JPS6248722A - Optically anisotropic polyester - Google Patents
Optically anisotropic polyesterInfo
- Publication number
- JPS6248722A JPS6248722A JP60187500A JP18750085A JPS6248722A JP S6248722 A JPS6248722 A JP S6248722A JP 60187500 A JP60187500 A JP 60187500A JP 18750085 A JP18750085 A JP 18750085A JP S6248722 A JPS6248722 A JP S6248722A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- acid
- tables
- structural unit
- polyester
- 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 abstract description 36
- 125000003118 aryl group Chemical group 0.000 abstract description 12
- 238000002844 melting Methods 0.000 abstract description 11
- 230000008018 melting Effects 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 abstract description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000000465 moulding Methods 0.000 abstract description 5
- 238000006068 polycondensation reaction Methods 0.000 abstract description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- -1 aromatic dicarboxylic acids Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- XCZKKZXWDBOGPA-UHFFFAOYSA-N 2-phenylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(C=2C=CC=CC=2)=C1 XCZKKZXWDBOGPA-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- AKOGNYJNGMLDOA-UHFFFAOYSA-N (4-acetyloxyphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C=C1 AKOGNYJNGMLDOA-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- KUZVIVNLNXNLAQ-UHFFFAOYSA-N (4-acetyloxy-3-methylphenyl) acetate Chemical compound CC(=O)OC1=CC=C(OC(C)=O)C(C)=C1 KUZVIVNLNXNLAQ-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- 235000010893 Bischofia javanica Nutrition 0.000 description 1
- 240000005220 Bischofia javanica Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000282994 Cervidae Species 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- YXZUGYXICVZUOK-UHFFFAOYSA-N benzene-1,4-diol;propanoic acid Chemical compound CCC(O)=O.CCC(O)=O.OC1=CC=C(O)C=C1 YXZUGYXICVZUOK-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003210 poly(4-hydroxy benzoic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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450℃以下で溶融成形可能ですぐれた機械的
性質と光学異方性を有する成形品を与え得る新規な光学
異方性ポリエステルに関するものである。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel optically anisotropic polyester that can be melt-molded at temperatures below 450°C and can provide molded products having excellent mechanical properties and optical anisotropy. It is something.
く従来の技術〉
近年グラスチックの高性能化に対する要求がますます高
まり、櫃々の新規性能を有するポリマが致多く開発され
市場に提供されているが、なかでも特に分子鎖の平行な
配列を特徴とする光学異方性の液晶ポリマがすぐれた機
械的性質を有する点で注目されている。(Conventional technology) In recent years, there has been an increasing demand for higher performance glass materials, and many polymers with new performance properties have been developed and offered on the market. The optically anisotropic liquid crystal polymer is attracting attention because of its excellent mechanical properties.
この液晶ポリマとしては全芳香族ポリエステルが広く知
られており例えばp−ヒドロキシ安息香績のホモポリマ
およびコポリマが”EKONOL’という商標で市販さ
れている。しかしながらp−ヒドロ千シ安息香峡ホモポ
リマはその融点があまりにも高すぎて溶融成形可能であ
るため、p−ヒドロキシ安息香績に種々の成分を共1台
し、その融点を下げる方法が検討され、たとえば、p−
ヒドロやシ安息香d )こフェニルハイドロキノン、テ
レフタルwtおよび/または2,6−ナツタVンジカル
ボ/dを共11合する方法(公表特許公報55−500
215(り 、 p−ヒドロキシ安息香績に2,6−シ
ヒドロキ7六7タレンとテレフタル酸を共重合する方法
(特開昭54−50594号公報)などが提案されてい
る。Fully aromatic polyesters are widely known as such liquid crystal polymers, and for example, p-hydroxybenzoic homopolymers and copolymers are commercially available under the trademark "EKONOL." However, p-hydroxybenzoic homopolymers have a low melting point. Since the temperature is too high and it is possible to melt and mold it, methods of lowering the melting point by adding various components to p-hydroxybenzoic acid have been studied.
A method of co-combining phenylhydroquinone, terephthal wt and/or 2,6-natsuta Vundicarbo/d (Publication Patent Publication No. 55-500)
A method of copolymerizing 215 (ri, p-hydroxybenzoic acid) with 2,6-dihydroxy767talene and terephthalic acid (Japanese Unexamined Patent Publication No. 54-50594) has been proposed.
〈発明が解決しようとする問題点〉
しかるにこれらの方法で得られる光学異方性ポリエステ
ルは融点が450℃以丁と比較的低い反面、その紡出糸
の弾性率はいまだに不十分であり、さらに一層の高弾性
率化が望まれている。<Problems to be solved by the invention> However, although the optically anisotropic polyester obtained by these methods has a relatively low melting point of 450°C or more, the elastic modulus of the spun yarn is still insufficient, and Even higher modulus of elasticity is desired.
