JP2011201254A - Antistatic releasable polyester film - Google Patents
Antistatic releasable polyester film Download PDFInfo
- Publication number
- JP2011201254A JP2011201254A JP2010072830A JP2010072830A JP2011201254A JP 2011201254 A JP2011201254 A JP 2011201254A JP 2010072830 A JP2010072830 A JP 2010072830A JP 2010072830 A JP2010072830 A JP 2010072830A JP 2011201254 A JP2011201254 A JP 2011201254A
- Authority
- JP
- Japan
- Prior art keywords
- group
- antistatic
- carbon atoms
- polyester film
- hydrocarbon group
- 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 42
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 35
- 239000002216 antistatic agent Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- -1 halogen ion Chemical class 0.000 claims description 78
- 125000004432 carbon atom Chemical group C* 0.000 claims description 55
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 17
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- 125000006353 oxyethylene group Chemical group 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 9
- 238000000576 coating method Methods 0.000 abstract description 59
- 239000011248 coating agent Substances 0.000 abstract description 53
- 150000002430 hydrocarbons Chemical group 0.000 description 29
- 239000010410 layer Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 16
- 239000011247 coating layer Substances 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002390 adhesive tape Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000009998 heat setting Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 description 2
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 2
- 150000002918 oxazolines Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 229920006163 vinyl copolymer Polymers 0.000 description 2
- PWCXTRRIWYREPK-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-(3-prop-2-enoyloxypropyl)azanium Chemical compound C[N+](C)(CCCOC(=O)C=C)CCO PWCXTRRIWYREPK-UHFFFAOYSA-N 0.000 description 1
- ZBVNHRJWNBTZFH-UHFFFAOYSA-N 2-methyl-n-[(2-methylpropan-2-yl)oxymethyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCOC(C)(C)C ZBVNHRJWNBTZFH-UHFFFAOYSA-N 0.000 description 1
- FAVWXKQADKRESO-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-1-ene Chemical group CC=C.CC(=C)C(O)=O FAVWXKQADKRESO-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006201 3-phenylpropyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BQJZWXWBNFULDQ-UHFFFAOYSA-N C(C)S(=O)(=O)[O-].C(C=C)(=O)NCCC[NH+](C)C Chemical compound C(C)S(=O)(=O)[O-].C(C=C)(=O)NCCC[NH+](C)C BQJZWXWBNFULDQ-UHFFFAOYSA-N 0.000 description 1
- KDKJSOWJUFHFPY-UHFFFAOYSA-M CS(=O)(=O)[O-].C(C(=C)C)(=O)OCCCC[N+](C)(C)C Chemical compound CS(=O)(=O)[O-].C(C(=C)C)(=O)OCCCC[N+](C)(C)C KDKJSOWJUFHFPY-UHFFFAOYSA-M 0.000 description 1
- ZNWVZYPIAAJSDG-UHFFFAOYSA-O C[N+](C)(CCCNC(=O)C=C)CCO Chemical compound C[N+](C)(CCCNC(=O)C=C)CCO ZNWVZYPIAAJSDG-UHFFFAOYSA-O 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- SSIBHSVOPMBIRN-UHFFFAOYSA-O [N+](=O)([O-])[O-].C(C(=C)C)(=O)NCCCCCC[NH+](CCO)CCO Chemical compound [N+](=O)([O-])[O-].C(C(=C)C)(=O)NCCCCCC[NH+](CCO)CCO SSIBHSVOPMBIRN-UHFFFAOYSA-O 0.000 description 1
- BCHOWGBJFFSLBJ-UHFFFAOYSA-O [N+](=O)([O-])[O-].C(C=C)(=O)NCCC[N+](C)(C)C Chemical compound [N+](=O)([O-])[O-].C(C=C)(=O)NCCC[N+](C)(C)C BCHOWGBJFFSLBJ-UHFFFAOYSA-O 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- IJADSUMYKFHCSZ-UHFFFAOYSA-O bis(2-hydroxyethyl)-[6-(2-methylprop-2-enoyloxy)hexyl]azanium nitrate Chemical compound [N+](=O)([O-])[O-].C(C(=C)C)(=O)OCCCCCC[NH+](CCO)CCO IJADSUMYKFHCSZ-UHFFFAOYSA-O 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- VPSUXBODZRIPAW-UHFFFAOYSA-N dimethyl(3-prop-2-enoyloxypropyl)azanium ethanesulfonate Chemical compound C(C)S(=O)(=O)[O-].C(C=C)(=O)OCCC[NH+](C)C VPSUXBODZRIPAW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000005417 glycidoxyalkyl group Chemical group 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- OCJBEKTXBNACJF-UHFFFAOYSA-M methanesulfonate trimethyl(2-prop-2-enoyloxyethyl)azanium Chemical compound CS(=O)(=O)[O-].C(C=C)(=O)OCC[N+](C)(C)C OCJBEKTXBNACJF-UHFFFAOYSA-M 0.000 description 1
- XLRRGZMMUOZPBI-UHFFFAOYSA-N methanesulfonate trimethyl-[2-(prop-2-enoylamino)ethyl]azanium Chemical compound CS(=O)(=O)[O-].C(C=C)(=O)NCC[N+](C)(C)C XLRRGZMMUOZPBI-UHFFFAOYSA-N 0.000 description 1
- HQLRUSLQCAVPQW-UHFFFAOYSA-N methanesulfonate trimethyl-[4-(2-methylprop-2-enoylamino)butyl]azanium Chemical compound CS(=O)(=O)[O-].C(C(=C)C)(=O)NCCCC[N+](C)(C)C HQLRUSLQCAVPQW-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- YGRMNBNGHHDGCX-UHFFFAOYSA-N n-(ethoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCNC(=O)C(C)=C YGRMNBNGHHDGCX-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- ZNWWOXZIYMHLKZ-UHFFFAOYSA-N n-(hexoxymethyl)prop-2-enamide Chemical compound CCCCCCOCNC(=O)C=C ZNWWOXZIYMHLKZ-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- JLOVAZFUZOTELM-UHFFFAOYSA-N n-[(2-methylpropan-2-yl)oxymethyl]prop-2-enamide Chemical compound CC(C)(C)OCNC(=O)C=C JLOVAZFUZOTELM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZTLOWOHIHXUWDJ-UHFFFAOYSA-N trimethyl(3-prop-2-enoyloxypropyl)azanium nitrate Chemical compound [N+](=O)([O-])[O-].C(C=C)(=O)OCCC[N+](C)(C)C ZTLOWOHIHXUWDJ-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
Description
本発明は帯電防止離型性ポリエステルフィルムに関するものであり、詳しくは離型剤としてシリコーン化合物を用い、帯電防止剤と併用したときに塗膜均一性が向上する帯電防止離型性ポリエステルフィルムに関する。 The present invention relates to an antistatic releasable polyester film, and more particularly to an antistatic releasable polyester film that uses a silicone compound as a release agent and improves coating film uniformity when used in combination with an antistatic agent.
ポリエステルフィルムを基材とする離型フィルムはカード用、ラベル用、印刷用、粘着用、セラミック成形用、転写箔用等の各種離型用途に利用されている。通常、このようなポリエステルフィルムを基材とする離型フィルムは、離型機能を発現する物質をポリエステルフィルム表面に塗布し、積層することによって作成される。離型機能を発現する物質としてシリコーン化合物が使用されることが多い。しかしながら、シリコーン化合物被膜は、そのシリコーンの主鎖結合ならびに立体構造により電荷の漏洩がなく、帯電しやすい。すなわち、主鎖の−Ｓｉ−Ｏ−Ｓｉ−結合は、−Ｃ−Ｃ−結合に比し、イオン性は帯びているものの基本的にはσ結合であり、共役２重結合等のように電荷の非局在化はできない。また、Ｓｉに結合する２つのメチル基は主鎖の外側に向いていて疎水場を形成し、空気中の水分及び不純物イオンを通しての電荷の漏洩が極めて困難である。このようなシリコーン化合物を塗布したフィルムは、当然帯電性が高く、フィルム同士がブロッキングしやすいため種々の障害を生ずる。そこで、シリコーン化合物を含む離型フィルムに帯電防止性機能を付与することが行われている。 Release films based on polyester films are used for various release applications such as cards, labels, printing, adhesives, ceramic molding, and transfer foils. Usually, the release film which uses such a polyester film as a base material is produced by applying and laminating a substance exhibiting a release function on the surface of the polyester film. Silicone compounds are often used as substances that exhibit a mold release function. However, the silicone compound film is easily charged without leakage of charge due to the main chain bond and the three-dimensional structure of the silicone. In other words, the -Si-O-Si- bond in the main chain is basically σ bond but has ionicity as compared to the -C-C- bond, and is charged like a conjugated double bond. Cannot be delocalized. Further, the two methyl groups bonded to Si face the outside of the main chain to form a hydrophobic field, and it is extremely difficult to leak charges through moisture and impurity ions in the air. A film coated with such a silicone compound naturally has high chargeability, and the films tend to block each other, and thus various obstacles occur. Therefore, an antistatic function is imparted to a release film containing a silicone compound.
まず、シリコーン化合物と帯電防止機能を有する化合物を混合させた塗剤をフィルム表面に積層することで、帯電防止性機能を有した離型フィルムが提案されている（特許文献１）。この手法の場合、帯電防止性機能を有する化合物がシリコーン化合物と混じりにくい化合物であり、不均一な塗膜となり、離型性能や帯電防止性能が不安定な品質になる場合がある。 First, a release film having an antistatic function has been proposed by laminating a coating material in which a silicone compound and a compound having an antistatic function are mixed on the film surface (Patent Document 1). In the case of this method, a compound having an antistatic function is a compound that is difficult to mix with a silicone compound, resulting in a non-uniform coating film, which may result in unstable mold release performance or antistatic performance.
そこで、シリコーン化合物と帯電防止性機能を有する化合物を混合させない方法が提案されている。例えば、シリコーン化合物塗膜の反対面に、帯電防止性塗膜を積層することが提案されている（特許文献２、３）。しかしながら、この方法であると塗工工程が２回となるため、手間がかかることや、塗工工程が２回になることでフィルム表面への傷や異物の付着発生が多くなりやすい。別の方法として、帯電防止性塗膜の上に、離型層を塗工して積層し、帯電防止性機能を付与することが提案されている（特許文献４）。しかし、帯電防止性塗膜上に離型層を積層する方法では塗布工程が煩雑となり、精度の高い塗工技術が必要となって均一な塗膜が得にくい傾向にある。
さらに、シリコーン化合物と帯電防止性機能を有する化合物とを化学的に混合させた帯電防止性機能を有した離型フィルムも提案されている（特許文献５）。この手法だと塗膜は均一化するが、特殊な化合物となるため安定的なこの化合物の製造ができない場合がある。
Therefore, a method has been proposed in which a silicone compound and a compound having an antistatic function are not mixed. For example, it has been proposed to laminate an antistatic coating film on the opposite surface of the silicone compound coating film (Patent Documents 2 and 3). However, with this method, the coating process is performed twice, so that it takes time and the coating process is performed twice, so that scratches and adhesion of foreign matter to the film surface tend to increase. As another method, it has been proposed that a release layer is applied and laminated on an antistatic coating film to impart an antistatic function (Patent Document 4). However, in the method of laminating the release layer on the antistatic coating film, the coating process is complicated, and it is difficult to obtain a uniform coating film because a highly accurate coating technique is required.
Furthermore, a release film having an antistatic function obtained by chemically mixing a silicone compound and a compound having an antistatic function has also been proposed (Patent Document 5). With this method, the coating film becomes uniform, but since it becomes a special compound, it may not be possible to produce this compound stably.
一方、熱可塑性高分子用の帯電防止剤として、耐熱性が改善され、再利用が可能なカチオンポリマーが種々提案されており（特許文献６、７）、またかかる帯電防止剤を用いた帯電防止性ポリエステルフィルムが提案されている（特許文献８、９）。しかしながら、これら特許文献６〜９において、離型性能も付与する観点での検討はなされていない。
このように、シリコーン化合物を用いた離型性ポリエステルフィルムについて、シリコーン離型剤と帯電防止剤とを併用したときに簡便かつ安定的に生産でき、しかも塗膜均一性が高く、離型性、帯電防止性の品質が安定している塗膜層が求められているのが現状である。
On the other hand, various antistatic agents for thermoplastic polymers that have improved heat resistance and can be reused have been proposed (Patent Documents 6 and 7), and antistatic agents using such antistatic agents have been proposed. A conductive polyester film has been proposed (Patent Documents 8 and 9). However, in these Patent Documents 6 to 9, no examination is made from the viewpoint of imparting release performance.
Thus, for a releasable polyester film using a silicone compound, it can be easily and stably produced when a silicone release agent and an antistatic agent are used in combination, and the coating film uniformity is high, and the releasability, The present condition is that a coating layer having a stable antistatic quality is required.
本発明の目的はかかる従来技術の問題点を解消し、離型性ポリエステルフィルムの離型剤としてシリコーン化合物を用い、かかる離型剤と帯電防止剤とを併用したときに、簡便かつ安定的に生産でき、しかも塗膜均一性が高く、離型性、帯電防止性の品質が安定した帯電防止離型性ポリエステルフィルムを提供することにある。 The object of the present invention is to solve the problems of the prior art, use a silicone compound as a release agent for a releasable polyester film, and easily and stably when such a release agent and an antistatic agent are used in combination. An object of the present invention is to provide an antistatic releasable polyester film that can be produced, has high coating uniformity, and has stable releasability and antistatic properties.
本発明者等は、前記課題を解決するために鋭意検討した結果、離型剤としてシリコーン化合物を用いた離型性ポリエステルフィルムに、帯電防止性を付与する帯電防止剤としてポリオキシアルキレン鎖を含有するカチオンポリマーを使用した場合に、従来用いられていたポリオキシアルキレン鎖を含有しないカチオンポリマーと比較して離型剤と帯電防止剤との相溶性が著しく向上し、優れた塗膜均一性が得られることにより帯電防止離型層のヘーズが向上し、塗布斑が目立ちにくくなる結果、同じ塗膜中でこれらの剤を一緒に用いることができ、簡便かつ安定的に生産できること、しかもこれら離型剤と帯電防止剤が均一分散しているため、離型性、帯電防止性の双方の品質が安定になることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have included a polyoxyalkylene chain as an antistatic agent that imparts antistatic properties to a releasable polyester film using a silicone compound as a releasing agent. When the cationic polymer is used, the compatibility between the release agent and the antistatic agent is remarkably improved compared to the conventionally used cationic polymer containing no polyoxyalkylene chain, and excellent coating uniformity is obtained. As a result, the haze of the antistatic release layer is improved and the coating spots are less noticeable. As a result, these agents can be used together in the same coating film, and can be produced easily and stably. Since the mold agent and the antistatic agent are uniformly dispersed, it has been found that both the mold release property and the antistatic property are stable, and the present invention has been completed.
すなわち本発明の目的は、ポリエステルフィルムおよびその少なくとも一方の面に帯電防止剤および離型剤を含む帯電防止層を有する帯電防止離型性ポリエステルフィルムであって、該帯電防止剤がポリオキシアルキレン鎖を含有するカチオンポリマーであり、該離型剤がシリコーン化合物である帯電防止離型性ポリエステルフィルムによって達成される。 That is, an object of the present invention is an antistatic releasable polyester film having a polyester film and an antistatic layer containing an antistatic agent and a release agent on at least one surface thereof, wherein the antistatic agent has a polyoxyalkylene chain. It is achieved by an antistatic release polyester film in which the release agent is a silicone compound.
また本発明の帯電防止離型性ポリエステルフィルムは、好ましい態様として、該カチオンポリマーが、下記式（１）または下記式（２）で表わされる単量体から形成された構成単位Ａ、および下記式（３）または下記式（４）で表わされる単量体から形成された構成単位Ｂを含んでなること、
該カチオンポリマーが、さらに下記式（５）で表わされる単量体から形成された構成単位Ｃを含んでなること、
カチオンポリマーの全構成単位を基準として構成単位Ａを６０モル％以上９９．９モル％以下、構成単位Ｂを０．１モル％以上４０モル％以下の範囲で含んでなること、
シリコーン化合物がポリジメチルシロキサン、エポキシ基含有シリコーン、アミノ基含有シリコーン、および炭素数６以上の炭化水素基を有するシリコーンからなる群から選ばれる少なくとも１種であること、の少なくともいずれか１つを具備するものも包含する。
In addition, the antistatic release polyester film of the present invention has, as a preferred embodiment, a structural unit A in which the cationic polymer is formed from a monomer represented by the following formula (1) or the following formula (2), and the following formula: (3) or comprising a structural unit B formed from a monomer represented by the following formula (4):
The cationic polymer further comprises a structural unit C formed from a monomer represented by the following formula (5):
Comprising from 60 mol% to 99.9 mol% of the structural unit A and 0.1 mol% to 40 mol% of the structural unit B based on the total structural units of the cationic polymer;
The silicone compound is at least one selected from the group consisting of polydimethylsiloxane, epoxy group-containing silicone, amino group-containing silicone, and silicone having a hydrocarbon group having 6 or more carbon atoms. It also includes what to do.
本発明の帯電防止離型性ポリエステルフィルムは、塗膜均一性が高く、簡便かつ安定的に生産でき、しかも離型性、帯電防止性の品質が安定していることから、カード用、ラベル用、印刷用、粘着用、セラミック成形用、転写箔用などの離型性が求められる各種の用途に好適に用いることができる。 The antistatic releasable polyester film of the present invention has high coating uniformity, can be produced easily and stably, and has stable releasability and antistatic properties. It can be suitably used for various applications requiring releasability such as printing, adhesive, ceramic molding, and transfer foil.
以下、本発明を詳細に説明する。
［ポリエステルフィルム］
本発明のポリエステルフィルムを構成するポリエステルは、芳香族二塩基酸またはそのエステル形成性誘導体とジオールまたはそのエステル形成性誘導体とから合成される線状飽和ポリエステルである。かかるポリエステルの具体例として、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリ（１，４−シクロヘキシレンジメチレンテレフタレート）、ポリエチレン−２，６−ナフタレートを例示することができる。
Hereinafter, the present invention will be described in detail.
[Polyester film]
The polyester constituting the polyester film of the present invention is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), and polyethylene-2,6-naphthalate.
ポリエステルは、これらポリエステルのうちの１つを主たる成分とする共重合体であってもよく、またはブレンドしたものであってもよい。ここで「主たる成分」とは、ポリエステルの繰り返し単位のモル数を基準として８０モル％以上である。また主たる成分の割合は、８５モル％以上であることが好ましく、９０モル％以上であることがさらに好ましい。また、共重合成分またはブレンド成分はポリエステルの繰り返し単位のモル数を基準として２０モル％以下であり、好ましくは１５モル％以下、さらに好ましくは１０モル％以下である。ポリエステルとしてポリエチレンテレフタレートが力学的物性と成形性のバランスがよいので特に好ましい。 The polyester may be a copolymer having one of these polyesters as a main component, or may be a blend. Here, the “main component” is 80 mol% or more based on the number of moles of the repeating unit of the polyester. The ratio of the main component is preferably 85 mol% or more, and more preferably 90 mol% or more. The copolymer component or blend component is 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, based on the number of moles of the repeating unit of the polyester. Polyethylene terephthalate is particularly preferred as the polyester because it has a good balance between mechanical properties and moldability.
ポリエステルフィルムは、例えば二酸化珪素、炭酸カルシウム、カオリン、シリコーン粒子などの無機または有機滑剤、着色剤、帯電防止剤、酸化防止剤を含有してもよい。
ポリエステルフィルムは、例えば次の方法で製造することができる。すなわち、ポリエステルをフィルム状に溶融押出し、キャスティングドラムで冷却固化させて非晶未延伸フィルムとし、縦方向（以下、連続製膜方向、長手方向、ＭＤ方向と称することがある）および横方向（以下、幅方向、ＴＤ方向と称することがある）に延伸する。縦方向の延伸は例えば温度６０〜１３０℃、好ましくは９０〜１２５℃で、２．０〜４．０倍、好ましくは２．５〜３．５倍に延伸する。横方向の延伸は、例えば温度６０〜１３０℃、好ましくは９０〜１２５℃で、２．０〜４．０倍、好ましくは３．０〜４．０倍に延伸する。二軸延伸後の面積倍率は１３以下とすることが好ましい。
The polyester film may contain, for example, inorganic or organic lubricants such as silicon dioxide, calcium carbonate, kaolin, and silicone particles, colorants, antistatic agents, and antioxidants.
The polyester film can be produced, for example, by the following method. That is, polyester is melt-extruded into a film shape, cooled and solidified with a casting drum to form an amorphous unstretched film, and the longitudinal direction (hereinafter sometimes referred to as a continuous film-forming direction, the longitudinal direction, and the MD direction) and the lateral direction (hereinafter referred to as the “non-stretched film”). , Sometimes referred to as the width direction and the TD direction). Stretching in the machine direction is, for example, at a temperature of 60 to 130 ° C., preferably 90 to 125 ° C., and is stretched by 2.0 to 4.0 times, preferably 2.5 to 3.5 times. Stretching in the transverse direction is, for example, stretched at a temperature of 60 to 130 ° C., preferably 90 to 125 ° C., and 2.0 to 4.0 times, preferably 3.0 to 4.0 times. The area magnification after biaxial stretching is preferably 13 or less.
なお、フィルムの延伸後には熱固定処理を行なうことが好ましい。熱固定処理は、最終延伸温度より高く融点以下の温度内で１〜３０秒の時間内行なうことが好ましい。例えばポリエチレンテレフタレートフィルムでは１５０〜２５０℃の温度、２〜３０秒の時間の範囲で選択して熱固定することが好ましい。その際、２０％以内の制限収縮もしくは伸長、または定長下で行ない、また２段以上で行なってもよい。
ポリエステルフィルムの厚みは、ハンドリング性、成形性などの点から必要な強度を得るために、好ましくは１２〜１００μｍ、さらに好ましくは２５〜７５μｍである。
In addition, it is preferable to perform a heat setting process after extending | stretching a film. The heat setting treatment is preferably performed within a time period of 1 to 30 seconds within a temperature higher than the final stretching temperature and not higher than the melting point. For example, in the case of a polyethylene terephthalate film, it is preferable to select and heat-set at a temperature of 150 to 250 ° C. and a time of 2 to 30 seconds. At that time, it may be performed under a limited contraction or expansion within 20%, or under a constant length, or may be performed in two or more stages.
The thickness of the polyester film is preferably 12 to 100 μm, and more preferably 25 to 75 μm, in order to obtain necessary strength from the viewpoints of handling properties and moldability.
［帯電防止離型層］
本発明の帯電防止離型性ポリエステルフィルムは、ポリエステルフィルムの少なくとも一方の面に、帯電防止剤および離型剤を含む帯電防止離型層を有し、該帯電防止剤がポリオキシアルキレン鎖を含有するカチオンポリマーであり、該離型剤がシリコーン化合物であることを特徴としている。
[Antistatic release layer]
The antistatic release polyester film of the present invention has an antistatic release layer containing an antistatic agent and a release agent on at least one surface of the polyester film, and the antistatic agent contains a polyoxyalkylene chain. And the release agent is a silicone compound.
（カチオンポリマー）
ポリオキシアルキレン鎖を含有するカチオンポリマーとして、例えば下記式（１）または下記式（２）で表わされる単量体から形成された構成単位Ａ、および下記式（３）または下記式（４）で表わされる単量体から形成された構成単位Ｂを含むカチオンポリマーが挙げられる。
(Cationic polymer)
As a cationic polymer containing a polyoxyalkylene chain, for example, the structural unit A formed from a monomer represented by the following formula (1) or the following formula (2), and the following formula (3) or the following formula (4) And a cationic polymer containing the structural unit B formed from the represented monomer.
構成単位Ａを形成する式（１）で表わされる単量体の具体例として、アクリロイルアミノエチルトリメチルアンモニウムメチルスルホン酸塩、アクリロイルアミノプロピルジメチルアンモニウムエチルスルホン酸塩、アクリロイルアミノプロピル２−ヒドロキシエチルジメチルアンモニウム硝酸塩、アクリロイルアミノプロピルトリメチルアンモニウム硝酸塩、メタクリロイルアミノブチルトリメチルアンモニウムメチルスルホン酸塩、メタクリロイルアミノヘキシルジ（２−ヒドロキシエチル）アンモニウム硝酸塩等が挙げられる。 Specific examples of the monomer represented by the formula (1) forming the structural unit A include acryloylaminoethyltrimethylammonium methylsulfonate, acryloylaminopropyldimethylammonium ethylsulfonate, acryloylaminopropyl 2-hydroxyethyldimethylammonium. Examples thereof include nitrate, acryloylaminopropyltrimethylammonium nitrate, methacryloylaminobutyltrimethylammonium methylsulfonate, methacryloylaminohexyldi (2-hydroxyethyl) ammonium nitrate, and the like.
構成単位Ａを形成する式（２）で表わされる単量体の具体例として、アクリロイルオキシエチルトリメチルアンモニウムメチルスルホン酸塩、アクリロイルオキシプロピルジメチルアンモニウムエチルスルホン酸塩、アクリロイルオキシプロピル２−ヒドロキシエチルジメチルアンモニウム硝酸塩、アクリロイルオキシプロピルトリメチルアンモニウム硝酸塩、メタクリロイルオキシブチルトリメチルアンモニウムメチルスルホン酸塩、メタクリロイルオキシヘキシルジ（２−ヒドロキシエチル）アンモニウム硝酸塩等が挙げられる。 Specific examples of the monomer represented by the formula (2) forming the structural unit A include acryloyloxyethyltrimethylammonium methylsulfonate, acryloyloxypropyldimethylammonium ethylsulfonate, acryloyloxypropyl 2-hydroxyethyldimethylammonium. Examples thereof include nitrate, acryloyloxypropyltrimethylammonium nitrate, methacryloyloxybutyltrimethylammonium methylsulfonate, methacryloyloxyhexyl di (2-hydroxyethyl) ammonium nitrate, and the like.
また、構成単位Ｂを形成する式（３）で表わされる単量体の具体例として、アクリル酸ポリオキシエチレン、アクリル酸ポリオキシプロピレン、アクリル酸オキシエチレンオキシプロピレン、アクリル酸ポリオキシエチレンオキシプロピレン、アクリル酸オキシエチレンポリオキシプロピレン、アクリル酸ポリオキシエチレンポリオキシプロピレン、メタクリル酸ポリオキシエチレン、メタクリル酸ポリオキシプロピレン、メタクリル酸オキシエチレンオキシプロピレン、メタクリル酸ポリオキシエチレンオキシプロピレン、メタクリル酸オキシエチレンポリオキシプロピレン、メタクリル酸ポリオキシエチレンポリオキシプロピレン、クロトン酸ポリオキシプロピレン、クロトン酸オキシエチレンオキシプロピレン、クロトン酸ポリオキシエチレンオキシプロピレン、クロトン酸オキシエチレンポリオキシプロピレン、クロトン酸ポリオキシエチレンポリオキシプロピレン等が挙げられる。 Specific examples of the monomer represented by the formula (3) forming the structural unit B include polyoxyethylene acrylate, polyoxypropylene acrylate, oxyethylene oxypropylene acrylate, polyoxyethylene oxypropylene acrylate, Oxyethylene polyoxypropylene acrylate, polyoxyethylene polyoxypropylene acrylate, polyoxyethylene methacrylate, polyoxypropylene methacrylate, oxyethylene oxypropylene methacrylate, polyoxyethylene oxypropylene methacrylate, oxyethylene polyoxymethacrylate methacrylate Propylene, polyoxyethylene methacrylate, polyoxypropylene, crotonic acid polyoxypropylene, crotonic acid oxyethyleneoxypropylene, crotonic acid polyoxy Chi Ren oxypropylene, crotonic acid polyoxypropylene, polyoxyethylene polyoxypropylene etc. crotonic acid.
構成単位Ｂを形成する式（４）で表わされる単量体の具体例として、α−アリル−ω−ヒドロキシ（ポリオキシエチレン）、α−アリル−ω−ヒドロキシ（ポリオキシプロピレン）、α−アリル−ω−ヒドロキシ（オキシエチレンオキシプロピレン）、α−アリル−ω−ヒドロキシ（ポリオキシエチレンオキシプロピレン）、α−アリル−ω−ヒドロキシ（ポリオキシエチレンポリオキシプロピレン）、α−メタリル−ω−ヒドロキシ（ポリオキシエチレン）、α−メタリル−ω−ヒドロキシ（ポリオキシプロピレン）、α−メタリル−ω−ヒドロキシ（オキシエチレンオキシプロピレン）、α−メタリル−ω−ヒドロキシ（ポリオキシエチレンオキシプロピレン）、α−メタリル−ω−ヒドロキシ（ポリオキシエチレンポリオキシプロピレン）等が挙げられる。 Specific examples of the monomer represented by the formula (4) that forms the structural unit B include α-allyl-ω-hydroxy (polyoxyethylene), α-allyl-ω-hydroxy (polyoxypropylene), α-allyl. -Ω-hydroxy (oxyethyleneoxypropylene), α-allyl-ω-hydroxy (polyoxyethyleneoxypropylene), α-allyl-ω-hydroxy (polyoxyethylene polyoxypropylene), α-methallyl-ω-hydroxy ( Polyoxyethylene), α-methallyl-ω-hydroxy (polyoxypropylene), α-methallyl-ω-hydroxy (oxyethyleneoxypropylene), α-methallyl-ω-hydroxy (polyoxyethyleneoxypropylene), α-methallyl -Ω-hydroxy (polyoxyethylene polyoxypropylene) and the like It is.
本発明のカチオンポリマーが、式（１）または（２）で表わされる単量体で構成されるカチオン成分を含有する構成単位Ａを必須成分として含むことにより、帯電防止剤としての機能が発現する。
また本発明のカチオンポリマーは、式（３）または（４）で表わされる単量体で構成されるポリオキシアルキレン鎖を含有する構成単位Ｂを必須成分として含むことにより、シリコーン化合物との相溶性が向上し、帯電防止剤とシリコーン化合物を同じ塗膜中で用いたときに優れた塗膜均一性が得られ、帯電防止離型層のヘーズが良好になるため塗布斑がめだちにくくなり、しかもこれら離型剤と帯電防止剤が均一分散しているため、離型性、帯電防止性の双方の品質が安定になる。構成単位Ｂにおけるポリオキシアルキレン鎖は、２〜２０の繰り返し数であり、さらに好ましくは５〜１５、特に好ましくは８〜１５である。
When the cationic polymer of the present invention contains the structural unit A containing a cationic component composed of the monomer represented by the formula (1) or (2) as an essential component, the function as an antistatic agent is exhibited. .
Further, the cationic polymer of the present invention contains a structural unit B containing a polyoxyalkylene chain composed of a monomer represented by the formula (3) or (4) as an essential component, so that it is compatible with a silicone compound. And improved coating uniformity when antistatic agent and silicone compound are used in the same coating, and haze of antistatic release layer is improved, so that coating spots are less likely to appear. Since the release agent and the antistatic agent are uniformly dispersed, the quality of both the release property and the antistatic property becomes stable. The polyoxyalkylene chain in the structural unit B is a repeating number of 2 to 20, more preferably 5 to 15, and particularly preferably 8 to 15.
これら構成単位Ａおよび構成単位Ｂは、カチオンポリマーの全構成単位を基準として、構成単位Ａを６０モル％以上９９．９モル％以下の範囲で含むことが好ましく、また構成単位Ｂを０．１モル％以上４０モル％以下の範囲で含むことが好ましい。また、構成単位Ａの含有量はより好ましくは６５モル％以上９０モル％以下、さらに好ましくは６５モル％以上８０モル％以下であり、構成単位Ｂの含有量はより好ましくは１０モル％以上３５モル％以下、さらに好ましくは２０モル％以上３５モル％以下である。
構成単位Ａが下限値に満たない場合、十分な帯電防止性能が発現しないことがある。また構成単位Ａが上限値を超える場合、相対的に構成単位Ｂが減るため、シリコーン化合物との相溶性が悪くなり、塗膜均一性が低下することがある。構成単位Ｂが下限値に満たない場合、シリコンーン化合物とカチオンポリマーが十分に相溶しないため、相分離が生じてしまい、塗膜が均一になりにくく、さらに離型性、帯電防止性の品質にばらつきが生じやすい。また、構成単位Ｂが上限値を超える場合、カチオンポリマーの耐熱性、耐湿性が低下するため、塗工膜のブロッキング耐性が低下する場合がある。
The structural unit A and the structural unit B preferably include the structural unit A in a range of 60 mol% or more and 99.9 mol% or less based on all the structural units of the cationic polymer. It is preferable to contain in mol% or more and 40 mol% or less. Further, the content of the structural unit A is more preferably 65 mol% or more and 90 mol% or less, further preferably 65 mol% or more and 80 mol% or less, and the content of the structural unit B is more preferably 10 mol% or more and 35 mol% or less. The mol% or less, more preferably 20 mol% or more and 35 mol% or less.
When the structural unit A is less than the lower limit, sufficient antistatic performance may not be exhibited. Further, when the structural unit A exceeds the upper limit value, the structural unit B is relatively decreased, so that the compatibility with the silicone compound is deteriorated, and the coating film uniformity may be decreased. When the structural unit B is less than the lower limit value, the silicone compound and the cationic polymer are not sufficiently compatible with each other, so that phase separation occurs, the coating film is difficult to be uniform, and the mold release property and antistatic property are improved. Variations are likely to occur. Further, when the structural unit B exceeds the upper limit value, the heat resistance and moisture resistance of the cationic polymer are lowered, so that the blocking resistance of the coating film may be lowered.
本発明のカチオンポリマーは、さらに下記式（５）で表わされる単量体から形成された構成単位Ｃを含むことが好ましい。
本発明のカチオンポリマーがさらに構成単位Ｃを含むことによって、樹脂自体の凝集力が向上し、塗膜を強固にすることができる。
構成単位Ｃを形成する式（５）で表わされる単量体の具体例として、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−エトキシメチルアクリルアミド、Ｎ−ブトキシメチルアクリルアミド、Ｎ−ターシャリーブチルオキシメチルアクリルアミド、Ｎ−ヘキシルオキシメチルアクリルアミド、Ｎ−メトキシメチルメタクリルアミド、Ｎ−エトキシメチルメタクリルアミド、Ｎ−ブトキシメチルメタクリルアミド、Ｎ−ターシャリーブチルオキシメチルメタクリルアミド、Ｎ−ヘキシルオキシメチルメタクリルアミド等が挙げられるが、なかでもＮ−メチロールアクリルアミド、Ｎ−メトキシメチルアクリルアミド、Ｎ−ブトキシメチルアクリルアミドが好ましい。
When the cationic polymer of the present invention further contains the structural unit C, the cohesive force of the resin itself is improved and the coating film can be strengthened.
Specific examples of the monomer represented by the formula (5) forming the structural unit C include N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxymethyl acrylamide, N-tertiary butyloxymethyl acrylamide, N-hexyloxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl methacrylamide, N-butoxymethyl methacrylamide, N-tertiary butyloxymethyl methacrylamide, N-hexyl Examples include oxymethyl methacrylamide, among which N-methylol acrylamide, N-methoxymethyl acrylamide, and N-butoxymethyl acrylamide are preferable.
本発明のカチオンポリマーが式（５）で表わされる単量体から形成された構成単位Ｃを含む場合、構成単位Ｃの含有量はカチオンポリマーの全構成単位を基準として、１モル％以上３０モル％以下の範囲で含むことが好ましく、さらに好ましくは５モル％以上２５モル％以下の範囲である。構成単位Ｃの含有量が下限値に満たない場合、塗膜の凝集力が低下することがある。一方、構成単位Ｃの含有量が上限値を超える場合、カチオンポリマー自体の造膜性が悪くなり、塗膜外観に影響を及ぼす場合がある。 When the cationic polymer of the present invention includes the structural unit C formed from the monomer represented by the formula (5), the content of the structural unit C is 1 mol% or more and 30 mol based on the total structural unit of the cationic polymer. % Or less, and more preferably 5 mol% or more and 25 mol% or less. When content of the structural unit C is less than a lower limit, the cohesion force of a coating film may fall. On the other hand, when the content of the structural unit C exceeds the upper limit, the film forming property of the cationic polymer itself is deteriorated, which may affect the appearance of the coating film.
本発明のカチオンポリマーには、柔軟性、硬度調整や水分散化等の必要に応じて、一般的なビニル共重合体の構成単位Ｄを導入してもよい。具体例として、アルキルアクリレート、アルキルメタクリレート、スチレン、αーメチルスチレン等が挙げられる。ここで、アルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、２ーエチルヘキシル基、シクロヘキシル基等が挙げられる。
これら一般的なビニル共重合体の構成単位Ｄを導入する場合は、カチオンポリマーの全構成単位を基準として、１モル％以上４０モル％以下の範囲で含むことが好ましく、さらに好ましくは５モル％以上３０モル％以下の範囲である。これらは一例であり、構成単位Ｄはこれらに限定されるものではない。
A structural unit D of a general vinyl copolymer may be introduced into the cationic polymer of the present invention as necessary for flexibility, hardness adjustment, water dispersion and the like. Specific examples include alkyl acrylate, alkyl methacrylate, styrene, α-methylstyrene, and the like. Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a 2-ethylhexyl group, and a cyclohexyl group.
When the structural unit D of these general vinyl copolymers is introduced, it is preferably contained in the range of 1 mol% to 40 mol%, more preferably 5 mol%, based on the total structural units of the cationic polymer. It is the range of 30 mol% or less. These are examples, and the structural unit D is not limited to these.
本発明のカチオンポリマーは、数平均分子量が５０００〜１００００００であることが好ましく、７０００〜１０００００であることがさらに好ましい。カチオンポリマーの数平均分子量が下限値に満たないと帯電防止性が十分でないことがある。またカチオンポリマーの数平均分子量が上限値を超える場合は塗膜が均一になりにくいことがある。 The cationic polymer of the present invention preferably has a number average molecular weight of 5,000 to 1,000,000, and more preferably 7,000 to 100,000. If the number average molecular weight of the cationic polymer is less than the lower limit, the antistatic property may not be sufficient. In addition, when the number average molecular weight of the cationic polymer exceeds the upper limit, the coating film may be difficult to be uniform.
本発明のカチオンポリマーは、ラジカル共重合により得ることができる。ラジカル共重合それ自体は、公知の方法、通常は水または水と水溶性有機溶媒との混合溶媒を用いた水性溶液中で行なうことができる。例えば、各構成単位を所定量ずつ水に溶解させて合計で１０〜４５重量％含む水溶液を調製した後、窒素ガス雰囲気下において、これにラジカル開始剤を加え、５０〜８０℃で４〜８時間ラジカル重合反応させる。用いるラジカル開始剤としては、重合反応温度下において分解し、ラジカル発生するものであれば、その種類は特に制限されないが、水溶性のラジカル開始剤を用いるのが好ましい。かかる水溶性のラジカル開始剤としては、過硫酸カリウム、過硫酸アンモニウム、過酸化水素、２，２−アゾビス（２−アミジノプロパン）二塩酸塩等が挙げられる。これらは、亜硫酸塩やＬ−アスコルビン酸の如き還元性物質更にはアミン等と組み合わせ、レドックス開始剤として用いることもできる。また、乳化重合とする場合は、適正な界面活性剤を用いることで、同様に実施できる。 The cationic polymer of the present invention can be obtained by radical copolymerization. The radical copolymerization itself can be carried out by a known method, usually an aqueous solution using water or a mixed solvent of water and a water-soluble organic solvent. For example, each constituent unit is dissolved in water in a predetermined amount to prepare an aqueous solution containing a total of 10 to 45% by weight, and then a radical initiator is added thereto under a nitrogen gas atmosphere, and the mixture is added at 50 to 80 ° C. for 4 to 8 Allow time radical polymerization reaction. The radical initiator to be used is not particularly limited as long as it decomposes at a polymerization reaction temperature and generates radicals, but a water-soluble radical initiator is preferably used. Examples of the water-soluble radical initiator include potassium persulfate, ammonium persulfate, hydrogen peroxide, 2,2-azobis (2-amidinopropane) dihydrochloride, and the like. These can also be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid, or an amine. Moreover, when setting it as emulsion polymerization, it can implement similarly by using an appropriate surfactant.
（シリコーン化合物）
本発明において、離型性を発現させるためにシリコーン化合物が用いられ、かかるシリコーン化合物として、ポリジメチルシロキサン、エポキシ基含有シリコーン、アミノ基含有シリコーン、および炭素数６以上の炭化水素基を有するシリコーンからなる群から選ばれる少なくとも１種を用いることが好ましい。
離型剤としてシリコーン化合物を用いることにより、どのような環境下でも離型性が高く、多種多様な用途に使用できる。これらのシリコーン化合物の中でも、特にポリジメチルシロキサンや、エポキシ基含有シリコーンまたはアミノ基含有シリコーンといったシリコーン化合物が離型剤としてよく用いられるものの、カチオンポリマーと混ざりにくい化合物であり、本発明のポリオキシアルキレン鎖を含有するカチオンポリマーを用いた場合の塗膜均一性の改良効果が特に高くなる。また、特にエポキシ基含有シリコーンまたはアミノ基含有シリコーンといった極性成分を有するシリコーン化合物は、本発明のポリオキシアルキレン鎖を含有するカチオンポリマーとの相溶性がさらに良好となり、塗膜均一性が向上することから好ましい。
(Silicone compound)
In the present invention, a silicone compound is used to develop releasability. Examples of the silicone compound include polydimethylsiloxane, epoxy group-containing silicone, amino group-containing silicone, and silicone having a hydrocarbon group having 6 or more carbon atoms. It is preferable to use at least one selected from the group consisting of
By using a silicone compound as a release agent, the release property is high in any environment and can be used for a wide variety of applications. Among these silicone compounds, especially polydimethylsiloxane, silicone compounds such as epoxy group-containing silicone or amino group-containing silicone are often used as mold release agents, but are difficult to mix with cationic polymers, and the polyoxyalkylene of the present invention The effect of improving the uniformity of the coating film is particularly high when a cationic polymer containing a chain is used. In particular, a silicone compound having a polar component such as an epoxy group-containing silicone or an amino group-containing silicone is more compatible with the cationic polymer containing the polyoxyalkylene chain of the present invention, and the coating film uniformity is improved. To preferred.
ポリジメチルシロキサンとして、２５℃における粘度が１００〜１０００００センチストークスの範囲であるポリジメチルシロキサンが好ましい。粘度が１００センチストークスよりも低いと離型性が十分でないことがある。一方、粘度が１０００００センチストークスよりも高くなると粘度が高く、かつ分子量も大きくなるため、カチオンポリマーとの相溶性が低下することがある。 As the polydimethylsiloxane, polydimethylsiloxane having a viscosity at 25 ° C. in the range of 100 to 100,000 centistokes is preferable. If the viscosity is lower than 100 centistokes, the releasability may not be sufficient. On the other hand, when the viscosity is higher than 100,000 centistokes, the viscosity is high and the molecular weight is also large, so that the compatibility with the cationic polymer may be lowered.
エポキシ基含有シリコーンのエポキシ基として、γ−グリシドキシプロピル基、β−グリシドキシエチル基、γ−グリシドキシ−β−メチル−プロピル基といったグリシドキシアルキル基、２−グリシドキシカルボニル−エチル基、２−グリシドキシカルボニル−プロピル基といったグリシドキシカルボニルアルキル基が挙げられる。粘度についてはポリジメチルシロキサンと同様の範囲であることが好ましい。 As epoxy groups of epoxy group-containing silicones, glycidoxyalkyl groups such as γ-glycidoxypropyl group, β-glycidoxyethyl group, γ-glycidoxy-β-methyl-propyl group, 2-glycidoxycarbonyl-ethyl And a glycidoxycarbonylalkyl group such as 2-glycidoxycarbonyl-propyl group. The viscosity is preferably in the same range as polydimethylsiloxane.
アミノ基含有シリコーンのアミノ基として、３−アミノプロピル基、３−アミノ−２−メチル−プロピル基、２−アミノエチル基といった１級アミノアルキル基、Ｎ−（２−アミノエチル）−３−アミノプロピル基、Ｎ−（２−アミノエチル）−２−アミノエチル基といった１級および２級アミノアルキル基を有する有機基が挙げられる。粘度についてはポリジメチルシロキサンと同様の範囲であることが好ましい。 As the amino group of the amino group-containing silicone, primary aminoalkyl group such as 3-aminopropyl group, 3-amino-2-methyl-propyl group, 2-aminoethyl group, N- (2-aminoethyl) -3-amino Examples thereof include organic groups having primary and secondary aminoalkyl groups such as propyl group and N- (2-aminoethyl) -2-aminoethyl group. The viscosity is preferably in the same range as polydimethylsiloxane.
炭素数６以上の炭化水素基を有するシリコーンとして、炭素数６以上のアルキル変性シリコーン、炭素数６以上のアラルキル変性シリコーン、炭素数６以上のアルキルアラルキル共変性シリコーン、アリール変性シリコーンが例表わされる。これらの炭素数６以上の炭化水素基を有するシリコーンを用いた場合は、帯電防止離型層表面の離型性能を維持しつつ、濡れ性を向上させることができる。 Examples of the silicone having a hydrocarbon group having 6 or more carbon atoms include alkyl-modified silicones having 6 or more carbon atoms, aralkyl-modified silicones having 6 or more carbon atoms, alkylaralkyl co-modified silicones having 6 or more carbon atoms, and aryl-modified silicones. When silicone having a hydrocarbon group having 6 or more carbon atoms is used, wettability can be improved while maintaining the release performance of the surface of the antistatic release layer.
かかる炭素数６以上の炭化水素基を有するシリコーンとして、下記式（６）で表わされる化合物が例表わされる。
上式中、Ｒ20は同一もしくは異種の炭素数１〜５の飽和または不飽和の１価炭化水素基であり、具体的には、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、などの飽和炭化水素基、シクロペンチル基などの飽和脂環式炭化水素基が例示され、特にメチル基が好ましい。 In the above formula, R 20 is the same or different C 1-5 saturated or unsaturated monovalent hydrocarbon group, specifically, methyl group, ethyl group, propyl group, butyl group, pentyl group, And saturated alicyclic hydrocarbon groups such as a cyclopentyl group, and a methyl group is particularly preferable.
また、Ｒ21は同一もしくは異種の炭素数６〜２０の飽和または不飽和の１価炭化水素基であり、例えばアルキル基が挙げられ、具体的には、へキシル基、へプチル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基が例示され、特にドデシル基、テトラデシル基が好ましい。また、アルキル基以外のＲ21としてアラルキル基が挙げられ、具体的には、ベンジル基、４−メチルベンジル基、ｐ−メトキシベンジル基、ジフェニルメチル基、２−フェニルエチル基、２−フェニルプロピル基、３−フェニルプロピル基が例示され、特に２−フェニルプロピル基が好ましい。またＲ21の他の例としてアリール基が挙げられ、特にフェニル基が好ましい。
これらの中でも、Ｒ21の炭素数６〜２０の炭化水素基として、帯電防止剤との相溶性がより良好なフェニル基が最も好ましく用いることができる。
R 21 is the same or different monovalent or unsaturated monovalent hydrocarbon group having 6 to 20 carbon atoms, and examples thereof include an alkyl group, specifically, a hexyl group, a heptyl group, an octyl group. Nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and eicosyl group are exemplified, and dodecyl group and tetradecyl group are particularly preferable. Examples of R 21 other than an alkyl group include an aralkyl group. Specific examples include a benzyl group, a 4-methylbenzyl group, a p-methoxybenzyl group, a diphenylmethyl group, a 2-phenylethyl group, and a 2-phenylpropyl group. , 3-phenylpropyl group is exemplified, and 2-phenylpropyl group is particularly preferable. Another example of R 21 is an aryl group, and a phenyl group is particularly preferable.
Among these, a phenyl group having better compatibility with the antistatic agent can be most preferably used as the hydrocarbon group having 6 to 20 carbon atoms of R 21 .
（界面活性剤）
本発明で用いるシリコーン成分は、塗工時の取扱易さ、作業環境から水分散液あるいは乳化液の形態で使用するのが好ましい。良好な水分散、乳化液の形態を得るには、界面活性剤の使用が好ましく、塗液の他の成分との分散安定性のため、ノニオン系界面活性剤が特に好ましい。
(Surfactant)
The silicone component used in the present invention is preferably used in the form of an aqueous dispersion or an emulsion from the viewpoint of ease of handling during coating and the working environment. In order to obtain a good aqueous dispersion and emulsion form, the use of a surfactant is preferred, and a nonionic surfactant is particularly preferred because of its dispersion stability with other components of the coating liquid.
（架橋剤）
帯電防止離型層には、塗膜の凝集力を向上させるために、さらに架橋剤を添加させることが好ましい。架橋剤としては、エポキシ化合物、オキサゾリン化合物、メラミン化合物、イソシアネート化合物を例示することができ、その他カップリング剤を用いることもできる。取り扱い易さや塗液のポットライフが長いことからエポキシ化合物、オキサゾリン化合物を用いることが好ましく、カップリング剤を用いることも好ましい。
(Crosslinking agent)
In order to improve the cohesive strength of the coating film, it is preferable to further add a crosslinking agent to the antistatic release layer. Examples of the crosslinking agent include epoxy compounds, oxazoline compounds, melamine compounds, and isocyanate compounds, and other coupling agents can also be used. Epoxy compounds and oxazoline compounds are preferably used because of easy handling and the pot life of the coating liquid, and a coupling agent is also preferably used.
（帯電防止離型層の組成比）
本発明の帯電防止離型層における各添加剤の割合は、帯電防止離型層の重量を基準として本発明のカチオンポリマー、すなわち帯電防止剤が３５〜９０重量％、シリコーン化合物からなる離型剤が１〜５０重量％、界面活性剤が０〜１５重量％であることが好ましい。
また帯電防止剤の含有量は３５〜７０重量％であることがより好ましく、３５〜６５重量％であることがさらに好ましい。シリコーン離型剤の含有量は１０〜４０重量％であることがより好ましく、２０〜３０重量％であることがさらに好ましい。界面活性剤の含有量は５〜１２重量％であることがより好ましい。
(Composition ratio of antistatic release layer)
The proportion of each additive in the antistatic release layer of the present invention is such that the cationic polymer of the present invention, that is, the antistatic agent is 35 to 90% by weight based on the weight of the antistatic release layer, and the release agent comprises a silicone compound. Is preferably 1 to 50% by weight, and the surfactant is preferably 0 to 15% by weight.
The content of the antistatic agent is more preferably 35 to 70% by weight, and further preferably 35 to 65% by weight. The content of the silicone release agent is more preferably 10 to 40% by weight, and further preferably 20 to 30% by weight. The content of the surfactant is more preferably 5 to 12% by weight.
本発明のカチオンポリマーからなる帯電防止剤が下限値に満たないと帯電防止性能が不足し、加工工程でのゴミ等の付着が多くなり、欠点等の発生が多くなる場合があり、一方、上限値を超えると相対的にシリコーン成分の含有量が低下し、離型性能が低下することがある。また、シリコーン化合物からなる離型剤が下限値に満たないと離型性能が低下することがあり、一方、上限値を超えると塗膜均一性が低下することがある。界面活性剤については、下限値に満たないと均一塗工性が低下することがあり、一方上限値を超えると発泡しやすくなり、泡因の塗工欠陥が発生しやすくなる場合がある。 If the antistatic agent comprising the cationic polymer of the present invention is less than the lower limit value, the antistatic performance is insufficient, the adhesion of dust and the like in the processing step increases, and the occurrence of defects may increase, while the upper limit When the value is exceeded, the content of the silicone component is relatively lowered, and the release performance may be lowered. Moreover, if the release agent which consists of silicone compounds is less than a lower limit, mold release performance may fall, and on the other hand, when it exceeds an upper limit, coating-film uniformity may fall. When the surfactant is less than the lower limit value, the uniform coating property may be lowered. On the other hand, when the upper limit value is exceeded, foaming is likely to occur and coating defects due to foam may easily occur.
また、帯電防止離型層がさらに架橋剤を含む場合、架橋剤の含有量は１〜３０重量％であることが好ましく、２〜２０重量％であることがさらに好ましい。さらに架橋剤を含む場合に、架橋剤の含有量が下限値に満たないと塗膜凝集力が下がり、耐傷性が低下することがあり、一方、上限値を超える場合は架橋密度が高くなり、造膜性が低下して塗布外観が低下することがある。 When the antistatic release layer further contains a crosslinking agent, the content of the crosslinking agent is preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. In addition, when the crosslinking agent is included, the content of the crosslinking agent is less than the lower limit value, the coating film cohesive force may be reduced, and the scratch resistance may be reduced. The film-forming property may decrease and the coating appearance may decrease.
（帯電防止離型層の形成方法）
本発明において帯電防止離型層の塗設に用いられる上記組成物は、塗布層を形成させるために、水溶液、水分散液あるいは乳化液等の水性塗液（以下、水性塗布液と称することがある）の形態で使用されることが好ましい。
本発明に用いる水性塗布液の固形分濃度は、該塗布液の重量を基準として通常２０重量％以下、好ましくは１〜１０重量％である。固形分濃度が下限に満たないとポリエステルフィルムへの塗れ性が不足することがある。また固形分濃度が上限を超えると塗液の安定性や塗布層の外観が低下することがある。
(Method of forming antistatic release layer)
In the present invention, the composition used for coating the antistatic release layer is an aqueous coating solution such as an aqueous solution, aqueous dispersion or emulsion (hereinafter referred to as an aqueous coating solution) in order to form a coating layer. It is preferable to be used in the form of
The solid content concentration of the aqueous coating solution used in the present invention is usually 20% by weight or less, preferably 1 to 10% by weight, based on the weight of the coating solution. If the solid content concentration is less than the lower limit, the applicability to the polyester film may be insufficient. Moreover, when solid content concentration exceeds an upper limit, the stability of a coating liquid and the external appearance of a coating layer may fall.
水性塗布液のポリエステルフィルムへの塗布は、任意の段階で実施することができるが、ポリエステルフィルムの製造過程で実施するのが好ましく、さらには配向結晶化が完了する前のポリエステルフィルムに塗布するのが好ましい。
ここで、結晶配向が完了する前のポリエステルフィルムとは、未延伸フィルム、未延伸フィルムを縦方向または横方向の何れか一方に配向せしめた一軸配向フィルム、さらには縦方向および横方向の二方向に低倍率延伸配向せしめたもの（最終的に縦方向また横方向に再延伸せしめて配向結晶化を完了せしめる前の二軸延伸フィルム）等を含むものである。なかでも、未延伸フィルムまたは一方向に配向せしめた一軸延伸フィルムに、上記組成物の水性塗液を塗布し、そのまま縦延伸および／または横延伸と熱固定とを施すのが好ましい。
Application of the aqueous coating solution to the polyester film can be carried out at any stage, but it is preferably carried out during the production process of the polyester film, and is further applied to the polyester film before the completion of orientational crystallization. Is preferred.
Here, the polyester film before the crystal orientation is completed is an unstretched film, a uniaxially oriented film in which the unstretched film is oriented in either the longitudinal direction or the transverse direction, and further in two directions, the longitudinal direction and the transverse direction. And the like that have been oriented at a low magnification (biaxially stretched film before being finally re-stretched in the machine direction or the transverse direction to complete orientation crystallization). In particular, it is preferable to apply the aqueous coating liquid of the above composition to an unstretched film or a uniaxially stretched film oriented in one direction, and perform longitudinal stretching and / or lateral stretching and heat setting as it is.
水性塗布液をフィルムに塗布する際には、塗布性を向上させるための予備処理としてフィルム表面にコロナ表面処理、火炎処理、プラズマ処理等の物理処理を施すか、あるいは組成物と共に前述のような界面活性剤を併用することが好ましい。
塗布方法としては、公知の任意の塗工法が適用できる。例えばロールコート法、グラビアコート法、ロールブラッシュ法、スプレーコート法、エアーナイフコート法、含浸法、カーテンコート法等を単独または組合せて用いることができる。
When an aqueous coating solution is applied to a film, the film surface is subjected to a physical treatment such as a corona surface treatment, a flame treatment, a plasma treatment or the like as a pretreatment for improving the coatability, or as described above together with the composition. It is preferable to use a surfactant in combination.
As a coating method, any known coating method can be applied. For example, a roll coating method, a gravure coating method, a roll brush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method and the like can be used alone or in combination.
（帯電防止離型層の厚み）
帯電防止離型層の厚みは、乾燥後の厚みとして、好ましくは０．０１〜０．１μｍ、さらに好ましくは０．０１〜０．０６μｍである。帯電防止離型層の厚みが下限値に満たないと帯電防止性や離型性が十分に発現しないことがあり、また上限値を超えると塗布液を高濃度にしたり、塗布量を増やす必要があるため塗布しにくくなる傾向にあり、塗工性が不均一になることがある。
(Thickness of antistatic release layer)
The thickness of the antistatic release layer is preferably 0.01 to 0.1 μm, more preferably 0.01 to 0.06 μm, as the thickness after drying. If the thickness of the antistatic release layer is less than the lower limit value, the antistatic property and release property may not be sufficiently developed, and if the upper limit value is exceeded, it is necessary to increase the coating liquid or increase the coating amount. Therefore, it tends to be difficult to apply, and the coatability may be uneven.
以下、実施例を挙げて本発明をさらに詳細に説明する。なお、各種物性は下記の方法により評価した。またｗｔ％は重量％を表わす。 Hereinafter, the present invention will be described in more detail with reference to examples. Various physical properties were evaluated by the following methods. Moreover, wt% represents weight%.
（１）塗布層ヘーズ（帯電防止離型層のヘーズ）
ＪＩＳ Ｋ７１３６に準じ、日本電色工業社製のヘーズ測定器（ＮＤＨ−２０００）を使用して、下記式（Ｉ）より塗布層ヘーズを測定した。
塗布層ヘーズ＝フィルムヘーズ−塗布層未塗工フィルムヘーズ ・・・（Ｉ）
Ａ＋：０．１％未満
Ａ：０．１〜０．４％未満
Ｂ：０．４〜０．８％未満
Ｃ：０．９％以上
この評価で、Ａまでが実用性能を満足する。
(1) Haze of coating layer (haze of antistatic release layer)
According to JIS K7136, the haze measuring device (NDH-2000) by Nippon Denshoku Industries Co., Ltd. was used, and the coating layer haze was measured from the following formula (I).
Coating layer haze = film haze-coating layer uncoated film haze (I)
A +: Less than 0.1% A: Less than 0.1-0.4% B: Less than 0.4-0.8% C: 0.9% or more In this evaluation, up to A satisfies practical performance.
（２）塗布層均一性
三波長の蛍光灯の光をフィルム表面に当て、正反射光で塗布状況を観察する。
Ａ＋：塗布層が均一である。
Ａ：極弱い斑がある。
Ｂ：弱い斑がある。
Ｃ：強い斑がある。
この評価で、Ａまでが実用性能を満足する。
(2) Uniformity of coating layer The light of a three-wavelength fluorescent lamp is applied to the film surface, and the coating state is observed with specular reflection light.
A +: The coating layer is uniform.
A: There are extremely weak spots.
B: There are weak spots.
C: There are strong spots.
In this evaluation, up to A satisfies practical performance.
（３）帯電防止性
サンプルフィルムの帯電防止層表面の表面固有抵抗を、タケダ理研社製・固有抵抗測定器を使用し、測定温度２３℃、測定湿度６０％の条件で、印加電圧１００Ｖで１分後の表面固有抵抗値（Ω／□）を測定する。尚、表面固有抵抗値は１×１０13［Ω／□］以下が好ましく、１×１０12以下が更に好ましい。
(3) Antistatic property The surface resistivity of the antistatic layer surface of the sample film is 1 at an applied voltage of 100 V under the conditions of a measurement temperature of 23 ° C. and a measurement humidity of 60% using a specific resistance measuring device manufactured by Takeda Riken. Measure the surface resistivity (Ω / □) after a minute. The surface resistivity is preferably 1 × 10 13 [Ω / □] or less, more preferably 1 × 10 12 or less.
