JPS63168430A - Wholly aromatic polyester - Google Patents
Wholly aromatic polyesterInfo
- Publication number
- JPS63168430A JPS63168430A JP62000650A JP65087A JPS63168430A JP S63168430 A JPS63168430 A JP S63168430A JP 62000650 A JP62000650 A JP 62000650A JP 65087 A JP65087 A JP 65087A JP S63168430 A JPS63168430 A JP S63168430A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- units
- mol
- iii
- temperature
- 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.)
- Granted
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 67
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 claims abstract description 5
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- 238000000465 moulding Methods 0.000 abstract description 5
- VRHXYAWPPOZFLR-UHFFFAOYSA-N 2,7,8-trioxatricyclo[7.2.2.23,6]pentadeca-1(11),3(15),4,6(14),9,12-hexaene Chemical group C1=CC(O2)=CC=C1OOC1=CC=C2C=C1 VRHXYAWPPOZFLR-UHFFFAOYSA-N 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 28
- 239000007924 injection Substances 0.000 description 25
- 238000002347 injection Methods 0.000 description 25
- 238000006116 polymerization reaction Methods 0.000 description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 230000007704 transition Effects 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001125 extrusion Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 8
- -1 isophthalic acid Chemical class 0.000 description 7
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 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
- 238000001746 injection moulding Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- NFTLBCXRDNIJMI-UHFFFAOYSA-N 6-acetyloxynaphthalene-2-carboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(OC(=O)C)=CC=C21 NFTLBCXRDNIJMI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000013307 optical fiber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- AKOGNYJNGMLDOA-UHFFFAOYSA-N (4-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C=C1 AKOGNYJNGMLDOA-UHFFFAOYSA-N 0.000 description 1
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 description 1
- SJJCQDRGABAVBB-UHFFFAOYSA-N 1-hydroxy-2-naphthoic acid Chemical compound C1=CC=CC2=C(O)C(C(=O)O)=CC=C21 SJJCQDRGABAVBB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- CEYHCFWLAASWDU-UHFFFAOYSA-N [4-(4-acetyloxyphenoxy)phenyl] acetate Chemical compound C1=CC(OC(=O)C)=CC=C1OC1=CC=C(OC(C)=O)C=C1 CEYHCFWLAASWDU-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000009864 tensile test Methods 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
- 239000004408 titanium dioxide Substances 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は６−ヒドロキシ−２−ナフトエ酸、４−ヒドロ
キシ安息香酸、テレフタルばおよび４，４′−ジヒドロ
キシジフェニルエーテル訪導体より４かれ３５０℃以下
の温度で光学的に異方性の溶融相を形成する全芳香族ポ
リエステルに関し、本ポリエステルよシカ学的性能、特
に耐靭性、耐衝撃性のすぐれた各種成形物、特にフィル
ムおよび射出成形物が得られる。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention uses 6-hydroxy-2-naphthoic acid, 4-hydroxybenzoic acid, terephthalate, and 4,4'-dihydroxydiphenyl ether as a conductor. Regarding fully aromatic polyesters that form an optically anisotropic melt phase at a temperature of can get.
近年、有機高分子材料の高性能化に対する産業界の要求
を満足させる素材として、光学的に異方性の溶融相を形
成するポリエステル類、謂ゆるサーモトロピック液晶ポ
リエステルが注目され該ボリエステルに関する研究開発
が活発にくシ広げられている。かかるポリマーはその分
子鎖がぜん断応力下において容易に一方向に配向する性
質を有していることから、該ポリマーよシ強度、弾性率
で代表される力学的性能のすぐれた繊維、フィルム、射
出成形品など各種成形品が得られることが知られている
。更に該ポリマーの内、芳香環のみから溝成される全芳
香族サーモトロピック液晶ポリエステルは極めて良好な
耐熱性を示すことが知られている。In recent years, polyesters that form an optically anisotropic melt phase, so-called thermotropic liquid crystal polyesters, have attracted attention as materials that satisfy industrial demands for higher performance organic polymer materials, and research and development regarding these polyesters has been conducted. is being actively spread. Since the molecular chains of such polymers have the property of easily orienting in one direction under shear stress, these polymers can be used as fibers, films, and injection moldable materials with excellent mechanical performance represented by strength and elastic modulus. It is known that various molded products such as molded products can be obtained. Furthermore, among these polymers, fully aromatic thermotropic liquid crystal polyesters, which are composed of only aromatic rings, are known to exhibit extremely good heat resistance.
このように、サーモトロピック液晶ポリエステルは高性
能素材としてすぐれたものであるが未だいくつかの解決
すべき問題点も残されている。As described above, thermotropic liquid crystal polyester is excellent as a high-performance material, but there are still some problems that need to be solved.
該ポリエステルより得られた各種成形品は剛直な分子鎖
が一方向に高度に配向しているため該方向（流動方向）
の力学的性能は犬であるが、流動方向に直交方向の力学
的性能が小であシ、力学的性能の異方性が大である。更
に該成形物の破断伸度は通常著しく小であり５チ以下と
なる。また剛直な分子が高度に一方向に配向しているた
め成形品は耐靭性に劣シ、耐衝撃性は必ずしも充分では
ない。Various molded products obtained from this polyester have rigid molecular chains highly oriented in one direction (flow direction).
Although the mechanical performance is excellent, the mechanical performance in the direction perpendicular to the flow direction is small and the anisotropy of the mechanical performance is large. Furthermore, the elongation at break of the molded product is usually extremely low, less than 5 inches. Furthermore, since the rigid molecules are highly oriented in one direction, the molded product has poor toughness and impact resistance is not necessarily sufficient.
このようなことから、サーモトロピック液晶ポリエステ
ルは、主として一方向の強度が要求される高性能繊維と
しては非常に適した素材ではあるが、フィルム、あるい
は射出成形品としては必ずしもすべての点で満足できる
ものではない。即ち該ポリエステルよシ通常の溶融押し
出しによりフィルムを得た場合には押し出し方向に直交
する方向の強度が著しく小なため、フィルムは流れ方向
にそって裂けやすい性質を有す。また、射出成形品の耐
衝撃性が必ずしも満足すべき程高くはなく、また、該成
形品の表面は非常にフィブリル化しやすいという欠点を
有する。更に、力学的異方性を低減化するため、ガラス
繊維を共存させて射出成形を行なうと該成形品の耐衝外
性は著しく低下する。For these reasons, thermotropic liquid crystal polyester is an extremely suitable material for high-performance fibers that primarily require strength in one direction, but it is not necessarily satisfactory in all respects as a film or injection molded product. It's not a thing. That is, when a film is obtained from the polyester by ordinary melt extrusion, the strength in the direction perpendicular to the extrusion direction is extremely low, so that the film tends to tear along the flow direction. In addition, the impact resistance of the injection molded product is not necessarily high enough to be satisfactory, and the surface of the molded product is highly susceptible to fibrillation. Furthermore, if injection molding is performed in the presence of glass fibers in order to reduce mechanical anisotropy, the impact resistance of the molded product will be significantly reduced.
