JPH03188133A - Polyester film - Google Patents
Polyester filmInfo
- Publication number
- JPH03188133A JPH03188133A JP32777289A JP32777289A JPH03188133A JP H03188133 A JPH03188133 A JP H03188133A JP 32777289 A JP32777289 A JP 32777289A JP 32777289 A JP32777289 A JP 32777289A JP H03188133 A JPH03188133 A JP H03188133A
- Authority
- JP
- Japan
- Prior art keywords
- formulas
- tables
- formula
- polyester
- mathematical
- 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
- 229920006267 polyester film Polymers 0.000 title claims abstract description 12
- 229920000728 polyester Polymers 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 19
- 239000000470 constituent Substances 0.000 claims 1
- 238000000465 moulding Methods 0.000 claims 1
- 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 abstract description 3
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 description 8
- 239000005020 polyethylene terephthalate Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 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 2
- 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 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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 1
- ZYZWCJWINLGQRL-UHFFFAOYSA-N 4-phenylcyclohexa-2,4-diene-1,1-diol Chemical group C1=CC(O)(O)CC=C1C1=CC=CC=C1 ZYZWCJWINLGQRL-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 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
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PJANUNZPZUHMPM-UHFFFAOYSA-N phenyl 2-phenoxyacetate Chemical compound C=1C=CC=CC=1OC(=O)COC1=CC=CC=C1 PJANUNZPZUHMPM-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はポリエステルフィルム、さらに詳しくは高弾性
率で寸法安定性の優れたポリエステルフィルムに間する
。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyester film, and more particularly to a polyester film having a high modulus of elasticity and excellent dimensional stability.
〈従来の技術〉
磁気テープのベースなどに用いられるポリエステルフィ
ルムに対して、使用目的の高度化に伴いより一層高弾性
率かつ寸法安定性の良好な素材が要求されている。<Prior Art> Polyester films used as bases of magnetic tapes, etc., are required to have higher elastic modulus and better dimensional stability as the purpose of use becomes more sophisticated.
ポリエチレンテレフタレートのような比較的柔軟類のポ
リマに、光学異方性を有する液晶ポリマのような剛直分
子鎖ポリマをブレンドし、ポリエステルフィルムの機械
的強度、寸法安定性を改善する試みが検討されている（
国際公開ＷＯ３７１０５９１９号公報）。Attempts are being considered to improve the mechanical strength and dimensional stability of polyester films by blending relatively flexible polymers such as polyethylene terephthalate with rigid molecular chain polymers such as liquid crystal polymers that have optical anisotropy. There is (
International Publication No. WO37105919).
〈発明が解決しようとする課題〉
しかしながら、ポリエチレンテレフタレートのような比
教的柔軟鎖なポリマに、液晶ポリマのような剛直類ポリ
マをブレンドする場合、剛直類ポリマの分散性が必ずし
も十分とはいえず、透明性、均一性の点で満足のできる
ものは得られていない。<Problems to be Solved by the Invention> However, when blending a rigid polymer such as a liquid crystal polymer with a flexible chain polymer such as polyethylene terephthalate, the dispersibility of the rigid polymer may not necessarily be sufficient. However, it has not been possible to obtain anything satisfactory in terms of transparency and uniformity.
本発明は上述の間肋を解決し、機械的特性に優れ、熱収
縮率が低く、しかも寸法安定性に優れた上、透明性、均
一性が改善されたポリエステルフィルムを得ることを課
題とする。The object of the present invention is to solve the above-mentioned interribs, and to obtain a polyester film that has excellent mechanical properties, low heat shrinkage, excellent dimensional stability, and improved transparency and uniformity. .
く課題を解決するための手段〉
本発明者らは、上記課題を解決すべく鋭意検討した結果
本発明に到達した。Means for Solving the Problems> The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems.
