JPS63179966A - Anti-fogging synthetic resin film - Google Patents
Anti-fogging synthetic resin filmInfo
- Publication number
- JPS63179966A JPS63179966A JP1285487A JP1285487A JPS63179966A JP S63179966 A JPS63179966 A JP S63179966A JP 1285487 A JP1285487 A JP 1285487A JP 1285487 A JP1285487 A JP 1285487A JP S63179966 A JPS63179966 A JP S63179966A
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- film
- antifogging
- fogging
- resin film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 36
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000003094 microcapsule Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims description 6
- 235000013305 food Nutrition 0.000 abstract description 7
- 229920000915 polyvinyl chloride Polymers 0.000 abstract description 6
- 239000004800 polyvinyl chloride Substances 0.000 abstract description 6
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- 244000045561 useful plants Species 0.000 abstract description 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 abstract 1
- 229920003023 plastic Polymers 0.000 abstract 1
- 239000004033 plastic Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- -1 polyethylene Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- YDQUROLTIDVHRK-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)CC(O)(C(O)=O)CC(O)=O YDQUROLTIDVHRK-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- RAKMKCZMVZBODU-PIQLPZBWSA-L barium(2+);(z)-12-hydroxyoctadec-9-enoate Chemical compound [Ba+2].CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O.CCCCCCC(O)C\C=C/CCCCCCCC([O-])=O RAKMKCZMVZBODU-PIQLPZBWSA-L 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- VSJDEWYENWWMAV-UHFFFAOYSA-N chloroethene;2-methylprop-2-enoic acid Chemical compound ClC=C.CC(=C)C(O)=O VSJDEWYENWWMAV-UHFFFAOYSA-N 0.000 description 1
- SQNNHEYXAJPPKH-UHFFFAOYSA-N chloroethene;prop-2-enoic acid Chemical compound ClC=C.OC(=O)C=C SQNNHEYXAJPPKH-UHFFFAOYSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
「産業上の利用分野」
本発明は、防曇性合成樹脂フィルムに関するものである
。更に詳しくは、低温時における防曇性に優れ、フィル
ム使用開始直後の防曇性に優れ、かつ、高温時における
防曇持続性の優れた防曇性合成樹脂フィルムに関するも
のである。DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to an anti-fog synthetic resin film. More specifically, the present invention relates to an antifogging synthetic resin film that has excellent antifogging properties at low temperatures, excellent antifogging properties immediately after the film is used, and excellent antifogging durability at high temperatures.
「従来の技術」
従来から、水蒸気を透過しない熱可塑性合成樹脂フィル
ムにより、野菜や肉類等の食品を包装した場合、水滴が
フィルム内面を覆い、フィルム自体のもっている透明性
を損う現象が多発した。これら水滴は、透明フィルムを
曇らして内容物を見にくくするばかりでなく、結露した
水滴が収納食品に付着し、変質を促進する。``Conventional technology'' Conventionally, when food products such as vegetables and meat are packaged using thermoplastic synthetic resin films that do not transmit water vapor, water droplets often cover the inner surface of the film, damaging the transparency of the film itself. did. These water droplets not only cloud the transparent film and make it difficult to see the contents, but also the condensed water droplets adhere to the stored food and promote deterioration.
他方、農業用分野で使用される合成樹脂フィルムは、ハ
ウス（温室）やトンネルの被覆資材としての用途が主で
あるが、この用途でもフィルムの防曇性は、重要な性能
である。被覆資材として使用される場合には、土壌又は
栽培植物から蒸発する水分により、フィルム内面に水滴
が付着して不透明となり、また太陽光線を反射したり遮
断したりして、栽培植物の発育を損うぽかりでなく、結
露した水滴が栽培植物に落下し、病気発生、品質低下の
原因となる。On the other hand, synthetic resin films used in the agricultural field are mainly used as covering materials for greenhouses and tunnels, and the anti-fogging properties of the film are also an important performance in this application. When used as a covering material, moisture evaporating from soil or cultivated plants causes water droplets to adhere to the inner surface of the film, making it opaque, and also reflecting or blocking sunlight, damaging the growth of cultivated plants. Instead of condensation, water droplets fall onto cultivated plants, causing disease and quality deterioration.
