JP5522777B2 - Anti-fogging propylene resin sheet - Google Patents
Anti-fogging propylene resin sheet Download PDFInfo
- Publication number
- JP5522777B2 JP5522777B2 JP2009237123A JP2009237123A JP5522777B2 JP 5522777 B2 JP5522777 B2 JP 5522777B2 JP 2009237123 A JP2009237123 A JP 2009237123A JP 2009237123 A JP2009237123 A JP 2009237123A JP 5522777 B2 JP5522777 B2 JP 5522777B2
- Authority
- JP
- Japan
- Prior art keywords
- propylene
- sheet
- based resin
- antifogging
- resin sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 title claims description 116
- 239000011347 resin Substances 0.000 title claims description 116
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 104
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 102
- 239000003795 chemical substances by application Substances 0.000 claims description 57
- 239000002667 nucleating agent Substances 0.000 claims description 37
- -1 sucrose fatty acid ester Chemical class 0.000 claims description 31
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 25
- 229930195729 fatty acid Natural products 0.000 claims description 25
- 239000000194 fatty acid Substances 0.000 claims description 25
- 235000021588 free fatty acids Nutrition 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 15
- 150000004665 fatty acids Chemical class 0.000 claims description 13
- 229930006000 Sucrose Natural products 0.000 claims description 11
- 239000005720 sucrose Substances 0.000 claims description 11
- 238000002845 discoloration Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004711 α-olefin Substances 0.000 claims description 8
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000000047 product Substances 0.000 description 42
- 238000000576 coating method Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 229920001155 polypropylene Polymers 0.000 description 15
- 239000004743 Polypropylene Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- 235000019645 odor Nutrition 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 235000013305 food Nutrition 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000008188 pellet Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 10
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- 239000000243 solution Substances 0.000 description 8
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- 238000011156 evaluation Methods 0.000 description 7
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- 235000021314 Palmitic acid Nutrition 0.000 description 5
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
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- PIYNPBVOTLQBTC-UHFFFAOYSA-N 1-[8-propyl-2,6-bis(4-propylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound O1C2C(CCC)OC(C=3C=CC(CCC)=CC=3)OC2C(C(O)CO)OC1C1=CC=C(CCC)C=C1 PIYNPBVOTLQBTC-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000003851 corona treatment Methods 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
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- 239000000706 filtrate Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 4
- 238000003856 thermoforming Methods 0.000 description 4
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- 235000021360 Myristic acid Nutrition 0.000 description 3
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 3
- GCSPRLPXTPMSTL-IBDNADADSA-N [(2s,3r,4s,5s,6r)-2-[(2s,3s,4s,5r)-3,4-dihydroxy-2,5-bis(hydroxymethyl)oxolan-2-yl]-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[C@@]1([C@]2(CO)[C@H]([C@H](O)[C@@H](CO)O2)O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O GCSPRLPXTPMSTL-IBDNADADSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052901 montmorillonite Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- DCAFJGSRSBLEPX-UHFFFAOYSA-N tris(2,3-dibutylphenyl) phosphite Chemical compound CCCCC1=CC=CC(OP(OC=2C(=C(CCCC)C=CC=2)CCCC)OC=2C(=C(CCCC)C=CC=2)CCCC)=C1CCCC DCAFJGSRSBLEPX-UHFFFAOYSA-N 0.000 description 2
- 238000007666 vacuum forming Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NZNCZGXUHYDOQG-UHFFFAOYSA-N 2-(3,5-ditert-butylphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1 NZNCZGXUHYDOQG-UHFFFAOYSA-N 0.000 description 1
- YHEYEPDRELFHFM-UHFFFAOYSA-N 2-methyl-2-phenylhexanoic acid Chemical compound CCCCC(C)(C(O)=O)C1=CC=CC=C1 YHEYEPDRELFHFM-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
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- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920003355 Novatec® Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
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- 238000010828 elution Methods 0.000 description 1
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- 235000013373 food additive Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
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- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 description 1
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- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical class [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Chemical class 0.000 description 1
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- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
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- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、防曇性、透明性に優れたプロピレン系樹脂シートに関し、さらに詳しくは、透明性と防曇性に優れ、かつ再生使用しても変色や臭気の少ない防曇性プロピレン系樹脂シートに関する。 The present invention relates to a propylene resin sheet having excellent antifogging properties and transparency, and more specifically, an antifogging propylene resin sheet having excellent transparency and antifogging properties and less discoloration and odor even when recycled. About.
透明性に優れている非結晶性の熱可塑性樹脂であるポリスチレン、ポリ塩化ビニール、ポリエチレンテレフタレート等は、内容物を見分けることが可能であるため、シート状に加工され、さらに熱成形によって食品の容器や蓋材として広く活用されている。
しかし、これらの非結晶性樹脂は、近年電子レンジ加熱食品の増加に伴い、耐熱不良や耐衝撃不良等で容器や蓋が変形したり、割れたりして問題があり、容器や蓋製造業者からは透明で防曇性が有り、しかも耐熱性や耐衝撃性のある材料が望まれていた。
一方、結晶性のポリプロピレン系樹脂シートは、耐熱性や耐衝撃性には強いが透明性が劣り、その表面が極めて疎水性であるため、容器や蓋材として使用した場合、内容物の水蒸気が表面に微小水滴として付着し、内容物を見分けることが困難であると言う防曇性の問題があった。
Polystyrene, polyvinyl chloride, polyethylene terephthalate, etc., which are non-crystalline thermoplastic resins with excellent transparency, can be distinguished from each other, so they are processed into sheets, and food containers are formed by thermoforming. It is widely used as a cover material.
However, these non-crystalline resins have a problem in that the containers and lids are deformed or cracked due to poor heat resistance and shock resistance, etc. in recent years due to the increase in foods heated in microwave ovens. The material has been desired to be transparent, antifogging, heat resistant and impact resistant.
On the other hand, a crystalline polypropylene resin sheet is strong in heat resistance and impact resistance but poor in transparency, and its surface is extremely hydrophobic. There was a problem of anti-fogging property that it adhered to the surface as fine water droplets and it was difficult to distinguish the contents.
ポリプロピレン系樹脂シートの透明性は、シート加工時に鏡面加工を施された金属ロールや金属ベルトで急速に冷却固化させるといった方法、さらにプロピレンとα−オレフィンとの共重合を行って結晶性を低下させたポリプロピレン系樹脂を用いる方法、さらにポリプロピレン系樹脂に核剤を添加する方法等（特許文献１）で、実用レベルの透明性まで改良がされてきた。 The transparency of the polypropylene resin sheet reduces crystallinity by rapidly cooling and solidifying with a metal roll or metal belt that has been mirror-finished during sheet processing, and by copolymerizing propylene and α-olefin. In addition, a method using a polypropylene resin, a method of adding a nucleating agent to a polypropylene resin, etc. (Patent Document 1) have been improved to a practical level of transparency.
一方、ポリプロピレン系樹脂シートの防曇性は、シート加工時にそのライン上でポリプロピレン系樹脂を冷却固化した後、コロナ処理、プラズマ処理、フレーム処理等を施すことによって疎水性を改良し、液体状の防曇剤を塗布しながら乾燥してシートを巻き取る方法（特許文献２、特許文献３、特許文献４等）で、防曇性を付与できるようになってきた。 On the other hand, the antifogging property of the polypropylene resin sheet improves the hydrophobicity by cooling and solidifying the polypropylene resin on the line at the time of sheet processing, and then applying corona treatment, plasma treatment, flame treatment, etc. It has become possible to impart antifogging properties by a method (Patent Document 2, Patent Document 3, Patent Document 4, etc.) of winding and drying a sheet while applying an antifogging agent.
ところが、近年、経済性や環境保護の観点から、資源の再利用が積極的に進められるようになってきた。食品の容器や蓋材等も例外ではなく、防曇剤を塗布したシートや製品であっても再生使用が求められるようになってきた。
特に、シートから熱成形で容器や蓋材を生産すると、どうしても容器や蓋材製品を打ち抜いた後のシートロス部分が発生する。さらに、容器や蓋材製品を回収して再生使用することも求められることになる。
シートや製品の再生使用にあたっては、シートや製品を粉砕してバージン原料と混合し、シート成形機にかける方法や、シートや製品を粉砕したあと、押出機にて溶融混練してペレット（粒）状に加工してバージン原料と混合し、シート成形機にかける方法が行われる。
この場合、再生使用の割合にもよるが、押出機にて溶融混練してペレット（粒）状に加工した方が、原料の嵩密度が安定するために、シート成形加工が安定する。
However, in recent years, the reuse of resources has been actively promoted from the viewpoint of economic efficiency and environmental protection. Food containers and lids are no exception, and sheets and products coated with an antifogging agent have been required to be recycled.
In particular, when a container or a lid material is produced from a sheet by thermoforming, a sheet loss portion is inevitably generated after the container or lid material is punched out. Furthermore, it is also required to collect and recycle containers and lid products.
When reusing sheets and products, the sheets and products are pulverized and mixed with virgin raw materials, and then applied to a sheet molding machine. After pulverizing the sheets and products, they are melt-kneaded in an extruder and pellets (grains) The sheet is processed into a shape, mixed with the virgin raw material, and applied to a sheet forming machine.
In this case, although depending on the ratio of recycle use, the sheet forming process is more stable when the raw material is melt kneaded and processed into pellets (grains) because the bulk density of the raw material is more stable.
この際、防曇剤が塗布されたポリプロピレン系樹脂シートやそれを用いて得た製品を粉砕してシート成形すると著しい茶褐色に変色して臭気が激しくなることが判明した。特に、嵩密度の安定のために、シートや製品の粉砕品を押出機にて溶融混練してペレット（粒）状に加工すると、さらに激しい変色、臭気が発生することが明らかになってきた。 At this time, it was found that when a polypropylene resin sheet coated with an antifogging agent or a product obtained using the same was pulverized to form a sheet, the color changed to marked brown and the odor became intense. In particular, in order to stabilize the bulk density, it has become clear that when a pulverized sheet or product is melt-kneaded with an extruder and processed into pellets (grains), further severe discoloration and odor are generated.
このように、非結晶性樹脂の有する欠点である耐熱不良や耐衝撃不良等で容器や蓋が変形したり、割れたりするという問題を解決するために用いるポリプロピレン系樹脂シートを、防曇性の要求される容器や蓋材として効率よく使用するためには、この欠点を改良する必要があったが、未だ実現されず、その開発が希求されている。 Thus, the polypropylene resin sheet used for solving the problem that the container and the lid are deformed or cracked due to the heat resistance failure and the impact resistance failure which are the disadvantages of the amorphous resin, In order to use it efficiently as a required container or lid, it was necessary to improve this drawback, but it has not been realized yet and its development is desired.
本発明の目的は、上記従来技術の問題点に鑑み、透明性と防曇性に優れ、かつ再生使用しても変色や臭気の少ない防曇性プロピレン系樹脂シートを提供することにある。 An object of the present invention is to provide an anti-fogging propylene-based resin sheet that is excellent in transparency and anti-fogging properties and has little discoloration and odor even when recycled.
本発明者らは、上記課題を解決すべく鋭意検討した結果、特定のプロピレン系樹脂に特定の造核剤を特定の割合で配合してなるプロピレン系樹脂組成物を用いて形成された特定のプロピレン系樹脂シートの少なくとも片面に、特定の防曇剤を特定の塗布量で塗布したところ、透明性と防曇性を維持しながら再生使用しても変色の少ない防曇性プロピレン系樹脂シートが得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific propylene resin composition is formed by using a specific propylene resin and a specific nucleating agent blended in a specific ratio. When a specific anti-fogging agent is applied to at least one side of the propylene-based resin sheet at a specific application amount, an anti-fogging propylene-based resin sheet that is less discolored even when recycled is used while maintaining transparency and anti-fogging properties. As a result, the present invention was completed.
すなわち、本発明の第１の発明によれば、厚みが０．１〜２ｍｍのプロピレン系樹脂シートの少なくとも片面に、固形分量で０．０２〜２ｇ／ｍ２の炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルからなる防曇剤を塗布してなる、再生使用しても変色や臭気の少ないプロピレン系樹脂シートであって、上記プロピレン系樹脂シートは、ＭＦＲが０．２〜３０ｇ／１０分のプロピレン系樹脂１００重量部に対し、下記の一般式（１）で表される造核剤０．０１〜０．５重量部の割合で配合してなるプロピレン系樹脂組成物から形成され、かつ炭素数６〜２２の遊離脂肪酸の含有量が５０ｐｐｍ以下であることを特徴とする防曇性プロピレン系樹脂シートが提供される。 That is, according to the first invention of the present invention, at least one surface of a propylene-based resin sheet having a thickness of 0.1 to 2 mm is made of 0.02 to 2 g / m 2 of a fatty acid having 6 to 22 carbon atoms having a solid content of 0.02 to 2 g / m 2 . A propylene-based resin sheet that is coated with a defogging agent composed of a sucrose fatty acid ester and has little discoloration and odor even when reused. The propylene-based resin sheet has an MFR of 0.2 to 30 g / 10 min. It is formed from a propylene-based resin composition formed by blending 0.01 to 0.5 parts by weight of a nucleating agent represented by the following general formula (1) with respect to 100 parts by weight of a propylene-based resin, and carbon. The content of the free fatty acid of several 6-22 is 50 ppm or less, The antifogging propylene-type resin sheet characterized by the above-mentioned is provided.
［但し、式中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６は、炭素数が１〜２０のアルキル基である。］
[In the formula, n is an integer of 0 to 2, and R 1 to R 5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group. A group, a halogen group and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms. ]
また、本発明の第２の発明によれば、第１の発明において、前記プロピレン系樹脂が、プロピレン含量１００〜９０重量％とα−オレフィン含量０〜１０重量％とのランダム共重合体であることを特徴とする防曇性プロピレン系樹脂シートが提供される。 According to the second invention of the present invention, in the first invention, the propylene-based resin is a random copolymer having a propylene content of 100 to 90% by weight and an α-olefin content of 0 to 10% by weight. An antifogging propylene-based resin sheet is provided.
また、本発明の第３の発明によれば、第２の発明において、α−オレフィンが、エチレンであることを特徴とする防曇性プロピレン系樹脂シートが提供される。 According to a third aspect of the present invention, there is provided an antifogging propylene-based resin sheet characterized in that in the second aspect, the α-olefin is ethylene.
また、本発明の第４の発明によれば、第１〜３のいずれかの発明において、０．３５ｍｍ厚シートのヘイズ値（ＨＡＺＥ値）が１０以下であることを特徴とする防曇性プロピレン系樹脂シートが提供される。
本発明の第５の発明によれば、第１発明の防曇性プロピレン系樹脂シートを再生してなる再生樹脂とプロピレン系樹脂とを含む再生プロピレン系樹脂組成物からなるプロピレン系樹脂シートが提供される。
本発明の第６の発明によれば、炭素数６〜２２の遊離脂肪酸の含有量が５０ｐｐｍ以下であることを特徴とする再生プロピレン系樹脂組成物からなるプロピレン系樹脂シートが提供される。
According to a fourth invention of the present invention, in any one of the first to third inventions, the haze value (HAZE value) of the 0.35 mm thick sheet is 10 or less, and the antifogging propylene A resin sheet is provided.
According to a fifth aspect of the present invention, there is provided a propylene-based resin sheet comprising a recycled propylene-based resin composition comprising a recycled resin obtained by regenerating the antifogging propylene-based resin sheet of the first invention and a propylene-based resin. Is done.
According to a sixth aspect of the present invention, there is provided a propylene-based resin sheet comprising a regenerated propylene-based resin composition, wherein the content of free fatty acids having 6 to 22 carbon atoms is 50 ppm or less.
本発明によれば、透明性と防曇性に優れ、かつ再生使用しても変色の少ない防曇性プロピレン系樹脂シートを提供することができる。そしてこれらのシートは、経済性、環境性に優れ、食品日用品の包装や医療電子部品の分野に好適に使用することができる。
このシートおよび成形品は、内容物の温度変化、室内環境の温度、湿度の変化、気候、季節、温度、湿度の変化があっても、それに対応しても、適正な透明性および防曇性などを維持する製品を提供できる。
According to the present invention, it is possible to provide an anti-fogging propylene-based resin sheet that is excellent in transparency and anti-fogging property and has little discoloration even when recycled. These sheets are excellent in economic efficiency and environmental friendliness, and can be suitably used in the fields of food daily necessities packaging and medical electronic parts.
This sheet and molded product have appropriate transparency and anti-fogging properties regardless of changes in the temperature of the contents, temperature in the indoor environment, changes in humidity, climate, seasons, temperature and humidity. We can provide products that maintain the above.
本発明は、上記したように、特定のプロピレン系樹脂シートの少なくとも片面に、特定の防曇剤を塗布してなる再生使用しても変色の少ない防曇性プロピレン系樹脂シートである。
以下、本発明の防曇性プロピレン系樹脂シートを形成する組成物の構成成分やその製造方法、防曇剤、さらにはそれらを用いた防曇性プロピレン系樹脂シートの製造方法等について詳細に説明する。
As described above, the present invention is an anti-fogging propylene resin sheet that is less discolored even when recycled by coating a specific anti-fogging agent on at least one surface of the specific propylene resin sheet.
Hereinafter, the constituents of the composition forming the antifogging propylene resin sheet of the present invention, the production method thereof, the antifogging agent, and the production method of the antifogging propylene resin sheet using them will be described in detail. To do.
造核剤の使用による価格の高騰、成形加工時の臭気の発生、温度などの加工条件の制御、さらには特に食品、医療材料のような容器、トレー、パック、ボトルなどの成形品から造核剤の溶出による安全性、衛生性という点も考慮しなければならない。しかし、一方で、造核剤による透明性、剛性などを高める為には、少なくとも所定の量を添加する必要がある。そこで、公知の造核剤として、例えばソルビトール系、リン酸金属塩、カルボン酸金属塩、安息香酸ナトリウム、ロジンの金属塩などの各種公知の優れた造核剤のうち、ＭＦＲが０．２〜３０ｇ／１０分のプロピレン系樹脂において、それを厚さ０．１〜２ｍｍのシートにした場合に、シートの厚さに適合した透明性、ブリードアウト、価格、再生性、二次加工などにおいて、その造核剤の性能を維持して、シートの真空成形、エンボス加工、加圧成形などの二次加工に耐えられる合理的な造核剤を鋭意検討した結果、一般式（１）の造核剤をポリプロピレン系樹脂１００重量部に対して、０．０１〜０．５重量部という最小限の添加量にすれば、一応造核剤の優れた機能を維持することができるので、プロピレン系樹脂シートの透明性、剛性、熱変形温度および曲げ弾性率の向上などが一応達成できるということ、および塗布した防曇剤とも適合するという最良の形態を知見したものである。 Increased price due to the use of nucleating agents, generation of odors during molding, control of processing conditions such as temperature, and nucleation from molded products such as containers, trays, packs, bottles, especially food and medical materials Consideration must also be given to the safety and hygiene due to elution of the agent. However, on the other hand, it is necessary to add at least a predetermined amount in order to improve transparency, rigidity, and the like by the nucleating agent. Therefore, as a known nucleating agent, for example, among various known excellent nucleating agents such as sorbitol, metal phosphate, metal carboxylate, sodium benzoate, metal salt of rosin, MFR is 0.2 to In a propylene-based resin of 30 g / 10 min, when it is made into a sheet having a thickness of 0.1 to 2 mm, in transparency, bleed out, price, reproducibility, secondary processing, etc. suitable for the thickness of the sheet, As a result of earnest examination of a rational nucleating agent that can withstand the secondary processing such as vacuum forming, embossing and pressure forming of the sheet while maintaining the performance of the nucleating agent, the nucleation of the general formula (1) If the additive is made a minimum addition amount of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the polypropylene resin, the excellent function of the nucleating agent can be maintained. Sheet transparency, stiffness , The fact that such improvement in heat distortion temperature and flexural modulus tentatively be achieved, and both coated anti-fogging agent is obtained by finding the best mode of being compatible.
プロピレン系樹脂シートの透明性、剛性などは内部添加剤である造核剤により達成できるが、そのシートまたはその成形品として使用する際の、環境、例えば、室内の環境または内容物の温度および湿度条件の違いにおいて使用する場合に、或いは季節などにおける気候条件の違いに基づいて使用する場合に留意しなければならないことは、シートおよび成形品の透明性などが、水蒸気、曇、水滴という外部的な環境要因により、せっかくに造核剤により改良された透明性が曇ることによって無意味となることもあり、その対策が必要である。このように本発明は、そのシートおよび成形品の透明性などを、内部型の特定の造核剤の添加により改良するというプロピレン系樹脂の本質的に材料面からと、主に外部環境からの影響に配慮して透明性を維持するという塗布による外部型の特定の防曇剤を組み合わせるという材料兼構造の面から、全環境対応型の透明性を有する防曇性プロピレン系樹脂シートを提供できたものである。 The transparency and rigidity of the propylene-based resin sheet can be achieved by a nucleating agent that is an internal additive, but the environment, for example, the indoor environment or the temperature and humidity of the contents when used as the sheet or its molded product. When used in different conditions or based on differences in climatic conditions such as the seasons, it is important to note that the transparency of sheets and molded products is an external factor such as water vapor, cloudiness, and water droplets. Due to various environmental factors, the transparency improved by the nucleating agent may become meaningless due to clouding, and countermeasures are necessary. As described above, the present invention improves the transparency of the sheet and the molded product by the addition of a specific nucleating agent of the internal mold, essentially from the material aspect of the propylene resin, and mainly from the external environment. We can provide an anti-fogging propylene resin sheet with transparency that is environmentally friendly, in terms of material and structure by combining a specific external anti-fogging agent by coating that maintains transparency in consideration of the influence. It is a thing.
特に、外部型として防曇剤をシートや成形品に塗布されている場合に、具体的なそれの使用条件においては、例えば、水、空気、熱、温度、マイクロ波、光線、物理的または化学的な条件と直接に接触する機会が多いという、過酷な条件に曝された場合に、比較的容易に表面から流出や分解する場合もあり、さらには、防曇剤の持続性、安定性、衛生性、無毒性、安全性などを考慮して、できる限りその要件を満たす防曇剤を選定することに留意しなければならない。
その結果、一般式（１）の造核剤を含むプロピレン系樹脂シートに適合性の良い、例えば、グリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、各種界面活性剤のような、各種公知防曇剤を、技術的、安全性、衛生面などの多くの観点から検討した結果、本発明の、防曇剤として、炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルを使用することが最も有効であり、また、その塗布量は固形分量で、０．０２〜２ｇ／ｍ２であり、このエステル化合物および塗布量が、特定の防曇剤と付加的にまたは相乗的に作用して、再生利用の可能性を含む、多面的に防曇剤の持続性、衛生性、安全性の機能が長期的に安定に、安全に機能するということを知見したものである。
In particular, when an antifogging agent is applied to a sheet or a molded product as an external mold, specific use conditions thereof include, for example, water, air, heat, temperature, microwave, light, physical or chemical When exposed to harsh conditions where there are many opportunities to come into direct contact with other conditions, they may spill or decompose from the surface relatively easily. In consideration of hygiene, non-toxicity, safety, etc., it should be noted that anti-fogging agents that meet the requirements are selected as much as possible.
As a result, various known anti-fogging agents such as glycerin fatty acid ester, sorbitan fatty acid ester, various surfactants, etc., which have good compatibility with the propylene-based resin sheet containing the nucleating agent of the general formula (1) As a result of examination from many viewpoints such as health, safety, and hygiene, it is most effective to use a sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms as an antifogging agent of the present invention. The coating amount is 0.02 to 2 g / m 2 in terms of solid content, and the ester compound and the coating amount act additionally or synergistically with a specific antifogging agent to include the possibility of recycling. It has been found that the functions of anti-fogging agents in a multifaceted manner such as sustainability, hygiene and safety function stably and safely over the long term.
一方で、特定の造核剤を含み、且つ防曇剤が塗布されたプロピレン系樹脂シートは、成形、二次加工というような熱成形によりシートから容器や蓋材を生産する場合に、容器や蓋材製品を打ち抜いた後のシートのロス部分が発生するために、そのロス材料を回収して再生使用することも有り得る。さらには、製品の出荷残り、または、リスク管理の為の計画以上の過剰生産による在庫品、納品後の仕様、寸法或いは大きさなどの変更などの理由による返品、リサイクルによる回収した廃プロピレン系樹脂を再生使用するという、省資源、ＣＯ２の対策というような地球規模の課題からすれば、この再生利用の対応まで解決することが必要である。このシートや製品の再生使用にあたっては、シートや製品を粉砕してバージン原料と混合して、成形材料にすることが好ましい。再生使用した場合に、再生樹脂の品質が成形シートに多く影響する為に、再生樹脂の品質が悪いと、バージン原料の配合割合を多くしなければならず、再生樹脂の使用促進や価値を低下させるために、再生樹脂の品質を重要視しなければならない。 On the other hand, a propylene-based resin sheet containing a specific nucleating agent and coated with an antifogging agent is used when a container or a lid is produced from a sheet by thermoforming such as molding or secondary processing. Since a lost portion of the sheet after the lid product is punched is generated, the lost material may be recovered and reused. In addition, the remaining propylene-based resin recovered by recycling or recycling due to reasons such as changes in the inventory, post-delivery specifications, dimensions or size, etc., due to unmanufactured products beyond the risk management plan. From the viewpoint of global issues such as resource conservation and CO 2 countermeasures for recycling, it is necessary to solve this recycling response. When the sheet or product is recycled and used, the sheet or product is preferably pulverized and mixed with a virgin raw material to form a molding material. When recycled, the quality of the recycled resin greatly affects the molded sheet. If the quality of the recycled resin is poor, the blending ratio of the virgin raw material must be increased, reducing the use and value of the recycled resin. Therefore, the quality of the recycled resin must be emphasized.
再生利用において、鋭意検討した結果、特に残留の防曇剤である炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルが再生成形品である、再生シートの、特に色相（ＹＩ値）に大きく影響することが判明した。そして、原因物質は追及した結果、防曇剤からの、炭素数６〜２２の遊離脂肪酸であることを突き止めたものである。この遊離脂肪酸は、市販の蔗糖脂肪酸エステルに潜在的に含まれているもの、或いは、防曇剤として使用している間に、分解、遊離により発生したものを含むことが予測される。そして、再生利用する再生樹脂に含まれる炭素数６〜２２の遊離脂肪酸の含有量５０ｐｐｍ以下が再生シートの色相（ＹＩ値）の観点から許容できる範囲であり、例えば、４２ｐｐｍ、３３ｐｐｍ、２５ｐｐｍ、１８ｐｐｍ、９ｐｐｍ、３ｐｐｍと少ない傾向にあることが好ましい。この遊離脂肪酸の含有量５０ｐｐｍ以下ということは、通常は、０．０５〜３５ｐｐｍの再生樹脂を単独で使用するか、またはそれにバージン樹脂をブレンドして任意に使用するための許容できる含有量である。 As a result of diligent study in recycling, the sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms, which is a residual antifogging agent, has a great influence on the hue (YI value) of a recycled sheet, particularly a recycled molded product. There was found. As a result of pursuing, the causative substance has been found to be a free fatty acid having 6 to 22 carbon atoms from the antifogging agent. This free fatty acid is expected to include those potentially contained in commercially available sucrose fatty acid esters, or those generated by decomposition and release during use as antifogging agents. The content of free fatty acids having 6 to 22 carbon atoms contained in the recycled resin to be recycled is 50 ppm or less from the viewpoint of the hue (YI value) of the recycled sheet. For example, 42 ppm, 33 ppm, 25 ppm, 18 ppm , 9 ppm, preferably 3 ppm. This free fatty acid content of 50 ppm or less is usually an acceptable content for using 0.05 to 35 ppm of a regenerated resin alone or optionally blending it with a virgin resin. .
この、再生シートに脂肪酸の混入する直接の理由は、防曇剤である炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルの塗布量に関係して、その塗布量が多くなれば、必然的に遊離脂肪酸の含有量が単調に多くなる傾向を示す。したがって、再生樹脂の遊離脂肪酸の含有量５０ｐｐｍ以下にするためには、標準的な防曇剤である炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルの塗布量を、固形分量で０．０２〜２ｇ／ｍ２にすれば、必要とする防曇剤の効果を最大限に発揮するとともに、その廃品である再生シートからの再生樹脂の色相、臭気などの低い特性を維持しながら、再生使用することができるための許容できる範囲である。固形分量を２．５ｇ／ｍ２、５ｇ／ｍ２と単調に増加させると、再生樹脂の遊離脂肪酸の含有量５０ｐｐｍ以上になるリスクを伴う。勿論０．０１ｇ／ｍ２、０．０１５ｇ／ｍ２の領域になれば、防曇剤の効果が発現できなくなる。固形分量で０．０２〜２ｇ／ｍ２の範囲は、防曇性、色相などにおいて、安定した効果が連続的に期待される臨界性のある領域である。 The direct reason that fatty acids are mixed into the recycled sheet is related to the coating amount of sucrose fatty acid ester of fatty acid having 6 to 22 carbon atoms, which is an antifogging agent, and inevitably liberates when the coating amount increases. It shows a tendency that the fatty acid content increases monotonously. Therefore, in order to make the content of the free fatty acid in the recycled resin 50 ppm or less, the coating amount of sucrose fatty acid ester of fatty acid having 6 to 22 carbon atoms, which is a standard antifogging agent, is 0.02 to 2 g in solid content. / M 2 to maximize the effects of the required anti-fogging agent and to recycle while maintaining low properties such as hue and odor of recycled resin from recycled sheets that are waste products. This is an acceptable range for If monotonically increased solids content and 2.5g / m 2, 5g / m 2, involves a risk of more content 50ppm of free fatty acids recycled resin. Of course 0.01 g / m 2, if the area of 0.015 g / m 2, the effect of the anti-fogging agent can not be exhibited. The range of 0.02 to 2 g / m 2 in terms of solid content is a critical region where a stable effect is expected continuously in antifogging properties, hue, and the like.
再生樹脂（プロピレン系樹脂）とバージン樹脂（プロピレン系樹脂）のブレンドは、ペレットの状態で、成形時にブレンドすることが多いが、通常は、バージン樹脂１〜９９重部と再生樹脂を９９〜１重量部と、好ましくはバージン樹脂２０〜８０重量と再生樹脂８０〜２０重量部と、任煮にブレンドすることができる。そのブレンド量の加減は、再生樹脂の品質に影響されることが多く、再生樹脂が遊離脂肪酸を、例えば６０ｐｐｍというように比較的多く含むような品質の場合には、それにブレンドするバージン樹脂の量を相対的に多くすることにより、５０ｐｐｍ以下に調整することができる。 A blend of recycled resin (propylene resin) and virgin resin (propylene resin) is often in the form of pellets and blended at the time of molding. Usually, 1 to 99 parts by weight of virgin resin and 99 to 1 of recycled resin are used. By weight, preferably 20-80 parts by weight of virgin resin and 80-20 parts by weight of recycled resin can be blended in a boil. The amount of blending is often affected by the quality of the recycled resin, and if the recycled resin is of a quality that contains a relatively large amount of free fatty acid, for example, 60 ppm, the amount of virgin resin blended with it. By relatively increasing the ratio, it can be adjusted to 50 ppm or less.
具体的に、プロピレン系樹脂１００重量部にＭｉｌｌａｄ ＮＸ８０００造核剤０．３重量部、蔗糖ラウリン酸エステル（固形分塗布量０．０４ｇ／ｍ２）を塗布した仕様のシートを再生樹脂として使用する実施態様を示すと以下のとおりになる。
仕様 １ ２ ３ ４ ５ ６
バージン樹脂（重量部） ９５ ８５ ６８ ５０ ３５ ２０
再生樹脂（重量部） ５ １５ ３２ ５０ ６５ ８０
遊離脂肪酸（ＰＰＭ） １ ６ ８ １１ １６ ２２
以下に最も好ましい態様を示す。
Specifically, a sheet having specifications in which Millad NX8000 nucleating agent 0.3 parts by weight and sucrose laurate (solid content coating amount 0.04 g / m 2 ) are applied to 100 parts by weight of a propylene resin as a recycled resin. An embodiment is as follows.
Specifications 1 2 3 4 5 6
Virgin resin (parts by weight) 95 85 68 50 35 20
Recycled resin (parts by weight) 5 15 32 50 65 80
Free fatty acid (PPM) 1 6 8 11 16 22
The most preferred embodiment is shown below.
［１］構成成分
１．プロピレン系樹脂
本発明で用いられるプロピレン系樹脂のＭＦＲは、通常、０．２〜３０ｇ／１０分、好ましくは、０．３〜１５ｇ／１０分、さらに好ましくは、０．４〜１０／１０分である。ＭＦＲが上記の数値範囲を下回ると成形加工時の表面が荒れて製品の外観が損なわれ、一方、ＭＦＲが上記の数値範囲を上回ると製品の衝撃強度が低下する。
[1] Component 1 Propylene-based resin The MFR of the propylene-based resin used in the present invention is usually 0.2 to 30 g / 10 minutes, preferably 0.3 to 15 g / 10 minutes, and more preferably 0.4 to 10/10 minutes. It is. When the MFR is below the above numerical range, the surface during molding is roughened and the appearance of the product is impaired. On the other hand, when the MFR exceeds the above numerical range, the impact strength of the product is reduced.
本発明で用いられるプロピレン系樹脂は、プロピレン単独重合体でも良いが、プロピレンとα−オレフィンとのランダム或いはブロック共重合体が好ましい。これらは、それぞれ単独で用いてもよく、混合して使用しても差し支えない。
α−オレフィンとしては、エチレン、ブテン−１、ペンテン−１、ヘキセン−１、４−メチル−ペンテン−１等を用いることができる。中でもプロピレンとエチレンとのランダム共重合体が好ましい。プロピレンとエチレンとのランダム共重合体では、エチレン含量は、０．１〜１０重量％が好ましく、０．２〜５重量％がさらに好ましく、０．４〜３．５重量％が特に好ましい。エチレン含量が０．１重量％を下回ると製品の衝撃強度が損なわれ、一方、エチレン含量が１０重量％を上回ると製品の剛性が低下する。
具体的には、プロピレン−エチレン共重合体、プロピレン−ブテン−１共重合体、プロピレン−エチレン−ブテン−１共重合体、プロピレン−ペンテン−１共重合体、プロピレン−ヘキセン−１共重合体、プロピレン−４−メチル−ペンテン−１共重合体などの各種の二元または三元共重合体が挙げられる。
The propylene resin used in the present invention may be a propylene homopolymer, but is preferably a random or block copolymer of propylene and an α-olefin. These may be used alone or in combination.
As the α-olefin, ethylene, butene-1, pentene-1, hexene-1, 4-methyl-pentene-1, or the like can be used. Among these, a random copolymer of propylene and ethylene is preferable. In the random copolymer of propylene and ethylene, the ethylene content is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and particularly preferably 0.4 to 3.5% by weight. If the ethylene content is less than 0.1% by weight, the impact strength of the product is impaired. On the other hand, if the ethylene content exceeds 10% by weight, the rigidity of the product is lowered.
Specifically, a propylene-ethylene copolymer, a propylene-butene-1 copolymer, a propylene-ethylene-butene-1 copolymer, a propylene-pentene-1 copolymer, a propylene-hexene-1 copolymer, Various binary or ternary copolymers such as propylene-4-methyl-pentene-1 copolymer may be mentioned.
本発明に用いられるプロピレン系樹脂は、任意の重合法で製造することができ、スラリー法、気相法、バルク法等が使用できる。
プロピレン系樹脂は、後述の方法によって得られるもののほか市販品を使用することができる。市販品としては、例えば、チーグラー系触媒を使用した製品としては日本ポリプロ社製ノバテックＰＰ（商品名）シリーズ、メタロセン系触媒を使用した製品としては日本ポリプロ社製ウインテック（商品名）シリーズのなかから本発明の範囲に適合するものを使用することができる。
The propylene-based resin used in the present invention can be produced by any polymerization method, and a slurry method, a gas phase method, a bulk method, or the like can be used.
As the propylene-based resin, commercially available products can be used in addition to those obtained by the method described later. Examples of commercially available products include Novatec PP (trade name) series manufactured by Nippon Polypro Co., Ltd. as products using Ziegler catalysts, and Wintech (trade name) series manufactured by Nippon Polypro Co., Ltd. as products using metallocene catalysts. To those that fall within the scope of the present invention.
２．造核剤
本発明では、下記の一般式（１）で表される造核剤が用いられる。
2. Nucleating agent In the present invention, a nucleating agent represented by the following general formula (1) is used.
［但し、式中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６は、炭素数が１〜２０のアルキル基である。］
上記一般式（１）の中でも、好ましくは、ｎは０〜２の整数であり、Ｒ１、Ｒ２、Ｒ４およびＲ５は、それぞれ水素原子であり、Ｒ３およびＲ６は、同一または異なって、それぞれ炭素数が１〜２０のアルキル基であり、またさらに好ましくは、ｎは０〜２の整数であり、Ｒ１、Ｒ２、Ｒ４およびＲ５は、それぞれ水素原子であり、Ｒ３は、−ＣＨ３、−ＣＨ２ＣＨ３、−ＣＨ２ＣＨ２ＣＨ３、−ＣＨ２ＣＨ２ＣＨ２ＣＨ３、−ＣＨ２ＣＨ＝ＣＨ２、−ＣＨ（ＣＨ３）ＣＨ＝ＣＨ２、−ＣＨ２ＣＨ−Ｘ１−ＣＨ２−Ｘ２、−ＣＨ２ＣＨ−Ｘ３−ＣＨ２ＣＨ３、−ＣＨ２ＣＨ−Ｘ４−ＣＨ２ＯＨもしくは−ＣＨ２ＯＨ−ＣＨ（ＯＨ）−ＣＨ２ＯＨであり（但し、Ｘ１〜Ｘ４は、それぞれ独立したハロゲン基である。）、Ｒ６は、炭素数が１〜２０のアルキル基である。
[In the formula, n is an integer of 0 to 2, and R 1 to R 5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group. A group, a halogen group and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms. ]
Among the general formula (1), preferably, n is an integer of 0 to 2, R 1 , R 2 , R 4 and R 5 are each a hydrogen atom, and R 3 and R 6 are the same or Differently, each is an alkyl group having 1 to 20 carbon atoms, and more preferably, n is an integer of 0 to 2, and R 1 , R 2 , R 4 and R 5 are each a hydrogen atom, R 3 represents —CH 3 , —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH 2 CH 2 CH 2 CH 3 , —CH 2 CH═CH 2 , —CH (CH 3 ) CH═CH 2. , —CH 2 CH—X 1 —CH 2 —X 2 , —CH 2 CH—X 3 —CH 2 CH 3 , —CH 2 CH—X 4 —CH 2 OH or —CH 2 OH—CH (OH) — a CH 2 OH (where, X 1 to X 4 are each independently And a halogen group.), R 6 is an alkyl group having 1 to 20 carbon atoms.
本発明に用いられる造核剤は、得られる防曇性プロピレン系樹脂シートに、従来の造核剤では実現が不可能なほどの非常に優れた透明性を与えることができる。また、従来の造核剤よりも高い結晶化温度を与えることが可能なため、併せて成形加工性の改良を実現することができる。 The nucleating agent used in the present invention can give the resulting antifogging propylene-based resin sheet very excellent transparency that is impossible to achieve with conventional nucleating agents. Moreover, since it is possible to give a crystallization temperature higher than that of the conventional nucleating agent, it is possible to improve molding processability.
本発明に用いられる造核剤の製造方法としては、ＷＯ２００５／１１１１３４号公報等に記載の方法を挙げることができる。市販品としても、容易に入手することができ、例えば、Ｍｉｌｌａｄ ＮＸ８０００（ミリケン・アンド・カンパニー社製）を挙げることができる。 Examples of the method for producing the nucleating agent used in the present invention include the methods described in WO 2005/111134. Commercially available products can also be easily obtained, and examples include Millad NX8000 (Milken & Company).
また、上記造核剤を添加する場合の配合割合は、プロピレン系樹脂１００重量部に対して、０．０１〜０．５重量部、好ましくは０．０３〜０．４５重量部、さらに好ましくは０．０５〜０．４重量部である。該造核剤の配合量が、０．０１重量部を下回ると得られる製品の透明性が充分でなく、０．５重量部を上回るとそれ以上の効果が期待できず経済的に不利となるばかりか、成形品表面へのブリードアウトが激しくなって透明性が損なわれる。 The blending ratio when adding the nucleating agent is 0.01 to 0.5 parts by weight, preferably 0.03 to 0.45 parts by weight, more preferably 100 parts by weight of the propylene resin. 0.05 to 0.4 parts by weight. If the blending amount of the nucleating agent is less than 0.01 parts by weight, the transparency of the resulting product is not sufficient, and if it exceeds 0.5 parts by weight, no further effect can be expected, which is economically disadvantageous. In addition, the bleedout to the surface of the molded product becomes intense and the transparency is impaired.
３．その他の添加剤
本発明では、これらの必須成分の他に付加的成分を本発明の効果を損なわない範囲で添加することができる。それらの付加的成分としては、通常のポリプロピレンに用いられる酸化防止剤、光安定剤、紫外線吸収剤、滑剤、帯電防止剤、防曇剤、分子量調整剤（過酸化物）、核剤、着色剤、中和剤、ハイドロタルサイト類、各種フィラー等の各種助剤、プロピレン単独あるいは他のα−オレフィンとの共重合体、低密度ポリエチレン、高密度ポリエチレン等の他の重合体、各種熱可塑性エラストマー、無機または有機充填剤等を挙げることができる。
3. Other Additives In the present invention, in addition to these essential components, additional components can be added as long as the effects of the present invention are not impaired. These additional components include antioxidants, light stabilizers, UV absorbers, lubricants, antistatic agents, antifogging agents, molecular weight modifiers (peroxides), nucleating agents, and coloring agents used in ordinary polypropylene. , Various auxiliary agents such as neutralizers, hydrotalcites, various fillers, propylene alone or copolymers with other α-olefins, other polymers such as low density polyethylene and high density polyethylene, various thermoplastic elastomers And inorganic or organic fillers.
［２］［組成物の調製］
本発明に用いられるプロピレン系樹脂組成物の製造方法は、上記成分の添加順序や用いる装置に特に限定されないが、一般に使用されるヘンシェルミキサー、Ｖブレンター、リボンブレンダー、バンバリーミキサー、ニーダーブレンダー又は押出機の如き通常の混合機または混錬機を用いて所定時間混合し、通常の押出機にて粒状とする方法が好ましい。
又、本発明で用いられるプロピレン系樹脂組成物は、造核剤を目的とする配合量よりあらかじめ多く配合しておき、シートの製造前にプロピレン系樹脂で目的量に希釈する所謂マスターバッチの方式を取ることもできる。
また、本発明においては、本発明により製造された防曇性シートを再生使用するために、使用済みの防曇性シートを粉砕機等により粉砕した後、あるいはその粉砕品を溶融混錬して再生ペレットとした後、バージン原料に混合し、新しいプロピレン系樹脂組成物とすることができる。
しかし、その際、再生ペレットの配合には、その中の遊離脂肪酸により生じると思われる変色の面からおのずと限度があり、組成物全体で、遊離脂肪酸の含有量が５０ｐｐｍ以下となるように新しい樹脂組成物を調製する必要がある。遊離脂肪酸の含有量が５０ｐｐｍを上回ると、変色が激しくなる。
[2] [Preparation of composition]
The production method of the propylene-based resin composition used in the present invention is not particularly limited to the order of addition of the above components and the apparatus to be used, but generally used Henschel mixer, V blender, ribbon blender, Banbury mixer, kneader blender or extruder A method of mixing for a predetermined time using an ordinary mixer or kneader as described above and granulating with an ordinary extruder is preferred.
In addition, the propylene resin composition used in the present invention is a so-called masterbatch method in which a nucleating agent is compounded in advance in a larger amount than the target compounding amount, and diluted to the target amount with the propylene resin before the production of the sheet. You can also take.
In the present invention, in order to recycle and use the antifogging sheet produced according to the present invention, the used antifogging sheet is pulverized by a pulverizer or the like, or the pulverized product is melt-kneaded. After making a regenerated pellet, it can be mixed with a virgin raw material to obtain a new propylene-based resin composition.
However, in that case, there is a natural limit to the blending of the regenerated pellets in terms of discoloration that appears to be caused by the free fatty acids therein, and a new resin is used so that the content of free fatty acids in the entire composition is 50 ppm or less. A composition needs to be prepared. When the content of free fatty acid exceeds 50 ppm, discoloration becomes severe.
［３］［シートとその製造方法］
１．プロピレン系樹脂シート
本発明に用いられるプロピレン系樹脂シートの厚みは、０．１〜２ｍｍであることが好ましく、０．１５〜１．５ｍｍがさらに好ましく、０．２〜１ｍｍが特に好ましい。
厚みが０．１ｍｍを大きく下回る場合は、製品の剛性が損なわれ、厚みが２ｍｍを大きく上回る場合は、シートの透明性が充分ではなくなる。
本発明の一般式（１）で表される造核剤は、０．０１〜０．５重量部添加するだけでポリプロピレン樹脂シートの透明性、剛性、熱変形温度、曲げ弾性率が最も適正に向上するが、シートの厚みが０．０８ｍｍ、０．０５ｍｍ、０．０１ｍｍというように、０，１ｍｍ以下の範囲になれば、造核剤が機能して、シートの剛性が低下する傾向にあり、しかも、防曇剤の塗布にも支障となるために、製品として造核剤の適正な発現の為に許容できるシートの厚さの下限値は０．１ｍｍ程度である。一方で、シートの厚さが２ｍｍ以上、例えば、２．５ｍｍ、３ｍｍ、５ｍｍといったシートの厚さになれば透明性を所定値以上に上げることが造核剤では十分に対応できない場合があり、所定の透明性が得られにくくなる。シートが例えば５ｍｍと厚くなれば、シートの表面、内部との冷却温度に違いなどが発生することも予測され、温度管理が微妙になり、透明性に若干の違いが発生することも予測され、品質管理上、相当に留意しなければならないというリスクを伴う。そうすれば、０．１５ｍｍ、０．３５ｍｍ、０．６ｍｍ、１ｍｍ、１．２ｍｍ、１．８ｍｍというような、シートの厚さ０．１〜２ｍｍの範囲が、一般式（１）の造核剤の機能を安定に、適正に、発現する為の許容できる範囲である。
[3] [Sheet and its manufacturing method]
1. Propylene Resin Sheet The thickness of the propylene resin sheet used in the present invention is preferably 0.1 to 2 mm, more preferably 0.15 to 1.5 mm, and particularly preferably 0.2 to 1 mm.