（４）離型性
帯電防止離型表面に粘着テープ（日東電工株式会社製、製品名「Ｎｏ．３１Ｂ」）を貼合せ、５ｋｇの圧着ローラーで圧着し２０時間放置後、帯電防止離型表面と粘着テープとの剥離力を引張試験機にて測定した。なお、剥離強度の好ましい範囲は３００ｇ／１０ｍｍ以下である。剥離強度が３００ｇ／１０ｍｍより大きいと、離型フィルムを貼り付けた積層シートから樹脂シート等を剥離分離して使用する際に剥離が困難となることがある。
(4) Releasability Adhesive tape (product name “No. 31B” manufactured by Nitto Denko Corporation) is pasted on the antistatic release surface, pressed with a 5 kg pressure roller and left for 20 hours, and then the antistatic release surface. The peel strength between the adhesive tape and the adhesive tape was measured with a tensile tester. In addition, the preferable range of peeling strength is 300 g / 10mm or less. If the peel strength is greater than 300 g / 10 mm, it may be difficult to separate the resin sheet or the like from the laminated sheet to which the release film is attached.
（５）塗布層厚み
包埋樹脂でフィルムを固定し断面をミクロトームで切断し、２％オスミウム酸で６０℃、２時間染色して、透過型電子顕微鏡（日本電子製JEM2010）を用いて、塗布層の厚みを測定した。
(5) Coating layer thickness The film is fixed with an embedding resin, the cross section is cut with a microtome, stained with 2% osmic acid at 60 ° C. for 2 hours, and coated using a transmission electron microscope (JEM2010, manufactured by JEOL Ltd.). The layer thickness was measured.
［実施例１〜７、比較例１〜３］
平均粒子径が１．５μｍの酸化ケイ素の粒子を０．０１ｗｔ％を含む溶融ポリエチレンテレフタレート（［η］＝０．６３ｄｌ／ｇ、Ｔｇ＝７８℃）をダイより押出し、常法により冷却ドラムで冷却して未延伸フィルムとし、次いで縦方向に３．４倍に延伸した後、表１に示す塗布層構成成分からなる塗布液（３ｗｔ％塗布液）をロールコーターで均一に塗布した。
次いで、この塗布フィルムを引き続いて１１０℃で乾燥し、１４０℃で横方向に３．７倍に延伸し、更に２３０℃で熱固定して表１に示す塗膜（帯電防止離型層）を有する二軸延伸ポリエステルフィルム（厚さ３８μｍ）を得た。これら実施例フィルムは、一回の工程で帯電防止性と離型性の両機能を安定して有する層を製膜でき、高い生産性が得られた。
[Examples 1-7, Comparative Examples 1-3]
Molten polyethylene terephthalate ([η] = 0.63 dl / g, Tg = 78 ° C.) containing 0.01 wt% of silicon oxide particles having an average particle diameter of 1.5 μm is extruded from a die and cooled by a cooling drum in a conventional manner. The film was stretched 3.4 times in the longitudinal direction, and then a coating solution (3 wt% coating solution) composed of the coating layer constituents shown in Table 1 was uniformly coated on a roll coater.
Subsequently, this coated film was subsequently dried at 110 ° C., stretched 3.7 times in the transverse direction at 140 ° C., and further heat-set at 230 ° C. to form a coating film (antistatic release layer) shown in Table 1. A biaxially stretched polyester film (thickness: 38 μm) was obtained. These example films were capable of forming a layer having both antistatic properties and releasability functions in a single step, and high productivity was obtained.
帯電防止剤１：下記式（１）に示す構造が７０モル％／メトキシポリエチレングリコール（ｎ＝９）メタクリレート３０モル％からなる共重合体である。
帯電防止剤２：下記式（１）に示す構造が７０モル％／メトキシポリエチレングリコール（ｎ＝９）メタクリレート２０モル％／Ｎ−メチロールアクリルアミド１０モル％からなる共重合体である。
帯電防止剤３：下記式（２）に示す構造が７０モル％／メトキシポリエチレングリコール（ｎ＝９）メタクリレート２０モル％／Ｎ−メチロールアクリルアミド１０モル％からなる共重合体である。
帯電防止剤４：ポリオキシアルキレン鎖非含有カチオンポリマー（第一工業製薬株式会社製 商品名「シャロールＤＣ−３０３Ｐ」）
帯電防止剤５：ポリオキシアルキレン鎖非含有アニオンポリマー ポリスチレンスルホン酸ナトリウム（東ソー有機化学株式会社製 商品名「ポリナスＰＳ−５０」）
Antistatic agent 4: Polyoxyalkylene chain-free cationic polymer (trade name “Charol DC-303P” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Antistatic agent 5: Anionic polymer containing no polyoxyalkylene chain Sodium polystyrene sulfonate (trade name “Polynas PS-50” manufactured by Tosoh Organic Chemical Co., Ltd.)
シリコーン１：ポリジメチルシロキサン（信越化学工業株式会社製 商品名「ＫＭ−８６２Ｔ」）
シリコーン２：アミノ基変性シリコーン（信越化学工業株式会社製 商品名「Ｘ−５１−１１７８」）
シリコーン３：エポキシ基変性シリコーン（信越化学工業株式会社製 商品名「Ｐｏｌｏｎ ＭＦ−１８Ｔ」）
シリコーン４：フェニル基変性シリコーン（信越化学工業株式会社製 商品名「Ｘ−５２−８１４８」）
架橋剤：オキサゾリン化合物（株式会社日本触媒製 商品名「エポクロスＷＳ−７００」）
界面活性剤：ポリオキシアルキレンアルキルエーテル（三洋化成株式会社製 商品名「ナロアクティーＣＬ−８５」）
Silicone 1: Polydimethylsiloxane (trade name “KM-862T” manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone 2: amino group-modified silicone (trade name “X-51-1178” manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone 3: Epoxy group-modified silicone (trade name “Polon MF-18T” manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone 4: Phenyl group-modified silicone (trade name “X-52-8148” manufactured by Shin-Etsu Chemical Co., Ltd.)
Crosslinking agent: Oxazoline compound (trade name “Epocross WS-700” manufactured by Nippon Shokubai Co., Ltd.)
Surfactant: Polyoxyalkylene alkyl ether (trade name “Naroacty CL-85” manufactured by Sanyo Chemical Co., Ltd.)
本発明の帯電防止離型性ポリエステルフィルムは、塗膜均一性が高く、簡便かつ安定的に生産でき、しかも離型性、帯電防止性の品質が安定していることから、カード用、ラベル用、印刷用、粘着用、セラミック成形用、転写箔用などの離型性が求められる各種の用途に好適に用いることができる。 The antistatic releasable polyester film of the present invention has high coating uniformity, can be produced easily and stably, and has stable releasability and antistatic properties. It can be suitably used for various applications requiring releasability such as printing, adhesive, ceramic molding, and transfer foil.
Claims (5)
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| JP2021091127A (en) * | 2019-12-09 | 2021-06-17 | 三菱ケミカル株式会社 | Release film |
| WO2022220355A1 (en) * | 2021-04-14 | 2022-10-20 | (주)케이에프엠 | Release film and method for manufacturing artificial leather by using same |
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| JP2005350517A (en) * | 2004-06-08 | 2005-12-22 | Takemoto Oil & Fat Co Ltd | Antistatic agent for thermoplastic polymer, antistatic method of thermoplastic polymer molded article, and thermoplastic polymer molded article having antistatic property |
| JP2006187951A (en) * | 2005-01-06 | 2006-07-20 | Teijin Dupont Films Japan Ltd | In-mold transfer film |
| JP2007237433A (en) * | 2006-03-06 | 2007-09-20 | Teijin Dupont Films Japan Ltd | Polyester film for in-mold transfer |
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| JP2005350517A (en) * | 2004-06-08 | 2005-12-22 | Takemoto Oil & Fat Co Ltd | Antistatic agent for thermoplastic polymer, antistatic method of thermoplastic polymer molded article, and thermoplastic polymer molded article having antistatic property |
| JP2006187951A (en) * | 2005-01-06 | 2006-07-20 | Teijin Dupont Films Japan Ltd | In-mold transfer film |
| JP2007237433A (en) * | 2006-03-06 | 2007-09-20 | Teijin Dupont Films Japan Ltd | Polyester film for in-mold transfer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2021091127A (en) * | 2019-12-09 | 2021-06-17 | 三菱ケミカル株式会社 | Release film |
| JP7424020B2 (en) | 2019-12-09 | 2024-01-30 | 三菱ケミカル株式会社 | release film |
| WO2022220355A1 (en) * | 2021-04-14 | 2022-10-20 | (주)케이에프엠 | Release film and method for manufacturing artificial leather by using same |
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