上記欠点を改良するため、合成樹脂フィルムの表面に親
水性を付与すべく、基体樹脂成分にいわゆる防曇剤を配
合する方法が広く行なわれている（例えば、特公昭３８
−４１７４号公報、特公昭４５−３６０１４号公報、特
公昭４６−６３５２号公報、特公昭５２−４２８２０号
公報、特開昭５７−８２３６号公報等参照）。In order to improve the above-mentioned drawbacks, a method is widely used in which a so-called antifogging agent is added to the base resin component in order to impart hydrophilicity to the surface of the synthetic resin film (for example,
-4174, Japanese Patent Publication No. 45-36014, Japanese Patent Publication No. 46-6352, Japanese Patent Publication No. 52-42820, Japanese Patent Publication No. 57-8236, etc.).
食品包装合成樹脂フィルムにあっては、食品を包装し冷
所に長期間保存された場合でも、防曇性を発揮する必要
がある。他方、農業用に供される合成樹脂フィルムにあ
っては、冬季の低温期においても防曇性を発揮し、夏季
の高温期においても防曇性が着しく損われるようなこと
がないものでなければならない。Synthetic resin films for food packaging must exhibit antifogging properties even when food is packaged and stored in a cold place for a long period of time. On the other hand, synthetic resin films used for agricultural purposes must exhibit antifogging properties even during low temperatures in winter, and do not suffer from significant loss of antifogging properties even during high temperatures in summer. There must be.
「発明が解決しようとする問題点」
しかしながら、上記公報に記載の技術では、（１）低温
時の防曇性（低温特性）がよく、（２） フィルム使用
開始直後における防曇性が良く、かつ
（３）高温にさらされても防曇性が長期間持続する（持
続性の優れた）
という三つの性質を同時に満足させうるには不充分であ
った。"Problems to be Solved by the Invention" However, the technology described in the above publication has (1) good anti-fogging properties at low temperatures (low-temperature properties), (2) good anti-fogging properties immediately after the film starts to be used, and (3) the antifogging properties last for a long period of time even when exposed to high temperatures (excellent durability).
本発明者らは、かかる状況にあって、上記三つの性質を
兼備した防曇性合成樹脂フィルムを提供することを目的
として鋭意検討した結果、マイクロカプセル化した防曇
剤を使用することにより、本発明の目的を達成しうろこ
とを見い出し本発明を完成するに到った。Under such circumstances, the present inventors have conducted extensive studies with the aim of providing an antifogging synthetic resin film that combines the above three properties, and have found that by using a microencapsulated antifogging agent, The inventors have found a way to achieve the object of the present invention and have completed the present invention.
「問題点を解決するだめの手段」
しかして、本発明の要旨とするところは、防曇剤を芯物
質とするマイクロカプセルを含有することを特徴とする
防曇性合成樹脂フィルムに存する。"Means for Solving the Problems" The gist of the present invention resides in an antifogging synthetic resin film characterized by containing microcapsules having an antifogging agent as a core substance.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明において合成樹脂とは、一般に、フィルム形成性
の熱可塑性合成樹脂があげられる。具体的には、ポリ塩
化ビニル、塩化ビニル−酢酸ビニル共重合体、塩化ビニ
ル−アクリル酸エステル共重合体、塩化ビニル−メタク
リル酸エステル共重合体等の塩化ビニルＰ、樹脂； ポ
リエチレン、ポリプロピレン、エチレン−酢酸ビニル共
重合体、エチレン−アクリル酸共重合体、エチレン−ア
クリル酸エステル共重合体、エチレン−メタクリル酸エ
ステル共重合体、エチレン−ブチレン共重合３一
体等のオレフィン系樹脂； ポリエチレンテレフタレー
ト、ポリアミド、ポリメチルメタクリレート、ポリアク
リル酸エステル、ポリメタクリル酸エステル、ポリスチ
レン、スチレン−アクリロニトリル共重合体、ＡＢＳ樹
脂、ポリカーボネート、ポリ酢酸ビニル、含フツ素樹脂
等もしくはこれら重合体のブレンド物等をいい、これら
を防曇性合成樹脂フィルムの基材として用いる。農業用
掩蓋物の用途には、耐候性、光透過性、経済性、強度、
加工性、作業性等の観点から、塩化ビニル系樹脂及びオ
レフィン系樹脂が好適であり、最も有利には軟質ポリ塩
化ビニルである。In the present invention, the synthetic resin generally includes film-forming thermoplastic synthetic resins. Specifically, vinyl chloride P, resins such as polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer; polyethylene, polypropylene, ethylene; - Olefin resins such as vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid ester copolymer, ethylene-butylene copolymer 3 monolith; polyethylene terephthalate, polyamide , polymethyl methacrylate, polyacrylic ester, polymethacrylic ester, polystyrene, styrene-acrylonitrile copolymer, ABS resin, polycarbonate, polyvinyl acetate, fluorine-containing resin, etc., or blends of these polymers, etc. is used as a base material for an antifogging synthetic resin film. Agricultural cover uses include weather resistance, light transmittance, economy, strength,
From the viewpoint of processability, workability, etc., vinyl chloride resins and olefin resins are preferred, and soft polyvinyl chloride is most advantageous.
本発明の防曇性合成樹脂フィルムは、上述の合成樹脂に
防曇剤を芯物質とするマイクロカプセルを配合してフィ
ルム化したものである。本発明におけるマイクロカプセ
ルは、通常の製造技術、例えば界面重合法、コアセルベ
ーション法、静電合体法、界面反応法等により製造が可
能であり、カプセル壁の材質としては、ポリアミド、ポ
リエステル、ゼラチン、デンプン、ワックス、炭酸カル
シウム、シリカ等が挙げられる。The antifogging synthetic resin film of the present invention is a film obtained by blending microcapsules having an antifogging agent as a core substance with the above-mentioned synthetic resin. The microcapsules of the present invention can be manufactured by ordinary manufacturing techniques, such as interfacial polymerization, coacervation, electrostatic coalescence, and interfacial reaction, and the capsule wall materials include polyamide, polyester, gelatin, etc. , starch, wax, calcium carbonate, silica, etc.
マイクロカプセルの芯物質となる防曇剤としては、多価
アルコールの部分的カルボン酸エステル、多価アルコー
ルの部分的カルボン酸エステルのエチレンオキサイド又
はプロピレンオキサイド付加物などの非イオン型界面活
性剤、高級アルコール硫酸エステルのアルカリ金属塩、
アルキルアリルスルホネート等の７ニオン型界面活性剤
、高級アルキルアミン塩、脂肪酸誘導体などのカチオン
型界面活性剤等が挙げられ、これらを単独又は２種以上
併用してマイクロカプセル化してもよい。Antifogging agents that serve as the core material of microcapsules include nonionic surfactants such as partial carboxylic acid esters of polyhydric alcohols, ethylene oxide or propylene oxide adducts of partial carboxylic acid esters of polyhydric alcohols, and high-grade surfactants. Alkali metal salts of alcohol sulfates,
Examples include 7-ion type surfactants such as alkylaryl sulfonates, higher alkyl amine salts, and cation type surfactants such as fatty acid derivatives, and these may be used alone or in combination of two or more types to form microcapsules.