このようなことから、本発明者らは、特に溶融押し出し
によりフィルム化が容易であり、また、高い耐ｗＪ撃性
を有する射出成形品を与えるサーモトロピック液晶ポリ
エステルを得るべく鋭意検討した結果本発明を完成する
に至った。本発明に従えば、本質的に下記のくり返し単
位１、Ｉｔ、ＩＩＩおよび■よりなり、かつそれぞれが
下記の組成からなり
■ −０−Ｑ−ＣＯ−２５〜８０モルチ■−０Ｃ−Ｑ−
ＣＯ−５〜３０モルチ
１ｖ −０−Ｑ−０−Ｑ−０−５〜３０モルチ但し、単
位■と■のモル数は実質的に等しい量で存在シ、ペンタ
フルオロフェノール中、０．１重ｆｌ／容量チの１度、
６０℃で測定した時に０．５４ｔ／ｆ以上の対数粘度を
有し、３５０℃以下の温度で光学的に異方性の溶融相を
形成する全芳香族ポリエステルが提供される。For this reason, the present inventors have conducted intensive studies to obtain a thermotropic liquid crystal polyester that can be easily formed into a film by melt extrusion and that can provide an injection molded product having high wJ impact resistance.As a result, the present invention has been developed. I was able to complete it. According to the present invention, it consists essentially of the following repeating units 1, It, III and ■, each of which has the following composition: ■ -0-Q-CO-25 to 80 moles ■-0C-Q-
CO-5 to 30 mole 1v -0-Q-0-Q-0-5 to 30 mole fl/capacity 1 degree,
A wholly aromatic polyester is provided that has a logarithmic viscosity of 0.54 t/f or more when measured at 60°C and forms an optically anisotropic melt phase at a temperature of 350°C or less.
単位ｌは６−オキシ−２−す７トイル部分であり、６−
ヒドａキシ−２−ナフトエ酸およびその誘導体から導か
れる。単位Ｉはポリエステル中、３〜３０モル係の範囲
内の量で存在する。The unit l is the 6-oxy-2-su7toyl moiety, 6-
Derived from hydroxy-2-naphthoic acid and its derivatives. Unit I is present in the polyester in an amount ranging from 3 to 30 molar parts.
単位■は４−オキシベンゾイル部分であシ４−ヒドロキ
シ安息香酸およびその誘導体から導かれる。単位■はポ
リエステル中、２５〜８０モルチ、好ましくは３０〜７
０モルチの範囲内の量で存在する。The unit (2) is a 4-oxybenzoyl moiety derived from 4-hydroxybenzoic acid and its derivatives. The unit (■) is 25 to 80 mol, preferably 30 to 7 in polyester.
Present in an amount within the range of 0 molar.
単位■はテレフタロイル部分であり、テレフタル酸およ
びその誘導体から導かれる。単位■はポリエステル中５
〜３０モルチ、好ま１〜くは１０〜２５モルチの範囲内
の量で存在する。The unit ■ is a terephthaloyl moiety and is derived from terephthalic acid and its derivatives. Unit ■ is 5 in polyester
It is present in an amount ranging from 1 to 30 moles, preferably from 1 to 25 moles.
単位ＩＶＵ４．４’−ジオキシジフェニルエーテル部分
−ＩＤ％ ４．４’−ジヒドロキシジフェニルエーテル
およびその誘導体よシ導かれる。単位■はポリエステル
中５〜３０モルチ、好ましくは１０〜２５モル−〇範囲
内の量で存在する。なお、単位■と単位■はポリエステ
ル中、実質的に等しいモル数で存在することが必要であ
る。Unit IVU4.4'-Dioxydiphenyl ether moiety-ID% 4.4'-Dihydroxydiphenyl ether and derivatives thereof are derived. The units {circle around (2)} are present in the polyester in an amount ranging from 5 to 30 moles, preferably from 10 to 25 moles. Incidentally, it is necessary that the unit (2) and the unit (2) exist in substantially the same number of moles in the polyester.
上述した単位■から単位■の各芳香環において、芳香環
に結合している水素原子の少なくとも一部は、炭素数１
〜４のアルキル基、炭素数１〜４のアルコキシル基、ハ
ロゲン、あるいはフェニル基で置換されていてもよい。In each of the aromatic rings from unit ■ to unit ■ mentioned above, at least some of the hydrogen atoms bonded to the aromatic ring have a carbon number of 1
It may be substituted with a ~4 alkyl group, a C1-4 alkoxyl group, a halogen, or a phenyl group.
しかしながら通常の場合には、環の置換基は存在しない
方が生成したポリエステルの結晶性が大であシ、また該
ポリエステルから得られる各種成形品の物性がすぐれて
いるので望ましい。However, in normal cases, the absence of ring substituents is desirable because the crystallinity of the polyester produced is greater and the physical properties of various molded products obtained from the polyester are excellent.
本発明のポリエステルは、単位Ｉから単位■が前記に規
定した範囲内の量で存在し、かつペンタフルオロフェノ
ール中、０．１ｉ量／容量チの濃度、６０℃で測定した
時に０．５ ｄｔ／ｆ以上の対数粘度を有し、かつ３５
０℃以下の温度で光学的に異方性の溶融相を形成するこ
とが必要である。対数粘度が０．５ｄｌｌｆよシ小さい
場合には該ポリエステルよシ得られた各種成形品の力学
的物性が低く好ましくない。好ましくは対数粘度は１．
０ ｄｉ／ １以上がよい。対数粘度の上限としては通
常１０ｄｌｌ？以下、好ましくは７．５ｄｌｌ？以下で
あることが重合のしやすさ、ポリエステルの成形加工の
容易さ、および得られた各種成形品の物性などの面で望
ましい。The polyester of the present invention is such that the units I to ■ are present in an amount within the range specified above and have a concentration of 0.5 dt in pentafluorophenol when measured at 60° C. at a concentration of 0.1 i amount/volume /f or more, and has a logarithmic viscosity of 35
It is necessary to form an optically anisotropic melt phase at temperatures below 0°C. When the logarithmic viscosity is less than 0.5 dllf, the mechanical properties of various molded products obtained from the polyester are undesirably low. Preferably the logarithmic viscosity is 1.
0 di/1 or more is preferable. The upper limit of logarithmic viscosity is usually 10 dll? Below, preferably 7.5dll? The following values are desirable in terms of ease of polymerization, ease of molding of polyester, and physical properties of various molded products obtained.