すなわち、本発明は、下記構造単位■、■および■を必
須構成成分とし、構造単位の、■、■および■から選ば
れた構造単位からなり、構造単位■が〔■＋■＋■〕の
５０〜７０モル％であり、かつ構造単位■／■のモル比
が１００１０〜５０１５０であり、融点２５０℃未満で
あるサーモトロピック液晶ポリエステル（＾）０゜１〜
３０重量％と下記０式の構成式で表わされる半芳香族ポ
リエステル（Ｂ）９９．９〜７０重量％からなる組成物
をフィルム状に成形したフィルムであって、上記サーモ
トロピック液晶ポリエステルの粒子が該フィルム中に、
平均分散粒子径５四以下で分散し）式の構成式で表わさ
れる半芳香族ポリエステルフィルムを提供するものであ
る。That is, the present invention has the following structural units (■, ■, and Thermotropic liquid crystal polyester (^) 0°1 to 50 to 70 mol%, and the molar ratio of the structural unit ■/■ is 10010 to 50150, and the melting point is less than 250°C
30% by weight and 99.9 to 70% by weight of a semi-aromatic polyester (B) represented by the following formula 0, which is formed into a film shape, wherein the particles of the thermotropic liquid crystal polyester are In the film,
The present invention provides a semi-aromatic polyester film which is dispersed with an average dispersed particle size of 54 or less and is represented by the structural formula of the following formula.
＋０冗）−Ｃｏ−ト
（０−Ｒ１−０）−
−（−０−ＣＨ２ＣＨ２−０＋−
・・・・・Φ
・・・・・佃
・・−・（
Ｈ３
から選ばれた１種以上の基を示し、Ｒ２、Ｒ３は各々か
ら運ばれた１種以上の基を示し、Ｒ２とＲ３は同じであ
ってもよい、Ｘは塩素または水素原子を示す、また、構
造単位０は実質的に構造単位〔■＋■〕と等モルである
。また、０式中、ｎは２．４．６から運ばれた整数であ
る。）本発明におけるサーモトロピック液晶ポリエステ
ル（Ａ）の上記構造単位■は、ｐ−しドロキシ安息香酸
から生成したポリエステルの構造単位を、上記ｍ遣単位
■は４，４′−ジヒドロキシビフェニル、４．４゛−ジ
ヒドロキシ−３，３′５．５′−テトラメチルビフェニ
ル、ハイドロキノン、フェニルハイドロキノン、２．６
−シヒドロキシナフタレン、ｔ−ブチルハイドロキノン
、２．２−ビス（４−しドロキシフェニル）プロパン（
ビスフェノールＡ）および４．４′−ジヒドロキシジフ
ェニルエーテルから選ばれた１種以上のジヒドロキシ化
合物から生成した構造単位を、上記構造単位■はエチレ
ングリコールから生成した構造単位を、上記構造単位■
はテレフタル酸、イソフタル酸、４．４′−ジフェニル
ジカルボン酸、２，６−ナフタレンジカルボン酸、１．
２−ビス（フェノキシ）エタン−４，４′−ジカルボン
酸および１．２−ビス（２−クロルフェノキシ）エタン
−４，４′−ジカルボン酸から選ばれた１種以上の芳香
族ジカルボン酸から生成した構造単位を示す。+0 red) -Co-to(0-R1-0)- -(-0-CH2CH2-0+- ......Φ...Tsukuda...-(One or more types selected from H3 group, R2 and R3 represent one or more groups carried from each, R2 and R3 may be the same, X represents a chlorine or hydrogen atom, and the structural unit 0 is substantially It is equimolar with the structural unit [■+■]. Also, in the formula 0, n is an integer derived from 2.4.6.) The above structural unit (■) of the thermotropic liquid crystal polyester (A) in the present invention is the structural unit of polyester produced from p-hydroxybenzoic acid, and the m-unit (2) is 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'5,5'-tetramethylbiphenyl. , hydroquinone, phenylhydroquinone, 2.6
-cyhydroxynaphthalene, t-butylhydroquinone, 2,2-bis(4-droxyphenyl)propane (
The above structural unit (■) is a structural unit generated from one or more dihydroxy compounds selected from bisphenol A) and 4,4'-dihydroxydiphenyl ether, and the above structural unit (■) is a structural unit generated from ethylene glycol.
are terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1.
Produced from one or more aromatic dicarboxylic acids selected from 2-bis(phenoxy)ethane-4,4'-dicarboxylic acid and 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid It shows the structural unit.
本発明におけるサーモトロピック液晶ポリエステル（＾
）は上記構造単位〔■十■十■〕または〔■＋■＋■＋
■〕からなる共重合体であり、構造単位■が〔■＋■〕
の５０〜７０モル％であり、構造単位■を含む場合、構
造単位■が〔■十■十■〕の５０〜７０モル％である。Thermotropic liquid crystal polyester in the present invention (^
) is the above structural unit [■10■10■] or [■＋■＋■＋
■], and the structural unit ■ is [■+■]
When the structural unit (■) is included, the structural unit (■) accounts for 50 to 70 mole% of [■10■10■].