更１こ、本発明のマイクロカプセルは、それぞれ単独又
は２種以上を組み合わせて使用することができる。又、
必要に応じて、マイクロカプセル化した防曇剤と同じが
あるいは異なる他の防曇剤１種あるいは２ｆ１ｍ以上を
マイクロカプセルに加えて配合してもよい。この時配合
する防曇剤は上記マイクロカプセルの芯物質となる防曇
剤の中から選べばよい。Furthermore, the microcapsules of the present invention can be used alone or in combination of two or more. or,
If necessary, one type of other antifogging agent or 2f1m or more, which is the same as or different from the microencapsulated antifogging agent, may be added to the microcapsules. The antifogging agent to be added at this time may be selected from among the antifogging agents used as the core material of the microcapsules.
マイクロカプセルの合成樹脂への配合量は配合すべきマ
イクロカプセルの種類や粒径、合成樹脂の種類に応じて
広範に変えることができるが、一般的には配合すべき合
成樹脂１６０重量部当り、少なくとも０．１重量部とす
る。また配合量の上限は厳密に制約されるものではない
が、あまり多量に配合すると透明性を阻害するため、通
常は１０重量部以下である。前記、マイクロカプセルに
加えて配合する防曇剤も、あまり多量に配合するとブリ
ードアウトや白濁を生ずるおそれがあるので、通常は、
合成樹脂１００重量部当り、５重量部以下とする。The amount of microcapsules to be blended into the synthetic resin can vary widely depending on the type and particle size of the microcapsules to be blended and the type of synthetic resin, but generally, per 160 parts by weight of the synthetic resin to be blended, It should be at least 0.1 part by weight. Although the upper limit of the amount to be blended is not strictly limited, it is usually 10 parts by weight or less since transparency will be impaired if too much is blended. The above-mentioned anti-fogging agent that is blended in addition to the microcapsules may cause bleed-out or clouding if it is blended in too large a quantity, so it is usually
The amount shall be 5 parts by weight or less per 100 parts by weight of synthetic resin.
本発明に係る防曇性合成樹脂フィルムは、必要に応じて
、通常の各種樹脂添加物、例えば可塑剤、滑剤、熱安定
剤、帯電防止剤、紫外線吸収剤、霧発生防止剤、防かび
剤、光安定剤、顔料、染料等を、通常の量で含むことが
で外る。The antifogging synthetic resin film according to the present invention may contain various usual resin additives, such as plasticizers, lubricants, heat stabilizers, antistatic agents, ultraviolet absorbers, antifogging agents, and fungicides, as necessary. , light stabilizers, pigments, dyes, etc., in conventional amounts.
例えば、本発明において好適な軟質ポリ塩化ビニルにつ
いていえば、重合度が約１０００〜２５００のポリ塩化
ビニル１００重量部に対して、可塑剤を約３０〜７０重
量部の割合で配合することができる。用いうる好適な可
塑剤としては、例えばジ−ｎ−オクチル７タレート、ジ
ー２−エチルへキシル７タレート、ジベンジル７タレー
ト、ジイソデシル７タレート、ジドデシル７タレート、
ジイソデシル７タレート等の７タル酸誘導体；ジイソオ
クチル７タレート等のイソフタル酸誘導体； ジ−ｎ−
ブチルアジペート、ジオクチルアシペーＦ等のアジピン
酸誘導体； ジ−ｎ−ブチルマレート等のマレイン酸誘
導体； トリーローブチルシトレート等のクエン酸誘導
体； モノブチルイタコネート等のイタコン酸誘導体；
プチルオレーート等のオレイン酸誘導体； グリセリ
ンモノシトレート等のリシノール酸誘導体； その他ト
リクレジルホスフェート、トリキシレニルホスフェート
、エポキシ化大豆油、エポキシ樹脂系可塑剤等があげら
れる。For example, regarding flexible polyvinyl chloride suitable for the present invention, a plasticizer can be blended in a ratio of about 30 to 70 parts by weight to 100 parts by weight of polyvinyl chloride having a degree of polymerization of about 1000 to 2500. . Suitable plasticizers that can be used include, for example, di-n-octyl 7-talate, di-2-ethylhexyl 7-talate, dibenzyl 7-talate, diisodecyl 7-thaleate, didodecyl 7-thalet,
Heptatalic acid derivatives such as diisodecyl 7-talate; Isophthalic acid derivatives such as diisooctyl 7-talate; Di-n-
Adipic acid derivatives such as butyl adipate and dioctyl acipate F; Maleic acid derivatives such as di-n-butyl maleate; Citric acid derivatives such as trilobyl citrate; Itaconic acid derivatives such as monobutyl itaconate;
Oleic acid derivatives such as butyl oleate; ricinoleic acid derivatives such as glycerin monocitrate; and others such as tricresyl phosphate, tricylenyl phosphate, epoxidized soybean oil, and epoxy resin plasticizers.