そこで本発明者らは溶融成形可能で超弾性率に代表され
る機械的性質と光学異方性が均衡にすぐれた光学異方性
ポリエステルの取得を目的として鋭意検討した結果、p
−とドロキク安息香端とハイドロイノ7.4.4’−ジ
フェニルジカルボン酸およびテレフタル酸力為らなるポ
リエステル(特開昭58−91721号公II)および
7エ二ルハイドロキノンと4.4’−yyエニルノカル
ボン酸からなるポリエステル(特開昭59−41329
号公報)およびp−ヒドロキシ安息香績と7エ′−ルハ
イトロΦノット4.4’−ジフェニルジカルボン酸から
なるポリエステル(特開11859−41328号公報
)が高弾性率成形品を与えることを見い出し出願を行な
っているがF記(3造からなるポリエステルが更に高弾
性率化することを見い出し、本発明をなすに至った。Therefore, the present inventors conducted intensive studies with the aim of obtaining an optically anisotropic polyester that is melt moldable and has excellent balance between mechanical properties represented by superelastic modulus and optical anisotropy.
- and dorokiku benzoic end and hydroino 7.4.4'-Diphenyldicarboxylic acid and terephthalic acid polyester (JP-A-58-91721 II) and 7-enylhydroquinone and 4.4'-yyenyl Polyester consisting of nocarboxylic acid (JP-A-59-41329
They discovered that a polyester consisting of p-hydroxybenzoic acid and 7 ether hytroΦ knots 4,4'-diphenyldicarboxylic acid (Japanese Unexamined Patent Publication No. 11859-41328) could give a molded article with a high elastic modulus and filed an application. However, it was discovered that a polyester consisting of three structures (F) has an even higher modulus of elasticity, and the present invention was completed.
く問題点を解決するための手段〉
すなわち、本発明は下記構造単位(I)〜■からなり単
位(I)が全体の0〜90モル%、単位C(II) 十
I+(ト)+(V)〕が全体の100〜10モル%から
なり、単位〔(I)十(2)〕と〔■+(V)〕が実質
的に等モルの割合からなり(Jl) / ((I)十■
〕のモル比が100〜20モル%でありq0/〔(至)
+(V)〕のモル比が100〜50モル%であることを
特徴とする溶融成形可能な光学異方性ポリエステルを提
供するものである。Means for Solving the Problems> That is, the present invention consists of the following structural units (I) to V)] constitutes 100 to 10 mol% of the total, and the units [(I) 10(2)] and [■ + (V)] constitute substantially equal molar proportions (Jl) / ((I) 10 ■
] is 100 to 20 mol% and q0/[(to)
+(V)] is 100 to 50 mol%.
鞄−()−〇± ・・・・・([)鞄
−X−0± ・・・・・l&。Bag-()-〇± ......([) Bag-X-0± ......l&.
しE から遭ばれたー」以上の基を示す。ShiE "I was attacked by someone."
ただし、単位(I八(I)、0わ、(V)からなりYが
本発明の光学異方性ポリエステルにおいて上記構造単位
(I)はp−ヒドロキ7安息香瀘力為ら性成したポリエ
ステルの(4造単位を示す。However, in the optically anisotropic polyester of the present invention, the structural unit (I) is composed of units (I8 (I), 0W, (V)), and the structural unit (I) is p-hydroxy7benzoic acid. (Indicates 4 units.
また構造単位(I)1@はハイドロキノンなどの−11
1f88ジヒドロキシ化合物のヒトcI中7基の水素原
子を除去した構造単位を、
構造単位[有]、■は4.4′−ジフェニルジカルボン
酸などの芳香族ジカルボン酸のヒドロチンル基を除去し
た構造単位を示し、
芳香族ジヒドロキシ化合物と芳香族ジカル17ノ城とを
実質的に等モルの割合になるように這合せ、しめた際の
それぞれの構造単位を示す。In addition, the structural unit (I) 1@ is -11 such as hydroquinone
1f88 is a structural unit obtained by removing the 7 hydrogen atoms in human cI of a dihydroxy compound, and ■ is a structural unit obtained by removing the hydrotinle group of an aromatic dicarboxylic acid such as 4,4'-diphenyldicarboxylic acid. The structural units of the aromatic dihydroxy compound and the aromatic radical 17 are shown when the aromatic dihydroxy compound and the aromatic radical are mixed together in a substantially equimolar ratio.