いずれの場合も５０モル％未満では、液晶性が良好なた
めポリエチレンテレフタレートなどの比較的柔軟鎖のポ
リマ中での分散性が不良であり、７０モル％より多いと
液晶性を示しにくくなり、剛直性が不十分となり十分な
フィルム特性の改善かできないためいずれの場合も好ま
しくない。In either case, if it is less than 50 mol%, the liquid crystallinity is good and the dispersibility in relatively flexible chain polymers such as polyethylene terephthalate is poor. Either case is unfavorable because the properties of the film become insufficient and the film properties cannot be sufficiently improved.
また、Ｗ４造単位■／■のモル比は１００１０〜５０１
５０であり１００１０〜７５／２５が好ましい。In addition, the molar ratio of W4 building units ■/■ is 10010 to 501
50 and preferably 10010 to 75/25.
なお、構造単位■は実質的に構造単位〔■十■〕と等モ
ルである。Incidentally, the structural unit (■) is substantially equimolar to the structural unit [■10■].
本発明におけるサーモトロピック液晶ポリエステル（＾
）は融点が２５０℃未満であることが必須である。融点
が２５０℃以上の場合、配合時に半芳香族ポリエステル
（Ｂ）との分散状態が不均一になったりするため好まし
くない、ここで融点とは示差走査熱量測定において昇温
速度２０℃／分の条件で観測される吸熱ピークのピーク
温度をさす。Thermotropic liquid crystal polyester in the present invention (^
) must have a melting point of less than 250°C. If the melting point is 250°C or higher, it is not preferable because the dispersion state with the semi-aromatic polyester (B) may become uneven during compounding. Here, the melting point is defined as a temperature increase rate of 20°C/min in differential scanning calorimetry. Refers to the peak temperature of the endothermic peak observed under certain conditions.
また、本発明における液晶ポリエステル（＾）の対数粘
度は０．２〜２．０ａｌｔが好ましく、０゜２〜１．０
ａ／ｇがさらに好ましく、０．３〜０．７ａ／ｒが特に
好ましい、ここでいう対数粘度とはペンタフルオロフェ
ノール中α１ｔ／ａの濃度、６０℃の温度で測定した値
である。Further, the logarithmic viscosity of the liquid crystal polyester (^) in the present invention is preferably 0.2 to 2.0 alt, and 0°2 to 1.0 alt.
a/g is more preferable, and 0.3 to 0.7 a/r is particularly preferable. The logarithmic viscosity here is a value measured at a concentration of α1t/a in pentafluorophenol and a temperature of 60°C.
本発明におけるサーモトロピック液晶ポリエステル（Ａ
）の製造方法は、特に制限がなく、公知のポリエステル
の重縮合法に準じて製造できる。たとえば代表的な方法
として、エチレングリコールと芳香族ジカルボン酸から
なるオリゴマあるいはポリマまたは芳香族ジカルボン酸
のビス（β−ヒドロキシエチル）エステルの存在下でｐ
−しドロキシ安息香酸、４．４′−ジヒドロキシビフェ
ニルなどの芳香族ジヒドロキシ化合物、テレフタル酸な
どの芳香族ジカルボン酸に無水酢酸を反応させて、フェ
ノール性水酸基をアセチル化した後、脱酢酸重縮合反応
によって製造する方法などが挙げられる。Thermotropic liquid crystal polyester (A
) is not particularly limited, and can be produced according to known polyester polycondensation methods. For example, as a typical method, p
- Aromatic dihydroxy compounds such as didroxybenzoic acid, 4,4'-dihydroxybiphenyl, and aromatic dicarboxylic acids such as terephthalic acid are reacted with acetic anhydride to acetylate the phenolic hydroxyl groups, followed by deacetic acid polycondensation reaction. Examples include a method of manufacturing by.