また、防曇性合成樹脂フィルムに含ませうる滑剤または
熱安定剤としては、例えば、ポリエチレンワックス、ビ
スアマイド、ステアリン酸、ステアリン酸亜鉛、ステア
リン酸バリウム、ステアリン酸カルシウム、リシノール
酸バリウム、亜リン酸エステル類等があげられる。紫外
線吸収剤としては、例えば、ベンゾトリアゾール系、ベ
ンゾエート系、ベンゾフェノン系、シアノアクリレート
系、フェニルサリシレート系等の紫外線吸収剤があげら
れる。また、霧発生防止剤としては、例えば、炭素数３
〜２０のポリフルオロアルキル基と炭素数２〜４０のポ
リアルキレンオキサイド基を含有するフッ素含有有機化
合物； 例えばケイ素原子に結合する全置換基のうち少
なくとも５０％がメチル基であるポリオルガノシロキサ
ン化合物又はポリアルキレンオキサイド基を含有するポ
リシロキサン化合物、脂肪酸ビスアマイド等があげられ
る。光安定剤としては、例えば、ヒンダードアミン系化
合物があげられる。Examples of lubricants or heat stabilizers that can be included in the antifogging synthetic resin film include polyethylene wax, bisamide, stearic acid, zinc stearate, barium stearate, calcium stearate, barium ricinoleate, and phosphorous esters. etc. can be mentioned. Examples of the ultraviolet absorber include benzotriazole-based, benzoate-based, benzophenone-based, cyanoacrylate-based, and phenylsalicylate-based ultraviolet absorbers. In addition, as a fog generation prevention agent, for example, carbon number 3
A fluorine-containing organic compound containing ~20 polyfluoroalkyl groups and a polyalkylene oxide group having 2 to 40 carbon atoms; For example, a polyorganosiloxane compound in which at least 50% of all substituents bonded to silicon atoms are methyl groups, or Examples include polysiloxane compounds containing polyalkylene oxide groups, fatty acid bisamides, and the like. Examples of the light stabilizer include hindered amine compounds.
これら樹脂添加物は、通常の含有量、具体的には前記合
成樹脂１００重量部当り、５重量部以下の少量で含ませ
うる。These resin additives may be included in a usual amount, specifically, in a small amount of 5 parts by weight or less per 100 parts by weight of the synthetic resin.
本発明の防曇性合成樹脂フィルムは、前記合成樹脂に防
曇剤を芯物質とするマイクロカプセルを配合し、更に要
すれは防曇剤、又は各種樹脂添加物を含ませ、通常の配
合技術、混合技術、例えぼりポンプレンダ−、バンバリ
ーミキサ−、スーパーミキサー、エクストル−グー、ロ
ールミルその他の配合機、混合機を用いることにより均
一に配合し、これをフィルム化する。フィルム化するに
は、それ自体公知の方法、例えば溶融押出法、溶液流延
法、カレンダー法等を採用すればよい。The antifogging synthetic resin film of the present invention is produced by blending microcapsules containing an antifogging agent as a core substance with the synthetic resin, and further containing an antifogging agent or various resin additives if necessary, using a conventional compounding technique. The mixture is uniformly blended using a mixing technique such as a pump blender, a Banbury mixer, a super mixer, an extrusion blender, a roll mill, or other blenders or mixers, and then the mixture is formed into a film. To form a film, a method known per se, such as a melt extrusion method, a solution casting method, a calender method, etc., may be employed.
本発明に係る防曇性合成樹脂フィルムは、余り薄いと強
度が不充分で好ましくなく、逆に余り厚すぎると包装用
の用途、農業用の用途等に用いると々、切断、接着等の
作業に不便をきたすので、０．０１〜０．５１１Ｉ＋ｎ
の範囲とするのがよい。If the antifogging synthetic resin film according to the present invention is too thin, the strength will be insufficient, which is undesirable.On the other hand, if it is too thick, it will be used for packaging purposes, agricultural purposes, etc., and may be used for cutting, gluing, etc. 0.01 to 0.511I+n.
It is recommended that the range be within the range of .
以上説明したとおり、本発明に係る防曇性合成樹脂フィ
ルムは、従来がら使用されている各種防曇性合成樹脂フ
ィルムと同様、各種食品の包装用、有用植物栽培用のハ
ウス又はトンネルの掩蓋用として、利用することができ
る。As explained above, the anti-fog synthetic resin film according to the present invention, like the various anti-fog synthetic resin films conventionally used, can be used for packaging various foods and for covering greenhouses or tunnels for cultivating useful plants. It can be used as.
「発明の効果」
本発明に係る防曇性合成樹脂フィルムは、次のように特
別に顕著な効果を発揮する。"Effects of the Invention" The antifogging synthetic resin film according to the present invention exhibits the following particularly remarkable effects.
（１）本発明に係る防曇性合成樹脂フィルムは、低温時
における防曇性に優れているので、冷蔵する食品の包装
用に使用しても、水滴が内面に付着しにくいし、ハウス
（温室）の被覆用に使用していて冬季外気温が低下しで
も、水滴がフィルム内面に付着しにくい。(1) The anti-fogging synthetic resin film of the present invention has excellent anti-fogging properties at low temperatures, so even when used for packaging refrigerated foods, water droplets are unlikely to adhere to the inner surface of the house. Even when the outside temperature drops during the winter when the film is used to cover a greenhouse, water droplets are less likely to adhere to the inner surface of the film.
（２）本発明に係る防曇性合成樹脂フィルムは、フィル
ム使用開始直後から優れた防曇効果を発揮する。(2) The antifogging synthetic resin film according to the present invention exhibits an excellent antifogging effect immediately after the film is used.
（３）本発明に係る防曇性合成樹脂フィルムを、ハウス
の掩蓋用として使用した場合には、夏季の高温期におい
ても優れた防曇性を発揮し、長期間の使用に供しても、
優れた防曇性を持続する。(3) When the anti-fogging synthetic resin film according to the present invention is used for the cover of a house, it exhibits excellent anti-fogging properties even in the high temperature period of summer, and even when used for a long period of time,
Maintains excellent anti-fog properties.
「実施例」
以下、本発明を実施例にもとづいて詳細に説明するが、
本発明はその要旨を超えない限り、以下の例に限定され
るものではない。“Examples” The present invention will be explained in detail based on Examples below.
The present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例１〜４、比較例１〜３
ポリ塩化ビニル（Ｐ＝１３００） １００重量部ジオ
クチル７タレート ４２重量部トリクレジル
ホスフェート ５ 〃エポキシ樹脂（エピコー
ト８２Ｂ） ４ｉｔカルシウム−亜鉛系液状安定剤
３ 〃カルシウムー亜鉛系粉末安定剤 ２
〃紫外線吸収剤（チヌビンＰ） ０．１１を防
霧剤（旭硝子（株）社製、サーフロンＳ−１４５：固形
分３０重量％）０．３／／を基本組成とし、これに第１
表に示すマイクロカプセル又は防曇剤を配合した。なお
、実施例で使用したマイクロカプセルにおける芯物質す
なわち防曇剤の占める割合は５０重量％である。Examples 1 to 4, Comparative Examples 1 to 3 Polyvinyl chloride (P=1300) 100 parts by weight Dioctyl 7-talate 42 parts by weight Tricresyl phosphate 5 Epoxy resin (Epicote 82B) 4 it Calcium-zinc liquid stabilizer 3 Calcium-zinc powder stabilizer 2
〃Ultraviolet absorber (Tinuvin P) 0.11 is the basic composition of the antifogging agent (Surflon S-145, manufactured by Asahi Glass Co., Ltd., solid content 30% by weight) 0.3//, and the first
The microcapsules or antifogging agent shown in the table were blended. Incidentally, the proportion of the core substance, that is, the antifogging agent in the microcapsules used in the examples was 50% by weight.
得られた混合物を、１８０℃に加温されたカレンダーロ
ールに供給し、混練したのち、常法により厚さ０ 、
Ｉ ＩＩｕｎのフィルム７種を作成した。 得られた各
フィルムについて、次の方法に従って、防曇持続性及び
低温時の防曇性を評価し、結果を第２表に示した。The resulting mixture was fed to a calender roll heated to 180°C, kneaded, and then rolled to a thickness of 0 by a conventional method.
Seven types of I IIun films were created. Each film obtained was evaluated for antifogging durability and antifogging performance at low temperatures according to the following method, and the results are shown in Table 2.
く防曇持続性〉 愛知県名古屋市の圃場に、間口２ｍ、棟高２ｍ。Long anti-fog durability A field in Nagoya City, Aichi Prefecture, with a width of 2m and a ridge height of 2m.
奥行２０ｍの片屋根型ハウスに、昭和６０年８月２０日
から９力月間前記７種のフィルムを被覆し、各々のフィ
ルムの防曇性を定期的に肉眼で観察した。A single-roof type house with a depth of 20 m was coated with the above seven types of films for nine months from August 20, 1985, and the antifogging properties of each film were periodically observed with the naked eye.
第２表における「防曇持続性」の数値は、それぞれ次の
ような意義を有する。The numerical values for "anti-fog durability" in Table 2 have the following meanings.
「１」・・・水が薄膜状に付着し、水滴が認められない
状態。"1": Water adheres in a thin film and no water droplets are observed.
「２」・・・水が薄膜状に付着しているが、わずかに大
粒の水滴が認められる状態。"2": Water is attached in a thin film, but slightly large water droplets are observed.
「３」・・・水が薄膜状に付着しているが、部分的に大
粒の水滴の付着が認められる状態。"3": Water is attached in a thin film, but large water droplets are observed to be attached in some areas.
「４」・・・部分的に細かい水滴の付着が認められる状
１１！。"4"...Fine water droplets are observed in some areas 11! .
「５」・・・フィルム内表面全体に、細かい水滴の付着
が認められる状態。"5": A state in which fine water droplets are observed on the entire inner surface of the film.
〈低温時の防曇性〉
室温を５℃に調節した室内に、２０℃に温度調節した水
を入れた水槽を置き、この水槽の上部を試料のフィルム
で覆い、フィルム表面（水槽の水面と対向する面）への
水滴の付着状況を、肉眼で観察した。<Anti-fogging properties at low temperatures> Place a water tank containing water adjusted to 20°C in a room with room temperature adjusted to 5°C, cover the top of this tank with the sample film, and place the film surface (the water surface of the tank) The state of adhesion of water droplets to the opposing surface was observed with the naked eye.
第２表における「低温時の防曇性」の評価記号は、それ
ぞれ次のような意義を有する。The evaluation symbols for "antifogging properties at low temperatures" in Table 2 have the following meanings.
「ａ」・・・ 細かい水滴が試験開始後３０分以内に消
失する。"a"... Fine water droplets disappear within 30 minutes after the start of the test.
ｒｂＪ・・・ 細かい水滴が試験開始後３０分ないし６
０分以内に消失する６
「ｃ」・・・ 試験開始後６０分経過しても、細かい水
滴は消失しない。rbJ... Fine water droplets appear for 30 minutes or 6 minutes after the start of the test.
Disappears within 0 minutes 6 "c"... Fine water droplets do not disappear even after 60 minutes have passed from the start of the test.
優れており、防曇持続性において優れて−する。It has excellent anti-fog durability.
第 ２ 表 第２表より次のことが明らかとなる。Table 2 The following becomes clear from Table 2.
（１）本発明に係わるフィルムは、ハウスに被覆した直
後から優れた防曇性を発揮する。(1) The film according to the present invention exhibits excellent antifogging properties immediately after being coated on a house.
（２）本発明に係わるフィルムは、低温時の防曇性も優
れている。(2) The film according to the present invention also has excellent antifogging properties at low temperatures.
（３）実施例１のフィルムは、比較例１のフィルムより
も防曇持続性において優れている。(3) The film of Example 1 is superior to the film of Comparative Example 1 in antifogging durability.
（４）実施例２〜４のフィルムは、比較例２のフィルム
よりも使用中期、末期における防曇性が一１６＝
特許出願人 三菱化成ビニル株式会社
代 理 人 弁理士 長谷用 −
（ほか１名）(4) The films of Examples 2 to 4 have better anti-fog properties in the middle and final stages of use than the film of Comparative Example 2. given name)
Claims (2)
ることを特徴とする防曇性合成樹脂フィルム。(1) An anti-fog synthetic resin film characterized by containing microcapsules containing an anti-fog agent as a core substance.
が合成樹脂１００重量部に対し、０．１〜１０重量部で
ある特許請求の範囲第１項記載の防曇性合成樹脂フィル
ム。(2) The antifogging synthetic resin film according to claim 1, wherein the amount of microcapsules containing an antifogging agent as a core substance is 0.1 to 10 parts by weight per 100 parts by weight of the synthetic resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1285487A JPS63179966A (en) | 1987-01-22 | 1987-01-22 | Anti-fogging synthetic resin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1285487A JPS63179966A (en) | 1987-01-22 | 1987-01-22 | Anti-fogging synthetic resin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63179966A true JPS63179966A (en) | 1988-07-23 |
Family
ID=11816985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1285487A Pending JPS63179966A (en) | 1987-01-22 | 1987-01-22 | Anti-fogging synthetic resin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63179966A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996011108A1 (en) * | 1994-10-06 | 1996-04-18 | At Plastics Inc. | Articles formed of multilayered film having antifog properties |
| US5585186A (en) * | 1994-12-12 | 1996-12-17 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective, and anti-fogging properties |
| US5846650A (en) * | 1996-05-10 | 1998-12-08 | Minnesota Mining And Manufacturing Company | Anti-reflective, abrasion resistant, anti-fogging coated articles and methods |
| US5873931A (en) * | 1992-10-06 | 1999-02-23 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
| US6040053A (en) * | 1996-07-19 | 2000-03-21 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
-
1987
- 1987-01-22 JP JP1285487A patent/JPS63179966A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5873931A (en) * | 1992-10-06 | 1999-02-23 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
| US5997621A (en) * | 1992-10-06 | 1999-12-07 | Minnesota Mining And Manufacturing Co. | Coating composition having anti-reflective and anti-fogging properties |
| WO1996011108A1 (en) * | 1994-10-06 | 1996-04-18 | At Plastics Inc. | Articles formed of multilayered film having antifog properties |
| US5585186A (en) * | 1994-12-12 | 1996-12-17 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective, and anti-fogging properties |
| US5723175A (en) * | 1994-12-12 | 1998-03-03 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
| US5846650A (en) * | 1996-05-10 | 1998-12-08 | Minnesota Mining And Manufacturing Company | Anti-reflective, abrasion resistant, anti-fogging coated articles and methods |
| US6040053A (en) * | 1996-07-19 | 2000-03-21 | Minnesota Mining And Manufacturing Company | Coating composition having anti-reflective and anti-fogging properties |
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