CN108883596B - Liquid-repellent resin sheet and article using same - Google Patents
Liquid-repellent resin sheet and article using same Download PDFInfo
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- CN108883596B CN108883596B CN201780016423.4A CN201780016423A CN108883596B CN 108883596 B CN108883596 B CN 108883596B CN 201780016423 A CN201780016423 A CN 201780016423A CN 108883596 B CN108883596 B CN 108883596B
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- Prior art keywords
- liquid
- resin sheet
- convex
- sheet according
- resins
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- 229920005989 resin Polymers 0.000 title claims abstract description 255
- 239000011347 resin Substances 0.000 title claims abstract description 253
- 239000005871 repellent Substances 0.000 title claims abstract description 141
- 239000007788 liquid Substances 0.000 claims abstract description 138
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 39
- 239000010419 fine particle Substances 0.000 claims abstract description 35
- 239000011342 resin composition Substances 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 17
- 230000002940 repellent Effects 0.000 claims description 52
- 229920001577 copolymer Polymers 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 35
- 229920005672 polyolefin resin Polymers 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 29
- 239000004677 Nylon Substances 0.000 claims description 21
- 229920001778 nylon Polymers 0.000 claims description 21
- 239000000565 sealant Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229920001225 polyester resin Polymers 0.000 claims description 14
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims description 13
- 239000004645 polyester resin Substances 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 10
- 229920000178 Acrylic resin Polymers 0.000 claims description 10
- 150000001720 carbohydrates Chemical class 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011737 fluorine Substances 0.000 claims description 9
- 239000011164 primary particle Substances 0.000 claims description 9
- 235000013305 food Nutrition 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 239000005022 packaging material Substances 0.000 claims description 5
- 239000004566 building material Substances 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 125
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- 238000000034 method Methods 0.000 description 24
- 239000002585 base Substances 0.000 description 23
- 239000000178 monomer Substances 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229910002012 Aerosil® Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
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- 238000000576 coating method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920000305 Nylon 6,10 Polymers 0.000 description 4
- 229920000007 Nylon MXD6 Polymers 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
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- 239000002356 single layer Substances 0.000 description 4
- 150000003440 styrenes Chemical class 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 2
- ZLYYJUJDFKGVKB-UPHRSURJSA-N (z)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C/C(Cl)=O ZLYYJUJDFKGVKB-UPHRSURJSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- DPQHRXRAZHNGRU-UHFFFAOYSA-N 2,4,4-trimethylhexane-1,6-diamine Chemical compound NCC(C)CC(C)(C)CCN DPQHRXRAZHNGRU-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 2
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- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000227653 Lycopersicon Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005103 alkyl silyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])[H] 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
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical group C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 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
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 235000015094 jam Nutrition 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000021395 porridge Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000011962 puddings Nutrition 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 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
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000015113 tomato pastes and purées Nutrition 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 235000013618 yogurt Nutrition 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
- Bag Frames (AREA)
Abstract
A liquid-repellent resin sheet having stable liquid repellency against pressure from a liquid can be obtained by using a resin sheet having a convex-shaped layer (1) and a liquid-repellent layer (2), wherein the convex-shaped layer (1) has at least 1 type of fine convex shape (1a) and contains a thermoplastic resin composition, the surface having the convex shape (1a) has the liquid-repellent layer (2) containing hydrophobic inorganic fine particles and a binder resin, the content of the hydrophobic inorganic fine particles in the liquid-repellent layer (2) is more than 80 mass% and 95 mass% or less, and the content of the binder resin is 5 mass% or more and less than 20 mass%.
Description
Technical Field
The present invention relates to a liquid-repellent resin sheet and an article using the liquid-repellent resin sheet.
Background
Conventionally, paper materials and polymer materials have been used as packaging materials for foods and daily necessities such as refreshing drinks, fruit juice drinks, favorite foods and drinks. For example, patent document 1 proposes a liquid-repellent resin sheet in which a resin sheet is provided with a concavo-convex shape and a surface thereof is coated with a water-repellent agent.
However, the liquid-repellent resin sheet described in patent document 1 has a phenomenon in which a liquid is attracted to the surface of the liquid-repellent resin sheet by the pressure applied from the liquid, that is, a decrease or loss of the liquid repellency occurs, and there is a problem in the stability of the liquid repellency.
Patent document 1: international publication No. 2014/087695.
Disclosure of Invention
The invention provides a resin sheet having stable liquid repellency against pressure from liquid and an article using the resin sheet.
The present inventors have studied various means for exhibiting liquid repellency, and as a result, have found that a liquid repellency stable to a pressure from a liquid can be imparted to a sheet surface by providing a sheet surface with a fine convex shape and providing a liquid repellent layer containing hydrophobic inorganic fine particles and a binder resin at a specific ratio, and have completed the present invention.
The present invention for solving the above problems is configured as follows.
(1) A liquid-repellent resin sheet comprising a convex-shaped layer having at least 1 fine convex shape and containing a thermoplastic resin composition, and a liquid-repellent layer containing hydrophobic inorganic fine particles and a binder resin on the convex-shaped surface of the convex-shaped layer, wherein the content of the hydrophobic inorganic fine particles in the liquid-repellent layer is more than 80% by mass and 95% by mass or less, and the content of the binder resin is 5% by mass or more and less than 20% by mass.
(2) The liquid-repellent resin sheet according to (1), wherein the sheet has liquid repellency to an aqueous liquid containing a sugar.
(3) The liquid-repellent resin sheet according to (1) or (2), wherein the thermoplastic resin composition has a melt mass flow rate of 5g/10min or more at 230 ℃.
(4) The liquid-repellent resin sheet according to any one of (1) to (3), wherein the thermoplastic resin composition contains a polyolefin-based resin composition.
(5) The liquid-repellent resin sheet according to (4), wherein the polyolefin resin composition contains 35 to 100% by mass of a polyolefin resin.
(6) The liquid-repellent resin sheet according to any one of (1) to (5), wherein the hydrophobic inorganic fine particles are hydrophobic silica fine particles having trimethylsilyl groups on the surface.
(7) The liquid-repellent resin sheet according to any one of (1) to (6), wherein the hydrophobic inorganic fine particles have an average primary particle diameter of 5nm to 1000 nm.
(8) The liquid-repellent resin sheet according to any one of (1) to (7), wherein the binder resin comprises 1 or more resins selected from olefin copolymers and fluorine copolymers.
(9) The liquid-repellent resin sheet according to any one of (1) to (8), wherein the convex shapes are 1 st convex shapes and 2 nd convex shapes, the height of the 1 st convex shapes and the height of the 2 nd convex shapes are each 20 μm to 150 μm, and the distance between the apexes of adjacent convex shapes is 20 μm to 100 μm.