光学的に異方性の溶融相の形成の確認は、当業者によく
知られているように、加熱装置を備えた偏光顕微鏡を用
い、直光ニコル下で試料の薄片、好ましくは５〜２０μ
ｍ程度の薄片を一定の昇温速度下で観察し、一定温度以
上で光を透過することを見ることによシ行ないえる。な
お、本観察においては高温度下で、カバーグラス間には
さんだ試料に軽く圧力を加えるか、あるいはカバーグラ
スをずシ動かすことによってよシ確実に偏光の透過を観
察しえる。本観察において、偏光を透過し始める温度が
光学的に異方性の溶融相への転移温度である。また、こ
の転移温度は示差走査熱量計（ＤＳＣ）を用いて一定の
昇温速度、通常の場合１０〜ｂ
測した時の吸熱ピークの位置によっても決定でき−りは
通常の結晶性ポリマーの等方相への結晶融解ピークに比
較して非常に小さいので測定には充分注意を払う必要が
ある。一つ以上の吸熱ピークが表われることもあるが最
も大なピークを与える温度を転移温度とみなしてよい。Confirmation of the formation of an optically anisotropic molten phase can be carried out using a polarized light microscope equipped with a heating device, as is well known to those skilled in the art, under direct Nicol light, by examining thin sections of the sample, preferably 5-20μ
This can be done by observing a thin piece of about m in diameter under a constant heating rate and observing that light passes through it at a certain temperature or higher. In this observation, transmission of polarized light can be observed more reliably by applying slight pressure to the sample sandwiched between cover glasses or by moving the cover glasses at high temperatures. In this observation, the temperature at which polarized light begins to pass through is the transition temperature to an optically anisotropic molten phase. In addition, this transition temperature can also be determined by the position of the endothermic peak when measured using a differential scanning calorimeter (DSC) at a constant temperature increase rate, typically 10 - b. Since it is very small compared to the crystal melting peak in the square phase, it is necessary to pay close attention to the measurement. Although one or more endothermic peaks may appear, the temperature giving the largest peak may be regarded as the transition temperature.
偏光顕微鏡による観察によシ求められた転移温度と、Ｄ
ＳＣ測定による転移温度が同一でない場合もあるが、か
かる場合は、いずれか高い方の温度を本発明の異方性の
溶融相への転移温度とみなすこととする。この転移温度
が３５０℃よシ高い場合には、ポリマーの重合が容易で
はなく、得られたポリマーの溶融成形加工性が悪く、か
つ得られ九各種成形品の力学的瞼性が劣る。The transition temperature determined by observation with a polarizing microscope and D
In some cases, the transition temperatures determined by SC measurement are not the same, but in such a case, the higher temperature is regarded as the transition temperature to the anisotropic melt phase of the present invention. If this transition temperature is higher than 350° C., polymerization of the polymer is not easy, the resulting polymer has poor melt molding processability, and the mechanical properties of the various molded products obtained are poor.
本発明においては単位ｉから単位■が前記に規定した範
囲内でポリエステル中存在することが必須であシ、その
ことによってはじめて３５０℃以下で光学的に異方性の
溶融相を形成するサーモトロピック液晶ポリエステルが
得られる。特に単位■の４，４′−ジオキシジフェニル
エーテル部分カ、５〜３０モル嘔存在することによって
該ポリエステルより破断伸度が大で、耐靭性、耐衝撃性
が著しく大で、力学的異方性の小で表面フィブリル化の
ない各種成形品が得られる。単位■が３０モル−を越え
て存在する場合には、３５０℃以下の温度で光学的に異
方性の溶融相を形成するポリエステルは得られない。ま
た、単位■が５モルチより少ない場合には３５０℃以下
で光学的に異方性の溶融相を形成するポリエステルは得
られるが、該ポリエステルから得られた各種成形物、例
えば、射出成形品は衝撃強度が小となり、力学的異方性
が大で、表面フィブリル化が著しい。また、単位Ｉが存
在することによってポリエステルの光学的に異方性の溶
融相への転移温度が低下し、かつ、ポリエステルの溶融
粘度も低下し、溶融成形加工性の面で好ましく、かつ、
得られた各種成形品の耐靭性、例えば射出成形品の耐衝
撃性が大となる。In the present invention, it is essential that the unit i to the unit ■ be present in the polyester within the range specified above. A liquid crystal polyester is obtained. In particular, the presence of 5 to 30 moles of the 4,4'-dioxydiphenyl ether moiety of the unit (3) results in higher elongation at break, significantly higher toughness and impact resistance, and greater mechanical anisotropy than the polyester. Various molded products with small surface fibrillation can be obtained. If the unit (2) is present in an amount exceeding 30 moles, a polyester that forms an optically anisotropic melt phase at temperatures below 350°C cannot be obtained. In addition, when the unit (■) is less than 5 molty, a polyester that forms an optically anisotropic melt phase at 350°C or less can be obtained, but various molded products obtained from the polyester, such as injection molded products, cannot be obtained. Impact strength is low, mechanical anisotropy is large, and surface fibrillation is significant. Further, the presence of unit I lowers the transition temperature of the polyester to an optically anisotropic melt phase, and also lowers the melt viscosity of the polyester, which is preferable in terms of melt moldability, and
The toughness of the various molded products obtained, for example, the impact resistance of injection molded products, is increased.
例えば、後の比較例から明らかなように単位■および単
位■が各々１５モルチで、単位■が７０モルチよシなる
ポリエステルより得られた射出成形品のノツチ付アイゾ
ツト衝撃強度は極めて小であるが、単位■および単位■
が各々１５モルチであり、かつ単位Ｉが５モルチ共存し
たポリエステルからは極めて衝撃強度の大な射出成形品
が得られる。単位Ｉが３０モルチを越えて存在しても、
その成形品の物性は顕著には低下しないが単位Ｉを与え
る原料化合物である６−ヒドロキシ−２−ナフトエ醜は
通常、単位■の原ｆ十化合物である４−ヒドロキシ安息
香酸に較べて高価であることから好ましくない。For example, as is clear from the later comparative example, the notched Izot impact strength of an injection molded product obtained from a polyester in which the units (■) and (2) are each 15 molar and the unit (2) is 70 molar is extremely low. , unit■ and unit■
An injection molded article having an extremely high impact strength can be obtained from a polyester having 15 molt each and 5 molt of unit I coexisting therein. Even if unit I is present in excess of 30 moles,
Although the physical properties of the molded product do not deteriorate significantly, 6-hydroxy-2-naphthoate, which is the raw material compound that provides unit I, is usually more expensive than 4-hydroxybenzoic acid, which is the base compound of unit II. I don't like it for certain reasons.
特開昭５９−６２６３０号公報には、−ｏｏ、００”−
。In Japanese Patent Application Laid-open No. 59-62630, -oo, 00''-
.
Ｉｔ 、Ｉｔ
−ｏ＠−ｃｏ−，−０−Ａｒ−０−オよび−Ｃ−Ａｒ−
Ｃ−なる構成成分よりなり、約４００℃以下の温度で異
方性の溶融相を形成するポリエステルが開示されており
、芳香族ジオキシ成分のＡｒの具体例としてなどと同時
に本発明の構成成分である
一ｏ ＝ｏ−ｏ −ｏ−ｏ−も例示されている。しかし
ながら、該公報の実施例中に例示されているＡｒとして
は０および−Ｑ−Ｑ−のみであり、該ポリエステルから
得られ念繊維の破断伸度は紡糸したままでは高々１．８
％であり、また射出成形品のノツチ付アイゾツト衝撃強
度も１８に１・創／ｃｎ１から２９に１・口／ｃＷ１と
、後で述べる本発明のポリエステルから得られる射出成
形品のそれに較べて小さい。更に、後の比較例からも明
らかなように、ジカルボン酸成分として、イソフタル酸
のような非直線配向性の化合物を使用せず、テレフタル
酸のみを使用した場合には −ｏ−ｏ−ｏ−ｏ−ｏ−に
代えて。It , It -o@-co-, -0-Ar-0-o and -C-Ar-
A polyester consisting of a constituent component C-, which forms an anisotropic melt phase at a temperature of about 400° C. or less, is disclosed, and as a specific example of the aromatic dioxy component Ar, it can also be used as a constituent component of the present invention. A certain o=o-o -o-o- is also exemplified. However, the Ar exemplified in the examples of the publication is only 0 and -Q-Q-, and the elongation at break of the fiber obtained from the polyester is at most 1.8 as it is spun.
