TWI617590B - 嵌段共聚物組成物及薄片 - Google Patents
嵌段共聚物組成物及薄片 Download PDFInfo
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- TWI617590B TWI617590B TW102116184A TW102116184A TWI617590B TW I617590 B TWI617590 B TW I617590B TW 102116184 A TW102116184 A TW 102116184A TW 102116184 A TW102116184 A TW 102116184A TW I617590 B TWI617590 B TW I617590B
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- Prior art keywords
- block copolymer
- copolymer composition
- molecular weight
- mass
- vinyl aromatic
- Prior art date
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- 229920001400 block copolymer Polymers 0.000 title claims abstract description 184
- 239000000203 mixture Substances 0.000 title claims abstract description 103
- -1 vinyl aromatic hydrocarbon Chemical class 0.000 claims abstract description 79
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 61
- 150000001993 dienes Chemical class 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 239000001993 wax Substances 0.000 claims description 37
- 239000004215 Carbon black (E152) Substances 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 25
- 150000002430 hydrocarbons Chemical class 0.000 claims description 25
- 239000011342 resin composition Substances 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 239000012748 slip agent Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000004200 microcrystalline wax Substances 0.000 claims description 10
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 claims description 6
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 claims description 6
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 5
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000005022 packaging material Substances 0.000 abstract description 18
- 230000000704 physical effect Effects 0.000 abstract description 6