(10) The liquid-repellent resin sheet according to any one of (1) to (9), wherein the thickness of the convex-shaped layer is 50 μm to 200 μm.
(11) The liquid-repellent resin sheet according to any one of (1) to (10), wherein a contact angle of a surface on the side having the liquid-repellent layer when contacted with a liquid containing a saccharide is 130 ° or more, and a roll-off angle is 40 ° or less.
(12) The liquid-repellent resin sheet according to any one of (1) to (11), wherein, on the surface of the convex-shaped layer, liquid repellency is maintained even if a pressure of 866Pa is applied from the liquid.
(13) The liquid-repellent resin sheet according to any one of (1) to (12), wherein 1 or more layers of a base material layer comprising 1 or more resins selected from styrene-based resins, olefin-based resins, polyester-based resins, nylon-based resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins are laminated on the other surface of the convex-shaped layer having the convex surface.
(14) The liquid-repellent resin sheet according to (13), wherein a sealant resin layer containing at least 1 resin selected from the group consisting of a modified olefin polymer resin and a thermoplastic elastomer is formed between the convex layer and the base layer.
(15) An article wherein the liquid-repellent resin sheet described in any one of (1) to (14) is used.
(16) The article according to (15), wherein the article is a living article, a packaging material or a building material.
(17) The article according to (16), wherein the article is a food container, a bag, a raincoat, an umbrella, wallpaper or a member in water.
According to the present invention, a liquid-repellent resin sheet having liquid repellency that is stable against pressure from a liquid, and an article using the resin sheet can be provided.
Drawings
Fig. 1 is a schematic longitudinal sectional view showing a liquid-repellent resin sheet according to a first embodiment of the present invention.
Fig. 2 is a schematic plan view of the liquid-repellent resin sheet of fig. 1.
Fig. 3 is a schematic longitudinal side sectional view of another aspect of the liquid-repellent resin sheet according to the first embodiment of the present invention.
Fig. 4 is a schematic plan view of the liquid-repellent resin sheet of fig. 3.
Fig. 5 is a schematic longitudinal side sectional view showing a laminated structure of a liquid-repellent resin sheet according to a second embodiment of the present invention.
Fig. 6 is a schematic longitudinal side sectional view showing a laminated structure of a liquid-repellent resin sheet according to a third embodiment of the present invention.
Fig. 7 is a schematic longitudinal side sectional view showing a laminated structure of a liquid-repellent resin sheet according to a fourth embodiment of the present invention.
Fig. 8 is a diagram showing evaluation criteria of the pressure test of the present invention.
Detailed Description
[ first embodiment ]
As shown in fig. 1, the liquid-repellent resin sheet according to the first embodiment of the present invention comprises a convex-shaped layer (1) and a liquid-repellent layer (2), wherein the convex-shaped layer (1) has at least 1 kind of fine convex shapes (1a) and contains a thermoplastic resin composition, the surface having the convex shapes (1a) has the liquid-repellent layer (2) containing hydrophobic inorganic fine particles and a binder resin, the content of the hydrophobic inorganic fine particles in the liquid-repellent layer exceeds 80% by mass and is 95% by mass or less, the content of the binder resin is 5% by mass or more and is less than 20% by mass, and the liquid-repellent resin sheet has liquid repellency.
< convex layer >
The convex-shaped layer may be formed using a thermoplastic resin composition. Examples of the thermoplastic resin composition include polyolefin resins, polystyrene resins, polyester resins, and polyvinylidene fluoride resins. For example, when used as a food container, the polyolefin resin is preferable, and the polyolefin resin is particularly preferably contained in an amount of 35% by mass or more. By setting the polyolefin resin to 35% by mass or more, the transfer property of the convex shape can be improved. The polyolefin resin composition preferably has a melt mass flow rate of 5g/10min or more, more preferably 15g/10 min or more at 230 ℃. By setting the melt mass flow rate to 5g/10min or more, the transferability of the convex shape can be improved. The melt mass flow rate was calculated by measuring the mass flow rate at regular intervals (g/10 minutes) in accordance with JIS K7210. As standard conditions, the melt mass flow rate was measured at a test temperature of 190 ℃ to 230 ℃ under a load of 2.16kg to 10.00 kg.
The polyolefin resin is a resin mainly containing a polymer containing an α -olefin as a monomer, and particularly preferably contains a polyethylene resin and a polypropylene resin. The polyethylene resin includes high-density polyethylene, low-density polyethylene, linear medium-density polyethylene, and a copolymer or graft copolymer mainly composed of ethylene, and also includes a mixture thereof. Examples of the copolymer include an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid ester copolymer, an ethylene-methacrylic acid ester copolymer, and an ethylene-vinyl acetate-vinyl chloride copolymer, and examples of the graft copolymer include a styrene-ethylene graft copolymer.
Further, as the polypropylene resin, homopolypropylene, random polypropylene, block polypropylene and the like can be cited. When homopolypropylene is used, the structure of the homopolypropylene may be any of isotactic, atactic and syndiotactic structures. When random polypropylene is used, the alpha-olefin copolymerized with propylene is preferably one having 2 to 20 carbon atoms, more preferably 4 to 12 carbon atoms, and examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, and 1-decene. When the block polypropylene is used, a block copolymer (block polypropylene), a block copolymer or a graft copolymer containing a rubber component, and the like can be exemplified. These olefin resins may be used alone or in combination with other olefin resins.
The thermoplastic resin composition may contain other additives within a range not detrimental to the effects of the present invention. Examples of the other additives include stabilizers, surfactants, lubricants, fillers, foaming agents, coloring materials, and nucleating agents.
(convex shape)
The convex layer has 1 or more kinds of fine convex shapes. The convex shape may be 1 kind of convex shape as shown in fig. 1, and preferably has a 1 st convex shape and a 2 nd convex shape which are different in shape as shown in fig. 3. The convex shape may have 3 or more kinds of convex shapes having different shapes. Here, when the convex shape has the 1 st convex shape and the 2 nd convex shape, the height of the 1 st convex shape is higher than the height of the 2 nd convex shape. The arrangement of the 1 st and 2 nd convex shapes is not limited, and the 1 st and 2 nd convex shapes are preferably arranged alternately from the viewpoint of liquid repellency. The convex shape is not particularly limited, and may be arranged in a checkerboard pattern or in a staggered pattern. To further maintain liquid repellency, the arrangement is preferably staggered. The method for forming the convex layer is not particularly limited, and a known method can be used. Examples of the method include a method in which the surface of the resin sheet is formed by casting (casting) using a transfer roller and a contact roller, each of which has a concavo-convex shape formed by a laser engraving method; a method of heating the sheet with a belt mold and transferring the unevenness by pressing.