%, and the notched isot impact strength of the injection molded product is 1 in 18/cn1 to 1 in 29 wound/cW1, which is smaller than that of the injection molded product obtained from the polyester of the present invention, which will be described later. . Furthermore, as is clear from the later comparative examples, when only terephthalic acid is used as the dicarboxylic acid component without using a non-linearly oriented compound such as isophthalic acid, -o-o-o- Instead of o-o-.
−０−０−０−を用いた場合には、３５０℃以下の温度
で異方性の溶融相を形成するポリエステルは得ることは
できない。このように、該公報にはいくつかの具体例の
一つとして、本出願特許と同一の組成のポリマーも例示
されているように見えるが、本出願特許の組み合わせに
よるポリエステルのみが３５０℃以下の温度で異方性の
溶融相を形成し、該ポリエステルから得られた成形物は
破断伸度が犬で耐靭性、耐衝撃性がすぐれることは記載
されていないばかりでなく、何ら示唆もされていない。When -0-0-0- is used, a polyester that forms an anisotropic melt phase at a temperature of 350°C or lower cannot be obtained. As described above, the publication appears to include a polymer having the same composition as the patent of this application as one of several specific examples, but only the polyester according to the combination of the patent of this application has a temperature of 350°C or less. It is not stated that the polyester forms an anisotropic melt phase at different temperatures, and that molded products obtained from the polyester have excellent toughness and impact resistance with a break elongation of 100%. Not yet.
Ｔｈｅ Ｂｒ１ｔｉｓｈ Ｐｏｌｙｍｅｒ Ｊｏｕｒｎ
ａ１誌１９８０年１２月号１５４頁から始まるＪａｃｋ
ｓｏｎ Ｊｒ、の論文には−ｏ −ｏ−ｏ −ｏ−ｏ−
などの化合物は、ポリエステルの融点を低下嘔ぜるのに
有効であることが記載さＨａ
重合したポリエステルより得られた射出成形物の力学的
性能は一〇（シζン０−を用いた場合に較べて低下して
おりノツチ付アイゾツト衝撃強度もわずか０．６ ｆｔ
−１ｄ／ｉｎ （３，３Ｋｇ・ｃｒ＋ｔ／ｃｍ）にす
ぎない。The Br1tish Polymer Journal
a1 magazine December 1980 issue starting from page 154 Jack
Son Jr.'s paper contains -o -o-o -o-o-
It has been described that compounds such as Ha are effective in lowering the melting point of polyester and the mechanical performance of injection moldings obtained from polymerized polyester is 10 (when using The impact strength of notched Izotsu is only 0.6 ft.
-1d/in (3.3Kg・cr+t/cm).
従って、単位【から単位■を本発明の範囲内で用いるこ
とによってのみ、３５０℃以下の温度で光学的に異方性
の溶融相を形成するサーモトロビッタ液晶ポリエステル
が得られ、該ポリエステル二り耐靭性にすぐれた各種成
形物が得られることは上述の文献からは何ら示唆される
ことはない。Therefore, only by using the units [ to ■ within the scope of the present invention, thermotrovitta liquid crystalline polyesters that form an optically anisotropic melt phase at temperatures below 350°C can be obtained, and the polyesters The above-mentioned documents do not suggest that various molded products with excellent toughness can be obtained.
本発明のポリエステルは種々のエステル生成反応によっ
て製造されうるが、通常は溶融重合によシ製造される。Although the polyester of the present invention can be produced by various ester-forming reactions, it is usually produced by melt polymerization.
通常の場合には、単位１１単位■および単位■はそれら
を与える出発原料化合物の水酸基を低級アルキルエステ
ルの形に変換した形ステルが最も好ましい。In the usual case, most preferably the units (11) and (2) are stellates in which the hydroxyl group of the starting material compound providing them is converted into a lower alkyl ester.
重合に際しては、総単量体重量の約０．００１〜１重量
％、好ましくは約０．００５〜ｏ、 ｓ １量チの範囲
内の量で公知のエステル交換触媒音用いると、重合速度
の点で好ましい結果が得られる。エステル交換触媒の具
体例としては、カルボン酸のアルカリ又はアルカリ土類
金属塩、アルキルスズオキシド、ジアリールスズオキシ
ド、アルキルスズ酸、二酸化チタン、アルコキシチタン
シリケート、チタンアルコキシド、ルイス酸、ハロゲン
化水素などを挙げることができる。溶仙重合は通常２０
０〜３７５℃の温度範囲で、窒素、アルゴン等の不活性
ガス雰囲気下、好ましくは該ガスの流動下、若しくは、
減圧下において実施される。重合の進行に伴なって出発
ヒドロキシ化合物のエステル化化合物の釉類に応じて、
例えば酢酸エステルを用いた場合には酢酸が留出してく
るので、この留出量および重合体の粘性に応じて、反応
温度を段階的に上昇させ、また減圧度を調整する。重合
時間は通常１〜１０時間の範囲である。溶融重合が終了
したのち、重合体を微小に粉砕し、融点以下の温度で同
相にて更に重合を進め、重合度を上昇させることもでき
る。During polymerization, a known transesterification catalyst is used in an amount within the range of about 0.001 to 1% by weight of the total monomer weight, preferably about 0.005 to 1% by weight, to increase the polymerization rate. Favorable results can be obtained in this respect. Specific examples of transesterification catalysts include alkali or alkaline earth metal salts of carboxylic acids, alkyl tin oxides, diaryl tin oxides, alkyl stannic acids, titanium dioxide, alkoxy titanium silicates, titanium alkoxides, Lewis acids, hydrogen halides, etc. be able to. Melting polymerization is usually 20
At a temperature range of 0 to 375°C, under an inert gas atmosphere such as nitrogen or argon, preferably under a flow of the gas, or
It is carried out under reduced pressure. As the polymerization progresses, the starting hydroxy compound is esterified, depending on the glaze of the compound.
For example, when acetic acid ester is used, acetic acid is distilled out, so the reaction temperature is raised stepwise and the degree of vacuum is adjusted depending on the amount of distilled out and the viscosity of the polymer. Polymerization time is usually in the range of 1 to 10 hours. After the melt polymerization is completed, the polymer can be finely pulverized and the polymerization can be further carried out in the same phase at a temperature below the melting point to increase the degree of polymerization.
かかる方法により得られたポリエステル中の各くり返し
単位の組成比は、各原料化合物の仕込み組成比と実質的
に同一である。The composition ratio of each repeating unit in the polyester obtained by this method is substantially the same as the charged composition ratio of each raw material compound.