When the thickness is much less than 0.1 mm, the rigidity of the product is impaired, and when the thickness is much more than 2 mm, the transparency of the sheet is not sufficient.
The nucleating agent represented by the general formula (1) of the present invention has the most appropriate transparency, rigidity, heat distortion temperature, and flexural modulus of the polypropylene resin sheet only by adding 0.01 to 0.5 parts by weight. Although the sheet thickness is in the range of 0.1 mm or less, such as 0.08 mm, 0.05 mm, and 0.01 mm, the nucleating agent functions and the sheet rigidity tends to decrease. In addition, since the coating of the antifogging agent is also hindered, the lower limit value of the sheet thickness that can be allowed for proper expression of the nucleating agent as a product is about 0.1 mm. On the other hand, if the thickness of the sheet is 2 mm or more, for example, 2.5 mm, 3 mm, or 5 mm, the nucleating agent may not be able to sufficiently cope with increasing the transparency to a predetermined value or more. It becomes difficult to obtain predetermined transparency. If the sheet becomes thicker, for example, 5 mm, it is also predicted that a difference in the cooling temperature between the surface and the inside of the sheet will occur, temperature management will be subtle, and a slight difference in transparency will also occur. This involves the risk of having to pay considerable attention to quality control. Then, the range of the sheet thickness of 0.1 to 2 mm such as 0.15 mm, 0.35 mm, 0.6 mm, 1 mm, 1.2 mm, and 1.8 mm is the nucleation of the general formula (1). This is an acceptable range for expressing the function of the agent stably and appropriately.
また、本発明に用いられるプロピレン系樹脂シートは、０．３５ｍｍ厚シートのＨＡＺＥ値が１０以下である。ＨＡＺＥ値がこの範囲であると、透明性の必要とする食品の包装に好適に利用できる。 The propylene-based resin sheet used in the present invention has a 0.35 mm thick sheet having a HAZE value of 10 or less. When the HAZE value is within this range, it can be suitably used for packaging foods that require transparency.
一方、本発明に用いられるプロピレン系樹脂シートは、再生・再使用の観点から、遊離脂肪酸の含有量が５０ｐｐｍ以下であることが必要であり、好ましくは４０ｐｐｍ以下である。遊離脂肪酸の含有量が本発明の範囲を上回ると、本発明により防曇剤を塗付したシートを再生使用した時に変色が激しくなるため、望ましくない。
なお、本発明においては、遊離脂肪酸とは、炭素数６〜２２の脂肪酸であり、ステアリン酸、パルチミン酸、ミチスチン酸、オレイン酸、ベヘニン酸、ラウリン酸、エリカ酸等の１種以上の混合物を言う。
On the other hand, the propylene-based resin sheet used in the present invention needs to have a free fatty acid content of 50 ppm or less, preferably 40 ppm or less, from the viewpoint of regeneration and reuse. If the content of the free fatty acid exceeds the range of the present invention, it is not desirable because discoloration becomes severe when the sheet coated with the antifogging agent according to the present invention is recycled.
In the present invention, the free fatty acid is a fatty acid having 6 to 22 carbon atoms, and is a mixture of one or more of stearic acid, palmitic acid, myristic acid, oleic acid, behenic acid, lauric acid, ericic acid and the like. say.
２．シートの成形
本発明に用いられるプロピレン系樹脂シートは、押出しシート成形、カレンダー成形等によって得られる。
押出しシート成形としては、単軸又は二軸のスクリュー押出機を通してコートハンダーダイからシート状に押出される。押出されたシートは、内部で冷却水や油が循環している金属ロール表面に、エアーナイフ、エアーチャンバー、硬質ゴムロール、スチールベルト、金属ロール等にて押さえつけ冷却固化されてシートに製造される。又、シート両面をスチールベルトで挟んで冷却固化することもできる。押出しシートは、単層の他に多層シートも使用できる。多層シートとしては、本発明のプロピレン系樹脂組成物の押出機に加え、複数の押出機を用い、フィードブロックやマルチマニホールドを用いてガスバリア樹脂層、接着樹脂層、再生樹脂層、華燭樹脂層、等を重ねた多層シートとすることが出来る。
さらに、押出しシート成形、カレンダー成形されたシートは、真空成形、真空圧空成形、熱盤圧空成形等の熱成形により各種容器や蓋材に加工することができる。
2. Sheet Forming The propylene-based resin sheet used in the present invention is obtained by extrusion sheet forming, calendar forming, or the like.
As extrusion sheet forming, the sheet is extruded from a coat solder die through a single-screw or twin-screw extruder. The extruded sheet is pressed and solidified by cooling with an air knife, an air chamber, a hard rubber roll, a steel belt, a metal roll or the like on the surface of a metal roll through which cooling water or oil circulates, and is manufactured into a sheet. It is also possible to cool and solidify both sides of the sheet with a steel belt. In addition to a single layer, a multilayer sheet can be used as the extruded sheet. As a multilayer sheet, in addition to the propylene-based resin composition extruder of the present invention, using a plurality of extruders, using a feed block and a multi-manifold, a gas barrier resin layer, an adhesive resin layer, a recycled resin layer, a candle resin layer, It can be set as the multilayer sheet which piled up etc.
Further, extruded sheet molding and calendered sheet can be processed into various containers and lid materials by thermoforming such as vacuum forming, vacuum pressure forming, hot platen pressure forming and the like.
［４］［防曇性シートとその製造方法］
１．防曇剤
本発明で使用される防曇剤は、炭素数６〜２２の脂肪酸の蔗糖脂肪酸エステルがであり、この化合物は、食品用添加物として認められており、安全性の点で最も好ましい。
この中では、ステアリン酸、パルチミン酸、ミチスチン酸、オレイン酸、ベヘニン酸、ラウリン酸、エリカ酸の蔗糖脂肪酸エステルが特に好適である。
本発明で使用される蔗糖脂肪酸エステルは、市販品を使用できる。市販品としては、三菱化学フーズ社製のリョートーシュガーエステル（商品名）を挙げる事ができる。
[4] [Anti-fogging sheet and manufacturing method thereof]
1. Antifogging agent The antifogging agent used in the present invention is a sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms, and this compound is recognized as a food additive and is most preferable in terms of safety. .
Of these, sucrose fatty acid esters of stearic acid, palmitic acid, myristic acid, oleic acid, behenic acid, lauric acid and ericic acid are particularly preferred.
A commercial item can be used for the sucrose fatty acid ester used in the present invention. Examples of commercially available products include Ryoto Sugar Ester (trade name) manufactured by Mitsubishi Chemical Foods.
本発明で使用される防曇剤の塗付量は、０．０２〜２ｇ／ｍ２である。塗付量が０．０１ｇ／ｍ２、０．００８ｇ／ｍ２というようにこの範囲を下回るとシートの防曇性が不足し、塗付量がこの範囲を、たとえば、２．３ｇ／ｍ２、３．０ｇ／ｍ２というように、上回ると一定のそれ以上の効果が期待できないばかりか、シート表面がべた付いて透明性が損なわれる。さらに、遊離の脂肪酸の含有量を増大させることにもなり、最大２ｇ／ｍ２の範囲が適切である。そすると、塗布量が０．０３ｇ／ｍ２、０．０４ｇ／ｍ２、０．０８ｇ／ｍ２、１．２ｇ／ｍ２、１．８ｇ／ｍ２、のような０．０２〜２ｇ／ｍ２が適切である。 The coating amount of the antifogging agent used in the present invention is 0.02 to 2 g / m 2 . If the coating amount falls below this range, such as 0.01 g / m 2 and 0.008 g / m 2 , the antifogging property of the sheet becomes insufficient, and the coating amount falls within this range, for example, 2.3 g / m 2 , 3 If it exceeds 0.0 g / m 2, not only a certain effect can be expected, but also the sheet surface becomes sticky and the transparency is impaired. Furthermore, the content of free fatty acids is also increased, and a range of maximum 2 g / m 2 is appropriate. Then, the coating amount is 0.02 to 2 g / m 2 such as 0.03 g / m 2 , 0.04 g / m 2 , 0.08 g / m 2 , 1.2 g / m 2 , 1.8 g / m 2 . m 2 is appropriate.
２．防曇剤の塗布方法
本発明に用いられるプロピレン系樹脂シートに防曇剤を塗布する際には、あらかじめシートをコロナ処理、プラズマ処理、フレーム処理等の酸化処理を施すことが、防曇剤の安定に有効である。この中ではコロナ処理によって、シート表面の濡れ張力を３５〜５５ダイン、好ましくは３６〜４５ダインの範囲となるよう処理されるのが好ましい。濡れ張力がこの範囲を上回るとシートの酸化臭が発生して好ましくない。濡れ張力がこの範囲を下回ると防曇剤のシートへの接着性が損なわれる。
酸化処理されたシートへの防曇剤の塗付は、防曇剤を０．０１〜１０重量％の防曇剤溶液として塗付後、乾燥する方法を用いる。防曇剤溶液に用いる溶媒としては、例えば、水、アルコール等で防曇剤を溶解し、且つポリプロピレン系樹脂シートを溶解しない溶液で、しかも適用分野によっては安全性を充たす溶媒を適宜選択して用いるのが良い。前記該シートへの防曇剤固形分としては、０．０２〜２．０ｇ／ｍ２塗布する。防曇剤の塗付量がこの範囲を下回ると防曇性能が不足し、防曇剤の塗付量がこの範囲を上回るとべた付きによる該シート間のブロッキングが発生して好ましくない。
上記の防曇剤の塗付法は、各種のロール印刷法やどぶ漬け法や吹き付け法等、いずれの方法でも使用できる。前記塗布法は、シート成形後に引き続いて行うインラインコートやシート成形・巻取り後に巻き戻し工程で行うアウトラインコートする方法等で実施できる。
防曇剤塗布後の乾燥方法としては、蒸気や電気で熱した乾燥炉（溶媒が水の場合は、１００℃以上が好ましい。）にシートを通して、溶媒を蒸発させる方法等が挙げられるが、特に制限はない。
2. Application method of anti-fogging agent When applying the anti-fogging agent to the propylene-based resin sheet used in the present invention, the sheet is subjected to oxidation treatment such as corona treatment, plasma treatment, flame treatment, etc. in advance. It is effective for stability. Among these, the sheet surface is preferably treated by corona treatment so that the wetting tension of the sheet surface is in the range of 35 to 55 dynes, preferably 36 to 45 dynes. If the wetting tension exceeds this range, an oxidized odor of the sheet is generated, which is not preferable. If the wetting tension is below this range, the adhesion of the antifogging agent to the sheet is impaired.
Application of the antifogging agent to the oxidized sheet is performed by applying the antifogging agent as an antifogging agent solution of 0.01 to 10% by weight and then drying. As the solvent used in the antifogging agent solution, for example, a solution that dissolves the antifogging agent with water, alcohol, etc. and that does not dissolve the polypropylene resin sheet, and depending on the application field, appropriately select a solvent that satisfies safety. It is good to use. As an antifogging agent solid content to the said sheet | seat, 0.02-2.0 g / m < 2 > is apply | coated. When the coating amount of the antifogging agent is below this range, the antifogging performance is insufficient, and when the coating amount of the antifogging agent exceeds this range, blocking between the sheets due to stickiness is not preferable.
The above antifogging agent can be applied by any method such as various roll printing methods, soaking methods, and spraying methods. The coating method can be carried out by in-line coating performed after sheet forming or outline coating performed in a rewinding step after sheet forming / winding.
Examples of the drying method after applying the antifogging agent include a method of evaporating the solvent through a sheet through a drying furnace heated by steam or electricity (when the solvent is water, 100 ° C. or higher is preferable). There is no limit.