本発明の光学異方性ポリエステルはその融点j! 45
0℃以下であり、通常の溶融成形により、すぐれた機械
的性質を有するm紬、フィルム、各d成形品などを容易
tこ成形することが可能である。ここで例えば特開昭5
8−91721号公報に記載されるP−ヒドロ牛シ安息
香峡、ハイドロキノン、および4,4′−ジフェニルジ
カルボン酸、テレフタル酸からなるポリエステルは融点
が450℃以下と比較的低く弾性率も66GPa と
比較的高い値を示すが、本発明の光学異方性ポリエステ
ルは上記公報記載のポリエステルに比し溶融流動性が良
好であり、弾性率が著しく高いという利点を有している
。The optically anisotropic polyester of the present invention has a melting point j! 45
The temperature is 0°C or lower, and it is possible to easily mold pongees, films, various molded products, etc. with excellent mechanical properties by ordinary melt molding. Here, for example,
The polyester consisting of P-hydrobycinbenzoin, hydroquinone, 4,4'-diphenyldicarboxylic acid, and terephthalic acid described in Publication No. 8-91721 has a relatively low melting point of 450°C or less and an elastic modulus of 66 GPa. However, the optically anisotropic polyester of the present invention has the advantages of better melt fluidity and significantly higher elastic modulus than the polyester described in the above-mentioned publication.
本発明の光学異方性ポリエステルにおいて上記構造単位
(I)は0〜90モル%、特に15〜80モル%が好ま
しく90モル%を越えると芳香族ポリエステルの融点が
上昇して溶融流動性及び機械的性質が低下するため好ま
しくない。(I)/((I) +([) )の七々比は
100〜20モル%であり好ましくは100〜30モル
%である。In the optically anisotropic polyester of the present invention, the content of the structural unit (I) is preferably 0 to 90 mol%, particularly preferably 15 to 80 mol%. This is undesirable because the physical properties deteriorate. The ratio of (I)/((I) + ([)) is 100 to 20 mol%, preferably 100 to 30 mol%.
一方、(V’)/((n+(V)]の−T=ル比は10
0〜50モル%であり好ましくは100〜56モル%で
ある。On the other hand, the -T=le ratio of (V')/((n+(V)) is 10
It is 0 to 50 mol%, preferably 100 to 56 mol%.
本発明の光学異方性ポリエステルにおいて上記構造単位
Iを形成する芳香族ジヒドロキシ成分とは、クロルハイ
ドロキノン、メチルハイドロキノン、フェニルハイドロ
キノン、 tert−ブチルハイドロキノ7.4.4
’−ジヒドロキシビ7工二ル、216 ’:’ヒトa
4シナフタ7ノ、2.7−ジヒドロキシナフタレンから
選ばれた成分である。The aromatic dihydroxy component forming the structural unit I in the optically anisotropic polyester of the present invention is chlorohydroquinone, methylhydroquinone, phenylhydroquinone, tert-butylhydroquinone7.4.4
'-Dihydroxybi-7-Dyl, 216':'Human a
It is a component selected from 4-sinaphthalene, 2,7-dihydroxynaphthalene.
また上記構造単位■を形成するジカルボン酸成分とは、
テレフタル酸、2.6−ナフタレンジカルボンfi、l
、2−ビス(フェノキシ)エタン−4,4’−ジカルボ
ン酸、1.2−ビス(2−クロ/l/フェノキシ)エタ
ン−4,4′−ジカルボン酸および4,4′−ジカルボ
キシジフェニルエーテルから選ばれた1種以上のジカル
ボン酸成分である。In addition, the dicarboxylic acid component forming the above structural unit (■) is
Terephthalic acid, 2,6-naphthalenedicarbone fi,l
, 2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 1,2-bis(2-chloro/l/phenoxy)ethane-4,4'-dicarboxylic acid and 4,4'-dicarboxydiphenyl ether One or more selected dicarboxylic acid components.
これらのうち面を形成する芳香族ジヒドロキシ成分とし
てはフェニルハイドロキノンまたはtert−メチルハ
イドロキノンである。Among these, the aromatic dihydroxy component forming the surface is phenylhydroquinone or tert-methylhydroquinone.
本発明の光学異方性ポリエステルは従来のポリエステル
のsra合法に準じて′IJ4清でき、製法については
特に制限がないが、代表的な製法としては次の(I)〜
(3)法が挙げられる。The optically anisotropic polyester of the present invention can be purified according to the conventional SRA method for polyester, and there are no particular restrictions on the manufacturing method, but typical manufacturing methods include the following (I) ~
(3) One example is the law.
(I) P−ア七トー?7安息香酸およびハイドロギ
ノンジアセテート、ハイドロキノンジプロピオネートな
どの芳香族ジヒドロキン化合物のジエステルと4.4′
−ジフェニルジカルボン酸を主体とする芳香族ジカルボ
ン酸から脱モノカルボ/酸這縮合によって製造する方法
。(I) P-a seven to? 7 Benzoic acid and diesters of aromatic dihydroquine compounds such as hydroginone diacetate and hydroquinone dipropionate and 4.4'
- A method for producing aromatic dicarboxylic acids, mainly diphenyldicarboxylic acid, by demonocarboxylation/acid condensation.
