JPH04166309A - Manufacture of liquid crystalline polymer film or sheet - Google Patents
Manufacture of liquid crystalline polymer film or sheetInfo
- Publication number
- JPH04166309A JPH04166309A JP29468090A JP29468090A JPH04166309A JP H04166309 A JPH04166309 A JP H04166309A JP 29468090 A JP29468090 A JP 29468090A JP 29468090 A JP29468090 A JP 29468090A JP H04166309 A JPH04166309 A JP H04166309A
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- film
- temperature
- liquid crystalline
- roll
- 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.)
- Pending
Links
- 229920000106 Liquid crystal polymer Polymers 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229920000728 polyester Polymers 0.000 claims abstract description 22
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009477 glass transition Effects 0.000 claims abstract description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 5
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- -1 polyethylene terephthalate Polymers 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 abstract description 3
- 239000005020 polyethylene terephthalate Substances 0.000 abstract description 3
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 2
- 230000004927 fusion Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 7
- 238000003490 calendering Methods 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJFXRHURBJZNAO-UHFFFAOYSA-N 3-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001802 infusion Methods 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
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 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
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- UTNSTOOXQPHXJQ-UHFFFAOYSA-N 2-[4-[4-(2-hydroxyethoxy)phenyl]sulfonylphenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1S(=O)(=O)C1=CC=C(OCCO)C=C1 UTNSTOOXQPHXJQ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 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 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241001114813 Macna Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-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
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Liquid Crystal Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は厚みムラの少ない液晶フィルム乃至シートを提
供するのに適した製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a manufacturing method suitable for providing a liquid crystal film or sheet with less uneven thickness.
（従来の技術および発明が解決しようとする課題）異方
性溶融物を形成し得るポリエステル、いわゆるサーモド
ロピンク液晶性ポリエステルは、その多くが溶融成型可
能であり、高耐熱性、高寸法安定性、高強度、高弾性率
、高ガスバリヤ−性などの性質を持つため、繊維、フィ
ルム、射出成型品などとして応用が注目され、一部はす
でに実用化されていることは周知の通りである。しかし
ながら、液晶ポリマー（ポリエステル）の特徴でもある
が、その著しい一軸配向性が問題となり一般に二軸配向
フィルム乃至シートを得ることは難しく、Ｔダイ法によ
る製造法では非常な困難性を伴う。しかし、インフーシ
ョン法のごとく長さ方向（ＭＤ）だけでなく横方向（Ｔ
Ｄ）にも応力を加える方法を採用すると縦横に二軸配向
したフィルム乃至シートを得ることできる。しかしなが
ら、インフーション法による製膜によればそのダイ構造
からリップの隙間調整に限界がありフィルム乃至シート
の厚みムラはＴダイ法に比べ格段に劣るものである。(Prior art and problems to be solved by the invention) Many of the polyesters that can form anisotropic melts, so-called thermodropink liquid crystalline polyesters, can be melt-molded and have high heat resistance and high dimensional stability. As it is well known, it has properties such as high strength, high elastic modulus, and high gas barrier properties, so it has attracted attention for its application as fibers, films, injection molded products, etc., and some of it has already been put into practical use. However, a characteristic of liquid crystal polymers (polyesters) is their remarkable uniaxial orientation, which generally makes it difficult to obtain biaxially oriented films or sheets, and the production method using the T-die method is extremely difficult. However, as in the infusion method, it is not only the longitudinal direction (MD) but also the transverse direction (T
If the method of applying stress to D) is also adopted, a film or sheet biaxially oriented in the vertical and horizontal directions can be obtained. However, film formation by the infusion method has a limit in lip gap adjustment due to its die structure, and the thickness unevenness of the film or sheet is much inferior to that of the T-die method.
本発明は、このような問題点ないすぐれた液晶ポリマー
フィルムを製造することを課題としてなされたものであ
る。The present invention has been made with the object of producing an excellent liquid crystal polymer film that does not have these problems.