３．防曇性シート等
本発明の防曇性ポリプロピレン系樹脂シートは、防曇性、透明性および再生使用に極めて優れているので、食品、化粧品、日用品の包装製品や、ＩＣチップや液晶パネルなど電子部品の梱包トレー、ディスプレー用の箱などの産業部材に最適である。
シートや製品の再生使用にあたっては、シートや製品を粉砕してバージン原料と混合し、シート成形機にかける方法や、シートや製品を粉砕したあと、押出機にて溶融混練してペレット（粒）状に加工してバージン原料と混合し、シート成形機にかける方法が行われる。
この場合、再生使用の割合にもよるが、押出機にて溶融混練してペレット（粒）状に加工した方が、原料の嵩密度が安定するために、シート成形加工が安定する。
3. Anti-fogging sheet, etc. The anti-fogging polypropylene resin sheet of the present invention is extremely excellent in anti-fogging property, transparency and reusable use, so that it can be used for packaging products for food, cosmetics, daily necessities, electronic devices such as IC chips and liquid crystal panels. Most suitable for industrial parts such as parts packing trays and display boxes.
When reusing sheets and products, the sheets and products are pulverized and mixed with virgin raw materials, and then applied to a sheet molding machine. After pulverizing the sheets and products, they are melt-kneaded in an extruder and pellets (grains) The sheet is processed into a shape, mixed with the virgin raw material, and applied to a sheet forming machine.
In this case, although depending on the ratio of recycle use, the sheet forming process is more stable when the raw material is melt kneaded and processed into pellets (grains) because the bulk density of the raw material is more stable.
以下に実施例を挙げて、本発明をさらに具体的に説明するが、本発明は、その要旨を超えない限り、これら実施例に制約されるものではない。なお、各実施例および比較例で用いた物性値の測定方法、評価法は、以下のとおりである。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. In addition, the measuring method and evaluation method of the physical property values used in each example and comparative example are as follows.
Ｉ．測定方法、評価方法
１）ＭＦＲ
ＭＦＲは、ＪＩＳ−Ｋ７２１０（２３０℃、２．１６ｋｇ荷重）に準拠して測定した。
I. Measurement method and evaluation method 1) MFR
MFR was measured based on JIS-K7210 (230 degreeC, 2.16kg load).
２）引張弾性率
引張弾性率は、厚み０．３５ｍｍのシートに対して成形１日後にＪＩＳ−Ｋ７１２７に準拠して測定した。
2) Tensile elastic modulus Tensile elastic modulus was measured based on JIS-K7127 after 1 day for a sheet having a thickness of 0.35 mm.
３）ヘイズ値（ＨＡＺＥ値）
ＨＡＺＥは、厚み０．３５ｍｍのシートに対して成形１日後にＪＩＳ−Ｋ７１３６に準拠して測定した。
3) Haze value (HAZE value)
HAZE was measured according to JIS-K7136 one day after molding on a sheet having a thickness of 0.35 mm.
４）エチレンの含量
エチレンの含量は、下記の条件の１３Ｃ−ＮＭＲ法によって計測された値である。
装置：日本電子社製 ＪＥＯＬ−ＧＳＸ２７０
濃度：３００ｍｇ／２ｍＬ
溶媒：オルソジクロロベンゼン
4) Ethylene content The ethylene content is a value measured by the 13 C-NMR method under the following conditions.
Apparatus: JEOL-GSX270 manufactured by JEOL Ltd.
Concentration: 300 mg / 2 mL
Solvent: Orthodichlorobenzene
５）防曇性
８０℃の湯にシートの防曇材塗布面をかざし、水滴の付着状況を観察した。
○：水滴が全く付着せず、良く透視できる。
△：大きな水滴が付き、７０％以上透視できる。
×：細かい水滴が付き、３０％以下しか透視できない。
5) Antifogging property The antifogging material application surface of the sheet was held over 80 ° C. hot water, and the state of water droplet adhesion was observed.
○: Water droplets do not adhere at all and can be seen well.
(Triangle | delta): A big water droplet is attached and 70% or more can be seen through.
X: A fine water droplet is attached and only 30% or less can be seen through.
６）遊離脂肪酸量
シートをアルミ箔で挟み、２１０℃で熱プレス加工して３℃に冷却し１００μｍ以下のフィルムに成形した。
次いで、このフィルム１．２５ｇを１ｃｍ×１ｃｍ程度の大きさに裁断してフラスコに入れ、クロロホルム３０ｍＬを用いて２回抽出した。クロロホルム３０ｍＬを加え、還流冷却下、６０℃の湯浴中で１時間、超音波照射した。湯浴から取り出して室温まで静置冷却した後、ろ紙を用いてろ過して１度目のろ液を回収する。残ったフィルムにさらにクロロホルム３０ｍＬを加えて還流冷却下、６０℃の湯浴中で１５分間、超音波照射した。湯浴から取り出して室温まで静置冷却した後、先ほどと同じろ紙を用いてろ過して２度目のろ液を回収する。残ったフィルムとフラスコをさらに１５ｍＬのクロロホルムで洗い、洗液を先ほどと同じろ紙を用いてろ過して回収した。全てのろ液（洗液も含む）を合わせてナスフラスコに入れ、溶媒を減圧留去して抽出物を得た。
得られた抽出物にクロロホルム２ｍＬを（ホールピペット等を用いて）正確に加え、よく混合して得られた溶液をフィルターでろ過してガスクロマトグラフ測定用試料溶液を得た。
得られたガスクロマトグラフ測定用試料溶液を以下の条件で測定し、標準溶液の保持時間と一致するピークから、ミリスチン酸、パルミチン酸、ステアリン酸のピーク面積をそれぞれ求めた。
装置：島津ＧＣ−２０１０
装置条件
検出器：ＦＩＤ検出器
気化室温度：３２０℃
検出器温度：３５０℃
圧力制御：８０ｋＰａで１５分間置き、５０ｋＰａ／ｍｉｎの速度で５８０ｋＰａまで昇圧する。
カラム温度：１１０℃から１５℃／ｍｉｎの速度で３４１℃まで昇温し、９．６分間保つ。
カラム：Ｊ＆Ｗ Ｓｃｉｅｎｔｉｆｉｃ， ＤＢ−５ＭＳ （膜厚０．２５μｍ，φ０．２５ｍｍ×５ｍ）
注入量：１．０μＬ
標準溶液：１００ｍＬメスフラスコにミリスチン酸、パルミチン酸、ステアリン酸をそれぞれ１２．５ｍｇ程度量りとり、クロロホルムを加えて正確に１００ｍＬにした溶液。
以下の計算式によりそれぞれの遊離脂肪酸量を定量した。
シート中の遊離ミリスチン酸濃度（ｐｐｍ）
＝（測定試料溶液のミリスチン酸ピーク面積）÷（標準溶液のミリスチン酸ピーク面積）
×０．１２５（ｍｇ／ｍＬ）×２（ｍＬ）÷１２５０（ｍｇ）×１００００００
以下同様にして遊離パルミチン酸、遊離ステアリン酸のトータル濃度を求め、遊離脂肪酸含有量（ｗｔｐｐｍ）とした。
6) Amount of free fatty acid The sheet was sandwiched between aluminum foils, hot pressed at 210 ° C., cooled to 3 ° C., and formed into a film of 100 μm or less.
Next, 1.25 g of this film was cut into a size of about 1 cm × 1 cm, put into a flask, and extracted twice using 30 mL of chloroform. 30 mL of chloroform was added, and ultrasonic irradiation was performed for 1 hour in a 60 ° C. hot water bath under reflux cooling. After taking out from a hot water bath and standing and cooling to room temperature, it filters using a filter paper and collects the 1st filtrate. 30 mL of chloroform was further added to the remaining film, and ultrasonic irradiation was performed for 15 minutes in a 60 ° C. hot water bath under reflux cooling. After removing from the hot water bath and allowing to cool to room temperature, it is filtered using the same filter paper as before, and the second filtrate is recovered. The remaining film and flask were further washed with 15 mL of chloroform, and the washing was collected by filtration using the same filter paper as before. All the filtrates (including the washings) were combined and placed in an eggplant flask, and the solvent was distilled off under reduced pressure to obtain an extract.
To the obtained extract, 2 mL of chloroform was accurately added (using a whole pipette or the like), and the solution obtained by mixing well was filtered through a filter to obtain a sample solution for gas chromatograph measurement.
The obtained sample solution for gas chromatograph measurement was measured under the following conditions, and the peak areas of myristic acid, palmitic acid, and stearic acid were determined from peaks that coincided with the retention time of the standard solution.
Device: Shimadzu GC-2010
Equipment conditions Detector: FID detector Vaporization chamber temperature: 320 ° C
Detector temperature: 350 ° C
Pressure control: Place at 80 kPa for 15 minutes, and increase the pressure to 580 kPa at a rate of 50 kPa / min.
Column temperature: The temperature is raised from 110 ° C. to 341 ° C. at a rate of 15 ° C./min, and maintained for 9.6 minutes.
Column: J & W Scientific, DB-5MS (film thickness 0.25 μm, φ0.25 mm × 5 m)
Injection volume: 1.0 μL
Standard solution: A solution in which about 12.5 mg of myristic acid, palmitic acid, and stearic acid were weighed in a 100 mL volumetric flask, respectively, and chloroform was added to make exactly 100 mL.
The amount of each free fatty acid was quantified by the following calculation formula.
Free myristic acid concentration in the sheet (ppm)
= (Myristic acid peak area of measurement sample solution) ÷ (Myristic acid peak area of standard solution)
× 0.125 (mg / mL) × 2 (mL) ÷ 1250 (mg) × 1000000
In the same manner, the total concentration of free palmitic acid and free stearic acid was determined and used as the free fatty acid content (wtppm).
７）臭気
再生シート８０ｇを裁断し広口瓶に入れ、臭気の有無を確認した。
○：臭いが感じられない。
×：特有の臭いがある。
7) Odor 80 g of the recycled sheet was cut and placed in a wide-mouthed jar, and the presence or absence of odor was confirmed.
○: No smell is felt.
X: There is a peculiar smell.
ＩＩ．材料
１）プロピレン系樹脂
プロピレン系樹脂として、以下のプロピレン系樹脂（Ａ）、プロピレン系樹脂（Ｂ）を用いた。
（１）プロピレン系樹脂（Ａ）の製造
II. Material 1) Propylene resin As propylene resin, the following propylene resin (A) and propylene resin (B) were used.
(1) Production of propylene resin (A)
［触媒の製造］
攪拌翼と還流装置を取り付けた５Ｌセパラブルフラスコに、純水１，７００ｇを投入し、９８％硫酸５００ｇを滴下した。そこへ、平均粒径１８μｍに造粒したモンモリロナイト（原料として水澤化学工業社製、ベンクレイＳＬを用いた）を３００ｇ添加後、攪拌した。その後９０℃で２時間反応させた。このスラリーをろ過、洗浄した。回収したケーキに２７％硫酸リチウム水溶液１，２３０ｇを加え、９０℃で２時間反応させた。このスラリーをろ過し、さらに、ろ液のｐＨが４以上となるまで洗浄した。回収したケーキを１００℃で予備乾燥した後に２００℃で２時間乾燥した。その結果、２７５ｇの化学処理モンモリロナイトを得た。
１Ｌフラスコに、化学処理モンモリロナイト２０ｇを加え、ヘプタン１２９ｍｌとトリイソブチルアルミニウムのヘプタン溶液７１ｍｌ（５０ｍｍｏｌ）を加え、室温で１時間攪拌した。その後、ヘプタンで残液率１／１００まで洗浄し、最後にスラリー量を１００ｍｌに調製した。さらに、トリノルマルオクチルアルミニウムのヘプタン溶液３ｍｌ（１ｍｍｏｌ）を加えて、１０分間室温で攪拌した。
２００ｍｌフラスコ中で、（ｒ）−ジメチルシリレンビス［１，１’−｛２−メチル−４−（４−クロロフェニル）−４Ｈ−アズレニル｝］ハフニウム（３００μｍｏｌ）にヘプタン（５０ｍｌ）を加えてスラリーとした後、上記１Ｌフラスコに加えて室温で６０分間攪拌した。その後、ヘプタン１８１ｍｌを加えて触媒スラリーを調製した。
[Manufacture of catalyst]
Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 1,700 g of pure water was added, and 500 g of 98% sulfuric acid was added dropwise. Thereto, 300 g of montmorillonite granulated to an average particle size of 18 μm (manufactured by Mizusawa Chemical Industry Co., Ltd., Benclay SL) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was filtered and washed. To the collected cake, 1,230 g of a 27% lithium sulfate aqueous solution was added and reacted at 90 ° C. for 2 hours. This slurry was filtered and further washed until the pH of the filtrate reached 4 or higher. The recovered cake was pre-dried at 100 ° C. and then dried at 200 ° C. for 2 hours. As a result, 275 g of chemically treated montmorillonite was obtained.
To a 1 L flask, 20 g of chemically treated montmorillonite was added, 129 ml of heptane and 71 ml (50 mmol) of a heptane solution of triisobutylaluminum were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the residue was washed with heptane to a residual liquid ratio of 1/100, and finally the amount of slurry was adjusted to 100 ml. Furthermore, 3 ml (1 mmol) of a heptane solution of trinormal octyl aluminum was added and stirred at room temperature for 10 minutes.
In a 200 ml flask, heptane (50 ml) was added to (r) -dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4H-azurenyl}] hafnium (300 μmol) to form a slurry. Then, in addition to the 1 L flask, the mixture was stirred at room temperature for 60 minutes. Thereafter, 181 ml of heptane was added to prepare a catalyst slurry.
［予備重合］
窒素で十分置換を行った内容積１．０Ｌの撹拌式オートクレーブに、上記触媒スラリーを全量導入した。温度が４０℃に安定したところでプロピレンを１０ｇ／時間の速度で供給し、温度を維持した。４時間後プロプレンの供給を停止し、さらに１時間維持した。予備重合終了後、残モノマーをパージし、撹拌を停止させ、十分窒素置換を行った１Ｌフラスコにスラリーを抜き出した。このスラリーを減圧乾燥して予備重合触媒を６３．４ｇ回収した。
[Preliminary polymerization]
The entire amount of the catalyst slurry was introduced into a stirring autoclave having an internal volume of 1.0 L that had been sufficiently replaced with nitrogen. When the temperature was stabilized at 40 ° C., propylene was supplied at a rate of 10 g / hour to maintain the temperature. After 4 hours, the supply of proprene was stopped and maintained for another hour. After completion of the prepolymerization, the residual monomer was purged, the stirring was stopped, and the slurry was extracted into a 1 L flask that had been sufficiently purged with nitrogen. This slurry was dried under reduced pressure to recover 63.4 g of a prepolymerized catalyst.
［重合］
内容積２００Ｌの誘導撹拌機付オートクレーブ内をプロピレンで十分置換した後に、十分に脱水処理した液化プロピレン４５ｋｇを導入し３０℃に保持した。これに、トリイソブチルアルミニウムのヘプタン溶液４７０ｍｌ（５０ｇ／ｌ）を加えた。水素２．０ＮＬ、エチレンを０．９ｋｇ導入し、上記予備重合触媒１．７ｇをアルゴンで圧入した。温度６５℃まで４０分かけて昇温し、６５℃で２時間反応させた。また、この間水素を０．１２ｇ／ｈｒの定速で導入した。その後、エタノール１００ｍｌを圧入して、反応を停止させ、残ガスをパージした。その結果、１８．４ｋｇのプロピレン系樹脂（Ａ）が得られた。該樹脂のＭＦＲは、１．４ｇ／１０ｍｉｎ、エチレン含量１．３重量％であった。
[polymerization]
After sufficiently replacing the interior of the autoclave with an induction stirrer with an internal volume of 200 L with propylene, 45 kg of sufficiently dehydrated liquefied propylene was introduced and maintained at 30 ° C. To this, 470 ml (50 g / l) of a heptane solution of triisobutylaluminum was added. Hydrogen 2.0NL and ethylene 0.9kg were introduced, and 1.7g of the prepolymerized catalyst was injected with argon. The temperature was raised to 65 ° C. over 40 minutes, and the reaction was carried out at 65 ° C. for 2 hours. During this time, hydrogen was introduced at a constant speed of 0.12 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the remaining gas was purged. As a result, 18.4 kg of propylene resin (A) was obtained. The resin had an MFR of 1.4 g / 10 min and an ethylene content of 1.3% by weight.
（２）プロピレン系樹脂（Ｂ）の製造
内容積２００リットルの攪拌式重合槽により、プロピレン−エチレンランダム共重合体の製造を実施した。重合槽内をプロピレンで充分置換した後、脱水・脱酸素したｎ−ヘプタン６０リットルを導入し、ジエチルアルミニウムクロライド３０．０ｇ、ソルベー社タイプ三塩化チタン触媒１０ｇをプロピレン雰囲気下、６０℃で導入した。
重合槽内の温度を６０℃に昇温した後、プロピレンを５．９ｋｇ／時間、エチレンを０．１８ｋｇ／時間のフィード速度で導入し、併用する水素は、気相部の水素濃度１．１ｖｏｌ．％で制御した。６時間重合を継続した後、プロピレンとエチレンの導入を止め、さらに重合槽内の温度を６０℃で６０分間継続させた。
このようにして得られたスラリーを、濾過、乾燥して３２．０ｋｇのパウダー状のプロピレン−エチレンランダム共重合体であるプロピレン系樹脂（Ｂ）を得た。得られたプロピレン系樹脂（Ｂ）は、ＭＦＲ＝１．０ｇ／１０分、エチレン含有量＝２．５重量％であった。
(2) Production of propylene-based resin (B) Propylene-ethylene random copolymer was produced in a stirring polymerization tank having an internal volume of 200 liters. After sufficiently replacing the inside of the polymerization tank with propylene, 60 liters of dehydrated and deoxygenated n-heptane was introduced, and 30.0 g of diethylaluminum chloride and 10 g of Solvay type titanium trichloride catalyst were introduced at 60 ° C. in a propylene atmosphere. .
After raising the temperature in the polymerization tank to 60 ° C., propylene is introduced at a feed rate of 5.9 kg / hour and ethylene is introduced at a feed rate of 0.18 kg / hour. . %. After the polymerization was continued for 6 hours, the introduction of propylene and ethylene was stopped, and the temperature in the polymerization tank was further continued at 60 ° C. for 60 minutes.
The slurry thus obtained was filtered and dried to obtain 32.0 kg of a propylene-based resin (B) which is a powdery propylene-ethylene random copolymer. The obtained propylene-based resin (B) had MFR = 1.0 g / 10 min and ethylene content = 2.5% by weight.
２）造核剤
造核剤として、以下の化合物を用いた。
（１）Ｍｊｌｌａｄ ＮＸ８０００（ミリケン・アンド・カンパニー社製）：下記化学構造式（２）
2) Nucleating agent The following compounds were used as the nucleating agent.
(1) Mjllad NX8000 (manufactured by Milliken & Company): chemical structural formula (2)
（２）アデカスタブＮＡ２１： ビス（２，４，８，１０−テトラ−ｔｅｒｔ−ブチル−６−ヒドロキシ−１２Ｈ−ジベンゾ［ｄ，ｇ］［１，２，３］ジオキサホスホシン−６−オキシド）水酸化アルミニウム塩と有機化合物の複合体（旭電化社製）
（３）ゲルオールＭＤ：１，３： ２，４−ジ（ｐ−メチルベンジリデン）ソルビトール（新日本理化社製）
(2) Adekastab NA21: Bis (2,4,8,10-tetra-tert-butyl-6-hydroxy-12H-dibenzo [d, g] [1,2,3] dioxaphosphocin-6-oxide) Complex of aluminum hydroxide salt and organic compound (Asahi Denka Co., Ltd.)
(3) Gelol MD: 1,3: 2,4-di (p-methylbenzylidene) sorbitol (manufactured by Shin Nippon Rika Co., Ltd.)
３）防曇剤
防曇剤として、以下の化合物を用いた。
（１）リョートーシュガーエステルＬＷＡ−１５７０： 蔗糖ラウリン酸エステル（三菱化学フーズ社製）
3) Antifogging agent The following compounds were used as an antifogging agent.
(1) Ryoto sugar ester LWA-1570: Sucrose laurate (manufactured by Mitsubishi Chemical Foods)
［実施例１］
１−１）組成物の調製
プロピレン系樹脂（Ａ）１００重量部に対し、造核剤としてＭｉｌｌａｄ ＮＸ８０００：（ミリケン・アンド・カンパニー社製）０．３重量部、さらに酸化防止剤として〔テトラキス（３，５−ジ−ｔ−ブチルフェニルプロピオネート）〕メタン０．０３重量部（商品名：チバスペシャリティケミカル（株）製イルガノックスＲＡ１０１０）とトリス（ジブチルフェニル）フォスファイト（商品名：チバスペシャリティケミカル（株）製イルガフォス１６８）０．１重量部を添加してヘンシェルミキサーにて混合しプロピレン系樹脂組成物を得た後、２６０℃に加熱されたスクリュー径が５０ｍｍの押出機にて押出し、粒状物とした。
[Example 1]
1-1) Preparation of Composition With respect to 100 parts by weight of the propylene-based resin (A), Millad NX8000 as a nucleating agent (manufactured by Milliken & Company) 0.3 parts by weight, and further as an antioxidant [Tetrakis ( 3,5-di-t-butylphenylpropionate)] 0.03 part by weight of methane (trade name: Irganox RA1010 manufactured by Ciba Specialty Chemicals) and tris (dibutylphenyl) phosphite (trade name: Ciba Specialty Chemical) Irgafos 168) 0.1 part by weight was added and mixed with a Henschel mixer to obtain a propylene-based resin composition, which was then extruded with an extruder having a screw diameter of 50 mm heated to 260 ° C. It was a thing.
１−２）押出シートの作製
得られた粒状物を２３０℃に加熱されたスクリュー径４０ｍｍの押出シート成形機にて幅７５０ｍｍ、ダイリップ間隔０．８ｍｍのコートハンガーダイから水平方向に押出し、３０℃の水が内部で循環している鏡面加工された硬質クロムメッキの金属ロールで挟んで冷却固化し、片面にコロナ処理をかけて４０ダインとしながら厚み０．３５ｍｍのシートを製造した。得られたシートの物性の測定結果を第１表に示す。
1-2) Production of Extruded Sheet The obtained granular material was extruded in a horizontal direction from a coat hanger die having a width of 750 mm and a die lip interval of 0.8 mm in an extrusion sheet molding machine heated to 230 ° C. and having a screw diameter of 40 mm, and 30 ° C. The sheet was cooled and solidified with a mirror-finished hard chrome-plated metal roll in which water was circulated, and a sheet having a thickness of 0.35 mm was manufactured while corona treatment was applied to one side to make 40 dynes. The measurement results of the physical properties of the obtained sheet are shown in Table 1.
１−３）防曇剤の塗布
次いで、上記シートのコロナ処理面に、三菱化学フーズ社製のリョートーシュガーエステルＬＷＡ−１５７０（蔗糖ラウリン酸エステル）の４０倍水溶液をグラビアコーターにて４ｇ／ｍ２を塗付し、１２０℃の空気が循環している乾燥機にて乾燥後巻取り機にて巻き取って防曇シートを作成した。防曇剤固形分は０．０４ｇ／ｍ２の塗付量である。この防曇シートを５枚重ねて日本電色社製のカラーマシンにてＹＩ値を測定した。結果を第１表に示す。
1-3) Application of antifogging agent Next, a 40 times aqueous solution of Ryoto Sugar Ester LWA-1570 (sucrose laurate) manufactured by Mitsubishi Chemical Foods Co., Ltd. was applied to the corona-treated surface of the above sheet with a gravure coater. No. 2 was applied, dried with a drier in which air at 120 ° C. was circulated, and wound up with a winder to prepare an antifogging sheet. The antifogging agent solid content is a coating amount of 0.04 g / m 2 . Five of these anti-fogging sheets were stacked and the YI value was measured with a color machine manufactured by Nippon Denshoku. The results are shown in Table 1.
１−４）再生ペレットの作製
その後、上記防曇シートを、株式会社ホーライ製の粉砕機ＵＩ０３−３０１２０ＭＲＦＳ型で、φ９ｍｍ スクリーンにかけて粉砕品を得た。この粉砕品を２３０℃に加熱されたスクリュー径が４０ｍｍの押出機にて溶融混錬して再生ペレットを製造した。
1-4) Production of Recycled Pellets Thereafter, the above antifogging sheet was subjected to a φ9 mm screen using a crusher UI03-30120MRFS manufactured by Horai Co., Ltd. to obtain a pulverized product. This pulverized product was melt-kneaded with an extruder having a screw diameter of 40 mm heated to 230 ° C. to produce recycled pellets.
１−５）再生シートの製造
１−１）の粒状物５０重量部に対し、１−４）の再生ペレット５０重量部を混合して１−１）〜１−３）の方法で再生防曇シートを作成した。この防曇シートを５枚重ねて日本電色社製のカラーマシンにてＹＩ値を測定した。結果を第１表に示す。
1-5) Production of Recycled Sheet 50 parts by weight of the granulated material of 1-1) is mixed with 50 parts by weight of the regenerated pellets of 1-4), and regenerated antifog by the method of 1-1) to 1-3) Created a sheet. Five of these anti-fogging sheets were stacked and the YI value was measured with a color machine manufactured by Nippon Denshoku. The results are shown in Table 1.
［実施例２］
プロピレン系樹脂（Ｂ）１００重量部に対し、造核剤としてＭｉｌｌａｄ ＮＸ８０００：（ミリケン・アンド・カンパニー社製）０．３重量部、さらに酸化防止剤として〔テトラキス（３，５−ジ−ｔ−ブチルフェニルプロピオネート）〕メタン０．０３重量部（商品名：チバスペシャリティケミカル（株）製イルガノックスＲＡ１０１０）とトリス（ジブチルフェニル）フォスファイト（商品名：チバスペシャリティケミカル（株）製イルガフォス１６８）０．１重量部を添加してヘンシェルミキサーにて混合し、プロピレン系樹脂組成物を得た後、２６０℃に加熱されたスクリュー径が５０ｍｍの押出機にて押出し粒状物とした。
その後、この粒状物に実施例１の１−３）〜１−５）と同様の方法を適用し、再生防曇シートを作成した。その結果を第１表に示す。
[Example 2]
Millad NX8000: 0.3 parts by weight (made by Milliken & Company) as a nucleating agent and 100 parts by weight as an antioxidant [tetrakis (3,5-di-t-) Butylphenylpropionate)] 0.03 part by weight of methane (trade name: Irganox RA1010 manufactured by Ciba Specialty Chemicals Co., Ltd.) and Tris (dibutylphenyl) phosphite (trade name: Irgaphos 168 manufactured by Ciba Specialty Chemicals Co., Ltd.) .1 part by weight was added and mixed with a Henschel mixer to obtain a propylene-based resin composition, which was then extruded into a granulated product with an extruder heated at 260 ° C. and having a screw diameter of 50 mm.
Thereafter, the same method as in 1-3) to 1-5) of Example 1 was applied to the granular material to prepare a recycled antifogging sheet. The results are shown in Table 1.
［比較例１、２］
プロピレン系樹脂組成物の配合物を第２表に示す如く変えた以外は、実施例１と同様にして評価した。その結果を第２表に示す。
[Comparative Examples 1 and 2]
Evaluation was performed in the same manner as in Example 1 except that the composition of the propylene-based resin composition was changed as shown in Table 2. The results are shown in Table 2.
［比較例３］
シートへ塗布する防曇剤を三菱化学フーズ社製のリョートーシュガーエステルＬＷＡ−１５７０（蔗糖ラウリン酸エステル）の４倍水溶液をグラビアコーターにて１０ｇ／ｍ２を塗付、防曇剤固形分として２．５ｇ／ｍ２を塗付した以外は、実施例１と同様にして評価した。その結果を第２表に示す。
［比較例４］
比較例１で防曇剤を塗付しなかった以外は、実施例１と同様にして評価した。その結果を第２表に示す。
［比較例５］
実施例１で防曇剤を塗布しなかった以外は、実施例１と同様にして評価した。その結果を第２表に示す。
［比較例６］
プロピレン系樹脂組成物の配合を第２表に示す如く変え、防曇剤を塗布しなかった以外は実施例１と同様にして評価した。その結果を第２表に示す。
[Comparative Example 3]
Antifogging agent to be applied to the sheet was coated with 10 g / m 2 of a 4 times aqueous solution of Ryoto Sugar Ester LWA-1570 (sucrose lauric acid ester) manufactured by Mitsubishi Chemical Foods Co., Ltd. with a gravure coater, Evaluation was performed in the same manner as in Example 1 except that 2.5 g / m 2 was applied. The results are shown in Table 2.
[Comparative Example 4]
Evaluation was performed in the same manner as in Example 1 except that the antifogging agent was not applied in Comparative Example 1. The results are shown in Table 2.
[Comparative Example 5]
Evaluation was performed in the same manner as in Example 1 except that the antifogging agent was not applied in Example 1. The results are shown in Table 2.
[Comparative Example 6]
Evaluation was performed in the same manner as in Example 1 except that the composition of the propylene-based resin composition was changed as shown in Table 2 and no antifogging agent was applied. The results are shown in Table 2.
これらの結果より明らかなように、実施例１，２では、本願発明の防曇性プロピレン系樹脂シートは、ＨＡＺＥ値が小さく（透明性に優れ）、防曇性に優れ、再生しても色相変化や臭気が少ない事が解る。
これに対し、比較例１では、本願で特定する遊離脂肪酸の量が上回る為に、再生シートの色相が極めて悪く臭気が発生するのであった。比較例２では、本願で特定する脂肪酸金属塩の量は下回っている為、防曇性に優れ、再生シートの色相変化も少ないが、造核剤として配合しているゲルオールＭＤに特有の臭気がある為に、食品包装の分野には適さないものであった。比較例３では、防曇剤を本願で特定する以上の量を塗布している為にシートがべたついてしまい、巻き取ったシートを繰り出す際に接着跡がシートに残る為に外観、透明性が悪いものであった。また、比較例４では、本願で特定する脂肪酸金属塩の量が上回るが、防曇剤を塗付していないために、再生シートの色相変化が少ないものの、防曇性能が全く無いものであった。比較例５では、本願で特定する脂肪酸金属塩の量が下回り、透明性は優れているが、防曇剤を塗付していないために、再生シートの色相変化が少ないものの、防曇性能が全く無いものであった。比較例６では、造核剤を配合していない為に透明性が極めて悪く、さらに、防曇剤を塗布していない為に、防曇性能が全く無いものであった。
以上の各実施例のデータ、及び各比較例との対照結果より、本発明の防曇性プロピレン系樹脂シートが、従来の材料より、透明性や防曇性が優れ、かつ再生しても色相変化が少ないことが明白であり、本発明を構成する要件の合理性と有意性が実証され、従来技術への卓越性も明らかにされている。
As is clear from these results, in Examples 1 and 2, the antifogging propylene-based resin sheet of the present invention has a small HAZE value (excellent transparency), excellent antifogging properties, and hue even when regenerated. I understand that there is little change and odor.
On the other hand, in Comparative Example 1, since the amount of the free fatty acid specified in the present application exceeds, the hue of the recycled sheet is extremely poor and odor is generated. In Comparative Example 2, since the amount of the fatty acid metal salt specified in the present application is below, the antifogging property is excellent and the hue change of the recycled sheet is small, but there is an odor peculiar to the gelol MD blended as a nucleating agent. For this reason, it was not suitable for the field of food packaging. In Comparative Example 3, since the antifogging agent is applied in an amount more than specified in the present application, the sheet becomes sticky, and when the wound sheet is fed out, the adhesion mark remains on the sheet, so that the appearance and transparency are low. It was bad. Further, in Comparative Example 4, the amount of the fatty acid metal salt specified in the present application exceeds, but since the antifogging agent is not applied, the hue of the recycled sheet is small, but there is no antifogging performance. It was. In Comparative Example 5, the amount of the fatty acid metal salt specified in the present application is lower and the transparency is excellent, but since the antifogging agent is not applied, the hue change of the recycled sheet is small, but the antifogging performance is low. There was nothing at all. In Comparative Example 6, the transparency was very poor because no nucleating agent was blended, and furthermore, no antifogging performance was found because no antifogging agent was applied.
From the data of each of the above examples and the comparison result with each comparative example, the antifogging propylene-based resin sheet of the present invention has better transparency and antifogging properties than conventional materials, and even when reproduced, the hue. It is clear that there is little change, the rationality and significance of the requirements that make up the present invention are demonstrated, and the superiority to the prior art is also revealed.
以上、説明したように、本発明によれば、透明性と防曇性に優れ、かつ再生使用しても変色や臭気の少ない防曇性プロピレン系樹脂シートが得られるため、経済性、環境性に優れ、食品日用品の包装や医療電子部品の分野に好適に使用することができ、その産業上の有用性は非常に高い。 As described above, according to the present invention, an antifogging propylene-based resin sheet having excellent transparency and antifogging property and having little discoloration and odor even after being recycled can be obtained. It can be suitably used in the fields of food daily necessities packaging and medical electronic parts, and its industrial utility is very high.
Claims (6)
上記プロピレン系樹脂シートは、ＭＦＲが０．２〜３０ｇ／１０分のプロピレン系樹脂１００重量部に対し、下記の一般式（１）で表される造核剤０．０１〜０．５重量部の割合で配合してなるプロピレン系樹脂組成物から形成されている、炭素数６〜２２の遊離脂肪酸の含有量が５０ｐｐｍ以下であることを特徴とする防曇性プロピレン系樹脂シート。
［但し、式中、ｎは、０〜２の整数であり、Ｒ１〜Ｒ５は、同一または異なって、それぞれ水素原子もしくは炭素数が１〜２０のアルキル基、アルケニル基、アルコキシ基、カルボニル基、ハロゲン基およびフェニル基であり、Ｒ６は、炭素数が１〜２０のアルキル基である。］ An antifogging agent comprising a sucrose fatty acid ester of a fatty acid having 6 to 22 carbon atoms having a solid content of 0.02 to 2 g / m 2 is applied to at least one surface of a propylene-based resin sheet having a thickness of 0.1 to 2 mm. , A propylene-based resin sheet with little discoloration and odor even when recycled,
The propylene-based resin sheet is 0.01 to 0.5 parts by weight of a nucleating agent represented by the following general formula (1) with respect to 100 parts by weight of a propylene-based resin having an MFR of 0.2 to 30 g / 10 min. An antifogging propylene-based resin sheet, wherein the content of free fatty acids having 6 to 22 carbon atoms is 50 ppm or less, which is formed from a propylene-based resin composition blended at a ratio of
[In the formula, n is an integer of 0 to 2, and R 1 to R 5 are the same or different and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkoxy group, a carbonyl group. A group, a halogen group and a phenyl group, and R 6 is an alkyl group having 1 to 20 carbon atoms. ]
The propylene-based resin sheet comprising the regenerated propylene-based resin composition according to claim 5, wherein the content of free fatty acids having 6 to 22 carbon atoms is 50 ppm or less.
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