The height (h) of the convex shape is preferably 20 to 150. mu.m. By setting the height of the convex shape to 20 μm or more, sufficient liquid repellency can be ensured, and by setting the height of the convex shape to 150 μm or less, the dimension of the convex shape in the mold for imparting a convex shape can be stabilized. The thickness of the liquid repellent layer (100nm to 4000nm) described later is added to the height of the convex shape. The thickness of the convex layer is not particularly limited, and the height including the above convex may be 50 μm to 1000 μm.
The distance (t) between the apexes of adjacent convex shapes is preferably 20 to 100 μm. The vertex interval refers to an interval between adjacent convex shapes at the shortest distance, and refers to an interval between adjacent convex shapes even if the convex shapes are different from each other. By setting the apex interval to 20 μm or more, the convex shape dimension in the mold for imparting the convex shape can be stabilized. Further, by being 100 μm or less, the liquid repellency can be prevented from being lowered.
The height of the convex shape and the distance between the apexes of the convex shape can be measured using a laser microscope (for example, VK-X100 manufactured by KEYENCE CORPORATION).
When 2 kinds of convex shapes are used, the ratio of the height of the 2 nd convex shape to the height of the 1 st convex shape is preferably 0.4 to 0.8. By setting the height ratio to 0.4 or more and 0.8 or less, more effective liquid repellency can be obtained.
The bottom surface of the convex shape may be a conical shape such as a triangular pyramid, a rectangular pyramid, a hexagonal pyramid, an octagonal pyramid, a cone, a truncated pyramid shape, or a truncated cone shape.
< liquid-repellent layer >
The liquid repellent layer is formed on the surface of the convex layer with a substantially constant thickness so that the convex shape of the convex layer is maintained substantially as it is on the sheet surface. The liquid repellent layer is provided to maintain liquid repellency even after molding of the member, and is formed using hydrophobic inorganic fine particles and a binder resin. The thickness of the liquid repellent layer is preferably 100nm to 4000nm, and is not particularly limited as long as the effects of the present invention are obtained. Here, the term "liquid repellency" refers to liquid repellency to the extent that the saccharide-based liquid (saccharide-containing liquid) is sufficiently prevented from adhering to the resin sheet, and specifically refers to a contact angle of the liquid of these liquids with respect to the resin sheet of 130 ° or more and/or a roll off angle of 40 ° or less. The contact angle and the roll off angle can be measured with respect to the resin sheet by using an automatic contact angle meter (for example, DM-501 manufactured by synechia chemical co., ltd.). In addition, "even if applied from a liquid
The "liquid repellency is maintained by a pressure of 866 Pa" means liquid repellency that is stable against pressure from a liquid, that is, liquid repellency is maintained even when a pressure such as a pressure of 866Pa is applied to the liquid.
The liquid-repellent layer is characterized in that the content of the hydrophobic inorganic fine particles is more than 80 mass% and 95 mass% or less, and the content of the binder resin is 5 mass% or more and less than 20 mass%. Preferably, the content of the hydrophobic inorganic fine particles is 85 to 95 mass% and the content of the binder resin is 5 to 15 mass%. By having a composition in this range, stable liquid repellency can be obtained even in the case where pressure is given from the liquid. On the other hand, if the content of the hydrophobic inorganic fine particles is 80% by mass or less, a sufficiently stable liquid repellency may not be obtained when pressure is applied from a liquid, and if the content of the hydrophobic inorganic fine particles exceeds 95% by mass, the hydrophobic inorganic fine particles may peel off.
As a method for forming the liquid repellent layer on the convex surface, the following method is adopted: a dispersion liquid in which hydrophobic inorganic fine particles are added to isopropyl alcohol (IPA) is prepared in advance, and then mixed with a binder resin at an arbitrary ratio, and the mixture is applied to the convex surface by an applicator or the like.
(hydrophobic inorganic Fine particles)
The hydrophobic inorganic fine particles may be those having a hydrophobic group, and may be those hydrophobized by surface treatment. For example, hydrophobic silica fine particles having a trimethylsilyl group, a dimethylsiloxane group, an alkylsilyl group, an aminoalkylsilyl group, a methacryloylsilyl group, a dimethylpolysiloxane group, or a dimethylsilyl group on the surface are preferable. Further, fine particles obtained by subjecting hydrophilic inorganic fine particles to surface treatment with a silane coupling agent or the like to render the surface state hydrophobic may also be used. The kind of the inorganic substance is not limited as long as it has hydrophobicity. Among them, at least 1 kind of hydrophobic fumed silica, fused silica, alumina, titania, and the like can be used. The shape of these particles is not limited as long as they have hydrophobicity, and spherical and non-spherical (crushed) shapes can be used. The average primary particle diameter is preferably 5nm to 1000nm, more preferably 7nm to 200nm, and still more preferably 7nm to 25 nm. By setting the average primary particle diameter to 5nm to 1000nm, the liquid repellency satisfying the conditions of the present invention is obtained and the dispersibility in the binder resin is improved. The average primary particle size is a value obtained by taking a plurality of images while changing the field of view using a scanning electron microscope, measuring the diameters of 3000 to 5000 hydrophobic inorganic fine particles randomly extracted using image analysis software, and calculating the average value. Specific examples of these include silicas having the product names "AEROSIL R972", "AEROSIL R972V", "AEROSIL R972 CF", "AEROSIL R974", "AEROSIL RX 200", "AEROSIL RY 200" (manufactured by NIPPON AEROSIL co., LTD. (above)), and "AEROSIL R202", "AEROSIL R805", "AEROSIL R812S", and "AEROSIL RY 300" (manufactured by evonikowski co., LTD. (above)). The titanium dioxide may be named "AEROXIDE TiO 2T 805" (manufactured by Woodbis GmbH) or the like. The alumina is exemplified by fine particles obtained by treating the surface of the particles with a silane coupling agent, such as "AEROXIDEALU C" (manufactured by Woodbis corporation), to make the surface hydrophobic.
(Binder resin)
The binder resin is a dispersion liquid obtained by dispersing any 1 or more of an olefin copolymer and a fluorine copolymer in water. In the present specification, the content of the binder resin means the content of a solid component mainly composed of a resin in the binder resin used.
The olefin-based copolymer is a polymer containing α -olefin as a monomer, and includes polyethylene-based polymers and polypropylene-based polymers. Examples thereof include ionomers such as low density polyethylene, ultra-low density polyethylene (a copolymer of ethylene and an α -olefin), ethylene-vinyl acetate copolymer (EVA), ethylene-alkyl acrylate copolymer, ethylene-alkyl methacrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, low density polyethylene, and propylene-based elastomer materials. Commercially available products corresponding to the above include "CHEMIPEARL S-100" (manufactured by Mitsui chemical Co., Ltd.), "AQUATEX AC-3100", "AQUATEX EC-3500" (manufactured by Japan paint Resin Co., Ltd.), "Arrow base SE-1200", "Arrow base SD-1200", "Arrow base YA-4010" (manufactured by Nissan Yorkat Ltd.), and the like.