本発明のポリエステルは通常の溶融成形により、フィル
ム、シートあるいは射出成形品を始めとする各種成形品
に加工できる。本発明のポリエステルから得られる成形
品は従来提案されているサーモトロピック液晶ポリエス
テルから得られる成形品に較べて破断伸度が大であり、
かつ耐靭性がすぐれることから、フィルム、シートある
いは射出成形品として用いた場合に更にその特徴を活か
すことができる。The polyester of the present invention can be processed into various molded products including films, sheets, and injection molded products by conventional melt molding. Molded articles obtained from the polyester of the present invention have a higher elongation at break than molded articles obtained from conventionally proposed thermotropic liquid crystal polyesters,
Moreover, since it has excellent toughness, its characteristics can be further utilized when used as a film, sheet, or injection molded product.
本発明のポリエステルをその光学的に異方性の溶融相へ
の転移温度以上の温度（通常は５℃〜１００℃程度高い
温度）で溶融成形することにより、本発明のフィルム、
シート又は射出成形品が得られる。フィルム又はシート
は尚業者によく知られている通常のＴダイ法により得ら
れる。またインフレーション法により得ることも可能で
ある。By melt-molding the polyester of the present invention at a temperature higher than its transition temperature to an optically anisotropic melt phase (usually at a temperature about 5°C to 100°C higher), the film of the present invention,
A sheet or injection molded article is obtained. The film or sheet is obtained by the conventional T-die process well known to those skilled in the art. It can also be obtained by an inflation method.
本発明のフィルム又はシートは従来提案されているサー
モトロピックｇｋ晶ポリニスデルから得られるフィルム
又はシートに較べて破断伸度が犬であり、通常１０チ以
上であり靭性にすぐれる。でた押し出し方向（流動方向
）と、それに直交する方向の強度、弾性率等の力学的性
能の異方性が、従来提案されているサーモドロピンク液
晶ポリエステルから得られる押し出しフィルム又はシー
トに較べて小であることも本発明のポリエステルカニら
得られるフィルムの特徴の一つである。The film or sheet of the present invention has a higher elongation at break than conventionally proposed films or sheets obtained from thermotropic GK crystalline polynisder, usually 10 inches or more, and has excellent toughness. The anisotropy of mechanical properties such as strength and elastic modulus in the extrusion direction (flow direction) and in the direction perpendicular thereto is greater than that of extruded films or sheets obtained from conventionally proposed thermodropink liquid crystalline polyesters. Small size is also one of the characteristics of the film obtained from the polyester crab of the present invention.
本発明のポリエステルをその光学的に異方性の溶融相へ
の転移温度以上の温度で溶融押し出しすることによって
得られるフィルム又はシートは、製膜したままの状態で
押し出し方向の破断強度が１５ｋｆ／−以上、初期弾性
率が１５０ｋｆ／−以上を有する。The film or sheet obtained by melt extruding the polyester of the present invention at a temperature higher than its transition temperature to an optically anisotropic melt phase has a breaking strength in the extrusion direction of 15 kf/ - or more, the initial elastic modulus is 150 kf/- or more.
このようにして得られたフィルム又はシートは不活性ガ
ス雰囲気下、フィルム又はシートが融解しない温度下で
、一定時間例えば１０分から１００時間実質的に張力を
かけない状態で熱処理を行なうことによって、強度およ
び弾性率を上昇させることもできる。The film or sheet thus obtained is heat-treated in an inert gas atmosphere at a temperature that does not melt the film or sheet for a certain period of time, e.g. 10 minutes to 100 hours, with substantially no tension being applied, to increase its strength. and the elastic modulus can also be increased.
本発明の射出成形品は、通常の熱可塑性ポリマーと同様
にして得られる。金型は一般的な金型がすべて用いられ
る。また金型のゲートの種類としてもピンゲート、ファ
ンケート、サブマリンゲート、フィルムゲート等通常の
ものが用いられる。The injection molded article of the present invention is obtained in the same manner as ordinary thermoplastic polymers. All common molds are used. Also, common types of gates for the mold are used, such as pin gates, fan gates, submarine gates, and film gates.
本発明のポリエステルから得られる射出成形品は従来提
案されているサーモトロピック液晶ポリエステルから得
られる射出成形品に較べて力学的異方性が少ないので金
型およびゲートの設計は比較的容易である。金型の温度
としては５０〜１５０℃の範囲内が好ましい。射出圧力
は１５０〜１５００ｋｇ／ｃｒＡの範囲内で行なわれる
。本発明のポリエステルを該ポリエステルの光学的に異
方性の溶融相への転移温度以上の温度で射出成形するこ
とにより得られる射出成形品はＪＩＳ Ｋ７７１０の方
法に従ってノツチ付アイゾツト衝撃強度を測定した時に
は、ポリマーの流動方向に並行した方向で少なくとも３
０ ｋｙ・ｃｍ／ｃｐｎ、通常の場合には５０ｋｇ・ｃ
ｍ／ｃｍ以上であるＯ
本発明のポリエステルは靭性にすぐれていることから光
ファイバーの被覆材料としても、また有用である。すな
わち本発明のポリエステルはその破断伸度が従来提案さ
れているサーモトロピック液晶ポリエステルに較べて大
なため、石英よりなる光ファイバーと共押し出しするこ
とによって、機械的特性、熱的特性のすぐれた被覆ファ
イバーが形成される。Since the injection molded product obtained from the polyester of the present invention has less mechanical anisotropy than the injection molded product obtained from the conventionally proposed thermotropic liquid crystal polyester, the design of the mold and gate is relatively easy. The temperature of the mold is preferably in the range of 50 to 150°C. The injection pressure is within the range of 150 to 1500 kg/crA. The injection molded product obtained by injection molding the polyester of the present invention at a temperature equal to or higher than the transition temperature of the polyester to an optically anisotropic melt phase has a notched Izo impact strength when measured according to the method of JIS K7710. , at least 3 in the direction parallel to the flow direction of the polymer
0 ky・cm/cpn, 50kg・c in normal case
m/cm or more The polyester of the present invention has excellent toughness and is therefore also useful as a coating material for optical fibers. In other words, since the polyester of the present invention has a higher elongation at break than conventionally proposed thermotropic liquid crystal polyesters, by coextruding it with optical fibers made of quartz, coated fibers with excellent mechanical and thermal properties can be produced. is formed.
以下実施例により本発明を具体的に説明するが、本発明
は以下の実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to the following Examples.
実施例１
攪拌装置、ガス人口、蒸留ヘッドおよび凝縮器を備えた
内容１１のセパラブルフラスコに６−７セトキシー２−
ナフトエ酸２４．１５Ｆ（０，１０５モル）、４−アセ
トキシ安息香酸２４５．７Ｆ（１，３６５モル）、テレ
フタル酸５２．２’ｌ’（０，３１５モル）および４．
４′−ジアセトキシジフェニルエーテル９０．０’ｌ（
０，３１５モル）および触媒として酢酸ナトリウム０．
０１Ｆを仕込んだ。Example 1 A 6-7 setoxy 2-
Naphthoic acid 24.15F (0,105 mol), 4-acetoxybenzoic acid 245.7F (1,365 mol), terephthalic acid 52.2'l' (0,315 mol) and 4.
