JPH04263920A - Biaxially oriented polyester film - Google Patents
Biaxially oriented polyester filmInfo
- Publication number
- JPH04263920A JPH04263920A JP3023523A JP2352391A JPH04263920A JP H04263920 A JPH04263920 A JP H04263920A JP 3023523 A JP3023523 A JP 3023523A JP 2352391 A JP2352391 A JP 2352391A JP H04263920 A JPH04263920 A JP H04263920A
- Authority
- JP
- Japan
- Prior art keywords
- film
- particle size
- polyester
- antimony
- weight
- 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
- 229920006267 polyester film Polymers 0.000 title claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 30
- -1 imide compound Chemical class 0.000 claims abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 9
- 150000001463 antimony compounds Chemical class 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 abstract 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 36
- 229920000728 polyester Polymers 0.000 description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 13
- 239000003063 flame retardant Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical class [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000003746 surface roughness Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QRFTXHFUNIFHST-UHFFFAOYSA-N 4,5,6,7-tetrabromoisoindole-1,3-dione Chemical compound BrC1=C(Br)C(Br)=C2C(=O)NC(=O)C2=C1Br QRFTXHFUNIFHST-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 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
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical group C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical group O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-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
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HVYVMSPIJIWUNA-UHFFFAOYSA-N triphenylstibine Chemical compound C1=CC=CC=C1[Sb](C=1C=CC=CC=1)C1=CC=CC=C1 HVYVMSPIJIWUNA-UHFFFAOYSA-N 0.000 description 1
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は耐有機溶剤性に優れた難
燃性ポリエステルフィルムに関する。さらに詳しくは、
本発明はポリエステル自身の有する優れた機械的強度、
熱的性質、電気特性、耐薬品性等の特長を損なうことな
く難燃性が付与されたポリエステルフィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester film having excellent resistance to organic solvents. For more details,
The present invention is characterized by the excellent mechanical strength of polyester itself,
This invention relates to a polyester film that is imparted with flame retardancy without sacrificing features such as thermal properties, electrical properties, and chemical resistance.
【０００２】0002
【従来の技術および発明が解決しようとする課題】一般
に、ポリアルキレンテレフタレートを主成分とするポリ
エステルは高融点、高結晶性を有し、機械的強度、電気
絶縁性、寸法安定性、耐薬品性等の物理的、化学的特性
に優れているため、繊維、フィルム、成形材料として工
業的に広く利用されている。特に電気機器、自動車部品
等に使用されるフレキシブルプリント配線基板、面状発
熱体、メンブレンスイッチ等は汎用化されている用途で
ある。[Prior Art and Problems to be Solved by the Invention] Generally, polyester containing polyalkylene terephthalate as a main component has a high melting point and high crystallinity, and has good mechanical strength, electrical insulation, dimensional stability, and chemical resistance. Because of its excellent physical and chemical properties, it is widely used industrially as fibers, films, and molding materials. In particular, flexible printed wiring boards, sheet heating elements, membrane switches, etc. used in electrical equipment, automobile parts, etc. are widely used applications.
【０００３】しかしながら、ポリエステルは本質的に可
燃性であり、一度着火すると激しく燃焼することがよく
知られており、火災予防的見地からポリエステルに難燃
性を付与することが強く望まれている。一般にポリエス
テル成形体を難燃化する手段として、臭素などのハロゲ
ン含有化合物、リン化合物、金属化合物などをポリエス
テルに添加混合または共重合し溶融押出成形するかある
いは成形体の表面にこれら難燃性化合物を塗布する方法
が知られており、例えば特公昭５３−２９１９５号公報
、特公昭５５−５０９８５号公報、特公昭６２−６１２
３５号公報、あるいは特公平１−２０６６６号公報に具
体例が示されている。[0003] However, it is well known that polyester is essentially flammable and burns violently once ignited, so it is strongly desired to impart flame retardancy to polyester from the standpoint of fire prevention. Generally, as a means to make polyester molded bodies flame retardant, halogen-containing compounds such as bromine, phosphorus compounds, metal compounds, etc. are added to polyester, mixed or copolymerized, and melt extrusion molded, or these flame-retardant compounds are added to the surface of the molded body. For example, Japanese Patent Publication No. 53-29195, Japanese Patent Publication No. 55-50985, and Japanese Patent Publication No. 62-612.
Specific examples are shown in Publication No. 35 or Japanese Patent Publication No. 1-20666.
【０００４】しかしながら、難燃性化合物はそれ自身、
耐薬品性、特に耐有機溶剤性に乏しいものが多く、難燃
剤を含有するポリエステルを溶剤で処理すると難燃性を
損なうことがある。また、十分な難燃性を付与するため
には多量の難燃性化合物を添加する必要があり、そのた
め熱安定性や機械的強度等の物性低下を伴ったり、難燃
性化合物自身がポリエステルの成形温度で分解したり、
昇華したりする場合もある。特にフィルムが薄い場合は
、難燃剤に起因するゲル化物等の異物の生成や混入によ
って、フィルムの品質上あるいは製膜上致命的な欠陥と
なるため、適切な難燃化処理を施すことは極めて困難で
あった。However, flame retardant compounds themselves
Many polyesters have poor chemical resistance, especially resistance to organic solvents, and when polyester containing flame retardants is treated with a solvent, flame retardancy may be impaired. In addition, in order to impart sufficient flame retardancy, it is necessary to add a large amount of flame retardant compounds, which may result in a decrease in physical properties such as thermal stability and mechanical strength, or the flame retardant compounds themselves may Decomposes at molding temperature,
Sometimes it is sublimated. In particular, if the film is thin, it is extremely difficult to apply appropriate flame retardant treatment, as the formation or contamination of foreign substances such as gelled substances caused by flame retardants can cause fatal defects in film quality or film production. It was difficult.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
に鑑み鋭意検討した結果、ある特定の有機臭素化合物お
よびアンチモン化合物を特定量、ポリエステルに添加す
ることにより、ポリエステルの特性を損なうことなく難
燃性を付与し得ることを見いだし、本発明を完成するに
至った。すなわち本発明の要旨は、融点が２８０℃以上
、平均粒径が０．１〜１０μｍであり、分子内に臭素元
素および２個以上の窒素元素を有するイミド化合物（Ａ
）を臭素元素量として１〜２０重量％、平均粒径が０．
１〜１０μｍのアンチモン化合物（Ｂ）をアンチモン元
素量として１〜２０重量％、含有してなる、極限粘度が
０．４〜１．０である二軸延伸ポリエステルフィルムに
存する。[Means for Solving the Problems] As a result of intensive studies in view of the above-mentioned problems, the present inventors have found that by adding a specific amount of a specific organic bromine compound and an antimony compound to polyester, the properties of polyester may be impaired. The present inventors have discovered that flame retardancy can be imparted without the need for oxidation, and have completed the present invention. That is, the gist of the present invention is to provide an imide compound (A
) with a bromine element content of 1 to 20% by weight, and an average particle size of 0.
A biaxially stretched polyester film having an intrinsic viscosity of 0.4 to 1.0 and containing an antimony compound (B) of 1 to 10 μm in an amount of 1 to 20% by weight as an antimony element.
【０００６】以下、本発明を詳細に説明する。本発明で
いう熱可塑性ポリエステルとは、テレフタル酸、２，６
−ナフタレンジカルボン酸のような芳香族ジカルボン酸
またはそのエステルと、エチレングリコールを主たる出
発原料として得られるポリエステルを指すが、他の第三
成分を含有していても構わない。この場合、ジカルボン
酸成分としては、イソフタル酸、フタル酸、２，６−ナ
フタレンジカルボン酸、テレフタル酸、アジピン酸、セ
バシン酸、およびオキシカルボン酸成分（例えばｐ−オ
キシエトキシ安息香酸）などの一種または二種以上を用
いることがてきる。グリコール成分としては、エチレン
グリコール、プロピレングリコール、ブタンジオール、
１，４−シクロヘキサンジメタノール、ネオペンチルグ
リコールなどの一種または二種以上を用いることができ
る。The present invention will be explained in detail below. The thermoplastic polyester referred to in the present invention refers to terephthalic acid, 2,6
- It refers to a polyester obtained using an aromatic dicarboxylic acid such as naphthalene dicarboxylic acid or its ester and ethylene glycol as the main starting materials, but it may contain other third components. In this case, the dicarboxylic acid component is one or more of isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, terephthalic acid, adipic acid, sebacic acid, and oxycarboxylic acid component (for example, p-oxyethoxybenzoic acid). Two or more types can be used. Glycol components include ethylene glycol, propylene glycol, butanediol,
One or more types of 1,4-cyclohexanedimethanol, neopentyl glycol, etc. can be used.
【０００７】いずれにしても本発明のポリエステルは繰
り返し構造単位の８０％以上、さらに好ましくは９０％
以上がエチレンテレフタレート単位またはエチレン−２
，６−ナフタレート単位を有するポリエステルである。
また、本発明においては、かかるポリエステルの重合度
が低すぎると機械的強度が低下するし、逆に高すぎると
燃焼時に溶融物の溶融粘度が高く熱を放散しにくいため
か、難燃性評価法（例えばＪＩＳ Ｋ−７２０１）に
おける酸素指数（ＬＯＩ）が低下する傾向があり好まし
くない。従って、本発明におけるポリエステルフィルム
の極限粘度は０．４〜１．０、好ましくは０．５〜０．
９、さらに好ましくは０．５５〜０．８の範囲である。In any case, the polyester of the present invention has at least 80%, more preferably 90%, of repeating structural units.
The above is ethylene terephthalate unit or ethylene-2
, 6-naphthalate units. In addition, in the present invention, if the polymerization degree of the polyester is too low, the mechanical strength will decrease, and if it is too high, the melt viscosity of the melt will be high and it will be difficult to dissipate heat. The oxygen index (LOI) in the method (for example, JIS K-7201) tends to decrease, which is not preferable. Therefore, the intrinsic viscosity of the polyester film in the present invention is 0.4-1.0, preferably 0.5-0.
9, more preferably in the range of 0.55 to 0.8.
【０００８】本発明において用いる必須成分の一つであ
る化合物（Ａ）は、融点が２８０℃以上で分子内に臭素
元素および２個以上の窒素元素を有するイミド化合物で
あり、それは熱可塑性ポリエステルの難燃剤として作用
するものである。具体的にはエチレンビステトラブロモ
フタルイミド（下記（１）式）、あるいはエチレン（５
，６−ジブロモノルボルネン−２，３−ジカルボキシイ
ミド）（下記（２）式）等が挙げられるが、特に前者が
好ましく用いられる。Compound (A), which is one of the essential components used in the present invention, is an imide compound having a melting point of 280°C or higher and having a bromine element and two or more nitrogen elements in the molecule, and it is a thermoplastic polyester. It acts as a flame retardant. Specifically, ethylene bistetrabromophthalimide (formula (1) below) or ethylene (5
, 6-dibromonorbornene-2,3-dicarboximide) (formula (2) below), and the former is particularly preferably used.
【０００９】[0009]
【化１】[Chemical formula 1]
【００１０】これらの化合物は水および一般有機溶剤に
実質的に不溶である。一般にポリエチレテレフタレート
、ポリエチレンナフタレート等のポリエステルのフィル
ムは３００℃前後の高温下で製膜されるため、融点が２
８０℃未満である低分子化合物あるいはモノイミド化合
物は昇華が顕著であり、また、これらの化合物の分解温
度は融点に近いため好ましくない。These compounds are substantially insoluble in water and common organic solvents. Polyester films such as polyethylene terephthalate and polyethylene naphthalate are generally formed at high temperatures of around 300°C, so their melting point is 2.
Low-molecular compounds or monoimide compounds whose temperature is lower than 80°C are not preferred because they sublimate significantly and the decomposition temperature of these compounds is close to their melting point.
【００１１】本発明で用いる化合物（Ａ）の平均粒径は
０．１〜１０μｍであり、好ましくは０．１〜７μｍ、
さらに好ましくは０．２〜５μｍである。平均粒径が０
．１μｍ未満であると、最終的にフィルムとしたときの
滑り性が悪くなり、生産性に劣るため好ましくない。
一方、平均粒径が１０μｍを越えると、製膜時にフィル
ターが閉塞しやすくなったり、最終的に得られるフィル
ム中の粗大粒子量が増大して機械的強度が低下したりす
る。また、粒子の比表面積も小さくなり、難燃性が低下
するため好ましくない。The average particle size of the compound (A) used in the present invention is 0.1 to 10 μm, preferably 0.1 to 7 μm,
More preferably, it is 0.2 to 5 μm. Average particle size is 0
．． If it is less than 1 μm, the slipperiness of the final film will be poor, resulting in poor productivity, which is not preferable. On the other hand, if the average particle size exceeds 10 μm, the filter tends to become clogged during film formation, and the amount of coarse particles in the final film increases, resulting in a decrease in mechanical strength. In addition, the specific surface area of the particles also decreases, which is undesirable because flame retardancy decreases.
【００１２】化合物（Ａ）の粒径分布は、粒径２５μｍ
以下が９５重量％以上であることが好ましく、さらに好
ましくは粒径２０μｍ以下が９７重量％以上、特に好ま
しくは粒径が１５μｍ以下が９９重量％以上である。２
５μｍを超える粒子が５重量％を超えて存在すると、薄
いフィルムとした場合、製膜時の破断が多発し、生産性
が劣るだけでなく、電気特性を低下させるため好ましく
ない。化合物（Ａ）のフィルムへの添加量は臭素元素量
として１〜２０重量％、好ましくは３〜１０重量％であ
る。添加量が１重量％未満では難燃効果が不十分であり
、２０重量％を超えると機械的強度の低下が著しく好ま
しくない。The particle size distribution of compound (A) is 25 μm.
It is preferable that the following is 95% by weight or more, more preferably 97% by weight or more is particle size of 20 μm or less, and particularly preferably 99% by weight or more is particle size of 15 μm or less. 2
If particles larger than 5 μm are present in an amount exceeding 5% by weight, when a thin film is formed, breakage occurs frequently during film formation, which not only deteriorates productivity but also deteriorates electrical properties, which is not preferable. The amount of compound (A) added to the film is 1 to 20% by weight, preferably 3 to 10% by weight as the amount of bromine element. If the amount added is less than 1% by weight, the flame retardant effect will be insufficient, and if it exceeds 20% by weight, the mechanical strength will drop significantly, which is undesirable.
【００１３】本発明において用いられる（Ｂ）成分であ
る平均粒径が０．１〜１０μｍのアンチモン化合物は、
上記（Ａ）成分と併用添加することにより相乗的に難燃
性を向上させる難燃助剤として作用するものであり、か
かるアンチモン化合物としては各種のものが使用できる
。具体的には三酸化アンチモン、五酸化アンチモンなど
の酸化アンチモン、リン酸アンチモン、アンチモン酸ソ
ーダ、トリフェニルスチビンなどが挙げられ、中でも酸
化アンチモンが好ましい。The antimony compound having an average particle size of 0.1 to 10 μm, which is the component (B) used in the present invention, is
When added together with component (A), it acts as a flame retardant aid that synergistically improves flame retardancy, and various antimony compounds can be used. Specific examples include antimony oxides such as antimony trioxide and antimony pentoxide, antimony phosphate, sodium antimonate, and triphenylstibine, and among them, antimony oxide is preferred.
【００１４】これらのアンチモン化合物の平均粒径は（
Ａ）成分同様０．１〜１０μｍであることが必要であり
、好ましくは０．１〜７μｍ、さらに好ましくは０．２
〜５μｍである。また、かかる粒子の粒径分布は粒径２
５μｍ以下が９５重量％以上であることが好ましく、さ
らに好ましくは粒径２０μｍ以下が９７重量％以上、特
に好ましくは粒径が１５μｍ以下が９９重量％以上であ
る。化合物（Ｂ）のフィルムへの添加量はアンチモン元
素量として１〜２０重量％、好ましくは２〜１０重量％
である。添加量が１重量％未満では難燃効果が不十分で
あり、２０重量％を超えると機械的強度の低下が著しく
好ましくない。The average particle size of these antimony compounds is (
Like component A), it needs to be 0.1 to 10 μm, preferably 0.1 to 7 μm, more preferably 0.2
~5 μm. In addition, the particle size distribution of such particles is particle size 2
It is preferable that 95% by weight or more is 5 μm or less, more preferably 97% by weight or more is particle size 20 μm or less, and particularly preferably 99% by weight or more is particle size 15 μm or less. The amount of compound (B) added to the film is 1 to 20% by weight, preferably 2 to 10% by weight as the amount of antimony element.
It is. If the amount added is less than 1% by weight, the flame retardant effect will be insufficient, and if it exceeds 20% by weight, the mechanical strength will drop significantly, which is undesirable.
【００１５】本発明のポリエステルフィルムは、ポリエ
ステルと上記（Ａ）および（Ｂ）成分をポリエステルの
融点以上において溶融混練後シート化して得ることがで
きる。すなわち、かかる組成物を原料として、押出機に
て通常２６０〜３２０℃の温度で溶融混練し、ダイから
シート状に押出し、約７０℃以下の温度に冷却して実質
的に無定形のシートとする。次いで得られたシート状物
を縦および／または横方向に面積倍率で４倍以上、好ま
しくは８倍以上延伸し、さらに１５０〜２５０℃の温度
で熱処理を行うことにより製造することができる。The polyester film of the present invention can be obtained by melt-kneading the polyester and the components (A) and (B) above at a temperature higher than the melting point of the polyester, and then forming the film into a sheet. That is, such a composition is used as a raw material, melt-kneaded in an extruder at a temperature of usually 260 to 320°C, extruded from a die into a sheet, and cooled to a temperature of about 70°C or less to form a substantially amorphous sheet. do. Next, the obtained sheet-like product is stretched in the longitudinal and/or transverse directions by an area magnification of 4 times or more, preferably 8 times or more, and further heat-treated at a temperature of 150 to 250°C.
【００１６】なお、本発明においては、かかる組成物の
製造方法については特に限定されるものではない。例え
ば、あらかじめポリエステルチップ、（Ａ）成分および
（Ｂ）成分を均一に混合して押出機ホッパーに投入する
こともできるし、より均一な分散性を得るため、あらか
じめポリエステル中に（Ａ）成分および／または（Ｂ）
成分を高濃度に配合した、いわゆるマスターチップとポ
リエステルチップとを混合する方法も好ましく用いられ
る。[0016] In the present invention, there are no particular limitations on the method for producing such a composition. For example, it is possible to uniformly mix the polyester chips, components (A) and components (B) in advance and charge the mixture into the extruder hopper, or to obtain more uniform dispersion, the components (A) and /or (B)
A method of mixing so-called master chips and polyester chips in which components are blended at high concentrations is also preferably used.
【００１７】本発明におけるポリエステルには、本発明
の目的を損なわない程度であれば、他の特性向上を目的
として種々の添加物を配合することができる。例えば、
滑剤、熱安定剤、染料、顔料、帯電防止剤、紫外線吸収
剤等の添加物か挙げられ、必要に応じ適切な方法で必要
量添加することができる。また、各種用途における必要
特性、例えば印刷インクや銀ペースト等との接着性を改
良するために各種表面処理を行うこともできる。かかる
表面処理としては例えば各種プライマー処理、コロナ放
電処理、フラズマ処理、紫外線照射処理、溶剤処理、イ
オンプレーティング処理等が挙げられるが必要に応じて
かかる表面処理を本発明のフィルムの片面または両面に
適当な時期必要な量だけ行うことができる。また、これ
らの処理方法を複数回行ってもよいし、両面に行う場合
は同一処理を行ってもよく、異なっていてもよい。Various additives may be added to the polyester of the present invention for the purpose of improving other properties, as long as they do not impair the purpose of the present invention. for example,
Additives include lubricants, heat stabilizers, dyes, pigments, antistatic agents, ultraviolet absorbers, and the like, and can be added in the required amount by an appropriate method as required. In addition, various surface treatments can be performed to improve properties required for various uses, such as adhesion to printing inks, silver pastes, etc. Examples of such surface treatments include various primer treatments, corona discharge treatments, plasma treatments, ultraviolet irradiation treatments, solvent treatments, ion plating treatments, etc. If necessary, such surface treatments may be applied to one or both sides of the film of the present invention. You can do it as much as you need at the appropriate time. Further, these processing methods may be performed multiple times, and when performed on both sides, the same processing may be performed or different processing methods may be performed.
【００１８】このようにして従来のポリエステルフィル
ムの機械的特性、電気的特性、耐薬品性等を損なうこと
なく難燃性を高度に付与したフィルムを得ることができ
るが、本発明においては、さらにフィルム表面の中心線
平均粗さ（Ｒａ）が０．０１〜１．０μｍであることが
好ましく、Ｒａは好ましくは０．０２〜０．８μｍの範
囲である。Ｒａが０．０１μｍ未満であると滑り性を十
分付与できない。また、Ｒａが１．０μｍを超えると、
例えばフレキシブルプリント基板等の二次加工工程での
加工性が極めて悪くなるため好ましくない。In this way, it is possible to obtain a film that is highly flame retardant without impairing the mechanical properties, electrical properties, chemical resistance, etc. of conventional polyester films, but in the present invention, It is preferable that the center line average roughness (Ra) of the film surface is 0.01 to 1.0 μm, and Ra is preferably in the range of 0.02 to 0.8 μm. If Ra is less than 0.01 μm, sufficient slipperiness cannot be imparted. Moreover, when Ra exceeds 1.0 μm,
For example, it is not preferable because the workability in the secondary processing process of flexible printed circuit boards etc. becomes extremely poor.
【００１９】また、本発明のフィルム表面の粗大突起数
、すなわち２μｍ以上の高さを有する突起数は１００個
／ｍｍ２ 以下であることが好ましく、かかる突起数は
好ましくは３０個／ｍｍ２ 以下、さらに好ましくは１
０個／ｍｍ２ 以下である。粗大突起数が１００個／ｍ
ｍ２ を超えると電気特性、特に絶縁破壊電圧の低下が
著しくなるため好ましくない。[0019] Furthermore, the number of coarse protrusions on the surface of the film of the present invention, that is, the number of protrusions having a height of 2 μm or more, is preferably 100 protrusions/mm2 or less, preferably 30 protrusions/mm2 or less, and Preferably 1
0 pieces/mm2 or less. Number of coarse protrusions is 100/m
If it exceeds m2, the electrical properties, especially the dielectric breakdown voltage, will drop significantly, which is not preferable.
【００２０】[0020]
【実施例】以下、本発明を実施例により具体的に説明す
るが、本発明はその要旨を越えない限り、以下の実施例
に限定されるものではない。なお、本発明での測定およ
び評価は以下のとおりである。
（１）極限粘度
ポリエステルチップまたはフィルム約２ｇをフェノール
／テトラクロロエタン（５０／５０重量比）１００ｍｌ
に加え、１００〜１１０℃で加熱し、次いで、遠心分離
法を用いて（Ａ）成分および（Ｂ）成分を除去した溶液
部分を用い、ポリエステル成分の濃度が１ｇ／１００ｍ
ｌとなるよう調節した後、常法に従って極限粘度を測定
した。測定温度は３０．０℃とした。[Examples] The present invention will be explained in detail below using examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Note that the measurements and evaluations in the present invention are as follows. (1) About 2 g of intrinsic viscosity polyester chips or film in 100 ml of phenol/tetrachloroethane (50/50 weight ratio)
In addition, using a solution portion heated at 100 to 110°C and then centrifuged to remove components (A) and (B), the concentration of the polyester component was 1 g/100 m
After adjusting to 1, the intrinsic viscosity was measured according to a conventional method. The measurement temperature was 30.0°C.
【００２１】（２）難燃性
アンダーライターラボラトリーズ社発行のプラスチック
材料の燃焼性試験規格ＵＬ９４の垂直燃焼試験法に準じ
ＵＬ９４ＶＴＭランクを判定した。また、ＪＩＳＫ−７
２０１規格酸素指数法により極限酸素濃度（ＬＯＩ）を
測定した。(2) Flame Retardancy The UL94VTM rank was determined according to the vertical combustion test method of the UL94 flammability test standard for plastic materials published by Underwriter Laboratories. Also, JISK-7
The ultimate oxygen concentration (LOI) was measured by the 201 standard oxygen index method.
【００２２】（３）引張破断強度
（株）インテスコ製引張試験機インテスコモデル２００
１型を用いて、温度２３℃、湿度５０％ＲＨに調節され
た室内において、長さ５０ｍｍ、幅１５ｍｍの試料フィ
ルムを１００ｍｍ／ｍｉｎの速度で引張り、引張応力−
ひずみ曲線より次式によって算出した。(3) Tensile strength at break: Tensile testing machine Intesco Model 200 manufactured by Intesco Co., Ltd.
Using Type 1, a sample film with a length of 50 mm and a width of 15 mm was pulled at a speed of 100 mm/min in a room controlled at a temperature of 23°C and a humidity of 50% RH, and the tensile stress -
It was calculated from the strain curve using the following formula.
【００２３】
σ＝Ｆ／Ａ
σ；引張破壊強度（ｋｇ／ｍｍ２ ）
Ｆ；破壊時における荷重（ｋｇ）
Ａ；試験片の元の断面積（ｍｍ２ ）
（４）絶縁破壊電圧
ＪＩＳ Ｃ−２３１８に準じて行った。すなわち、１
００ｋＶ直、交流耐電圧試験機を用い、２３℃、５０％
ＲＨの雰囲気下にて１０００Ｖ／秒の昇圧速度で上昇さ
せ、フィルムが破壊し短絡したときの電圧を読みとった
。σ=F/A σ: Tensile breaking strength (kg/mm2) F: Load at breakdown (kg) A: Original cross-sectional area of test piece (mm2) (4) Dielectric breakdown voltage JIS C-2318 I followed the instructions. That is, 1
00kV direct, using an AC withstanding voltage tester, 23℃, 50%
The voltage was increased at a rate of 1000 V/sec in an RH atmosphere, and the voltage was read when the film was destroyed and a short circuit occurred.
【００２４】（５）中心線平均粗さ Ｒａ（μｍ）（
株）小坂研究所製表面粗さ測定機ＳＥ−３Ｆ型を使用し
、ＪＩＳ Ｂ−０６０１−１９７６の方法に準じて測
定した。詳細条件として触針径２μｍ、触針圧３０ｍｇ
、カットオフ値０．８ｍｍとし、フィルム表面から１２
本の断面曲線を求めて、それぞれのＲａ値を計算し、そ
の最大最小値を除いた１０本の平均値をそのフィルムの
中心線平均粗さＲａ（μｍ）とした。(5) Center line average roughness Ra (μm) (
The surface roughness was measured using a surface roughness measuring machine model SE-3F manufactured by Kosaka Laboratory Co., Ltd. according to the method of JIS B-0601-1976. Detailed conditions: stylus diameter 2μm, stylus pressure 30mg
, the cutoff value is 0.8 mm, and the distance from the film surface is 12 mm.
The cross-sectional curve of the book was determined, and the Ra value of each was calculated, and the average value of 10 curves excluding the maximum and minimum values was taken as the centerline average roughness Ra (μm) of the film.
【００２５】（６）粗大突起数（個／ｍｍ２ ）（株）
小坂研究所製表面粗さ測定機ＳＥ−３ＡＫ型を使用し、
触針径５μｍ、触針圧３０ｍｇ、カットオフ値０．８ｍ
ｍの条件にて、測定長さ２．５ｍｍ、サンプリングピッ
チ５μｍで５００本の走査を行い、突起高さと突起数を
測定した。ここでいう突起高さ（Ｘ，μｍ）は突起個数
が最大になる点の高さをＯレベルとし、このレベルから
の高さをもって突起高さとし（各突起高さにおける突起
数（Ｙ，個／ｍｍ２ ）の関係を図式化し、分布曲線と
して表わし、かかる分布曲線から３μｍを超える突起総
数をもって粗大突起数（個／ｍｍ２）とした）、測定は
フィルム長手方向に３点、それと直角方向に３点、計６
点行い、その平均値を測定値（個／ｍｍ２ ）とした。(6) Number of coarse protrusions (pcs/mm2) Co., Ltd.
Using the surface roughness measuring machine SE-3AK manufactured by Kosaka Laboratory,
Stylus diameter 5μm, stylus pressure 30mg, cutoff value 0.8m
The protrusion height and number of protrusions were measured by scanning 500 lines with a measurement length of 2.5 mm and a sampling pitch of 5 μm under the conditions of m. The protrusion height (X, μm) here is defined as the height of the point where the number of protrusions is maximum (O level), and the height from this level is the protrusion height (number of protrusions (Y, number/μm) at each protrusion height). mm2), and expressed it as a distribution curve, and from this distribution curve, the total number of protrusions exceeding 3 μm was defined as the number of coarse protrusions (pieces/mm2)), and the measurement was performed at 3 points in the longitudinal direction of the film and 3 points in the direction perpendicular to it. , total 6
The points were measured and the average value was taken as the measured value (pieces/mm2).
【００２６】（７）滑り性
平滑なガラス板上に、幅１５ｍｍ、長さ１５０ｍｍに切
り出したフィルム同士を２枚重ねてその上にゴム板を載
せ、さらにその上に２枚のフィルムの接圧が２ｇ／ｃｍ
２ となるよう荷重を載せて、２０ｍｍ／ｍｉｎでフィ
ルム同士を滑らせて摩擦力を測定し、５ｍｍ滑らせた点
での摩擦係数を動摩擦係数（Ｆ／Ｆμｄ）とし、下に示
す基準でランク分けした。(7) Sliding properties Two films cut out to a width of 15 mm and a length of 150 mm are stacked on top of each other on a smooth glass plate, a rubber plate is placed on top of that, and the contact pressure of the two films is placed on top of that. is 2g/cm
2. Measure the frictional force by sliding the films against each other at 20mm/min with a load applied so that I divided it.
【００２７】なお、測定は温度２３℃±１℃、温度５０
％±５％ＲＨの雰囲気で行った。
Ｆ／Ｆμｄ≦０．５０ …………………… ○（良
好）０．５０＜Ｆ／Ｆμｄ≦０．７０ ……… △
（普通）０．７０＜Ｆ／Ｆμｄ ……………………
×（不良）（８）粒子の平均粒径
（株）島津製作所製遠心沈降式粒度分布測定機ＳＡ−Ｃ
Ｐ３型を使用し、粉体試料を分散媒体中に均一に分散さ
せた懸濁液にて等価球形粒度分布を測定し、得られた粒
度分布測定値における積算値（重量基準）の５０％に相
当する等価球形粒度値を平均粒径とした。[0027] The measurement was carried out at a temperature of 23°C ± 1°C and a temperature of 50°C.
The test was carried out in an atmosphere of %±5% RH. F/Fμd≦0.50 ………………… ○ (Good) 0.50<F/Fμd≦0.70 ……… △
(Normal) 0.70<F/Fμd ………………
× (defective) (8) Average particle size of particles Centrifugal sedimentation type particle size distribution analyzer SA-C manufactured by Shimadzu Corporation
Using the P3 model, measure the equivalent spherical particle size distribution in a suspension in which the powder sample is uniformly dispersed in a dispersion medium, and calculate the particle size distribution to 50% of the integrated value (weight basis) in the obtained particle size distribution measurement value. The corresponding equivalent spherical particle size value was taken as the average particle size.
【００２８】（９）製膜性評価
溶融押出しした無定形シートを縦延伸後、横延伸する工
程において、溶融押出し、延伸あるいは熱固定時にフィ
ルムが破断する状況を次に示す３ランクにて判定評価し
た。(9) Evaluation of Film Formability In the process of vertically stretching and then laterally stretching a melt-extruded amorphous sheet, the situation in which the film breaks during melt-extrusion, stretching, or heat setting is judged and evaluated using the following three ranks. did.
【００２９】
○；ほとんどフィルム破断を起こさず生産性良好である
△；時々フィルム破断を生じ生産性に劣る×；頻繁に破
断を生じ、生産性が極めて悪い（１０）耐有機溶剤性
フィルムを汎用の有機溶剤であるメタノール、アセトン
、ベンゼンおよびクロロホルムに浸漬し、難燃剤の溶出
の有無を観察し、次に示すランクにて判定評価した。○: Almost no film breakage and good productivity △: Occasional film breakage and poor productivity ×: Frequent breakage and extremely poor productivity (10) Organic solvent resistant film is used for general purpose The samples were immersed in organic solvents such as methanol, acetone, benzene, and chloroform, and the presence or absence of flame retardant elution was observed and evaluated using the following ranks.
【００３０】
○；いずれの有機溶剤にも溶出しない
×；いずれかの有機溶剤に溶出する
実施例１
平均粒径２．０μｍのエチレンビステトラブロモフタル
イミド（１）、平均粒径０．７μｍの三酸化アンチモン
および極限粘度０．８３のポリエチレンテレフタレート
チップを１５０℃で１５時間乾燥後、各２７０℃、２９
０℃にて混練し、極限粘度０．５５、および０．６５の
４０重量％マスターバッチ（以下Ｍ．Ｂ．と略す）チッ
プを得た。得られた２種のＭ．Ｂ．を各臭素およびアン
チモン元素量が表１に示す配合量となるよう極限粘度０
．６６のポリエチレンテレフタレートチップを用いて希
釈配合した後、１８０℃にて４時間乾燥後、押出機にて
２９０℃で溶融し、４０℃冷却ドラム上にシート状に押
出し急冷して、実質的に無定形の未延伸シートを得た。
次いで得られたシートを縦方向に２．９倍、横方向に３
．２倍逐次延伸した後、２４５℃で６秒間熱処理して最
終的に５０μｍ厚の極限粘度０．６３の二軸延伸フィル
ムを得た。○; not eluted in any organic solvent ×; eluted in any organic solvent Example 1 Ethylene bistetrabromophthalimide (1) with an average particle size of 2.0 μm, 3 with an average particle size of 0.7 μm After drying antimony oxide and polyethylene terephthalate chips with an intrinsic viscosity of 0.83 at 150°C for 15 hours, they were each dried at 270°C and 29°C.
The mixture was kneaded at 0° C. to obtain 40% by weight masterbatch (hereinafter abbreviated as M.B.) chips with intrinsic viscosities of 0.55 and 0.65. The two types of M. B. The intrinsic viscosity is 0 so that the amount of each bromine and antimony element is as shown in Table 1.
．． After diluting and blending using No. 66 polyethylene terephthalate chips, it was dried at 180°C for 4 hours, melted at 290°C in an extruder, extruded into a sheet form on a 40°C cooling drum, and rapidly cooled to form a material that is virtually free. A regular unstretched sheet was obtained. Then, the obtained sheet was multiplied by 2.9 times in the vertical direction and 3 times in the horizontal direction.
．． After successive stretching of 2 times, heat treatment was performed at 245° C. for 6 seconds to finally obtain a biaxially stretched film having a thickness of 50 μm and an intrinsic viscosity of 0.63.
【００３１】得られたポリエステルフィルムの難燃性は
ＵＬ９４規格ＶＴＭ−Ｏランクに適合し、耐有機溶剤性
も優れていた。その他の特性は表１に示すように通常の
未処理のポリエチレンテレフタレートフィルム（比較例
１）とほぼ同等であり、特性の劣化は認められなかった
。The flame retardancy of the obtained polyester film conformed to the VTM-O rank of the UL94 standard, and the resistance to organic solvents was also excellent. As shown in Table 1, the other properties were almost the same as those of ordinary untreated polyethylene terephthalate film (Comparative Example 1), and no deterioration of properties was observed.
【００３２】実施例２
平均粒径１．５μｍのエチレン−（５，６−ジブロモノ
ルボルネン−２，３−ジカルボキシイミド）（２）、平
均粒径７μｍの三酸化アンチモンおよび極限粘度０．８
３のポリエチレンテレフタレートチップを１５０℃で１
５時間乾燥後、各２７０℃、２９０℃にて混練し、各極
限粘度０．６０、０．６５の４０重量％Ｍ．Ｂ．チップ
を得た。得られたＭ．Ｂ．を実施例１と同様に表１の配
合量となるように配合、フィルム化し、最終的に５０μ
ｍ厚の極限粘度０．５６の二軸延伸フィルムを得た。得
られたポリエステルフィルムの難燃性はＵＬ９４規格Ｖ
ＴＭ−Ｏランクに適合し、耐有機溶剤性も優れていた。
また、その他の特性は通常の未処理のポリエチレンテレ
フセタレートフィルム（比較例１）とほぼ同等であり、
特性の劣化は認められなかった。Example 2 Ethylene-(5,6-dibromonolbornene-2,3-dicarboximide) (2) with an average particle size of 1.5 μm, antimony trioxide with an average particle size of 7 μm, and an intrinsic viscosity of 0.8
3 polyethylene terephthalate chips at 150℃
After drying for 5 hours, kneading was carried out at 270°C and 290°C to obtain 40% by weight M.I. B. Got a tip. The obtained M. B. were blended and formed into a film in the same manner as in Example 1 to the amounts shown in Table 1, and the final film was 50 μm.
A biaxially stretched film with a thickness of m and an intrinsic viscosity of 0.56 was obtained. The flame retardancy of the obtained polyester film is UL94 standard V
It met the TM-O rank and had excellent organic solvent resistance. In addition, other properties are almost the same as ordinary untreated polyethylene terephcetalate film (Comparative Example 1),
No deterioration of characteristics was observed.
【００３３】実施例３，４及び比較例１〜４表１に示す
ように条件を変えるほかは実施例１と同様にして厚み５
０μｍの二軸延伸ポリエステルフィルムを得た。実施例
３，４においては満足すべき難燃性、耐溶剤性が得られ
た。これに対し、比較例１は極限粘度０．６６のポリエ
チレンテレフタレートのみを用いてフィルム化し、各種
特性を評価したものであるが、特に難燃性の点において
著しく劣っていた。Examples 3 and 4 and Comparative Examples 1 to 4 The same procedure as in Example 1 was carried out except that the conditions were changed as shown in Table 1.
A biaxially stretched polyester film of 0 μm was obtained. In Examples 3 and 4, satisfactory flame retardance and solvent resistance were obtained. On the other hand, in Comparative Example 1, a film was formed using only polyethylene terephthalate with an intrinsic viscosity of 0.66 and various properties were evaluated, and it was found to be significantly inferior, especially in terms of flame retardancy.
【００３４】また、比較例３は、実施例１においてエチ
レンビステトラブロモフタルイミドのＭ．Ｂ．の代わり
にテトラブロモフタルイミドの４０重量％Ｍ．Ｂ．（極
限粘度０．５５）を用いたものであるが、この場合溶融
押出時テトラブロモフタルイミドの昇華が著しくて、良
好な無定形シートが得られず、延伸加工することができ
なかった。Comparative Example 3 shows that the M.I. of ethylene bistetrabromophthalimide in Example 1 was B. of tetrabromophthalimide instead of 40% M.P. B. (intrinsic viscosity: 0.55), but in this case, sublimation of tetrabromophthalimide was significant during melt extrusion, and a good amorphous sheet could not be obtained and stretching could not be performed.
【００３５】[0035]
【表１】[Table 1]
【００３６】[0036]
【発明の効果】本発明のポリエステルフィルムは、機械
的強度、熱的性質、電気特性、耐薬品性等の特性を損な
うことなく、難燃性が付与されたものであり、その工業
的価値は高い。[Effect of the invention] The polyester film of the present invention is imparted with flame retardancy without impairing properties such as mechanical strength, thermal properties, electrical properties, and chemical resistance, and its industrial value is expensive.
Claims (1)
１〜１０μｍであり、分子内に臭素元素および２個以上
の窒素元素を有するイミド化合物（Ａ）を臭素元素量と
して１〜２０重量％、平均粒径が０．１〜１０μｍのア
ンチモン化合物（Ｂ）をアンチモン元素量として１〜２
０重量％含有してなる、極限粘度が０．４〜１．０であ
る二軸延伸ポリエステルフィルム。Claim 1: Melting point is 280°C or higher and average particle size is 0.
1 to 10 μm, an imide compound (A) having a bromine element and two or more nitrogen elements in the molecule is 1 to 20% by weight as a bromine element amount, and an antimony compound (B) having an average particle size of 0.1 to 10 μm. ) is 1 to 2 as the amount of antimony element.
A biaxially stretched polyester film containing 0% by weight and having an intrinsic viscosity of 0.4 to 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3023523A JPH04263920A (en) | 1991-02-18 | 1991-02-18 | Biaxially oriented polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3023523A JPH04263920A (en) | 1991-02-18 | 1991-02-18 | Biaxially oriented polyester film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04263920A true JPH04263920A (en) | 1992-09-18 |
Family
ID=12112809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3023523A Pending JPH04263920A (en) | 1991-02-18 | 1991-02-18 | Biaxially oriented polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04263920A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021700A1 (en) * | 1999-09-23 | 2001-03-29 | Eastman Chemical Company | Process for improving the melt stability of halogenated imides in pct formulations by addition of sodium antimonate |
| JP2001253959A (en) * | 2000-01-20 | 2001-09-18 | Mitsubishi Polyester Film Gmbh | Flame-retardant and ultraviolet light-resistant transparent oriented film and method of producing the same |
| JP2002187965A (en) * | 2000-09-29 | 2002-07-05 | Mitsubishi Polyester Film Gmbh | Transparent biaxially oriented thermally fixed film and its manufacturing method |
| JP2005126717A (en) * | 2003-10-20 | 2005-05-19 | Skc Co Ltd | Biaxially oriented, white flame-retardant polyester film |
| JP2011178975A (en) * | 2010-03-04 | 2011-09-15 | Toray Ind Inc | Polyester resin composition |
| JP2012155009A (en) * | 2011-01-24 | 2012-08-16 | Keyence Corp | Confocal microscope system, image processing method, and image processing program |
| JP2020203963A (en) * | 2019-06-14 | 2020-12-24 | ポリプラスチックス株式会社 | Method for producing flame-retardant thermoplastic polyester resin composition |
-
1991
- 1991-02-18 JP JP3023523A patent/JPH04263920A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001021700A1 (en) * | 1999-09-23 | 2001-03-29 | Eastman Chemical Company | Process for improving the melt stability of halogenated imides in pct formulations by addition of sodium antimonate |
| JP2001253959A (en) * | 2000-01-20 | 2001-09-18 | Mitsubishi Polyester Film Gmbh | Flame-retardant and ultraviolet light-resistant transparent oriented film and method of producing the same |
| JP2002187965A (en) * | 2000-09-29 | 2002-07-05 | Mitsubishi Polyester Film Gmbh | Transparent biaxially oriented thermally fixed film and its manufacturing method |
| JP2005126717A (en) * | 2003-10-20 | 2005-05-19 | Skc Co Ltd | Biaxially oriented, white flame-retardant polyester film |
| JP2011178975A (en) * | 2010-03-04 | 2011-09-15 | Toray Ind Inc | Polyester resin composition |
| JP2012155009A (en) * | 2011-01-24 | 2012-08-16 | Keyence Corp | Confocal microscope system, image processing method, and image processing program |
| JP2020203963A (en) * | 2019-06-14 | 2020-12-24 | ポリプラスチックス株式会社 | Method for producing flame-retardant thermoplastic polyester resin composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7229697B2 (en) | Hydrolysis-stable film comprising a polyester with a hydrolysis stabilizer and process for its production and its use | |
| DE69434360T2 (en) | PLASTICIZED POLYESTER FOR USE IN SHRINK FILMS | |
| EP1699845B1 (en) | Flame retardant polyester resin composition and articles formed therefrom | |
| KR20030074345A (en) | Biaxially oriented film with better surface quality based on crystallizable polymers, and process for producing the film | |
| JPH04263920A (en) | Biaxially oriented polyester film | |
| EP4201996A1 (en) | Polyester film comprising a polymeric phosphonate flame retardant | |
| JPS5818941B2 (en) | Polyester materials | |
| KR20030008155A (en) | PEN-PET-PEN Polymeric Film | |
| JPS5847420B2 (en) | Nannensei Polyester Materials | |
| JPS5828097B2 (en) | Polyester pine film | |
| RU2761548C2 (en) | Composition for hydrolytic stabilization of composite polyesters | |
| JP4665428B2 (en) | Biaxially oriented polyester film | |
| JPH02212525A (en) | Polyester film | |
| KR101552429B1 (en) | Polyester resin having an excellent surface-active and shielding property the light and preparing process thereof | |
| TWI769156B (en) | Composition for hydrolytic stabilization of polyesters | |
| DE102016119751A1 (en) | Polymer compounds for the production of polyester films with increased thermal conductivity | |
| JP2007002115A (en) | Polymer composition and biaxially oriented film | |
| KR20230138067A (en) | Flame retardant polyester film and manufacturing method thereof | |
| DE60319752T2 (en) | FLAME-REDUCING POLYESTER COMPOSITION AND ARTICLES MANUFACTURED THEREFROM | |
| JPH03227328A (en) | Polyester film | |
| KR20170107261A (en) | Polyester film and method for preparing the same | |
| JPH0741674A (en) | Polyphenylene sulfide resin composition and sheetlike material | |
| JPH02232257A (en) | Polyester film having anti-static effect | |
| JPH0717778B2 (en) | Polyester film containing fine bubbles | |
| JP2009079123A (en) | Flame retardant polyester film |