TW201925312A - 乙烯-乙烯醇系共聚物組成物、熔融成形用材料及多層結構體、及多層管 - Google Patents
乙烯-乙烯醇系共聚物組成物、熔融成形用材料及多層結構體、及多層管 Download PDFInfo
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- TW201925312A TW201925312A TW107141693A TW107141693A TW201925312A TW 201925312 A TW201925312 A TW 201925312A TW 107141693 A TW107141693 A TW 107141693A TW 107141693 A TW107141693 A TW 107141693A TW 201925312 A TW201925312 A TW 201925312A
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Abstract
本發明提供一種乙烯-乙烯醇系共聚物組成物,係著色經抑制且含有乙烯-乙烯醇系共聚物(A)、抗氧化劑(B)及山梨酸酯(C)之乙烯-乙烯醇系共聚物組成物,上述山梨酸酯(C)之含量為上述乙烯-乙烯醇系共聚物組成物每重量單位之0.00001~10ppm,且抗氧化劑(B)相對於山梨酸酯(C)之重量含有比例為抗氧化劑(B)/山梨酸酯(C)=500~1000000。
Description
本發明係關於含有乙烯-乙烯醇系共聚物(以下稱為「EVOH」)之乙烯-乙烯醇系共聚物組成物(以下稱為「EVOH樹脂組成物」)及使用了該組成物的熔融成形用材料、多層結構體及多層管,更詳細而言,係關於著色經抑制之EVOH樹脂組成物、由該EVOH樹脂組成物構成之熔融成形用材料及具備該EVOH樹脂組成物構成之層的多層結構體及多層管。
EVOH係透明性、氧氣等之氣體阻隔性、保香性、耐溶劑性、耐油性、機械強度等優異,並成形為薄膜、片、瓶等,廣泛使用作為食品包裝材料、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。此外,為了防止利用溫水循環方式所為之地暖系统之腐蝕等,亦使用作為用於該溫水循環用之多層結構之管中的其中1層之形成材料。
但,EVOH於分子內具有較為活性的羥基,故有容易因熱而分解之傾向。因此有熔融成形時發生著色、凝膠等問題且熔融安定性降低的傾向。對此,已知有藉由加入各種熱安定劑來解決的方法(例如參照專利文獻1)。
另一方面,長期間使用EVOH成形物時,有時會因使用環境使EVOH劣化,並發生臭氣、裂縫之情形。例如,就上述溫水循環用之多層管而言,有因長時間暴露於高溫而使空氣中的氧氣所致之劣化容易進行之傾向。為了抑制如此的劣化,已知有併用特定量之抗氧化劑與共軛多烯化合物的技術(例如參照專利文獻2)。
又,就農業用材料(青貯料薄膜(Silage film)、多層薄膜等)而言,由於在室外長時間使用,暴露於日光、地熱、風雨等,因此同樣可觀察到空氣中的氧氣所致之劣化容易進行之傾向。為了抑制如此的劣化,已知藉由摻合特定量之受阻胺系化合物,可獲得耐候性良好的青貯料薄膜(例如參照專利文獻3)。
[先前技術文獻]
[專利文獻]
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開昭63-286459號公報
[專利文獻2]國際公開第2011/125736號
[專利文獻3]日本特開2014-172928號公報
[專利文獻2]國際公開第2011/125736號
[專利文獻3]日本特開2014-172928號公報
[發明所欲解決之課題]
然而,即使使用上述各專利文獻的方法,針對EVOH之熔融成形時之著色的觀點而言,仍需求更進一步的改善。因此,強烈地希望一種著色經抑制之EVOH樹脂組成物。
[解決課題之手段]
[解決課題之手段]
本案發明者們,有鑑於上述實際情況致力進行探討,結果發現在EVOH樹脂組成物中併用抗氧化劑及特定微量之山梨酸酯,且將抗氧化劑與山梨酸酯之重量含有比例設為特定之範圍時會解決上述課題。
即,本發明之第1要旨為一種EVOH樹脂組成物,含有EVOH(A)、抗氧化劑(B)及山梨酸酯(C),且上述山梨酸酯(C)之含量為EVOH樹脂組成物每重量單位之0.00001~10ppm,抗氧化劑(B)相對於山梨酸酯(C)之重量含有比例為抗氧化劑(B)/山梨酸酯(C)=500~1000000。又,本發明之第2要旨係由上述EVOH樹脂組成物構成之熔融成形用材料,更進一步,第3要旨係具備由上述EVOH樹脂組成物構成之層的多層結構體,第4要旨係由上述多層結構體構成之多層管。
[發明之效果]
[發明之效果]
本發明之EVOH樹脂組成物係含有EVOH(A)、抗氧化劑(B)及山梨酸酯(C)之EVOH樹脂組成物,且上述山梨酸酯(C)之含量設定為EVOH樹脂組成物每重量單位之0.00001~10ppm,抗氧化劑(B)相對於山梨酸酯(C)之重量含有比例設定為抗氧化劑(B)/山梨酸酯(C)=500~1000000。藉此,抑制熔融混練、熔融成形等加熱所致之著色的效果優異。
又,上述抗氧化劑(B)之含量,若為EVOH樹脂組成物每重量單位之1~30000ppm,抑制著色效果會更加優異。
由本發明之EVOH樹脂組成物構成之熔融成形用材料,具有耐劣化性且抑制著色效果優異,故可作為各種成形物,例如食品、藥品、農藥等包裝材料,除此之外,尤其可理想地使用作為多層管用材料。
具備由本發明之EVOH樹脂組成物構成之層之多層結構體,具有耐劣化性且抑制著色效果優異,故可作為各種成形物,例如食品、藥品、農藥等包裝材料,除此之外,尤其可理想地使用作為多層管。
以下,針對本發明之構成詳細地進行說明,但此等為表示理想實施態様之一例,並不限定於這些內容。
<EVOH樹脂組成物>
本發明之EVOH樹脂組成物含有EVOH(A)、抗氧化劑(B)及山梨酸酯(C)。又,本發明之EVOH樹脂組成物係以EVOH(A)作為主成分。即,EVOH樹脂組成物中之EVOH(A)含量通常為70重量%以上,宜為80重量%以上,更宜為90重量%以上。以下,針對本發明之EVOH樹脂組成物之各成分依序進行說明。
本發明之EVOH樹脂組成物含有EVOH(A)、抗氧化劑(B)及山梨酸酯(C)。又,本發明之EVOH樹脂組成物係以EVOH(A)作為主成分。即,EVOH樹脂組成物中之EVOH(A)含量通常為70重量%以上,宜為80重量%以上,更宜為90重量%以上。以下,針對本發明之EVOH樹脂組成物之各成分依序進行說明。
[EVOH(A)]
使用於本發明之EVOH(A)通常係藉由將乙烯與乙烯酯系單體共聚合後進行皂化而獲得的樹脂,一般而言係稱為乙烯-乙烯醇系共聚物、乙烯-乙烯酯系共聚物皂化物之非水溶性的熱塑性樹脂。聚合法亦可使用公知的任意之聚合法,例如溶液聚合、懸浮聚合、乳化聚合,一般而言使用以甲醇作為溶劑之溶液聚合。獲得的乙烯-乙烯酯系共聚物之皂化亦可利用公知的方法施行。
即,使用於本發明之EVOH(A),係以乙烯結構單元與乙烯醇結構單元為主,通常含有未經皂化而殘存之些許量之乙烯酯結構單元。
使用於本發明之EVOH(A)通常係藉由將乙烯與乙烯酯系單體共聚合後進行皂化而獲得的樹脂,一般而言係稱為乙烯-乙烯醇系共聚物、乙烯-乙烯酯系共聚物皂化物之非水溶性的熱塑性樹脂。聚合法亦可使用公知的任意之聚合法,例如溶液聚合、懸浮聚合、乳化聚合,一般而言使用以甲醇作為溶劑之溶液聚合。獲得的乙烯-乙烯酯系共聚物之皂化亦可利用公知的方法施行。
即,使用於本發明之EVOH(A),係以乙烯結構單元與乙烯醇結構單元為主,通常含有未經皂化而殘存之些許量之乙烯酯結構單元。
作為上述乙烯酯系單體,考量由市場取得之容易性、製造時之雜質之處理效率佳的觀點,代表性而言係使用乙酸乙烯酯。此外,作為乙烯酯系單體,可舉例如甲酸乙烯酯、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。其中,更宜為碳數3~20,又更宜為碳數4~10,尤宜為碳數4~7之脂肪族乙烯酯。該等通常單獨使用,亦可因應需要同時使用多種。
EVOH(A)中之乙烯結構單元之含量可依據ISO14663來測定,通常為20~60莫耳%,宜為宜為25~50莫耳%,尤宜為25~45莫耳%。若該含量過少,有高濕下之氣體阻隔性、熔融成形性降低之傾向,反之若過多,則有氣體阻隔性降低之傾向。
EVOH(A)中之乙烯酯成分之皂化度可依據JIS K 6726(惟,EVOH係作為均勻溶解於水/甲醇溶劑之溶液而使用)進行測定,通常為90~100莫耳%,宜為95~100莫耳%,尤宜為99~100莫耳%。若該皂化度過低則有氣體阻隔性、熱安定性、耐濕性等降低之傾向。
又,上述EVOH(A)之熔體流動速率(MFR)(210℃、荷重2160g)通常為0.5~100g/10分鐘,宜為1~50g/10分鐘,尤宜為3~35g/10分鐘。若該MFR過高,則有製膜性降低之傾向。又,若MFR過低則有熔融擠壓變得困難之傾向。
又,使用於本發明之EVOH(A)在不妨礙本發明之效果的範圍內,亦可更含有來自以下所示的共聚單體之結構單元(例如通常為EVOH(A)之20莫耳%以下,宜為10莫耳%以下)。
作為上述共聚單體,可舉例如丙烯、1-丁烯、異丁烯等烯烴類、2-丙烯-1-醇、3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1-醇、3,4-二羥基-1-丁烯、5-己烯-1,2-二醇等含有羥基之α-烯烴類、其酯化物之3,4-二醯氧基-1-丁烯、3,4-二乙醯氧基-1-丁烯、2,3-二乙醯氧基-1-烯丙氧基丙烷、2-乙醯氧基-1-烯丙氧基-3-羥基丙烷、3-乙醯氧基-1-烯丙氧基-2-羥基丙烷、甘油單乙烯基醚、甘油單異丙烯基醚等含有羥基之α-烯烴類之醯化物等衍生物;1,3-羥基-2-亞甲基丙烷、1,5-羥基-3-亞甲基戊烷等羥甲基亞乙烯類;該等之酯化物之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-亞甲基丙烷等亞乙烯基二乙酸酯類;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之烷基乙烯基醚、羥基烷基乙烯基醚、烷氧基烷基乙烯基醚等乙烯基醚類、氯乙烯、氯化亞乙烯、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。該等可單獨使用或併用2種以上。
作為上述共聚單體,可舉例如丙烯、1-丁烯、異丁烯等烯烴類、2-丙烯-1-醇、3-丁烯-1-醇、4-戊烯-1-醇、5-己烯-1-醇、3,4-二羥基-1-丁烯、5-己烯-1,2-二醇等含有羥基之α-烯烴類、其酯化物之3,4-二醯氧基-1-丁烯、3,4-二乙醯氧基-1-丁烯、2,3-二乙醯氧基-1-烯丙氧基丙烷、2-乙醯氧基-1-烯丙氧基-3-羥基丙烷、3-乙醯氧基-1-烯丙氧基-2-羥基丙烷、甘油單乙烯基醚、甘油單異丙烯基醚等含有羥基之α-烯烴類之醯化物等衍生物;1,3-羥基-2-亞甲基丙烷、1,5-羥基-3-亞甲基戊烷等羥甲基亞乙烯類;該等之酯化物之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-亞甲基丙烷等亞乙烯基二乙酸酯類;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之烷基乙烯基醚、羥基烷基乙烯基醚、烷氧基烷基乙烯基醚等乙烯基醚類、氯乙烯、氯化亞乙烯、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。該等可單獨使用或併用2種以上。
且,上述之中,考量延伸處理、真空、壓空成形等二次成形性良好的觀點,宜為包含於側鏈具有一級羥基之結構單元之EVOH,尤其宜為包含於側鏈具有1,2-二醇之結構單元之EVOH。
EVOH(A)包含於側鏈具有一級羥基之結構單元的情況下,其含量通常為0.1~20莫耳%,更宜為0.1~15莫耳%,尤宜為0.1~10莫耳%。
又,上述EVOH(A)亦可為與相異之其他的EVOH之混合物,作為上述其他的EVOH,可列舉乙烯結構單元之含量相異者、於側鏈具有一級羥基之結構單元之含量相異者、皂化度相異者、熔體流動速率(MFR)相異者、其他的共聚合成分相異者等。
此外,本發明中使用的EVOH(A)亦可使用經胺甲酸乙酯化、縮醛化、氰乙基化、氧伸烷基化等「後改性」之EVOH。
[抗氧化劑(B)]
上述抗氧化劑(B)只要係具有捕捉EVOH(A)劣化而產生的自由基之作用之化合物即可,可使用各種樹脂用抗氧化劑。例如可列舉受阻酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑、受阻胺系抗氧化劑、苯並三唑系抗氧化劑、二苯基酮系抗氧化劑等。其中考量耐劣化性之效果特別優異之觀點,更宜為受阻酚系抗氧化劑、受阻胺系抗氧化劑。
上述抗氧化劑(B)只要係具有捕捉EVOH(A)劣化而產生的自由基之作用之化合物即可,可使用各種樹脂用抗氧化劑。例如可列舉受阻酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑、受阻胺系抗氧化劑、苯並三唑系抗氧化劑、二苯基酮系抗氧化劑等。其中考量耐劣化性之效果特別優異之觀點,更宜為受阻酚系抗氧化劑、受阻胺系抗氧化劑。
上述受阻酚系抗氧化劑本身熱安定性優異,另一方面具有捕捉為氧化劣化之原因的氧自由基之能力,作為抗氧化劑摻合於EVOH樹脂組成物時,防止氧化劣化之效果優異。
作為上述受阻酚系抗氧化劑,具體而言可舉例如新戊四醇-肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](BASF公司製「IRGANOX 1010」:熔點110-125℃、分子量1178)、十八基-3-(3,5-二第三丁基-4-羥苯基)丙酸酯(BASF公司製「IRGANOX 1076」:熔點50-55℃、分子量531)、N,N’-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥苯基)丙醯胺](BASF公司製「IRGANOX 1098」:熔點156-161℃、分子量637)、三甘醇-雙[3-(3-第三丁基-5-甲基-4-羥苯基)丙酸酯](BASF公司製「IRGANOX 245」:熔點76-79℃、分子量587)、1,6-己二醇-雙[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](BASF公司製「IRGANOX 259」:熔點104-108℃、分子量639)、2,2’-亞甲基-雙(4-甲基-6-第三丁基酚)(住友化學工業公司製「SUMILIZER MDP-S」:熔點約128℃、分子量341)、2-第三丁基-6-(3-第三丁基-2-羥基-5-甲苄基)-4-甲基苯基丙烯酸酯(住友化學工業公司製「SUMILIZER GM」:熔點約128℃、分子量395)、3,9-雙[2-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基]-1,1-二甲基乙基]-2,4,8,10-四氧雜螺[5,5]十一烷(住友化學工業公司製「SUMILIZER GA-80」:熔點約110℃、分子量741)等各種製品。其中宜為新戊四醇-肆[3-(3,5-二第三丁基-4-羥苯基)丙酸酯]、N,N’-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥苯基)丙醯胺]。
又,作為上述抗氧化劑(B),如上所述亦可適宜地使用上述受阻胺系抗氧化劑。將受阻胺系抗氧化劑作為抗氧化劑(B)摻合於EVOH樹脂組成物時,不只會防止EVOH(A)之熱劣化,亦有捕捉因EVOH(A)之熱分解而生成之醛類的效果,且可藉由減低分解氣體的產生來抑制成形時之孔隙或氣泡的產生。又,藉由捕捉醛類,將本發明之EVOH樹脂組成物使用於例如食品包裝容器材料時,醛類所致之臭氣損害內容物的味道之問題亦可獲得改善。
作為上述受阻胺系抗氧化劑宜列舉哌啶衍生物。尤其可理想地使用於4位具有取代基之2,2,6,6-四烷基哌啶衍生物。作為上述4位的取代基可列舉羧基、烷氧基、烷胺基。
又,上述受阻胺系抗氧化劑(具有受阻胺基之化合物)中,於受阻胺基之N位宜鍵結氫原子,就熱安定效果而言優異,亦可鍵結烷基。
作為上述受阻胺系抗氧化劑,具體而言可舉例如雙(2,2,6,6-四甲基-4-哌啶)癸二酸酯(BASF公司製「TINUVIN 770」:熔點81-85℃、分子量481)、雙(1,2,2,6,6-五甲基-4-哌啶)癸二酸酯及1,2,2,6,6-五甲基-4-哌啶癸二酸酯(混合物)(BASF公司製「TINUVIN 765」:液狀化合物、分子量509)、琥珀酸二甲酯・1-(2-羥乙基)-4-羥基-2,2,6,6-四甲基哌啶縮聚物(BASF公司製「TINUVIN 622LD」:熔點55-70℃、分子量3100-4000)、N,N’-雙(3-胺丙基)乙二胺・2,4-雙[N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶)胺基]-6-氯-1,3,5-三氮雜苯縮合物(BASF公司製「CHIMASSORB 119FL」:熔點130-140℃、分子量2000以上)、聚[[6-(1,1,3,3-四甲基丁基)胺基-1,3,5-三氮雜苯-2,4-二基][(2,2,6,6-四甲基-4-哌啶)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶)亞胺基]](BASF公司製「CHIMASSORB 944LD」:熔點100-135℃、分子量2000-3100)、雙(1,2,2,6,6-五甲基-4-哌啶)[[3,5-雙(1,1-二甲基乙基)-4-羥苯基]甲基]丁基丙二酸酯(BASF公司製「TINUVIN 144」:熔點146-150℃、分子量685)、N,N’-1,6-己烷二基雙[N-(2,2,6,6-四甲基-4-哌啶))-甲醯胺](BASF公司製「UVINUL 4050H」:熔點157℃、分子量450)、(BASF公司製「UVINUL 5050H」:熔點104-112℃、分子量約3500)等各種製品。其中,更宜為雙(2,2,6,6-四甲基-4-哌啶)癸二酸酯。
上述抗氧化劑(B)可單獨使用亦可併用2種以上之結構、組成、分子量等相異之抗氧化劑(B)。又,就上述抗氧化劑(B)之性狀而言,可使用粉末狀、顆粒狀、液體狀、糊狀、乳液狀等任意之形態者。
上述抗氧化劑(B)之熔點通常為200℃以下,宜為170℃以下。又,上述抗氧化劑(B)之熔點的下限通常為30℃。抗氧化劑(B)之熔點過高時,抗氧化劑(B)不會在擠製機內熔融,因此成形物中抗氧化劑(B)會局部化且有品質下降之傾向。
又,上述抗氧化劑(B)之分子量通常為100~8000。宜為200~5000,尤宜為300~2000。抗氧化劑(B)之分子量過低時,有抗氧化劑(B)自獲得的成形物之表面滲出之傾向,分子量過高時,有成形物中抗氧化劑(B)局部化而品質下降之傾向。
上述抗氧化劑(B)之含量通常係EVOH樹脂組成物每單位重量之1~30000ppm,宜為100~10000ppm,尤宜為1000~5000ppm。若含量過小,則有熱安定劑之摻合效果下降之傾向,若含量過大,則有抗氧化劑(B)自成形物的表面滲出之傾向。
又,就上述抗氧化劑(B)而言,併用2種類以上之結構、組成、分子量等相異的抗氧化劑(B)時,其總重量(總含量)宜在上述範圍內。
又,就上述抗氧化劑(B)而言,併用2種類以上之結構、組成、分子量等相異的抗氧化劑(B)時,其總重量(總含量)宜在上述範圍內。
上述抗氧化劑(B)之EVOH樹脂組成物每單位重量的含量可按照以下方式測定。首先,將EVOH樹脂組成物予以冷凍粉碎後之1g的試樣,於萃取溶劑中進行萃取,並對該萃取液定容,利用液相層析-紫外分光檢測器進行測定。另外,由抗氧化劑(B)之標準溶液製作檢量線,利用絕對檢量線法可定量抗氧化劑(B)之含量。
[山梨酸酯(C)]
本發明係藉由在EVOH樹脂組成物中摻合抗氧化劑(B)及特定微量的山梨酸酯(C),且將抗氧化劑(B)及山梨酸酯(C)之重量摻合比例設為特定範圍,達到抑制著色之顯著效果。
本發明係藉由在EVOH樹脂組成物中摻合抗氧化劑(B)及特定微量的山梨酸酯(C),且將抗氧化劑(B)及山梨酸酯(C)之重量摻合比例設為特定範圍,達到抑制著色之顯著效果。
本發明中,藉由對於在EVOH(A)中使用抗氧化劑(B)之系統併用特定微量之山梨酸酯(C),且抗氧化劑(B)及山梨酸酯(C)之重量摻合比例設為特定之範圍,可得到抑制著色效果優異之EVOH樹脂組成物。
本發明中,就著色受到抑制的理由而言,係山梨酸酯(C)極性低,即使微量亦容易均勻分散於EVOH樹脂組成物中。此外,據認為係藉由EVOH樹脂組成物受到加熱時特定微量之山梨酸酯(C)水解而產生山梨酸。並且,據推測係由於該山梨酸會捕捉自由基,因此可獲得優異的抑制著色效果。又,據推測會發生如下述之如觸媒循環般的狀態:水解後之山梨酸酯(C)之水解後的醇部位更會捕捉捕捉了自由基後的山梨酸,而生成山梨酸酯(C),生成之山梨酸酯(C)又再度因熱而水解。
如此,據推測由於持續有可捕捉自由基之山梨酸生成,在EVOH樹脂組成物中,可於自由基產生後及早捕捉自由基,而獲得優異的抑制著色效果。此外,據推測在本發明中,藉由併用抗氧化劑(B)及特定微量之山梨酸酯(C),並將抗氧化劑(B)及山梨酸酯(C)之重量摻合比例設為特定的範圍,上述循環會效率良好地作用,因此可獲得顯著的抑制著色效果。
如此,據推測由於持續有可捕捉自由基之山梨酸生成,在EVOH樹脂組成物中,可於自由基產生後及早捕捉自由基,而獲得優異的抑制著色效果。此外,據推測在本發明中,藉由併用抗氧化劑(B)及特定微量之山梨酸酯(C),並將抗氧化劑(B)及山梨酸酯(C)之重量摻合比例設為特定的範圍,上述循環會效率良好地作用,因此可獲得顯著的抑制著色效果。
作為上述山梨酸酯(C),可舉例如藉由山梨酸及醇、酚衍生物之縮合而獲得的山梨酸酯。具體而言可列舉山梨酸甲酯、山梨酸乙酯、山梨酸丙酯、山梨酸丁酯、山梨酸戊酯等山梨酸烷酯、山梨酸苯酯、山梨酸萘酯等山梨酸芳酯等。該等可單獨使用或併用2種以上。
其中,就山梨酸酯(C)而言,由於水解時產生之醇類的酸度較低時,不易發生EVOH樹脂組成物之著色,因此宜為山梨酸烷酯,更宜為烷氧基之碳數為1~5之山梨酸烷酯,特別宜為烷氧基之碳數為1~3之山梨酸烷酯,尤其宜為山梨酸甲酯、山梨酸乙酯。
山梨酸酯(C)之分子量通常為120~220,宜為120~200,尤宜為120~160。分子量為上述範圍時,有可有效地獲得抑制著色效果之傾向。
上述山梨酸酯(C)之含量為EVOH樹脂組成物每重量單位之0.00001~10ppm。宜為0.00005~5ppm,更宜為0.0001~4ppm,特別宜為0.0005~3ppm,尤其宜為0.001~1.5ppm。藉由將山梨酸酯(C)之含量設為上述範圍,可有效地獲得抑制著色效果。若山梨酸酯(C)之含量過多,則共軛雙鍵量過度增加而容易著色。
本發明之EVOH樹脂組成物中之山梨酸酯(C)含量在EVOH樹脂組成物係丸粒等成形物之情況,可利用以下的方法進行定量。即,首先將上述丸粒等成形物利用任意的方法粉碎(例如冷凍粉碎),溶解於碳數1~5之低級醇系溶劑並製成試樣。然後,藉由將上述試樣利用液相層析-質譜法(LC/MS/MS)進行測定,可定量山梨酸酯(C)之含量。
又,EVOH樹脂組成物為多層結構體等之與其他的熱塑性樹脂等組合而得之成形物時,例如若為多層結構體,將由欲測定之EVOH樹脂組成物構成之層利用任意的方法自多層結構體中取出後,可利用與上述相同的方法進行定量。
又,EVOH樹脂組成物中,抗氧化劑(B)相對於山梨酸酯(C)之重量含有比例為抗氧化劑(B)/山梨酸酯(C)=500~1000000。宜為1000~800000,尤宜為2000~650000。上述重量含有比例過小時,抑制著色效果降低。又,上述重量含有比例過大時,抑制著色效果亦降低。
[其他的熱塑性樹脂]
本發明之EVOH樹脂組成物中,除了EVOH(A)以外,作為樹脂成分,可更含有含量係如下述範圍內之其他的熱塑性樹脂:相對於EVOH樹脂組成物通常為30重量%以下,宜為10重量%以下。
本發明之EVOH樹脂組成物中,除了EVOH(A)以外,作為樹脂成分,可更含有含量係如下述範圍內之其他的熱塑性樹脂:相對於EVOH樹脂組成物通常為30重量%以下,宜為10重量%以下。
作為上述其他的熱塑性樹脂,具體而言可舉例如直鏈狀低密度聚乙烯、低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、乙烯-乙酸乙烯酯共聚物、離子聚合物、乙烯-丙烯共聚物、乙烯-α-烯烴(碳數4~20之α-烯烴)共聚物、乙烯-丙烯酸酯共聚物、聚丙烯、丙烯-α-烯烴(碳數4~20之α-烯烴)共聚物、聚丁烯、聚戊烯等烯烴之均聚物或共聚物、聚環狀烯烴、或將該等之烯烴之均聚物或共聚物利用不飽和羧酸或其酯予以接枝改性而得者等廣義的聚烯烴系樹脂、聚苯乙烯系樹脂、聚酯系樹脂、聚氯乙烯、聚偏二氯乙烯等氯乙烯系樹脂、聚醯胺系樹脂、丙烯酸系樹脂、乙烯酯系樹脂、聚酯彈性體、苯乙烯彈性體、聚胺甲酸酯彈性體、氯化聚乙烯、氯化聚丙烯等熱塑性樹脂。該等可單獨使用亦可併用2種以上。其中更以使用聚醯胺系樹脂或苯乙烯彈性體的情況,可顯著地發揮本發明之抑制著色效果因而理想。
[其他的添加劑]
本發明之EVOH樹脂組成物中,除了上述各成分之外,亦可因應需要,在不損及本發明之效果的範圍內(例如EVOH樹脂組成物全體之10重量%以下的含有比例),適當摻合乙二醇、甘油、己二醇等脂肪族多元醇等塑化劑;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)、高級脂肪酸之金屬鹽(例如硬脂酸鈣、硬脂酸鎂等)、高級脂肪酸酯(高級脂肪酸之甲酯、異丙酯、丁酯、辛酯等)、高級脂肪族醯胺(例如硬脂醯胺等、油醯胺等)、雙高級脂肪醯胺(例如乙烯雙硬脂醯胺等)、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)等潤滑劑;乾燥劑;去氧劑:無機填料;熱安定劑:光安定劑;阻燃劑;交聯劑;硬化劑;發泡劑;結晶成核劑;防霧劑;生物分解用添加劑;矽烷偶合劑;抗結塊劑;著色劑;抗靜電劑;紫外線吸收劑;抗菌劑;不溶性無機複鹽(例如水滑石等);界面活性劑;蠟等公知的添加劑。該等可單獨使用亦可併用2種以上。
本發明之EVOH樹脂組成物中,除了上述各成分之外,亦可因應需要,在不損及本發明之效果的範圍內(例如EVOH樹脂組成物全體之10重量%以下的含有比例),適當摻合乙二醇、甘油、己二醇等脂肪族多元醇等塑化劑;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)、高級脂肪酸之金屬鹽(例如硬脂酸鈣、硬脂酸鎂等)、高級脂肪酸酯(高級脂肪酸之甲酯、異丙酯、丁酯、辛酯等)、高級脂肪族醯胺(例如硬脂醯胺等、油醯胺等)、雙高級脂肪醯胺(例如乙烯雙硬脂醯胺等)、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)等潤滑劑;乾燥劑;去氧劑:無機填料;熱安定劑:光安定劑;阻燃劑;交聯劑;硬化劑;發泡劑;結晶成核劑;防霧劑;生物分解用添加劑;矽烷偶合劑;抗結塊劑;著色劑;抗靜電劑;紫外線吸收劑;抗菌劑;不溶性無機複鹽(例如水滑石等);界面活性劑;蠟等公知的添加劑。該等可單獨使用亦可併用2種以上。
作為上述熱安定劑,係以改善熔融成形時之熱安定性等各種物性為目的,可使用乙酸、丙酸、丁酸等有機酸類或該等之鹼金屬鹽(鈉鹽、鉀鹽等)、鹼土金屬鹽(鈣鹽、鎂鹽等)、鋅鹽等鹽;或硫酸、亞硫酸、碳酸、磷酸、硼酸等無機酸類、或該等之鹼金屬鹽(鈉鹽、鉀鹽等)、鹼土金屬鹽(鈣鹽、鎂鹽等)、鋅鹽等。
該等之中,尤宜摻合乙酸、包含硼酸及其鹽之硼化合物、乙酸鹽、磷酸鹽。
該等之中,尤宜摻合乙酸、包含硼酸及其鹽之硼化合物、乙酸鹽、磷酸鹽。
就上述熱安定劑而言,摻合乙酸時,其摻合量相對於EVOH(A)100重量份通常為0.001~1重量份,宜為0.005~0.2重量份,尤宜為0.01~0.1重量份。若乙酸之摻合量過少,則有乙酸之含有效果降低之傾向,反之若過多則有難以獲得均勻的薄膜之傾向。
又,就上述熱安定劑而言,摻合硼化合物時,其摻合量相對於EVOH(A)100重量份,按硼換算(灰化後利用ICP發射光譜法進行分析)通常為0.001~1重量份。若硼化合物之摻合量過少,則有硼化合物之含有效果降低之傾向,反之若過多則有難以獲得均勻的薄膜之傾向。
又,就上述熱安定劑而言,摻合乙酸鹽、磷酸鹽(包含磷酸氫鹽)時,其摻合量相對於EVOH(A)100重量份,按金屬換算(灰化後利用ICP發射光譜法進行分析)通常為0.0005~0.1重量份。若上述摻合量過少,則有其含有效果降低之傾向,反之若過多則有難以獲得均勻的薄膜之傾向。又,於EVOH樹脂組成物中摻合2種以上的鹽時,其總量宜在上述摻合量之範圍內。
[EVOH樹脂組成物之製造方法]
本發明之EVOH樹脂組成物係使用前述必要成分之EVOH(A)、抗氧化劑(B)及山梨酸酯(C)及因應需要摻合之上述各任意成分來製造,作為製造方法可舉例如乾摻法、熔融混合法、溶液混合法、含浸法等公知的方法,亦可將該等任意組合。
本發明之EVOH樹脂組成物係使用前述必要成分之EVOH(A)、抗氧化劑(B)及山梨酸酯(C)及因應需要摻合之上述各任意成分來製造,作為製造方法可舉例如乾摻法、熔融混合法、溶液混合法、含浸法等公知的方法,亦可將該等任意組合。
作為上述乾摻法,可舉例如(I)將含有EVOH(A)之丸粒、與抗氧化劑(B)及山梨酸酯(C)之至少一者使用滾動機等進行乾摻之方法等。
作為上述熔融混合法,可舉例如(II)將含有EVOH(A)之丸粒、與抗氧化劑(B)及山梨酸酯(C)之至少一者之乾摻物予以熔融混練並獲得丸粒或其他成形物之方法、(III)於熔融狀態之EVOH(A)中添加抗氧化劑(B)及山梨酸酯(C)之至少一者並予以熔融混練而獲得丸粒或其他成形物之方法。
作為上述溶液混合法,可舉例如(IV)使用市售之含有EVOH(A)的丸粒來製備溶液,於其中摻合抗氧化劑(B)及山梨酸酯(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(A)之製造過程中,使皂化後的EVOH之均勻溶液(水/醇溶液等)中含有抗氧化劑(B)及山梨酸酯(C)之至少一者後,凝固成形並造粒,進行固液分離並乾燥之方法。
作為上述含浸法,可舉例如(VI)使含有EVOH(A)之丸粒接觸含有抗氧化劑(B)及山梨酸酯(C)之至少一者之水溶液,並使抗氧化劑(B)及山梨酸酯(C)之至少一者含浸於上述丸粒中後進行乾燥之方法等。
又,上述各方法中,預先將EVOH(A)、與抗氧化劑(B)及山梨酸酯(C)之至少一者按照預定比例摻合,製作抗氧化劑(B)及山梨酸酯(C)之至少一者之濃度高的組成物(母料),並藉由摻合該組成物(母料)與EVOH(A),也可獲得所望之濃度的EVOH樹脂組成物。
此外,本發明中,可組合上述不同的手法。考量生產性之觀點,宜為藉由(V)在EVOH(A)之製造過程中,使皂化後之EVOH均勻溶液(水/醇溶液等)含有抗氧化劑(B)及山梨酸酯(C)後,凝固成形並造粒,進行固液分離並乾燥之方法獲得EVOH樹脂組成物丸粒。其中,考量可獲得生產性、本發明之效果更加顯著之EVOH樹脂組成物的觀點,宜為熔融混合法,尤宜為(II)之方法。
又,於EVOH樹脂組成物中摻合上述各任意成分時,亦可利用依照上述各製造方法之方法摻合於EVOH樹脂組成物中。
又,利用上述各方法而獲得的EVOH樹脂組成物之丸粒、於上述各方法使用之含有EVOH(A)之丸粒的形狀為任意,例如可採用球形、卵形、圓柱形、立方體形、長方體形等任意的形狀。丸粒的形狀通常為卵形或圓柱形,考量之後使用作為成形材料時之方便性之觀點,其大小於圓柱形時底面之直徑通常為1~6mm,宜為2~5mm,長度通常為1~6mm,宜為2~5mm。卵形時長徑通常為1.5~30mm,宜為3~20mm,更宜為3.5~10mm。短徑通常為1~10mm,宜為2~6mm,尤宜為2.5~5.5mm。測定該長徑及短徑之方法,例如將丸粒拿在手上觀察、使用游標尺等測量儀器測定長徑後,藉由目視及觸覺認定垂直於該長徑之剖面中為最大面積之剖面位置,並以相同的方式測定假設為該剖面時之短徑之方法。
又,本發明之EVOH樹脂組成物的含水率通常為0.01~0.5重量%,宜為0.05~0.35重量%,尤宜為0.1~0.3重量%。
又,本發明中之EVOH樹脂組成物的含水率係利用以下的方法進行測定、計算。
於室溫(25℃)下,將EVOH樹脂組成物作為試樣,利用電子天秤秤量乾燥前重量(W1)。然後,將該試樣於150℃之熱風乾燥機中乾燥5小時。乾燥後,於乾燥器中放涼30分鐘,並秤量EVOH樹脂組成物之溫度回復至室溫後之重量(W2),利用下列式進行計算。
含水率(重量%)=[(W1-W2)/W1]×100
於室溫(25℃)下,將EVOH樹脂組成物作為試樣,利用電子天秤秤量乾燥前重量(W1)。然後,將該試樣於150℃之熱風乾燥機中乾燥5小時。乾燥後,於乾燥器中放涼30分鐘,並秤量EVOH樹脂組成物之溫度回復至室溫後之重量(W2),利用下列式進行計算。
含水率(重量%)=[(W1-W2)/W1]×100
本發明之EVOH樹脂組成物係製備成丸粒、或粉末狀、液體狀等各種形態,並提供作為各種成形物之成形材料。尤其,本發明中,提供作為熔融成形用材料時,有更有效率地獲得本發明之效果的傾向因而理想。又,本發明之EVOH樹脂組成物亦包括混合了使用於本發明之EVOH樹脂組成物之EVOH(A)以外的樹脂而獲得的樹脂組成物。
本發明之EVOH樹脂組成物的丸粒可直接使用於熔融成形,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。作為上述潤滑劑,可使用前述潤滑劑。該潤滑劑含量通常為EVOH樹脂組成物之5重量%以下,宜為1重量%以下。
並且,就該成形物而言,以使用本發明之EVOH樹脂組成物成形而得之單層薄膜為代表,並可作為具有使用本發明之EVOH樹脂組成物成形而得之層之多層結構體供實用。
[多層結構體]
本發明之多層結構體,係具備由上述本發明之EVOH樹脂組成物構成之層者。由本發明之EVOH樹脂組成物構成之層(以下亦稱為「EVOH樹脂組成物層」)可藉由與以本發明之EVOH樹脂組成物以外之熱塑性樹脂為主成分之其他的基材(以下稱為「基材樹脂」)疊層,進一步賦予強度、或保護EVOH樹脂組成物層不受水分等之影響、或賦予其他的機能。
本發明之多層結構體,係具備由上述本發明之EVOH樹脂組成物構成之層者。由本發明之EVOH樹脂組成物構成之層(以下亦稱為「EVOH樹脂組成物層」)可藉由與以本發明之EVOH樹脂組成物以外之熱塑性樹脂為主成分之其他的基材(以下稱為「基材樹脂」)疊層,進一步賦予強度、或保護EVOH樹脂組成物層不受水分等之影響、或賦予其他的機能。
作為上述基材樹脂,可舉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(於主鏈及側鏈之至少一者具有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。該等可單獨使用亦可併用2種以上。
該等之中,為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,更宜為聚乙烯系樹脂、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,尤其聚環狀烯烴系樹脂可理想的用作於疏水性樹脂。
多層結構體之層構成當將本發明之EVOH樹脂組成物層設為a(a1、a2、…),基材樹脂層設為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,將製造該多層結構體之過程中產生的端部、不良品等予以再熔融成形而獲得之含有本發明之EVOH樹脂組成物與基材樹脂之混合物之回收層設為R時,亦可為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。多層結構體之層之數目共計通常為2~15,宜為3~10。上述層構成中,各層間亦可因應需要介隔含有黏接性樹脂之黏接性樹脂層。
作為上述黏接性樹脂,可使用公知者,可因應基材樹脂層「b」使用的熱塑性樹脂之種類適當選擇。可列舉將不飽和羧酸或其酐藉由加成反應、接枝反應等化學鍵結於聚烯烴系樹脂而獲得之含有羧基之改性聚烯烴系聚合物為代表。可舉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,可使用選自該等中之1種或2種以上之混合物。
多層結構體中,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,由於黏接性樹脂層係與EVOH樹脂組成物層相鄰,宜使用疏水性優異之黏接性樹脂。
上述基材樹脂、黏接性樹脂中,亦可在不妨礙本發明之旨趣之範圍內(例如相對於基材樹脂、黏接性樹脂通常為30重量%以下,宜為10重量%以下),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、防結塊劑、蠟等。該等可單獨使用亦可併用2種以上。
本發明之EVOH樹脂組成物與上述基材樹脂之疊層(包含介隔有黏接性樹脂層的情況)可利用公知的方法進行。可舉例如將基材樹脂進行熔融擠壓層合於本發明之EVOH樹脂組成物之薄膜、片材等之方法、將本發明之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的黏接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去除溶劑之方法等。該等之中,考量成本、環境之觀點,宜為共擠壓之方法。
上述多層結構體因應需要施行(加熱)延伸處理。延伸處理可為單軸延伸、雙軸延伸之任一者,為雙軸延伸時可同時延伸亦可逐次延伸。又,就延伸方法而言,亦可採用輥延伸法、拉幅延伸法、管式延伸法、延伸吹塑法、真空壓空成形等之中延伸倍率高者。延伸溫度係多層結構體之熔點附近的溫度,通常自40~170℃,宜為60~160℃左右之範圍中選擇。延伸溫度過低時有延伸性不良的傾向,過高時則有難以維持安定的延伸狀態之傾向。
又,延伸後為了賦予尺寸安定性,亦可進行熱固定。熱固定可利用公知的手段實施,例如將上述延伸薄膜保持在緊張狀態並於通常80~180℃,宜為100~165℃進行通常為2~600秒左右之熱處理。又,將由本發明之EVOH樹脂組成物而獲得之多層延伸薄膜用作收縮用薄膜時,為了賦予熱收縮性,可不進行上述熱固定而進行例如對於延伸後之薄膜吹送冷風並冷卻固定等處理。
又,亦可使用本發明之多層結構體來獲得杯、盤狀之多層容器。此情況下,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、模塞助壓式(plug assist)真空壓空成形法等。此外從多層型坯(吹塑前之中空管狀之預備成形物)獲得管、瓶狀之多層容器(疊層體構造)時採用吹塑成形法。具體而言,可列舉擠壓吹塑成形法(雙頭式、模具移動式、型坯轉移式、旋轉式、累積器式、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(擠壓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、射出成形線上式雙軸延伸吹塑成形法等)等。獲得之疊層體可因應需要進行熱處理、冷卻處理、壓延處理、印刷處理、乾層合處理、溶液或熔融塗佈處理、製袋加工、深抽拉加工、箱加工、管加工、分切加工等。
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、基材樹脂層及黏接性樹脂層之厚度,取決於層構成、基材樹脂之種類、黏接性樹脂之種類、用途、包裝形態、所需之物性等,無法一概而論,但多層結構體(包括經延伸者)之厚度通常為10~5000μm,宜為30~3000μm,尤宜為50~2000μm。EVOH樹脂組成物層通常為1~500μm,宜為3~300μm,尤宜為5~200μm,基材樹脂層通常為5~3000μm,宜為10~2000μm,尤宜為20~1000μm,黏接性樹脂層通常為0.5~250μm,宜為1~150μm,尤宜為3~100μm。
此外,多層結構體中EVOH樹脂組成物層與基材樹脂層之厚度之比(EVOH樹脂組成物層/基材樹脂層),於各層有多數時係厚度最厚之層之間之比,通常為1/99~50/50,宜為5/95~45/55,尤宜為10/90~40/60。又,多層結構體中EVOH樹脂組成物層與黏接性樹脂層之厚度比(EVOH樹脂組成物層/黏接性樹脂層)於各層有多數時厚度最厚之層之間之比,通常為10/90~99/1,宜為20/80~95/5,尤宜為50/50~90/10。
如上述獲得之由薄膜、片、延伸薄膜所構成之袋及杯、托盤、管、瓶等構成的容器、蓋材,可用作一般的食品、美乃滋、沙拉醬等調味料、味噌等發酵食品、沙拉油等油脂食品、飲料、化妝品、醫藥品等各種包裝材料容器。此外,由本發明之EVOH樹脂組成物構成之層,由於耐劣化性優異,作為青貯料薄膜、多層薄膜等農業用薄膜尤其有用。
[多層管]
本發明之多層管係具備由上述本發明之EVOH樹脂組成物所構成之層構成的多層構造之管。由本發明之EVOH樹脂組成物構成之層可藉由與以本發明之EVOH樹脂組成物以外之樹脂為主成分之其他的樹脂組成物構成之層進行疊層,進一步賦予強度、或保護EVOH樹脂組成物層不受水分等之影響、或賦予其他的機能。
本發明之多層管係具備由上述本發明之EVOH樹脂組成物所構成之層構成的多層構造之管。由本發明之EVOH樹脂組成物構成之層可藉由與以本發明之EVOH樹脂組成物以外之樹脂為主成分之其他的樹脂組成物構成之層進行疊層,進一步賦予強度、或保護EVOH樹脂組成物層不受水分等之影響、或賦予其他的機能。
本發明之多層管由於具備由以EVOH(A)為主成分之EVOH樹脂組成物構成之層,因此氣體阻隔性優異。又,即使長時間暴露於高溫,由EVOH樹脂組成物構成之層係耐劣化性優異,故即使於高溫下長時間使用,上述由EVOH樹脂組成物構成之層(EVOH樹脂組成物層)中亦會抑制氧化劣化所致之裂縫的產生。由於具備如此的特性,本發明之多層管可理想的使用作為例如溫水循環用管及區域冷暖供應系統用之隔熱多層管。
就本發明之多層管之層構成而言,可採用上述多層結構體之層構成。並且,作為上述多層管之一例,例如使用作為溫水循環用管時,一般而言採用3層構造之多層管,該多層管於最外層具備由本發明之EVOH樹脂組成物構成之層,於中間層具備使用黏接性樹脂形成之層,於最內層具備使用熱塑性樹脂形成之層之EVOH樹脂組成物層/黏接性樹脂層/熱塑性樹脂層之層構造。作為上述熱塑性樹脂,可舉例如聚烯烴如聚乙烯、聚丙烯、聚1-丁烯、聚4-甲基-1-戊烯等。其中又以聚乙烯,尤以高密度聚乙烯為理想。又,作為上述黏接性樹脂,可列舉與前述多層結構體中使用之黏接性樹脂相同者,例如將不飽和羧酸或其酐藉由加成反應、接枝反應等化學鍵結於聚烯烴系樹脂而獲得之含有羧基之改性聚烯烴系聚合物。
將本發明之多層管使用作為地板供暖系統管等溫水循環用管時,考量氣體阻隔性之觀點,宜如上所述將由本發明之EVOH樹脂組成物構成之層配置於最外層。即,藉由將由氣體阻隔性優異,進而耐劣化性亦優異之本發明之EVOH樹脂組成物構成之層配置於最外層,考量作為多層管之阻隔性之觀點為有利,同時,由於使用耐劣化性優異之本發明之EVOH樹脂組成物作為與空氣直接接觸之最外層的成形材料,可獲得具備良好阻隔性且抑制了氧化劣化所致之裂縫產生的多層管。
接下來針對多層管之製造方法進行說明。
本發明之多層管例如可藉由將本發明之EVOH樹脂組成物與黏接性樹脂共擠壓塗佈於由交聯聚烯烴等熱塑性樹脂構成之單層管的外周面上來製造。將本發明之EVOH樹脂組成物與黏接性樹脂進行共擠壓塗佈於上述單層管之外周面上時,可僅係將本發明之EVOH樹脂組成物與黏接性樹脂之經熔融的薄膜塗佈於單層管之外周面上,但上述單層管與塗佈層之間的黏接力有時會不充分,且有在長期間使用中塗佈層剝離並失去氣體阻隔性之可能性。由於如此情事,進行共擠壓塗佈前,宜預先將單層管之外周表面利用火焰處理及電暈放電處理之至少一者施行表面處理。
本發明之多層管例如可藉由將本發明之EVOH樹脂組成物與黏接性樹脂共擠壓塗佈於由交聯聚烯烴等熱塑性樹脂構成之單層管的外周面上來製造。將本發明之EVOH樹脂組成物與黏接性樹脂進行共擠壓塗佈於上述單層管之外周面上時,可僅係將本發明之EVOH樹脂組成物與黏接性樹脂之經熔融的薄膜塗佈於單層管之外周面上,但上述單層管與塗佈層之間的黏接力有時會不充分,且有在長期間使用中塗佈層剝離並失去氣體阻隔性之可能性。由於如此情事,進行共擠壓塗佈前,宜預先將單層管之外周表面利用火焰處理及電暈放電處理之至少一者施行表面處理。
就用以製造本發明之多層管之其他的多層成形方法而言,可列舉使用對應層成形材料之種類之數量(層之數量)的擠製機,以於上述擠製機內將經熔融之層成形材料之液流經重疊之層狀態下同時擠製成形,即利用所謂共擠壓成形來製造之方法。又,亦可採用乾疊層等多層成形方法。
本發明之多層管之製造方法宜經過於成形後立即以10~70℃的水進行冷卻之步驟。即,熔融成形後,宜藉由在由本發明之EVOH樹脂組成物構成之層固化前以10~70℃的水進行冷卻,使上述由EVOH樹脂組成物構成之層固化。上述冷卻水的溫度更宜為15~60℃,尤宜為20~50℃。冷卻水的溫度若過低,則有接續之二次加工步驟中使多層管彎曲時,彎曲部中由本發明之EVOH樹脂組成物構成之層容易因變形而產生裂縫之傾向。又,冷卻水的溫度若過高,亦有二次加工時彎曲部中由本發明之EVOH樹脂組成物構成之層容易因變形而產生裂縫之傾向。
藉由將利用上述方法獲得之多層管進行二次加工,可獲得各種成形體。就二次加工法而言,並無特別限定而可適當使用公知的二次加工法。可舉例如藉由將多層管加熱至80~160℃後,於變形成期望之形狀的狀態固定1分鐘~2小時來加工之方法等。
如上述而獲得之本發明之多層管,由於具有由本發明之EVOH樹脂組成物構成之層,具有耐劣化性且抑制著色效果優異。因此,作為溫水循環用管等尤其有用。
[實施例]
[實施例]
以下舉實施例具體地說明本發明,但本發明只要不超出其要旨,並不限於實施例之記載。
又,例中所記載的「份」、「%」,若無額外說明係意指重量基準。
又,例中所記載的「份」、「%」,若無額外說明係意指重量基準。
在實施例之前先準備以下的EVOH(A)之丸粒。
・EVOH(A):乙烯結構單元之含量29莫耳%,皂化度100莫耳%,MFR3.2g/10分鐘(210℃、荷重2160g)之乙烯-乙烯醇共聚物
・EVOH(A):乙烯結構單元之含量29莫耳%,皂化度100莫耳%,MFR3.2g/10分鐘(210℃、荷重2160g)之乙烯-乙烯醇共聚物
<實施例1>
將100份之上述EVOH(A)丸粒、0.3份之(EVOH樹脂組成物每重量單位之3000ppm)之作為抗氧化劑(B)的新戊四醇[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](BASF公司製「IRGANOX 1010」,分子量1178)、0.0000005份(EVOH樹脂組成物每重量單位之0.005ppm)之作為山梨酸酯(C)之山梨酸甲酯(FUJIFILM Wako Pure Chemical Corporation製,分子量126)利用塑性測定器(Brabender公司製)於230℃預熱5分鐘後,於230℃、50rpm下熔融混練5分鐘,然後冷卻固化而獲得塊狀的EVOH樹脂組成物。將獲得之EVOH樹脂組成物利用粉碎機(SOMETANI產業公司製,型號:SKR16-240)於旋轉刀片之轉數650rpm下粉碎而獲得粉碎物。該粉碎物係邊長1mm至5mm之小碎片。該樹脂組成物之含水率為0.16%。
將100份之上述EVOH(A)丸粒、0.3份之(EVOH樹脂組成物每重量單位之3000ppm)之作為抗氧化劑(B)的新戊四醇[3-(3,5-二第三丁基-4-羥苯基)丙酸酯](BASF公司製「IRGANOX 1010」,分子量1178)、0.0000005份(EVOH樹脂組成物每重量單位之0.005ppm)之作為山梨酸酯(C)之山梨酸甲酯(FUJIFILM Wako Pure Chemical Corporation製,分子量126)利用塑性測定器(Brabender公司製)於230℃預熱5分鐘後,於230℃、50rpm下熔融混練5分鐘,然後冷卻固化而獲得塊狀的EVOH樹脂組成物。將獲得之EVOH樹脂組成物利用粉碎機(SOMETANI產業公司製,型號:SKR16-240)於旋轉刀片之轉數650rpm下粉碎而獲得粉碎物。該粉碎物係邊長1mm至5mm之小碎片。該樹脂組成物之含水率為0.16%。
<實施例2>
將實施例1中之山梨酸甲酯之摻合量變更為0.0001份(EVOH樹脂組成物每重量單位之1ppm),除此以外,以與實施例1相同方式獲得實施例2之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.24%。
將實施例1中之山梨酸甲酯之摻合量變更為0.0001份(EVOH樹脂組成物每重量單位之1ppm),除此以外,以與實施例1相同方式獲得實施例2之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.24%。
<實施例3>
將實施例1中之山梨酸甲酯變更為山梨酸乙酯(FUJIFILM Wako Pure Chemical Corporation製,分子量140),除此以外,以與實施例1相同方式獲得實施例3之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.21%。
將實施例1中之山梨酸甲酯變更為山梨酸乙酯(FUJIFILM Wako Pure Chemical Corporation製,分子量140),除此以外,以與實施例1相同方式獲得實施例3之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.21%。
<實施例4>
將實施例1中之抗氧化劑(B)之摻合量變更為0.03份(EVOH樹脂組成物每重量單位之300ppm),除此以外,以與實施例1相同方式獲得實施例4之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.18%。
將實施例1中之抗氧化劑(B)之摻合量變更為0.03份(EVOH樹脂組成物每重量單位之300ppm),除此以外,以與實施例1相同方式獲得實施例4之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.18%。
<實施例5>
將實施例1中之抗氧化劑(B)之摻合量變更為0.003份(EVOH樹脂組成物每重量單位之30ppm),除此以外,以與實施例1相同方式獲得實施例5之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.20%。
將實施例1中之抗氧化劑(B)之摻合量變更為0.003份(EVOH樹脂組成物每重量單位之30ppm),除此以外,以與實施例1相同方式獲得實施例5之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.20%。
<實施例6>
將實施例4中之抗氧化劑(B)變更為N,N’-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥苯基)丙醯胺](BASF公司製「IRGANOX 1098」,分子量637),除此以外,以與實施例4相同方式獲得實施例6之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.16%。
將實施例4中之抗氧化劑(B)變更為N,N’-己烷-1,6-二基雙[3-(3,5-二第三丁基-4-羥苯基)丙醯胺](BASF公司製「IRGANOX 1098」,分子量637),除此以外,以與實施例4相同方式獲得實施例6之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.16%。
<實施例7>
將實施例1中之抗氧化劑(B)變更為雙(2,2,6,6-四甲基-4-哌啶)癸二酸酯(BASF公司製「TINUVIN 770」,分子量481),除此以外,以與實施例1相同方式獲得實施例7之EVOH樹脂組成物及其粉砕物。該樹脂組成物之含水率為0.20%。
將實施例1中之抗氧化劑(B)變更為雙(2,2,6,6-四甲基-4-哌啶)癸二酸酯(BASF公司製「TINUVIN 770」,分子量481),除此以外,以與實施例1相同方式獲得實施例7之EVOH樹脂組成物及其粉砕物。該樹脂組成物之含水率為0.20%。
<實施例8>
將實施例7中之抗氧化劑(B)之摻合量變更為0.03份(EVOH樹脂組成物每重量單位300ppm),除此以外,以與實施例7相同方式獲得實施例8之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.17%。
將實施例7中之抗氧化劑(B)之摻合量變更為0.03份(EVOH樹脂組成物每重量單位300ppm),除此以外,以與實施例7相同方式獲得實施例8之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.17%。
<比較例1>
實施例1中,除了未摻合山梨酸甲酯以外,以與實施例1相同方式獲得比較例1之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.20%。
實施例1中,除了未摻合山梨酸甲酯以外,以與實施例1相同方式獲得比較例1之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.20%。
<比較例2>
將實施例1中之山梨酸甲酯之摻合量變更為0.0015份(EVOH樹脂組成物每重量單位之15ppm),除此以外,以與實施例1相同方式獲得比較例2之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.14%。
將實施例1中之山梨酸甲酯之摻合量變更為0.0015份(EVOH樹脂組成物每重量單位之15ppm),除此以外,以與實施例1相同方式獲得比較例2之EVOH樹脂組成物及其粉碎物。該樹脂組成物之含水率為0.14%。
<比較例3>
實施例1中,除了未摻合抗氧化劑(B)及山梨酸酯(C)僅使用EVOH(A)以外,以與實施例1相同方式進行熔融混練並粉碎,而獲得比較例3之粉碎物。該EVOH(A)之含水率為0.11%。
實施例1中,除了未摻合抗氧化劑(B)及山梨酸酯(C)僅使用EVOH(A)以外,以與實施例1相同方式進行熔融混練並粉碎,而獲得比較例3之粉碎物。該EVOH(A)之含水率為0.11%。
利用以下所示之方法進行實施例1~8、比較例1~3之著色評估1及2。結果示於下列表1。
[著色評估1]
將上述各粉碎物作為試樣,利用視覺分析儀IRIS VA400(ALPHA MOS公司製),評估色號「3530」(R:216、G:200、B:168)相對於色號「4077」(R:248、G:232、B:216)所佔的比例(「3530」/「4077」)。色號「3530」係帶有濃黃色感的顏色,色號「4077」係帶有淡黃色感的顏色,其比例越大代表試樣越著色成黃色。
將上述各粉碎物作為試樣,利用視覺分析儀IRIS VA400(ALPHA MOS公司製),評估色號「3530」(R:216、G:200、B:168)相對於色號「4077」(R:248、G:232、B:216)所佔的比例(「3530」/「4077」)。色號「3530」係帶有濃黃色感的顏色,色號「4077」係帶有淡黃色感的顏色,其比例越大代表試樣越著色成黃色。
[著色評估2]
將上述之各粉碎物作為試樣,利用視覺分析儀IRIS VA400(ALPHA MOS公司製),評估色號「3530」(R:216、G:200、B:168)及「3531」(R:216、G:200、B:184)相對於色號「4077」(R:248、G:232、B:216)及「4078」(R:248、G:232、B:232)之總和所佔的比例(「3530+3531」/「4077+4078」)。色號「3530」及「3531」係帶有濃黃色感的顏色,色號「4077」及「4078」係帶有淡黃色感的顏色。濃黃色感之比例越大代表試樣越著色成黃色。
將上述之各粉碎物作為試樣,利用視覺分析儀IRIS VA400(ALPHA MOS公司製),評估色號「3530」(R:216、G:200、B:168)及「3531」(R:216、G:200、B:184)相對於色號「4077」(R:248、G:232、B:216)及「4078」(R:248、G:232、B:232)之總和所佔的比例(「3530+3531」/「4077+4078」)。色號「3530」及「3531」係帶有濃黃色感的顏色,色號「4077」及「4078」係帶有淡黃色感的顏色。濃黃色感之比例越大代表試樣越著色成黃色。
[表1]
如上述之表1所示,得知含有抗氧化劑(B)但不含山梨酸酯(C)之比較例1、含有抗氧化劑(B)及山梨酸酯(C)但山梨酸酯(C)之含量多之比較例2、不含抗氧化劑(B)及山梨酸酯(C)之比較例3,幾乎為同程度之著色度。
反觀,含有抗氧化劑(B)及特定微量之山梨酸酯(C)且抗氧化劑(B)與山梨酸酯(C)之重量含有比例在特定之範圍內的實施例1~8之EVOH樹脂組成物,獲得了相較於比較例1~3更加抑制著色之顯著效果。
使用上述獲得之各實施例的樹脂組成物製造之多層結構體、及由該多層結構體構成之多層管,皆具有耐劣化性且抑制著色。
上述實施例中,揭示了本發明之具體的形態,但上述實施例僅為例示,並沒有限定之含意。對於所屬領域中具有通常知識者中顯而易見的各種變形,亦考量在本發明之範圍內。
[產業上利用性]
[產業上利用性]
本發明之EVOH樹脂組成物由於具有耐劣化性且抑制著色效果優異,作為各種食品、美乃滋、沙拉醬等調味料、味噌等發酵食品、沙拉油等油脂食品、飲料、化妝品、醫藥品等各種之包裝材料尤其有用。並且,具備由本發明之EVOH樹脂組成物構成之層之多層結構體,由於具有耐劣化性且抑制著色效果優異,作為青貯料薄膜、多層薄膜等農業用薄膜尤其有用。更進一步,上述多層結構體作為溫水循環用多層管亦尤其有用。
Claims (5)
- 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)、抗氧化劑(B)及山梨酸酯(C),其特徵在於:該山梨酸酯(C)之含量為該乙烯-乙烯醇系共聚物組成物每單位重量之0.00001~10ppm,且抗氧化劑(B)相對於山梨酸酯(C)之重量含有比例為抗氧化劑(B)/山梨酸酯(C)=500~1000000。
- 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,該抗氧化劑(B)之含量為該乙烯-乙烯醇系共聚物組成物每單位重量之1~30000ppm。
- 一種熔融成形用材料,其特徵在於: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,其特徵在於: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。
- 一種多層管,其特徵在於:由如申請專利範圍第4項之多層結構體構成。
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