4'-diacetoxydiphenyl ether 90.0'l (
0.315 mol) and 0.315 mol) and sodium acetate as catalyst.
I prepared 01F.
次いでフラスコを真空に排気し、３回窒素で置換したの
ち、約３１７時の速度で乾燥した窒素を流しながら、２
５０℃に保ったバスに浸した。フラスコの内容物が溶融
しはじめ、スラリー状になった後に攪拌を開始し、同温
度で５０分間保持した。次いで約１０分かけてバス塩を
２８０℃に上昇させ同温度で５０分間保持したのち、更
にバス塩を３２０℃まで上昇させ、同温度で５０分間保
持した。この時までに１１０ｔ／の酢酸が留出した。次
いで系内を徐々に減圧にし、１０分で２０ツーｉｐにし
＊−ｏＬかるのちバス塩を３４０°Ｃ：て上昇させ減圧
度を約０．３ｕＨｆＫ保ち、重合を絖けた〇減圧開始４
０分波攪拌を停止し、窒素を導入し、系内を常圧にし、
フラスコを冷却した。フラスコ内容物が完全に固化する
前に内容物を取り出した。The flask was then evacuated, flushed with nitrogen three times, and then evacuated for 2 hours while flowing dry nitrogen at a rate of about 317 hours.
It was immersed in a bath kept at 50°C. After the contents of the flask began to melt and became a slurry, stirring was started and the temperature was maintained for 50 minutes. Next, the bath salt was raised to 280°C over about 10 minutes and held at the same temperature for 50 minutes, and then the bath salt was further raised to 320°C and held at the same temperature for 50 minutes. By this time, 110 t/l of acetic acid had been distilled out. Next, the pressure in the system was gradually reduced to 20 ip in 10 minutes*-oL, and then the bath salt was raised to 340°C, maintaining the degree of vacuum at about 0.3 uHfK, and polymerization was carried out.〇 Start of pressure reduction 4
0 Minute wave stirring was stopped, nitrogen was introduced, and the system was brought to normal pressure.
The flask was cooled. The flask contents were removed before they completely solidified.
得られたポリマーは２６０１であった。ポリマーを粉砕
したのち、１３０℃で１０時間７ｃ空乾燥した。得られ
たポリマーはペンタフルオロフェノール中、０．１重量
／′８量係のａ度、６０℃で測定した時に２．７２ ｄ
ｔ／？の対数粘度を示した。なお、対数粘度ηｉｎｈは
、次式により計算される。The obtained polymer was 2601. After the polymer was pulverized, it was air-dried at 130°C for 10 hours and 7cm. The resulting polymer had a molecular weight of 2.72 d when measured in pentafluorophenol at a degree of 0.1 weight/'8 weight at 60°C.
t/? It showed a logarithmic viscosity of Note that the logarithmic viscosity ηinh is calculated by the following formula.
ｔＯ； 溶媒であるペンタフルオロフェノールをウベ
ローデ型粘度計、６０″Ｃで４１Ｊ定した時の落下時間
。tO: Falling time when the solvent pentafluorophenol is fixed at 41 J using an Ubbelohde viscometer at 60″C.
ｔ ； 試料を溶解する溶液の落下時間。t: Falling time of the solution that dissolves the sample.
Ｃ； 試料の濃度（？／ｄｔ）
本ポリマーの微小片をリンカム社裂顕微鏡用加熱装ＲＴ
Ｉ（−６００内で窒素雰囲気下、１０℃／分の速度で昇
温し、偏光顕微鏡、直交ニコル下で観察したところ、２
７５℃より光を透過しはじめ２９０℃附近で透過光量は
更に大となり、本ポリマーは光学的に異方性の溶融相を
形成することが確認された。ｔた、Ｌ）ＳＣ（メト−Ｉ
Ｆ−Ｔ・３０００）Ｋより、２６０℃で１５分間熱処理
をしたのち、２０℃／分の昇温連関で測定したところ２
７１℃に吸熱ピークが観測された。C; Concentration of sample (?/dt) Microscopic pieces of this polymer were heated to a heating device RT for a Linkam microscope.
When the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere at I (-600°C) and observed under a polarizing microscope and crossed Nicols, 2
Light began to be transmitted from 75°C, and the amount of transmitted light became even larger around 290°C, confirming that this polymer forms an optically anisotropic molten phase. t, L) SC(meth-I
After heat treatment at 260℃ for 15 minutes from F-T・3000)K, measurements were taken at a temperature increase of 20℃/min.
An endothermic peak was observed at 71°C.
得うれたポリマーをペンタフルオロフェノール−トリフ
ルオロ酢酸溶液中で’ Ｈ−ＮＭＲ（ＪＯＥＬ ＧＸ−
５００）を測定した結果、各くり返し単位の組成比は仕
込み原料化合物の比と実質的に同一でめることが確認さ
れた。The obtained polymer was subjected to 'H-NMR (JOEL GX-
As a result of measuring 500), it was confirmed that the composition ratio of each repeating unit was substantially the same as the ratio of the raw material compounds charged.
本ポリマーを空気中１０℃／分の昇温速度で熱天秤によ
り重量減少を測定したところ、減量開始温度は４１２℃
であ！ｌｌ、５００℃までの重量減少は、５．２重量％
であった。When the weight loss of this polymer was measured using a thermobalance at a heating rate of 10°C/min in air, the weight loss initiation temperature was 412°C.
So! ll, weight loss up to 500°C is 5.2% by weight
Met.
得られたポリマーを用い、口端機械製小型射出成形機（
ＴＫ１４−ＩＡＰ型）により、シリンダ一温度；３１０
℃、射出圧；８００ ＬＣｆ／ｃｒＡ、フィルムゲート
を有する金型を用い、金型温度；１００℃で射出成形品
を作成した。なお、ゲートを工夫し、７′５ｍＸ１５ｍ
Ｘ２ｍｍの大きさの成形品で、長袖方向がポリマーの流
動方向と流動方向に直交する方向となるものを得た。得
られた成形品をＪＩＳ Ｋ７２０３に準じた方法により
曲げ強度および曲げ弾性率、ＪＩＳ Ｋ７１１０に準じ
た方法でノツチ付アイゾツト衝撃強度を測定した。結果
を第１表に示した。なお、本成形品は表面光沢があり、
非常になめらかであり、表面はフィブリル化しなかった
。Using the obtained polymer, a small injection molding machine manufactured by Kuchiha Kikai (
TK14-IAP type), cylinder temperature: 310
℃, injection pressure: 800 LCf/crA, and using a mold having a film gate, an injection molded product was produced at a mold temperature of 100°C. In addition, the gate has been devised and the gate is 7'5m x 15m.
A molded article having a size of 2 mm was obtained, with the long sleeve direction being perpendicular to the flow direction of the polymer. The bending strength and flexural modulus of the obtained molded product were measured according to a method according to JIS K7203, and the notched Izot impact strength was measured according to a method according to JIS K7110. The results are shown in Table 1. In addition, this molded product has a glossy surface.