なお、本発明の芳香族ポリエステルを重縮合する際には
上記■、■、■および■を構成する成分以外に、３．３
′−ジフェニルジカルボン酸、３．４′−ジフェニルジ
カルボン酸、２．２′−ジフェニルジカルボン酸などの
芳香族ジカルボン酸、ヘキサヒドロテレフタル酸などの
脂環式ジカルボン酸、レゾルシン、クロルハイドロキノ
ン、メチルハイドロキノン、２，７−ジしドロキシナフ
タレン、ビスフェノールＳなどの芳香族ジヒドロキシ化
合物、ｍ−ヒドロキシ安息香酸、６−ヒドロキシ−２−
ナフトエ酸などの芳香族ヒドロキシカルボン酸、ｐ−ア
ミンフェノール、ｐ−アミノ安息香酸および分子内にイ
ミド結合を有する芳香族イミドジカルボン酸、芳香族イ
ミドジヒドロキシ化合物、芳香族イミドヒドロキシカル
ボン酸などを本発明の目的を損なわない程度の小割合の
範囲でさらに共重合することも可能である。In addition, when polycondensing the aromatic polyester of the present invention, in addition to the components constituting the above-mentioned (1), (2), (2), and (3), 3.3
Aromatic dicarboxylic acids such as '-diphenyldicarboxylic acid, 3.4'-diphenyldicarboxylic acid and 2.2'-diphenyldicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, resorcinol, chlorohydroquinone, methylhydroquinone, Aromatic dihydroxy compounds such as 2,7-di-hydroxynaphthalene and bisphenol S, m-hydroxybenzoic acid, 6-hydroxy-2-
Aromatic hydroxycarboxylic acids such as naphthoic acid, p-aminephenol, p-aminobenzoic acid, aromatic imidodicarboxylic acids having an imide bond in the molecule, aromatic imidodihydroxy compounds, aromatic imidohydroxycarboxylic acids, etc. It is also possible to further copolymerize within a small proportion that does not impair the purpose of copolymerization.
一方、本発明のフィルムを構成するもう一つの成分であ
る半芳香族ポリエステル（Ｂ）は上記構造式■で示され
る。０式においてｎは２．４．６から選ばれる整数であ
るが、フィルムの弾性率、熱収縮率の点からｎ＝２が最
も好ましい。On the other hand, the semi-aromatic polyester (B), which is another component constituting the film of the present invention, is represented by the above structural formula (2). In formula 0, n is an integer selected from 2.4.6, but n=2 is most preferable from the point of view of the elastic modulus and heat shrinkage rate of the film.
半芳香族ポリエステル（Ｂ）は炭素数２．４または６の
アルキレングリコールと芳香族ジカルボン酸からなるポ
リエステルである。半芳香族ポリエステル（Ｂ）を構成
するジカルボン酸成分はテレフタル酸、イソフタル酸、
４．４′−ジフェニルジカルボン酸、２．６−ナフタレ
ンジカルボン酸、１，２−ビス（フェノキシ）エタン−
４，４−ジカルボン酸および１，２−ビス（２−クロル
フェノキシ）エタン−４，４′−ジカルボン酸から選ば
れた１種以上の芳香族ジカルボン酸である。The semi-aromatic polyester (B) is a polyester consisting of an alkylene glycol having 2.4 or 6 carbon atoms and an aromatic dicarboxylic acid. The dicarboxylic acid component constituting the semi-aromatic polyester (B) is terephthalic acid, isophthalic acid,
4.4'-diphenyldicarboxylic acid, 2.6-naphthalene dicarboxylic acid, 1,2-bis(phenoxy)ethane-
One or more aromatic dicarboxylic acids selected from 4,4-dicarboxylic acid and 1,2-bis(2-chlorophenoxy)ethane-4,4'-dicarboxylic acid.
本発明に使用する半芳香族ポリエステル（８）としては
、ポリエチレンテレフタレート、ポリエチレン−２，６
−ナフタレンジカルボキシレートが特に好ましい、半芳
香族ポリエステル（Ｂ）としては還元粘度０．５以上の
ものが好ましい。The semi-aromatic polyester (8) used in the present invention includes polyethylene terephthalate, polyethylene-2,6
-Naphthalene dicarboxylate is particularly preferred, and the semi-aromatic polyester (B) preferably has a reduced viscosity of 0.5 or more.