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- 238000000034 method Methods 0.000 description 43
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 26
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 22
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- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
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- 239000002994 raw material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
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- 238000004448 titration Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
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Abstract
提供一種適合食品容器、飲料容器、工業用容器、泡鼓包裝等各種包裝材料,具有優良的透明性、光澤、強度、剛性、成形加工性,也具有優良的防結塊性能、防堆疊性能,即便在混合乙烯基芳香族烴系聚合物使用之情形,前述特性也優良之物性平衡良好的嵌段共聚物組成物。
一種嵌段共聚物組成物,其係乙烯基芳香族烴與共軛二烯之嵌段共聚物組成物,其在分子量150000~300000之範圍具有分子量峰(peak)與錐形嵌段(tapered block)之嵌段共聚物成分(I)的共軛二烯含有率為10~20質量%,在分子量50000~140000之範圍具有分子量峰與錐形嵌段之嵌段共聚物成分(II)的共軛二烯含量為30~50質量%,嵌段共聚物組成物中的嵌段共聚物成分(I)與嵌段共聚物成分(II)之分子量峰面積比(I)/(II)為20/80~80/20。
Description
本發明係關於嵌段共聚物組成物及薄片。
由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物被廣泛的使用於食品容器、飲料容器、工業用容器(※包含各種托盤)、泡鼓包裝等各種包裝材料。對於包裝材料,有許多設計性的需求,且內容物需要能被清楚的看見,故包裝材料原料被要求要有優良的透明性、光澤。另一方面,由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物,由於有混合乙烯基芳香族烴系聚合物來使用作為包裝材料之情形,故此種樹脂組成物也需要良好的透明性。對於此課題,專利文獻1~2中有記載,使用具有特定聚合物構造之由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物,對於解決課題是有效的。
另外,於包裝材料用途也必須要有能承受實際使用之強度(拉伸強度、耐衝撃強度),以賦予這些物性為目的,而有使用共軛二烯含有率高之嵌段共聚物的手段。但是,於隨機地使用共軛二烯之含有率高的嵌段共聚物之情形,會變得缺乏與乙烯基芳香族烴系聚合物的相溶性,而難以確保良好的透明性、光澤。
另一方面,作為包裝材料的一般製造方法,
有將材料熔融混練並成形為薄片後,進行真空成形、壓空成形、加壓成形等熱成形,製成各種成形體之方法。
這些製程係有成形為薄片,並以輥狀態捲取保管後,再自輥將薄片反覆進行熱成形,得到成形品之離線形式;及薄片成形後,不經由以輥狀態保管,而直接熱成形,得到成形品之線上形式。在離線形式中,因薄片以彼此接觸之輥狀態長時間保管,故在使用由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物的情形,容易產生薄片彼此黏著無法剝下的現象(以下,簡稱為「結塊」)。若發生結塊不良,由於會無法使用於之後的熱成形等,故期望賦予防結塊性能。關於此課題,專利文獻3~5中記載,於該嵌段共聚物中使用烴系蠟,來作為有效防止結塊之手段。
然而,依照由乙烯基芳香族烴與共軛二烯所
構成之嵌段共聚物的構造,若隨機地選定烴系蠟來使用,也會有未展現充分的防結塊效果之情形,故需要使用適合使用之聚合物的烴系蠟。
又,在成形為包裝材料後,在經過以將成形
品彼此重疊狀態保管之過程的情形,於再將其各自分離來使用時,會有發生成形品的接觸面彼此卡住的現象(以下,簡稱為「堆疊」)。此現象在使用由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物之情形,係容易發生的,特別是隨著包裝材料的溝槽深,或成為形狀複雜之包裝材料,由於成形品彼此的接觸面積增加,使分離變
困難,而需要優良的防堆疊性能。近年來,由於形狀複雜的包裝材料增加,故對於材料期望實現更優良的防堆疊性能。
[專利文獻1]日本專利第4787480號公報
[專利文獻2]日本特開2006-143944號公報
[專利文獻3]日本專利第1958261號公報
[專利文獻4]日本特開2005-139326號公報
[專利文獻5]日本專利第4812946號公報
本發明之目的係在於提供適合各種形狀之食品容器、飲料容器、工業用容器、泡鼓包裝等各種包裝材料(※包含各種托盤)之具有優良的透明性、光澤、強度、剛性、成形加工性的材料,以及具有更優良的防結塊性能與防堆疊性能,且即便在混合乙烯基芳香族烴系聚合物而使用之情形,前述特性同樣優良之物性平衡良好的材料。
本發明係一種嵌段共聚物組成物,其係由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物組成物,其中,在分子量150000~300000之範圍有分子量峰(peak),且含有錐形嵌段(tapered block)之嵌段共聚物成分(I)
中之共軛二烯含有率為10~20質量%;而在分子量50000~140000之範圍有分子量峰,且含有錐形嵌段之嵌段共聚物成分(II)中之共軛二烯含有率為30~50質量%;分子量峰的面積比(I)/(II)為20/80~80/20;更佳係一種嵌段共聚物組成物,其中嵌段共聚物成分(I)在分子量180000~290000之範圍具有分子量峰,且含有錐形嵌段,並且共軛二烯的含有率為10~15質量%,而嵌段共聚物成分(II)在分子量60000~100000之範圍具有分子量峰,且含有錐形嵌段,並且共軛二烯含有率為30~40質量%,此外分子量峰的面積比(I)/(II)為40/60~60/40。另外,本發明係一種嵌段共聚物組成物,其含有嵌段共聚物成分(I)含有分子量80000~150000之乙烯基芳香族烴的聚合嵌段部分;及前述嵌段共聚物成分(II)含有分子量5000~40000之乙烯基芳香族烴的聚合嵌段部分。此外,本發明之嵌段共聚物組成物係在嵌段共聚物組成物中,含有總量0.03~1.0質量%之單獨烴系蠟,或烴系蠟與由硬脂酸硬脂酯、硬脂酸單甘油酯、芥酸醯胺、蘿酸醯胺所選出之至少1種以上;較佳為前述烴系蠟為熔點60~120℃之微晶蠟、或合成蠟、或微晶蠟與合成蠟之混合物中的任一種,並於嵌段共聚物組成物中含有0.03~0.5質量%;更佳為前述烴系蠟的熔點為80~110℃;前述由硬脂酸硬脂酯、硬脂酸單甘油酯、芥酸醯胺、蘿酸醯胺所選出的滑劑之總量,相對於嵌段共聚物組成物,係0.03~0.5質量%之嵌段共聚物組成物。此外,本發明係前述嵌段共聚物組成物與乙烯基芳香族烴系聚合物以30/70~100/0之質量比混
合而成的樹脂組成物、使用前述材料之薄片、及其容器。
藉由使用本發明之嵌段共聚物組成物,無論是在單獨使用該嵌段共聚物組成物之情形,或是混合該嵌段共聚物組成物與乙烯基芳香族烴系聚合物來使用之情形,均可實現優良的透明性、光澤、強度、剛性、成形加工性。此外,除了前述特性以外,在薄片及成形品的使用上,也能實現更優良的防結塊性能與防堆疊性能,讓各種形狀之包裝材料的製造及使用變容易。
本發明之嵌段共聚物組成物,係以由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物作為構成要素。
本發明之嵌段共聚物中所使用的乙烯基芳香族烴,可列舉出例如:苯乙烯、鄰甲基苯乙烯、對甲基苯乙烯、對第三丁基苯乙烯、2,4-二甲基苯乙烯、2,5-二甲基苯乙烯、α-甲基苯乙烯、乙烯基萘、乙烯基蒽等,其中較佳為苯乙烯。
本發明之嵌段共聚物中所使用的共軛二烯,可列舉出:1,3-丁二烯、2-甲基-1,3-丁二烯(異戊二烯)、2,3-二甲基-1,3-丁二烯、1,3-戊二烯、1,3-己二烯等,其
中較佳為1,3-丁二烯、異戊二烯。
本發明之嵌段共聚物,可藉由在經過脫水之
有機溶媒中,以有機鋰化合物作為起始劑,視需要讓無規化劑共存,將乙烯基芳香族烴及共軛二烯的單體加以聚合來製造。作為有機溶媒,可使用丁烷、戊烷、己烷、異戊烷、庚烷、辛烷、異辛烷等脂肪族烴,環己烷、甲基環己烷、乙基環己烷等脂環式烴,或苯、甲苯、乙基苯、二甲苯等芳香族烴等,其中較佳為環己烷。
有機鋰化合物係於分子中鍵結了1個以上鋰
原子之化合物,例如:除了乙基鋰、正丙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰等單官能有機鋰化合物以外,也可使用六亞甲基二鋰、丁二烯基二鋰、異戊二烯基二鋰等多官能有機鋰化合物,其中較佳為正丁基鋰。
作為無規化劑,主要係使用四氫呋喃(THF)
,其他還可使用醚類、胺類、硫醚類、磷醯胺、烷基苯磺酸鹽、鉀或鈉的烷氧化物等。醚類可列舉出例如:二甲基醚、二乙基醚、二苯基醚、二乙二醇二甲基醚、二乙二醇二丁基醚等。胺類除了三級胺,例如三甲胺、三乙胺、四甲基乙烯二胺以外,也可使用內環狀胺等。其他可使用三苯基膦、六甲基磷醯胺、烷基苯磺酸鉀(或鈉)、丁氧化鉀(或鈉)等作為無規化劑。
這些無規化劑的添加量,相對於100質量份的全部進料的單體,係10質量份以下,較佳為0.001~8質量份。添加時間可在聚合反應開始前,也可在聚合途中。又,也可視需要追加添加。
如此進行所得到之嵌段共聚物溶液,係藉由
添加用於將活性末端惰性化之充分量的水、醇、二氧化碳等聚合停止劑,將嵌段共聚物惰性化。作為自此嵌段共聚物溶液回收嵌段共聚物之方法,可使用將此溶液投入甲醇等貧溶媒加以析出之方法、藉由加熱輥等將溶媒蒸發來加以析出之方法(滾筒烘乾機法)、藉由濃縮器將溶液濃縮後以排氣式擠出機將溶媒除去之方法、將溶液分散於水中,再藉由吹進水蒸汽將溶媒加熱除去之方法(蒸汽汽提法)等任意方法。
在將複數種嵌段共聚物混合製成嵌段共聚物
組成物之情形,其混合方法可列舉出:在將經除去溶劑之嵌段共聚物彼此摻和後,投入擠出機,一邊加以熔融一邊混練、混合之方法,在將經除去溶劑前的嵌段共聚物之溶液彼此摻和後,除去溶劑以得到混合物之方法,在1個反應容器中聚合複數種嵌段共聚物來得到之方法,本發明之嵌段共聚物組成物,可使用前述的任一種混合方法。
本發明之嵌段共聚物組成物,視需要可含有
各種添加劑。主要添加劑可列舉出:可塑劑、抗氧化劑、耐候劑、滑劑、抗靜電劑、防霧劑、顏料等。
可塑劑可使用總稱為液體石蠟之石蠟油、液
態石蠟(Nujol)、礦物油、礦油精、松脂油、白油、揮發油、白礦油、石油精、礦油稀釋劑、石油精、水性石蠟、白礦物油等。
抗氧化劑可列舉出例如:丙烯酸2-第三丁基
-6-(3-第三丁基-2-羥基-5-甲基苄基)-4-甲基苯酯、丙烯酸2-[1-(2-羥基-3,5-二-第三戊基苯基)乙基]-4,6-二-第三戊基苯酯、3-(4-羥基-3,5-二-第三丁基苯基)丙酸正十八酯等酚系抗氧化劑,與亞磷酸2,2’-亞甲基雙(4,6-二-第三丁基苯酯)辛酯、亞磷酸參(2,4-二-第三丁基苯酯)等磷系抗氧化劑等例子。
耐候劑可列舉出例如:2-(2-羥基-3-第三丁基
-5-甲基苯基)-5-氯苯并三唑等苯并三唑系紫外線吸收劑或1,2,3,4-丁四羧酸肆(2,2,6,6-四甲基-4-哌啶酯)等受阻胺型耐候劑等例子。此外,前述的白油與聚矽氧油等也可作為耐候劑添加。
作為滑劑,除了脂肪酸、脂肪酸酯、脂肪酸
醯胺、丙三醇脂肪酸酯(甘油酯)、山梨醇酐脂肪酸酯、季戊四醇脂肪酸酯、蔗糖脂肪酸酯、丙二醇脂肪酸酯等以外,烴系蠟可列舉出聚乙烯蠟、費托(Fischer-Tropsch)蠟等合成蠟,石蠟、微晶蠟等天然蠟。
作為抗靜電劑,除了二壬基萘磺酸等陰離子界面活性劑、四級銨化合物等陽離子界面活性劑以外,可列舉出兩性離子界面活性劑、非離子界面活性劑等。作為抗靜電劑之使用方法,可使用捏合進樹脂內部之形態,與塗布於成形後的成形品表面之形態中的任一種。在不損害防結塊性能、防堆疊性能之範圍內,可使用抗靜電劑。
