JPH04248843A - Antistatic polyester film - Google Patents
Antistatic polyester filmInfo
- Publication number
- JPH04248843A JPH04248843A JP102891A JP102891A JPH04248843A JP H04248843 A JPH04248843 A JP H04248843A JP 102891 A JP102891 A JP 102891A JP 102891 A JP102891 A JP 102891A JP H04248843 A JPH04248843 A JP H04248843A
- Authority
- JP
- Japan
- Prior art keywords
- polyester
- film
- weight
- dicarboxylic acid
- polyester film
- 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 51
- 229920000728 polyester Polymers 0.000 claims abstract description 59
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 9
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000035699 permeability Effects 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- -1 polyethylene oxydicarboxylic acid Polymers 0.000 claims description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002253 acid Substances 0.000 abstract description 6
- 229920006280 packaging film Polymers 0.000 abstract description 3
- 239000012785 packaging film Substances 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 33
- 239000010410 layer Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 17
- 239000002245 particle Substances 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 8
- 239000002216 antistatic agent Substances 0.000 description 7
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000001639 calcium acetate Substances 0.000 description 6
- 235000011092 calcium acetate Nutrition 0.000 description 6
- 229960005147 calcium acetate Drugs 0.000 description 6
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920001515 polyalkylene glycol Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- RAADBCJYJHQQBI-UHFFFAOYSA-N 2-sulfoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 RAADBCJYJHQQBI-UHFFFAOYSA-N 0.000 description 2
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- PJFPFKALGCPVLG-UHFFFAOYSA-N cyclohexane;3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound C1CCCCC1.O=C1OCCOC(=O)C2=CC=C1C=C2 PJFPFKALGCPVLG-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 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
- 238000010030 laminating 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
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- XFEGRFIENDJTCK-UHFFFAOYSA-N 2-phenyl-2,3-dihydroindene-1,1-dicarboxylic acid Chemical compound C1C2=CC=CC=C2C(C(=O)O)(C(O)=O)C1C1=CC=CC=C1 XFEGRFIENDJTCK-UHFFFAOYSA-N 0.000 description 1
- IEEZXCFWEVKMQT-UHFFFAOYSA-N 4-(1-phenylpropyl)phenol Chemical compound C=1C=C(O)C=CC=1C(CC)C1=CC=CC=C1 IEEZXCFWEVKMQT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 102200063830 rs4880 Human genes 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、帯電防止性ポリエステ
ルフイルムに関するものであり、特に本発明は透明性・
機械的特性に優れたポリエステルフイルムに関するもの
である。[Industrial Application Field] The present invention relates to an antistatic polyester film, and in particular, the present invention relates to a transparent and antistatic polyester film.
This invention relates to a polyester film with excellent mechanical properties.
【０００２】0002
【従来の技術】ポリエステルフイルム、特にポリエチレ
ンテレフタレート、ポリエチレンナフタレートの如き芳
香族ポリエステルフイルムは優れた特性を有しているた
め、磁気記録テープ・ＯＨＰ用シート・フイルムコンデ
ンサー・各種包装材料・写真用フイルム等に広く用いら
れている。[Prior Art] Polyester films, especially aromatic polyester films such as polyethylene terephthalate and polyethylene naphthalate, have excellent properties and are used in magnetic recording tapes, OHP sheets, film capacitors, various packaging materials, and photographic films. It is widely used.
【０００３】しかしながら、かかるポリエステルは疎水
性であるため摩擦などによって極めて容易に帯電し、ポ
リエステルフイルムの成型時、加工時、使用時等におい
て好ましからざる障害を引き起こす。However, since such polyester is hydrophobic, it is extremely easily charged with electricity due to friction, etc., which causes undesirable problems during molding, processing, and use of polyester films.
【０００４】従来、この帯電を防止するため、ポリエス
テル成型物を後処理することによって、その表面に帯電
防止剤を付与する方法が主として採用されている。しか
しながら、この方法による帯電防止性は一時的なもので
あって、耐久性に劣る欠点がある。また、ポリエステル
の重合時あるいは溶融押出製膜時に帯電防止剤を添加混
入する方法も知られている。しかしながら、この方法に
よっても帯電防止性が十分でなく、経時でフイルム表面
の帯電防止剤が脱落する。[0004] Conventionally, in order to prevent this electrification, a method has been mainly adopted in which an antistatic agent is applied to the surface of the polyester molded product by post-treatment. However, the antistatic property obtained by this method is temporary and has the drawback of being inferior in durability. Also known is a method of adding and mixing an antistatic agent during polymerization of polyester or during melt extrusion film formation. However, even with this method, the antistatic property is not sufficient, and the antistatic agent on the surface of the film falls off over time.
【０００５】帯電防止性の耐久性を改善するため、ポリ
エステルにポリアルキレングリコールを共重合する方法
が知られている。しかしながら、この方法によて十分な
帯電防止性を付与するためにはポリエステルに対し２０
重量％以上共重合する必要があり、得られるポリエステ
ルフイルムは、透明性や機械的特性等の物性が著しく低
下してしまう。また、ポリアルキレングリコールは、重
合反応性が低いため、低重合物が残存し、高温熱履歴や
経時により、低重合物が表面にブリードアウトし、さま
ざまな障害をもたらしてしまう。In order to improve the durability of antistatic properties, a method is known in which polyester is copolymerized with polyalkylene glycol. However, in order to impart sufficient antistatic properties using this method, it is necessary to
It is necessary to copolymerize more than % by weight, and the resulting polyester film has significantly reduced physical properties such as transparency and mechanical properties. In addition, since polyalkylene glycol has low polymerization reactivity, low polymers remain, and due to high temperature thermal history and aging, the low polymers bleed out to the surface, causing various problems.
【０００６】[0006]
【発明が解決しようとする課題】すなわち本発明におけ
る課題は、ポリエステルフイルム本来の好ましい特性を
実質的に損なうことがなく、透明性・機械的特性・寸法
安定性の優れた帯電防止性を有するポリエステルフイル
ムを提供することにある。[Problems to be Solved by the Invention] That is, the object of the present invention is to provide a polyester film that does not substantially impair the desirable characteristics inherent in polyester film and that has antistatic properties with excellent transparency, mechanical properties, and dimensional stability. The goal is to provide film.
【０００７】[0007]
【課題を解決するための手段】本発明は、かかる課題を
解決するために次の構成を有する。すなわち、ポリエス
テルのジカルボン酸共重合成分として、金属スルホネー
トを有する芳香族ジカルボン酸及び／又はその誘導体を
２〜２０重量％と、（ａ）式で示される平均分子量６０
０〜２００００のポリエーテルジカルボン酸及び／又は
その誘導体を２〜２０重量％とを含むポリエステルより
なるフィルムであって、水蒸気透過率が１０．０ｇ／ｍ
２ ・２４ｈｒ／０．１ｍｍ以上、帯電量の半減期が２
秒以下であることを特徴とする帯電防止性ポリエステル
フイルムである。Means for Solving the Problems The present invention has the following configuration in order to solve the problems. That is, as the dicarboxylic acid copolymerization component of the polyester, 2 to 20% by weight of an aromatic dicarboxylic acid having a metal sulfonate and/or a derivative thereof, and an average molecular weight of 60 expressed by the formula (a).
A film made of polyester containing 0 to 20,000 polyether dicarboxylic acids and/or derivatives thereof in an amount of 2 to 20% by weight, and having a water vapor permeability of 10.0 g/m
2 ・24hr/0.1mm or more, the half-life of the amount of charge is 2
This is an antistatic polyester film characterized by an antistatic property of less than 2 seconds.
【０００８】
Ｒ１ ＯＯＣＣＨ２ −（Ｏ−Ｒ２ ）ｎ −
ＯＣＨ２ ＣＯＯＲ３ （ａ）（
Ｒ１ 、Ｒ３ ：Ｈまたは炭素数１〜８のアルキル基、
Ｒ２ ：炭素数２〜８のアルキレン基、ｎ：正の整数）
本発明のポリエステルフィルムに用いられる共重合ポリ
エステルは、金属スルホネートを有する芳香族ジカルボ
ン酸成分およびポリエーテルジカルボン酸成分を共重合
成分とし、これらはそれぞれ帯電防止剤として機能する
が、本発明においては、これらを併用することで水蒸気
透過性を向上させ、ひいては著しい帯電防止性を発現さ
せるものである。R1 OOCCH2 −(O−R2 )n −
OCH2 COOR3 (a)(
R1, R3: H or an alkyl group having 1 to 8 carbon atoms,
R2: alkylene group having 2 to 8 carbon atoms, n: positive integer)
The copolymerized polyester used in the polyester film of the present invention has a metal sulfonate-containing aromatic dicarboxylic acid component and a polyether dicarboxylic acid component as copolymerized components, each of which functions as an antistatic agent. By using these together, water vapor permeability is improved, and as a result, remarkable antistatic properties are exhibited.
【０００９】前記金属スルホネートを有する芳香族ジカ
ルボン酸としては、具体的には、５−ナトリウムスルホ
イソフタル酸、２ーナトリウムスルホテレフタル酸、４
ーナトリウムスルホフタル酸、４ーナトリウムスルホ−
２，６−ナフタレンジカルボン酸およびこれらのナトリ
ウムを他の金属、例えばカリウム、リチウムやアンモニ
ウム塩、ホスホニウム塩などで置換した化合物を挙げる
ことができる。金属スルホネートを有する芳香族ジカル
ボン酸成分の共重合割合としては、反応生成物のポリエ
ステルに対して２〜２０重量％、好ましくは５〜１５重
量％、特に好ましくは７〜１２重量％である。[0009] Specific examples of the aromatic dicarboxylic acid having a metal sulfonate include 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, and 4-sodium sulfoterephthalic acid.
-Sodium sulfophthalate, 4-sodium sulfophthalate
Examples include 2,6-naphthalene dicarboxylic acid and compounds in which sodium is substituted with other metals, such as potassium, lithium, ammonium salts, phosphonium salts, and the like. The copolymerization ratio of the aromatic dicarboxylic acid component having a metal sulfonate is 2 to 20% by weight, preferably 5 to 15% by weight, particularly preferably 7 to 12% by weight, based on the polyester of the reaction product.
【００１０】本発明のポリエステルフイルムを構成する
ポリエステルには、更に（ａ）式で示されるポリエーテ
ルジカルボン酸成分が共重合されていることが、フイル
ムに透明性、寸法安定性、機械的強度を付与する点で好
ましい。このポリエーテルジカルボン酸の平均分子量は
、６００〜２００００が好ましく、更には１０００〜１
５０００、特には２０００〜１００００の範囲にあるも
のが好ましい。平均分子量が６００以下の場合吸水性が
不十分となり、帯電防止性を十分に得ることができない
。また、２００００以上の分子量では逆にフイルムの透
明性や剛性が低下するため好ましくない。ポリエーテル
ジカルボン酸としては、ポリエチレンオキシジカルボン
酸、ポリテトラメチレンオキシジカルボン酸が好ましい
が、ポリエステルの重合反応性やフイルムの寸法安定性
の点で特に（ｂ）式で示されるポリエチレンオキシジカ
ルボン酸がより好ましい。The fact that the polyester constituting the polyester film of the present invention is further copolymerized with a polyether dicarboxylic acid component represented by formula (a) gives the film transparency, dimensional stability, and mechanical strength. It is preferable in that it can be given. The average molecular weight of this polyether dicarboxylic acid is preferably 600 to 20,000, more preferably 1,000 to 1
5,000, particularly preferably in the range of 2,000 to 10,000. When the average molecular weight is 600 or less, water absorption becomes insufficient and antistatic properties cannot be obtained sufficiently. On the other hand, a molecular weight of 20,000 or more is undesirable because the transparency and rigidity of the film decrease. As the polyether dicarboxylic acid, polyethylene oxydicarboxylic acid and polytetramethylene oxydicarboxylic acid are preferred, but polyethylene oxydicarboxylic acid represented by formula (b) is particularly preferred in terms of polymerization reactivity of polyester and dimensional stability of the film. preferable.
【００１１】
Ｒ１ ＯＯＣＣＨ２ −（Ｏ−ＣＨ２ ＣＨ２
）ｎ −ＯＣＨ２ ＣＯＯＲ２ （ｂ）（Ｒ１
、Ｒ２ ：Ｈまたは炭素数１〜８のアルキル基、ｎ：正
の整数）
また、ポリエーテルジカルボン酸成分の共重合割合とし
ては、反応生成物のポリエステルに対して２〜２０重量
％、好ましくは５〜１５重量％、特に好ましくは７〜１
２重量％である。R1 OOCCH2 -(O-CH2 CH2
)n -OCH2 COOR2 (b)(R1
, R2: H or an alkyl group having 1 to 8 carbon atoms, n: a positive integer) In addition, the copolymerization ratio of the polyether dicarboxylic acid component is 2 to 20% by weight, preferably 2 to 20% by weight based on the polyester of the reaction product. 5-15% by weight, particularly preferably 7-1
It is 2% by weight.
【００１２】本発明のポリエステルフイルムは、含水率
が０．５重量％以上である点に特徴があり、好ましくは
０．６〜５．０重量％である。含水率が０．５重量％未
満であると十分な帯電防止性を得ることはできない。逆
に含水率が大き過ぎると、吸湿による寸法安定性が悪化
する。The polyester film of the present invention is characterized in that its water content is 0.5% by weight or more, preferably 0.6 to 5.0% by weight. If the water content is less than 0.5% by weight, sufficient antistatic properties cannot be obtained. On the other hand, if the water content is too high, dimensional stability due to moisture absorption will deteriorate.
【００１３】本発明において、ポリエステルとは、芳香
族二塩基酸とグリコールを主要な構成成分とするポリエ
ステルであり、二塩基酸としては、テレフタル酸、イソ
フタル酸、フタル酸、ナフタレンジカルボン酸、ジフェ
ニルスルホンジカルボン酸、ジフェニルエーテルジカル
ボン酸、ジフェノキシエタンジカルボン酸、シクロヘキ
サンジカルボン酸、ジフェニルジカルボン酸、ジフェニ
ルチオエーテルジカルボン酸、ジフェニルケトンジカル
ボン酸、フェニルインダンジカルボン酸などを挙げるこ
とができる。また、グリコールとしては、エチレングリ
コール、プロピレングリコール、テトラメチレングリコ
ール、シクロヘキサンジメタノール、２，２−ビス（４
−ヒドロキシジフェニル）プロパン、２，２−ビス（４
−ヒドロキシエトキシフェニル）プロパン、ビス（４−
ヒドロキシフェニル）スルホン、ジエチレングリコール
、ネオペンチルグリコール、ハイドロキノン、シクロヘ
キサンジオールなどを挙げることができる。これらの成
分からなるポリエステルの中でも耐熱性、機械的強度、
寸法安定性等の点から、ポリエチレンテレフレート、シ
クロヘキサンジメチレンテレフタレート、ポリエチレン
ナフタレートが好ましい。[0013] In the present invention, polyester is a polyester whose main components are aromatic dibasic acid and glycol, and dibasic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, and diphenyl sulfone. Examples include dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenoxyethane dicarboxylic acid, cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenylthioether dicarboxylic acid, diphenyl ketone dicarboxylic acid, and phenylindane dicarboxylic acid. In addition, examples of glycol include ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis(4
-hydroxydiphenyl)propane, 2,2-bis(4
-hydroxyethoxyphenyl)propane, bis(4-
Examples include hydroxyphenyl) sulfone, diethylene glycol, neopentyl glycol, hydroquinone, and cyclohexanediol. Among polyesters made of these components, heat resistance, mechanical strength,
From the viewpoint of dimensional stability and the like, polyethylene terephrate, cyclohexane dimethylene terephthalate, and polyethylene naphthalate are preferred.
【００１４】本発明ポリエステルフイルムのガラス転移
温度は、５０℃以上が好ましく、更に好ましくは６０℃
以上である。ただし、これは２５℃５０％ＲＨの雰囲気
におかれたフイルムを示差走査熱量計で測定したもので
ある。ガラス転移温度が５０℃より低いと、例えば夏場
の高温下でフイルムが変形する恐れがあるため好ましく
ない。ガラス転移温度が高い方が耐熱性は向上する。The glass transition temperature of the polyester film of the present invention is preferably 50°C or higher, more preferably 60°C.
That's all. However, this was measured using a differential scanning calorimeter on a film placed in an atmosphere of 25° C. and 50% RH. If the glass transition temperature is lower than 50° C., the film may be deformed under high temperatures, for example, in summer, which is not preferable. The higher the glass transition temperature, the better the heat resistance.
【００１５】本発明ポリエステルフイルムの水蒸気透過
率は１０．０ｇ／ｍ２ ・２４ｈｒ／０．１ｍｍ以上で
あり、好ましくは１５．０ｇ／ｍ２ ・２４ｈｒ／０．
１ｍｍ以上であり、更に好ましくは１８．０ｇ／ｍ２
・２４ｈｒ／０．１ｍｍ以上である。本発明においては
、水蒸気透過率を増大させることによって帯電防止性を
発現させることが大きな特長である。The water vapor permeability of the polyester film of the present invention is 10.0 g/m 2 ·24 hr/0.1 mm or more, preferably 15.0 g/m 2 ·24 hr/0.
1 mm or more, more preferably 18.0 g/m2
- 24hr/0.1mm or more. A major feature of the present invention is that it exhibits antistatic properties by increasing water vapor permeability.
【００１６】なお、本発明のポリエステルフイルムの帯
電防止性を向上させるために、透明性、機械的特性を阻
害しない範囲の小割合であれば、帯電防止剤を添加して
も良い。帯電防止剤としては、四級アンモニウム塩類、
アミン類、イミダゾリン類、アミン酸化エチレン付加体
類、ポリアルキレングリコール類、ソルビタンエステル
類等々が挙げられる。その中でも例えばポリアルキレン
グリコールの場合、分子量が約６００〜２００００が好
ましく、ポリエチレングリコール、ポリプロピレングリ
コール、ポリテトラメチレングリコール、ポリエチレン
グリコール−ポリプロピレングリコール共重合体等が挙
げられる。これらの添加量は０〜１５重量％が好ましい
。[0016] In order to improve the antistatic properties of the polyester film of the present invention, an antistatic agent may be added in a small proportion that does not impair transparency and mechanical properties. As antistatic agents, quaternary ammonium salts,
Examples include amines, imidazolines, amine oxide ethylene adducts, polyalkylene glycols, sorbitan esters, and the like. Among them, for example, in the case of polyalkylene glycol, the molecular weight is preferably about 600 to 20,000, and examples thereof include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymer, and the like. The amount of these added is preferably 0 to 15% by weight.
【００１７】ポリエステルのジカルボン酸共重合成分が
、金属スルホネートを有する芳香族ジカルボン酸及び／
又はその誘導体を含み、更にポリエーテルジカルボン酸
及び／又はその誘導体を含む帯電防止ポリエステルをポ
リエステルＡとすると、本発明におけるポリエステルフ
イルムは多層構造であって、そのうちの一層がポリエス
テルＡ層であってもよい。ポリエステルＡ層以外の層を
ポリエステルＢ層あるいはＣ層とすると、本発明のポリ
エステルフイルムは、Ａ／Ｂの２層構造でもよく、Ａ／
Ｂ／Ａ、Ｂ／Ａ／ＢまたはＢ／Ａ／Ｃといった３層構造
でもよく、更にはそれ以上の多層構造でもよい。Ａ層の
ポリエステルは共重合であるため、ホモポリエステルに
比べ結晶性が低下しており、機械的特性や透明性、寸法
安定性等が低下してしまう。そこで、共重合ＰＥＴ層で
あるＡ層と、ＰＥＴ層あるいは他のホモポリマー層、あ
るいは他の共重合ポリマー層とを共押出することにより
、通常のＰＥＴフイルム並の透明性・機械的特性・寸法
安定性を維持しながら、帯電防止性を有するポリエステ
ルフイルムを提供することができる。更には、フイルム
の表面に易滑性や着色性等を付与する場合でも必要な添
加剤を表層のみ添加すればよく、フイルムの高透明性を
維持でき、またフイルムのコスト自身を下げることにも
つながる。[0017] The dicarboxylic acid copolymerization component of the polyester is an aromatic dicarboxylic acid having a metal sulfonate and/or
If polyester A is an antistatic polyester containing polyether dicarboxylic acid and/or a derivative thereof, and polyether dicarboxylic acid and/or a derivative thereof, the polyester film in the present invention has a multilayer structure, even if one of the layers is the polyester A layer. good. When the layer other than the polyester A layer is the polyester B layer or the polyester C layer, the polyester film of the present invention may have a two-layer structure of A/B.
It may have a three-layer structure such as B/A, B/A/B or B/A/C, or it may have a multi-layer structure. Since the polyester of Layer A is a copolymer, it has lower crystallinity than homopolyester, resulting in lower mechanical properties, transparency, dimensional stability, etc. Therefore, by co-extruding Layer A, which is a copolymerized PET layer, with a PET layer, other homopolymer layer, or other copolymer layer, we can achieve transparency, mechanical properties, and dimensions comparable to that of ordinary PET film. A polyester film having antistatic properties while maintaining stability can be provided. Furthermore, even when imparting slipperiness or coloration to the film surface, the necessary additives need only be added to the surface layer, allowing the film to maintain high transparency and reducing the cost of the film itself. Connect.
【００１８】また、本発明においては、共重合比によっ
てはフイルム加工時の高温熱処理にて低重合物が析出し
たり、経時によって低重合物が表面にブリードアウトす
る問題があるが、その際、Ａ層の片側または両側にＡ層
と異なるポリエステルＢ層を積層することによって、低
重合物の析出を抑制し、フイルムの透明性を維持するこ
とができる。ポリエステルＢ層としては、前述のポリエ
ステルが好ましく用いられるが、ポリエチレンテレフレ
ート、シクロヘキサンジメチレンテレフタレート、ポリ
エチレンナフタレートが特に好ましい。ポリエステルＢ
層の積層厚みとしては、０．０５〜２０μｍが好ましい
が、０．５〜１０μｍが特に好ましく、更には１〜５μ
ｍが好ましい。また、本発明のポリエステルフイルムに
は、吸水性が求められるが、そのため吸水性の小さいポ
リエステルＢを用いるとその積層厚みは、低重合物の析
出を抑制できる範囲内で薄くする必要がある。また、別
の手法として、ポリエステルＢ層自身に吸水性を付与し
てもよい。例えば、金属スルホネートを有する芳香族ジ
カルボン酸成分を共重合成分とした共重合ポリエステル
を用いるのが好ましい。金属スルホネートを有する芳香
族ジカルボン酸としては前述の化合物が挙げられるが、
共重合割合としては、反応生成物のポリエステルに対し
て１〜２０重量％、好ましくは３〜１２重量％、特に好
ましくは５〜１０重量％である。Furthermore, in the present invention, depending on the copolymerization ratio, low polymers may precipitate during high-temperature heat treatment during film processing, or the low polymers may bleed out onto the surface over time. By laminating the polyester B layer, which is different from the A layer, on one or both sides of the A layer, precipitation of low polymers can be suppressed and the transparency of the film can be maintained. As the polyester B layer, the above-mentioned polyesters are preferably used, and polyethylene terephrate, cyclohexane dimethylene terephthalate, and polyethylene naphthalate are particularly preferred. Polyester B
The laminated thickness of the layers is preferably 0.05 to 20 μm, particularly preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.
m is preferred. Further, the polyester film of the present invention is required to have water absorbency, so if polyester B with low water absorbency is used, the laminated thickness needs to be reduced within a range that can suppress the precipitation of low polymers. Moreover, as another method, water absorbency may be imparted to the polyester B layer itself. For example, it is preferable to use a copolymerized polyester containing an aromatic dicarboxylic acid component having a metal sulfonate as a copolymerization component. Examples of the aromatic dicarboxylic acid having a metal sulfonate include the above-mentioned compounds,
The copolymerization ratio is 1 to 20% by weight, preferably 3 to 12% by weight, particularly preferably 5 to 10% by weight based on the polyester of the reaction product.
【００１９】ポリエステルＢ層のガラス転移温度は、６
０℃以上であり、好ましくは６５℃以上、更に好ましく
は７０℃以上である。本発明の場合、ポリエステルＡ層
の強度がやや低くなるため、ガラス転移温度の比較的高
いポリエステルＢ層を積層することによって、強度が維
持されるわけである。The glass transition temperature of the polyester B layer is 6
The temperature is 0°C or higher, preferably 65°C or higher, and more preferably 70°C or higher. In the case of the present invention, since the strength of the polyester A layer is somewhat low, the strength is maintained by laminating the polyester B layer, which has a relatively high glass transition temperature.
【００２０】本発明において、Ａ層の厚みは特に限定さ
れないが、通常ポリエステルフイルム全厚みに対してＡ
層の厚みは１〜９９％の範囲内が好ましい。In the present invention, the thickness of layer A is not particularly limited, but usually the thickness of layer A is
The thickness of the layer is preferably within the range of 1 to 99%.
【００２１】多層積層をを行なう場合、この手段として
は具体的には複数の押出機ならびにフィールドブロック
、あるいはマルチマニフォールドダイによる共押出法が
例示される。[0021] When carrying out multilayer lamination, specific examples of this means include coextrusion using a plurality of extruders and field blocks, or a multi-manifold die.
【００２２】本発明のポリエステルフイルムのヘイズ値
は５％以下であり、好ましくは２％以下である。ヘイズ
値が５％を越えると透明性が求められる用途では障害と
なってくる。一般の共重合ポリエステルフイルムの場合
、前述のように低重合物がフイルム中に残存しやすいた
め経時によって、低重合物が表面にブリードアウトしや
すいためそれによって透明性が損なわれてしまう。本発
明の特長の一つはこの低重合物の析出による透明性の低
下が小さいことにある。例えば、４０℃９０％ＲＨの雰
囲気下に２週間放置しておいても、本発明のポリエステ
ルフイルムのヘイズ値は５％以下となる。The haze value of the polyester film of the present invention is 5% or less, preferably 2% or less. If the haze value exceeds 5%, it becomes an obstacle in applications requiring transparency. In the case of a general copolymerized polyester film, as mentioned above, low polymers tend to remain in the film, and over time, the low polymers tend to bleed out to the surface, thereby impairing transparency. One of the features of the present invention is that the decrease in transparency due to precipitation of low polymers is small. For example, even if it is left in an atmosphere of 40° C. and 90% RH for two weeks, the haze value of the polyester film of the present invention remains 5% or less.
【００２３】本発明によるポリエステルフイルムには、
用途に応じて易滑性を付与することも可能であり、易滑
性付与手段としては特に限定を加えるところではないが
、不活性無機化合物の練り込み、あるいは界面活性剤の
塗布等が一般的手法として用いられる。The polyester film according to the present invention includes:
It is also possible to impart slipperiness depending on the application, and there are no particular limitations on the means for imparting slipperiness, but common methods include kneading inert inorganic compounds or coating with surfactants. used as a method.
【００２４】かかる不活性無機粒子としては、ＳｉＯ２
、ＴｉＯ２ 、ＢａＳＯ４ 、ＣａＣＯ２ 、タルク
、カオリン等が例示される。また、上記のポリエステル
合成反応系に不活性な粒子を添加する外部粒子系による
易滑性付与以外にポリエステルの重合反応時に添加する
触媒等を析出させる内部粒子系による易滑性付与方法も
採用可能である。Such inert inorganic particles include SiO2
, TiO2, BaSO4, CaCO2, talc, kaolin, etc. In addition to the above-mentioned method of imparting slipperiness using an external particle system in which inert particles are added to the polyester synthesis reaction system, it is also possible to adopt a method of imparting slipperiness using an internal particle system that precipitates catalysts added during the polyester polymerization reaction. It is.
【００２５】これら易滑性付与手段には特に限定を加え
るものではないが、透明性が重要な要件となる用途にお
いては、上記易滑性付与方法では外部粒子系としてはポ
リエステルフイルムと比較的近い屈折率をもつＳｉＯ２
、あるいは析出する粒子径を比較的小さくすることが
可能な内部粒子系を選択することが望ましい。また、こ
れらの粒子系は、本発明のポリエステルフイルムのいず
れの層に添加してもよいが、表層に添加するのが好まし
い。[0025] Although there are no particular limitations on these means for imparting slipperiness, in applications where transparency is an important requirement, in the above method for imparting slipperiness, the external particle system is relatively similar to that of a polyester film. SiO2 with refractive index
Alternatively, it is desirable to select an internal particle system that allows the precipitated particle size to be relatively small. Further, these particle systems may be added to any layer of the polyester film of the present invention, but it is preferable to add them to the surface layer.
【００２６】本発明のポリエステルフイルムの１５０℃
、３０分における熱収縮率は２％以下が好ましく、更に
好ましくは１．５％以下である。ＴＡＣフイルムやＰＥ
Ｔフイルムの熱収縮率は、２％以下と小さいのに対して
、共重合ポリエステルフイルムの熱収縮率は一般に大き
くなる傾向があるが、本発明の共重合ポリエステルフイ
ルムの熱収縮率はＰＥＴフイルム以下であることも大き
な特長の一つである。フイルムを例えば写真感光材料用
支持体として使用する場合、疎水性であるポリエステル
フイルムやトリアセテートフイルムに親水性の乳剤層（
ゼラチンバインダー）を直接塗布しても必要な接着力は
得られない。そこで通常フイルムには下塗層を付与して
いるが、この工程ではフイルムに約１５０℃の熱がかけ
られる。また、塗布した乳剤の乾燥工程は１００〜１５
０℃で加熱される。フイルムがこれらの工程で変形・伸
縮しないことが好ましく、すなわちフイルムに熱寸法安
定性が求められるわけである。また、ＯＨＰ用シートの
場合、トナー固定時に１００〜２００℃の熱履歴を受け
るため、その際のフイルムの変形、平面性悪化、画像の
歪みは最小限にする必要があり、すなわち熱寸法安定性
が求められるわけである。150°C of the polyester film of the present invention
The heat shrinkage rate in 30 minutes is preferably 2% or less, more preferably 1.5% or less. TAC film and PE
The heat shrinkage rate of T film is as low as 2% or less, whereas the heat shrinkage rate of copolyester films generally tends to be large, but the heat shrinkage rate of the copolyester film of the present invention is lower than that of PET film. It is also one of its major features. When using a film as a support for a photographic material, for example, a hydrophilic emulsion layer (
Direct application of a gelatin binder (gelatin binder) does not provide the necessary adhesion. Therefore, a subbing layer is usually applied to the film, and in this process, the film is heated to about 150°C. In addition, the drying process of the coated emulsion is 100 to 15
Heated at 0°C. It is preferable that the film is not deformed or expanded or contracted during these steps, that is, the film is required to have thermal dimensional stability. In addition, in the case of OHP sheets, they undergo a thermal history of 100 to 200°C when toner is fixed, so it is necessary to minimize the deformation of the film, deterioration of flatness, and image distortion at that time, that is, thermal dimensional stability. is required.
【００２７】また、本発明のポリエステルフイルムの引
裂伝播抵抗が５００ｇ／ｍｍ以上が好ましく、更に好ま
しくは８００ｇ／ｍｍ以上である。Further, the tear propagation resistance of the polyester film of the present invention is preferably 500 g/mm or more, more preferably 800 g/mm or more.
【００２８】また、本発明のポリエステルフイルムの破
断強度は、８ｋｇ／ｍｍ２ 以上であり好ましくは１３
ｋｇ／ｍｍ２ 以上である。さらにヤング率は、３００
ｋｇ／ｍｍ２ 以上であり、好ましくは３５０ｋｇ／ｍ
ｍ２ 以上である。これら機械的強度が低下すると、フ
イルムを例えば写真感光材料用支持体として使用する場
合、フイルムがカメラ内での巻取時や機械による自動現
像・焼き付け時に外力によって容易に変形あるいは破断
してしまうおそれがあるわけである。[0028] Furthermore, the breaking strength of the polyester film of the present invention is 8 kg/mm2 or more, preferably 13 kg/mm2 or more.
kg/mm2 or more. Furthermore, Young's modulus is 300
kg/mm2 or more, preferably 350 kg/m
m2 or more. If the mechanical strength is reduced, when the film is used, for example, as a support for photographic light-sensitive materials, there is a risk that the film will be easily deformed or broken by external forces during winding in a camera or during automatic development/printing by a machine. There is a reason.
【００２９】本発明の共重合ポリエステルフイルムの原
料ポリマーの合成法は従来公知のポリエステルの製造方
法にしたがって製造できる。例えば酸性分をグリコール
成分と直接エステル化反応するか、または酸性分として
ジアルキルエステルを用いる場合はグリコール成分とで
エステル交換反応し、これを減圧下に加熱して余剰のグ
リコール成分を除去することにより、共重合ポリエステ
ルを得ることができる。この際必要に応じてエステル交
換反応触媒あるいは重合反応触媒を用い、あるいは耐熱
安定剤を添加することができる。もちろん実用上、着色
防止剤、酸化防止剤、結晶核剤、すべり剤、安定剤、ブ
ロッキング防止剤、紫外線吸収剤、粘度調節剤、消泡剤
、透明化剤、帯電防止剤などを添加させてもよい。The raw material polymer for the copolymerized polyester film of the present invention can be synthesized according to a conventionally known method for producing polyester. For example, by directly esterifying the acidic component with the glycol component, or when using a dialkyl ester as the acidic component, transesterifying the acidic component with the glycol component, and then heating this under reduced pressure to remove the excess glycol component. , a copolymerized polyester can be obtained. At this time, a transesterification reaction catalyst or a polymerization reaction catalyst may be used, or a heat-resistant stabilizer may be added, if necessary. Of course, for practical purposes, coloring inhibitors, antioxidants, crystal nucleating agents, slip agents, stabilizers, anti-blocking agents, ultraviolet absorbers, viscosity modifiers, antifoaming agents, clarifying agents, antistatic agents, etc. are added. Good too.
【００３０】前記にて得られた共重合ポリエステルは一
般に粒状に成型し、乾燥後溶融し、Ｔダイより共押出し
て、未延伸シートとする。溶融ポリエステルシートを冷
却ロールに接触させる際は、静電印加冷却法を適応する
ことが好ましい。The copolymerized polyester obtained above is generally formed into granules, dried, melted, and coextruded through a T-die to form an unstretched sheet. When bringing the molten polyester sheet into contact with a cooling roll, it is preferable to apply an electrostatic cooling method.
【００３１】フイルムに機械的強度を付与するには、Ｔ
ダイより押し出しした未延伸シートをさらに２軸延伸す
るのがよい。二軸延伸の場合、逐次二軸延伸法または同
時二軸延伸法を用いることができるが、最初に長手方向
、次に幅方向の延伸を行なう逐次二軸延伸法が好ましい
。In order to impart mechanical strength to the film, T
It is preferable to further biaxially stretch the unstretched sheet extruded from the die. In the case of biaxial stretching, a sequential biaxial stretching method or a simultaneous biaxial stretching method can be used, but a sequential biaxial stretching method in which stretching is performed first in the longitudinal direction and then in the width direction is preferred.
【００３２】延伸温度は、ガラス転移温度〜冷結晶化温
度の範囲で行なうのがよいが、本発明においては長手方
向の場合６０〜１００℃、幅方向の延伸の場合７０〜１
５０℃であることが望ましい。延伸倍率は通常２．０〜
５．０倍が適当である。フイルムの強度を高めるために
は、製膜性が低下しない範囲内で延伸倍率を高くした方
がよく、好ましくは３．５倍以上、特に好ましくは４．
０倍以上にである。また、縦、横延伸後、縦、横のいず
れかに再延伸してもかまわない。The stretching temperature is preferably from the glass transition temperature to the cold crystallization temperature, but in the present invention, the stretching temperature is 60 to 100°C in the longitudinal direction, and 70 to 100°C in the width direction.
The temperature is preferably 50°C. The stretching ratio is usually 2.0~
5.0 times is appropriate. In order to increase the strength of the film, it is better to increase the stretching ratio within a range that does not reduce film formability, preferably 3.5 times or more, particularly preferably 4.
It is more than 0 times. Further, after stretching in the longitudinal direction or in the transverse direction, it may be re-stretched in either the longitudinal direction or the transverse direction.
【００３３】フイルムの引裂伝播抵抗を向上させるため
には延伸倍率を高倍率にして長手方向及び横方向をバラ
ンスさせることが望ましく、好ましくは３．４倍以上、
特に好ましくは３．８倍以上で、長手方向と横方向の延
伸倍率の差が０．７以下が好ましく、更に好ましくは０
．５以下である。In order to improve the tear propagation resistance of the film, it is desirable to use a high stretching ratio to balance the longitudinal and lateral directions, preferably 3.4 times or more,
Particularly preferably, the stretching ratio is 3.8 times or more, and the difference between the stretching ratios in the longitudinal direction and the lateral direction is preferably 0.7 or less, and more preferably 0.
．． 5 or less.
【００３４】更に、延伸したフイルムに熱処理を施して
も良い。この場合の熱処理条件としては、定長下、弛緩
状態、微延伸状態のいずれでもよく、本発明のポリエス
テルフイルムの場合、１５０〜２２５℃好ましくは１７
０〜２２０℃の範囲で０．５〜６０秒間が好適である。
特に、本発明の場合、製膜性が低下しない範囲内で熱処
理温度は高い方がよく、これによって１５０℃の熱収縮
率が低下し、水蒸気透過率も増大し、更には帯電防止性
を向上させることができる。Furthermore, the stretched film may be subjected to heat treatment. The heat treatment conditions in this case may be any of a constant length, a relaxed state, and a slightly stretched state, and in the case of the polyester film of the present invention, 150 to 225°C, preferably 17
The temperature is preferably 0.5 to 60 seconds within the range of 0 to 220°C. In particular, in the case of the present invention, the heat treatment temperature should be higher within a range that does not reduce film formability, thereby reducing the heat shrinkage rate at 150°C, increasing the water vapor transmission rate, and further improving the antistatic property. can be done.
【００３５】特に本発明のポリエステルフイルムの場合
、高倍率で延伸を行なった後、高温で熱処理することに
より、破断強度及び引裂伝播抵抗をバランスよく高める
ことができ、しかも低熱収縮性、水蒸気透過性、帯電防
止性も良好となる。In particular, in the case of the polyester film of the present invention, by stretching it at a high magnification and then heat-treating it at a high temperature, it is possible to increase the breaking strength and tear propagation resistance in a well-balanced manner, and also to have low heat shrinkage and water vapor permeability. , antistatic properties are also improved.
【００３６】本発明のポリエステルフイルムの帯電量の
半減期は２秒以下であり、好ましくは１．５秒以下、更
に好ましくは１秒以下である。The half-life of the charge amount of the polyester film of the present invention is 2 seconds or less, preferably 1.5 seconds or less, and more preferably 1 second or less.
【００３７】本発明の共重合ポリエステルフイルムの厚
さとしては特に限定しないが、延伸フイルムの場合、３
〜３６０μｍ、無延伸フイルムの場合、５０〜２０００
μｍのものが好んで用いられる。写真フイルムの用途分
野の場合、２５〜２５０μが望ましく、更に望ましくは
４０〜１５０μの厚みが採用される。The thickness of the copolymerized polyester film of the present invention is not particularly limited, but in the case of a stretched film, the thickness is 3.
~360μm, 50~2000 for unstretched film
μm ones are preferably used. In the field of photographic film applications, a thickness of 25 to 250 .mu.m is preferred, more preferably a thickness of 40 to 150 .mu.m.
【００３８】本発明のポリエステルフイルムは接着性向
上およびコーティング液のぬれ特性を改良するため、フ
イルムにコロナ放電処理、薬液処理、火炎処理などの各
種表面処理を必要に応じて施すことができる。本発明で
はコロナ放電処理が好ましい。The polyester film of the present invention can be subjected to various surface treatments, such as corona discharge treatment, chemical treatment, and flame treatment, as necessary, in order to improve adhesion and wettability of the coating liquid. Corona discharge treatment is preferred in the present invention.
【００３９】本発明のポリエステルフイルムは、写真感
光材料の支持体またはカバー層の他、その優れた透明性
・熱寸法安定性・機械的特性を利用して、各種透明フイ
ルム、例えばＯＨＰ用フイルム、光学用フイルム、生鮮
食品用といった包装フイルム、磁気記録テープあるいは
磁気フロッピー用フイルム等に利用できる。The polyester film of the present invention can be used as a support or cover layer for photographic light-sensitive materials, as well as various transparent films, such as OHP films, by utilizing its excellent transparency, thermal dimensional stability, and mechanical properties. It can be used for optical films, packaging films for fresh foods, magnetic recording tapes, magnetic floppy films, etc.
【００４０】[0040]
【物性の測定方法】（１） ガラス転移温度、冷結晶化
温度ポリエステルフイルムあるいはポリエステル１０ｍ
ｇを、示差走査型熱量計にセットし、窒素気流下で２０
℃／ｍｉｎの速度で昇温していき、ベースラインが偏奇
し始める温度と、新たなベースラインに戻る温度との平
均値をガラス転移温度とした。また、結晶化に伴う発熱
ピーク温度を冷結晶化温度とした。。[Method for measuring physical properties] (1) Glass transition temperature, cold crystallization temperature polyester film or polyester 10m
g was set in a differential scanning calorimeter and heated for 20 g under a nitrogen stream.
The temperature was increased at a rate of .degree. C./min, and the average value of the temperature at which the baseline began to become eccentric and the temperature at which it returned to the new baseline was defined as the glass transition temperature. Furthermore, the exothermic peak temperature associated with crystallization was defined as the cold crystallization temperature. .
【００４１】（２） フイルムヘイズ
フイルムヘイズは、ＡＳＴＭ−Ｄ１００３−５２に従っ
て測定した。(2) Film Haze Film haze was measured according to ASTM-D1003-52.
【００４２】（３） 含水率
ポリエステルフイルムを２３℃、３０％ＲＨ、３時間の
条件で調湿した後、２３℃の蒸留水に１５分間浸漬させ
、しかる後に微量水分計（たとえば、三菱化成（株）製
ＣＡ−２０型）を用い乾燥温度１５０℃で行なった。(3) Moisture content: After conditioning the polyester film at 23° C. and 30% RH for 3 hours, it was immersed in distilled water at 23° C. for 15 minutes, and then tested using a trace moisture meter (for example, Mitsubishi Chemical Co., Ltd.). The drying temperature was 150°C.
【００４３】（４） 熱収縮率
１０ｍｍ幅２５０〜３００ｍｍ長さのフイルムサンプル
を２００ｍｍ間隔にマーキングし、サンプル支持板に一
定張力下で固定し、万能投影機（日本光学製Ｖ１６Ａ）
を用いてマーキング間隔の原長を測長した。測長したサ
ンプルに３ｇのクリップを用いて荷重をかけ、１５０℃
に設定した熱風オーブン中で回転させながら処理した。
処理したサンプルは、原長を測定した雰囲気下に２時間
放置後、原長測定法と同様にマーキング間隔を測長して
収縮率を求めた。(4) A film sample with a heat shrinkage rate of 10 mm, a width of 250 to 300 mm, and a length was marked at 200 mm intervals, and fixed under constant tension on a sample support plate using a universal projector (Nippon Kogaku V16A).
The original length of the marking interval was measured using A load was applied to the measured sample using a 3g clip, and the sample was heated at 150°C.
Processed with rotation in a hot air oven set to . The treated sample was left in the atmosphere in which the original length was measured for 2 hours, and then the shrinkage rate was determined by measuring the marking interval in the same manner as the original length measurement method.
【００４４】（５） 引裂伝播抵抗
軽荷重式引裂試験機（東洋精機（株）製））を用いて、
ＡＳＴＭ−Ｄ−１９２２に従って測定した。サンプルサ
イズは、５１×６４ｍｍで１３ｍｍの切れ込みを入れ、
残り５１ｍｍを引き裂いた時の指示値を読み取った。(5) Tear propagation resistance Using a light load type tear tester (manufactured by Toyo Seiki Co., Ltd.),
Measured according to ASTM-D-1922. The sample size was 51 x 64 mm with a 13 mm incision.
The indicated value was read when the remaining 51 mm was torn.
【００４５】（６） 破断強度・ヤング率ＪＩＳ−Ｚ１
７０２−１９７６に準じて、幅１０ｍｍ、長さ１００ｍ
ｍの短冊片で、引張り速度は破断強度の測定の際には３
００ｍｍ／分、初期弾性率は２０ｍｍ／分で測定した。(6) Breaking strength/Young's modulus JIS-Z1
702-1976, width 10mm, length 100m
m strip, the tensile speed is 3 when measuring the breaking strength.
The initial elastic modulus was measured at 20 mm/min.
【００４６】（７） 固有粘度 ｏ−クロロフェノール溶媒を用い、２５℃で測定した。(7) Intrinsic viscosity Measurement was performed at 25°C using o-chlorophenol solvent.
【００４７】（８） 帯電防止性
２０℃、６５％ＲＨにおける半減期によって示した。半
減期は、スタティックオネストメーター（宍戸商会製）
を使用し、１０ｋＶの静電圧を印加し、スイッチオフし
た後その時の帯電量が半分になるまでの時間（秒）であ
る。(8) Antistatic property: Indicated by half-life at 20° C. and 65% RH. The half-life is measured using a static honest meter (manufactured by Shishido Shokai).
This is the time (in seconds) it takes for the amount of charge to be halved after applying a static voltage of 10 kV and switching off.
【００４８】（９） 水蒸気透過性 ＪＩＳ−Ｚ０２０８に準じて測定した。(9) Water vapor permeability Measured according to JIS-Z0208.
【００４９】[0049]
【実施例】次に本発明を実施例によってさらに詳細に説
明する。EXAMPLES Next, the present invention will be explained in more detail by way of examples.
【００５０】実施例１
テレフタル酸ジメチル１００重量部、エチレングリコー
ル７０重量部、５ーナトリウムスルホイソフタル酸ジメ
チル１０重量部、平均分子量４０００のポリエチレンオ
キシジカルボン酸１０重量部に、酢酸カルシウム０．１
重量部および三酸化アンチモン０．０３重量部を添加し
、常法によりエステル交換反応を行なった。得られた生
成物にリン酸トリメチルエステル０．０５重量部を添加
し、徐々に昇温、減圧し、最終的に２８０℃、１ｍｍＨ
ｇ以下で重合を行ない固有粘度ＩＶ＝０．９の共重合ポ
リエステルを得た。Example 1 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 10 parts by weight of polyethyleneoxydicarboxylic acid having an average molecular weight of 4000, and 0.1 part of calcium acetate.
Parts by weight and 0.03 parts by weight of antimony trioxide were added, and a transesterification reaction was carried out by a conventional method. 0.05 parts by weight of phosphoric acid trimethyl ester was added to the obtained product, the temperature was gradually increased and the pressure was reduced, and finally the temperature was raised to 280°C and 1 mmH.
The copolymerized polyester having an intrinsic viscosity of IV=0.9 was obtained by carrying out the polymerization at less than 1.0 g.
【００５１】共重合ポリエステルを常法で乾燥した後、
２８０℃で溶融押出し、未延伸シートを作成した。次い
で、８０℃で縦方向に３．８倍、８５℃で横方向に４．
０倍逐次延伸した後、２１５℃で５秒間熱固定して厚さ
１００μｍの２軸延伸フイルムを得た。After drying the copolymerized polyester in a conventional manner,
An unstretched sheet was prepared by melt extrusion at 280°C. Then, it was heated 3.8 times in the longitudinal direction at 80°C and 4 times in the transverse direction at 85°C.
After sequentially stretching 0 times, the film was heat-set at 215° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 100 μm.
【００５２】実施例２
実施例１の共重合ポリエステルをポリエステルＡとして
用いた。Example 2 The copolymerized polyester of Example 1 was used as polyester A.
【００５３】ポリエステルＢとして固有粘度ＩＶ＝０．
７のポリエチレンテレフタレートを用い、不活性粒子と
して平均粒子径０．１μｍのＳｉＯ２ を０．２重量％
添加した。Intrinsic viscosity IV=0.
No. 7 polyethylene terephthalate was used, and 0.2% by weight of SiO2 with an average particle diameter of 0.1 μm was used as inert particles.
Added.
【００５４】ポリエステルを常法で乾燥した後、２基の
押出機と３層溶融共押出が可能な口金を備えた二軸延伸
製膜機を用い、一方の押出機にポリエステルＡを、他方
の押出機にポリエステルＢを供して、２８０℃で溶融し
、Ｂ／Ａ／Ｂ３層の共押出を行ない、未延伸シートを作
成した。次いで、８０℃で縦方向に３．８倍、８５℃で
横方向に４．０倍逐次延伸した後、２１０℃で５秒間熱
固定して厚さ１００μｍの２軸延伸フイルムを得た。
Ｂ／Ａ／Ｂの厚みは、５μｍ／９０μｍ／５μｍとなっ
た。After drying the polyester in a conventional manner, using a biaxial stretching film forming machine equipped with two extruders and a die capable of three-layer melt coextrusion, polyester A is placed in one extruder and polyester A is added to the other extruder. Polyester B was supplied to an extruder, melted at 280°C, and three layers of B/A/B were coextruded to produce an unstretched sheet. Next, the film was sequentially stretched 3.8 times in the machine direction at 80° C. and 4.0 times in the horizontal direction at 85° C., and then heat-set at 210° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 100 μm. The thicknesses of B/A/B were 5 μm/90 μm/5 μm.
【００５５】実施例３
テレフタル酸ジメチル１００重量部、エチレングリコー
ル７０重量部、５ーナトリウムスルホイソフタル酸ジメ
チル１０重量部、平均分子量４０００のポリテトラメチ
レンオキシジカルボン酸５重量部、アジピン酸ジメチル
５重量部に、酢酸カルシウム０．１重量部および三酸化
アンチモン０．０３重量部を添加して実施例１と同様に
固有粘度ＩＶ＝０．９の共重合ポリエステルＡを作成し
た。Example 3 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 5 parts by weight of polytetramethyleneoxydicarboxylic acid having an average molecular weight of 4000, 5 parts by weight of dimethyl adipate. 0.1 part by weight of calcium acetate and 0.03 part by weight of antimony trioxide were added to prepare a copolymerized polyester A having an intrinsic viscosity of IV=0.9 in the same manner as in Example 1.
【００５６】また、テレフタル酸ジメチル１００重量部
、エチレングリコール７０重量部、５ーナトリウムスル
ホイソフタル酸ジメチル１０重量部に酢酸カルシウム０
．１重量部および三酸化アンチモン０．０３重量部を添
加して固有粘度ＩＶ＝０．７５の共重合ポリエステルを
作成した。Further, 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, and 0 parts by weight of calcium acetate were added.
．． 1 part by weight and 0.03 part by weight of antimony trioxide were added to prepare a copolymerized polyester having an intrinsic viscosity of IV=0.75.
【００５７】実施例２と同様にＢ／Ａ／Ｂの３層共押出
を行なってシート化し、８５℃で縦方向に３．６倍、９
０℃で横方向に４．０倍逐次延伸した後、２００℃で５
秒間熱固定して厚さ１００μｍの２軸延伸フイルムを得
た。Ｂ／Ａ／Ｂの厚みは、５μｍ／９０μｍ／５μｍと
なった。Similar to Example 2, three-layer coextrusion of B/A/B was carried out to form a sheet, and the size was 3.6 times and 9 times in the longitudinal direction at 85°C.
After sequentially stretching 4.0 times in the transverse direction at 0°C, stretching 5 times at 200°C.
A biaxially stretched film having a thickness of 100 μm was obtained by heat setting for seconds. The thicknesses of B/A/B were 5 μm/90 μm/5 μm.
【００５８】実施例４
テレフタル酸ジメチル１００重量部、エチレングリコー
ル７０重量部、５ーナトリウムスルホイソフタル酸ジメ
チル１０重量部、平均分子量６０００のポリエチレンオ
キシジカルボン酸５重量部、平均分子量１０００のポリ
エチレングリコール５重量部に、酢酸カルシウム０．１
重量部および三酸化アンチモン０．０３重量部、不活性
粒子として平均粒子径０．１μｍのＳｉＯ２ を０．１
重量％添加して共重合ポリエステルＡを作成した。Example 4 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 5 parts by weight of polyethyleneoxydicarboxylic acid having an average molecular weight of 6,000, and 5 parts by weight of polyethylene glycol having an average molecular weight of 1,000. 0.1 part of calcium acetate
parts by weight and 0.03 parts by weight of antimony trioxide, and 0.1 parts by weight of SiO2 with an average particle size of 0.1 μm as inert particles.
A copolymerized polyester A was prepared by adding % by weight.
【００５９】ポリエステルＢとしては、固有粘度ＩＶ＝
０．７のポリエチレンテレフタレートを用い、実施例１
と同様の押出機及び口金を用いて、Ａ／Ｂ／Ａの３層共
押出を行なってシート化し、を作成し、更にシート化し
、８５℃で縦方向に３．６倍、９０℃で横方向に４．０
倍逐次延伸した後、２００℃で５秒間熱固定して厚さ１
００μｍの２軸延伸フイルムを得た。Ａ／Ｂ／Ａの厚み
は、３０μｍ／４０μｍ／３０μｍとなった。Polyester B has an intrinsic viscosity IV=
Example 1 using polyethylene terephthalate of 0.7
Using the same extruder and die, co-extrude three layers of A/B/A to form a sheet. 4.0 in direction
After successive stretching, heat set at 200℃ for 5 seconds to obtain a thickness of 1.
A biaxially stretched film of 00 μm was obtained. The thickness of A/B/A was 30 μm/40 μm/30 μm.
【００６０】比較例１
常法により固有粘度ＩＶ＝０．６５，不活性粒子として
平均粒子径０．１μｍのＳｉＯ２ を０．１重量％添加
したポリエチレンテレフタレートを作成し、更にシート
化し、９０℃で縦方向に３．５倍、９５℃で横方向に３
．８倍逐次延伸した後、２２０℃で５秒間熱固定して厚
さ１００μｍの２軸延伸フイルムを得た。Comparative Example 1 Polyethylene terephthalate with an intrinsic viscosity of IV=0.65 and 0.1% by weight of SiO2 with an average particle diameter of 0.1 μm added as inert particles was prepared by a conventional method, and then formed into a sheet and heated at 90°C. 3.5 times vertically, 3 times horizontally at 95℃
．． After sequentially stretching 8 times, the film was heat-set at 220° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 100 μm.
【００６１】比較例２
テレフタル酸ジメチル１００重量部、エチレングリコー
ル７０重量部、５ーナトリウムスルホイソフタル酸ジメ
チル１０重量部、平均分子量４０００のポリエチレング
リコール１０重量部に、酢酸カルシウム０．１重量部お
よび三酸化アンチモン０．０３重量部を添加して固有粘
度ＩＶ＝０．８０の共重合ポリエステルを作成し、更に
シート化し、８５℃で縦方向に３．６倍、９０℃で横方
向に４．０倍逐次延伸した後、１９５℃で５秒間熱固定
して厚さ１００μｍの２軸延伸フイルムを得た。Comparative Example 2 To 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, and 10 parts by weight of polyethylene glycol having an average molecular weight of 4000, 0.1 part by weight of calcium acetate and 3 parts by weight of calcium acetate were added. A copolymerized polyester with an intrinsic viscosity IV of 0.80 was prepared by adding 0.03 parts by weight of antimony oxide, which was further formed into a sheet, and was 3.6 times larger in the longitudinal direction at 85°C and 4.0 times larger in the transverse direction at 90°C. After sequential stretching, the film was heat-set at 195° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 100 μm.
【００６２】比較例３
テレフタル酸ジメチル１００重量部、エチレングリコー
ル７０重量部、５ーナトリウムスルホイソフタル酸ジメ
チル１０重量部、アジピン酸ジメチル１０重量部に、酢
酸カルシウム０．１重量部および三酸化アンチモン０．
０３重量部を添加して固有粘度ＩＶ＝０．８０の共重合
ポリエステルを作成し、更にシート化し、８５℃で縦方
向に３．６倍、９０℃で横方向に３．８倍逐次延伸した
後、２００℃で５秒間熱固定して厚さ１００μｍの２軸
延伸フイルムを得た。Comparative Example 3 100 parts by weight of dimethyl terephthalate, 70 parts by weight of ethylene glycol, 10 parts by weight of dimethyl 5-sodium sulfoisophthalate, 10 parts by weight of dimethyl adipate, 0.1 part by weight of calcium acetate, and 0 part by weight of antimony trioxide. ．．
A copolymerized polyester with an intrinsic viscosity of IV=0.80 was prepared by adding 03 parts by weight, which was further formed into a sheet, which was sequentially stretched 3.6 times in the machine direction at 85°C and 3.8 times in the transverse direction at 90°C. Thereafter, the film was heat-set at 200° C. for 5 seconds to obtain a biaxially stretched film with a thickness of 100 μm.
【００６３】表１、表２に実施例１〜３、比較例１〜３
の物性を示す。比較例１は、通常のポリエステルフイル
ムであり容易に帯電してしまうが、比較例２では、帯電
防止性に比較的良好であるものの熱寸法安定性やエージ
ング後の透明性が不十分であった。比較例３では、帯電
防止性・熱寸法安定性とも不十分であった。これに対し
、実施例１〜３では、透明性・機械的特性・熱寸法安定
性・帯電防止性に優れたフイルムが得られ、また４０℃
９０％ＲＨの条件でエージングしてもヘイズ値はほとん
ど変化せず透明性は維持されていた。Tables 1 and 2 show Examples 1 to 3 and Comparative Examples 1 to 3.
The physical properties of Comparative Example 1 is a normal polyester film and is easily charged, while Comparative Example 2 has relatively good antistatic properties but has insufficient thermal dimensional stability and transparency after aging. . In Comparative Example 3, both antistatic properties and thermal dimensional stability were insufficient. On the other hand, in Examples 1 to 3, films with excellent transparency, mechanical properties, thermal dimensional stability, and antistatic properties were obtained.
Even after aging at 90% RH, the haze value hardly changed and transparency was maintained.
【００６４】[0064]
【表１】[Table 1]
【００６５】[0065]
【表２】[Table 2]
【００６６】[0066]
【発明の効果】本発明のポリエステルフイルムは、透明
性・吸水性・機械的特性・耐熱性に優れた帯電防止ポリ
エステルフイルムであり、優れた熱寸法安定性により、
耐熱性が要求されるＯＨＰシートに利用することができ
、また良好な吸水性は例えば生鮮食品の包装フイルムに
利用することができる。更には、写真用フイルム、磁気
記録用フイルムなどにも利用できる。[Effects of the Invention] The polyester film of the present invention is an antistatic polyester film with excellent transparency, water absorption, mechanical properties, and heat resistance, and has excellent thermal dimensional stability.
It can be used for OHP sheets that require heat resistance, and its good water absorption properties can be used, for example, for packaging films for fresh foods. Furthermore, it can also be used for photographic films, magnetic recording films, etc.
Claims (4)
分として、金属スルホネートを有する芳香族ジカルボン
酸及び／又はその誘導体を２〜２０重量％と、（ａ）式
で示される平均分子量６００〜２００００のポリエーテ
ルジカルボン酸及び／又はその誘導体を２〜２０重量％
とを含むポリエステルよりなるフィルムであって、水蒸
気透過率が１０．０ｇ／ｍ２ ・２４ｈｒ／０．１ｍｍ
以上、帯電量の半減期が２秒以下であることを特徴とす
る帯電防止性ポリエステルフイルム。 Ｒ１ ＯＯＣＣＨ２ −（Ｏ−Ｒ２ ）ｎ −
ＯＣＨ２ ＣＯＯＲ３ （ａ）（
Ｒ１ 、Ｒ３ ：Ｈまたは炭素数１〜８のアルキル基、
Ｒ２ ：炭素数２〜８のアルキレン基、ｎ：正の整数）
1. A polyether having an average molecular weight of 600 to 20,000 represented by formula (a), containing 2 to 20% by weight of an aromatic dicarboxylic acid having a metal sulfonate and/or its derivative as a dicarboxylic acid copolymerization component of the polyester. 2-20% by weight of dicarboxylic acid and/or its derivatives
A film made of polyester containing and having a water vapor permeability of 10.0g/m2/24hr/0.1mm
As described above, the antistatic polyester film is characterized in that the half-life of the amount of charge is 2 seconds or less. R1 OOCCH2 −(O−R2 )n −
OCH2 COOR3 (a)(
R1, R3: H or an alkyl group having 1 to 8 carbon atoms,
R2: alkylene group having 2 to 8 carbon atoms, n: positive integer)
で示されるポリエチレンオキシジカルボン酸であること
を特徴とする特許請求の範囲第１項に記載の帯電防止性
ポリエステルフイルム。 Ｒ１ ＯＯＣＣＨ２ −（Ｏ−ＣＨ２ ＣＨ２
）ｎ −ＯＣＨ２ ＣＯＯＲ２ （ｂ）（Ｒ１
、Ｒ２ ：Ｈまたは炭素数１〜８のアルキル基、ｎ：正
の整数）2. The antistatic polyester film according to claim 1, wherein the polyether dicarboxylic acid is polyethylene oxydicarboxylic acid represented by formula (b). R1 OOCCH2 -(O-CH2 CH2
)n -OCH2 COOR2 (b)(R1
, R2: H or an alkyl group having 1 to 8 carbon atoms, n: a positive integer)
の少なくとも１層として、特許請求の範囲第１項に記載
のポリエステルフイルムを含むことを特徴とする帯電防
止性ポリエステルフイルム。3. An antistatic polyester film comprising the polyester film according to claim 1 as at least one layer of the polyester film having a multilayer structure.
イルムのヘイズ値が５％以下で、かつ１５０℃における
熱収縮率が２％以下であることを特徴とする特許請求の
範囲第１〜３項のいずれかに記載の帯電防止性ポリエス
テルフイルム。4. Claims 1 to 3, characterized in that the polyester film is biaxially oriented, has a haze value of 5% or less, and has a heat shrinkage rate of 2% or less at 150°C. The antistatic polyester film according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP102891A JP2982311B2 (en) | 1991-01-09 | 1991-01-09 | Antistatic polyester film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP102891A JP2982311B2 (en) | 1991-01-09 | 1991-01-09 | Antistatic polyester film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04248843A true JPH04248843A (en) | 1992-09-04 |
| JP2982311B2 JP2982311B2 (en) | 1999-11-22 |
Family
ID=11490108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP102891A Expired - Fee Related JP2982311B2 (en) | 1991-01-09 | 1991-01-09 | Antistatic polyester film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2982311B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0759459A2 (en) * | 1995-08-17 | 1997-02-26 | Teijin Limited | Thermoplastic resin composition superior in transparency and antistatic property |
| WO2002025377A1 (en) * | 2000-09-20 | 2002-03-28 | Hitachi Chemical Co., Ltd. | Photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| US7718104B2 (en) | 2001-12-12 | 2010-05-18 | Dupont Teijin Films Us Ltd. | Process for the production of brittle polymeric film |
| US11028299B2 (en) * | 2013-11-19 | 2021-06-08 | Mitsubishi Polyester Film, Inc | Anti-powdering and anti-static polymer film for digital printing |
-
1991
- 1991-01-09 JP JP102891A patent/JP2982311B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0759459A2 (en) * | 1995-08-17 | 1997-02-26 | Teijin Limited | Thermoplastic resin composition superior in transparency and antistatic property |
| EP0759459A3 (en) * | 1995-08-17 | 1997-10-01 | Teijin Ltd | Thermoplastic resin composition superior in transparency and antistatic property |
| WO2002025377A1 (en) * | 2000-09-20 | 2002-03-28 | Hitachi Chemical Co., Ltd. | Photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| US7078151B2 (en) | 2000-09-20 | 2006-07-18 | Hitachi Chemical Co., Ltd. | Photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| US7718104B2 (en) | 2001-12-12 | 2010-05-18 | Dupont Teijin Films Us Ltd. | Process for the production of brittle polymeric film |
| US8530045B2 (en) | 2001-12-12 | 2013-09-10 | DuPont Teijin Films U.S. Ltd. | Brittle polymeric film and tamper evident labels made therefrom |
| US11028299B2 (en) * | 2013-11-19 | 2021-06-08 | Mitsubishi Polyester Film, Inc | Anti-powdering and anti-static polymer film for digital printing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2982311B2 (en) | 1999-11-22 |
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