(2)P−オギ7安息香蛾のフェニルエステルおヨヒハ
イトI2平ノンなどの芳香族ジじドロキク化合物と4,
4′−ジフェニルジカルボン酸t゛ビのシlフェニルエ
ステルから脱フェノール慮縮合により製造する方法。(2) Aromatic didrochic compounds such as the phenyl ester of P-ogi7 benzoin moth, Oyohihite I2, and 4,
A method for producing 4'-diphenyldicarboxylic acid from cylphenyl ester by dephenolization condensation.
(3)P−オキン安息香酸および4,4′−ジフェニル
ジカルボン酸を主体とする芳香族ジカルボン酸に所望量
の2フエニルカーボネートな反応させてそれぞれジフェ
ニルエステルとした後、ハイドロキノンなどの芳S族ジ
ヒトa キシ化合物を加え脱フエノール重縮合反応によ
り製造する方法。(3) After reacting aromatic dicarboxylic acids mainly consisting of P-ochynebenzoic acid and 4,4'-diphenyldicarboxylic acid with a desired amount of diphenyl carbonate to form diphenyl esters, aromatic dicarboxylic acids such as hydroquinone etc. A method of manufacturing by adding a dihydroxy compound and performing a phenol-free polycondensation reaction.
重縮合反応に使用する船隊としては酢酸第1錫、テトラ
ブチルチタネート、酢酸鉛、酢酸ナトリウムおよび酢酸
カリタム、二酸化アンチ七ノなどの金属化合物が代表的
であり、とりわけ脱フェノール這縮合の際に有効である
。Typical examples of the fleet used in the polycondensation reaction are metal compounds such as stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate and potassium acetate, and anti-7-dioxide, which are particularly effective in dephenolization condensation. It is.
本発明の光学異方性ポリエステルは、ペンタンルオロフ
ェノール中で固有粘度を測定することが可能なものもあ
り、その際には0.1(重量/容1)96の濃度で60
℃で測定した値で0.35以上が好ましく、特に0.4
〜15.0が好ましい。Some of the optically anisotropic polyesters of the present invention can be measured for their intrinsic viscosity in pentanfluorophenol, at a concentration of 0.1 (weight/volume 1)96
The value measured at °C is preferably 0.35 or more, particularly 0.4
~15.0 is preferred.
また本発明の光学異方性ポリエステルの溶出粘度は、l
O〜15,000ボイズが好ましく、特に50〜10,
000ボイズがより好ましい。Further, the elution viscosity of the optically anisotropic polyester of the present invention is l
0 to 15,000 voids is preferred, particularly 50 to 10,
000 voids is more preferred.
なお、この溶融粘度は(液晶開始温度+40〜100℃
)ですり速度2,000〜4,000 (I/秒)の条
件下で高化式フローテスターによって測定した値である
。In addition, this melt viscosity is (liquid crystal starting temperature + 40 to 100℃
) at a sliding speed of 2,000 to 4,000 (I/sec) using a Koka type flow tester.
なお本発明の光学異方性ポリエステルを1縮合する際に
は、上記構造単位(I)〜(V))を構成する成分以外
にイソフタルd、3.3’−ジフェニルジカルボン1m
、3.4’−ジフェニルジ力ルポyIJ!、2.2′−
ジフェニルジカルボン酸、などの芳香衣ジカルボ7a1
ヘキサヒドロ戸レフタル酸などの脂環式ジカルボン酸、
および・n−オキン安、1香酸、2,6−オキンナ7ト
エ酸などの他の芳呑族オ争ジカルボン酸などを本発明の
目的を損なわない程度の少割合の範囲でさらに共這合せ
しめることができる。In addition, when condensing the optically anisotropic polyester of the present invention, in addition to the components constituting the above structural units (I) to (V)), 1 m of isophthal d and 3.3'-diphenyl dicarbonate are added.
, 3.4'-diphenyl dihydropyIJ! , 2.2'-
Aromatic dicarboxylic acid 7a1 such as diphenyldicarboxylic acid
Cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid,
and other aromatic acid dicarboxylic acids such as n-oquineic acid, monofluoroic acid, and 2,6-oquine-7toic acid, etc., in a small proportion that does not impair the purpose of the present invention. You can force it.
かくしてなる本発明の光学異方性ポリエステルは融点が
400℃以下と低く、押出成形、射出成形、圧縮成形、
プロー成形などの通常の溶融成形に供することができ、
la維、フィルム、三次元成形品、容重、ホースなどに
加工することが可能である。The optically anisotropic polyester of the present invention thus obtained has a low melting point of 400°C or less, and can be used for extrusion molding, injection molding, compression molding,
Can be subjected to normal melt molding such as blow molding,
It can be processed into la fibers, films, three-dimensional molded products, weights, hoses, etc.