本発明のフィルムはサーモトロピック液晶ポリエステル
（Ａ）と半芳香族ポリエステルＣＢ）を配合してなるも
のであるが、サーモトロピック液晶ポリエステル（Ａ）
の配合量は０．１〜３０重量％、好ましくは０．５〜１
０重量％、さらに好ましくは０．５〜５重量％であり、
半芳香族ポリエステル（Ｂ）の配合量は９９．９〜７０
重量％、好ましくは９９．５〜９０重量％、さらに好ま
しくは９９．５〜９５重量％である。サーモトロピック
液晶ポリエステルの配合量が０．１重量％未満では、高
弾性率で低熱収縮率という本発明の効果がほとんど認め
られず、３０重量％を越えるとブレンドポリマの製膜性
、延伸性が損なわれるためいずれの場合も好ましくない
。The film of the present invention is made by blending thermotropic liquid crystal polyester (A) and semi-aromatic polyester CB).
The blending amount is 0.1 to 30% by weight, preferably 0.5 to 1% by weight.
0% by weight, more preferably 0.5 to 5% by weight,
The blending amount of semi-aromatic polyester (B) is 99.9-70
% by weight, preferably 99.5-90% by weight, more preferably 99.5-95% by weight. If the amount of thermotropic liquid crystal polyester is less than 0.1% by weight, the effects of the present invention, such as high elastic modulus and low heat shrinkage rate, will hardly be observed, and if it exceeds 30% by weight, the film forming properties and stretchability of the blended polymer will deteriorate. Either case is unfavorable because the damage is caused.
また、本発明のフィルムを構成するサーモトロピック液
晶ポリエステル（＾）および半芳香族ポリエステルｆ８
）に対して必要に応じて他種の熱可塑性樹脂、酸化防止
剤、熱安定剤、滑剤、核生成剤、表面突起形成剤、離燃
剤などの無機および／、または有機添加剤を本発明の目
的を損なわない範囲内で添加してもよい。In addition, thermotropic liquid crystal polyester (^) and semi-aromatic polyester f8 constituting the film of the present invention
), if necessary, inorganic and/or organic additives such as other thermoplastic resins, antioxidants, heat stabilizers, lubricants, nucleating agents, surface protrusion forming agents, and flame retardants may be added to the present invention. It may be added within a range that does not impair the purpose.
サーモトロピック液晶ポリエステル（＾）、半芳香族ポ
リエステル（Ｂ）および必要に応じて添加するその他の
添加剤の配合方法については特に限定されないが、サー
モトロピック液晶ポリエステル（Ａ）を半芳香族ポリエ
ステル（Ｂ）中にできるだけ微分散させるのが好ましく
、公知の溶融混練法が好ましく使用できる。溶融混練の
方法としてはたとえばバンバリーミキサ−、ゴムロール
機、・ニーダ−１軸もしくは２軸押出機などが挙げられ
る。The method of blending the thermotropic liquid crystal polyester (^), the semi-aromatic polyester (B), and other additives added as necessary is not particularly limited. ) is preferably dispersed as finely as possible, and known melt-kneading methods can be preferably used. Examples of the melt-kneading method include a Banbury mixer, a rubber roll machine, a kneader, and a single-screw or twin-screw extruder.
２種のポリエステルを上記方法により混練し、−旦組成
物とした後、製膜用押出機に供してもよいが、製膜用押
出機中で配合と製膜を連続して行ってもよい。Two types of polyesters may be kneaded by the above method to form a composition, and then subjected to a film-forming extruder, or blending and film-forming may be performed continuously in a film-forming extruder. .
本発明のポリエステルフィルムの製膜方法については特
に限定するものではないが、たとえば押出機によりスリ
ット状のダイからシート状に押出し、未延伸フィルムを
得た後、公知の同時２軸延伸法あるいは逐次２軸延伸法
などにより延伸し、フィルムとすることが可能である。The method for forming the polyester film of the present invention is not particularly limited, but for example, after extruding it into a sheet from a slit-shaped die using an extruder to obtain an unstretched film, a known simultaneous biaxial stretching method or sequential It is possible to stretch the film using a biaxial stretching method or the like.
