-03-06 | Celanese Corp | Composition of polycarbonate and fully aromatic polyester |
| JPS60190449A (en) * | 1981-12-15 | 1985-09-27 | ヘキスト・セラニーズ・コーポレーション | Blend of polyalkylene terephthalate and high molecular weight fully aromatic polyester and manufacture |
| JPS58201850A (en) * | 1982-05-03 | 1983-11-24 | バイエル・アクチエンゲゼルシヤフト | Mixture of mesomorphous polycondensate and partially crystal thermoplast, manufacture and use |
| JPS6046225A (en) * | 1983-08-25 | 1985-03-13 | Sumitomo Chem Co Ltd | Preparation of aromatic polyester film |
| JPS6093406A (en) * | 1983-10-28 | 1985-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS6093407A (en) * | 1983-10-28 | 1985-05-25 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS6114616A (en) * | 1984-06-29 | 1986-01-22 | Nippon Telegr & Teleph Corp <Ntt> | Optical fiber core |
| JPS6259662A (en) * | 1985-09-10 | 1987-03-16 | Idemitsu Petrochem Co Ltd | Aromatic polyester resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS636046A (en) | 1988-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4299928A (en) | Impact modified polycarbonates | |
| US4981898A (en) | Polycarbonate-polyester blends | |
| US4284549A (en) | Polymer blends with improved hydrolytic stability | |
| CA1225183A (en) | Composition | |
| US4352907A (en) | Polyethyleneterephthalate ternary blends | |
| CA1182234A (en) | Glass-filled polycarbonate of improved impact strength | |
| JPH0526826B2 (en) | ||
| CA2074961A1 (en) | Solvent-resistant polycarbonate-polyester blends with improved impact properties | |
| US4758626A (en) | Melt of an amorphous aromatic polyester with a melt of a carboxy terminated polyacrylate oligomer | |
| US5624984A (en) | Liquid crystal polyester resin compositions and process for producing the same | |
| US5084527A (en) | Thermoplastic resin composition | |
| US4400491A (en) | Copolyester carbonates and the admixture thereof with known polycarbonates to give thermoplastic moulding compositions | |
| US4980418A (en) | Thermoplastic resins having excellent thermal resistance and moldability and processes for preparing same | |
| JPH0545625B2 (en) | ||
| JPH0715054B2 (en) | Composition | |
| JPH01163258A (en) | Composition | |
| US5191036A (en) | Thermoplastic resin composition | |
| JPH01163242A (en) | Composition | |
| US5286813A (en) | Melt kneading polycarbonate with compound containing carbon to carbon double bond | |
| JPS58167643A (en) | Reinforced polyalkylene terephthalate, manufacture and use | |
| US4448950A (en) | Polycarbonate having improved critical thickness | |
| JPH02145643A (en) | Liquid crystal polymer composition | |
| JPH04103656A (en) | Liquid crystal polyester resin composition | |
| JPH0346023B2 (en) | ||
| JPH0288667A (en) | Liquid crystal polyester resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |