JP6338959B2 - Composition for coating thermoplastic polymer film, method for producing modified thermoplastic polymer film, and modified thermoplastic polymer film - Google Patents
Composition for coating thermoplastic polymer film, method for producing modified thermoplastic polymer film, and modified thermoplastic polymer film Download PDFInfo
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- JP6338959B2 JP6338959B2 JP2014152759A JP2014152759A JP6338959B2 JP 6338959 B2 JP6338959 B2 JP 6338959B2 JP 2014152759 A JP2014152759 A JP 2014152759A JP 2014152759 A JP2014152759 A JP 2014152759A JP 6338959 B2 JP6338959 B2 JP 6338959B2
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- thermoplastic polymer
- polymer film
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- coating
- inorganic cation
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- 229920001169 thermoplastic Polymers 0.000 title claims description 54
- 239000000203 mixture Substances 0.000 title claims description 36
- 238000000576 coating method Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000011248 coating agent Substances 0.000 title claims description 17
- 150000001767 cationic compounds Chemical class 0.000 claims description 28
- 229910001411 inorganic cation Inorganic materials 0.000 claims description 28
- 239000000084 colloidal system Substances 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 22
- -1 organosilane compound Chemical class 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002897 polymer film coating Substances 0.000 claims description 12
- 235000011187 glycerol Nutrition 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 229940105990 diglycerin Drugs 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 5
- 238000012643 polycondensation polymerization Methods 0.000 claims description 4
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 8
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000000465 moulding Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- LVACOMKKELLCHJ-UHFFFAOYSA-N 3-trimethoxysilylpropylurea Chemical compound CO[Si](OC)(OC)CCCNC(N)=O LVACOMKKELLCHJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 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 3
- 229960002446 octanoic acid Drugs 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 101710148027 Ribulose bisphosphate carboxylase/oxygenase activase 1, chloroplastic Proteins 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 2
- UOKRBSXOBUKDGE-UHFFFAOYSA-N butylphosphonic acid Chemical compound CCCCP(O)(O)=O UOKRBSXOBUKDGE-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- SVMUEEINWGBIPD-UHFFFAOYSA-N dodecylphosphonic acid Chemical compound CCCCCCCCCCCCP(O)(O)=O SVMUEEINWGBIPD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- CTTJWXVQRJUJQW-UHFFFAOYSA-N 2,2-dioctyl-3-sulfobutanedioic acid Chemical compound CCCCCCCCC(C(O)=O)(C(C(O)=O)S(O)(=O)=O)CCCCCCCC CTTJWXVQRJUJQW-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- XBJNDZFSRLPXEO-UHFFFAOYSA-N 2-methylpropyl 2-methylpropane-1-sulfonate Chemical class CC(C)COS(=O)(=O)CC(C)C XBJNDZFSRLPXEO-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- PLXLQGPXPXIVKM-UHFFFAOYSA-N 3-chloropropyl(tripropoxy)silane Chemical compound CCCO[Si](CCCCl)(OCCC)OCCC PLXLQGPXPXIVKM-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 241001076272 Collinsia concolor Species 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-M n-octyl sulfate Chemical compound CCCCCCCCOS([O-])(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-M 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- WLGDAKIJYPIYLR-UHFFFAOYSA-N octane-1-sulfonic acid Chemical compound CCCCCCCCS(O)(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 1
- 229940067739 octyl sulfate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- IVNFTPCOZIGNAE-UHFFFAOYSA-N propan-2-yl hydrogen sulfate Chemical compound CC(C)OS(O)(=O)=O IVNFTPCOZIGNAE-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- UZZYXUGECOQHPU-UHFFFAOYSA-N sulfuric acid monooctyl ester Natural products CCCCCCCCOS(O)(=O)=O UZZYXUGECOQHPU-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 238000007601 warm air drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
Description
本発明は、製膜時や展張時の摩擦による流滴性能の低下がなく、それを塗布したフィルムを農業用ハウスに展張した後も長期間にわたって良好な流滴性を発揮する熱可塑性高分子フィルムコーティング用組成物、かかる組成物を使用する改質熱可塑性高分子フィルムの製造方法及びかかる製造方法によって得られる改質熱可塑性高分子フィルムに関する。 The present invention is a thermoplastic polymer that does not deteriorate in droplet performance due to friction during film formation or stretching, and that exhibits good droplet properties over a long period of time even after a film coated with the film is spread in an agricultural house The present invention relates to a film coating composition, a method for producing a modified thermoplastic polymer film using such a composition, and a modified thermoplastic polymer film obtained by such a production method.
従来、前記のような熱可塑性高分子フィルムコーティング用組成物として、水酸基含有ビニル単量体を主成分とした共重合体と炭素数１〜８の脂肪族アルコールに分散させたコロイド状シリカと界面活性剤と炭素数１〜８の脂肪族アルコールとを配合したもの（例えば、特許文献１参照）、アルミナゾルと粒子表面が正電化を有する酸性シリカゾルと水溶性又は水分散性の有機アニオン性化合物とを含有し、表面張力を調整したもの（例えば、特許文献２参照）、金属の酸化物コロイド又は水酸化物コロイドを用いたもの（例えば、特許文献３参照）、親水性無機コロイドと紫外線硬化樹脂と紫外線重合開始剤とを用いたもの（例えば、特許文献４参照）等が提案されている。しかし、これら従来の熱可塑性高分子フィルムコーティング用組成物には、それを塗布した熱可塑性高分子フィルムの製膜時や展張時に、摩擦により流滴性能が低下するという問題がある。 Conventionally, as a thermoplastic polymer film coating composition as described above, a copolymer mainly composed of a hydroxyl group-containing vinyl monomer, colloidal silica dispersed in a C1-C8 aliphatic alcohol, and an interface A blend of an activator and an aliphatic alcohol having 1 to 8 carbon atoms (for example, see Patent Document 1), an alumina sol, an acidic silica sol having a positively charged particle surface, a water-soluble or water-dispersible organic anionic compound, , With adjusted surface tension (for example, see Patent Document 2), using metal oxide colloid or hydroxide colloid (for example, see Patent Document 3), hydrophilic inorganic colloid and UV curable resin And those using an ultraviolet polymerization initiator (see, for example, Patent Document 4) have been proposed. However, these conventional thermoplastic polymer film coating compositions have a problem that the droplet performance deteriorates due to friction when the thermoplastic polymer film coated with the composition is formed or stretched.
本発明が解決しようとする課題は、製膜時や展張時の摩擦による流滴性能の低下がなく、それを塗布したフィルムを農業用ハウスに展張した後も長期間にわたって良好な流滴性を発揮する熱可塑性高分子フィルムコーティング用組成物、かかる組成物を使用する改質熱可塑性高分子フィルムの製造方法及びかかる製造方法によって得られる改質熱可塑性高分子フィルムを提供する処にある。 The problem to be solved by the present invention is that there is no drop in drop performance due to friction during film formation or stretching, and good dropability over a long period of time after a film coated with the film is spread on an agricultural house. The present invention provides a composition for coating a thermoplastic polymer film, a method for producing a modified thermoplastic polymer film using the composition, and a modified thermoplastic polymer film obtained by the production method.
本発明者らは、前記の課題を解決するべく研究した結果、熱可塑性高分子フィルムコーティング用組成物としては、特定の改質無機カチオンコロイドゾルと、アニオン界面活性剤と、特定の（ポリ）グリセリンとを特定割合で含有して成るものが正しく好適であることを見出した。 As a result of researches to solve the above-mentioned problems, the present inventors have found that a composition for coating a thermoplastic polymer film includes a specific modified inorganic cation colloid sol, an anionic surfactant, and a specific (poly). It has been found that those containing glycerin in a specific proportion are correctly suitable.
すなわち本発明は、下記の改質無機カチオンコロイドゾルを固形分換算で１００質量部に対し、アニオン界面活性剤を３〜１１質量部及び下記の（ポリ）グリセリンを４５〜３６０質量部の割合で含有して成ることを特徴とする熱可塑性高分子フィルムコーティング用組成物に係る。また本発明は、かかる熱可塑性高分子フィルムコーティング用組成物を用いる改質熱可塑性高分子フィルムの製造方法及びかかる製造方法によって得られる改質熱可塑性高分子フィルムに係る。 That is, in the present invention, the following modified inorganic cation colloidal sol is in a ratio of 3 to 11 parts by weight of anionic surfactant and 45 to 360 parts by weight of the following (poly) glycerin with respect to 100 parts by weight in terms of solid content. The present invention relates to a composition for coating a thermoplastic polymer film. The present invention also relates to a method for producing a modified thermoplastic polymer film using such a composition for coating a thermoplastic polymer film and a modified thermoplastic polymer film obtained by such a production method.
改質無機カチオンコロイドゾル：下記の無機カチオンコロイドゾルの存在下に、該無機カチオンコロイドゾルの固形分１００質量部当たり５〜１５質量部の割合となる量のシラノール形成性有機シラン化合物を加水分解処理し、更に生成したシラノール化合物を縮合重合させた改質無機カチオンコロイドゾル。 Modified inorganic cation colloid sol: In the presence of the following inorganic cation colloid sol, a silanol-forming organosilane compound in an amount of 5 to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cation colloid sol is hydrolyzed. A modified inorganic cation colloidal sol obtained by condensation polymerization of a silanol compound produced by treatment.
無機カチオンコロイドゾル：カチオンアルミナゾルを固形分換算で２０〜９０質量％及びカチオンシリカゾルを固形分換算で１０〜８０質量％（固形分換算で合計１００質量％）の割合で含有して成る無機カチオンコロイドゾル。 Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 90% by mass in terms of solids and cationic silica sol in a proportion of 10 to 80% by mass in terms of solids (total 100% in terms of solids) Sol.
（ポリ）グリセリン：グリセン、ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン、ノナグリセリン及びデカグリセリンから選ばれるもの (Poly) glycerin: selected from glycene, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin and decaglycerin
先ず、本発明に係る熱可塑性高分子フィルムコーティング用組成物（以下、本発明の組成物という）について説明する。本発明の組成物は、特定の改質無機カチオンコロイドゾルを固形分換算で１００質量部に対し、アニオン界面活性剤を３〜１１質量部及び特定の（ポリ）グリセリンを４５〜３６０質量部の割合で含有して成るものであるが、該無機カチオンコロイドゾルを固形分換算で１００質量部に対し、アニオン界面活性剤を５〜１０質量部及び（ポリ）グリセリンを７０〜２００質量部の割合で含有して成るものが好ましい。 First, the thermoplastic polymer film coating composition according to the present invention (hereinafter referred to as the composition of the present invention) will be described. The composition of the present invention comprises 3 to 11 parts by weight of an anionic surfactant and 45 to 360 parts by weight of a specific (poly) glycerin with respect to 100 parts by weight of a specific modified inorganic cation colloid sol. The inorganic cation colloidal sol is contained in a proportion of 100 parts by mass in terms of solid content, 5 to 10 parts by mass of an anionic surfactant and 70 to 200 parts by mass of (poly) glycerin. It is preferable to contain it.
本発明の組成物に供する改質無機カチオンコロイドゾルは、特定の無機カチオンコロイドゾルの存在下に、該無機カチオンコロイドゾルの固形分１００質量部当たり５〜１５質量部、好ましくは７〜１２質量部の割合となる量のシラノール形成性有機シラン化合物を加水分解処理し、更に生成したシラノール化合物を縮合重合させたものである。 The modified inorganic cation colloid sol used in the composition of the present invention is 5 to 15 parts by mass, preferably 7 to 12 parts by mass in the presence of the specific inorganic cation colloid sol per 100 parts by mass of the solid content of the inorganic cation colloid sol. The silanol-forming organic silane compound in an amount corresponding to a part ratio is hydrolyzed, and the resulting silanol compound is subjected to condensation polymerization.
前記の改質無機カチオンコロイドゾルの調製に用いる無機カチオンコロイドゾルは、カチオンアルミナゾルを固形分換算で２０〜９０質量％及びカチオンシリカゾルを固形分換算で１０〜８０質量％（固形分換算で合計１００質量％）の割合で含有して成るものであるが、カチオンアルミナゾルを固形分換算で５０〜８０質量％及びカチオンシリカゾルを固形分換算で２０〜５０質量％（固形分換算で合計１００質量％）の割合で含有してなるものが好ましい。 The inorganic cation colloid sol used for the preparation of the modified inorganic cation colloid sol has a cation alumina sol of 20 to 90% by mass in terms of solid content and a cation silica sol of 10 to 80% by mass in terms of solid content (total 100 in terms of solid content). The cation alumina sol is 50 to 80% by mass in terms of solid content and the cation silica sol is 20 to 50% by mass in terms of solid content (total 100% by mass in terms of solid content). What is contained in the ratio is preferably.
カチオンアルミナゾルは、いわゆるコロイダルアルミナであり、水分散液として市販されているものをそのまま使用することができる。そのような市販品として例えば、アルミナゾル１００、アルミナゾル２００、アルミナゾル５２０（以上、いずれも日産化学社製の商品名）、カタロイドＡＳ−１、カタロイドＡＳ−２（以上、いずれも日揮触媒化成社製の商品名）等が挙げられる。 The cationic alumina sol is so-called colloidal alumina, and a commercially available aqueous dispersion can be used as it is. Examples of such commercially available products include alumina sol 100, alumina sol 200, alumina sol 520 (all are trade names manufactured by Nissan Chemical Co., Ltd.), cataloid AS-1, and cataloid AS-2 (all are manufactured by JGC Catalysts & Chemicals, Inc.). Product name).
カチオンシリカゾルも、水分散液として市販されているものをそのまま使用することができる。そのような市販品としては例えば、スノーテックスＡＫ、スノーテックスＡＫ−Ｌ（以上、いずれも日産化学社製の商品名）等が挙げられる。 As the cationic silica sol, a commercially available aqueous dispersion can be used as it is. Examples of such commercially available products include Snowtex AK, Snowtex AK-L (all of which are trade names manufactured by Nissan Chemical Co., Ltd.).
また前記の改質無機カチオンコロイドゾルの調製に用いるシラノール形成性有機シラン化合物としては、１）メチルトリメトキシシラン、メチルトリエトキシシラン、ビニルトリクロロシラン、ビニルトリエトキシシラン、ビニルトリ（メトキシエトキシ）シラン、γ−クロロプロピルトリプロポキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、γ−ウレイドプロピルトリメトキシシラン、フェニルトリメトキシシラン等のトリアルコキシシラン類やシリルハライド類、２）ジメチルジメトキシシラン、γ−クロロプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン等のジアルコキシシラン類やシリルハライド類、３）トリメチルクロロシラン、トリメチルメトキシシラン等のモノアルコキシシラン類やシリルハライド類等が挙げられる。なかでもシラノール形成性有機シラン化合物としては、γ−グリシドキシプロピルトリメトキシシラン、γ−ウレイドプロピルトリメトキシシラン、メチルトリエトキシシランが好ましい。 The silanol-forming organosilane compound used for the preparation of the modified inorganic cation colloid sol includes 1) methyltrimethoxysilane, methyltriethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, Tris such as γ-chloropropyltripropoxysilane, γ-mercaptopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, phenyltrimethoxysilane, etc. Alkoxysilanes and silyl halides, 2) Dialkoxysilanes such as dimethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, and γ-glycidoxypropylmethyldimethoxysilane Halides, 3) trimethylchlorosilane, mono alkoxysilanes and silyl halides such as trimethyl methoxy silane, and the like. Among these, as the silanol-forming organic silane compound, γ-glycidoxypropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, and methyltriethoxysilane are preferable.
本発明の組成物に供するアニオン界面活性剤としては、１）酢酸、酪酸、オクタン酸、ヘキサン酸、カプロン酸、カプリル酸、ラウリン酸、オレイン酸等の脂肪族カルボン酸や、安息香酸、ｐ−トルイン酸等の芳香族カルボン酸等、これらのカルボン酸のアルカリ金属塩やアンモニウム塩等の塩、２）メタンスルホン酸、プロパンスルホン酸、オクチルスルホン酸、ドデシルスルホン酸等のアルキルスルホン酸や、ジイソブチルスルホコハク酸、ジオクチルスルホコハク酸等のエステル基を有するスルホン酸、更にはｐ−トルエンスルホン酸、ドデシルベンゼンスルホン酸等の芳香族スルホン酸等、これらのスルホン酸のアルカリ金属塩やアンモニウム塩等の塩、３）イソプロピル硫酸、オクチル硫酸、ラウリル硫酸等の硫酸エステルのアルカリ金属塩やアンモニウム塩等の塩、４）ブチルホスホン酸、ラウリルホスホン酸等のリン酸エステルのアルカリ金属塩やアンモニウム塩等の塩が挙げられるが、なかでもオクタン酸、ヘキサン酸等のモノカルボン酸の塩、メタンスルホン酸、ｐ−トルエンスルホン酸等のモノスルホン酸の塩及びブチルホスホン酸、ラウリルホスホン酸等のモノホスホン酸の塩から選ばれるものが好ましい。 Examples of the anionic surfactant to be used in the composition of the present invention include 1) aliphatic carboxylic acids such as acetic acid, butyric acid, octanoic acid, hexanoic acid, caproic acid, caprylic acid, lauric acid, oleic acid, benzoic acid, p- Aromatic carboxylic acids such as toluic acid, salts such as alkali metal salts and ammonium salts of these carboxylic acids, 2) alkylsulfonic acids such as methanesulfonic acid, propanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, and diisobutyl Sulfonic acids having an ester group such as sulfosuccinic acid and dioctylsulfosuccinic acid, and further aromatic sulfonic acids such as p-toluenesulfonic acid and dodecylbenzenesulfonic acid, salts such as alkali metal salts and ammonium salts of these sulfonic acids, 3) Sulfate esters such as isopropyl sulfate, octyl sulfate and lauryl sulfate 4) Salts such as lithium metal salts and ammonium salts, 4) Salts such as alkali metal salts and ammonium salts of phosphoric acid esters such as butylphosphonic acid and laurylphosphonic acid, among others, monocarboxylic acids such as octanoic acid and hexanoic acid Preferred are those selected from acid salts, monosulfonic acid salts such as methanesulfonic acid and p-toluenesulfonic acid, and monophosphonic acid salts such as butylphosphonic acid and laurylphosphonic acid.
本発明の組成物に供する（ポリ）グリセリンは、グリセン、ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン、ノナグリセリン及びデカグリセリンから選ばれるものであるが、なかでもグリセリン、ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン及びヘキサグリセリンから選ばれるものが好ましい。 The (poly) glycerin used in the composition of the present invention is selected from glycene, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin and decaglycerin. However, those selected from glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin and hexaglycerin are preferred.
次に本発明に係る改質熱可塑性高分子フィルムの製造方法（以下、本発明の製造方法という）について説明する。本発明の製造方法は、下記の第１工程及び下記の第２工程を経る製造方法である。 Next, the manufacturing method of the modified thermoplastic polymer film according to the present invention (hereinafter referred to as the manufacturing method of the present invention) will be described. The manufacturing method of this invention is a manufacturing method which passes through the following 1st process and the following 2nd process.
第１工程：熱可塑性高分子フィルムにコロナ放電処理をして、コロナ放電処理面のぬれ張力を３５〜７０ｍＮ／ｍにする工程 1st process: The process which makes the wetting tension | tensile_strength of a corona discharge treatment surface 35-70 mN / m by performing a corona discharge process to a thermoplastic polymer film
第２工程：第１工程で得た熱可塑性高分子フィルムのコロナ放電処理面に対し、前記した本発明の組成物を固形分として０．１〜２．０ｇ／ｍ２となるよう塗布する工程 2nd process: The process of apply | coating the above-mentioned composition of this invention to 0.1-2.0 g / m < 2 > as solid content with respect to the corona discharge treatment surface of the thermoplastic polymer film obtained at the 1st process.
本発明の製造方法に供する熱可塑性高分子フィルムとしては、１）ポリオレフィン系樹脂、２）ポリ塩化ビニル、塩化ビニル−メチルメタクリレート共重合体、ポリ塩化ビニリデン等の塩素系樹脂、３）ポリエチレンテレフタレート、ポリエチレンテレナフタレート等のポリエステル系樹脂等、農業用フィルムとして用いられている熱可塑性樹脂全般が挙げられる。ポリオレフィン系樹脂としては、α−オレフィンの単独重合、α−オレフィンを主成分とする異種単量体との共重合体が挙げられ、例えば、ポリエチレン、ポリプロピレン、エチレン−ブテン共重合体、エチレン−４−メチル−１−ペンテン共重合体、エチレン−ヘキセン共重合体等のエチレン−α−オレフィン共重合体、エチレン−酢酸ビニル共重合体、エチレン−メチルメタクリレート共重合体、エチレン−酢酸ビニル−メチルメタクリレート共重合体、アイオノマー樹脂等が挙げられる。これらの樹脂は、通常使用される酸化防止剤、耐候剤、紫外線吸収剤、赤外線吸収剤、滑剤、アンチブロッキング剤、防霧剤、保温剤、顔料等を必要に応じて含有することができる。これらの樹脂をフィルムに成形する方法としては、特に制限はなく、例えば、インフレーション成形法、Ｔダイ成形法等が挙げられる。成形に際して用いる樹脂は複数種類の樹脂をブレンドしてもよい。またフィルムは単層でも多層でもよく、目的に応じ、組み合わせて成形したフィルムを用いることができる。 The thermoplastic polymer film used in the production method of the present invention includes 1) polyolefin resin, 2) polyvinyl chloride, vinyl chloride-methyl methacrylate copolymer, chlorinated resin such as polyvinylidene chloride, 3) polyethylene terephthalate, General thermoplastic resins used as agricultural films, such as polyester resins such as polyethylene telenaphthalate, can be mentioned. Examples of the polyolefin-based resin include homopolymerization of α-olefin, and copolymers with different monomers mainly containing α-olefin, such as polyethylene, polypropylene, ethylene-butene copolymer, and ethylene-4. -Methyl-1-pentene copolymer, ethylene-α-olefin copolymer such as ethylene-hexene copolymer, ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate-methyl methacrylate Examples thereof include copolymers and ionomer resins. These resins can contain an antioxidant, a weathering agent, an ultraviolet absorber, an infrared absorber, a lubricant, an antiblocking agent, an antifogging agent, a heat retention agent, a pigment, and the like as required. There is no restriction | limiting in particular as a method of shape | molding these resin into a film, For example, the inflation molding method, T-die molding method, etc. are mentioned. The resin used for molding may be a blend of a plurality of types of resins. Further, the film may be a single layer or a multilayer, and a film formed by combining in accordance with the purpose can be used.
本発明の製造方法において、第１工程は、熱可塑性高分子フィルムにコロナ放電処理をして、コロナ放電処理面のぬれ張力を３５〜７０ｍＮ／ｍにする工程であるが、なかでもコロナ放電処理面のぬれ張力を３８〜６７ｍＮ／ｍにすることが好ましい。本発明において、ぬれ張力は、ＪＩＳ−Ｋ６７６８の記載に準じて測定される値である。 In the production method of the present invention, the first step is a step of subjecting the thermoplastic polymer film to corona discharge treatment so that the wetting tension of the corona discharge treatment surface is 35 to 70 mN / m. The surface wetting tension is preferably 38 to 67 mN / m. In the present invention, the wetting tension is a value measured according to the description of JIS-K6768.
また第２工程は、第１工程で得た熱可塑性高分子フィルムのコロナ放電処理面に対し、前記した本発明の組成物を固形分として０．１〜２．０ｇ／ｍ２となるよう塗布する工程である。本発明の組成物を熱可塑性高分子フィルムに塗布するには、公知の塗布法を用いることができる。これには例えば、スプレーコート法、浸漬コート法、ロールコート法、ドクターブレードコート法、ワイヤーバーコート法、エアナイフコート法等が挙げられる。 Moreover, a 2nd process apply | coated so that it may become 0.1-2.0 g / m < 2 > by making the above-mentioned composition of this invention into solid content with respect to the corona discharge treatment surface of the thermoplastic polymer film obtained at the 1st process. It is a process to do. In order to apply the composition of the present invention to the thermoplastic polymer film, a known coating method can be used. Examples thereof include a spray coating method, a dip coating method, a roll coating method, a doctor blade coating method, a wire bar coating method, and an air knife coating method.
最後に本発明に係る改質熱可塑性高分子フィルム（以下、本発明のフィルムという）について説明する。本発明のフィルムは、本発明の製造方法により得られる改質熱可塑性高分子フィルムである。かかる改質熱可塑性フィルムは、特に農業用ハウスに展張するフィルムとして有用である。 Finally, the modified thermoplastic polymer film according to the present invention (hereinafter referred to as the film of the present invention) will be described. The film of the present invention is a modified thermoplastic polymer film obtained by the production method of the present invention. Such a modified thermoplastic film is particularly useful as a film to be spread on an agricultural house.
以上説明した本発明によると、製膜時や展張時の摩擦による流滴性能の低下がなく、本発明のフィルムを農業用ハウスに展張した後も長期間にわたって良好な流滴性を発揮するという効果がある。 According to the present invention described above, there is no drop in the drip performance due to friction during film formation or spreading, and it demonstrates good drip properties over a long period of time after the film of the present invention is spread on an agricultural house. effective.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例及び比較例において、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to these examples. In the following Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（熱可塑性高分子フィルムコーティング用組成物の調製）
・実施例１（熱可塑性高分子フィルムコーティング用組成物（Ｐ−１）の調製）
水６１．４部、カチオンアルミナゾル（Ｘ１−１）３４１．５部（固形分換算で７０部）、カチオンシリカゾル（Ｘ２−１）１３０．４部（固形分換算で３０部）、及びシラノール形成性有機シラン化合物（Ｙ−１）１０部を混合して固形分濃度２０％の混合液を調製し、５０℃で５時間撹拌して加水分解処理し、更に縮合重合させて改質無機カチオンコロイドゾル（Ａ−１）を得た。次いで、この改質無機カチオンコロイドゾル（Ａ−１）の固形分換算で１００部に水９２０４部、アニオン界面活性剤（Ｂ−１）６部及び（ポリ）ジグリセリン（Ｃ−１）９０部を加えて撹拌し、固形分濃度２％の熱可塑性高分子フィルムコーティング用組成物（Ｐ−１）を得た。
Test Category 1 (Preparation of a composition for coating a thermoplastic polymer film)
Example 1 (Preparation of thermoplastic polymer film coating composition (P-1))
61.4 parts of water, 341.5 parts of cationic alumina sol (X1-1) (70 parts in terms of solid content), 130.4 parts of cationic silica sol (X2-1) (30 parts in terms of solid content), and silanol-forming properties 10 parts of an organic silane compound (Y-1) is mixed to prepare a mixed liquid having a solid content of 20%, stirred at 50 ° C. for 5 hours, hydrolyzed, and further subjected to condensation polymerization to form a modified inorganic cation colloid sol (A-1) was obtained. Subsequently, 9204 parts of water, 6 parts of anionic surfactant (B-1) and 90 parts of (poly) diglycerin (C-1) are added to 100 parts in terms of solid content of this modified inorganic cation colloid sol (A-1). And stirred to obtain a thermoplastic polymer film coating composition (P-1) having a solid content concentration of 2%.
・実施例２〜２７及び比較例１〜１７（熱可塑性高分子フィルムコーティング用組成物（Ｐ−２）〜（Ｐ−２７）及び（ＲＰ−１）〜（ＲＰ−１７）の調製）
実施例１の熱可塑性高分子フィルムコーティング用組成物（Ｐ−１）の調製と同様にして、改質無機カチオンコロイドゾル（Ａ−２）〜（Ａ−１７）及び（ＲＡ−１）〜（ＲＡ−９）を調製し、更に熱可塑性高分子フィルムコーティング用組成物（Ｐ−２）〜（Ｐ−２７）及び（ＲＰ−１）〜（ＲＰ−１７）を得た。以上の各例で調製した改質無機カチオンコロイドゾルの内容を表１及び表２にまとめて示し、また以上の各例で得た熱可塑性高分子フィルムコーティング用組成物の内容を表３及び表４にまとめて示した。
Examples 2 to 27 and Comparative Examples 1 to 17 (Preparation of thermoplastic polymer film coating compositions (P-2) to (P-27) and (RP-1) to (RP-17))
In the same manner as in the preparation of the thermoplastic polymer film coating composition (P-1) of Example 1, the modified inorganic cation colloid sols (A-2) to (A-17) and (RA-1) to ( RA-9) was prepared, and further thermoplastic polymer film coating compositions (P-2) to (P-27) and (RP-1) to (RP-17) were obtained. The contents of the modified inorganic cation colloid sol prepared in each of the above examples are summarized in Tables 1 and 2, and the contents of the thermoplastic polymer film coating composition obtained in each of the above examples are shown in Tables 3 and The results are summarized in FIG.
表１及び表２において、
Ｘ１−１：カチオンアルミナゾル（日産化学工業製の商品名アルミナゾル５２０）
Ｘ１−２：カチオンアルミナゾル（日産化学工業製の商品名アルミナゾル２００）
Ｘ１−３：カチオンアルミナゾル（日揮触媒化成製の商品名カタロイドＡＳ−１）
ＲＸ１−４：フュームドシリカ（日本アエロジル製の商品名アルミニウムオキサイドＣ）
Ｘ２−１：カチオンシリカゾル（日産化学工業製の商品名スノーテックスＡＫ）
ＲＸ２−２：アニオンシリカゾル（日産化学工業製の商品名スノーテックス３０）
Ｙ−１：γ−グリシドキシプロピルトリメトキシシラン
Ｙ−２：γ−ウレイドプロピルトリメトキシシラン
Ｙ−３：メチルトリエトキシシラン
In Table 1 and Table 2,
X1-1: Cationic alumina sol (trade name alumina sol 520 manufactured by Nissan Chemical Industries)
X1-2: Cationic alumina sol (trade name alumina sol 200 manufactured by Nissan Chemical Industries)
X1-3: Cationic alumina sol (trade name Cataloid AS-1 manufactured by JGC Catalysts & Chemicals)
RX1-4: Fumed silica (trade name Aluminum Oxide C manufactured by Nippon Aerosil)
X2-1: Cationic silica sol (trade name Snowtex AK manufactured by Nissan Chemical Industries)
RX2-2: Anion silica sol (trade name Snowtex 30 manufactured by Nissan Chemical Industries)
Y-1: γ-glycidoxypropyltrimethoxysilane Y-2: γ-ureidopropyltrimethoxysilane Y-3: methyltriethoxysilane
表３及び表４において、
Ａ−１〜Ａ−１７，ＲＡ−１〜ＲＡ−９：表１及び表２に記載の改質無機カチオンコロイドゾル
Ｂ−１：オクタン酸Ｎａ
Ｂ−２：ｐ−トルエンスルホン酸Ｎａ
Ｂ−３：ヘキサン酸Ｎａ
ＲＢ−４：ラウリルトリメチルアンモニウムクロライド
Ｃ−１：ジグリセリン
Ｃ−２：トリグリセリン
Ｃ−３：テトラグリセリン
Ｃ−４：ヘキサグリセリン
Ｃ−５：モノグリセリン
Ｃ−６：デカグリセリン
ＲＣ−７：メタノール
In Table 3 and Table 4,
A-1 to A-17, RA-1 to RA-9: Modified inorganic cation colloid sols described in Tables 1 and 2 B-1: Na octanoate
B-2: p-Toluenesulfonic acid Na
B-3: Na hexanoate
RB-4: lauryltrimethylammonium chloride C-1: diglycerin C-2: triglycerin C-3: tetraglycerin C-4: hexaglycerin C-5: monoglycerin C-6: decaglycerin RC-7: methanol
試験区分２（改質熱可塑性高分子フィルムの製造）
・実施例２８
エチレン・１−ブテン共重合体（エチレン共重合比率９６％、密度０．９３０ｇ／ｃｍ３、ＭＦＲ１．０ｇ／１０分）を、直径７５ｍｍでリップ間隙３ｍｍのダイを取り付けたインフレーション成形機に供し、樹脂押し出し温度２００℃及びＢＵＲ＝１．８の条件下でインフレーション成形を行ない、厚さ１５０μｍのオレフィン重合体フィルムを作製した。次いで、このオレフィン重合体フィルムにコロナ処理放電を施し、コロナ放電処理面のぬれ張力を４２ｍＮ／ｍとした後、かかるコロナ放電処理面に試験区分１で調製した熱可塑性高分子フィルムコーティング用組成物を固形分として０．３ｇ／ｍ２となるようグラビアコート法により塗布し、７０℃に温調した温風乾燥炉に１分間滞留させて、改質熱可塑性高分子フィルムを得た。
Test Category 2 (Manufacture of modified thermoplastic polymer film)
Example 28