本発明のポリエステルフィルムにおいては、サーモトロ
ピック液晶ポリエステル（Ａ）が半芳香族ポリエステル
（Ｂ）中に５１Ｊｍ以下の平均分散粒径で微分散してい
る必要があり、３ ｕｎ以下がより好ましい、また、こ
れにはサーモトロビツり液晶ポリエステル（＾）が半芳
香族ポリエステルＦＢ）中に見かけ上相溶し、粒子を形
成しないものも含まれる。平均分散粒子径が５μｍより
大きい場合、透明性が損なわれる上、低熱収縮率、高弾
性率という本発明の効果が小さいため好ましくない。In the polyester film of the present invention, the thermotropic liquid crystal polyester (A) must be finely dispersed in the semi-aromatic polyester (B) with an average dispersed particle size of 51 Jm or less, more preferably 3 un or less, and This includes those in which the thermotrovitreous liquid crystal polyester (^) is apparently compatible with the semi-aromatic polyester FB) and does not form particles. If the average dispersed particle size is larger than 5 μm, transparency is impaired and the effects of the present invention, such as low heat shrinkage and high elastic modulus, are not preferred.
〈実施例〉 以下に実施例により本発明をさらに説明する。<Example> The present invention will be further explained below with reference to Examples.
参考例Ｉ
Ｐ−ヒドロキシ安息香酸１５６重量部、４，４−ジヒド
ロキシビフェニル８４重量部、無水＾Ｙ酸２０７重量部
、テレフタル酸７５重量部および固有粘度が約０．６ｄ
ｉ／ｇのポリエチレンテレフタレート５６４重量部を撹
拌翼、留出管を備えた反応容器を仕込み、次の条件で脱
酢酸重合を行った。Reference Example I 156 parts by weight of P-hydroxybenzoic acid, 84 parts by weight of 4,4-dihydroxybiphenyl, 207 parts by weight of ^Y acid anhydride, 75 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 d.
A reaction vessel equipped with a stirring blade and a distillation tube was charged with 564 parts by weight of polyethylene terephthalate of i/g, and acetic acid depolymerization was carried out under the following conditions.
まず、窒素ガス雰囲気下に１００〜２５０℃で５時間、
２５０〜２８０℃で１．５時間反応させた後、２８０°
Ｃ１１時間で０．５關ｔ１ｇに減圧し、さらに２．２５
時間反応させ、重縮合を完結させたところ、はぼ理論量
の酢酸が留出し、下記の理論構造式を有する樹脂（ａ）
を得た。First, under a nitrogen gas atmosphere at 100 to 250°C for 5 hours,
After reacting at 250-280℃ for 1.5 hours, 280℃
C11 hours, the pressure was reduced to 0.5 t1g, and further 2.25
When the reaction was carried out for a period of time to complete the polycondensation, almost a theoretical amount of acetic acid was distilled out, resulting in a resin (a) having the following theoretical structural formula.
I got it.
ｋ ／ Ｊ！ ／ ｍ ／ ｎ ＝ ２５ ／ １０
／ ６５ ／ ７５また、このポリエステルを偏光顕微
鏡の試料台にのせ、昇温して、光学異方性の確認を行っ
た結果、液晶開始温度は２２４℃であり光学異方性を示
した。このポリエステルの対数粘度（０，１ｇ／ｄ１の
濃度でペンタフルオロフェノール中、６０℃で測定）は
０．６５ ａ／ ｒであり、３０４°Ｃ１すり速度１，
０００量秒での溶融粘度は９１０ボイズであった。また
、触点け２１４℃であった。K/J! / m / n = 25 / 10
/ 65 / 75 Further, this polyester was placed on a sample stage of a polarizing microscope and the temperature was raised to confirm optical anisotropy. As a result, the liquid crystal start temperature was 224° C., indicating optical anisotropy. The logarithmic viscosity of this polyester (measured at 60 °C in pentafluorophenol at a concentration of 0.1 g/d1) is 0.65 a/r, with a sliding rate of 1,
The melt viscosity at 000 mass seconds was 910 voids. The temperature at the touch point was 214°C.
実施例１
参考例１のサーモトロピック液晶ポリエステル（ａ）３
重量部と対数粘度０．６５（オルトクロロフェノール中
０．！５ｔ／ａ、２５℃で測定）のポリエチレンテレフ
タレート９７重量部を溶融混合後ペレタイズした。Example 1 Thermotropic liquid crystal polyester (a) 3 of Reference Example 1
parts by weight and 97 parts by weight of polyethylene terephthalate having a logarithmic viscosity of 0.65 (0.5 t/a in orthochlorophenol, measured at 25°C) were melt-mixed and pelletized.
このポリマを２６５〜２９５”ＣでＴダイよりシート状
に押出し、縦、横方向に２軸に延伸した。得られたフィ
ルムの押出軸方向の熱収縮率を１５０℃、３０分の条件
で測定したところ、サーモトロピック液晶ポリエステル
ｆａ）を添加しない場合に比べ約１３％ら改善されるこ
とがわかった。また、位相差顕微鏡で観察した液晶ポリ
エステル（ａ）の分散径は０．５ ｕｆｆｉ以下であり
極めて良好であった。This polymer was extruded into a sheet through a T-die at 265 to 295"C and stretched biaxially in the longitudinal and transverse directions. The heat shrinkage rate of the obtained film in the extrusion axis direction was measured at 150°C for 30 minutes. As a result, it was found that the dispersion diameter of liquid crystal polyester (a) was improved by about 13% compared to the case without adding thermotropic liquid crystal polyester fa).In addition, the dispersion diameter of liquid crystal polyester (a) observed with a phase contrast microscope was 0.5 uffi or less. It was extremely good.
参考例２
ｐ−アセトキシ安息香酸３１５量部および固有粘度が約
０．６ｄｌ／ｇのポリエチレンテレフタレート６２４重
量部を撹拌翼、留出管を備えた反応容器に仕込み、次の
条件で脱酢酸重合を行った。Reference Example 2 315 parts by weight of p-acetoxybenzoic acid and 624 parts by weight of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl/g were charged into a reaction vessel equipped with a stirring blade and a distillation tube, and acetic acid depolymerization was carried out under the following conditions. went.
まず、窒素ガス雰囲気下に２５０’Ｃまで０．５時間で
昇温し、２５０〜２８０°Ｃで１．５時間反応させた後
、２８０℃、１時間で０．５ｍ＋Ｈ（ｌに減圧し、さら
に３時間反応させたところほぼ理論量の酢酸が留出し、
下記の理論構造式を有する樹脂（ｂ）を得た。First, the temperature was raised to 250'C in a nitrogen gas atmosphere for 0.5 hours, and the reaction was carried out at 250 to 280°C for 1.5 hours. After a further 3 hours of reaction, almost the theoretical amount of acetic acid was distilled out.
A resin (b) having the following theoretical structural formula was obtained.
ｊ！ ／ ｍ ／ ｎ ＝ ３５ ／ ６５ ／ ６５
また、この樹脂は１９７℃以上で光学異方性を示した。j! / m / n = 35 / 65 / 65
Further, this resin exhibited optical anisotropy at temperatures of 197°C or higher.
この樹脂の対数粘度は０．３６であった。また、融点は
２０８℃であった。The logarithmic viscosity of this resin was 0.36. Moreover, the melting point was 208°C.
実施例２
参考例２の樹脂（ｂ）３重量部と対数粘度０．６５（オ
ルトクロロフェノール中０．’３ｔ／ａ、２゛５℃で測
定）のポリエチレンテレフタレート９７重量部を溶融混
合後ペレタイズした。このポリマを実施例１の方法で延
伸し、押出軸方向の熱収縮率を測定したところ（ｂ）を
添加しない場合に比べて約１１％も改善されることがわ
かりた、また分散径は１−であった。Example 2 3 parts by weight of the resin (b) of Reference Example 2 and 97 parts by weight of polyethylene terephthalate with a logarithmic viscosity of 0.65 (0.'3 t/a in orthochlorophenol, measured at 2.5°C) were melt-mixed and then pelletized. did. When this polymer was stretched by the method of Example 1 and the heat shrinkage rate in the extrusion axis direction was measured, it was found that it was improved by about 11% compared to the case where (b) was not added, and the dispersion diameter was 1 -It was.
〈発明の効果〉
本発明に従い得られる、限定された’ｆｆＡ’ａを有す
る融点２５０℃未満のサーモトロピック液晶ポリエステ
ルと半芳香族ポリエステルからなるポリエステルフィル
ムは、優れた機械的特性と低い熱収縮率を有しているた
め、磁気テープ用ベースフィルムをはじめフレキシブル
プリント回路基板などの用途に供することができる。<Effects of the Invention> The polyester film made of a thermotropic liquid crystal polyester with a melting point of less than 250°C and a semi-aromatic polyester having a limited 'ffA'a and a semi-aromatic polyester obtained according to the present invention has excellent mechanical properties and a low heat shrinkage rate. Therefore, it can be used for applications such as base films for magnetic tapes and flexible printed circuit boards.
Claims (1)
成分とし、構造単位（ I ）、（II）、（III）および（
IV）から選ばれた構造単位からなり、構造単位（III）
が〔（ I ）＋（II）＋（III）〕の５０〜７０モル％で
あり、かつ構造単位（ I ）／（II）のモル比が１００
／０〜５０／５０であり、融点２５０℃未満であるサー
モトロピック液晶ポリエステル（Ａ）０．１〜３０重量
％と下記（Ｖ）式の構成式で表わされる半芳香族ポリエ
ステル（Ｂ）９９．９〜７０重量％からなる組成物をフ
ィルム状に成形したフィルムであつて、上記サーモトロ
ピック液晶ポリエステルの粒子が該フィルム中に、平均
分散粒子径５μｍ以下で分散していることを特徴とする
ポリエステルフィルム。 ▲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） ▲数式、化学式、表等があります▼・・・・・・（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Ｒ＿１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▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ から選ばれた１種以上の基を示し、Ｒ＿２、Ｒ＿３は各
々▲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▼ から選ばれた１種以上の基を示し、Ｒ＿２とＲ＿３は同
じであってもよい。Ｘは塩素または水素原子を示す。ま
た、構造単位（IV）は実質的に構造単位〔（II）＋（I
II）〕と等モルである。また、（Ｖ）式中、ｎは２、４
、６から選ばれた整数である。）[Claims] The following structural units (I), (III) and (IV) are essential constituents, and the structural units (I), (II), (III) and (
Consisting of structural units selected from IV), structural units (III)
is 50 to 70 mol% of [(I) + (II) + (III)], and the molar ratio of structural units (I)/(II) is 100
0.1 to 30% by weight of a thermotropic liquid crystal polyester (A) having a melting point of less than 250° C. and a semi-aromatic polyester (B) represented by the following formula (V): 99. A polyester film obtained by molding a composition comprising 9 to 70% by weight into a film shape, wherein particles of the thermotropic liquid crystal polyester are dispersed in the film with an average dispersed particle size of 5 μm or less. film. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V) (However, R_1 in the formula is ▲Mathematical formula, chemical formula) There are , tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ Indicates one or more groups selected from R_2 and R_3, respectively ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
Indicates one or more groups selected from ▼, ▲Mathematical formulas, chemical formulas, tables, etc.▼, and R_2 and R_3 may be the same. X represents a chlorine or hydrogen atom. Moreover, the structural unit (IV) is substantially the structural unit [(II) + (I
II)]. In addition, in formula (V), n is 2, 4
, 6. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32777289A JP2910107B2 (en) | 1989-12-18 | 1989-12-18 | Polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32777289A JP2910107B2 (en) | 1989-12-18 | 1989-12-18 | Polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03188133A true JPH03188133A (en) | 1991-08-16 |
| JP2910107B2 JP2910107B2 (en) | 1999-06-23 |
Family
ID=18202813
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32777289A Expired - Fee Related JP2910107B2 (en) | 1989-12-18 | 1989-12-18 | Polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2910107B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06506498A (en) * | 1991-04-01 | 1994-07-21 | フオスター・ミラー・インコーポレイテツド | Extruded thermoplastic polymers with planar structure, liquid crystal polymers and mixtures thereof |
| JPH09314631A (en) * | 1996-03-26 | 1997-12-09 | Toray Ind Inc | Polyester film and manufacture thereof |
| JP2016221702A (en) * | 2015-05-27 | 2016-12-28 | 帝人フィルムソリューション株式会社 | Manufacturing method of polyester film and film obtained by the same |
-
1989
- 1989-12-18 JP JP32777289A patent/JP2910107B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06506498A (en) * | 1991-04-01 | 1994-07-21 | フオスター・ミラー・インコーポレイテツド | Extruded thermoplastic polymers with planar structure, liquid crystal polymers and mixtures thereof |
| JPH09314631A (en) * | 1996-03-26 | 1997-12-09 | Toray Ind Inc | Polyester film and manufacture thereof |
| JP2016221702A (en) * | 2015-05-27 | 2016-12-28 | 帝人フィルムソリューション株式会社 | Manufacturing method of polyester film and film obtained by the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2910107B2 (en) | 1999-06-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |