JPH0554494B2 - - Google Patents
Info
- Publication number
- JPH0554494B2 JPH0554494B2 JP60094683A JP9468385A JPH0554494B2 JP H0554494 B2 JPH0554494 B2 JP H0554494B2 JP 60094683 A JP60094683 A JP 60094683A JP 9468385 A JP9468385 A JP 9468385A JP H0554494 B2 JPH0554494 B2 JP H0554494B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- dispersion
- film
- polyester
- soluble organic
- 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.)
- Expired - Fee Related
Links
- 239000006185 dispersion Substances 0.000 claims description 62
- 229920000728 polyester Polymers 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000002245 particle Substances 0.000 claims description 47
- 238000000034 method Methods 0.000 claims description 35
- 150000002894 organic compounds Chemical class 0.000 claims description 27
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000010419 fine particle Substances 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 239000000314 lubricant Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229920001225 polyester resin Polymers 0.000 claims description 6
- 239000004645 polyester resin Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 35
- 239000011248 coating agent Substances 0.000 description 26
- 238000000576 coating method Methods 0.000 description 26
- -1 polypropylene Polymers 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229920006267 polyester film Polymers 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 238000006068 polycondensation reaction Methods 0.000 description 9
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920006026 co-polymeric resin Polymers 0.000 description 4
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 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 2
- 239000000155 melt Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- HBLRZDACQHNPJT-UHFFFAOYSA-N 4-sulfonaphthalene-2,7-dicarboxylic acid Chemical compound OS(=O)(=O)C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 HBLRZDACQHNPJT-UHFFFAOYSA-N 0.000 description 1
- WNKQDGLSQUASME-UHFFFAOYSA-N 4-sulfophthalic acid Chemical compound OC(=O)C1=CC=C(S(O)(=O)=O)C=C1C(O)=O WNKQDGLSQUASME-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910005793 GeO 2 Inorganic materials 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007340 Zn(OAc)2.2H2O Inorganic materials 0.000 description 1
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-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
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 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
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- XLIDPNGFCHXNGX-UHFFFAOYSA-N dialuminum;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Si+4] XLIDPNGFCHXNGX-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 230000001771 impaired effect Effects 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
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 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
- 239000010434 nepheline Substances 0.000 description 1
- 229910052664 nepheline Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- KJERPKPRIWFPGO-UHFFFAOYSA-N sodium;2-sulfoterephthalic acid Chemical compound [Na].OC(=O)C1=CC=C(C(O)=O)C(S(O)(=O)=O)=C1 KJERPKPRIWFPGO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Magnetic Record Carriers (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
（産業上の利用分野）
本発明は、透明性及び、滑り性を兼ね備えた熱
可塑性樹脂フイルム及びその製造法に関する。
（従来の技術）
熱可塑性樹脂フイルム、特に２軸延伸された、
ポリプロピレン、ポリエチレンテレフタレートフ
イルム等は、その優れた寸法安定性、機械的強
度、透明性等の性質から、包装材料用、金属蒸着
用、写真用、製図用、電気用、磁気テープ用その
他の各種の工業用途等の非常に多岐にわたる分野
での応用がなされている。しかしこれらいずれの
場合においても熱可塑性樹脂フイルムがすべての
性質において満足されているわけではない。殆ん
どの用途の場合、フイルムは単体で用いられるこ
とは少なく、何等かの２次加工がなされる。この
ためその加工時における作業性、製品の性能及び
品質の安定性等の点から、特に、表面の滑り性、
透明性等の特性は重要な課題とされている。例え
ば、滑り性においては、フイルム巻反の送り出
し、巻き取り、スリツト、カツテイング、コーテ
イング等、あらゆる目的の２次加工に必須の工程
である基本作業の能率を著しく左右するのみなら
ず製膜上特に巻取りが困難になると共に、得られ
たフイルムのユーザーにおける作業能率、例えば
包装用途であれば自動包装機における能率が、事
務用、製図用等のカツト用途であれば、つき揃い
性、送り性等の作業能率等が大きく左右される。
このため、従来からフイルム表面の滑り性を改善
する目的で、ワツクス系や脂肪酸アミド、脂肪酸
金属塩等の高級脂肪酸系化合物、有機ポリシロキ
サン或は、二酸化チタン、炭酸カルシウム、タル
ク、カオリン、硫酸バリウム、酸化アルミニウ
ム、二酸化硅素その他各種の不活性な無機化合物
粒子等のいわゆる滑剤をフイルム用合成樹脂中に
分散させることにより、その改善がはかられて来
た。
また、特にポリエステルフイルムの場合に限れ
ば上記以外の滑剤として、ポリエステル製造時に
使用する金属化合物触媒たとえば、アルカリ金属
化合物、アルカリ土類金属化合物等によつて微粒
子を形成せしめる方法や、ポリエステル製造時の
原料の１種であるテレフタル酸とカルシウム、リ
チウム等の金属とによる塩による粒子を発生させ
るいわゆる内部粒子法、これらの化合物粒子を予
め合成しておき、ポリエステル製造系へ添加する
方法等もあげられる。しかし、これら従来の滑剤
添加法による場合は、いずれの方法を用いても、
滑り性が向上すると同時に必らず透明性が低下す
るという難点を有しており、この相反する両者、
滑り性と透明性を共に完全な意味で満足すること
は不可能とされ、常に某しかの妥協が強いられて
来た。すなわち、透明性を無添加のものとほぼ同
一にして該フイルムの摩擦係数を大巾に低下させ
たフイルムは存在しなかつたのである。
更にナール加工等の形態的加工を巻きとる前に
施す方法があるが、二次加工でのスリツトでナー
ル加工部分がトリミングされたり、片側のみに存
在するようになるなど、従来の製造法は種々の問
題を有していた。
（発明が解決しようとする問題点）
本発明者らは、上記の問題を解決すべく鋭意研
究の結果、滑剤量が特定以下の熱可塑性樹脂より
得られるフイルムに、水に不溶性である特定のポ
リエステル共重合体と水溶性有機化合物及び水、
更に不活性粒子、及び要すれば他の添加物を含有
したコーテイング剤をコート法によつて積層する
ことによつてフイルムの再性利用ができ、かつコ
ーテイング工程において防爆安定性がよい透明且
つ易滑性が同時に改善されたコーテイングフイル
ム及びその製造法を提供するものである。
（問題点を解決するための手段）
本発明の第１は熱可塑性樹脂フイルムの少なく
とも片面(A)全ジカルボン酸成分に対し0.5〜15モ
ル％のスルホン酸金属塩基含有ジカルボン酸類と
多価アルコール類とから成る水不溶性ポリエステ
ル共重合体、(B)沸点が60〜200℃である水溶性有
機化合物、(C)水、(D)平均粒径が0.01〜10μmの不
活性微粒子とから成る水系ポリエステル樹脂分散
液を塗布してなる熱可塑性樹脂フイルムにおい
て、該水溶性有機化合物(B)の一部と水(C)の一部を
予め混合した水溶液中に所要量の不活性微粒子(D)
を予め添加し、ついで十分な分散前処理を施した
後、該分散液に対し所要量の水不溶性ポリエステ
ル樹脂(A)と残りの水溶性有機化合物(B)及び水(C)と
から成る樹脂分散液を添加し、それぞれの混合比
率が重量比で次式(1)、(2)、(3)をそれぞれ同時に満
足するごとく配合されてなることを特徴とする易
滑透明性フイルムである。
(A)／(B)＝100／20〜5000 ……(1)
(B)／(C)＝100／50〜10000 ……(2)
(A)／(D)＝100000／５〜3000 ……(3)
また本発明の第２は溶融押出し法により得られ
た未延伸または一軸方向に延伸された熱可塑性樹
脂フイルムの少なくとも片面に、(A)全ジカルボン
酸成分に対し0.5〜15モル％のスルホン酸金属塩
基含有ジカルボン酸類と多価アルコール類とから
成る水不溶性ポリエステル共重合体、(B)沸点が60
〜200℃である水溶性有機化合物、(C)水、(D)平均
粒径が0.01〜10μmの不活性微粒子とから成る水
系ポリエステル樹脂分散液を、予め該水溶性有機
化合物(B)の一部と水(C)の一部を混合した水溶液中
に所定量の不活性微粒子(D)を添加し、十分な分散
処理した後、該分散液に対し所要量の水不溶性ポ
リエステル樹脂(A)と残りの水溶性有機化合物(B)お
よび水(C)とから成る樹脂分散液を添加し、それぞ
れの混合比率が重量比で次式(1)、(2)、(3)をそれぞ
れ同時に満足するごとく配合方法で作製し、塗
布、乾燥後、少なくとも一軸方向に延伸処理する
事を特徴とする易滑透明性フイルムの製造法であ
る。
(A)／(B)＝100／20〜5000 ……(1)
(B)／(C)＝100／50〜10000 ……(2)
(A)／(D)＝100000／５〜3000 ……(3)
上記第１の発明の好ましい実施態様(1)は第１の
発明において熱可塑性樹脂フイルムが、滑剤含有
量が0.05重量％以下のポリエステルからなるフイ
ルムである。
上記第２の発明の好ましい実施態様(2)は第２の
発明において熱可塑性樹脂フイルムが、滑剤含有
が0.05重量％以下のポリエステルからなる製造法
である。上記第２の発明の別の好ましい、あるい
は実施態様(2)のより好ましい実施態様(3)は第２の
発明あるは実施態様(2)において分散前処理が超音
波分散処理である製造法である。
この発明の水系分散液に含有されるポリエステ
ル共重合体(A)は、スルホン酸金属塩基含有ジカル
ボン酸0.5〜15モル％と、スルホン酸金属塩基を
含有しないジカルボン酸85〜99.5モル％との混合
ジカルボン酸をグリコール成分と反応させて得ら
れた実質的に水不溶性のポリエステル共重合体で
ある。実質的に水不溶性とは、ポリエステル共重
合体を80℃の熱水中で撹拌しても熱水中にポリエ
ステル共重合体が消散しないことを意味し、具体
的にはポリエステル共重合体を過剰の80℃熱水中
で24時間撹拌処理した後のポリエステル共重合体
の重量減少が５重量％以下のものである。
上記のスルホン酸金属塩基含有ジカルボン酸と
しては、スルホテレフタル酸、５−スルホイソフ
タル酸、４−スルホフタル酸、４−スルホナフタ
レン−２，７−ジカルボン酸、５〔４−スルホフ
エノキシ〕イソフタル酸等の金属塩があげられ、
特に好ましいのは５−ナトリウムスルホイソフタ
ル酸、ナトリウムスルホテレフタル酸である。こ
れらのスルホン酸金属塩基含有ジカルボン酸成分
は、全ジカルボン酸成分に対して0.5〜15モル％
であり、15モル％を越えると水に対する分散性は
向上するがポリエステル共重合体の耐水性が著し
く低下し、また0.5モル％未満では水に対する分
散性が著しく低下する。ポリエステル共重合体の
水に対する分散性は、共重合組成分、水溶性有機
化合物の種類および配合比などによつて異なる
が、上記スルホン酸金属塩基含有ジカルボン酸は
水に対する分散性を損わない限り、少量の方が好
ましい。
スルホン酸金属塩基を含まないジカルボン酸と
しては、芳香族、脂肪族、脂環族のジカルボン酸
が使用できる。芳香族ジカルボン酸としては、テ
レフタル酸、イソフタル酸、オルソフタル酸、
２，６−ナフタレンジカルボン酸等をあげること
ができる。
これらの芳香族ジカルボン酸は全ジカルボン酸
成分の40モル％以上であることが好ましく、40モ
ル％未満ではポリエステル共重合体の機械的強度
や耐水性が低下する。脂肪族および脂環族のジカ
ルボン酸としては、コハク酸、アジピン酸、セバ
シン酸、１，３−シクロペンタンジカルボン酸、
１，２−シクロヘキサンジカルボン酸、１，３−
シクロヘキサンジカルボン酸、１，４−シクロヘ
キサンジカルボン酸などがあげられる。これらの
非芳香族ジカルボン酸成分を加えると、場合によ
つては接着性能が高められるが、一般的にはポリ
エステル共重合体の機械的強度や耐水性を低下さ
せる。
上記混合ジカルボン酸と反応させるグリコール
成分としては、炭素数２〜８個の脂肪族グリコー
ルまたは炭素数６〜12個の脂環族グリコールであ
り、具体的には、エチレングリコール、１，２−
プロピレングリコール、１，３−プロパンジオー
ル、１，４−ブタンジオール、ネオペンチルグリ
コール、１，６−ヘキサンジオール、１，２−シ
クロヘキサンジメタノール、１，３−シクロヘキ
サンジメタノール、１，４−シクロヘキサンジメ
タノール、ｐ−キシリレングリコール、ジエチレ
ングリコール、トリエチレングリコールなどであ
る。またポリエーテルとして、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などがあげられる。
ポリエステル共重合体は、通常の溶融重縮合に
よつて得られる。すなわち上記のジカルボン酸成
分およびグリコール成分を直接反応させて水を留
去しエステル化したのち、重縮合を行なう直接エ
ステル化法、あるいは上記ジカルボン酸成分のジ
メチルエステルとグリコール成分を反応させてメ
チルアルコールを留出しエステル交換を行なわせ
たのち重縮合を行なうエステル交換法などによつ
て得られる。その他、溶液重縮合、界面重縮合な
ども使用され、この発明のポリエステル共重合体
は重縮合の方法によつて限定されるものではな
い。
上記のポリエステル共重合体の水系分散液を得
るには、水溶性有機化合物とともに水に分散する
ことが必要である。例えば、上記ポリエステル共
重合体と水溶性有機化合物とを50〜200℃であら
かじめ混合し、この混合物に水を加え撹拌して分
散する方法、あるいは逆に、混合物を水に加え撹
拌して分散する方法、あるいはポリエステル共重
合体と水溶性有機化合物と水とを共存させて40〜
120℃で撹拌する方法がある。
上記水溶性有機化合物は、20℃で１の水に対
する溶解度が20ｇ以上の有機化合物であり、具体
的に脂肪族および脂環族のアルコール、エーテ
ル、エステル、ケトン化合物であり、例えばメタ
ノール、エタノール、イソプロパノール、ｎ−ブ
タノール等の１価アルコール類、エチレングリコ
ール、プロピレングリコール等のグリコール類、
メチルセロソルブ、エチルセロソルブ、ｎ−ブチ
ルセロソルブ等のグリコール誘導体、ジオキサ
ン、テトラヒドロフラン等のエーテル類、酢酸エ
チル等のエステル類、メチルエチルケトン等のケ
トン類である。これら水溶性有機化合物は、単独
または２種以上を併用することができる。上記化
合物のうち、水への分散性、フイルムへの塗布性
からみて、ブチルセロソルブ、エチルセロソルブ
が好適である。
上記(A)のポリエステル共重合体、(B)水溶性有機
化合物および(C)水の配合重量割合は
(A)／(B)＝100／20〜5000
(B)／(C)＝100／50〜10000
を満足することが重要である。ポリエステル共重
合体に対して水溶性有機化合物が少なく(A)／(B)が
100／20を越える場合は、水系分散液の分散性が
低下する。この場合、界面活性剤を添加すること
によつて、分散性を補助することができるが、界
面活性剤の量が多過ぎると接着性、耐水性が低下
する。逆に(A)／(B)が100／5000未満の場合、また
は(B)／(C)が100／50を越える場合は、水系分散液
の水溶性有機化合物量が多くなりコート時に溶剤
による爆発の危険性が生じ、このために防爆対策
を講ずる必要があり、さらに環境汚染、コスト高
となるので化合物回収を考慮する必要がある。
(B)／(C)が100／10000未満の場合は、水系分散液の
表面張力が大きくなり、フイルムへの濡れ性が低
下し、塗布斑を生じ易くなる。この場合、界面活
性剤の添加によつて濡れ性を改良することができ
るが、界面活性剤の量が多過ぎると上記したと同
様に接着性や耐水性が低下する。
更に、この分散液に添加する(D)不活性粒子とし
ては、胡粉、チヨーク、重質炭カル、軽微性炭カ
ル、極微細炭カル、塩基性炭酸マグネシウム、ド
ロマイト、特殊炭酸カルシウム、カオリン、焼成
クレー、バイロフイライト、ベントナイト、セリ
サライト、ゼオライト、ネフエリン、シナイト、
タルク、アタバルジヤナイト、合成珪酸アルミ、
合成珪酸カルシウム、珪藻土、珪石粉、含水微粉
珪酸、無水微粉珪酸、水酸化アルミニウム、酸化
アルミニウム、バライト、沈降性硫酸バリウム、
天性石膏、石膏、亜硫酸カルシウム、球状ガラス
微細粒子、中空ガラス球微粒子、その他各種の無
機系粒子または有機系微粒子、例えばベンゾグア
ナミン系樹脂、ポリスチレン系樹脂、アクリル系
樹脂等の架橋体等が挙げられる。これらは、透明
性と滑り性との関連において、いずれを用いても
良いが、特に好ましいのは、珪酸の微粒子であ
り、白色の酸化チタン、黒色のカーボンブラツク
等の粒子は、透明性の低下が著しく、好ましくな
い。用いるべき粒径は、0.01μ〜10μのものを用い
るのが好ましく、より好ましくは0.015〜5μであ
る。0.01μ以下の粒径のものでは、多量に用いな
ければならず、10μ以上では粗大突起が生じ表面
平滑性が要求される用途には好ましくなく、ま
た、突起密度が減少することから逆にすべり性は
悪くなる場合がある。
(A)に対して(D)の用いる量は重量比で(A)／(D)＝
100000／５〜3000の割合が良く、好ましくは(A)／
(D)＝100000／20〜500である。
(A)／(D)が100000／５を越えると、滑り性の向上
効果は得られず、また100000／3000未満の場合に
は透明性が悪化するため好ましくない。
また、必要により混合し得る(A)〜(D)以外の添加
剤としては、有機系、無機系の制電剤、接着性向
上剤、離型性向上剤その他の機能性付与剤が挙げ
られるが、これらは基本的に本発明の主旨である
透明性及び滑り性いずれをも大きく疎害しない限
りその添加物、添加量については何等制限するも
のではない。
以上の水系樹脂分散液組成物を、合成樹脂フイ
ルムにコーテイングするための該分散液の混合手
順は、水溶性有機化合物(B)の一部、好ましくは(B)
の合計所要量の98〜50重量％と、水(C)の一部好ま
しくは(C)の合計所要量の85〜30重量％とを予め混
合した水溶性有機化合物(B)の水溶液を作製し、該
水溶液中に不活性粒子(D)の所要量を添加し十分な
分散処理を行ない、可能な限り該不活性粒子の一
次粒子径を再現させた二次凝集粒子を含まない粒
子分散液(1)を作製する。この際の粒子分散方法と
しては、ホモミキサーに代表されるごときの高速
インペラー撹拌型分散機、ステンレス、ガラスそ
の他のボールまたはビーズ等を用い撹拌を行う方
式のミル型分散機、高圧力差による噴出力を応用
した高圧型均質分散機、超音波発振による微少振
動エネルギーを利用した超音波分散機その他各種
の方式の分散機を用いることが可能であり、いず
れも有効であるが特に本発明におけるごとく、合
計液量に対し被分散粒子量が比較的少ないごとき
希薄濃度系の分散法として本発明者等が鋭意検討
の結果超音波分散機を用いることが好適であるこ
とを見出した。その理由としては、高速インペラ
ー撹拌型、ボールミル方式、高圧式等の粒子衝
突・高剪断力下における分散方式は、粒子衝突確
立の高い高濃度系においてこそその効果を有効に
発揮するものの、本発明のごとき希薄濃度系にお
いてはむしろ効率が悪く、粒子濃度に拘らず粒子
に直接衝撃振動が与えられる超音波分散法が有利
に作用するものと考えられる。勿論本発明の効果
を損なわない程度に、超音波分散処理と同時ある
いは処理后に上記他の方式の分散法を併用しても
何等差しつかえない。
このようにして得られた粒子分散液(1)に対し、
一方前述の方法により予め重合された水不溶性共
重合体(A)と、残りの水溶性有機化合物(B)、好まし
くは合計所要量の２〜50重量％と残りの水(C)、好
ましくは合計所要量の15〜70重量％とから得られ
たポリエステル共重合体樹脂水系分散液（）を
添加混合する方法により、熱可塑性樹脂フイルム
特にポリエステル系フイルムコーテイング用とし
て好適な分散液組成物を得ることが出来る。
本発明の特徴の一つは、この水溶性有機化合物
(B)と水(C)をそれぞれ分割して粒子分散液（）と
ポリエステル共重合体樹脂水系分散液（）を、
別々に分割調合した後に均一混合液として塗布用
分散液組成物を得る点にあり、超音波分散に供す
る前の未分散不活性粒子(D)が、濃厚なポリエステ
ル共重合体樹脂分散液と接触するのを避け、超音
波分散処理によつて不活性粒子(D)を十分一次粒子
状態に分散した後に、希釈された該ポリエステル
共重合体樹脂と接触させる場合にのみ従来到底達
し得なかつたごとき粒子微分散樹脂液が得られる
ことを見出した点にある。
本コーテイング組成物は熱可塑性樹脂フイルム
全般に適用可能であるが、ポリプロピレン、ポリ
エステル、ポリアミド系等の延伸配向処理されて
なるフイルムに効果的に用いられ、特にポリエチ
レンテレフタレートを主体とするごときポリエス
テル系配向フイルムにおいて、密着性その他の点
で良好な効果を発揮するものである。
また本発明の特徴を最も効果的に発揮するため
には、該ポリエステル系配向フイルム中には、含
有せる滑剤の量が0.05重量％以下であることが透
明性の点から好ましい。
本発明におけるコーテイング用分散液組成物の
塗布方法は、通常の方法によつて行なうことが可
能であるが、特に熱可塑性樹脂が溶融押出しされ
た後の未延伸フイルム、あるいは、縦または、横
方向へ一軸に延伸された後のフイルムに塗布を行
ない、次いで二軸または一軸方向に延伸を行なつ
た後熱処理を行なうことにより二軸配向されたコ
ートフイルムを得る方法がコート被膜の密着性、
透明性及び経済性の見地から好ましい。特に塗膜
の乾燥性、作業性等を考慮した場合、一軸方向に
延伸した後塗布する方式が好ましく、縦方向に一
軸延伸された後塗布し、更に横方向に延伸するこ
とにより二軸配向フイルムを得る方法が特に好ま
しい。塗布されるべき面および塗布量は得られる
フイルムの目的、用途によつて異なるが、片面塗
布または両面塗布のいずれかが可能であり、塗布
量は二軸延伸後のフイルム上に存在する量として
0.005〜５ｇ／m2が好ましく0.01〜３ｍ／m2が特
に好ましい。塗布量が0.005ｇ／m2未満の場合は
所期の効果が得られず、５ｇ／m2を越えると、ブ
ロツキング等の弊害を生じやすい。
また、上記ポリエステル共重合体の水系分散液
を塗布する前に、ポリエステルフイルムにコロナ
放電処理を施すことによつて、水系分散液の塗布
性がよくなり、かつポリエステルフイルムとポリ
エステル共重合体塗膜との間の接着強度が改善さ
れる。
またインラインコート後あるいは二軸延伸後の
ポリエステル共重合体層に、コロナ放電処理、窒
素雰囲気下でのコロナ放電処理、紫外線照射処理
などを施すことによつてフイルム表面の濡れ性や
接着性を向上させることができる。
（実施例）
以下、実施例によつて本発明を説明する。例中
の部、％はいずれも特にことわらないかぎりすべ
て重量基準を意味する。
実施例 １
(1) 透明ポリエチレンテレフタレートの製造
エチレングリコール200ml中に水酸化鉛pbo・
pb（OH）22.2ｇ（pb0.95×10-2モル）を溶解、こ
の溶液にGeO22.0ｇ（1.9×10-2モル）を添加して
197℃のエチレングリコールの沸点で還流加熱す
ると約30分で透明な溶液が得られた。次にこの溶
液を重縮合触媒とするポリエチレンテレフタレー
トの製造を行なつた。ジメチルテレフタレート
620部、エチレングリコール480部、エステル交換
触媒として酢酸亜鉛Zn（OAc）2・2H2O0.036部を
エステル交換反応器にとり、エステル交換反応は
150℃より230℃に徐々に昇温しつつ行ない、120
分を要してメタノールの溜出を終つた。次いで内
容物を重縮合装置に移し、重縮合触媒として上記
触媒溶液2.7部を加え徐々に昇温すると共に減圧
し、１時間を要して280℃とし0.5mmHgの高減圧
下の重縮合反応を25分間行なつて得られたポリマ
ーは極限粘度0.63、融点262℃であつた。
(2) ポリエステル共重合体の製造
ジメチルテレフタレート117部（49モル％）、ジ
メチルイソフタレート117部（49モル％）、エチレ
ングリコール103部（50モル％）、ジエチレングリ
コール58部（50モル％）、酢酸亜鉛0.08部、三酸
化アンチモン0.08部を反応容器中で40〜220℃に
昇温させて３時間エステル交換反応させ、次いで
５−スルホイソフタル酸ナトリウム９部（２モル
％）を添加して220〜260℃、１時間エステル化反
応させ、更に減圧下（10〜0.2mmHg）で２時間重
縮合反応を行ない、平均分子量18000、軟化点140
℃のポリエステル共重合体を得た。
(3) ポリエステル共重合体水系分散液の製造
上記(2)により得られたポリエステル共重合体
300部とｎ−ブチルセロソルブ140部とを容器中で
150〜170℃、約３時間撹拌して、均一にして粘稠
な溶融液を得、この溶融液に水560部を徐々に添
加し約１時間後に均一な淡白色の固形分濃度30％
の安定な水分散液を得た。
(4) 塗布用分散液の調合
ｎ−ブチルセロソルブ10部、イソプロピルアル
コール45部、イオン交換水45部とをそれぞれ混合
し、水系混合溶媒を作製し、これに平均粒径2.5μ
の無水珪酸0.015部を添加した後、超音波分散機
（日本精機(株)製）を用いて高周波出力600W、発振
周波数20KHzで15分間の分散処理を行い、十分分
散された無水珪酸粒子分散液を得た。次いで該粒
子分散液80部に対し、前記(3)で得られたポリエス
テル共重合体水系分散液20部を混合し、均一にな
るまで良く撹拌し塗布液とした。塗布液中の共重
合ポリエステル樹脂／無水珪酸粒子の割合は
100000／200であつた。
(5) コートフイルムの製造
(1)で製造したポリエチレンテレフタレートを
280〜300℃で溶融押出し、15℃の冷却ロールで冷
却して厚さ約1000ミクロンの未延伸フイルムを
得、この未延伸フイルムを周速の異なる85℃の一
対のロール間で縦方向に3.5倍延伸した。次いで
前記の塗布液をロールコーター方式で塗布し、70
℃の熱風で乾燥し、次いでテンターで98℃で横方
向に3.5倍延伸し、さらに200〜210℃で熱固定し
厚さ100ミクロンの二軸延伸コーテイングポリエ
ステルフイルムを得た。コート剤塗布量は0.06
ｇ／m2であつた。
得られたフイルムの評価結果を表−１に示し
た。
実施例 ２
分散用ポリエステル共重合体における５−スル
ホイソフタル酸ナトリウムを10モル％、ジメチル
テレフタレートを45モル％、ジメチルイソフタレ
ートを45モル％に変更する以外は、実施例１とま
つたく同様の方法で二軸延伸コーテイングポリエ
ステルフイルムを得た。
得られたフイルムの評価結果を表−１に示し
た。
比較例 １
分散用ポリエステル共重合体における５−スル
ホイソフタル酸ナトリウムを0.2モル％とし、ジ
メチルテレフタレート、ジメチルイソフタレート
をそれぞれ49.9モル％とする以外は実施例と同様
にしてポリエステル共重合体を得た。得られたポ
リエステル共重合体を実施例１と同様の方法で水
系分散液を製造することを試みたが、水に対する
分散性が著しく不良であり安定な水系分散液を得
ることが出来なかつた。
比較例 ２
分散用ポリエステル共重合体における５−スル
ホイソフタル酸ナトリウムを20モル％とし、ジメ
チルテレフタレート、ジメチルイソフタレートを
それぞれ40モル％とする以外は、実施例１とまつ
たく同様の方法で二軸延伸コーテイングポリエス
テルフイルムを得た。得られたフイルムの評価結
果を表−１に示した。
実施例 ３
用いる無水珪酸粒子の平均粒径を0.04μとし添
加量を0.03部とし、共重合ポリエステル／無水珪
酸粒子の割合を100000／400とする以外は、実施
例１とまつたく同様の方法で二軸延伸コーテイン
グポリエステルフイルムを得た。得られたフイル
ムの評価結果を表−１に示した。
比較例 ３
用いる無水珪酸粒子の平均粒径を20μとする以
外は、実施例１とまつたく同様の方法で二軸延伸
コーテイングポリエステルフイルムを得た。
得られたフイルムの評価結果を表−１に示す。
比較例 ４
用いる無水珪酸粒子の平均粒径を0.007μとする
以外は、実施例１とまつたく同様の方法で二軸延
伸コーテイングポリエステルフイルムを得た。
得られたフイルムの評価結果を表−１に示す。
実施例 ４
超音波分散機による分散処理を、ホモミキサー
（特殊機化工業(株)製）により3600rpm×15分間の
分散処理に変更する以外は、実施例１とまつたく
同様の方法で二軸延伸コーテイングポリエステル
フイルムを得た。得られたフイルムの評価結果を
表−１に示す。
比較例 ５
ｎ−ブチルセロソルブ、イソプロピルアルコー
ル、イオン交換水から成る水系混合溶媒中に無水
珪酸粒子を添加した後分散処理を行なわない以外
は、実施例１とまつたく同様の方法で二軸延伸コ
ーテイングポリエステルフイルムを得た。得られ
たフイルムの評価結果を表−１に示す。
比較例 ６
塗布用分散液の調合手順を、ポリエステル共重
合体水系分散液20部中に2.5μ無水珪酸粒子0.015
部を直接添加した後超音波分散処理を行ない、次
いでｎ−ブチルセロソルブ、イソプロピルアルコ
ール及び水とから成る水系混合溶媒80部と混合す
るごとく変更する以外は、実施例１とまつたく同
様の方法で二軸延伸コーテイングポリエステルフ
イルムを得た。得られたフイルムの評価結果を表
−１に示す。
比較例 ７
塗布用分散液の調合手順を、ポリエステル共重
合体水系分散液20部とｎ−ブチルセロソルブ、イ
ソプロピルアルコール、水からなる水系混合溶媒
80部とを混合した後、2.5μの無水珪酸粒子を添加
し、次いで超音波分散処理を行なうごとく変更す
る以外は実施例１とまつたく同様の方法で二軸延
伸コーテイングポリエステルフイルムを得た。得
られたフイルムの評価結果を表−１に示す。
比較例 ８
塗布用分散液の調合手順をｎ−ブチルセロソル
ブ、イソプロピルアルコール、水からなる水系混
合溶媒80部中に2.5μの無水珪酸を添加した後ポリ
エステル共重合体水系分散液20部を混合し、次い
で超音波分散処理を行なう方法に変更する以外
は、実施例１とまつたく同様の方法で二軸延伸コ
ーテイングフイルムを得た。得られたフイルムの
評価結果を表−１に示す。
表中、TPAはテレフタル酸換算、IPAはイソ
フタル酸換算、SSIは５−スルホイソフタル酸ナ
トリウムを示す。
表中ヘーズはJIS K6714に準じ、日本精密光学
社製ヘーズメーターを用いて測定した。
摩擦係数は、ASTM−1894に準じ、東洋精機
社製テンシロンを使用し、塗布面と未塗布面とを
合わせて測定した値である。
ブロツキング性は、塗布面と未塗布面とを密着
させて８×12cmに切断し、これを２枚のシリコー
ンゴムシートで挟着し、更にガラス板で挟み、ガ
ラス板上から２Kgの荷重を掛け、これを40℃、80
％RHの雰囲気中で24時間放置し、しかる後にフ
イルムを取外してフイルム間のブロツキング状態
を目視で判定し、ブロツキング面積の５％以下を
〇、0.5〜20％を△、20％以上を×で示した。塗
工面状態の判定は、得られたコーテイングフイル
ム表面を目視判定及び微分干渉顕微鏡写真撮影に
より行ない、次の様にランク分けした。
(Industrial Application Field) The present invention relates to a thermoplastic resin film having both transparency and slipperiness, and a method for producing the same. (Prior art) Thermoplastic resin film, especially biaxially stretched,
Due to their excellent dimensional stability, mechanical strength, and transparency, polypropylene and polyethylene terephthalate films are used for packaging materials, metal deposition, photography, drafting, electrical applications, magnetic tapes, and other applications. It has been applied in a wide variety of fields such as industrial use. However, in all of these cases, the thermoplastic resin film does not satisfy all properties. In most applications, the film is rarely used alone, but undergoes some kind of secondary processing. Therefore, from the viewpoint of workability during processing, product performance, and quality stability, especially the slipperiness of the surface,
Characteristics such as transparency are considered important issues. For example, slipperiness not only significantly affects the efficiency of basic operations such as film unwinding, winding, slitting, cutting, and coating, which are essential steps for secondary processing for all purposes, but also has a particularly strong influence on film production. In addition to making winding difficult, the user's work efficiency for the resulting film, for example, the efficiency of an automatic packaging machine if it is used for packaging, but the consistency and feedability of the film if it is used for cutting such as office work or drafting. The work efficiency etc. will be greatly affected.
For this reason, for the purpose of improving the slipperiness of the film surface, waxes, fatty acid amides, higher fatty acid compounds such as fatty acid metal salts, organic polysiloxanes, titanium dioxide, calcium carbonate, talc, kaolin, barium sulfate, etc. Improvements have been made by dispersing so-called lubricants such as particles of aluminum oxide, silicon dioxide, and various other inert inorganic compounds into synthetic resins for films. In addition, especially in the case of polyester film, lubricants other than those mentioned above may be used, such as a method of forming fine particles with a metal compound catalyst used during polyester production, such as an alkali metal compound or an alkaline earth metal compound, or a method of forming fine particles with a metal compound catalyst used during polyester production. Examples include the so-called internal particle method in which particles are generated from a salt of terephthalic acid, a type of raw material, and a metal such as calcium or lithium, and a method in which these compound particles are synthesized in advance and added to the polyester production system. . However, when using these conventional lubricant addition methods, no matter which method is used,
It has the disadvantage that transparency necessarily decreases at the same time as slipperiness improves, and these two contradictory
It has been considered impossible to fully satisfy both slipperiness and transparency, and a certain compromise has always been forced. In other words, there has never been a film in which the transparency is almost the same as that without additives and the coefficient of friction is significantly lowered. Furthermore, there are methods in which morphological processing such as knurl processing is performed before winding, but there are various conventional manufacturing methods, such as the knurled part being trimmed with a slit in secondary processing, or existing only on one side. I had this problem. (Problems to be Solved by the Invention) As a result of intensive research in order to solve the above problems, the present inventors have found that a film obtained from a thermoplastic resin having a lubricant amount below a certain level has a specific lubricant content that is insoluble in water. polyester copolymer, water-soluble organic compound and water,
Furthermore, by laminating a coating agent containing inert particles and other additives by a coating method, the film can be reused and can be made transparent and easy to use with good explosion-proof stability in the coating process. The present invention provides a coating film with improved lubricity and a method for producing the same. (Means for Solving the Problems) The first aspect of the present invention is that at least one side of a thermoplastic resin film (A) contains 0.5 to 15 mol% of sulfonic acid metal base-containing dicarboxylic acids and polyhydric alcohols based on the total dicarboxylic acid components. A water-based polyester consisting of (B) a water-soluble organic compound with a boiling point of 60 to 200°C, (C) water, and (D) inert fine particles with an average particle size of 0.01 to 10 μm. In a thermoplastic resin film coated with a resin dispersion, a required amount of inert fine particles (D) is added to an aqueous solution in which a part of the water-soluble organic compound (B) and a part of water (C) are mixed in advance.
is added in advance and then subjected to sufficient pre-dispersion treatment, to the dispersion is added a resin consisting of the required amount of water-insoluble polyester resin (A), the remaining water-soluble organic compound (B) and water (C). This is an easily slippery and transparent film characterized in that a dispersion is added and the mixing ratio of each is such that the weight ratio satisfies the following formulas (1), (2), and (3) at the same time. (A)／(B)＝100／20〜5000 …(1) (B)／(C)＝100／50〜10000……(2) (A)／(D)＝100000／5〜3000 … ...(3) In addition, the second aspect of the present invention is to add (A) 0.5 to 15 mol % of the total dicarboxylic acid component to at least one side of an unstretched or uniaxially stretched thermoplastic resin film obtained by a melt extrusion method. A water-insoluble polyester copolymer consisting of a dicarboxylic acid containing a sulfonic acid metal group and a polyhydric alcohol, (B) a boiling point of 60
A water-based polyester resin dispersion consisting of a water-soluble organic compound at ~200°C, (C) water, and (D) inert fine particles with an average particle size of 0.01 to 10 μm is preliminarily mixed with one of the water-soluble organic compounds (B). A predetermined amount of inert fine particles (D) is added to an aqueous solution containing a portion of water (C) and a portion of water (C) is added, and after thorough dispersion treatment, a required amount of water-insoluble polyester resin (A) is added to the dispersion. A resin dispersion consisting of the remaining water-soluble organic compound (B) and water (C) is added, and the mixing ratio of each satisfies the following formulas (1), (2), and (3) at the same time in terms of weight ratio. This is a method for producing an easily slippery and transparent film, which is produced by a compounding method, coated, dried, and then stretched in at least one axis. (A)／(B)＝100／20〜5000 …(1) (B)／(C)＝100／50〜10000……(2) (A)／(D)＝100000／5〜3000 … (3) In the preferred embodiment (1) of the first invention, the thermoplastic resin film is a film made of polyester having a lubricant content of 0.05% by weight or less. A preferred embodiment (2) of the second invention is a manufacturing method in which the thermoplastic resin film is made of polyester containing a lubricant of 0.05% by weight or less. Another preferred embodiment (3) of the embodiment (2) of the second invention is a manufacturing method in which the dispersion pretreatment is an ultrasonic dispersion treatment in the second invention or embodiment (2). be. The polyester copolymer (A) contained in the aqueous dispersion of the present invention is a mixture of 0.5 to 15 mol% of a dicarboxylic acid containing a sulfonic acid metal base and 85 to 99.5 mol% of a dicarboxylic acid containing no sulfonic acid metal base. It is a substantially water-insoluble polyester copolymer obtained by reacting dicarboxylic acid with a glycol component. Substantially water-insoluble means that the polyester copolymer does not dissipate in hot water even if the polyester copolymer is stirred in hot water at 80°C, and specifically, the polyester copolymer does not dissipate in hot water. The weight loss of the polyester copolymer after being stirred in 80°C hot water for 24 hours is 5% by weight or less. Examples of the above-mentioned dicarboxylic acids containing sulfonic acid metal groups include metals such as sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, and 5[4-sulfophenoxy]isophthalic acid. salt was given,
Particularly preferred are 5-sodium sulfoisophthalic acid and sodium sulfoterephthalic acid. These sulfonic acid metal base-containing dicarboxylic acid components are 0.5 to 15 mol% of the total dicarboxylic acid components.
If it exceeds 15 mol%, the water dispersibility will improve, but the water resistance of the polyester copolymer will be significantly reduced, and if it is less than 0.5 mol%, the water dispersibility will decrease significantly. The dispersibility of the polyester copolymer in water varies depending on the copolymer composition, the type and blending ratio of the water-soluble organic compound, etc., but the above dicarboxylic acid containing a sulfonic acid metal group can be used as long as it does not impair the dispersibility in water. , a small amount is preferred. As the dicarboxylic acid containing no sulfonic acid metal base, aromatic, aliphatic, and alicyclic dicarboxylic acids can be used. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid,
Examples include 2,6-naphthalene dicarboxylic acid. It is preferable that these aromatic dicarboxylic acids account for 40 mol% or more of the total dicarboxylic acid components, and if it is less than 40 mol%, the mechanical strength and water resistance of the polyester copolymer will decrease. Aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, 1,3-cyclopentanedicarboxylic acid,
1,2-cyclohexanedicarboxylic acid, 1,3-
Examples include cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Addition of these non-aromatic dicarboxylic acid components may improve adhesive performance in some cases, but generally reduces the mechanical strength and water resistance of the polyester copolymer. The glycol component to be reacted with the mixed dicarboxylic acid is an aliphatic glycol having 2 to 8 carbon atoms or an alicyclic glycol having 6 to 12 carbon atoms, and specifically, ethylene glycol, 1,2-
Propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol These include methanol, p-xylylene glycol, diethylene glycol, triethylene glycol, and the like. Examples of polyethers include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polyester copolymers are obtained by conventional melt polycondensation. In other words, there is a direct esterification method in which the above dicarboxylic acid component and glycol component are directly reacted, water is distilled off and esterified, and then polycondensation is performed, or the dimethyl ester of the above dicarboxylic acid component and the glycol component are reacted to form methyl alcohol. It can be obtained by a transesterification method, etc., which involves distilling off, transesterifying, and then polycondensing it. In addition, solution polycondensation, interfacial polycondensation, etc. may also be used, and the polyester copolymer of the present invention is not limited by the polycondensation method. In order to obtain the aqueous dispersion of the polyester copolymer described above, it is necessary to disperse it in water together with a water-soluble organic compound. For example, the above polyester copolymer and a water-soluble organic compound are mixed in advance at 50 to 200°C, and water is added to this mixture and dispersed by stirring, or conversely, the mixture is added to water and dispersed by stirring. method, or by coexisting a polyester copolymer, a water-soluble organic compound, and water.
There is a method of stirring at 120℃. The above-mentioned water-soluble organic compound is an organic compound having a solubility in water of 20 g or more at 20°C, and specifically includes aliphatic and alicyclic alcohols, ethers, esters, and ketone compounds, such as methanol, ethanol, Monohydric alcohols such as isopropanol and n-butanol, glycols such as ethylene glycol and propylene glycol,
These include glycol derivatives such as methyl cellosolve, ethyl cellosolve, and n-butyl cellosolve, ethers such as dioxane and tetrahydrofuran, esters such as ethyl acetate, and ketones such as methyl ethyl ketone. These water-soluble organic compounds can be used alone or in combination of two or more. Among the above compounds, butyl cellosolve and ethyl cellosolve are preferred in terms of dispersibility in water and coatability on films. The weight ratio of the above polyester copolymer (A), (B) water-soluble organic compound, and (C) water is (A)/(B)=100/20~5000 (B)/(C)=100/ It is important to satisfy the range of 50 to 10,000. Compared to polyester copolymers, (A)/(B) has less water-soluble organic compounds.
When the ratio exceeds 100/20, the dispersibility of the aqueous dispersion decreases. In this case, dispersibility can be assisted by adding a surfactant, but if the amount of surfactant is too large, adhesiveness and water resistance will decrease. On the other hand, if (A)/(B) is less than 100/5000 or (B)/(C) exceeds 100/50, the amount of water-soluble organic compounds in the aqueous dispersion will increase and the solvent may be used during coating. There is a risk of explosion, which requires taking explosion-proof measures, and furthermore, it causes environmental pollution and increases costs, so it is necessary to consider compound recovery.
When (B)/(C) is less than 100/10,000, the surface tension of the aqueous dispersion increases, the wettability to the film decreases, and coating spots are likely to occur. In this case, the wettability can be improved by adding a surfactant, but if the amount of the surfactant is too large, the adhesiveness and water resistance decrease as described above. Furthermore, the inert particles (D) added to this dispersion include chalk, chiyolk, heavy carbon, light carbon, ultrafine carbon, basic magnesium carbonate, dolomite, special calcium carbonate, kaolin, and calcined carbon. Clay, birofluorite, bentonite, serisarite, zeolite, nepheline, sinite,
Talc, attabuldianite, synthetic aluminum silicate,
Synthetic calcium silicate, diatomaceous earth, silica powder, hydrous fine silicic acid, anhydrous fine silicic acid, aluminum hydroxide, aluminum oxide, barite, precipitated barium sulfate,
Examples include natural gypsum, gypsum, calcium sulfite, spherical glass fine particles, hollow glass sphere fine particles, and various other inorganic particles or organic fine particles, such as crosslinked products of benzoguanamine resin, polystyrene resin, acrylic resin, and the like. Any of these may be used in relation to transparency and slipperiness, but particularly preferred are fine particles of silicic acid, and particles of white titanium oxide, black carbon black, etc. is extremely undesirable. The particle size to be used is preferably 0.01μ to 10μ, more preferably 0.015 to 5μ. Particles with a particle size of 0.01μ or less must be used in large quantities, and particles with a diameter of 10μ or more produce coarse protrusions, making them undesirable for applications that require surface smoothness.In addition, the density of protrusions decreases, resulting in slippage. Sex can get worse. The amount of (D) used for (A) is (A)/(D) = weight ratio
A ratio of 100000/5 to 3000 is good, preferably (A)/
(D)=100000/20-500. If (A)/(D) exceeds 100,000/5, the effect of improving slipperiness cannot be obtained, and if it is less than 100,000/3,000, transparency deteriorates, which is not preferable. Additionally, additives other than (A) to (D) that may be mixed if necessary include organic and inorganic antistatic agents, adhesion improvers, mold release improvers, and other functional agents. However, there are no restrictions on the additives or the amounts added, as long as they do not significantly impair both transparency and slipperiness, which are basically the gist of the present invention. The mixing procedure for coating a synthetic resin film with the above water-based resin dispersion composition includes a part of the water-soluble organic compound (B), preferably (B).
An aqueous solution of the water-soluble organic compound (B) is prepared by pre-mixing 98 to 50% by weight of the total required amount of water (C) and a portion of water (C), preferably 85 to 30% by weight of the total required amount of (C). Then, add the required amount of inert particles (D) to the aqueous solution and perform sufficient dispersion treatment to obtain a particle dispersion containing no secondary agglomerated particles that reproduces the primary particle size of the inert particles as much as possible. Make (1). Particle dispersion methods at this time include a high-speed impeller stirring type disperser such as a homomixer, a mill type disperser using stainless steel, glass or other balls or beads for stirring, and jetting using a high pressure difference. It is possible to use a high-pressure type homogeneous dispersion machine that applies force, an ultrasonic dispersion machine that uses minute vibration energy generated by ultrasonic oscillation, and other various types of dispersion machines, and all of them are effective, but in particular, as in the present invention, As a result of extensive studies, the present inventors have found that it is suitable to use an ultrasonic dispersion machine as a dispersion method for a dilute concentration system in which the amount of particles to be dispersed is relatively small relative to the total liquid volume. The reason for this is that dispersion methods under particle collisions and high shear forces, such as high-speed impeller agitation type, ball mill method, and high pressure type, are effective only in high-concentration systems with a high probability of particle collision. In a dilute concentration system such as this, the efficiency is rather low, and it is thought that the ultrasonic dispersion method, in which impact vibration is applied directly to the particles regardless of the particle concentration, works advantageously. Of course, to the extent that the effects of the present invention are not impaired, there is no harm in using other dispersion methods described above simultaneously with or after the ultrasonic dispersion treatment. For the particle dispersion liquid (1) obtained in this way,
On the other hand, the water-insoluble copolymer (A) previously polymerized by the above-mentioned method, the remaining water-soluble organic compound (B), preferably 2 to 50% by weight of the total required amount, and the remaining water (C), preferably A dispersion composition suitable for thermoplastic resin film, particularly polyester film coating, is obtained by adding and mixing an aqueous polyester copolymer resin dispersion () obtained from 15 to 70% by weight of the total required amount. I can do it. One of the features of the present invention is that this water-soluble organic compound
Separate (B) and water (C) to obtain a particle dispersion () and a polyester copolymer resin aqueous dispersion ().
The point is to obtain a coating dispersion composition as a uniform mixture after separately dividing and blending, and the undispersed inert particles (D) before being subjected to ultrasonic dispersion come into contact with a concentrated polyester copolymer resin dispersion. This was achieved only when the inert particles (D) were sufficiently dispersed into a primary particle state by ultrasonic dispersion treatment and then brought into contact with the diluted polyester copolymer resin. The present invention is based on the discovery that a resin liquid containing finely dispersed particles can be obtained. Although the present coating composition can be applied to thermoplastic resin films in general, it is effectively used for stretched and oriented films made of polypropylene, polyester, polyamide, etc., and is particularly effective for films made of stretched and oriented polyester films, such as those made mainly of polyethylene terephthalate. In films, it exhibits good effects in terms of adhesion and other aspects. In order to most effectively exhibit the features of the present invention, it is preferable from the viewpoint of transparency that the amount of lubricant contained in the oriented polyester film is 0.05% by weight or less. The coating dispersion composition of the present invention can be applied by a conventional method, but in particular, it can be applied to an unstretched film after the thermoplastic resin has been melt-extruded, or to an unstretched film in the vertical or horizontal direction. The method of obtaining a biaxially oriented coated film by coating the film after being uniaxially stretched, then biaxially or uniaxially stretching, and then heat-treating the film is a method that improves the adhesion of the coated film.
Preferable from the viewpoint of transparency and economy. In particular, when considering the drying properties and workability of the coating film, it is preferable to apply the film after stretching it uniaxially. Particularly preferred is a method for obtaining . The surface to be coated and the amount to be coated vary depending on the purpose and use of the film to be obtained, but either single-sided or double-sided coating is possible, and the coated amount is based on the amount present on the film after biaxial stretching.
0.005 to 5 g/m 2 is preferred, and 0.01 to 3 m/m 2 is particularly preferred. When the coating amount is less than 0.005 g/m 2 , the desired effect cannot be obtained, and when it exceeds 5 g/m 2 , problems such as blocking are likely to occur. In addition, by subjecting the polyester film to corona discharge treatment before applying the aqueous dispersion of the polyester copolymer described above, the coating properties of the aqueous dispersion can be improved, and the coating of the polyester film and polyester copolymer can be improved. The adhesive strength between the two is improved. In addition, the wettability and adhesion of the film surface can be improved by subjecting the polyester copolymer layer after inline coating or biaxial stretching to corona discharge treatment, corona discharge treatment under a nitrogen atmosphere, ultraviolet irradiation treatment, etc. can be done. (Example) The present invention will be explained below with reference to Examples. All parts and percentages in the examples are by weight unless otherwise specified. Example 1 (1) Production of transparent polyethylene terephthalate Lead hydroxide pbo in 200ml of ethylene glycol
Dissolve 2.2g of pb(OH) 2 (pb0.95×10 -2 mol) and add 2.0g of GeO 2 (1.9×10 -2 mol) to this solution.
When heated under reflux at the boiling point of ethylene glycol at 197°C, a clear solution was obtained in about 30 minutes. Next, polyethylene terephthalate was produced using this solution as a polycondensation catalyst. dimethyl terephthalate
620 parts of ethylene glycol, 480 parts of ethylene glycol, and 0.036 parts of zinc acetate Zn (OAc) 2.2H 2 O as a transesterification catalyst were placed in a transesterification reactor.
The temperature was gradually increased from 150℃ to 230℃, and the temperature was increased to 120℃.
It took several minutes to complete the distillation of methanol. Next, the contents were transferred to a polycondensation apparatus, 2.7 parts of the above catalyst solution was added as a polycondensation catalyst, the temperature was gradually raised and the pressure was reduced, and the temperature was raised to 280°C over 1 hour to carry out the polycondensation reaction under a high vacuum of 0.5 mmHg. The polymer obtained after 25 minutes had an intrinsic viscosity of 0.63 and a melting point of 262°C. (2) Production of polyester copolymer Dimethyl terephthalate 117 parts (49 mol%), dimethyl isophthalate 117 parts (49 mol%), ethylene glycol 103 parts (50 mol%), diethylene glycol 58 parts (50 mol%), acetic acid 0.08 parts of zinc and 0.08 parts of antimony trioxide were heated to 40 to 220°C in a reaction vessel and transesterified for 3 hours, and then 9 parts of sodium 5-sulfoisophthalate (2 mol%) was added to Esterification reaction was carried out at 260°C for 1 hour, and polycondensation reaction was further carried out for 2 hours under reduced pressure (10 to 0.2 mmHg), with an average molecular weight of 18,000 and a softening point of 140.
A polyester copolymer was obtained. (3) Production of polyester copolymer aqueous dispersion Polyester copolymer obtained by the above (2)
300 parts and 140 parts of n-butyl cellosolve in a container.
Stir at 150-170℃ for about 3 hours to obtain a homogeneous and viscous melt. 560 parts of water is gradually added to this melt, and after about 1 hour, a uniform pale white solid content of 30% is obtained.
A stable aqueous dispersion of was obtained. (4) Preparation of dispersion liquid for coating 10 parts of n-butyl cellosolve, 45 parts of isopropyl alcohol, and 45 parts of ion-exchanged water were mixed to prepare an aqueous mixed solvent.
After adding 0.015 parts of silicic anhydride, dispersion treatment was performed for 15 minutes using an ultrasonic dispersion machine (manufactured by Nippon Seiki Co., Ltd.) at a high frequency output of 600 W and an oscillation frequency of 20 KHz to obtain a sufficiently dispersed silicic anhydride particle dispersion. I got it. Next, 20 parts of the aqueous polyester copolymer dispersion obtained in step (3) above was mixed with 80 parts of the particle dispersion, and the mixture was thoroughly stirred until homogeneous to obtain a coating liquid. The ratio of copolymerized polyester resin/silicic anhydride particles in the coating solution is
It was 100000/200. (5) Production of coated film The polyethylene terephthalate produced in (1) is
Melt extrusion at 280-300°C and cooling with a cooling roll at 15°C to obtain an unstretched film with a thickness of approximately 1000 microns. Stretched twice. Next, apply the above coating liquid using a roll coater method, and apply it for 70 minutes.
The film was dried with hot air at 100°C, then stretched 3.5 times in the transverse direction at 98°C using a tenter, and further heat-set at 200 to 210°C to obtain a biaxially stretched coated polyester film with a thickness of 100 microns. Coating agent application amount is 0.06
g/ m2 . The evaluation results of the obtained film are shown in Table-1. Example 2 The same method as in Example 1 except that sodium 5-sulfoisophthalate in the polyester copolymer for dispersion was changed to 10 mol%, dimethyl terephthalate to 45 mol%, and dimethyl isophthalate to 45 mol%. A biaxially stretched coated polyester film was obtained. The evaluation results of the obtained film are shown in Table-1. Comparative Example 1 A polyester copolymer was obtained in the same manner as in Example except that sodium 5-sulfoisophthalate in the polyester copolymer for dispersion was 0.2 mol%, and dimethyl terephthalate and dimethyl isophthalate were each 49.9 mol%. . An attempt was made to produce an aqueous dispersion of the obtained polyester copolymer in the same manner as in Example 1, but the dispersibility in water was extremely poor and a stable aqueous dispersion could not be obtained. Comparative Example 2 Biaxial treatment was carried out in exactly the same manner as in Example 1, except that sodium 5-sulfoisophthalate in the polyester copolymer for dispersion was 20 mol%, and dimethyl terephthalate and dimethyl isophthalate were each 40 mol%. A stretched coated polyester film was obtained. The evaluation results of the obtained film are shown in Table-1. Example 3 The same method as in Example 1 was carried out, except that the average particle size of the silicic anhydride particles used was 0.04μ, the amount added was 0.03 parts, and the ratio of copolyester/silicic anhydride particles was 100000/400. A biaxially stretched coated polyester film was obtained. The evaluation results of the obtained film are shown in Table-1. Comparative Example 3 A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1, except that the average particle size of the silicic anhydride particles used was 20 μm. Table 1 shows the evaluation results of the obtained film. Comparative Example 4 A biaxially stretched coated polyester film was obtained in exactly the same manner as in Example 1, except that the average particle size of the silicic anhydride particles used was 0.007 μm. Table 1 shows the evaluation results of the obtained film. Example 4 The same method as in Example 1 was used except that the dispersion treatment using the ultrasonic dispersion machine was changed to the dispersion treatment using a homo mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 3600 rpm for 15 minutes. A stretched coated polyester film was obtained. Table 1 shows the evaluation results of the obtained film. Comparative Example 5 A biaxially stretched coated polyester was prepared in the same manner as in Example 1, except that silicic anhydride particles were added to an aqueous mixed solvent consisting of n-butyl cellosolve, isopropyl alcohol, and ion-exchanged water, and then no dispersion treatment was performed. I got the film. Table 1 shows the evaluation results of the obtained film. Comparative Example 6 The procedure for preparing a dispersion for coating was as follows: 0.015 2.5μ silicic anhydride particles were added to 20 parts of an aqueous polyester copolymer dispersion.
Example 1 was carried out in exactly the same manner as in Example 1, except that 1 part was directly added, followed by ultrasonic dispersion treatment, and then mixed with 80 parts of an aqueous mixed solvent consisting of n-butyl cellosolve, isopropyl alcohol, and water. An axially stretched coated polyester film was obtained. Table 1 shows the evaluation results of the obtained film. Comparative Example 7 The procedure for preparing a coating dispersion was carried out using an aqueous mixed solvent consisting of 20 parts of a polyester copolymer aqueous dispersion, n-butyl cellosolve, isopropyl alcohol, and water.
A biaxially stretched coated polyester film was obtained in the same manner as in Example 1, except that 80 parts of silicic acid were mixed with 80 parts, 2.5 μm silicic anhydride particles were added, and then ultrasonic dispersion treatment was performed. Table 1 shows the evaluation results of the obtained film. Comparative Example 8 The procedure for preparing a dispersion for coating was as follows: 2.5μ of silicic anhydride was added to 80 parts of an aqueous mixed solvent consisting of n-butyl cellosolve, isopropyl alcohol, and water, and then 20 parts of a polyester copolymer aqueous dispersion was mixed. Next, a biaxially stretched coating film was obtained in the same manner as in Example 1, except that the method was changed to an ultrasonic dispersion treatment. Table 1 shows the evaluation results of the obtained film. In the table, TPA is equivalent to terephthalic acid, IPA is equivalent to isophthalic acid, and SSI is sodium 5-sulfoisophthalate. The haze in the table was measured according to JIS K6714 using a haze meter manufactured by Nippon Seimitsu Kogaku. The friction coefficient is a value measured on both coated and uncoated surfaces using Tensilon manufactured by Toyo Seiki Co., Ltd. in accordance with ASTM-1894. Blocking properties were determined by placing the coated and uncoated surfaces in close contact, cutting them into 8 x 12 cm pieces, sandwiching them between two silicone rubber sheets, sandwiching them between glass plates, and applying a 2 kg load from above the glass plates. , this at 40℃, 80
%RH for 24 hours, then remove the film and visually judge the blocking state between the films. 5% or less of the blocking area is ○, 0.5 to 20% is △, and 20% or more is ×. Indicated. The condition of the coated surface was determined by visual inspection and differential interference microscopic photography of the surface of the coating film obtained, and was ranked as follows.
【表】【table】
【表】【table】
【表】
＊ 水不溶性ポリエステル共重合体(A)に対する量
（発明の効果）
以上実施例で示したごとく、本発明の方法によ
つて得られたフイルムは、いずれも透明性及び滑
り性が共に優れ、均一性、作業性にも優れている
ことがわかる。また水不溶性ポリエステル共重合
体のカルボン酸成分中スルホン酸金属塩基含有成
分が少なすぎると分散性が不良となること（比較
例１）、多すぎるとブロツキング性が不良となる
こと（比較例２）がわかる。添加すべき不活性粒
子の粒径が大きすぎると、透明性、滑り性共に不
充分となり塗工面の粗大突起が多くなること（比
較例３）また粒径が小さすぎると、滑り性が不充
分となり凝集を生じやすいこと（比較例４）がわ
かる。また塗布用分散液の調合方法が本発明法と
異なる場合（比較例５〜８）は、同一組成の場合
であつても、粒子分散性が不充分となり良好な塗
工面が得られ難いことが判る。[Table] * Amount relative to water-insoluble polyester copolymer (A) (effect of the invention) As shown in the examples above, the films obtained by the method of the present invention have both transparency and slipperiness. It can be seen that it has excellent uniformity and workability. Furthermore, if the amount of the sulfonic acid metal base-containing component in the carboxylic acid component of the water-insoluble polyester copolymer is too small, the dispersibility will be poor (Comparative Example 1), and if it is too large, the blocking property will be poor (Comparative Example 2). I understand. If the particle size of the inert particles to be added is too large, both transparency and slip properties will be insufficient, resulting in a large number of coarse protrusions on the coated surface (Comparative Example 3).If the particle size is too small, slip properties will be insufficient. It can be seen that aggregation is likely to occur (Comparative Example 4). Furthermore, when the method of preparing the dispersion for coating differs from the method of the present invention (Comparative Examples 5 to 8), even if the composition is the same, the particle dispersibility may be insufficient and it may be difficult to obtain a good coated surface. I understand.
Claims (1)
全ジカルボン酸成分に対し0.5〜15モル％のスル
ホン酸金属塩基含有ジカルボン酸類と多価アルコ
ール類とから成る水不溶性ポリエステル共重合
体、(B)沸点が60〜200℃である水溶性有機化合物、
(C)水、(D)平均粒径が0.01〜10μmの不活性微粒子
とから成る水系ポリエステル樹脂分散液を塗布し
てなる熱可塑性樹脂フイルムにおいて、該水溶性
有機化合物(B)の一部と水(C)の一部を予め混合した
水溶液中に所要量の不活性微粒子(D)を予め添加
し、ついで十分な分散前処理を施した後、該分散
液に対し所要量の水不溶性ポリエステル樹脂(A)と
残りの水溶性有機化合物(B)及び水(C)とから成る樹
脂分散液を添加し、それぞれの混合比率が重量比
で次式(1)、(2)、(3)をそれぞれ同時に満足するごと
く配合されてなることを特徴とする易滑透明性フ
イルム。 (A)／(B)＝100／20〜5000 ……(1) (B)／(C)＝100／50〜10000 ……(2) (A)／(D)＝100000／５〜3000 ……(3) ２ 熱可塑性樹脂フイルムが、滑剤含有量が0.05
重量％以下のポリエステルからなる特許請求の範
囲第１項記載のフイルム。 ３ 溶融押出し法により得られた未延伸または一
軸方向に延伸された熱可塑性樹脂フイルムの少な
くとも片面に、(A)全ジカルボン酸成分に対し0.5
〜15モル％のスルホン酸金属塩基含有ジカルボン
酸類と多価アルコール類とから成る水不溶性ポリ
エステル共重合体、(B)沸点が60〜200℃である水
溶性有機化合物、(C)水、(D)平均粒径が0.01〜
10μmの不活性微粒子とから成る水系ポリエステ
ル樹脂分散液を、予め該水溶性有機化合物(B)の一
部と水(C)の一部を混合した水溶液中に所定量の不
活性微粒子(D)を添加し、十分な分散処理した後、
該分散液に対し所要量の水不溶性ポリエステル樹
脂(A)と残りの水溶性有機化合物(B)および水(C)とか
ら成る樹脂分散液を添加し、それぞれ混合比率が
重量比で次式(1)、(2)、(3)をそれぞれ同時に満足す
るごとき配合方法で作製し、塗布、乾燥後、少な
くとも一軸方向に延伸処理する事を特徴とする易
滑透明性フイルムの製造法。 (A)／(B)＝100／20〜5000 ……(1) (B)／(C)＝100／50〜10000 ……(2) (A)／(D)＝100000／５〜3000 ……(3) ４ 熱可塑性樹脂フイルムが滑剤含有量が0.05重
量％以下のポリエステルからなる特許請求の範囲
第３項記載の製造法。 ５ 分散前処理が超音波分散処理である特許請求
の範囲第３項ないし第４項いずれかに記載の製造
法。[Claims] 1. On at least one side of the thermoplastic resin film (A)
A water-insoluble polyester copolymer consisting of a dicarboxylic acid containing a sulfonic acid metal base and a polyhydric alcohol in an amount of 0.5 to 15 mol% based on the total dicarboxylic acid component; (B) a water-soluble organic compound having a boiling point of 60 to 200°C;
In a thermoplastic resin film coated with an aqueous polyester resin dispersion consisting of (C) water and (D) inert fine particles with an average particle size of 0.01 to 10 μm, part of the water-soluble organic compound (B) A required amount of inert fine particles (D) is added in advance to an aqueous solution in which a portion of water (C) is mixed in advance, and then, after sufficient dispersion pretreatment, the required amount of water-insoluble polyester is added to the dispersion. A resin dispersion consisting of the resin (A), the remaining water-soluble organic compound (B), and water (C) is added, and the mixing ratio of each is expressed by the following formulas (1), (2), and (3) in terms of weight ratio. An easy-to-lubricate and transparent film characterized by being formulated to satisfy each of the following at the same time. (A)／(B)＝100／ 20〜5000 ……(1) (B)／(C)＝100／50〜10000……(2) (A)／(D)＝100000／5〜3000… …(3) 2 The thermoplastic resin film has a lubricant content of 0.05
2. The film according to claim 1, comprising not more than % by weight of polyester. 3. On at least one side of an unstretched or uniaxially stretched thermoplastic resin film obtained by melt extrusion, (A) 0.5% of the total dicarboxylic acid component.
A water-insoluble polyester copolymer consisting of ~15 mol% of a dicarboxylic acid containing a metal sulfonic acid group and a polyhydric alcohol, (B) a water-soluble organic compound with a boiling point of 60 to 200°C, (C) water, (D ) Average particle size is 0.01~
A predetermined amount of inert fine particles (D) is added to an aqueous solution in which a part of the water-soluble organic compound (B) and a part of water (C) are mixed in advance. After adding and sufficiently dispersing,
A resin dispersion consisting of the required amount of water-insoluble polyester resin (A), the remaining water-soluble organic compound (B) and water (C) is added to the dispersion, and the mixing ratio of each is expressed by the following formula (by weight): A method for producing an easily slippery transparent film, which is prepared by a compounding method that satisfies each of 1), (2), and (3) at the same time, and is coated, dried, and then stretched in at least one axis. (A)／(B)＝100／20〜5000 …(1) (B)／(C)＝100／50〜10000……(2) (A)／(D)＝100000／5〜3000 … ...(3) 4. The manufacturing method according to claim 3, wherein the thermoplastic resin film is made of polyester having a lubricant content of 0.05% by weight or less. 5. The manufacturing method according to any one of claims 3 to 4, wherein the dispersion pretreatment is an ultrasonic dispersion treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9468385A JPS61254637A (en) | 1985-05-02 | 1985-05-02 | Slippery transparent film and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9468385A JPS61254637A (en) | 1985-05-02 | 1985-05-02 | Slippery transparent film and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61254637A JPS61254637A (en) | 1986-11-12 |
| JPH0554494B2 true JPH0554494B2 (en) | 1993-08-12 |
Family
ID=14117003
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9468385A Granted JPS61254637A (en) | 1985-05-02 | 1985-05-02 | Slippery transparent film and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61254637A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62152850A (en) * | 1985-12-27 | 1987-07-07 | 東洋紡績株式会社 | Thermoplastic-resin film laminate and manufacture thereof |
| JPS63265636A (en) * | 1987-04-23 | 1988-11-02 | Toray Ind Inc | Laminated polyester film |
| JPH01236247A (en) * | 1988-03-16 | 1989-09-21 | Toyobo Co Ltd | Coated polyester film |
| JP3929569B2 (en) * | 1997-10-02 | 2007-06-13 | 日本合成化学工業株式会社 | Manufacturing method of antiglare treatment layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5688454A (en) * | 1979-12-21 | 1981-07-17 | Toyobo Co Ltd | Aqueous dispersion |
| JPS5783450A (en) * | 1980-11-14 | 1982-05-25 | Toray Industries | Composite film |
| JPS5829626A (en) * | 1981-08-18 | 1983-02-21 | Teijin Ltd | Manufacture of readily adhesive polyester film |
| JPS5842675A (en) * | 1981-09-08 | 1983-03-12 | Toyobo Co Ltd | Water-based polyester hot-melt adhesive |
-
1985
- 1985-05-02 JP JP9468385A patent/JPS61254637A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5688454A (en) * | 1979-12-21 | 1981-07-17 | Toyobo Co Ltd | Aqueous dispersion |
| JPS5783450A (en) * | 1980-11-14 | 1982-05-25 | Toray Industries | Composite film |
| JPS5829626A (en) * | 1981-08-18 | 1983-02-21 | Teijin Ltd | Manufacture of readily adhesive polyester film |
| JPS5842675A (en) * | 1981-09-08 | 1983-03-12 | Toyobo Co Ltd | Water-based polyester hot-melt adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61254637A (en) | 1986-11-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |