TW201905073A - 熔融成形用乙烯-乙烯醇系共聚物組成物、丸粒及多層結構體 - Google Patents
熔融成形用乙烯-乙烯醇系共聚物組成物、丸粒及多層結構體Info
- Publication number
- TW201905073A TW201905073A TW107122170A TW107122170A TW201905073A TW 201905073 A TW201905073 A TW 201905073A TW 107122170 A TW107122170 A TW 107122170A TW 107122170 A TW107122170 A TW 107122170A TW 201905073 A TW201905073 A TW 201905073A
- Authority
- TW
- Taiwan
- Prior art keywords
- evoh resin
- ethylene
- resin composition
- alkaline earth
- earth metal
- Prior art date
Links
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 title claims abstract description 176
- 238000000465 moulding Methods 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 239000008188 pellet Substances 0.000 title claims description 26
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 55
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 160
- 238000006243 chemical reaction Methods 0.000 claims description 16
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- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 claims 1
- 239000011342 resin composition Substances 0.000 abstract description 110
- 238000010438 heat treatment Methods 0.000 abstract description 29
- 238000004040 coloring Methods 0.000 abstract description 9
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 159
- 229920005989 resin Polymers 0.000 description 96
- 239000011347 resin Substances 0.000 description 96
- 238000000034 method Methods 0.000 description 53
- 239000010410 layer Substances 0.000 description 47
- -1 Hydroxyalkyl vinylidene diacetates Chemical class 0.000 description 34
- 239000000047 product Substances 0.000 description 22
- 238000002156 mixing Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 229920001567 vinyl ester resin Polymers 0.000 description 17
- 239000002585 base Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 15
- 239000005977 Ethylene Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 229920006223 adhesive resin Polymers 0.000 description 12
- 239000004840 adhesive resin Substances 0.000 description 12
- 229920005672 polyolefin resin Polymers 0.000 description 12
- 238000001035 drying Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000007127 saponification reaction Methods 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 239000000806 elastomer Substances 0.000 description 5
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001734 carboxylic acid salts Chemical class 0.000 description 4