The fluorine-containing copolymer is a hydrocarbon-based resin containing fluorine, and preferably contains the copolymer (1) and the copolymer (2) described below. The copolymer (1) and the copolymer (2) may contain the following structural units (a) to (d). However, the copolymer (1) contains the structural unit (a) and the structural unit (b), and the copolymer (2) contains the structural unit (a) and the structural unit (c). The copolymer (1) mainly contributes to the development of liquid repellency of the resin sheet, and the copolymer (2) mainly contributes to the durability of the resin sheet.
The structural unit (a) is a group obtained by substituting fluorine atoms for some or all of the hydrogen atoms of an alkyl group, and has 1 to 6 carbon atoms. The structural unit (a) may be a chain polyfluoroalkyl group having 1 or more unsaturated groups such as carbon-carbon unsaturated double bonds. As the unsaturated group, (meth) acrylate is preferable.
The structural unit (b) is preferably a monomer having a saturated hydrocarbon group having 16 to 40 carbon atoms, more preferably a (meth) acrylate containing an alkyl group having 16 to 40 carbon atoms, and still more preferably stearyl (meth) acrylate or behenyl (meth) acrylate.
The structural unit (c) is a monomer derived from a monomer containing no fluorine atom and having a crosslinkable functional group. As the crosslinkable functional group, an isocyanate group, a blocked isocyanate group, an alkoxysilyl group, an amino group, an alkoxymethylamide group, a silanol group, an ammonium group, an amide group, an epoxy group, a hydroxyl group, an oxazoline group, a carboxyl group, an alkenyl group, a sulfonic group, and the like are preferable. Further, epoxy group, hydroxyl group, blocked isocyanate group, alkoxysilyl group, amino group, and carboxyl group are more preferable.
The monomer forming the structural unit (c) is preferably a (meth) acrylate, a compound having 2 or more copolymerizable groups, a vinyl ether or a vinyl ester.
The structural unit (c) may be derived from a mixture of 2 or more species. The structural unit (c) mainly affects the film forming property of the liquid repellent film, the adhesiveness of the liquid repellent composition to a substrate, and the adhesion, and contributes to the improvement of the durability.
The structural unit (d) is a structural unit derived from a monomer having a polymerizable group other than the structural units (a), (b) and (c). Further, a monomer which is excellent in film-forming property and gives a uniform copolymer solution or dispersion is preferable. As the structural unit (d), vinyl chloride, vinylidene chloride, cyclohexyl methacrylate, polyoxyethylene di (meth) acrylate, alkyl ether of polyoxyethylene di (meth) acrylate, and dioctyl maleate are particularly preferable. The structural unit (d) can contribute to improvement in adhesion of the composition to a substrate and improvement in dispersibility.
Examples of commercially available products corresponding to these compounds include "Asahiguard AG-E070", "Asahiguard AG-E550D" (manufactured by Asahi glass Co., Ltd.), "UNIDYNE TG-5546", "UNIDYNE TG-5671", "UNIDYNE TG-6071" (manufactured by Daikin INDUSTRIES, LTD.), and the like.
< aqueous liquid >
The aqueous liquid in the present embodiment is a liquid having fluidity with water as a solvent, and the viscosity of the liquid is not limited. Particularly, it includes a liquid for food such as a liquid containing saccharides. Specifically, it comprises yogurt, jelly, pudding, jam, syrup, tomato sauce, fruit juice, porridge, honey, molasses, liquid sugar, etc.
[ second embodiment ]
As shown in fig. 5, an example of the resin sheet according to the second embodiment of the present invention is a resin sheet in which a sealant resin layer (3) is formed between a convex layer (1) having a liquid-repellent layer (2) laminated on the surface thereof and a base material layer (4). That is, the layer structure of the resin sheet according to the second embodiment includes, from top to bottom, the liquid-repellent layer (2), the convex layer (1), the sealant resin layer (3), and the base material layer (4). Here, the liquid repellent layer and the convex layer are the same as those described in the first embodiment, and therefore, the description thereof is omitted. However, the thickness of the convex layer is preferably 50 μm to 200 μm. By making the thickness of the film 50 μm or more, transfer failure of the convex shape can be prevented. Further, by being 200 μm or less, the production cost can be prevented from becoming high.
< substrate layer >
The substrate layer is preferably a styrene resin (impact-resistant polystyrene, polybutadiene-polystyrene-polyacrylonitrile graft polymer, etc.), an olefin resin (polyethylene, polypropylene, etc.), a polycarbonate, a polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), a nylon resin (nylon 6, polypropylene, etc.),
Nylon-66, etc.), ethylene-vinyl alcohol copolymers, acrylic resins, and other thermoplastic resins. In addition, in the case of lamination, there are lamination by coextrusion, extrusion layer synthesis type using a non-stretched film and a biaxially stretched film, and lamination by dry layer synthesis type.
As the base layer, a polyester resin is preferable. For example, as the polyester resin to be the base layer, polyethylene terephthalate, polybutylene terephthalate, polyethylene 2, 6-naphthalate, polyethylene terephthalate, and a polyester resin obtained by copolymerizing a diol component such as diethylene glycol, neopentyl glycol, or polyalkylene glycol, and a dicarboxylic acid component such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, or 2, 6-naphthalenedicarboxylic acid, as a copolymerization component can be used.
If necessary, additives such as a coloring agent such as a pigment or a dye, a release agent such as silicone oil, a fibrous reinforcing agent such as glass fiber, a coloring agent such as talc, clay, or silica, a salt compound of a sulfonic acid and an alkali metal, an antistatic agent such as polyalkylene glycol, an ultraviolet absorber, and an antibacterial agent may be added to the base layer in a range not to impair the effects of the present invention. Further, the waste resin generated in the manufacturing step of the multilayer resin sheet of the present invention may also be mixed and used.
< sealing agent resin layer >
The sealant resin layer exhibits adhesion between the convex layer and the base material layer. The resin component includes 100 mass% of the modified olefin polymer resin and 100 parts by mass of the thermoplastic elastomer.
The modified olefin polymer is preferable for the sealant resin layer. Typical examples of the modified olefin polymer resin include olefin resins such as olefins having 2 to about 8 carbon atoms such as ethylene, propylene and 1-butene, copolymers of these olefins with other olefins having 2 to about 20 carbon atoms such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, and copolymers of these olefins with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters and styrene; the olefin rubber such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer is modified under the grafting reaction conditions with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, or its acid halide, amide, imide, anhydride, ester, or other derivatives, specifically, maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, or glycidyl maleate.