It was very smooth and the surface was not fibrillated.
実施例２
実施例１の方法に準じて６−アセトキシ−２−ナフトエ
酸、４−アセトキシ安息香酸、テレフタル酸および４，
４′−ジアセトキシジフェニルエーテルのモル比が１５
／４５／２０／２０となる割合で仕込んで重合を行なっ
た。得られたポリマーの対数粘度は２．６５ ｄｔ／ｒ
であり、偏光顕微鏡およびＤＳＣによる測定の結果２７
１℃以上で光学的に異方性の溶融相を形成することが確
認された。Example 2 6-acetoxy-2-naphthoic acid, 4-acetoxybenzoic acid, terephthalic acid and 4,
The molar ratio of 4'-diacetoxydiphenyl ether is 15
Polymerization was carried out at a ratio of /45/20/20. The logarithmic viscosity of the obtained polymer was 2.65 dt/r
The results of measurements using a polarizing microscope and DSC27
It was confirmed that an optically anisotropic molten phase was formed at 1° C. or higher.
得られたポリマーを実施例１と同様にして射出成形を行
なった結果得られた試験片の力学的性能を第１表に示し
た。The obtained polymer was injection molded in the same manner as in Example 1, and the mechanical properties of the test pieces obtained are shown in Table 1.
得られたポリマーをスリットＩｓ １００１ｐｍ 、
スリット間隔０．２０の１゛−ダイを有する製膜装置を
用いて、シリンダ一温度３１０’Ｃ，押ｌ〜出し速度１
５？／分の条件で押し出しフィルムを作成したところ、
厚さ６０μｍのフィルムが安定に得られた。本フィルム
より試験片を作成し、引つす侵り速度１０係／分で、引
っ張り試験を行なったところ、次の結果が得られた。The obtained polymer was slit Is 1001pm,
Using a film forming apparatus having a 1-die with a slit interval of 0.20, the cylinder temperature was 310'C, and the extrusion speed was 1 to 1.
5? When an extruded film was made under the conditions of /min,
A film with a thickness of 60 μm was stably obtained. A test piece was prepared from this film and subjected to a tensile test at a pulling rate of 10 parts/min, and the following results were obtained.
押し出し方向 押し出し方向に直交方向引っ張り強度：
２０．１ ｋｇＡノ ５．６ｋｖ／Ｊ初期
弾性率： ２３４ ｋｆ／Ｍｊ２０１ 陽／−ｇ！
ｉ断伸度： ２４．１チ １５，１ ％また
、このフィルムを窒素流通子実質的に弛緩した状態で２
５０℃で２時間、２６０℃で５時間２７０℃で５時間、
次いで２８０℃で５時間熱処理を行なったところ、フィ
ルムの強伸度、弾性率は次のようになった。Extrusion direction Tensile strength perpendicular to the extrusion direction:
20.1 kgA 5.6 kv/J Initial elastic modulus: 234 kf/Mj201 positive/-g!
i Breaking elongation: 24.1 cm 15.1% Also, this film was passed through a nitrogen flow sensor in a substantially relaxed state at 2
2 hours at 50℃, 5 hours at 260℃, 5 hours at 270℃,
When the film was then heat treated at 280° C. for 5 hours, the strength and elongation and elastic modulus of the film were as follows.
押し出し方向 押し出し方向に直交方向引っ張り強度
２７．１ ｋｇ／ｆｆ ７．１３ ｋｇ
／ ｄ美
初期弾率３２５ ｋｇ／ｉｊ ２３６ ｋｑ／ｍｊ
破断伸度 １９．６チ １３．７ 係実施例３お
よび４
実施例１の方法に準じて、６−アセドギシー２−ナフト
エ酸、４−アセトヤシ安息香酸、テレフタル酸および４
．４７−ジアセトキシジフェニルエーテルのモル比がそ
れぞれ２０／３０／２５ ／２５および１５／６０／１
２．５／１２．５となる割合で仕込んで−ｉｆ合を行な
った。得られたポリマーの対数粘度はそれぞれ２．７１
ｄｔ／Ｐおよび３．３５ ｄｌｌ？であり、偏死鎚微
攪およびＤＳＣによる測定の結果、それぞれ２７１℃お
よび２７６℃以とで光学的に異方性の溶融相を形成する
ことが確認された。Extrusion direction Tensile strength perpendicular to the extrusion direction
27.1 kg/ff 7.13 kg
/ d beauty initial bullet rate 325 kg/ij 236 kq/mj
Elongation at break 19.6 cm 13.7 Examples 3 and 4 According to the method of Example 1, 6-aceto-2-naphthoic acid, 4-acetocobenzoic acid, terephthalic acid and
．． The molar ratio of 47-diacetoxydiphenyl ether is 20/30/25/25 and 15/60/1, respectively.
The -if combination was carried out at a ratio of 2.5/12.5. The logarithmic viscosity of the obtained polymers was 2.71, respectively.
dt/P and 3.35 dll? As a result of micro-stirring with a dead hammer and measurement using DSC, it was confirmed that an optically anisotropic molten phase was formed at temperatures above 271°C and 276°C, respectively.
得られたポリマーを実施例１と同様にして射出成形を行
なった結果、得られた試験片の力学的性能を第１表に示
した。The obtained polymer was injection molded in the same manner as in Example 1, and the mechanical properties of the obtained test pieces are shown in Table 1.
比較例１
実施例１の方法に準じて、４−アセトキシ安息香酸、テ
レフタル酸および４，４′−ジアセトキシジフェニルエ
ーテルのモル比が７０／１５／１５の割合で仕込んで重
合を行なった。得られたポリマーの対数粘度は２．６８
ｄｔ／ｆ！であった。またこのポリマーは偏光顕微鏡
による観察の結果約３２５℃で光学的に異方性の溶融相
を形成することがわかった。Comparative Example 1 Polymerization was carried out according to the method of Example 1 by charging 4-acetoxybenzoic acid, terephthalic acid and 4,4'-diacetoxydiphenyl ether in a molar ratio of 70/15/15. The logarithmic viscosity of the obtained polymer was 2.68
dt/f! Met. Further, as a result of observation using a polarizing microscope, it was found that this polymer forms an optically anisotropic melt phase at about 325°C.
このポリマーを用いて実施例１に準じて射出成形品を作
成した。但し、シリンダ一温度は３４０℃とした。得ら
れた成形品の力学的性能を第１表に示す。第１表かられ
かるように、本組成のポリエステルから得られた成形品
の優撃強朋は著しく小さい。An injection molded article was produced using this polymer according to Example 1. However, the cylinder temperature was 340°C. Table 1 shows the mechanical performance of the molded product obtained. As can be seen from Table 1, the impact strength of the molded articles obtained from the polyester of this composition is extremely small.
比較例２
実施例１の方法に準じて、６−アセトキシ−２−ナフト
エ酸、４−アセトキシ安息香酸、テレフタル酸および４
，４′−ジアセトキシジフェニルエーテルのモル比が１
０／２０／３５／３５となる割合で仕込んで重合を行な
った。この場合には３２０℃で減圧し始めると系内の粘
度が著しく上昇し始め、減圧開始後２０分位でパス塩を
３７０℃にまで上昇させても、系内は固化したままであ
り、均一に攪拌することは不可能であった。得られたポ
リマーは極めて脆（，４００℃以下で射出成形を行うこ
とはできなかった。Comparative Example 2 According to the method of Example 1, 6-acetoxy-2-naphthoic acid, 4-acetoxybenzoic acid, terephthalic acid and
, 4'-diacetoxydiphenyl ether molar ratio is 1
Polymerization was carried out by charging at a ratio of 0/20/35/35. In this case, when pressure reduction starts at 320°C, the viscosity in the system begins to rise significantly, and even if the pass salt is raised to 370°C about 20 minutes after the start of pressure reduction, the system remains solidified and uniform. It was impossible to stir the mixture. The resulting polymer was extremely brittle and could not be injection molded at temperatures below 400°C.
比較例３〜５
実施例１において、４．４−ジアセトキシジフェニルエ
ーテルに代えて、それぞれ４．４′−ジアセトキシシフ
エール−２，２−プロパン、４．４′−ジアセトヤシジ
フェニルスルホン、およびハイドロキノンジアセテート
を用いたこと以外は全く同一の条件で各原料化合物を仕
込んで重合を行なった。その結果、いずれの場合にも反
応後期に系内の粘度が急速に上昇し、攪拌が困難となり
、パス塩を３７５℃まで上昇させても系内は溶融ぜず、
固化したままであった。このことからこれらの場合には
３５０℃以下で溶融相を形成するポリエステルは形成さ
れないことがわかる。Comparative Examples 3 to 5 In Example 1, 4.4'-diacetoxydiphenyl ether was replaced with 4.4'-diacetoxydiphenyl ether-2,2-propane, 4.4'-diacetoxydiphenyl sulfone, and Polymerization was carried out by charging each raw material compound under exactly the same conditions except that hydroquinone diacetate was used. As a result, in either case, the viscosity within the system rapidly increased in the late stage of the reaction, making stirring difficult, and even when the pass salt was raised to 375°C, the system did not melt.
It remained solidified. This shows that in these cases, polyester that forms a melt phase at temperatures below 350° C. is not formed.
以下示白
〔発明の効果〕
本発明により力学的物性の異方性が小で耐衝撃性の極め
てすぐれた射出成形品および破断伸度が犬で強度のすぐ
ノシたフィルムが得らｔしる成形加工性にすぐハたサー
モトロピック）友晶ポリエステルが提供さｔする。[Effects of the Invention] The present invention makes it possible to obtain an injection molded product with small anisotropy of mechanical properties and excellent impact resistance, and a film with excellent strength and low elongation at break. Thermotropic (thermotropic) polyester is readily moldable.
Claims (1)
V（環に結合している水素原子の少くとも一部は置換基
により置換されていてもよい）よりなり、かつそれぞれ
が下記の組成からなり I ▲数式、化学式、表等があります▼ ３〜３０モル
％ II▲数式、化学式、表等があります▼ ２５〜８０モル
％ III▲数式、化学式、表等があります▼ ５〜３０モル
％ IV▲数式、化学式、表等があります▼ ５〜３０モル％ 但し、単位IIIとIVのモル数は実質的に等しい量で存在
し、ペンタフルオロフェノール中、０．１重量／容量％
の濃度、６０℃で測定した時に０．５ｄｌ／ｇ以上の対
数粘度を有し、３５０℃以下の温度で光学的に異方性の
溶融相を形成する全芳香族ポリエステル。 ２、くり返し単位 I 、II、IIIおよびIVがそれぞれ３〜
３０モル％、３０〜７０モル％、１０〜２５モル％およ
び１０〜２５モル％の範囲内であることを特徴とする特
許請求の範囲第１項記載の全芳香族ポリエステル。[Claims] 1. Repeating units essentially as follows: I, II, III and I
V (at least some of the hydrogen atoms bonded to the ring may be substituted with a substituent), and each has the following composition I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 3～ 30 mol% II ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 25-80 mol% III ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 5-30 mol% IV ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 5-30 mol %, provided that the moles of units III and IV are present in substantially equal amounts, and 0.1% w/v in pentafluorophenol.
A wholly aromatic polyester having a logarithmic viscosity of 0.5 dl/g or more when measured at 60°C or higher and forming an optically anisotropic melt phase at a temperature of 350°C or lower. 2. Repeating units I, II, III and IV are each 3~
The wholly aromatic polyester according to claim 1, characterized in that the content thereof is within the ranges of 30 mol%, 30 to 70 mol%, 10 to 25 mol%, and 10 to 25 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62000650A JP2544731B2 (en) | 1987-01-05 | 1987-01-05 | Wholly aromatic polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62000650A JP2544731B2 (en) | 1987-01-05 | 1987-01-05 | Wholly aromatic polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63168430A true JPS63168430A (en) | 1988-07-12 |
| JP2544731B2 JP2544731B2 (en) | 1996-10-16 |
Family
ID=11479586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62000650A Expired - Lifetime JP2544731B2 (en) | 1987-01-05 | 1987-01-05 | Wholly aromatic polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2544731B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02241083A (en) * | 1989-03-15 | 1990-09-25 | Mitsubishi Kasei Corp | Sealing material for hybrid ic substrate |
| WO2005049690A1 (en) * | 2003-11-20 | 2005-06-02 | Polyplastics Co., Ltd. | Component of signal reader and component of sensor |
| WO2024198932A1 (en) * | 2023-03-28 | 2024-10-03 | 珠海万通特种工程塑料有限公司 | Liquid crystal polyester and preparation method therefor and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55144024A (en) * | 1979-04-23 | 1980-11-10 | Celanese Corp | Polyester of 66hydroxyy22naphthoic acid* pphydroxybenzoic acid* aromatic diol and aromatic diacid which are readily accepted melt processing |
| JPS5962630A (en) * | 1982-07-26 | 1984-04-10 | セラニ−ズ・コ−ポレイシヨン | Anisotropic melt-processable polyester containing relativelylow concentration 6-oxy-2-naphthoyl portion |
-
1987
- 1987-01-05 JP JP62000650A patent/JP2544731B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55144024A (en) * | 1979-04-23 | 1980-11-10 | Celanese Corp | Polyester of 66hydroxyy22naphthoic acid* pphydroxybenzoic acid* aromatic diol and aromatic diacid which are readily accepted melt processing |
| JPS5962630A (en) * | 1982-07-26 | 1984-04-10 | セラニ−ズ・コ−ポレイシヨン | Anisotropic melt-processable polyester containing relativelylow concentration 6-oxy-2-naphthoyl portion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02241083A (en) * | 1989-03-15 | 1990-09-25 | Mitsubishi Kasei Corp | Sealing material for hybrid ic substrate |
| WO2005049690A1 (en) * | 2003-11-20 | 2005-06-02 | Polyplastics Co., Ltd. | Component of signal reader and component of sensor |
| WO2024198932A1 (en) * | 2023-03-28 | 2024-10-03 | 珠海万通特种工程塑料有限公司 | Liquid crystal polyester and preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2544731B2 (en) | 1996-10-16 |
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