（課題を解決するための手段）
本発明者らは、上記課題に対して鋭意検討を重ねた結果
、サーモトロピック液晶性ポリエステルからなるフィル
ム乃至シートを（Ａ）フィルム乃至シートの温度がガラ
ス転移温度以上融解温度以 ４下の温度範囲内、（Ｂ）
ロールカレンダの線圧が１００ｋｇ／ｃｍ以上、３００
０ ）ｃｇ／ｃｍ以下の範囲内でロールカレンダ処理す
ることを特徴とする液晶ポリマーフィルム乃至シートの
製造法を要旨とする本発明に到達した。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have determined that (A) the temperature of the film or sheet is the glass transition temperature; Within the temperature range of 4 or above and below the melting temperature, (B)
Linear pressure of roll calender is 100kg/cm or more, 300
We have arrived at the present invention, which is a method for producing a liquid crystal polymer film or sheet, which is characterized by roll calendering within a range of 0.0 cg/cm or less.
融点以上の温度でロールカレンダ処理しようとしてもフ
ィルムは熱劣化したりフィルムがロールに融着したりし
て処理できない。また、ロールカレンダの線圧はロール
カレンダの処理温度により決定されるべきものであるが
、１００ｋｇ／Ｃ１１以下の線圧では厚みむらを充分解
消することはできない。また、線圧３０００ｋｇ／Ｃ′
ｍ以上にするとフィルム、シートは目標厚みにコントロ
ールすることが困難となったり性能のバランスが悪くな
る場合がある。Even if roll calendering is attempted at a temperature higher than the melting point, the film will suffer thermal deterioration or will be fused to the roll, making it impossible to process. Further, the linear pressure of the roll calender should be determined by the processing temperature of the roll calender, but thickness unevenness cannot be sufficiently eliminated with a linear pressure of 100 kg/C11 or less. Also, the linear pressure is 3000kg/C'
If the thickness exceeds m, it may become difficult to control the film or sheet to the target thickness, or the performance may become unbalanced.
本発明のロールカレンダ法によれば、ポリマーを溶融さ
せることなく高い圧力により上記課題を全うさせること
が可能である。すなはち、液晶ポリマーフィルム乃至シ
ートの物性、分子配向などを実質的に維持しつつ厚みム
ラを減少せしめる方法として有効なことを見いだしたこ
とはきわめて高い工業的効果につながるものである。According to the roll calender method of the present invention, it is possible to accomplish the above-mentioned problems using high pressure without melting the polymer. In other words, the discovery of an effective method for reducing thickness unevenness while substantially maintaining the physical properties, molecular orientation, etc. of a liquid crystal polymer film or sheet will lead to extremely high industrial effects.
本発明においてサーモトロピック液晶性ポリエステルと
は、光学異方性溶融物を形成する性質を持つポリエステ
ルのことであり、溶融状態にあるポリマーが９０°に交
差した偏光子を備える光学系において、偏光を通過させ
る性質を持つポリエステルを意味する。かかるポリエス
テルの代表例は、■ｐ−ヒドロキシ安安息香酸主成分と
するポリエステル、■２−ヒドロキシ−６−カルボキシ
ナフタレンを主成分とするポリエステル、■テレフタル
酸とハイドロキノン類を主成分とするポリエステル、■
ｐ−ヒドロキシ安息香酸成分とポリエチレンテレフタレ
ート成分とからなるポリエステルがあり、本発明の目的
を損なわない範囲で、イソフタル酸、メタヒドロキシ安
息香酸、４，４”−ジカルボキシビフェニル、２，６−
ナフタレンジカルボン酸、４．４゛−ジカルボキシジフ
ェニルエーテル、レゾルシン、ハイドロキノン、２゜６
ジヒドロキシナフタレン、４，４゛−ジヒドロキシビフ
ェニル、２−フェニルハイドロキノン、２．２−ビス（
４−ヒドロキシフェニル）プロパン、ビス（４−ヒドロ
キシフェニル）スルホン、２．２−ビス（４−βヒドロ
キシエトキシフェニル）プロパン、ビス（４−βヒドロ
キシエトキシフェニル）スルホン等の芳香族成分の他、
マロン酸、コハク酸、スペリン酸、アジピン酸、アゼラ
イン酸、セバシン酸、ドデカンニ酸、エイコニ酸、トリ
メチレングリコール、プロピレングリコール、１．４−
ブタンジオール、１．６−ヘキサンジオール、ジエチレ
ングリコール、トリエチレングリコール、ポリエチレン
グリコール等の脂肪族成分、１．４−シクロヘキサンジ
カルボン酸、１．４−シクロヘキサンジメタツール等の
脂環族成分を適宜共重合成分として含んでもよく、また
、難燃剤、耐熱剤、耐光剤、つや消し剤、顔料等の添加
剤を含んでいてもさしつかえない。In the present invention, thermotropic liquid crystalline polyester refers to a polyester that has the property of forming an optically anisotropic melt, and in an optical system equipped with polarizers crossed at 90 degrees, the polymer in a molten state is polarized. Refers to polyester that has the property of allowing water to pass through it. Typical examples of such polyesters include: ■ polyesters whose main components are p-hydroxybenzoic acid, ■ polyesters whose main components are 2-hydroxy-6-carboxynaphthalene, ■ polyesters whose main components are terephthalic acid and hydroquinones, and ■
There is a polyester consisting of a p-hydroxybenzoic acid component and a polyethylene terephthalate component, and isophthalic acid, metahydroxybenzoic acid, 4,4''-dicarboxybiphenyl, 2,6-
Naphthalene dicarboxylic acid, 4.4゛-dicarboxydiphenyl ether, resorcinol, hydroquinone, 2゜6
Dihydroxynaphthalene, 4,4゛-dihydroxybiphenyl, 2-phenylhydroquinone, 2,2-bis(
In addition to aromatic components such as 4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, 2.2-bis(4-βhydroxyethoxyphenyl)propane, and bis(4-βhydroxyethoxyphenyl)sulfone,
Malonic acid, succinic acid, speric acid, adipic acid, azelaic acid, sebacic acid, dodecanniic acid, eiconic acid, trimethylene glycol, propylene glycol, 1.4-
Appropriate copolymerization of aliphatic components such as butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, polyethylene glycol, etc., and alicyclic components such as 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexane dimetatool, etc. It may be included as a component, and may also contain additives such as flame retardants, heat-resistant agents, light-resistant agents, matting agents, and pigments.
上記のうち、特に好ましいのは■のタイプのポリエステ
ルであり、ｐ−ヒドロキシ安息香酸成分が３０〜７４モ
ル％、テレフタル酸成分３５〜７４モル％、エチレング
リコール３５〜１３モル％からなるポリエステルは溶融
成型性・加工性に優れており、例えばポリエチレンテレ
フタレートとアセトキシ安息香酸とを混合し、次いで加
温し溶融してアシドリシス反応を行い、更に減圧し重合
させる方法で製造することができる。Among the above, particularly preferred is type (1) polyester, which is a polyester containing 30 to 74 mol% of p-hydroxybenzoic acid component, 35 to 74 mol% of terephthalic acid component, and 35 to 13 mol% of ethylene glycol. It has excellent moldability and processability, and can be produced, for example, by mixing polyethylene terephthalate and acetoxybenzoic acid, then heating and melting to perform an acidolysis reaction, and then polymerizing under reduced pressure.
次に本発明におけるサーモトロピック液晶性ポリエステ
ルからなるフィルムの製造方法としては、インフレーシ
ョン法が有効で、それにはサーモトロピック液晶性ポリ
エステルからなる任意のものが選ばれる。その場合は長
さ方向（ＭＤ）とこれに直角の方向（ＴＤ）の配向度合
のバランスがとれていることが実用上好ましく、引張り
強度であられした場合、ＭＤとＴＤＯ比が５：１〜１：
３さらに好ましくは４：ｌ〜１：２であることがよい。Next, as a method for producing a film made of thermotropic liquid crystalline polyester in the present invention, an inflation method is effective, and any film made of thermotropic liquid crystalline polyester can be selected for this method. In that case, it is practically preferable that the degree of orientation in the longitudinal direction (MD) and the direction perpendicular to this direction (TD) be balanced, and in the case of tensile strength, the MD to TDO ratio is 5:1 to 1. :
3, more preferably 4:1 to 1:2.
成型品のロールカレンダ処理はスチールニスチー ルロ
ールカレンダが好ましいが、スチール：ゴム系ロールお
よび／またはゴム系ロール：ゴム系ロールでも差し支え
ない。また、ロールの加圧方法は、バネ式および機械式
、油圧、エアー、電磁、水圧式環如何なる方法を用いて
も良く、好ましくは加圧力の大きい方がよい。ロール加
熱方法は、媒体加熱や誘導加熱等あるが加圧力に見合っ
たロール温度の設定が大切であり、加熱方法は如何なる
方法を用いても良い。For roll calendering of molded products, a steel varnish roll calender is preferred, but steel: rubber rolls and/or rubber rolls: rubber rolls may also be used. Further, the method for pressurizing the roll may be any one of spring type, mechanical type, hydraulic pressure, air type, electromagnetic type, and hydraulic ring type, and preferably, the higher the pressure is, the better. Roll heating methods include medium heating, induction heating, etc., but it is important to set the roll temperature commensurate with the pressing force, and any heating method may be used.
（実施例） 以下実施例により本発明をさらに具体的に説明する。(Example) The present invention will be explained in more detail with reference to Examples below.
実施例１、比較例１〜３
固有粘ルが０．７１のポリエステルのチップとｐ−アセ
トキシ安息香酸の粉末とを２０／８０のモル比で反応機
に仕込み、反応機中で減圧下、原料を充分乾燥したのち
窒素ガスを微量流しながら、２８０″Ｃに昇温し、すべ
ての原料が溶融してから４０分間その温度に保って酢酸
を流出させ、アシドリシス反応をおこなった。その後、
９０分間でフルハキュウム（ＩＴｏｒｒ）となるような
減圧スケジュールで減圧を開始、溶融相で重縮合反応さ
せてから常法によりチップ化した。得られたポリエステ
ル樹脂の融解温度は２８０ ”Ｃで陳温結晶化温度は２
２０°Ｃ、ガラス転移温度は７９°Ｃで、熔融下で液晶
性を示し、固有粘度ガラス０．７２であった。このポリ
マーをインフレーション法で製膜して得られた厚さ５０
μの二軸配向フィルムについて次のような実験をおこな
った。Example 1, Comparative Examples 1 to 3 Polyester chips with an intrinsic viscosity of 0.71 and p-acetoxybenzoic acid powder were charged into a reactor at a molar ratio of 20/80, and the raw materials were mixed under reduced pressure in the reactor. After sufficiently drying, the temperature was raised to 280''C while flowing a small amount of nitrogen gas, and after all the raw materials had melted, the temperature was kept at that temperature for 40 minutes to allow acetic acid to flow out and an acidolysis reaction was performed.After that,
Depressurization was started according to a depressurization schedule such that full hacuum (ITorr) was achieved in 90 minutes, a polycondensation reaction was performed in the molten phase, and then chips were formed by a conventional method. The melting temperature of the obtained polyester resin was 280"C, and the crystallization temperature was 2.
The temperature was 20°C, the glass transition temperature was 79°C, it exhibited liquid crystallinity under melting, and the glass had an intrinsic viscosity of 0.72. A film with a thickness of 50 mm obtained by forming this polymer by the inflation method
The following experiment was conducted on a μ biaxially oriented film.
本発明における融点の求め方は、示差熱走査熱量測定装
置（Ｐｅｒｋｉｎ Ｅ１ｍｅｒ社製）を使用し、試料約
１５■を２０°Ｃの昇温・陵部速度で測定した。The melting point in the present invention was determined using a differential thermal scanning calorimeter (manufactured by Perkin Elmer) on approximately 15 cm of a sample at a heating rate of 20° C. and a ridge speed.
ガラス転移温度は粘弾性測定装置Ｒｈｅｏｖｉｂｒｏｎ
を使用し、２°Ｃ／分の昇温速度で測定した。The glass transition temperature is measured using the viscoelasticity measuring device Rheovibron.
The measurement was carried out using a heating rate of 2°C/min.
（１）ロールカレンダー処理；
マクナパワーロールカレンダ（ベルマテンク社製）を用
い線圧１５０．３００．３５ｏｏｋｇ／Ｃｌ１１、ロー
ル温度５０．１６０．２９０″Ｃ、ロール周速３ｍ／分
の条件でフィルムを処理した。(1) Roll calendering: Process the film using a Macna Power roll calender (manufactured by Belmatenk) under the conditions of linear pressure 150.300.35ookg/Cl11, roll temperature 50.160.290″C, and roll circumferential speed 3m/min. did.
（２）厚みムラの評価；
ＭＩＣＲＯＦＩＮＥ厚み計（ユニオンツール社製）を用
い幅３０ｃｍのフィルムをＩＣｌｌＩ間隔で測定し平均
値とバラツキで表示した。(2) Evaluation of thickness unevenness: A film with a width of 30 cm was measured at ICllI intervals using a MICROFINE thickness meter (manufactured by Union Tool Co., Ltd.), and the average value and variation were expressed.
（３）フィルムの力学的性質変化の評価；ロールカレン
ダー処理前後のフィルムの引張り強度を比較した。(3) Evaluation of changes in mechanical properties of the film: The tensile strength of the film before and after roll calendering was compared.
これらの実験結果をまとめたのが表１である。Table 1 summarizes these experimental results.
この表からロールカレンダー処理は力学的性質をほとん
ど低下させずに厚みムラを軽減するのにきわめて有効で
あることがわかる。It can be seen from this table that roll calendering is extremely effective in reducing thickness unevenness without substantially reducing mechanical properties.
表１
（発明の効果）
本発明の方法は、インフレーションで製造した液晶ポリ
マーフィルムの欠点である厚みムラを軽減するのに効果
があり、工業的に実施することが容易であって、その価
値はきわめて高いものである。Table 1 (Effects of the invention) The method of the present invention is effective in reducing thickness unevenness, which is a drawback of liquid crystal polymer films produced by inflation, and is easy to implement industrially. It is extremely expensive.
特許出願人 ユニチカ株式会社Patent applicant: Unitika Co., Ltd.
Claims (1)
チレングリコールを主成分とするサーモトロピック液晶
性ポリエステルからなるフィルム乃至シートを（Ａ）フ
ィルム乃至シートの温度がガラス転移温度以上融解温度
以下の温度範囲内、（Ｂ）ロールカレンダの線圧が１０
０ｋｇ／ｃｍ以上、３０００ｋｇ／ｃｍ以下の範囲内で
ロールカレンダ処理することを特徴とする液晶ポリマー
フィルム乃至シートの製造法。(1) A film or sheet made of thermotropic liquid crystalline polyester containing p-hydroxybenzoic acid, terephthalic acid, and ethylene glycol as main components (A) The temperature of the film or sheet is within a temperature range of not less than the glass transition temperature and not more than the melting temperature. , (B) The linear pressure of the roll calender is 10
A method for producing a liquid crystal polymer film or sheet, characterized by performing roll calender treatment within a range of 0 kg/cm or more and 3000 kg/cm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29468090A JPH04166309A (en) | 1990-10-30 | 1990-10-30 | Manufacture of liquid crystalline polymer film or sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29468090A JPH04166309A (en) | 1990-10-30 | 1990-10-30 | Manufacture of liquid crystalline polymer film or sheet |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04166309A true JPH04166309A (en) | 1992-06-12 |
Family
ID=17810917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29468090A Pending JPH04166309A (en) | 1990-10-30 | 1990-10-30 | Manufacture of liquid crystalline polymer film or sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04166309A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5534209A (en) * | 1994-03-15 | 1996-07-09 | Japan Gore-Tex, Inc. | Method for manufacturing a liquid crystal polymer film and a liquid crystal polymer film made thereby |
| US6027771A (en) * | 1993-02-25 | 2000-02-22 | Moriya; Akira | Liquid crystal polymer film and a method for manufacturing the same |
| US7030181B2 (en) | 2001-04-11 | 2006-04-18 | Eastman Chemical Company | Films prepared from plasticized polyesters |
| US7235623B2 (en) | 2003-11-26 | 2007-06-26 | Eastman Chemical Company | Polyester compositions for calendering |
| US7285587B2 (en) | 2002-12-20 | 2007-10-23 | Eastman Chemical Company | Flame retardant polyester compositions for calendering |
| US7354653B2 (en) | 2003-12-18 | 2008-04-08 | Eastman Chemical Company | High clarity films with improved thermal properties |
-
1990
- 1990-10-30 JP JP29468090A patent/JPH04166309A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6027771A (en) * | 1993-02-25 | 2000-02-22 | Moriya; Akira | Liquid crystal polymer film and a method for manufacturing the same |
| US5534209A (en) * | 1994-03-15 | 1996-07-09 | Japan Gore-Tex, Inc. | Method for manufacturing a liquid crystal polymer film and a liquid crystal polymer film made thereby |
| US7030181B2 (en) | 2001-04-11 | 2006-04-18 | Eastman Chemical Company | Films prepared from plasticized polyesters |
| US7285587B2 (en) | 2002-12-20 | 2007-10-23 | Eastman Chemical Company | Flame retardant polyester compositions for calendering |
| US7235623B2 (en) | 2003-11-26 | 2007-06-26 | Eastman Chemical Company | Polyester compositions for calendering |
| US7354653B2 (en) | 2003-12-18 | 2008-04-08 | Eastman Chemical Company | High clarity films with improved thermal properties |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1169748A (en) | Multiaxially oriented high performance laminates comprised of uniaxially oriented sheets of thermotropic liquid crystal polymers | |
| US6656578B2 (en) | Process for producing aromatic liquid crystalline polyester and film thereof | |
| JPS61130046A (en) | Manufacture of laminated film | |
| CN102362217A (en) | White film for reflector | |
| JPS6289722A (en) | Polyester from 3-hydroxy-4'-(4-hydroxyphenyl) benzophenone or 3, 4'-dihydroxybenzophenone and carboxylic acid | |
| JPH04166309A (en) | Manufacture of liquid crystalline polymer film or sheet | |
| JPS6189816A (en) | Manufacture of laminated film | |
| KR101831879B1 (en) | Polyester fiber using binder Having Advanced Adhesive Strength | |
| JPH04166323A (en) | Manufacture of liquid crystalline polymer film and sheet | |
| JPS6232029A (en) | Polyester film and its preparation | |
| JPH04168129A (en) | Production of liquid crystal polymer film | |
| JP2001342243A (en) | Aromatic liquid crystal polyester film and method for producing the same | |
| JP5492569B2 (en) | Polyester resin, process for producing the same, and biaxially oriented polyester film using the same | |
| JPH0462144A (en) | Treatment of liquid crystal polymer molded article | |
| JPH03152132A (en) | Liquid crystal polymer film and production thereof | |
| JPS5853418A (en) | Preparation of polyester film | |
| KR101525826B1 (en) | White film and A method of manufacturing Opaque White film | |
| US5132068A (en) | Processes for producing transparent copolyester films | |
| JPS61148237A (en) | Molded polyester article and production thereof | |
| JPH04166322A (en) | Manufacture of liquid crystalline polymer film | |
| JP2016147985A (en) | Weather proof compact | |
| JPH0481426A (en) | Production of liquid crystalline polymer film | |
| JPS63101416A (en) | Wholly aromatic polyester polymer | |
| JPH03223339A (en) | Transparent polyester film and sheet | |
| JP3238424B2 (en) | Transparent polyester film, sheet and method for producing the same |