Among them, preferred is an ethylene-propylene-diene copolymer or an ethylene-propylene or 1-butene copolymer rubber modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof.
The thickness of the sealant resin layer is preferably 20 to 90 μm, and more preferably 40 to 80 μm. If the thickness is less than 20 μm, interlayer peeling may occur between the convex layer and the base layer, and if the thickness exceeds 90 μm, the production cost may increase.
[ third embodiment ]
As shown in fig. 6, the resin sheet according to the third embodiment of the present invention is a resin sheet in which the convex layer (1) and the base layer (4) are directly laminated without using the sealant resin layer (3) shown in the second embodiment. That is, the resin sheet according to the third embodiment has a layer structure in which the liquid-repellent layer (2), the convex layer (1), and the base material layer (4) are formed from the top down, and the sealant resin layer is removed from the thermoplastic resin sheet according to the second embodiment. Here, the liquid repellent layer and the convex-shaped layer are the same as those in the first and second embodiments, and therefore, the description thereof is omitted. On the other hand, the base layer (4) in the present embodiment preferably has sufficient adhesiveness to the convex layer.
Therefore, in the resin sheet according to the third embodiment, a styrene resin excellent in adhesion to the convex layer is preferably used as the base layer. The styrene resin is preferably a styrene base layer comprising 60 to 15 mass%, more preferably 55 to 15 mass%, of a polystyrene resin and 40 to 85 mass%, more preferably 45 to 85 mass%, of an impact-resistant polystyrene resin. Further, a styrene-based resin composition to which a hydrogenated styrene-based thermoplastic elastomer is added may be used. When a polystyrene resin and a hydrogenated styrene thermoplastic elastomer are used in combination, a styrene resin composition containing 90 to 95 mass% of a polystyrene resin and 5 to 10 mass% of a hydrogenated styrene thermoplastic elastomer is preferable. In this case, if the amount of the hydrogenated styrene-based thermoplastic elastomer added is less than 5% by mass, the adhesiveness to the convex layer may be insufficient, resulting in interlayer peeling, and if it exceeds 10% by mass, the production cost may be increased.
[ fourth embodiment ]
As shown in fig. 7, the resin sheet according to the fourth embodiment of the present invention is a resin sheet in which a liquid-repellent layer (2), a convex layer (1), a 1 st sealant resin layer (3a), an oxygen-barrier base layer (5), a 2 nd sealant resin layer (3b), and a base layer (4) are laminated in this order. The composition of the 1 st sealant resin layer and the 2 nd sealant resin layer may be the same or different. The thickness of the convex layer is preferably 50 to 250 μm. If the thickness is less than 50 μm, the transfer of the convex shape may be defective. When the thickness exceeds 200. mu.m, the production cost may be increased.
< substrate layer >
As the resin used as the base layer in the fourth embodiment, a nylon-based resin or a methacrylic acid ester-based resin is preferable. Examples of the nylon-based resin include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, aliphatic diamines such as hexamethylenediamine, decamethylenediamine and 2,2, 4-or 2,4, 4-trimethylhexamethylenediamine, polycondensates of diamine units such as alicyclic diamine such as 1, 3-or 1, 4-bis (aminomethyl) cyclohexane or bis (p-aminocyclohexylmethane), aromatic diamine such as m-xylylenediamine or p-xylylenediamine, dicarboxylic acid units such as aliphatic dicarboxylic acid such as adipic acid, suberic acid or sebacic acid, alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid, aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, and copolymers thereof. Specifically, nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6/6T, nylon 6I/6T, etc., and among them, nylon 6 and nylon MXD6 are preferable.
The methacrylate-based resin is not particularly limited in structure, and the like, as long as it is a vinyl polymer based on a methacrylate monomer. Examples of the methacrylate ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, and hexyl methacrylate. Among them, methyl methacrylate is particularly preferable. In the methacrylate monomer, an alkyl group such as a propyl group, a butyl group, a pentyl group, and a hexyl group may be a straight chain or branched. The methacrylate ester resin to be blended in the resin composition of the present embodiment may be a single polymer of a methacrylate ester monomer or a copolymer of a plurality of methacrylate ester monomers. Or may have a monomer unit derived from ethylene, propylene, butadiene, styrene, α -methylstyrene, acrylonitrile, acrylic acid, or the like, which is a known vinyl compound other than methacrylate.
< oxygen Barrier substrate layer >
Examples of the oxygen barrier base layer include ethylene-vinyl alcohol copolymer resins and nylon resins. Among them, an ethylene-vinyl alcohol copolymer resin is preferable in view of processability and moldability.
The ethylene-vinyl alcohol copolymer resin is usually obtained by saponifying an ethylene-vinyl acetate copolymer, and has an ethylene content of 10 to 65 mol%, preferably 20 to 50 mol%, and a saponification degree of 90% or more, preferably 95% or more, for providing oxygen barrier properties, processability, and moldability.
Further, as for the nylon-based resin, examples thereof include lactam polymers such as caprolactam and laurolactam, polymers of aminocarboxylic acids such as 6-aminocaproic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid, aliphatic diamines such as hexamethylenediamine, decamethylenediamine and dodecamethylenediamine, 2, 4-or 2,4, 4-trimethylhexamethylenediamine, alicyclic diamines such as 1, 3-or 1, 4-bis (aminomethyl) cyclohexane and bis (p-aminocyclohexylmethane), condensates of diamine units such as aromatic diamines such as m-xylylenediamine and p-xylylenediamine with aliphatic dicarboxylic acids such as adipic acid, suberic acid and sebacic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and copolymers thereof.
Specific examples of the nylon-based resin include nylon 6, nylon 9, nylon 11, nylon 12, nylon 66, nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6/6T, and nylon 6I/6T, and among them, nylon 6 and nylon MXD6 are preferable.
< sealing agent resin layer >
The modified olefin polymer is preferable for the sealant resin layer. Typical examples of the modified olefin polymer resin include olefin resins such as olefins having 2 to about 8 carbon atoms such as ethylene, propylene and 1-butene, copolymers of these olefins with other olefins having 2 to about 20 carbon atoms such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene and 1-decene, and copolymers of these olefins with vinyl compounds such as vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters and styrene; the olefin rubber such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-1-butene copolymer, propylene-1-butene copolymer is modified under the grafting reaction conditions with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, or its acid halide, amide, imide, anhydride, ester, or other derivatives, specifically, maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, or glycidyl maleate.
Among them, ethylene-based resins, propylene-based resins, or ethylene-propylene or 1-butene copolymer rubbers modified with an unsaturated dicarboxylic acid or an anhydride thereof, particularly maleic acid or an anhydride thereof, are preferable.
The thickness of the sealant resin layer is preferably 10 μm to 50 μm, and more preferably 20 μm to 40 μm on both sides. If the thickness is less than 10 μm, sufficient interlayer adhesion strength may not be obtained, and if the thickness exceeds 50 μm, the production cost may increase.
[ production of liquid-repellent resin sheet ]
The method for producing the resin sheet of the present invention is not limited, and any method can be used, and typically, the method includes the steps of: a single-layer sheet having at least 1 or more kinds of convex shapes on one surface thereof or a laminated resin sheet including the convex-shaped layer is produced, and finally a liquid repellent layer is formed on the convex-shaped surface.
First, in the case of producing a single-layer sheet having at least 1 or more kinds of convex shapes on one surface or a laminated resin sheet including the layer having a convex shape, any resin sheet molding method can be used. Examples thereof include the following methods: in the case of a single layer, 1 single screw extruder was used, and in the case of a plurality of layers, a plurality of single screw extruders were used to melt-extrude the respective raw material resins, and a resin sheet was obtained by a T-die. In the case of multiple layers, a multi-manifold die may be used. However, the layer structure of each embodiment of the resin sheet of the present invention is basically as described above, and for example, as long as physical properties and the like do not show deterioration, waste materials generated in the steps of manufacturing the resin sheet and the member of the present invention may be added to the base material layer or may be laminated as an additional layer.
Then, the convex shape is formed on the single-layer or multi-layer resin sheet, and this method is not particularly limited, and any method known to those skilled in the art may be used. Examples of the method include a method of manufacturing by an extrusion molding method, a method of manufacturing by a photolithography method (lithography method), a method of manufacturing by a hot press method, and a method of manufacturing by using a pattern roll and a UV curable resin.
Finally, a liquid repellent layer containing a specific amount of hydrophobic inorganic fine particles and a binder resin is formed on the surface of the convex-shaped layer. The method for forming the liquid repellent layer is not particularly limited, and for example, a known coating method such as roll coating, gravure coating, bar coating, knife coating, brush coating, or powder electrostatic method can be used. The solvent used in the preparation of the coating liquid is not particularly limited, and other than water, for example, an organic solvent such as alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyl diglycol, pentylene glycol, n-pentane, n-hexane, and hexanol can be suitably selected. In this case, a small amount of a dispersant, a coloring agent, an anti-settling agent, a viscosity adjusting agent, or the like may be used in combination.
[ article ]
The liquid-repellent resin sheet of the present invention can be suitably used for articles requiring the liquid repellency described above. The following are specifically described below.
The liquid-repellent resin sheet of the present invention can be used as a packaging material for food containers, bags and the like, a daily use article such as a raincoat, an umbrella and the like, a member for water use in kitchens, bathrooms, toilets and the like, a building material such as wallpaper and the like.
For example, by using the liquid-repellent resin sheet of the present invention in a food container, a bag, or the like, effects of preventing the contents from adhering to the inner wall of the container or the like, facilitating complete use of the contents at the end, and reducing labor for cleaning the container when sorting garbage can be obtained.
For example, when the liquid-repellent resin sheet of the present invention is used for rain gear such as raincoats and umbrellas, the effect that water droplets are difficult to adhere to hands such as water droplets when folded can be obtained.
For example, when the liquid-repellent resin sheet of the present invention is used for a bathroom wall panel, the effect of preventing water droplets from adhering thereto can be obtained.
For example, by using the liquid-repellent resin sheet of the present invention for an interior material or the like, an effect that dirt or the like is less likely to adhere can be obtained.
Examples
The present invention will be described specifically below with reference to examples and comparative examples, but the present invention is not limited to the contents of the examples.
Various raw materials used in examples and the like are as follows.
(1) Convex shaped layer
(A) Random polypropylene "PM 921V" (manufactured by sun heteroisomorphism Ltd.), melt mass flow rate: 25g/10min (test temperature: 230 ℃ C., load: 2.16 kg).
(2) Liquid repellent layer
(B) Hydrophobic inorganic fine particles: hydrophobic silica "AEROSIL R812S" (manufactured by gaindonggsi corporation), average primary particle diameter: 7nm, trimethylsilyl modification.
(C) Hydrophobic inorganic fine particles: hydrophobic silica "AEROSIL R8200" (manufactured by degussa corporation, n.), average primary particle diameter: 12nm, trimethylsilyl modification.
(D) Hydrophobic inorganic fine particles: hydrophobic silica "AEROSIL NAX 50" (manufactured by allicel corporation, japan), average primary particle diameter: 30nm, trimethylsilyl modification.
(E) Binder resin: olefin copolymer "AQUATEX AC-3100" (manufactured by Japan paint resins Co., Ltd.), ethylene-methacrylic acid copolymer resin.
(F) Binder resin: fluorine copolymer "Asahiguard AG-E550D" (manufactured by Asahi glass Co., Ltd.), (meth) acrylate-based fluorine copolymer resin.
Evaluation methods for various properties of the resin sheet produced in examples and the like are as follows.
(1) Observation of convex shape
The height of the convex shape and the distance between the apexes of the convex shape were measured by a laser microscope VK-X100 (manufactured by Kenzhi). In addition, in order to measure the height of the convex shape and the distance between the apexes, a sample of the convex shape cross section was produced using a microtome. The height of the convex shape was measured from any 3 positions of the resin sheet, 10 heights of the same shape were measured, and the arithmetic average of the 30 measured values was used. When the number of the convex shapes is 2 or more, the heights of the 1 st convex shape and the 2 nd convex shape are determined by the same method. For the vertex intervals, 10 vertex intervals of adjacent convex shapes were measured from any 3 positions of the resin sheet, and the arithmetic mean of 30 measured values thereof was used. When the number of the convex shapes is 2 or more, the distance between the 1 st convex shape and the 2 nd convex shape is measured, and the arithmetic average of 30 measured values thereof is used.
(2) Contact angle and roll off angle
The contact angle and the roll off angle of the resin sheet were measured by using an automatic contact angle meter DM-501 (manufactured by kyowa interface science). The test solution used was pure honey (manufactured by Nissan Honey Co., Ltd.) and tomato paste (manufactured by Koguo Meiji Co., Ltd. (カゴメ Co., Ltd.), and the amount of the solution added was 8. mu.L in the contact angle measurement and 20. mu.L in the roll angle measurement. When the contact angle is 130 ° or more, it can be judged that the liquid repellency is high, and the adhesion of the liquid can be prevented. Further, if the roll-off angle is 40 ° or less, it can be determined that the liquid repellency is high, and the adhesion of the liquid can be prevented.
(3) Pressure test
The test liquid 1g was placed on a resin sheet, and a cylindrical polypropylene case (hereinafter referred to as a cylindrical case) was further placed on the liquid to perform a pressure test. The cylinder shell has a diameter of 32mm, a weight of 70g and a pressure of 866Pa applied to the liquid. After pressurization, the residual liquid adhering to the resin sheet when the cylindrical case was removed was evaluated visually on a 5-scale with a state of no adhesion at all being "5" and a state of maximum adhesion being "1", as shown in fig. 8. In the 5-level evaluation, if the evaluation is "4" or more, it is determined that adhesion is suppressed.
< example 1 (layer Structure of FIG. 1) >
A1-stage 65mm single-screw extruder was used to extrude a resin sheet by the T die method. The extruded sheet was cast by a transfer roller and a contact roller having a surface provided with a convex-concave shape by a laser engraving method, thereby obtaining a resin sheet having a convex-shaped layer having a convex shape provided on the surface.
Then, in order to form a liquid-repellent layer on the surface of the convex-shaped layer, a dispersion (a mixture of purified water and isopropyl alcohol as solvents) was prepared by mixing hydrophobic silica and a binder resin at a composition ratio of 90 mass% of hydrophobic silica and 10 mass% of binder resin in the liquid-repellent layer. The mixed dispersion was applied to the surface of the convex layer using a bar coater, and dried at 90 ℃ to form a liquid repellent layer.
< examples 2 to 8 and comparative examples 1 to 5>
Resin sheets according to examples 2 to 8 and comparative examples 1 to 5 were produced and evaluated in the same manner as in example 1, except that the composition of the liquid-repellent layer, the presence of the liquid-repellent layer, and the presence of the convex shape were set as shown in table 1. The composition of the liquid repellent layer is shown in table 1, and the results are shown in table 2.
In comparative examples 1 to 3, the content of silica fine particles and the content of the binder resin in the liquid repellent layer were changed, and the liquid repellent layer was not formed in comparative example 4, and the convex shape was not provided in comparative example 5.
[ Table 1]
[ Table 2]
The following can be understood from the results shown in table 2.
With respect to the liquid repellency (contact angle, roll off angle, pressure test) of each liquid on the sheet, the results of the contact angle of 130 ° or more, the roll off angle of 40 ° or less, and the pressure test of 4 or more were obtained for all of examples 1 to 8. In contrast, in comparative example 1, the liquid repellent layer peeled off in the pressurization test, and the formed liquid repellent layer could not be maintained. In comparative example 2, the contact angle was 130 ° or more and the roll-off angle was 40 ° or less, but the contact angle was 3 or less in the pressure test. In comparative example 3, the contact angle was 130 ° or more, but the roll-off angle was 40 ° or more, and was 2 or less in the pressure test. In comparative examples 4 and 5, no effect was obtained with respect to any of the contact angle, the roll off angle, and the press test.
Although the present invention has been described above by using various embodiments, it is needless to say that the technical scope of the present invention is not limited to the scope described in the above embodiments. It will be apparent to those skilled in the art that various changes and modifications can be made in the above embodiments. The present invention is not limited to the above embodiments, and various modifications and improvements can be made without departing from the scope of the present invention.
Description of the reference numerals
1a convex shape; 1b convex apex; 1c the 1 st lobe apex; 1d 2 nd lobe apex; h convex height; t convex shape vertex interval; 2, liquid repellent layer; 3a sealant resin layer; 3a 1 st sealant resin layer; 3b a 2 nd sealant resin layer; 4 a base material layer; 5 oxygen barrier substrate layer.
Claims (53)
1. A liquid-repellent resin sheet, wherein,
the liquid repellent layer comprises a convex layer having at least 1 fine convex shape and containing a thermoplastic resin composition, and a liquid repellent layer containing hydrophobic inorganic fine particles and a binder resin on the convex surface of the convex layer,
the content of the hydrophobic inorganic fine particles in the liquid-repellent layer is more than 80% by mass and not more than 95% by mass, and the content of the binder resin is not less than 5% by mass and not more than 20% by mass.
2. The liquid-repellent resin sheet according to claim 1,
which has liquid repellency to aqueous liquids containing sugars.
3. The liquid-repellent resin sheet according to claim 1,
the thermoplastic resin composition has a melt mass flow rate of 5g/10min or more at 230 ℃.
4. The liquid-repellent resin sheet according to claim 2,
the thermoplastic resin composition has a melt mass flow rate of 5g/10min or more at 230 ℃.
5. The liquid-repellent resin sheet according to claim 1,
the thermoplastic resin composition contains a polyolefin resin composition.
6. The liquid-repellent resin sheet according to claim 2,
the thermoplastic resin composition contains a polyolefin resin composition.
7. The liquid-repellent resin sheet according to claim 3,
the thermoplastic resin composition contains a polyolefin resin composition.
8. The liquid-repellent resin sheet according to claim 4,
the thermoplastic resin composition contains a polyolefin resin composition.
9. The liquid-repellent resin sheet according to claim 5,
the polyolefin resin composition contains 35 to 100 mass% of a polyolefin resin.
10. The liquid-repellent resin sheet according to claim 6,
the polyolefin resin composition contains 35 to 100 mass% of a polyolefin resin.
11. The liquid-repellent resin sheet according to claim 7,
the polyolefin resin composition contains 35 to 100 mass% of a polyolefin resin.
12. The liquid-repellent resin sheet according to claim 8,
the polyolefin resin composition contains 35 to 100 mass% of a polyolefin resin.
13. The liquid-repellent resin sheet according to any one of claims 1 to 12,
the hydrophobic inorganic fine particles are hydrophobic silica fine particles having a trimethylsilyl group on the surface.
14. The liquid-repellent resin sheet according to any one of claims 1 to 12,
the hydrophobic inorganic fine particles have an average primary particle diameter of 5nm to 1000 nm.
15. The liquid repellent resin sheet according to claim 13,
the hydrophobic inorganic fine particles have an average primary particle diameter of 5nm to 1000 nm.
16. The liquid-repellent resin sheet according to any one of claims 1 to 12 and 15,
the binder resin contains 1 or more resins selected from olefin copolymers and fluorine copolymers.
17. The liquid repellent resin sheet according to claim 13,
the binder resin contains 1 or more resins selected from olefin copolymers and fluorine copolymers.
18. The liquid repellent resin sheet according to claim 14,
the binder resin contains 1 or more resins selected from olefin copolymers and fluorine copolymers.
19. The liquid-repellent resin sheet according to any one of claims 1 to 12, 15 and 17 to 18,
the convex shape is composed of a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are respectively 20 mu m to 150 mu m, and the distance between the vertexes of the adjacent convex shapes is 20 mu m to 100 mu m.
20. The liquid repellent resin sheet according to claim 13,
the convex shape is composed of a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are respectively 20 mu m to 150 mu m, and the distance between the vertexes of the adjacent convex shapes is 20 mu m to 100 mu m.
21. The liquid repellent resin sheet according to claim 14,
the convex shape is composed of a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are respectively 20 mu m to 150 mu m, and the distance between the vertexes of the adjacent convex shapes is 20 mu m to 100 mu m.
22. The liquid repellent resin sheet according to claim 16,
the convex shape is composed of a 1 st convex shape and a 2 nd convex shape, the height of the 1 st convex shape and the height of the 2 nd convex shape are respectively 20 mu m to 150 mu m, and the distance between the vertexes of the adjacent convex shapes is 20 mu m to 100 mu m.
23. The liquid-repellent resin sheet according to any one of claims 1 to 12, 15, 17 to 18, and 20 to 22,
the thickness of the convex layer is 50-200 μm.
24. The liquid repellent resin sheet according to claim 13,
the thickness of the convex layer is 50-200 μm.
25. The liquid repellent resin sheet according to claim 14,
the thickness of the convex layer is 50-200 μm.
26. The liquid repellent resin sheet according to claim 16,
the thickness of the convex layer is 50-200 μm.
27. The liquid repellent resin sheet according to claim 19,
the thickness of the convex layer is 50-200 μm.
28. The liquid-repellent resin sheet according to any one of claims 1 to 12, 15, 17 to 18, 20 to 22, and 24 to 27,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
29. The liquid repellent resin sheet according to claim 13,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
30. The liquid repellent resin sheet according to claim 14,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
31. The liquid repellent resin sheet according to claim 16,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
32. The liquid repellent resin sheet according to claim 19,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
33. The liquid repellent resin sheet according to claim 23,
the surface having the liquid-repellent layer has a contact angle of 130 DEG or more and a roll-off angle of 40 DEG or less when it is contacted with a liquid containing a saccharide.
34. The liquid-repellent resin sheet according to any one of claims 1 to 12, 15, 17 to 18, 20 to 22, 24 to 27, and 29 to 33,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
35. The liquid repellent resin sheet according to claim 13,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
36. The liquid repellent resin sheet according to claim 14,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
37. The liquid repellent resin sheet according to claim 16,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
38. The liquid repellent resin sheet according to claim 19,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
39. The liquid repellent resin sheet according to claim 23,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
40. The liquid repellent resin sheet according to claim 28,
on the surface of the convex-shaped layer, liquid repellency was maintained even if a pressure of 866Pa was applied from the liquid.
41. The liquid-repellent resin sheet according to any one of claims 1 to 12, 15, 17 to 18, 20 to 22, 24 to 27, 29 to 33, and 35 to 40,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
42. The liquid repellent resin sheet according to claim 13,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
43. The liquid repellent resin sheet according to claim 14,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
44. The liquid repellent resin sheet according to claim 16,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
45. The liquid repellent resin sheet according to claim 19,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
46. The liquid repellent resin sheet according to claim 23,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
47. The liquid repellent resin sheet according to claim 28,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
48. The liquid repellent resin sheet according to claim 34,
and a base material layer comprising 1 or more layers laminated on the other surface of the convex layer having the convex surface, wherein the base material layer comprises 1 or more resins selected from styrene resins, olefin resins, polyester resins, nylon resins, ethylene-vinyl alcohol copolymer resins, and acrylic resins.
49. The liquid repellent resin sheet according to claim 41,
and a sealant resin layer formed between the convex layer and the base material layer, wherein the sealant resin layer contains at least 1 resin selected from a modified olefin polymer resin and a thermoplastic elastomer.
50. The liquid-repellent resin sheet according to any one of claims 42 to 48,
and a sealant resin layer formed between the convex layer and the base material layer, wherein the sealant resin layer contains at least 1 resin selected from a modified olefin polymer resin and a thermoplastic elastomer.
51. An article of manufacture, wherein,
a liquid-repellent resin sheet according to any one of claims 1 to 50.
52. The article of claim 51, wherein,
it is a daily product, a packaging material or a building material.
53. The article of claim 52, wherein,
it is a component of food container, bag, raincoat, umbrella, wallpaper or water place.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016050225 | 2016-03-14 | ||
| JP2016-050225 | 2016-03-14 | ||
| PCT/JP2017/010114 WO2017159654A1 (en) | 2016-03-14 | 2017-03-14 | Liquid-repellent resin sheet and article using same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108883596A CN108883596A (en) | 2018-11-23 |
| CN108883596B true CN108883596B (en) | 2021-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780016423.4A Active CN108883596B (en) | 2016-03-14 | 2017-03-14 | Liquid-repellent resin sheet and article using same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6941597B2 (en) |
| CN (1) | CN108883596B (en) |
| TW (1) | TW201800224A (en) |
| WO (1) | WO2017159654A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2019073331A (en) * | 2017-10-19 | 2019-05-16 | 住友ベークライト株式会社 | Packing material and packing body |
| KR102374818B1 (en) * | 2017-11-28 | 2022-03-15 | 주식회사 엘지에너지솔루션 | Laminate Sheet with Modified Internal Surface and Pouch-Type Battery Comprising the Same |
| EP4324871A3 (en) * | 2018-06-20 | 2024-05-01 | Toppan Printing Co., Ltd. | Liquid-repellent structure, production method thereof, wrapping material, and separation sheet |
| US20210300651A1 (en) * | 2018-08-03 | 2021-09-30 | Cryovac, Llc | Super-hydrophobic thermoplastic films for packaging and packages made therefrom |
| KR20210061993A (en) * | 2018-09-21 | 2021-05-28 | 도판 인사츠 가부시키가이샤 | Resin composition for liquid-repellent layer formation, and liquid-repellent film, liquid-repellent laminate, packaging material, and container using the same |
| JP7452416B2 (en) * | 2019-03-07 | 2024-03-19 | 東洋紡株式会社 | laminated film |
| CN115244114A (en) * | 2020-03-12 | 2022-10-25 | 凸版印刷株式会社 | Liquid-repellent structure, method for producing liquid-repellent structure, coating liquid for forming liquid-repellent layer, and packaging material |
| EP4119604A4 (en) * | 2020-03-12 | 2023-08-30 | Toppan Inc. | Liquid-repellant structure, production method for liquid-repellant structure, coating liquid for liquid-repellant layer formation, and packaging material |
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- 2017-03-14 CN CN201780016423.4A patent/CN108883596B/en active Active
- 2017-03-14 TW TW106108362A patent/TW201800224A/en unknown
- 2017-03-14 WO PCT/JP2017/010114 patent/WO2017159654A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6941597B2 (en) | 2021-09-29 |
| TW201800224A (en) | 2018-01-01 |
| JPWO2017159654A1 (en) | 2019-01-17 |
| CN108883596A (en) | 2018-11-23 |
| WO2017159654A1 (en) | 2017-09-21 |
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