TWI808979B - 乙烯-乙烯醇系共聚物組成物、丸粒及多層結構體 - Google Patents
乙烯-乙烯醇系共聚物組成物、丸粒及多層結構體 Download PDFInfo
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- TWI808979B TWI808979B TW107122176A TW107122176A TWI808979B TW I808979 B TWI808979 B TW I808979B TW 107122176 A TW107122176 A TW 107122176A TW 107122176 A TW107122176 A TW 107122176A TW I808979 B TWI808979 B TW I808979B
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- resin composition
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- iron
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- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 51
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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 abstract 6
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- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 6
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
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- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- JSNRRGGBADWTMC-UHFFFAOYSA-N (6E)-7,11-dimethyl-3-methylene-1,6,10-dodecatriene Chemical compound CC(C)=CCCC(C)=CCCC(=C)C=C JSNRRGGBADWTMC-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
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Abstract
就著色受到抑制,熱穩定性優異的乙烯-乙烯醇系共聚物組成物而言,本發明提供一種乙烯-乙烯醇系共聚物組成物,含有乙烯-乙烯醇系共聚物(A)、具有共軛多烯結構之化合物(B)及鐵化合物(C);其特徵為:上述鐵化合物(C)之含量,在每單位重量之乙烯-乙烯醇系共聚物組成物中按金屬換算為0.01~20ppm。
Description
本發明關於以乙烯-乙烯醇系共聚物(以下,稱為「EVOH樹脂」。)作為主成分之EVOH樹脂組成物、由EVOH樹脂組成物構成之丸粒及多層結構體,更詳細而言,係關於加熱後之著色受到抑制且熱穩定性優異的EVOH樹脂組成物、由EVOH樹脂組成物構成之丸粒及具備由該EVOH樹脂組成物構成之層的多層結構體。
EVOH樹脂具有優異的透明性、氧氣等氣體阻隔性、保香性、耐溶劑性、耐油性、機械強度等,被成形為薄膜、片材、瓶等,並廣泛用作食品包裝材料、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。
但,EVOH樹脂由於分子內具有相對較具活性的羥基,故有容易因熱而劣化的傾向。因此,會有熔融成形時容易發生著色問題的傾向。
另一方面,就能抑制熔融成形時之魚眼、凝膠、條紋(streak)等缺點的產生,並可形成外觀性優異之容器、薄膜等成形品的樹脂組成物而言,已知一種樹脂組成物,含有EVOH樹脂(A)及不飽和醛(B),上述不飽和醛(B)相對於樹脂組成物
的含量為0.01ppm以上100ppm以下(例如,參照專利文獻1)。該樹脂組成物中,藉由進一步含有共軛多烯化合物,可抑制熔融成形時之氧化劣化。
並記載:藉此,該樹脂組成物可進一步抑制魚眼等缺點的產生及著色,並可改善成形品的外觀性,且長期運行(long-run)性亦更優異。
[先前技術文獻]
[專利文獻]
[專利文獻1]國際公開第2013/146961號
但,如上述不飽和醛之醛化合物,有即使為微量亦常會成為惡臭的原因之虞,尤其會有在曝露於高溫之成形步驟中揮發而使作業環境惡化之疑慮,故難以採用。因此,尋求加熱時不易發生熱劣化,可獲得高品質之成形物的EVOH樹脂組成物。
本案發明人等鑒於上述實情而進行努力研究的結果,發現併用微量的鐵化合物與具有共軛多烯結構之化合物時可解決上述課題。以往,具有共軛多烯結構之化合物作為EVOH樹脂之熱穩定劑係公知,但藉由將其與微量的鐵化合物併用以改善EVOH樹脂之熱穩定性之情事尚未為人們所知。本發明中意外地發現:將特定微量的鐵化合物與具有共軛多烯結構之化合物併用時,EVOH樹脂組成物之熱穩定性得到改善,且長期運行成形性良好。
亦即,本發明之第1要旨係一種EVOH樹脂組成物,含有EVOH樹脂(A)、具有共軛多烯結構之化合物(B)及鐵化合物(C);且上述鐵化合物(C)之金屬換算含量,在每單位重量之EVOH樹脂組成物中為0.01~20ppm。又,本發明之第2要旨係由上述EVOH樹脂組成物構成之丸粒,進一步第3要旨係具備由EVOH樹脂組成物構成之層的多層結構體。
本發明之EVOH樹脂組成物,係含有EVOH樹脂(A)、具有共軛多烯結構之化合物(B)及鐵化合物(C)的EVOH樹脂組成物,且上述鐵化合物(C)之金屬換算含量,在每單位重量之EVOH樹脂組成物中為0.01~20ppm,故加熱後之著色受到抑制,熱穩定性優異。
又,上述具有共軛多烯結構之化合物(B)之含量,在每單位重量之EVOH樹脂組成物中為1~30000ppm的話,可進一步抑制加熱後之著色,熱穩定性更優異。
進一步,上述具有共軛多烯結構之化合物(B)之含量相對於上述鐵化合物(C)之金屬換算含量的重量比率,為具有共軛多烯結構之化合物(B)/鐵化合物(C)=0.2~50000的話,可更進一步抑制加熱後之著色,熱穩定性又更優異。
由本發明之EVOH樹脂組成物構成之丸粒,加熱後之著色受到抑制,故可理想地用作各種成形物,例如用作食品、藥品、農藥等之包裝材料。
具備由本發明之EVOH樹脂組成物構成之層的多層結構體,品質良好,故作為例如食品、藥品、農藥等之包裝材料係特別有用。
以下,針對本發明之構成進行詳細說明,但該等係顯示理想實施態樣之一例,並不限定於該等內容。
<EVOH樹脂組成物>
本發明之EVOH樹脂組成物,係以EVOH樹脂(A)作為主成分,並含有具有共軛多烯結構之化合物(B)及鐵化合物(C)者。本發明之EVOH樹脂組成物,基礎樹脂為EVOH樹脂(A)。亦即,EVOH樹脂組成物中之EVOH樹脂(A)之含量通常為70重量%以上,宜為80重量%以上,更佳為90重量%以上,特佳為95重量%以上。以下,針對各成分依序進行說明。
[EVOH樹脂(A)]
本發明中使用之EVOH樹脂(A)係通常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的樹脂,為非水溶性的熱塑性樹脂。就上述乙烯酯系單體而言,考量經濟性的方面,一般而言係使用乙酸乙烯酯。
就乙烯與乙烯酯系單體之共聚的聚合法而言,可利用公知的任意聚合法,例如,可利用溶液聚合、懸浮聚合、乳液聚合等來實施,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-乙烯酯系共聚物的皂化也可利用公知的方法實施。
以此種方式製得之EVOH樹脂(A),係以來自乙烯之結構單元與乙烯醇結構單元為主體,並含有些許未皂化而殘存的乙烯酯結構單元。
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,代表性地係使用乙酸乙烯酯。作為其他乙烯酯系單體,例如可列舉: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(vinyl-versatate)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,特佳為碳數4~7之脂肪族乙烯酯。該等通常係單獨使用,但視需要也可同時使用多種。
EVOH樹脂(A)中之乙烯結構單元之含量,可藉由使乙烯酯系單體與乙烯共聚時的乙烯壓力來控制,通常為20~60莫耳%,宜為25~50莫耳%,特佳為25~35莫耳%。該含量過低時,會有高濕下之氣體阻隔性、熔融成形性降低的傾向,反之過高時,會有氣體阻隔性降低的傾向。此外,該乙烯結構單元之含量可依據ISO 14663進行測定。
EVOH樹脂(A)中之乙烯酯成分的皂化度,可藉由將乙烯-乙烯酯系共聚物予以皂化時的皂化觸媒(通常使用氫氧化鈉等鹼性觸媒)的量、溫度、時間等來控制,通常為90~100莫耳%,宜為95~100莫耳%,特佳為99~100莫耳%。該皂化度過低時,會有氣體阻隔性、熱穩定性、耐濕性等降低的傾向。該EVOH樹脂(A)的皂化度可依據JIS K6726(惟,EVOH樹脂係以均勻溶解於水/甲醇溶劑而得的溶液的形式使用)進行測定。
又,EVOH樹脂(A)的熔體流動速率(MFR)(210℃、荷重2160g)通常為0.5~100g/10分鐘,宜為1~50g/10分鐘,特佳為3~35g/10分鐘。該MFR過大時,會有損及製膜時之穩定性的傾向,過小時會有黏度變得過高,熔融擠製變困難的傾向。該MFR係EVOH樹脂之聚合度的指標,可藉由使乙烯與乙烯酯系單體共聚時的聚合引發劑的量、溶劑的量來調整。
本發明中使用之EVOH樹脂(A),在不損及本發明之效果的範圍內(例如,EVOH樹脂(A)之20莫耳%以下),可進一步含有來自以下所示之共聚單體的結構單元。
前述共聚單體可列舉: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-1,2-二醇等含有羥基之α-烯烴類或其酯化物、醯化物等衍生物;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、苯二甲酸(酐)、馬來酸(酐)、衣康酸(酐)等不飽和酸類或其鹽或烷基之碳數為1~18之這些不飽和脂肪酸的單或二烷基酯類;丙烯醯胺、烷基之碳數為1~18之N-烷基丙烯醯胺、N,N-二甲基丙烯醯胺、2-丙烯醯胺丙磺酸或其鹽、丙烯醯胺丙基二甲基胺或其酸鹽或其4級鹽等丙烯醯胺類;甲基丙烯醯胺、烷基之碳數為1~18之N-烷基甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺、2-甲基丙烯醯胺丙磺酸或其鹽、甲基丙烯醯胺丙基二甲基胺或其酸鹽或其4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;烷基乙烯基醚、羥基烷基乙烯基醚、
烷氧基烷基乙烯基醚等烷基之碳數為1~18之乙烯基醚類;氯乙烯、偏二氯乙烯、氟乙烯、偏二氟乙烯、溴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、氯丙烯等鹵化烯丙基化合物類;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-甲基丙磺酸等共聚單體。該等可單獨使用或將2種以上併用。
尤其考量保持氣體阻隔性且二次成形性良好的觀點,於側鏈具有1級羥基的EVOH樹脂為較佳,其中,宜為使含有羥基之α-烯烴類共聚而得的EVOH樹脂,為於側鏈具有1,2-二醇結構的EVOH樹脂特佳。尤其於側鏈具有1級羥基時,其含量通常為0.1~20莫耳%,更佳為0.5~15莫耳%,特佳為1~10莫耳%。
又,本發明中使用之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。
進一步,本發明中使用之EVOH樹脂(A)也可為與其他不同的EVOH樹脂之混合物,該其他的EVOH樹脂可列舉:乙烯結構單元之含量不同者、皂化度不同者、聚合度不同者、共聚成分不同者等。其中,宜使用乙烯結構單元之含量不同的2種以上之EVOH樹脂。
[具有共軛多烯結構之化合物(B)]
本發明中使用之具有共軛多烯結構之化合物(B),係為碳-碳雙鍵與碳-碳單鍵交替地連接而成之結構,且碳-碳雙鍵數為2個以上,即所謂具有共軛雙鍵之化合物。具有共軛多烯結構之化合物(B),也可為2個碳-碳雙鍵與1個碳-碳單鍵交替地連接而成之結構的共軛二烯化合物、3個碳-碳雙鍵與2個碳-碳單鍵交替地連
接而成之結構的共軛三烯化合物、或更多數目的碳-碳雙鍵與碳-碳單鍵交替地連接而成之結構的共軛多烯化合物。惟,上述具有共軛多烯結構之化合物(B)不包括桂皮酸類等芳香族羧酸類、及對苯二酚、苯醌等醌類。
又,共軛的碳-碳雙鍵數為8個以上的話,會有因共軛多烯化合物本身的顏色而造成成形物著色之疑慮,故宜具有共軛的碳-碳雙鍵數為7個以下之多烯結構。進一步,由2個以上之碳-碳雙鍵構成的上述共軛雙鍵也可在1分子中有多數組而彼此不共軛。例如,如桐油般在同一分子內有3個共軛三烯的化合物也包括在具有共軛多烯結構之化合物(B)中。
作為如此之具有共軛多烯結構之化合物(B),例如可列舉:異戊二烯、2,3-二甲基-1,3-丁二烯、2,3-二乙基-1,3-丁二烯、2-第三丁基-1,3-丁二烯、1,3-戊二烯、2,3-二甲基-1,3-戊二烯、2,4-二甲基-1,3-戊二烯、3,4-二甲基-1,3-戊二烯、3-乙基-1,3-戊二烯、2-甲基-1,3-戊二烯、3-甲基-1,3-戊二烯、4-甲基-1,3-戊二烯、1,3-己二烯、2,4-己二烯、2,5-二甲基-2,4-己二烯、1,3-辛二烯、1,3-環戊二烯、1,3-環己二烯、1-苯基-1,3-丁二烯、1,4-二苯基-1,3-丁二烯、1-甲氧基-1,3-丁二烯、2-甲氧基-1,3-丁二烯、1-乙氧基-1,3-丁二烯、2-乙氧基-1,3-丁二烯、2-硝基-1,3-丁二烯、氯丁二烯、1-氯-1,3-丁二烯、1-溴-1,3-丁二烯、2-溴-1,3-丁二烯、富烯(fulvene)、環庚三烯酮(tropone)、羅勒烯(ocimene)、水芹烯(phellandrene)、香葉烯(myrcene)、菌綠烯(farnesene)、西柏烯(cembrene);山梨酸、山梨酸酯、山梨酸鹽等山梨酸類;樅酸(abietic acid)等由2個碳-碳雙鍵之共軛結構形成的共軛二烯化合物;1,3,5-己三烯、2,4,6-辛三烯-1-羧酸、桐油酸(eleostearic acid)、桐油、膽鈣化醇(cholecalciferol)等由3個碳-碳雙鍵之共軛結構形成的共軛三烯化合物;環辛四烯、2,4,6,8-癸四烯-1-羧酸、視網醇(retinol)、視網酸(retinoic acid)等由4個
以上之碳-碳雙鍵之共軛結構形成的具有共軛多烯結構之化合物等。此外,關於如1,3-戊二烯、香葉烯、菌綠烯般具有多個立體異構體者,可使用其中任意者。就具有共軛多烯結構之化合物(B)而言,亦可將2種類以上之該具有共軛多烯結構之化合物予以併用。該等可單獨使用或將2種以上併用。
就具有共軛多烯結構之化合物(B)而言,該等具有共軛多烯結構之化合物中,考量與水之親和性高的觀點,宜為具有羧基者,為具有羧基之鏈狀化合物更佳,為山梨酸類,尤其為山梨酸特佳。
上述具有共軛多烯結構之化合物(B)的分子量,考量生產性及操作性的觀點,通常為30~500,宜為50~400,特佳為100~300。又,考量生產性及操作性的觀點,上述具有共軛多烯結構之化合物(B)之1分子中的碳數通常為4~30,宜為4~20,特佳為4~10。
本發明之EVOH樹脂組成物中之具有共軛多烯結構之化合物(B)的含量,在每單位重量之EVOH樹脂組成物中,通常為1~30000ppm,宜為10~10000ppm,特佳為30~1000ppm,尤佳為50~500ppm。具有共軛多烯結構之化合物(B)的含量過多時,會有損及生產性的傾向,過少時會有熱穩定性降低的傾向。
上述EVOH樹脂組成物中之具有共軛多烯結構之化合物(B)的含量,例如可使用液體層析-紫外分光檢測器依下列步驟進行測定。此外,下列步驟係以使用山梨酸之情形作為示例而進行記載,但其他具有共軛多烯結構之化合物(B),也可藉由使用適合於該化合物之萃取溶劑,並以同樣的步驟進行測定。
[具有共軛多烯結構之化合物(B)之含量的測定方法]
(1)對於將EVOH樹脂組成物進行結凍粉碎而得的粉末1g,添加萃取溶劑(蒸餾水:甲醇=1:1、體積比)8mL。
(2)對於該溶液於溫度20℃、靜置狀態實施1小時的超音波處理,將樹脂中之山梨酸萃取出,冷卻後利用萃取溶劑定容至10mL。又,也可視需要稀釋成任意倍率。
(3)將上述溶液利用孔尺寸0.45μm之過濾器進行過濾後,以液體層析-紫外分光檢測器測定萃取溶液中之山梨酸。
(4)由使用上述萃取溶劑製得的山梨酸之標準溶液製作檢量線,利用絕對檢量線法對山梨酸之含量進行定量。
[HPLC測定條件]
LC系統:Agilent1260/1290[Agilent Technologies公司製]
檢測器:Agilent1260 infinity二極體陣列檢測器[Agilent Technologies公司製]
管柱:Cadenza CD-C18(100×3.0mm、3μm)[Imtakt公司製]
管柱溫度:40℃
移動相A:含有0.05%甲酸之5%乙腈的水溶液
移動相B:含有0.05%甲酸之95%乙腈的水溶液
時間程序:0.0→5.0分鐘 B%=30%
5.0→8.0分鐘 B%=30%→50%
8.0→10.0分鐘 B%=50%
10.0→13.0分鐘 B%=50%→30%
13.0→15.0分鐘 B%=30%
流量:0.2mL/分鐘
UVV檢測波長:190~400nm
定量波長:262nm
此外,上述HPLC測定條件中之「%」意指體積%。
[鐵化合物(C)]
本發明之EVOH樹脂組成物之特徵為:含有上述EVOH樹脂(A)、上述具有共軛多烯結構之化合物(B),並含有鐵化合物(C),且該鐵化合物(C)之含量為特定微量。本發明之EVOH樹脂組成物由於具有如上述之構成,故可抑制著色,熱穩定性優異。
一般而言,EVOH樹脂會因熱劣化而發生著色。據認為其原因為:因熱導致EVOH樹脂所具有的羥基發生脫水,並於EVOH樹脂之主鏈生成雙鍵,該部位成為反應起始點而使脫水受到促進,形成共軛多烯結構。
又,由含有鐵化合物(C)的EVOH樹脂組成物成形而成的製品,據認為會因鐵離子而造成著色,故本領域的技術人員通常會避免鐵化合物的使用。但,在本發明中意外地發現:藉由在EVOH樹脂組成物中含有微量的鐵化合物(C),可獲得加熱後之著色受到抑制的EVOH樹脂組成物。
鐵能以2價及3價的離子形式存在。藉由併用微量的鐵化合物與具有共軛多烯結構之化合物來獲得本發明之效果的理由據推測係因為發生如下之循環:所併用之具有共軛多烯結構之化合物(B)常會將3價的鐵離子還原,而生成2價的鐵離子,該2價的鐵離子再次將具有共軛多烯結構之化合物(B)還原,藉此取回具有共軛多烯結構之化合物(B)的活性。
此外,就該鐵化合物(C)而言,在EVOH樹脂組成物中以例如鐵之氧化物、鐵之氫氧化物、鐵之氯化物、鐵鹽的形式存在,除此以外,亦可以離子化狀態、或與樹脂、其他配位體相互作用而得之錯合物的狀態存在。作為上述鐵之氧化物,例如可列舉氧化鐵(III)、四氧化三鐵、氧化鐵(II)等。作為上述鐵之氯化物,例如可列舉氯化鐵(II)、氯化鐵(III)等。作為上述鐵之氫氧化物,例如可列舉氫氧化鐵(II)、氫氧化鐵(III)等。作為上述鐵鹽,例如可列舉磷酸鐵、硫酸鐵等無機鹽、羧酸(乙酸、丁酸、硬脂酸等)鐵等有機鹽。該等可單獨使用或將2種以上併用。
考量於EVOH樹脂組成物中之分散性的觀點,鐵化合物(C)宜為水溶性。又,考量分散性與生產性的觀點,其分子量通常為100~10000,宜為100~1000,特佳為100~500。
就本發明之EVOH樹脂組成物而言,鐵化合物(C)之金屬換算含量,在每單位重量之EVOH樹脂組成物中為0.01~20ppm。該鐵化合物(C)之金屬換算含量宜為0.03~8ppm,特佳為0.05~3ppm,尤佳為0.05~1.5ppm。鐵化合物(C)之含量過少的話,著色抑制效果變得不充分,反之過多的話,成形物發生著色。
此處,鐵化合物(C)之含量可藉由如下方式求出:將EVOH樹脂組成物0.5g利用紅外線加熱爐進行灰化處理(氧氣氣流中650℃、1小時)後,使剩餘的灰分溶解於酸,並利用純水定容,將其作為試樣溶液,利用ICP-MS(Agilent Technologies公司製,7500ce型,標準添加法)進行測定。
就本發明之EVOH樹脂組成物而言,具有共軛多烯結構之化合物(B)之含量相對於上述鐵化合物(C)之金屬換算含量的重量比率(具有共軛多烯結構之化合物(B)/鐵化合物(C)),通常為0.2~50000,宜為1~25000,特佳為5~10000,尤佳為50~5000。該比率過大時,會有妨礙熱穩定性的傾向,過小時會有成形物發生著色的傾向。
[其他熱塑性樹脂]
本發明之EVOH樹脂組成物中,可在不損及本發明之效果的範圍(例如,EVOH樹脂組成物之通常30重量%以下,宜為20重量%以下,特佳為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的熱塑性樹脂。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。該等可單獨使用或將2種以上併用。
[其他摻合劑]
又,本發明之EVOH樹脂組成物中,在不損及本發明之效果的範圍內,也可含有一般摻合於EVOH樹脂之摻合劑。例如可摻合:無機複鹽(例如,菱水鎂鋁石(hydrotalcite)等)、塑化劑(例如,乙二醇、甘油、己烷二醇等脂肪族多元醇等)、吸氧劑[例如,鋁粉、亞硫酸鉀、光觸媒氧化鈦等無機系吸氧劑;抗壞血酸、其脂肪酸酯、金屬鹽等、對苯二酚、没食子酸、含有羥基之酚醛樹脂等多元苯酚
類、雙-水楊醛-亞胺鈷、四伸乙基五胺鈷、鈷-希夫鹼錯合物、卟啉類、大環狀多元胺錯合物、聚乙烯亞胺-鈷錯合物等含氮化合物與鐵以外之過渡金屬的配位結合體、胺基酸類與含有羥基之還原性物質之產物、三苯基甲基化合物等有機化合物系吸氧劑;含氮樹脂與鐵以外之過渡金屬之配位結合體(例如,間二甲苯二胺(MXD)尼龍與鈷之組合)、含有三級氫之樹脂與鐵以外之過渡金屬之摻配物(例如,聚丙烯與鈷之組合)、含有碳-碳不飽和鍵之樹脂與鐵以外之過渡金屬之摻配物(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、進一步於該等摻合物添加光起始劑(二苯甲酮等)、過氧化物捕捉劑(市售的抗氧化劑等)、除臭劑(活性碳等)而得者等高分子系吸氧劑]、熱穩定劑、光穩定劑、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、防黏連劑、填充材(例如,無機填料等)等。該等化合物可單獨使用或將2種以上併用。
[EVOH樹脂組成物之製造方法]
就使用上述各成分來製造本發明之EVOH樹脂組成物的方法而言,例如可列舉乾摻配法、熔融混合法、溶液混合法、含浸法等公知的方法等,也可將該等任意組合。
作為上述乾摻配法,例如可列舉(i)將EVOH樹脂(A)的丸粒、具有共軛多烯結構之化合物(B)及鐵化合物(C)利用轉筒等進行乾摻配的方法等。
作為上述熔融混合法,例如可列舉:(ii)將EVOH樹脂(A)的丸粒、具有共軛多烯結構之化合物(B)及鐵化合物(C)之乾摻配物進行熔融混練,而得到丸粒、成
形物的方法;(iii)於熔融狀態的EVOH樹脂(A)中添加具有共軛多烯結構之化合物(B)及鐵化合物(C)並進行熔融混練,而得到丸粒、成形物的方法等。
作為上述溶液混合法,例如可列舉:(iv)使用市售的EVOH樹脂(A)的丸粒製備溶液,並於其中摻合具有共軛多烯結構之化合物(B)及鐵化合物(C),使其凝固成形並丸粒化,進行固液分離並乾燥的方法;(v)在EVOH樹脂(A)的製造過程中,使皂化前之乙烯-乙烯酯系共聚物溶液、EVOH樹脂的均勻溶液(水/醇溶液等)中含有具有共軛多烯結構之化合物(B)及鐵化合物(C)後,使其凝固成形並丸粒化,進行固液分離並乾燥的方法。
作為上述含浸法,例如可列舉(vi)使EVOH樹脂(A)的丸粒,與含有具有共軛多烯結構之化合物(B)及鐵化合物(C)之水溶液接觸,而使EVOH樹脂(A)丸粒中含有具有共軛多烯結構之化合物(B)及鐵化合物(C),然後進行乾燥的方法。
本發明中,可組合上述不同的方法。其中,考量生產性、獲得本發明之效果更為顯著的EVOH樹脂組成物的觀點,宜為熔融混合法,為(ii)之方法特佳。
此外,藉由上述各方法獲得之本發明之EVOH樹脂組成物丸粒、上述各方法中使用之EVOH樹脂(A)的丸粒的形狀係任意。例如有球形、橢圓形、圓柱形、立方體形、長方體形等,通常為橢圓形、或圓柱形,就其大小而言,考量之後作為成形材料使用時的便利性的觀點,橢圓形的情況,短徑通常為1~10mm,宜為2~6mm,更佳為2.5~5.5mm,長徑通常為1.5~30mm,宜為3~20mm,更佳為3.5~10mm。又,圓柱形的情況,底面直徑通常為1~6mm,宜為2~5mm,長度通常為1~6mm,宜為2~5mm。
又,上述各方法中使用之鐵化合物(C),如前述,宜使用水溶性的鐵化合物,例如可列舉:氧化鐵(III)、四氧化三鐵、氧化鐵(II)等鐵之氧化物;氯化鐵(II)、氯化鐵(III)等鐵之氯化物;氫氧化鐵(II)、氫氧化鐵(III)等鐵之氫氧化物;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。此外,就該鐵化合物(C)而言,如前述,在EVOH樹脂組成物中係以上述鹽的形式存在,除此以外,還可以離子化狀態、或與樹脂、其他配位體相互作用而得之錯合物的狀態存在。
又,作為上述(vi)之方法中使用之含有鐵化合物(C)的水溶液,可使用上述鐵化合物(C)之水溶液、藉由將鐵鋼材料浸漬於含有各種藥劑之水中而使鐵離子溶出者。此外,此時EVOH樹脂組成物中之鐵化合物(C)之含量(金屬換算),可利用浸漬EVOH樹脂(A)的丸粒之水溶液中之鐵化合物(C)的濃度、浸漬溫度、浸漬時間等來控制。就上述浸漬溫度、浸漬時間而言,通常為0.5~48小時,宜為1~36小時,浸漬溫度通常為10~40℃,宜為20~35℃。該浸漬後之丸粒可利用公知的方法進行固液分離,並利用公知的乾燥方法進行乾燥。該乾燥方法可採用各種乾燥方法,可為靜置乾燥、流動乾燥中之任意者。又,亦可將該等組合來實施。
本發明之EVOH樹脂組成物丸粒的含水率通常為0.01~0.5重量%,宜為0.05~0.35重量%,特佳為0.1~0.3重量%。
此外,本發明中之EVOH樹脂組成物丸粒的含水率係利用以下之方法測定、算出。
利用電子天秤稱量EVOH樹脂組成物丸粒的乾燥前重量(W1),稱量於150℃之熱風乾燥機中使其乾燥5小時,並在乾燥器中放冷30分鐘後的重量(W2),利用下式算出。
含水率(重量%)=[(W1-W2)/W1]×100
又,本發明之EVOH樹脂組成物的熱穩定性,可藉由重量減少比例來評價,本發明之EVOH樹脂組成物中之重量減少比例通常為0.7~1.1%,宜為0.8~1.0%,特佳為0.9%。重量減少比例的數值過小(重量減少過少)的話,會有EVOH樹脂組成物幾乎未分解,熔融成形時隨時間經過發生增黏,長期運行成形性降低的傾向,重量減少比例的數值過大(重量減少過多)的話,表示EVOH樹脂組成物過度分解,因EVOH樹脂組成物分解所產生的氣體等導致發生起泡,會有對成形品等的外觀造成不良影響的傾向。
上述重量減少比例,係由將已粉碎成1~5mm見方之EVOH樹脂組成物的粉碎品5mg,利用熱重量測定裝置(Perkin Elmer公司製,Pyris 1 TGA)於氮氣環境下、氣流速度:20mL/分鐘、溫度:230℃、時間:1小時之條件下進行測定而獲得的加熱前後之重量依下式算出。
重量減少比例(%)=[(Wa-Wb)/Wa]×100
上述Wa意指加熱前重量,Wb意指加熱後重量。
以此種方式獲得之EVOH樹脂組成物的丸粒,可直接供至熔融成形,但考量使熔融成形時之進料性穩定的觀點,使公知的潤滑劑附著於丸粒的表面亦佳。就潤滑劑的種類而言,例如可列舉:碳數12以上之高級脂肪酸(例如,月桂酸、肉豆蔻酸、棕櫚酸、硬脂酸、二十二酸、油酸等)、高級脂肪酸酯(例如,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、肉豆蔻醯胺、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,分子量約500~10000之低分子量聚乙烯、或低分子量聚丙烯等、或其酸改性物)、碳數6以上之高級醇、酯低聚物、氟化乙烯樹脂等。又,該丸粒上之潤滑劑量通常為EVOH樹脂組成物之5重量%以下,宜為1重量%以下。
本發明之EVOH樹脂組成物,能以丸粒、或粉末狀、液體狀之各種形態的EVOH樹脂組成物的形式製備,並作為各種成形物的成形材料提供。尤其在本發明中,作為熔融成形用之材料提供時,會有更有效率地獲得本發明之效果的傾向,係較佳。此外,本發明之EVOH樹脂組成物亦可為在上述EVOH樹脂組成物中將EVOH樹脂(A)以外的樹脂予以混合而獲得的樹脂組成物。
另外,就該成形物而言,能以使用本發明之EVOH樹脂組成物進行成形而得的單層薄膜的形式,或以具有使用本發明之EVOH樹脂組成物進行成形而得之層的多層結構體的形式實際使用。
[多層結構體]
本發明之多層結構體,係具備上述由本發明之EVOH樹脂組成物構成之層。藉由將由本發明之EVOH樹脂組成物構成之層(以下,稱為「EVOH樹脂組成物層」。)與以本發明之EVOH樹脂組成物以外之熱塑性樹脂作為主成分的其他基材(以下,稱為「基材樹脂」。)予以疊層,可進一步賦予強度,或保護EVOH樹脂組成物層免受水分等的影響,或賦予其他功能。
作為上述基材樹脂,例如可列舉: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(於主鏈及側鏈中之至少一者具有環狀烯烴結構的聚合物)等(未改性)聚烯烴系樹脂;包括將該等聚烯烴類以不飽和羧酸或其酯進行接枝改性而得的不飽和羧酸改性聚烯烴系樹脂等改性烯烴系樹脂的廣義的聚烯烴系樹脂;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(亦包括共聚聚醯胺)、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。該等可單獨使用或將2種以上併用。
該等之中,宜為係疏水性樹脂的聚醯胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚苯乙烯系樹脂,更佳為聚乙烯系樹脂、聚丙烯系樹脂、聚環狀烯烴系樹脂及它們的不飽和羧酸改性聚烯烴系樹脂等聚烯烴系樹脂。
就多層結構體之層結構而言,將本發明之EVOH樹脂組成物層定義為a(a1、a2、...),基材樹脂層定義為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等任意的組合。又,將在製造該多層結構體的過程中產生的端部、不良品等進行再熔融成形而獲得的含有本發明之EVOH樹脂組成物與基材樹脂之混合物的再利用層定義為R時,也可為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。多層結構體的層數以總數計通
常為2~15,宜為3~10。上述層結構中,各層之間亦可視需要插入含有黏接性樹脂之黏接性樹脂層。
上述黏接性樹脂可使用公知者,只要因應基材樹脂層「b」所使用之熱塑性樹脂的種類適當選擇即可。代表性地可列舉:將不飽和羧酸或其酐利用加成反應、接枝反應等化學性地鍵結於聚烯烴系樹脂而得的含有羧基之改性聚烯烴系聚合物。上述含有羧基之改性聚烯烴系聚合物,例如可列舉: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。另外,可使用選自於該等中的1種或2種以上之混合物。
多層結構體中,於本發明之EVOH樹脂組成物層與基材樹脂層之間使用黏接性樹脂層時,考量黏接性樹脂層位於EVOH樹脂組成物層之兩側,宜使用疏水性優異的黏接性樹脂。
上述基材樹脂、黏接性樹脂中,在不損及本發明之主旨的範圍(例如,相對於樹脂全體為30重量%以下,宜為10重量%以下)內,也可含有習知的塑化劑、填料、黏土(蒙脫石等)、著色劑、抗氧化劑、抗靜電劑、潤滑劑、成核劑、抗黏連劑、蠟等。該等可單獨使用或將2種以上併用。
使用本發明之EVOH樹脂組成物所形成之EVOH樹脂組成物層與上述基材樹脂層之疊層(包括插入有黏接性樹脂層的情形)可利用公知的方法進行。例如可列舉:將基材樹脂熔融擠製層合於本發明之EVOH樹脂組成物的薄膜、片材等的
方法;將本發明之EVOH樹脂組成物熔融擠製層合於基材樹脂層的方法;將EVOH樹脂組成物與基材樹脂進行共擠製的方法;將EVOH樹脂組成物層與基材樹脂層利用有機鈦化合物、異氰酸酯化合物、聚酯系化合物、聚胺甲酸酯化合物等公知的黏接劑進行乾疊合的方法;將EVOH樹脂組成物之溶液塗覆在基材樹脂層上後將溶劑除去的方法等。該等之中,考慮成本、環境的觀點,宜為進行共擠製的方法。
之後視需要對如上述之多層結構體施以(加熱)延伸處理。延伸處理可為單軸延伸、雙軸延伸中之任意者,雙軸延伸的情況可為同時延伸,亦可為逐次延伸。又,延伸方法亦可採用輥延伸法、拉幅延伸法、管狀延伸法、延伸吹塑法、真空壓空成形等中之延伸倍率高者。延伸溫度為多層結構體之熔點附近的溫度,通常選自40~170℃之範圍,宜選自約60~160℃之範圍。延伸溫度過低時,會有延伸性變得不良的傾向,過高時會有難以維持穩定的延伸狀態的傾向。
此外,為了於延伸後賦予尺寸穩定性,也可實施熱固定。熱固定能以習知的方法實施,例如將上述延伸薄膜邊保持緊張狀態邊於通常80~180℃,較佳為100~165℃實施通常約2~600秒的熱處理。又,將由本發明之EVOH樹脂組成物獲得之多層延伸薄膜作為收縮用薄膜使用時,為了賦予熱收縮性,不會實施上述熱固定,只要實施例如以冷風噴吹延伸後的薄膜並進行冷卻固定等處理即可。
又,也可視情形使用本發明之多層結構體來獲得杯、盤狀的多層容器。此時,通常採用抽拉成形法,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。此外,從多層型坯(吹塑前之中空管狀的預成形物)獲得管、瓶狀的多層容器(疊層體結構)時係採用吹塑成形法。
具體而言可列舉:擠製吹塑成形法(雙頭式、模具移動式、型坯移動式、旋轉式、蓄積式、水平型坯式等)、冷型坯式吹塑成形法、射出吹塑成形法、雙軸延伸吹塑成形法(擠製式冷型坯雙軸延伸吹塑成形法、射出式冷型坯雙軸延伸吹塑成形法、射出成形內嵌式雙軸延伸吹塑成形法等)等。獲得之疊層體可視需要實施熱處理、冷卻處理、壓延處理、印刷處理、乾疊合處理、溶液或熔融塗層處理、製袋加工、深抽拉加工、箱體加工、管材加工、分切加工等。
多層結構體(包含已延伸者)的厚度,進一步,構成多層結構體之EVOH樹脂組成物層、基材樹脂層及黏接性樹脂層的厚度,係取決於層結構、基材樹脂的種類、黏接性樹脂的種類、用途、包裝形態、所要求的物性等而不能一概而論,但多層結構體(包含已延伸者)的厚度通常為10~5000μm,宜為30~3000μm,特佳為50~2000μm。EVOH樹脂組成物層通常為1~500μm,宜為3~300μm,特佳為5~200μm,基材樹脂層通常為5~3000μm,宜為10~2000μm,特佳為20~1000μm,黏接性樹脂層通常為0.5~250μm,宜為1~150μm,特佳為3~100μm。
另外,多層結構體中之EVOH樹脂組成物層相對於基材樹脂層的厚度比(EVOH樹脂組成物層/基材樹脂層),各層為多數時按厚度最厚的層彼此的比來計算,通常為1/99~50/50,宜為5/95~45/55,特佳為10/90~40/60。又,多層結構體中之EVOH樹脂組成物層相對於黏接性樹脂層的厚度比(EVOH樹脂組成物層/黏接性樹脂層),各層為多數時按厚度最厚的層彼此的比來計算,通常為10/90~99/1,宜為20/80~95/5,特佳為50/50~90/10。
由如上述獲得之薄膜、片材、延伸薄膜所構成的袋及杯、盤、管、瓶等構成的容器、蓋材,除了作為一般食品的包裝材料容器係有用之外,作為美乃滋、
調味醬等調味料、味噌等發酵食品、沙拉油等油脂食品、飲料、化粧品、醫藥品等的各種包裝材料容器亦為有用。尤其由本發明之EVOH樹脂組成物構成之層,著色受到抑制,且熱穩定性優異,故作為食品、藥品、農藥等的包裝材係特別有用。
[實施例]
以下,舉實施例對本發明進行具體地說明,但本發明只要不超出其要旨,並不限定於實施例之記載。
此外,示例中的「份」,除非另有說明,否則意指重量基準。
在實施例之前,先準備下列EVOH樹脂(A)的丸粒,並分析該EVOH樹脂(A)含有的鐵化合物(C)。
.EVOH樹脂(A):乙烯結構單元之含量29莫耳%、皂化度99.6莫耳%、MFR 3.9g/10分鐘(210℃、荷重2160g)的乙烯-乙烯醇共聚物
[鐵化合物(C)之含量的測定]
將上述EVOH樹脂(A)之丸粒粉碎而得的樣品0.5g利用紅外線加熱爐進行灰化處理(氧氣氣流中650℃、1小時)後,使灰分溶解於酸,並利用純水定容,將其作為試樣溶液。使用下列ICP-MS(Agilent Technologies公司製ICP質量分析裝置7500ce型),將該溶液以標準添加法進行測定。其結果鐵化合物(C)之含量按金屬換算為0ppm。
<實施例1>
將上述EVOH樹脂(A)的丸粒100份、作為具有共軛多烯結構之化合物(B)的山梨酸(分子量112)0.01份(在每單位重量之EVOH樹脂組成物中為100ppm)、作為鐵化合物(C)的磷酸鐵(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(在每單位重量之EVOH樹脂組成物中按金屬換算為0.1ppm),利用塑性測定儀(Plastograph)(Brabender公司製)於230℃預熱5分鐘後,進行5分鐘的熔融混練,得到實施例1的EVOH樹脂組成物。將獲得之EVOH樹脂組成物利用粉碎機(SOMETANI SANGYO公司製,型式:SKR16-240)以650rpm進行粉碎,得到粉碎物。該粉碎物為1~5mm見方的小片。
<實施例2>
將實施例1中之磷酸鐵(III)n水合物的摻合量變更為0.00034份(在每單位重量之EVOH樹脂組成物中按金屬換算為1ppm),除此以外,與實施例1同樣進行,得到實施例2的EVOH樹脂組成物。
<實施例3>
將實施例1中之磷酸鐵(III)n水合物的摻合量變更為0.0034份(在每單位重量之EVOH樹脂組成物中按金屬換算為10ppm),除此以外,與實施例1同樣進行,得到實施例3的EVOH樹脂組成物。
<比較例1>
未摻合實施例1中之磷酸鐵(III)n水合物,除此以外,同樣進行,得到比較例1的EVOH樹脂組成物。
利用下列所示之方法進行實施例1~3及比較例1之EVOH樹脂組成物的著色評價及熱穩定性評價。結果顯示於後述表1。
[著色評價]
使用日本電色工業公司製分光色差計SE6000,測定將EVOH樹脂組成物之粉碎品在空氣環境下之烘箱內進行150℃、5小時加熱而得的EVOH樹脂組成物之YI值。此時,將上述加熱後的EVOH樹脂組成物填充於內徑32mm、高度30mm之圓筒,並以平滿的狀態進行測定。該值越大,意指EVOH樹脂組成物越會著色成黃色。
[熱穩定性評價]
使用上述獲得之EVOH樹脂組成物的粉碎物5mg,由利用熱重量測定裝置(Perkin Elmer公司製,Pyris 1 TGA)於氮氣環境下、氣流速度:20mL/分鐘、溫度:230℃、時間:1小時之條件下測得的加熱前後之重量,依下式算出重量減少比例。
重量減少比例(%)=[(Wa-Wb)/Wa]×100
上述Wa意指加熱前重量,Wb意指加熱後重量。
將獲得之重量減少比例的小數點後第2位四捨五入,並依下列評價基準進行熱穩定性的評價。
A:0.9% 熱穩定性特別優異
B:0.8%、或1.0% 熱穩定性非常優異
C:0.7%、或1.1% 熱穩定性優異
D:0.6% 熱穩定性差
E:~0.5%、或1.2%以上~ 熱穩定性非常差
含有具有共軛多烯結構之化合物(B)但不含鐵化合物(C)的比較例1的EVOH樹脂組成物中,加熱後YI值為58.7之高,反觀實施例1~3的EVOH樹脂組成物中,相較於比較例1為更低的值,係良好。
又,含有具有共軛多烯結構之化合物(B)但不含鐵化合物(C)的比較例1的EVOH樹脂組成物中,重量減少比例為1.2%之高,欠缺熱穩定性,反觀使用本發明之樹脂組成物的實施例1~3的EVOH樹脂組成物中,相較於比較例1,熱穩定性亦更良好。
上述實施例中顯示了本發明的具體形態,但上述實施例僅為單純的例示,並不作限定性解釋。對本領域的技術人員而言明顯的各種變化皆意欲包括於本發明之範圍內。
[產業上利用性]
本發明之EVOH樹脂組成物,著色受到抑制,且熱穩定性優異,故除了作為各種食品的包裝材料係有用之外,作為美乃滋、調味醬等調味料、味噌等發酵
食品、沙拉油等油脂食品、飲料、化粧品、醫藥品等的各種包裝材料係特別有用。
Claims (4)
- 一種乙烯-乙烯醇系共聚物組成物,含有乙烯-乙烯醇系共聚物(A)、具有共軛多烯結構之化合物(B)及鐵化合物(C);其特徵為:該乙烯-乙烯醇系共聚物組成物中之該乙烯-乙烯醇系共聚物(A)之含量為70重量%以上;該具有共軛多烯結構之化合物(B)之含量,在每單位重量之乙烯-乙烯醇系共聚物組成物中為1~10000ppm;該鐵化合物(C)之金屬換算含量,在每單位重量之乙烯-乙烯醇系共聚物組成物中為0.01~20ppm。
- 如申請專利範圍第1項之乙烯-乙烯醇系共聚物組成物,其中,該具有共軛多烯結構之化合物(B)之含量相對於該鐵化合物(C)之金屬換算含量的重量比率,為具有共軛多烯結構之化合物(B)/鐵化合物(C)=0.2~50000。
- 一種丸粒,係由如申請專利範圍第1或2項之乙烯-乙烯醇系共聚物組成物構成。
- 一種多層結構體,具備由如申請專利範圍第1或2項之乙烯-乙烯醇系共聚物組成物構成之層。
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