なお成形時ンこは本発明の光学異方性ポリエステルに対
し、ガラスa維、炭素繊維、アスベストなどの強化剤、
充てん剤、核剤、顔料、酸化防止剤嘱安定剤、可塑剤、
滑剤、離型剤および難燃剤などの添加剤や他の熱可塑性
樹脂を添加して、成形品に所望の特性を付与することカ
;できる。In addition, during molding, reinforcing agents such as glass a fiber, carbon fiber, asbestos, etc. are added to the optically anisotropic polyester of the present invention.
Fillers, nucleating agents, pigments, antioxidants, stabilizers, plasticizers,
Additives such as lubricants, mold release agents, and flame retardants, as well as other thermoplastic resins, can be added to impart desired properties to the molded article.
本発明の新規な光学異方性ポリニスデルから得られる成
形品は、その平行な分子配列に起因して良好な光学異方
性を有し、4城的性質が極めてすぐれている。The molded article obtained from the novel optically anisotropic polynisdel of the present invention has good optical anisotropy due to its parallel molecular arrangement, and has extremely excellent four-dimensional properties.
なお、このようにして得られた成形、〜7.は、熱処理
によって強度な端UOさせることができ、弾性率をも多
くの場合増加させることができる。In addition, the molding obtained in this way, ~7. can be made stronger by heat treatment, and the elastic modulus can also be increased in many cases.
この熱処理は、成形品を不活性雰囲気(例えば窒素、ア
ルゴン、ヘリウムまたは水蒸気)中または酸素含有fJ
B気(例えば空気)中でポリマの融点以下の温度で熱処
理することによってけなうことができる。この熱処理は
緊張下であってもなくてもよく、数分〜数日の間で行な
うことができる。This heat treatment can be carried out in an inert atmosphere (e.g. nitrogen, argon, helium or water vapor) or in an oxygen-containing fJ
This can be done by heat treatment in B gas (eg air) at a temperature below the melting point of the polymer. This heat treatment may or may not be under tension and can be carried out for a period of several minutes to several days.
〈実施例〉 以下に実施例により本発明をざら(こ説明する。<Example> The present invention will be briefly explained below with reference to Examples.
実施例1
重合用試験管にP−アセトキン安息香酸6.48F(ふ
6×10モル)、ハイドロキノ/ジアセテートlsp
(I2x 10モル)、tert−ブチA/ /Itイ
ドロ千ノンジアセf−ト3.Op(L2x 10 ’モ
ル)および4,4′−2フエニルジカルボン酸5.81
1 (Z4 X 10 ’モル)を仕込み次の条1t−
で脱酢酸重合を行なった。Example 1 P-acetoquine benzoic acid 6.48F (6 x 10 mol) and hydroquino/diacetate lsp in a polymerization test tube
(I2x 10 mol), tert-butyA/ /Itidrothinone diacet3. Op (L2x 10' mol) and 4,4'-2 phenyldicarboxylic acid 5.81
1 (Z4
Acetic acid depolymerization was carried out.
まず窒素ガス雰囲気下に250〜350 ℃テ3.0時
間反応させた1、350℃で0.5fif(gに減圧し
、さらに10時間反応させ重縮合を完結させたところ、
はぼ理論量の酢酸がρ出し茶色のポリマが得られた。First, the reaction was carried out at 250 to 350°C for 3.0 hours in a nitrogen gas atmosphere, then the pressure was reduced to 0.5f (g) at 350°C, and the reaction was further carried out for 10 hours to complete the polycondensation.
A stoichiometric amount of acetic acid was extracted and a brown polymer was obtained.
このポリマの理論構造式は次のとおりであり、そのポリ
エステルの元素分析結果は第1表のとおり理論値とよい
一致を示した。また、このポリマーの熱特性を示差走査
M)1計(パーキンエルマー1型)で測定したところ融
点265℃であつた。The theoretical structural formula of this polymer is as follows, and the elemental analysis results of the polyester showed good agreement with the theoretical values as shown in Table 1. Further, the thermal properties of this polymer were measured with a differential scanning M) 1 meter (PerkinElmer type 1), and the melting point was 265°C.
m/2 n = 6/4 (モル比)
第1表
ただし、酸素含4 し)は(I00%−C%−H%)か
ら算出した。m/2 n = 6/4 (molar ratio) Table 1 (with the exception of oxygen) was calculated from (I00%-C%-H%).
また、このポリエステルを偏光顕g:Iaの試料台にの
せ、昇温して7エアーを」えて光学異方性の確認2行な
った結果、液晶開始温度は260℃であり良好な光学異
方性を示した。In addition, this polyester was placed on a sample stage of a polarized light microscope (g: Ia), the temperature was raised, and air was applied to confirm the optical anisotropy.As a result, the liquid crystal initiation temperature was 260°C, indicating good optical anisotropy. showed that.
このポリエステルをフローテスターに供し紡糸温度34
0℃、口金孔径0.3鵡φで紡糸を行ない0.08ff
−の紡出糸を得た。なお芯心粘度はずり速度2,500
(I/秒)で1,800ボイズであった。This polyester was subjected to a flow tester at a spinning temperature of 34
Spinning was carried out at 0°C with a spinneret hole diameter of 0.3mmφ and 0.08ff.
A spun yarn of - was obtained. Note that the core viscosity is at a shear rate of 2,500
(I/sec) was 1,800 voices.
この紡出糸を東洋ボールドクイ/(株)社製レオパイグ
ロンDDV−1−EAを用いて周波数110市、昇温速
度2℃/分、チャック間距離4owで弾性率を測定した
ところ30℃で108 GPaと極めて高弾性率であっ
た。The elastic modulus of this spun yarn was measured using a Rheopyglon DDV-1-EA manufactured by Toyo Bold Kui Co., Ltd. at a frequency of 110 degrees, a temperature increase rate of 2°C/min, and a distance between chucks of 4ow, it was 108 GPa at 30°C. The elastic modulus was extremely high.
実施例2
重合試験管にP−アセトキノ安息香酸5.4f(3X1
0’モル)、ハイドロキノンジアセテート5.82F
(3X10 モル)、4.4′−ジブエニルジ力ルボ
/酸3.631 (L5XlO”モル) 、2.6−ナ
フタVンジカルボン酸3.241 (I5XlOモル)
を実施例1と同じ条件でJt縮合反応を行なった。Example 2 P-acetoquinobenzoic acid 5.4f (3X1
0'mol), hydroquinone diacetate 5.82F
(3X10 moles), 4.4'-dibutenyl dicarboxylic acid 3.631 (L5X1O" moles), 2.6-naphthalene dicarboxylic acid 3.241 (I5X1O" moles)
A Jt condensation reaction was carried out under the same conditions as in Example 1.
このポリエステルの理論構造式は次のとおりであり、こ
の/リエステルの元素分析結果は表2のとおり理論1直
とよい一致をした。またこのポリマーの熱持住を示差走
査、鴇及計(パーキンエルマ15)で測定したところ1
点は279℃であった。The theoretical structural formula of this polyester is as follows, and the elemental analysis results of this polyester were in good agreement with theory 1 as shown in Table 2. In addition, the heat retention of this polymer was measured using differential scanning and a tokimeter (Perkin Elma 15).
The point was 279°C.
l /+n/n = 5/2.5/ 2.5 (モル比
)第 2 表
ただし、酸素含ik(%)は(I00%−C%−H%)
から算出した。l /+n/n = 5/2.5/ 2.5 (molar ratio) Table 2 However, oxygen content ik (%) is (I00%-C%-H%)
Calculated from.
また、このポリエステルを偏光顕微鏡の試料台にのせ昇
温しで光学異方性の61認を行なった結果、液晶開始温
度は256℃であり良好な光学異方性を示した。Further, this polyester was placed on a sample stand of a polarizing microscope and the temperature was raised to check the optical anisotropy. As a result, the liquid crystal initiation temperature was 256° C., indicating good optical anisotropy.
このポリエステルを70−テスターに供し紡糸温度34
0℃、口金孔径0.3同φで紡糸を行ない0.07Wφ
の紡出糸を得た。なお溶融粘度はすり速度2,800
(I/l)で1,500 、j?イズであった。この紡
出糸を東洋ボールドフィン(I)1%レオバイフa y
DDV−1−EA ヲ用イテ周波allOA、昇1速
度2℃/分、チャックを1距!40mで弾注賛を重合用
試験WにP−アセトキノ安息香酸10.08=> (5
,6X l O−”モル)、ハイドロキノンシアでデー
) 1721 (L4X10 モk) 、 2.6−
+ 7 タvンシカルボン酸2.27 t (L05
x 10 モル)、 イソフタk ea 0.581
(0,35X 10 −v=ル)を仕込み実施例1の
条件に従って反応温度330℃で11縮合を行ない融点
281℃の光学異方性ポリエステルを得た。This polyester was subjected to a 70-tester and the spinning temperature was 34
Spinning was carried out at 0°C with a spinneret hole diameter of 0.3Wφ and 0.07Wφ.
A spun yarn was obtained. The melt viscosity is the sliding speed of 2,800
(I/l) 1,500, j? It was Is. This spun yarn is used as Toyo Boldfin (I) 1% Leo Bif a y
DDV-1-EA ヲItem frequency allOA, rising speed 2℃/min, chuck 1 distance! P-acetoquinobenzoic acid 10.08 => (5
, 6
+ 7 tannic carboxylic acid 2.27 t (L05
x 10 mol), isophtha k ea 0.581
(0.35X 10 -v=L) was charged and 11 condensations were carried out at a reaction temperature of 330°C according to the conditions of Example 1 to obtain an optically anisotropic polyester having a melting point of 281°C.
このポリエステルを用いて、紡糸温度340℃で紡糸を
行ないt)、06”φの紡出糸を得弾性率を測定したと
ころ30℃で56GPaと本発明のポリエステルよりも
低弾性率であった。Using this polyester, spinning was carried out at a spinning temperature of 340°C (t) to obtain a spun yarn with a diameter of 06" and the elastic modulus was measured. The elastic modulus was 56 GPa at 30°C, which was lower than the polyester of the present invention.
実施例3〜13、比較実施例2〜4
慮合川試験管にP−1セトキシ安息香酸(I) −・イ
ドロギノンジアセテート(I)、クロルノ1イドロキノ
/ジrセテート■、メチルノ飄イドロキノンジアセテー
トGLフェニル/Sイドロキノンジアセテート(7)
、tert−プチルノ1イドロキノンノアセテート(V
T)、4.4′−ジヒドロキ/ビフェニルG1.2.6
−ジヒドコキシf7タレ;101)、1217−ジヒド
ロキ7ナフタv y CX)力為らなるジアセテート成
分ト4.4’−ジフェニルジカルボノ酸<X>、2.6
−ナノタレンジカルボノ酸(XI)、1.2−ビス(2
−10ルフエノキン)エタノ−4,4′−シカルボ/酸
(4)、1,2−ビス(フェノキ7)エタン−4,4’
−シカk g :/ 酸(XI)、テv フp #
Ia(Iff)からなるジカルボyIti成分とを各々
第3表tこ示すごとく組合わせてンアセテート成分;ジ
カルボ/酸成分モ1し喀いjJ5ように1台用試験管に
仕込み実施例1と同様に重縮合反応を行なった。得られ
たポリマの光学異方性の確認を行なったとこ実施例2〜
4)は融点が高かったり溶融粘度が高くて流動性が不良
であった。Examples 3 to 13, Comparative Examples 2 to 4 P-1 setoxybenzoic acid (I) - idroginone diacetate (I), chlorno-1 hydroquino/dir-acetate ■, and methyl-hydroquinone diacetate in a Chiaikawa test tube. Acetate GL phenyl/S hydroquinone diacetate (7)
, tert-butylno-hydroquinone noacetate (V
T), 4,4'-dihydroxy/biphenyl G1.2.6
-dihydrocoxyf7 sauce; 101), 1217-dihydrokoxy7naphthavy CX) diacetate component consisting of 4.4'-diphenyldicarbonoic acid <X>, 2.6
-nanotaledicarbonoic acid (XI), 1,2-bis(2
-10rufenoquine) ethano-4,4'-cicarbo/acid (4), 1,2-bis(phenoxy7)ethane-4,4'
- deer kg: / acid (XI), te v p #
Combine the dicarboxy and Iti components consisting of Ia (Iff) as shown in Table 3, and add the acetate component and dicarboxylic acid component to a single test tube in the same manner as in Example 1. A polycondensation reaction was carried out. When the optical anisotropy of the obtained polymer was confirmed, Example 2~
Sample 4) had a high melting point and high melt viscosity, resulting in poor fluidity.
〈発明の効果〉
本発明の芳香族ポリエステルは溶融成形可能であり高弾
性率の成形品を得ることができるので、金属代替グラス
チックとして二/)ニアリンググラスチックなど檎々の
用途に使用することができる。<Effects of the Invention> Since the aromatic polyester of the present invention can be melt-molded and molded products with high elastic modulus can be obtained, it can be used in various applications such as nearing glass as a metal substitute glass. I can do it.