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- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
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- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 240000008415 Lactuca sativa Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000004380 ashing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 235000012045 salad Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- 239000004278 EU approved seasoning Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000021107 fermented food Nutrition 0.000 description 2
- MSNWSDPPULHLDL-UHFFFAOYSA-K ferric hydroxide Chemical compound [OH-].[OH-].[OH-].[Fe+3] MSNWSDPPULHLDL-UHFFFAOYSA-K 0.000 description 2
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- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 2
- BMTOKWDUYJKSCN-UHFFFAOYSA-K iron(3+);phosphate;dihydrate Chemical compound O.O.[Fe+3].[O-]P([O-])([O-])=O BMTOKWDUYJKSCN-UHFFFAOYSA-K 0.000 description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
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- FFHDFBALZJMPST-UHFFFAOYSA-N 3-ethoxy-2-(ethoxymethyl)prop-1-ene Chemical compound CCOCC(=C)COCC FFHDFBALZJMPST-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- WTRHVJKXJQHIOP-UHFFFAOYSA-N 3-propoxy-2-(propoxymethyl)prop-1-ene Chemical compound CCCOCC(=C)COCCC WTRHVJKXJQHIOP-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明提供一種熔融成形用乙烯-乙烯醇系共聚物組成物,作為加熱後之著色受到抑制之乙烯-乙烯醇系共聚物及多層結構體,含有乙烯-乙烯醇系共聚物(A)、鹼土類金屬化合物(B)及鐵化合物(C),鐵化合物(C)之含量就乙烯-乙烯醇系共聚物組成物之每單位重量而言按金屬換算係為0.01~20ppm。
Description
本發明係關於以乙烯-乙烯醇系共聚物(以下有時簡稱「EVOH樹脂」)作為主成分之熔融成形用EVOH樹脂組成物、丸粒及多層結構體,更詳言之,係關於加熱後之著色受到抑制之熔融成形用EVOH樹脂組成物、丸粒及多層結構體。
EVOH樹脂的透明性、氧氣等氣體的阻隔性、保香性、耐溶劑性、耐油性、機械強度等優異,成形為薄膜、片、瓶等且廣泛作為食品包裝材料、醫藥品包裝材料、工業藥品包裝材料、農藥包裝材料等各種包裝材料使用。
但是EVOH樹脂因為在分子內有比較活潑的羥基,即使在幾乎無氧狀態之擠壓成形機內部,仍會於高溫熔融狀態發生氧化、交聯反應,有發生著色、凝膠化等問題的傾向。為了解決該課題,例如專利文獻1揭示一種樹脂組成物,其特徵為係含有乙烯含量為20~60莫耳%、皂化度為90莫耳%以上之乙烯-乙酸乙烯酯共聚物皂化物(A)、乙酸(B)、乙酸鎂及/或乙酸鈣(C)而成,且(B)之含量相對於(A)100重量份為0.05重量份以下、(C)之含量按金屬換算係相對於(A)100重量份為0.001~0.02重量份,藉由使用此樹脂組成物,熔融成形時之長期性優異,可獲得少有魚眼、條紋、著色、且外觀性優良的成形物,而且將該成形物製成疊層體時的臭味減少,即使經延伸、深抽拉等二次加工後,該疊層體之層間黏著性仍優良。 [先前技術文獻] [專利文獻]
[專利文獻1]日本特開平11-106592號公報
(發明欲解決之課題)
近年來,伴隨成形裝置中之進料模組、模形狀之多樣化、最終製品中之多層結構體之薄膜化、層數增加等各種高功能化的要求,成形裝置有高功能化的傾向。反之,有樹脂在因為高功能化而變得複雜的成形裝置內發生熱劣化且著色等而製品之生產性降低的傾向,需進一步改善。 (解決課題之方式)
本案發明人等有鑑於上述實情而努力研究,結果,發現:藉由併用鹼土類金屬化合物及微量鐵化合物來作為EVOH樹脂之摻合劑,加熱時可獲得著色抑制效果。
亦即,本發明之第1要旨係一種熔融成形用EVOH樹脂組成物,含有EVOH樹脂(A)、鹼土類金屬化合物(B)及鐵化合物(C),其特徵為鐵化合物(C)之含量為EVOH樹脂組成物之每單位重量,按金屬換算係為0.01~20ppm。第2要旨為一種丸粒,係由上述熔融成形用EVOH樹脂組成物構成。再者,本發明之第3要旨為一種多層結構體,具備由上述熔融成形用EVOH樹脂組成物構成之層。 (發明之效果)
本發明之熔融成形用EVOH樹脂組成物,含有EVOH樹脂(A)、鹼土類金屬化合物(B)及鐵化合物(C),鐵化合物(C)之含量,就EVOH樹脂組成物之每單位重量按金屬換算係為0.01~20ppm,可抑制熔融成形等加熱時之著色。
又,本發明之中,尤其上述鹼土類金屬化合物(B)之含量若就EVOH樹脂組成物之每單位重量按金屬換算係為0.1~500ppm,則能成為更抑制熔融成形等加熱時之著色者。
本發明之中,若上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為0.005~50000,則能成為更抑制熔融成形等加熱時之著色者。
再者,本發明之中,尤其若上述鹼土類金屬化合物(B)為羧酸鹽,則能成為更抑制熔融成形等加熱時之著色者。
又,由本發明之熔融成形用EVOH樹脂組成物構成之丸粒,因為抑制在熔融成形等加熱時之著色的效果良好,適合以熔融成形製成作為各種成形物之例如食品、藥品、農藥等包裝材料。
具備由本發明之熔融成形用EVOH樹脂組成物構成層之多層結構體,例如作為食品、藥品、農藥等包裝材料特別有用。
以下針對本發明之構成詳細説明,但它們係理想實施態樣之一例,不限於該等內容。
本發明之熔融成形用EVOH樹脂組成物使用之EVOH樹脂組成物,係以EVOH樹脂(A)作為主成分,並含有鹼土類金屬化合物(B)及鐵化合物(C)。本發明之熔融成形用EVOH樹脂組成物中,基礎樹脂為EVOH樹脂(A)。亦即,EVOH樹脂組成物中之EVOH樹脂(A)之含量通常70重量%以上,較佳為80重量%以上,更佳為90重量%以上,尤佳為95重量%以上。以下有時本發明之熔融成形用EVOH樹脂組成物稱為「EVOH樹脂組成物」。 以下針對各成分説明。
[EVOH樹脂(A)] 本發明使用之EVOH樹脂(A),通常係藉由使乙烯與乙烯酯系單體之共聚物即乙烯-乙烯酯系共聚物進行皂化而獲得之樹脂,為非水溶性之熱塑性樹脂。就上述乙烯酯系單體而言,考量經濟性方面,一般而言使用乙酸乙烯酯。
作為乙烯與乙烯酯系單體之聚合法,可使用公知之任意聚合法,例如:溶液聚合、懸浮聚合、乳劑聚合等來進行,但一般而言係使用以甲醇作為溶劑之溶液聚合。獲得之乙烯-乙烯酯系共聚物之皂化也可利用公知方法進行。
依此方式製造之EVOH樹脂(A),係以來自乙烯之結構單元及乙烯醇結構單元為主,並含有未皂化而殘存的若干量的乙烯酯結構單元。
作為上述乙烯酯系單體,考量市場取得性、製造時之雜質處理效率良好的觀點,以使用乙酸乙烯酯為代表。其他乙烯酯系單體,例如:甲酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、叔碳酸乙烯酯等脂肪族乙烯酯、苯甲酸乙烯酯等芳香族乙烯酯等,通常可使用碳數3~20,較佳為碳數4~10,尤佳為碳數4~7之脂肪族乙烯酯。它們通常係單獨使用但也可視需要同時使用多種。
EVOH樹脂(A)中之乙烯結構單元之含量,可利用使乙烯酯系單體與乙烯共聚合時之乙烯之壓力來控制,通常為20~60莫耳%,較佳為25~50莫耳%,尤佳為25~35莫耳%。該含量若過低,會有在高濕下之氣體阻隔性、延伸性降低之傾向,若反之過高時,會有氣體阻隔性降低之傾向。 又,該乙烯結構單元之含量可依據ISO14663來測定。
EVOH樹脂(A)中之乙烯酯成分之皂化度,可利用將乙烯-乙烯酯系共聚物進行皂化時之皂化觸媒(通常使用氫氧化鈉等鹼性觸媒)之量、溫度、時間等來控制,通常為90~100莫耳%,較佳為95~100莫耳%,尤佳為99~100莫耳%。該皂化度若過低,氣體阻隔性、熱安定性、耐濕性等有降低之傾向。 該EVOH樹脂(A)之皂化度可依據JIS K6726(惟EVOH樹脂係以均勻溶解於水/甲醇溶劑之溶液的形態使用)來測定。
又,該EVOH樹脂(A)之熔體流動速率(MFR)(210℃、負荷2160g),通常為0.5~100g/10分,較佳為1~50g/10分,尤佳為3~35g/10分。該MFR若過大,會有損及製膜時之安定性之傾向,若過小會有黏度過高而難以進行熔融擠壓的傾向。 該MFR係成為EVOH樹脂之聚合度之指標,可以藉由乙烯與乙烯酯系單體進行共聚合時之聚合起始劑之量、溶劑之量來調整。
本發明使用之EVOH樹脂(A)中,在不妨礙本發明效果之範圍內(例如:EVOH樹脂(A)之10莫耳%以下),也可進一步含有來自以下所示之共聚單體之結構單元。 上述共聚單體可列舉丙烯、1-丁烯、異丁烯等烯烴類、3-丁烯-1-醇、3-丁烯-1,2-二醇、4-戊烯-1-醇、5-己烯-1,2-二醇等含羥基之α-烯烴類、其酯化物、醯基化物等衍生物;2-亞甲基丙烷-1,3-二醇、3-亞甲基戊烷-1,5-二醇等羥基烷基亞乙烯類;1,3-二乙醯氧基-2-亞甲基丙烷、1,3-二丙醯氧基-2-亞甲基丙烷、1,3-二丁醯氧基-2-亞甲基丙烷等羥基烷基亞乙烯二乙酸酯類;丙烯酸、甲基丙烯酸、巴豆酸、鄰苯二甲酸(酐)、馬來酸(酐)、衣康酸(酐)等不飽和酸類或其鹽或碳數1~18之單或二烷酯類;丙烯醯胺、碳數1~18之N-烷基丙烯醯胺、N,N-二甲基丙烯醯胺、2-丙烯醯胺丙烷磺酸或其鹽、丙烯醯胺丙基二甲胺或其酸鹽或其四級鹽等丙烯醯胺類;甲基丙烯醯胺、碳數1~18之N-烷基甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、2-甲基丙烯醯胺丙烷磺酸或其鹽、甲基丙烯醯胺丙基二甲胺或其酸鹽或其四級鹽等甲基丙烯醯胺類;N-乙烯基吡咯烷酮、N-乙烯基甲醯胺、N-乙烯基乙醯胺等N-乙烯基醯胺類;丙烯腈、甲基丙烯腈等氰化乙烯類;碳數1~18之烷基乙烯醚、羥基烷基乙烯醚、烷氧基烷基乙烯醚等乙烯醚類;氯乙烯、偏二氯乙烯、氟化乙烯、氟化亞乙烯、溴化乙烯等鹵化乙烯化合物類;三甲氧基乙烯基矽烷等乙烯基矽烷類;乙酸烯丙酯、氯化丙烯等鹵化丙烯化合物類;烯丙醇、二甲氧基烯丙醇等烯丙醇類;三甲基-(3-丙烯醯胺-3-二甲基丙基)-氯化銨、丙烯醯胺-2-甲基丙烷磺酸等共聚單體。可將它們單獨使用或併用2種以上。
尤其側鏈有1級羥基之EVOH樹脂,考量保持著氣體阻隔性且二次成形性良好之觀點較理想,其中,將含羥基之α-烯烴類進行共聚合而得之EVOH樹脂較理想,尤其側鏈有1,2-二醇結構之EVOH樹脂較佳。 尤其為側鏈有1級羥基之EVOH樹脂的情形,來該具1級羥基之單體之結構單元之含量通常為EVOH樹脂之0.1~20莫耳%,更好為0.5~15莫耳%,尤佳為1~10莫耳%。
又,本發明使用之EVOH樹脂(A)也可為經胺甲酸酯化、縮醛化、氰基乙基化、氧伸烷基化等「後改性」者。
再者,本發明使用之EVOH樹脂(A),也可為和不同之其他EVOH樹脂之混合物,該其他EVOH樹脂可列舉皂化度不同者、聚合度不同者、共聚合成分不同者等。
[鹼土類金屬化合物(B)] 本發明之EVOH樹脂組成物,為含有鹼土類金屬化合物(B)之樹脂組成物,相對於EVOH樹脂組成物全體,鹼土類金屬化合物(B)按重量基準計通常含量為1~1000ppm。上述鹼土類金屬化合物(B)之含量較佳為10~800ppm,尤佳為50~500ppm。 又,鹼土類金屬化合物(B)之按金屬重量換算之含量,相對於EVOH樹脂組成物全體通常為0.1~500ppm,較佳為0.5~300ppm,更佳為1~200ppm,尤佳為2~150ppm。 上述含量若過多,有熱安定性降低之傾向,若過少,則有EVOH樹脂組成物之成形性降低之傾向。
又,成為上述鹼土類金屬化合物(B)之含有比例之基準之EVOH樹脂組成物,係含有EVOH樹脂(A)、鹼土類金屬化合物(B)、鐵化合物(C)、視需要摻合之各種添加劑等之作為最終製品之EVOH樹脂組成物。
本發明使用之鹼土類金屬化合物(B)之鹼土類金屬種類,例如:鈹、鎂、鈣、鍶、鋇、鐳。可將它們單獨使用或併用2種以上。其中,考量市場取得性、經濟性之觀點,較佳為鎂、鈣。
本發明使用之鹼土類金屬化合物(B)可列舉上述鹼土類金屬之鹽、氧化物、氫氧化物等。其中,考量經濟性、分散性之觀點,鹼土類金屬氧化物或鹼土類金屬鹽較理想,尤其鹼土類金屬鹽為較佳。上述鹼土類金屬氧化物,例如:氧化鎂、氧化鈣等。上述鹼土類金屬鹽,例如:碳酸鹽、碳酸氫鹽、磷酸鹽、硼酸鹽、硫酸鹽、氯化物鹽等無機鹽、羧酸鹽。 本發明使用之鹼土類金屬化合物(B),考量經濟性、分散性之觀點,宜排除蒙特石等層狀無機化合物、水滑石等複鹽較佳。
其中,考量加熱時之黏度下降效果優異之觀點,羧酸鹽為較佳。該羧酸鹽可列舉飽和或不飽和之羧酸鹽。例如:乙酸鹽、丁酸鹽、丙酸鹽、庚酸鹽、癸酸鹽、月桂酸鹽、棕櫚酸鹽、硬脂酸鹽、12羥基硬脂酸鹽、二十二酸鹽、褐煤酸鹽等一元羧酸鹽、草酸鹽、丙二酸鹽、琥珀酸鹽、己二酸鹽、辛二酸鹽、癸二酸鹽等二元羧酸鹽等。可單獨使用它們中的1種或併用2種以上。考量市場取得性之觀點,較佳為直鏈飽和羧酸鹽,更佳為一元羧酸鹽。 該羧酸鹽之陰離子之碳數通常為2~25,考量生產性之觀點,較佳為2~22,尤佳為6~20。 又,使用多數種鹼土類金屬化合物(B)時,鹼土類金屬化合物之含量為全部鹼土類金屬化合物(B)合計的含量。
而且,上述鹼土類金屬化合物(B)之形態,可採用例如:固體狀(粉末、微粉末、屑片等)、半固體狀、液體狀、糊劑狀、溶液狀、乳劑狀(水分散液)等任意性狀者。其中,粉末狀較佳。
本發明之EVOH樹脂組成物中,鹼土類金屬化合物(B)之含量,例如可將本發明之EVOH樹脂組成物進行加熱灰化後以鹽酸等進行酸處理,於獲得之溶液中加入純水予以定容以作為檢液,以原子吸光光度計來測定。
[鐵化合物(C)] 本發明之EVOH樹脂組成物,特徵為:含有EVOH樹脂(A)、鹼土類金屬化合物(B)及鐵化合物(C)且鐵化合物(C)之摻合量為特定微量。發現:藉由採用該構成,EVOH樹脂組成物加熱後之著色會受抑制。
一般,已知藉由於EVOH樹脂摻合鹼土類金屬鹽,會有加熱時隨時間經過黏度減小的傾向。該機轉雖不詳,據推測是由於摻合鹼土類金屬化合物使EVOH樹脂組成物呈鹼性,可能有些陰離子成為親核劑,奪取鍵結在EVOH樹脂之主鏈碳的氫等而引起主鏈之分解反應,並切斷EVOH樹脂之主鏈。EVOH樹脂之加熱後之著色,據推測是因為上述反應時在EVOH樹脂之主鏈生成雙鍵結構,該結構再度成為反應起點,引起脱水反應等,並在EVOH樹脂之主鏈形成多烯結構。
本發明中,藉由併用鹼土類金屬化合物(B)與特定微量之鐵化合物(C),該著色受抑制。亦即,鐵以3價離子的形式為安定,推測即使是微量,仍會配位在如上述EVOH樹脂之主鏈之雙鍵並形成螯合物等而安定化,抑制多烯結構之形成。 又,本發明中,意外發現藉由併用鹼土類金屬化合物(B)與鐵化合物(C),加熱時之隨時間經過之減黏效果會增強。
本發明之EVOH樹脂組成物中,鐵化合物(C)之含量就EVOH樹脂組成物之每單位重量而言按金屬換算係為0.01~20ppm。較佳為0.03~8ppm,尤佳為0.05~3ppm、特佳為0.05~0.8ppm。 上述鐵化合物(C)之含量若過少則加熱後之著色抑制效果有降低之傾向,反之若過多則成形物有著色之傾向。
在此,鐵化合物(C)之含量係以下列方法測定。 <鐵化合物(C)之分析> 將EVOH樹脂組成物丸粒之粉碎物0.5g於紅外線加熱爐、氧氣流中於650℃進行1小時灰化處理,將灰分進行酸溶解並以純水定容後,作為試樣溶液。將此溶液以Agilent Technologies公司製 ICP質量分析裝置 7500ce型,以ICP-MS標準添加法進行測定。
又,該鐵化合物(C)在EVOH樹脂組成物中,以例如:氧化物、氫氧化物、氯化物、鐵鹽的形式存在,此外也可以經離子化之狀態、或和樹脂、其他配位子交替作用之錯合物之狀態存在。上述氧化物,例如:氧化鐵(III)、四氧化三鐵、氧化鐵(II)等。上述氯化物,例如:氯化鐵(II)、氯化鐵(III)等。上述氫氧化物,例如:氫氧化鐵(II)、氫氧化鐵(III)等。上述鐵鹽,例如:磷酸鐵、硫酸鐵等無機鹽、羧酸(乙酸、丁酸、硬脂酸等)鐵等有機鹽。可將它們單獨使用或併用2種以上。
考量在EVOH樹脂組成物中之分散性之觀點,鐵化合物(C)宜為水溶性較佳。又,考量分散性與生產性之觀點,其分子量為通常100~10000,較佳為100~1000,尤佳為100~500。
本發明使用之EVOH樹脂組成物中,前述鹼土類金屬化合物(B)之含量相對於上述鐵化合物(C)之金屬換算含量之重量比,通常為0.2~50000,較佳為1~10000,尤佳為50~8000,特佳為800~5000。 又,前述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比,通常0.005~50000,較佳為1~30000,尤佳為10~10000で,特佳為30~5000。 上述値若太大,會有妨礙熱安定性的傾向,若過小則有成形物著色之傾向。
[其他熱塑性樹脂] 在本發明使用之EVOH樹脂組成物中,可於不妨礙本發明之效果之範圍(例如通常為EVOH樹脂組成物之30重量%以下,較佳為20重量%以下,尤佳為10重量%以下)內含有EVOH樹脂(A)以外之熱塑性樹脂。 其他熱塑性樹脂可使用公知之熱塑性樹脂。例如:具體而言,可列舉聚醯胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚苯乙烯系樹脂、聚氯乙烯系樹脂、聚碳酸酯系樹脂、聚丙烯酸系樹脂、離子聚合物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、乙烯-甲基丙烯酸共聚物、乙烯-甲基丙烯酸酯共聚物、聚偏二氯乙烯、乙烯酯系樹脂、聚酯彈性體、聚胺甲酸酯彈性體、氯化聚乙烯、氯化聚丙烯等。可將它們單獨使用或併用2種以上。
[其他摻合劑] 又,本發明之EVOH樹脂組成物中,在不妨礙本發明之效果之範圍內,也可含有一般在EVOH樹脂中摻合之摻合劑。可摻合例如:塑化劑(例如乙二醇、甘油、己烷二醇等脂肪族多元醇等)、氧吸收劑[例如:鋁粉、亞硫酸鉀、光觸媒氧化鈦等無機系氧吸收劑;抗壞血酸、進而其脂肪酸酯、鹼土類金屬以外之金屬鹽等、氫醌、没食子酸、含羥基之苯酚醛樹脂等多元苯酚類、雙水楊醛-亞胺鈷、四乙烯五胺鈷、鈷-希夫鹼錯合物、卟啉類、大環狀聚胺錯合物、聚乙烯亞胺-鈷錯合物等含氮化合物與鐵以外之過渡金屬之配位結合體、萜烯化合物、胺基酸類與含羥基之還原性物質之反應產物、三苯基甲基化合物等有機化合物系氧吸收劑;含氮樹脂與鐵以外之過渡金屬之配位結合體(例如:甲基亞二甲苯二胺(MXD)尼龍與鈷之組合)、含三級氫之樹脂與鐵以外之過渡金屬之摻混物(例如聚丙烯與鈷之組合)、含碳-碳不飽和鍵之樹脂與鐵以外之過渡金屬之摻混物(例如聚丁二烯與鈷之組合)、光氧化崩壞性樹脂(例如聚酮)、蒽醌聚合物(例如聚乙烯基蒽醌)等、進而於該等摻合物中添加了光起始劑(二苯酮等)、過氧化物捕捉劑(市售抗氧化劑等)、消臭劑(活性碳等)者等之高分子系氧吸收劑]、熱安定劑、光安定劑、紫外線吸收劑、著色劑、抗靜電劑、界面活性劑(惟不包括作為潤滑劑使用者)、抗菌劑、抗黏連劑、填充材(例如無機填料等)等。該等化合物可單獨使用或併用2種以上。
[EVOH樹脂組成物之製造方法] 製造本發明之EVOH樹脂組成物之方法,例如:乾摻混法、熔融混合法、溶液混合法、含浸法等公知之方法,可將它們任意地組合。
乾摻混法,例如(i)將EVOH樹脂(A)丸粒、與鹼土類金屬化合物(B)及鐵化合物(C)之至少一者使用滾動機等進行乾摻混之方法等。
熔融混合法,例如:(ii)將EVOH樹脂(A)丸粒、與鹼土類金屬化合物(B)及鐵化合物(C)之至少一者的乾摻混物進行熔融混練,並獲得丸粒、成形物之方法、(iii)於熔融狀態之EVOH樹脂(A)中添加鹼土類金屬化合物(B)及鐵化合物(C)至少一者並熔融混練,獲得丸粒、成形物之方法等。
溶液混合法,例如:(iv)使用市售之EVOH樹脂(A)丸粒製備成溶液,於其中摻合鹼土類金屬化合物(B)及鐵化合物(C)之至少一者,凝固成形並造粒,進行固液分離並乾燥之方法、(v)於EVOH樹脂(A)之製造過程,使EVOH樹脂之均勻溶液(水/醇溶液等)中含有鹼土類金屬化合物(B)及鐵化合物(C)之至少一者後,凝固成形並造粒,進行固液分離而乾燥之方法等。
含浸法,例如(vi)使EVOH樹脂(A)丸粒接觸含有鹼土類金屬化合物(B)及鐵化合物(C)之至少一者之水溶液,使EVOH樹脂(A)丸粒中含有鹼土類金屬化合物(B)及鐵化合物(C)之至少一者後進行乾燥之方法等。
本發明中,可將上述不同方法予以組合。其中,考量生產性、獲得本發明之效果更顯著之樹脂組成物之觀點,熔融混合法較理想,尤其(ii)的方法較佳。
又,利用上述各方法獲得之本發明之EVOH樹脂組成物丸粒、各方法使用之EVOH樹脂(A)丸粒之形狀為任意。例如:球形、卵形、圓柱形、立方體形、直方體形等,通常為卵形或圓柱形,考量之後作為成形材料時之方便性之觀點,其大小於卵形時短徑通常為1~10mm,較佳為2~6mm,又更佳為2.5~5.5mm,長徑通常為1.5~30mm,較佳為3~20mm,又更佳為3.5~10mm。又,圓柱形時底面之直徑通常為1~6mm,較佳為2~5mm,長度通常為1~6mm,較佳為2~5mm。
又,上述各方法使用之鐵化合物(C)如前述,較佳為水溶性之鐵化合物,例如:氧化鐵(III)、四氧化三鐵、氧化鐵(II)等氧化物、氯化鐵(II)、氯化鐵(III)等氯化物、氫氧化鐵(II)、氫氧化鐵(III)等氫氧化物、磷酸鐵、硫酸鐵等無機鹽、羧酸(乙酸、丁酸、硬脂酸等)鐵等有機鹽等鐵鹽。又,該鐵化合物(C),如前述,在EVOH樹脂組成物中除了以上述鹽的形式存在以外,也能以經離子化之狀態、或以樹脂、其他化合物作為配位子之錯合物之狀態存在。
又,作為上述(vi)的方法使用之含有鐵化合物之水溶液,可使用上述鐵化合物之水溶液、藉由使鐵鋼材料浸於含各種藥劑之水以使鐵離子溶出而得者。又,於此情形,EVOH樹脂組成物中之鐵化合物(C)之含量(金屬換算)可以利用浸漬EVOH樹脂(A)丸粒之水溶液中之鐵化合物之濃度、浸漬溫度、浸漬時間等來控制。上述浸漬溫度、浸漬時間通常為0.5~48小時,較佳為1~36小時,浸漬溫度通常為10~40℃,較佳為20~35℃。 該EVOH樹脂組成物丸粒以公知之方法進行固液分離並以公知之乾燥方法進行乾燥。該乾燥方法可採用各種乾燥方法,可為靜置乾燥、流動乾燥中之任一者。又,可以將它們組合進行。
本發明之EVOH樹脂組成物之含水率通常為0.01~0.5重量%,較佳為0.05~0.35重量%,尤佳為0.1~0.3重量%。
又,本發明之EVOH樹脂組成物之含水率係依下列方法測定、計算。 以電子天平稱量EVOH樹脂組成物之乾燥前重量(W1),於150℃之熱風乾燥機中使其乾燥5小時,並於乾燥器中放冷30分鐘後稱重得到重量(W2),依下式算出。 含水率(重量%)=[(W1-W2)/W1]×100
以此方式獲得之EVOH樹脂組成物之丸粒,可直接供熔融成形,但考量使熔融成形時之進料性安定之觀點,使丸粒之表面附著公知之潤滑劑亦為理想。潤滑劑之種類可列舉高級脂肪酸(例如月桂酸、肉豆蔲酸、棕櫚酸、硬脂酸、二十二酸、油酸等)、高級脂肪酸酯(高級脂肪酸之甲酯、異丙酯、丁酯、辛酯等)、高級脂肪醯胺(例如:月桂醯胺、肉豆蔲醯胺、棕櫚醯胺、硬脂醯胺、二十二醯胺等飽和高級脂肪醯胺;油醯胺、芥醯胺等不飽和高級脂肪醯胺、乙烯雙硬脂醯胺、乙烯雙油醯胺、乙烯雙芥醯胺、乙烯雙月桂醯胺等雙高級脂肪醯胺等)、低分子量聚烯烴(例如分子量500~10000左右之低分子量聚乙烯、或低分子量聚丙烯等、或其酸改性品)、高級醇、酯寡聚物、氟化乙烯樹脂等。該潤滑劑之含量通常為EVOH樹脂組成物之5重量%以下,較佳為1重量%以下。
本發明之EVOH樹脂組成物,係製成丸粒、或粉末狀、液體狀這類各式各樣的形態之EVOH樹脂組成物,來提供作為各種成形物之熔融成形用材料。又,本發明之EVOH樹脂組成物中,也包括混合本發明之EVOH樹脂組成物中使用的EVOH樹脂(A)以外之樹脂而獲得之樹脂組成物。
就該成形物而言,主要能以使用本發明之EVOH樹脂組成物丸粒成形而得之單層薄膜,及具使用本發明之EVOH樹脂組成物丸粒成形而得之層之多層結構體的形式供實用。
[多層結構體] 使用本發明之熔融成形用EVOH樹脂組成物獲得之多層結構體,具有由上述EVOH樹脂組成物構成之層。使用本發明之熔融成形用EVOH樹脂組成物獲得之含EVOH樹脂組成物之層(以下簡單稱「EVOH樹脂組成物層」),可以藉由和本發明之EVOH樹脂組成物以外之以熱塑性樹脂作為主成分之其他基材(以下有時將基材中使用的樹脂簡稱「基材樹脂」)進行疊層,而進一步賦予強度、或保護EVOH樹脂組成物層免受水分等影響、或賦予其他功能。
上述基材樹脂,例如:直鏈狀低密度聚乙烯、低密度聚乙烯、超低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、乙烯-丙烯(嵌段及無規)共聚物、乙烯-α-烯烴(碳數4~20之α-烯烴)共聚物等聚乙烯系樹脂、聚丙烯、丙烯-α-烯烴(碳數4~20之α-烯烴)共聚物等聚丙烯系樹脂、聚丁烯、聚戊烯、聚環狀烯烴系樹脂(於主鏈及側鏈至少一者具環狀烯烴結構之聚合物)等(未改性)聚烯烴系樹脂、將該等聚烯烴類利用不飽和羧酸或其酯予以接枝改性而得之不飽和羧酸改性聚烯烴系樹脂等包括改性烯烴系樹脂之廣義之聚烯烴系樹脂、離子聚合物、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚酯系樹脂、聚醯胺系樹脂(也包括共聚合聚醯胺)、聚氯乙烯、聚偏二氯乙烯、丙烯酸系樹脂、聚苯乙烯系樹脂、乙烯酯系樹脂、聚酯系彈性體、聚胺甲酸乙酯系彈性體、聚苯乙烯系彈性體、氯化聚乙烯、氯化聚丙烯等鹵化聚烯烴、芳香族或脂肪族聚酮類等。
該等之中,係疏水性樹脂之聚醯胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚苯乙烯系樹脂較理想,更佳為聚乙烯系樹脂、聚丙烯系樹脂、聚環狀烯烴系樹脂及該等之不飽和羧酸改性聚烯烴系樹脂等聚烯烴系樹脂。
多層結構體之層構成,當令由本發明之熔融成形用EVOH樹脂組成物獲得之EVOH樹脂組成物層為a(a1、a2、・・・)、基材樹脂層為b(b1、b2、・・・)時,可為a/b、b/a/b、a/b/a、a1/a2/b、a/b1/b2、b2/b1/a/b1/b2、b2/b1/a/b1/a/b1/b2等任意組合。又,當令將該多層結構體製造過程發生之端部、不良品等予以再熔融成形獲得之含有上述EVOH樹脂組成物與本發明之EVOH樹脂組成物以外之熱塑性樹脂之混合物之回收層作為R時,可以為b/R/a、b/R/a/b、b/R/a/R/b、b/a/R/a/b、b/R/a/R/a/R/b等。多層結構體之層之數目,共計通常2~15,較佳為3~10。上述層構成中,各層間視需要也可插入含黏著性樹脂之黏著性樹脂層。
上述黏著性樹脂可使用公知品,可因應基材樹脂「b」使用之熱塑性樹脂之種類適當選擇。可列舉將不飽和羧酸或其酐利用加成反應、接枝反應等而化學鍵結在聚烯烴系樹脂而獲得之含羧基之改性聚烯烴系聚合物為代表。上述含羧基之改性聚烯烴系聚合物,例如:馬來酸酐接枝改性聚乙烯、馬來酸酐接枝改性聚丙烯、馬來酸酐接枝改性乙烯-丙烯(嵌段及無規)共聚物、馬來酸酐接枝改性乙烯-丙烯酸乙酯共聚物、馬來酸酐接枝改性乙烯-乙酸乙烯酯共聚物、馬來酸酐改性聚環狀烯烴系樹脂、馬來酸酐接枝改性聚烯烴系樹脂等。並且,可使用從其中選出之1種或2種以上之混合物。
多層結構體中,從本發明之熔融成形用EVOH樹脂組成物獲得之EVOH樹脂組成物層與基材樹脂層之間,若使用黏著性樹脂層時黏著性樹脂層位在EVOH樹脂組成物層之兩側,故宜使用疏水性優異之黏著性樹脂較佳。
上述基材樹脂、黏著性樹脂中,在不妨礙本發明之意旨之範圍內(例如相對於樹脂全體為30重量%以下,較佳為10重量%以下),可使用以往已知之塑化劑、填料、黏土(蒙特石(montmorillonite)等)、著色劑、抗氧化劑、抗靜電劑、潤滑劑、成核材、抗黏連劑、蠟等。可將它們單獨使用或併用2種以上。
使用本發明之熔融成形用EVOH樹脂組成物而獲得之EVOH樹脂組成物層與上述基材樹脂層間的疊層(包括插入黏著性樹脂層的情形),可利用公知方法進行。例如:將基材樹脂進行熔融擠壓層合於EVOH樹脂組成物之薄膜、片等之方法、將EVOH樹脂組成物進行熔融擠壓層合於基材樹脂層之方法、將EVOH樹脂組成物與基材樹脂進行共擠壓之方法、將EVOH樹脂組成物(層)與基材樹脂(層)使用有機鈦化合物、異氰酸酯化合物、聚酯系化合物、聚胺甲酸酯化合物等公知之黏著劑進行乾層合之方法、在基材樹脂上塗佈EVOH樹脂組成物之溶液後將溶劑除去之方法等。該等之中,考慮成本、環境之觀點,進行共擠壓之方法較佳。
如上述多層結構體,之後視需要進行(加熱)延伸處理。延伸處理可為單軸延伸、雙軸延伸任一者,雙軸延伸的情形可為同時延伸也可逐次延伸。又,延伸方法可採用輥延伸法、拉幅延伸法、管式延伸法、延伸吹塑法、真空壓空成形等當中延伸倍率較高者。延伸溫度為多層結構體熔點附近之溫度,通常從40~170℃,較佳為60~160℃左右之範圍中選擇。延伸溫度若過低則延伸性不良,若過高則難以維持安定的延伸狀態。
又,延伸後為了賦予尺寸安定性,也可進行熱固定。熱固定可利用周知手段實施,例如將上述延伸薄膜保持緊張狀態於通常80~180℃,較佳為100~165℃進行通常2~600秒左右的熱處理。又,使用由本發明之熔融成形用EVOH樹脂組成物獲得之多層延伸薄膜作為收縮用薄膜時,為了賦予熱收縮性,可不進行上述熱固定,例如對於延伸後之薄膜吹送冷風並進行冷卻固定等處理。
又,也可視情形,使用上述多層結構體來獲得杯狀、托盤狀之多層容器。於此情形,通常採用引伸成形法,具體而言可列舉真空成形法、壓空成形法、真空壓空成形法、柱塞輔助式真空壓空成形法等。進而可從多層型坏(parison)(吹塑前之中空管狀之預備成形物)獲得管狀、瓶狀之多層容器(疊層體結構)時,採用吹塑成形法。具體而言,擠壓吹塑成形法(雙頭式、模具移動式、型坏偏移式、旋轉式、累積器式、水平型坏式等)、冷型坏式吹塑成形法、射出吹塑成形法、雙軸延伸吹塑成形法(擠壓式冷型坏雙軸延伸吹塑成形法、射出式冷型坏雙軸延伸吹塑成形法、射出成形線上式雙軸延伸吹塑成形法等)等。獲得之疊層體可以因應必要,進行熱處理、冷卻處理、壓延處理、印刷處理、乾層合處理、溶液或熔融塗覆處理、製袋加工、深抽拉加工、箱加工、管加工、分裂加工等。
多層結構體(包括經延伸者)之厚度,進而構成多層結構體之EVOH樹脂組成物層、基材樹脂層及黏著性樹脂層之厚度,取決於層構成、基材樹脂之種類、黏著性樹脂之種類、用途、包裝形態、要求之物性等,不能一概而論,但多層結構體(包括經延伸者)之厚度通常為10~5000μm,較佳為30~3000μm,尤佳為50~2000μm。EVOH樹脂組成物層通常為1~500μm,較佳為3~300μm,尤佳為5~200μm,基材樹脂層通常為5~3000μm,較佳為10~2000μm,尤佳為20~1000μm,黏著性樹脂層通常為0.5~250μm,較佳為1~150μm,尤佳為3~100μm。
再者,多層結構體中,EVOH樹脂組成物層相對於基材樹脂層之厚度之比(EVOH樹脂組成物層/基材樹脂層),於各層有多數時,厚度最厚之層之間之比通常為1/99~50/50,較佳為5/95~45/55,尤佳為10/90~40/60。又,多層結構體中,EVOH樹脂組成物層相對於黏著性樹脂層之厚度比(EVOH樹脂組成物層/黏著性樹脂層),於各層有多數時,按厚度最厚之層之間之比,通常為10/90~99/1,較佳為20/80~95/5,尤佳為50/50~90/10。
如上述獲得之由薄膜、片、延伸薄膜構成之袋及杯、托盤、管、瓶等而成的容器、蓋材,可作為一般食品、以及蛋黃醬、沙拉等調味料、味噌等發酵食品、沙拉油等油脂食品、飲料、化粧品、醫藥品等各種的包裝材料容器。 [實施例]
以下舉實施例對於本發明具體説明,但本發明只要不超過其要旨不限於實施例的記載。 又,例中「份」,若未特別指明,係指重量基準。
在實施例前,準備下列EVOH樹脂(A)之丸粒,並測定於此EVOH樹脂(A)含有的鐵化合物(C)的含量。 ・EVOH樹脂(A):乙烯結構單元之含量29莫耳%、皂化度99.6莫耳%、MFR3.9g/10分(210℃、負荷2160g)之乙烯-乙烯醇共聚物
[鐵化合物(C)之含量之測定] 將上述EVOH樹脂(A)之丸粒進行粉碎而得的樣本0.5g以紅外線加熱爐進行灰化處理(氧氣流中650℃、1小時),將灰分進行酸溶解並以純水定容後,作為試樣溶液。將此溶液使用下列ICP-MS(Agilent Technologies公司製ICP質量分析裝置 7500ce型)以標準添加法測定。其結果,鐵化合物(C)之含量,按金屬換算係為0ppm。
<實施例1> 將上述EVOH樹脂(A)之丸粒100份、作為鹼土類金屬化合物(B)之硬脂酸鎂(堺化學工業公司製、SM-PG)0.01份、作為鐵化合物(C)之磷酸鐵(III)n水合物(和光純藥工業公司製、230℃乾燥減量20.9重量%)0.000034份以PLASTOGRAPH (Brabender公司製)於230℃進行5分鐘預熱後,進行5分鐘熔融混練,獲得EVOH樹脂組成物。將獲得之EVOH樹脂組成物以粉碎機(SOMETANI產業公司製、SKR16-240)於650rpm粉碎,獲得粉碎物。該粉碎物為1~5mm四方之小片。 該EVOH樹脂組成物中之鹼土類金屬化合物(B)之金屬換算含量,按鎂換算係為4ppm。又,鐵化合物(C)之金屬換算含量為0.1ppm。上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為40。
<實施例2> 將實施例1中之磷酸鐵(III)n水合物之摻合量變更為0.00034份,除此以外和實施例1同樣進行,獲得實施例2之EVOH樹脂組成物及其粉碎物。 該EVOH樹脂組成物中之鹼土類金屬化合物(B)之金屬換算含量,按鎂換算係為4ppm。又,鐵化合物(C)之金屬換算含量為1ppm。上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為4。
<實施例3> 將實施例1中之磷酸鐵(III)n水合物之摻合量變更為0.0034份,除此以外和實施例1同樣進行,獲得實施例3之EVOH樹脂組成物及其粉碎物。 該EVOH樹脂組成物中之鹼土類金屬化合物(B)之金屬換算含量,按鎂換算係為4ppm。又,鐵化合物(C)之金屬換算含量為10ppm。上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為0.4。
<實施例4> 將實施例1中改為使用0.01份之氧化鎂(協和化學工業公司製、Kyowamag 30)作為鹼土類金屬(B),除此以外和實施例1同樣進行,獲得實施例4之EVOH樹脂組成物及其粉碎物。 該EVOH樹脂組成物中之鹼土類金屬化合物(B)之金屬換算含量,按鎂換算係為60ppm。又,鐵化合物(C)之金屬換算含量為0.1ppm。上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為600。
<實施例5> 將實施例1中之硬脂酸鎂之摻合量變更為0.03份,除此以外和實施例1同樣進行,獲得實施例5之EVOH樹脂組成物及其粉碎物。 該EVOH樹脂組成物中之鹼土類金屬化合物(B)之金屬換算含量,按鎂換算係為12ppm。又,鐵化合物(C)之金屬換算含量為0.1ppm。上述鹼土類金屬化合物(B)之金屬換算含量相對於上述鐵化合物(C)之金屬換算含量之重量比為120。
<比較例1> 實施例1中,未摻合磷酸鐵(III)n水合物,除此以外同樣進行,獲得比較例1之EVOH樹脂組成物及其粉碎物。
依下列所示方法進行實施例1~5及比較例1之EVOH樹脂組成物之著色評價及熱安定性評價。結果示於後表1。
[著色評價] 將上述EVOH樹脂組成物之粉碎物作為樣本,以日本電色工業公司製分光色差計 SE6000測定加熱前之YI値。此時係在內徑32mm、高度30mm之圓筒填充並擊打樣本的狀態供測定。又,將該樣本於空氣氣體環境下之烘箱內於150℃進行5小時加熱處理後,同樣地測定加熱後之YI値。計算加熱後之YI値相對於該加熱前之YI値之比。該値越大表示樹脂組成物在加熱後越著色成黃色。
[動態黏度行為] 將上述EVOH樹脂組成物之粉碎物以Plastograph(Brabender公司製)於230℃50rpm之條件下預熱5分鐘後,進行120分鐘熔融混合。將測定開始起算第5分鐘的轉矩除以測定開始時(第0分鐘)之轉矩所得的數値進行評價。該値越低,係指加熱時黏度上昇越受抑制。又,將測定開始時(第0分鐘)之轉矩除以測定結束時(第120分鐘)時點的轉矩所得的數値進行評價。該値越高,係指經時的黏度上昇越受抑制,動態黏度行為優良。
【表1】
使用了本發明之EVOH樹脂組成物之實施例1~5,比起不含有鐵化合物(C)之比較例1,加熱前後之YI値之比較小。由該結果可知:本發明之熔融成形用EVOH樹脂組成物在加熱時之著色受抑制。 再者,使用了本發明之熔融成形用EVOH樹脂組成物之實施例1~5,比起不含有鐵化合物(C)之比較例1,動態黏度行為(5分/0分)降低,動態黏度行為(0分/120分)上昇。此係指由於加熱,隨時間經過,EVOH樹脂組成物黏度下降,可知長期成形性良好。
上述實施例係針對本發明之具體形態揭示,但上述實施例只是單純例示,不做限定性解釋。對於該技術領域中具通常知識者而言為明顯的各式各樣的變形,也意欲包括在本發明之範圍內。 [產業利用性]
本發明之熔融成形用EVOH樹脂組成物,加熱後之著色受抑制且長期成形性優良,故作為各種食品、及蛋黃醬、沙拉醬等調味料、味噌等發酵食品、沙拉油等油脂食品、飲料、化粧品、醫藥品等各種的包裝材料有用。
Claims (6)
- 一種熔融成形用乙烯-乙烯醇系共聚物組成物,含有乙烯-乙烯醇系共聚物(A)、鹼土類金屬化合物(B)及鐵化合物(C),其特徵為:鐵化合物(C)之含量,就乙烯-乙烯醇系共聚物組成物之每單位重量而言按金屬換算係為0.01~20ppm。
- 如申請專利範圍第1項之熔融成形用乙烯-乙烯醇系共聚物組成物,其中,該鹼土類金屬化合物(B)之含量,就乙烯-乙烯醇系共聚物組成物之每單位重量而言按金屬換算係為0.1~500ppm。
- 如申請專利範圍第1或2項之熔融成形用乙烯-乙烯醇系共聚物組成物,其中,該鹼土類金屬化合物(B)之金屬換算含量相對於該上述鐵化合物(C)之金屬換算含量之重量比為0.005~50000。
- 如申請專利範圍第1或2項之熔融成形用乙烯-乙烯醇系共聚物組成物,其中,該鹼土類金屬化合物(B)為羧酸鹽。
- 一種丸粒,係由如申請專利範圍第1至4項中任一項之熔融成形用乙烯-乙烯醇系共聚物組成物構成。
- 一種多層結構體,其特徵為:具備由如申請專利範圍第1至4項中任一項之熔融成形用乙烯-乙烯醇系共聚物組成物構成之層。
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