An ethylene / 1-butene copolymer (ethylene copolymer ratio 96%, density 0.930 g / cm 3 , MFR 1.0 g / 10 min) was subjected to an inflation molding machine equipped with a die having a diameter of 75 mm and a lip gap of 3 mm, Inflation molding was carried out under the conditions of a resin extrusion temperature of 200 ° C. and BUR = 1.8 to produce an olefin polymer film having a thickness of 150 μm. Next, the olefin polymer film is subjected to corona treatment discharge, the wet tension of the corona discharge treatment surface is set to 42 mN / m, and then the thermoplastic polymer film coating composition prepared in Test Category 1 on the corona discharge treatment surface. Was applied by a gravure coating method so as to have a solid content of 0.3 g / m 2, and allowed to stay in a warm air drying furnace adjusted to 70 ° C. for 1 minute to obtain a modified thermoplastic polymer film.
・実施例２９〜５５及び比較例１８〜３５
実施例２８の改質熱可塑性高分子フィルムの製造と同様にして、実施例２９〜５５及び比較例１８〜３５の改質熱可塑性高分子フィルムを製造した。以上の各例で製造した改質熱可塑性高分子フィルムの内容を表５及び表６にまとめて示した。
Examples 29 to 55 and comparative examples 18 to 35
The modified thermoplastic polymer films of Examples 29 to 55 and Comparative Examples 18 to 35 were produced in the same manner as in the production of the modified thermoplastic polymer film of Example 28. Tables 5 and 6 collectively show the contents of the modified thermoplastic polymer films produced in the above examples.
試験区分３（改質熱可塑性高分子フィルムの評価）
・流滴性の評価
試験区分２で製造した各改質熱可塑性高分子フィルムを、ハウスの内温３０℃でハウスの外温１０℃に調節した１５度の傾斜面を有するテストハウスに１ｍ２張り、１日後及び３０日後に水滴付着状況を観察し、水滴防止効果すなわち流滴性を以下の基準で評価した。結果を表５及び表６にまとめて示した。
Test category 3 (evaluation of modified thermoplastic polymer film)
The & antidropping of each modified thermoplastic polymer film produced in evaluation test category 2, 1 m 2 in test houses having an inclined surface of 15 degrees was adjusted to an external temperature 10 ° C. house at an internal temperature 30 ° C. House Tension was observed after 1 day and 30 days, and the state of water droplet adhesion was observed, and the water droplet prevention effect, that is, the droplet property, was evaluated according to the following criteria. The results are summarized in Tables 5 and 6.
流滴性の評価基準
５：水滴の付着無し
４：水滴の付着面積が１０％未満
３：水滴の付着面積が１０％以上〜５０％未満
２：水滴の付着面積が５０％以上〜８０％未満
１：水滴の付着面積が８０％以上
Evaluation criteria of flowability 5: No water droplet adhesion 4: Water droplet adhesion area less than 10% 3: Water droplet adhesion area of 10% to less than 50% 2: Water droplet adhesion area of 50% to less than 80% 1: Water drop adhesion area is 80% or more
・耐擦傷性の評価
摩擦試験機（学振型染色堅牢度試験機、大栄科学精機製作所社製）のアームの摩擦面にビニールテープを貼って３００ｇの荷重をかけ、試験区分２で製造した各改質熱可塑性高分子フィルムの塗布面１００ｃｍ２に１０往復摩擦させた後、摩擦させた部分に湯気を当て、水滴が付着して生じる曇部分により、塗膜の剥離程度を観察し、塗膜の耐剥離強度すなわち耐擦傷性を以下の基準で評価した。結果を表５及び表６にまとめて示した。
・ Evaluation of scratch resistance Each of the test pieces manufactured in Test Category 2 by applying a 300 g load on a friction surface of an arm of a friction tester (Gakushin dyeing fastness tester, manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) and applying a load of 300 g. After 10 reciprocating rubs on the coated surface of the modified thermoplastic polymer film 10 cm 2 , steam is applied to the rubbed part, and the degree of peeling of the paint film is observed by the cloudy part produced by water droplets attached. The peel strength, that is, the scratch resistance, was evaluated according to the following criteria. The results are summarized in Tables 5 and 6.
耐擦傷性の評価基準
５：塗膜の剥がれ無し
４：塗膜の剥がれ面積が１０％未満
３：塗膜の剥がれ面積が１０％以上〜５０％未満
２：塗膜の剥がれ面積が５０％以上〜８０％未満
１：塗膜の剥がれ面積が８０％以上
Evaluation criteria of scratch resistance 5: No peeling of the coating film 4: The peeling area of the coating film is less than 10% 3: The peeling area of the coating film is 10% to less than 50% 2: The peeling area of the coating film is 50% or more ˜less than 80% 1: peeling area of coating film is 80% or more
・液安定性の評価
試験区分１で調製した熱可塑性高分子フィルムコーティング用組成物を、密閉容器中にて、室温２０℃で静置保管した際の分離の状況を観察し、分離するまでの時間により以下の基準で評価した。結果を表５及び表６にまとめて示した。
・ Evaluation of liquid stability Observe the state of separation when the thermoplastic polymer film coating composition prepared in Test Category 1 is stored in a closed container at room temperature of 20 ° C. The following criteria were evaluated according to time. The results are summarized in Tables 5 and 6.
液安定性の評価基準
５：２４時間以上分離無し
４：１２時間以上〜２４時間未満分離無し
３：６時間以上〜１２時間未満分離無し
２：２時間以上〜６時間未満分離無し
１：２時間未満に分離
Evaluation criteria of liquid stability 5: No separation for 24 hours or more 4: No separation for 12 hours or more to less than 24 hours 3: No separation for 6 hours or more to less than 12 hours 2: No separation for 2 hours or more to less than 6 hours 1: 2 hours Less than
表５及び表６の結果からも明らかなように、本発明の組成物を塗布すると、製膜時や展張時の摩擦による流滴性能の低下がなく、製造したフィルムを農業用ハウスに展張した後も長期間にわたって良好な流滴性を発揮することが解る。 As is apparent from the results of Tables 5 and 6, when the composition of the present invention was applied, there was no drop in the drip performance due to friction during film formation or spreading, and the produced film was spread in an agricultural house. It can be seen that the liquid droplets can be exhibited well over a long period of time.
Claims (6)
改質無機カチオンコロイドゾル：下記の無機カチオンコロイドゾルの存在下に、該無機カチオンコロイドゾルの固形分１００質量部当たり５〜１５質量部の割合となる量のシラノール形成性有機シラン化合物を加水分解処理し、更に生成したシラノール化合物を縮合重合させた改質無機カチオンコロイドゾル。
無機カチオンコロイドゾル：カチオンアルミナゾルを固形分換算で２０〜９０質量％及びカチオンシリカゾルを固形分換算で１０〜８０質量％（固形分換算で合計１００質量％）の割合で含有して成る無機カチオンコロイドゾル。
（ポリ）グリセリン：グリセン、ジグリセリン、トリグリセリン、テトラグリセリン、ペンタグリセリン、ヘキサグリセリン、ヘプタグリセリン、オクタグリセリン、ノナグリセリン及びデカグリセリンから選ばれるもの。 The following modified inorganic cation colloid sol contains 3 to 11 parts by weight of an anionic surfactant and 45 to 360 parts by weight of the following (poly) glycerin with respect to 100 parts by weight in terms of solid content. A composition for coating a thermoplastic polymer film.
Modified inorganic cation colloid sol: In the presence of the following inorganic cation colloid sol, a silanol-forming organosilane compound in an amount of 5 to 15 parts by mass per 100 parts by mass of the solid content of the inorganic cation colloid sol is hydrolyzed. A modified inorganic cation colloidal sol obtained by condensation polymerization of a silanol compound produced by treatment.
Inorganic cation colloid sol: Inorganic cation colloid comprising cation alumina sol in a proportion of 20 to 90% by mass in terms of solids and cationic silica sol in a proportion of 10 to 80% by mass in terms of solids (total 100% in terms of solids) Sol.
(Poly) glycerin: One selected from glycene, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, heptaglycerin, octaglycerin, nonaglycerin and decaglycerin.
第１工程：熱可塑性高分子フィルムにコロナ放電処理をして、コロナ放電処理面のぬれ張力を３５〜７０ｍＮ／ｍにする工程
第２工程：第１工程で得た熱可塑性高分子フィルムのコロナ放電処理面に対し、請求項１〜３のいずれか一つの項記載の熱可塑性高分子フィルムコーティング用組成物を固形分として０．１〜２．０ｇ／ｍ２となるよう塗布する工程 The manufacturing method of the modified thermoplastic polymer film characterized by passing through the following 1st process and the following 2nd process.
1st process: The process which corona discharge-treats to a thermoplastic polymer film, and sets the wetting tension of a corona discharge process surface to 35-70 mN / m 2nd process: The corona of the thermoplastic polymer film obtained at the 1st process The process of apply | coating the composition for thermoplastic polymer film coating as described in any one of Claims 1-3 with respect to a discharge process surface so that it may become 0.1-2.0 g / m < 2 > as solid content.
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