Claims (1)
体の0〜90モル%、単位〔(II)+(III)+(IV)
+(V)〕が全体の100〜10モル%からなり、単位
〔(II)+(III)〕と〔(IV)+(V)〕が実質的に
等モルの割合からなり、(II)/〔(II)+(III)〕
のモル比が100〜20モル%であり(IV)/〔(IV)
+(V)〕のモル比が100〜50モル%であることを
特徴とする溶融成形可能な光学異方性ポリエステル。 ▲数式、化学式、表等があります▼・・・・・( I ) ▲数式、化学式、表等があります▼・・・・・(II) −(O−X−O)−・・・・・(III) ▲数式、化学式、表等があります▼・・・・・(IV) ▲数式、化学式、表等があります▼・・・・・(V) (ただし式中のXは▲数式、化学式、表等があります▼
、▲数式、化学式、表等があります▼、▲数式、化学式
、表等があります▼、▲数式、化学式、表等があります
▼、▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼および ▲数式、化学式、表等があります▼から選ばれた基を示
し、Yは▲数式、化学式、表等があります▼、▲数式、
化学式、表等があります▼、▲数式、化学式、表等があ
ります▼、 ▲数式、化学式、表等があります▼および▲数式、化学
式、表等があります▼ から選ばれた一種以上の基を示す。 ただし、単位( I )、(II)、(IV)、(V)からな
りYが▲数式、化学式、表等があります▼からなる組み
合せ及び単位(II)、(III)、(IV)からなりXが▲
数式、化学式、表等があります▼からなる組み合せを除
く)。[Claims] Consisting of the following structural units (I) to (V), the unit (I) is 0 to 90 mol% of the total, and the unit [(II) + (III) + (IV)
+(V)] consists of 100 to 10 mol% of the total, the units [(II) + (III)] and [(IV) + (V)] consist of substantially equimolar proportions, and (II) / [(II) + (III)]
The molar ratio of (IV)/[(IV)
+(V)] is 100 to 50 mol%. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) −(O−X−O)−・・・・・・(III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V) (However, X in the formula is ▲Mathematical formula, chemical formula There are tables, etc.▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas, Y indicates a group selected from ▼ There are tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, and Y indicates ▲ There are mathematical formulas, chemical formulas, tables, etc.
Indicates one or more groups selected from ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. . However, combinations where Y consists of units (I), (II), (IV), and (V) and where Y consists of X is ▲
There are mathematical formulas, chemical formulas, tables, etc. (excluding combinations consisting of ▼).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60187500A JPS6248722A (en) | 1985-08-28 | 1985-08-28 | Optically anisotropic polyester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60187500A JPS6248722A (en) | 1985-08-28 | 1985-08-28 | Optically anisotropic polyester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6248722A true JPS6248722A (en) | 1987-03-03 |
JPH048448B2 JPH048448B2 (en) | 1992-02-17 |
Family
ID=16207146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60187500A Granted JPS6248722A (en) | 1985-08-28 | 1985-08-28 | Optically anisotropic polyester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6248722A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62235321A (en) * | 1986-04-05 | 1987-10-15 | Mitsui Petrochem Ind Ltd | Aromatic polyester |
JPS62292832A (en) * | 1986-06-13 | 1987-12-19 | Toray Ind Inc | Heat-resistant aromatic polyester |
JPS63112620A (en) * | 1986-10-29 | 1988-05-17 | Toray Ind Inc | Heat-resistant aromatic polyester of good flow |
US5025082A (en) * | 1988-08-24 | 1991-06-18 | Mitsubishi Kasei Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
WO1994029365A1 (en) * | 1993-06-15 | 1994-12-22 | Nippon Petrochemicals Company, Limited | Wholly aromatic polyester, composition thereof, and molded article made therefrom |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5465795A (en) * | 1977-11-04 | 1979-05-26 | Asahi Chem Ind Co Ltd | Preparation of aromatic polyester |
JPS5761046A (en) * | 1980-09-30 | 1982-04-13 | Asahi Chem Ind Co Ltd | Aromatic polyamide-polyester resin composition |
JPS60221422A (en) * | 1984-04-17 | 1985-11-06 | Mitsubishi Chem Ind Ltd | Production of polyester copolymer |
-
1985
- 1985-08-28 JP JP60187500A patent/JPS6248722A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5465795A (en) * | 1977-11-04 | 1979-05-26 | Asahi Chem Ind Co Ltd | Preparation of aromatic polyester |
JPS5761046A (en) * | 1980-09-30 | 1982-04-13 | Asahi Chem Ind Co Ltd | Aromatic polyamide-polyester resin composition |
JPS60221422A (en) * | 1984-04-17 | 1985-11-06 | Mitsubishi Chem Ind Ltd | Production of polyester copolymer |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62235321A (en) * | 1986-04-05 | 1987-10-15 | Mitsui Petrochem Ind Ltd | Aromatic polyester |
JPS62292832A (en) * | 1986-06-13 | 1987-12-19 | Toray Ind Inc | Heat-resistant aromatic polyester |
JPS63112620A (en) * | 1986-10-29 | 1988-05-17 | Toray Ind Inc | Heat-resistant aromatic polyester of good flow |
US5025082A (en) * | 1988-08-24 | 1991-06-18 | Mitsubishi Kasei Corporation | Aromatic polyester, aromatic polyester-amide and processes for producing the same |
WO1994029365A1 (en) * | 1993-06-15 | 1994-12-22 | Nippon Petrochemicals Company, Limited | Wholly aromatic polyester, composition thereof, and molded article made therefrom |
Also Published As
Publication number | Publication date |
---|---|
JPH048448B2 (en) | 1992-02-17 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
EXPY | Cancellation because of completion of term |