防霧劑可列舉出:丙三醇脂肪酸酯、聚丙三醇脂肪酸酯、山梨醇酐脂肪酸酯及其環氧乙烷加成物等
多元醇的脂肪酸酯。防霧劑之使用方法可列舉出:捏合進樹脂內部之形態,與成形後塗布於成形品表面之形態等。在不損害防結塊性能、防堆疊性能之範圍內,可使用防霧劑。
本發明之嵌段共聚物組成物,視需要可含有
填充材料。藉由添加填充材料所得到之效果,主要可列出:高強度化、高剛性化、賦予防結塊性能、賦予防堆疊性能、賦予滑性、隔熱化、導電化、絕緣化、降低成本、著色等,依目的,可使用無機填充材料、有機填充材料、或其雙方。
填充材料可列舉出:耐衝擊聚苯乙烯(HIPS)
、乙烯基芳香族烴-(甲基)丙烯酸酯及/或(甲基)丙烯酸共聚物之交聯珠、乙烯基芳香族烴共聚物之交聯珠等有機物填充材料、二氧化矽珠、石英珠等無機物填充材料。
為了得到良好的透明性,較佳係使用HIPS、乙烯基芳香族烴-(甲基)丙烯酸酯及/或(甲基)丙烯酸共聚物之交聯珠、乙烯基芳香族烴共聚物之交聯珠。其調配比相對於100質量份的樹脂組成物,係10質量份以下,較佳為0.05~5質量份,更佳為0.1~3質量份。這些可以在不損害各種成形品之外觀的範圍內使用。
本發明之嵌段共聚物組成物,必須有結構不
同之嵌段共聚物成分(I)與嵌段共聚物成分(II)。本發明之嵌段共聚物組成物係含有:在以凝膠滲透層析法測定所得到之分子量分布中,在分子量150000~300000之範圍具有分子量峰之嵌段共聚物成分(I)。該嵌段共聚物成分(I)
的分子量峰若低於150000,則會造成流動性變得過高,除了使成形加工性降低以外,在將乙烯基芳香族烴之聚合嵌段導入該嵌段共聚物中之情形,聚合嵌段的分子量會降低,導致在與乙烯基芳香族烴系聚合物混合使用之情形,透明性會惡化。若高於300000,則會造成流動性變得過低,使成形加工性降低。嵌段共聚物成分(I)的更佳分子量範圍為180000~290000。
嵌段共聚物成分(I)中的共軛二烯含有率較
佳為10~20質量%,更佳為10~15質量%。在小於10質量%時,除了造成強度過度降低以外,在與共軛二烯含有率高的嵌段共聚物成分混合時,還會導致相溶性降低與透明性惡化。若大於20質量%,除了造成剛性過度降低以外,在與乙烯基芳香族烴系聚合物混合使用時,還會導致相溶性降低與透明性惡化。
嵌段共聚物成分中的共軛二烯之含量,能由
已知的一般鹵素加成法來得到。一般的鹵素加成法的範例可舉出:以能將該試料完全溶解之溶媒將其溶解後,添加過量的氯化碘/四氯化碳溶液使其充分反應,以硫代硫酸鈉/乙醇溶液滴定未反應的氯化碘,由所得到之雙鍵量算出共軛二烯含量之方法。
本發明之嵌段共聚物組成物係含有:在分子
量50000~140000之範圍具有分子量峰之嵌段共聚物成分(II)。該嵌段共聚物成分(II)的分子量峰若低於50000,則會造成強度過低,若大於140000,則會導致流動性降低與透明性惡化。嵌段共聚物成分(II)的更佳分子量範圍為
60000~100000。
嵌段共聚物成分(II)之共軛二烯含有率,較佳
為30~50質量%,更佳為30~40質量%。在小於30質量%時,因會造成強度過度降低,而不佳。若大於50質量%,除了透明性降低以外,還會導致與嵌段共聚物成分(I)的相溶性降低與透明性惡化。
本發明之嵌段共聚物組成物係含有:前述嵌
段共聚物成分(I)與嵌段共聚物成分(II)。嵌段共聚物成分(I)的剛性及與乙烯基芳香族烴系聚合物之相溶性優良,嵌段共聚物成分(II)的補強性優良。嵌段共聚物成分(I)與嵌段共聚物成分(II)的存在比(質量比),大致與凝膠滲透層析法的分子量峰之面積比一致,這些嵌段共聚物成分(I)與(II)的分子量峰之面積比(I)/(II)較佳為20/80~80/20,更佳為40/60~60/40。嵌段共聚物成分(I)的峰面積比若低於20,或嵌段共聚物成分(II)的峰面積比若高於80,除了造成剛性過度降低以外,還會導致與乙烯基芳香族烴系聚合物的相溶性降低、透明性惡化。嵌段共聚物成分(I)的峰面積比若高於80,或嵌段共聚物成分(II)的峰面積比若低於20,則會造成強度過度降低。
前述嵌段共聚物成分(I)中的乙烯基芳香族
烴之聚合嵌段的分子量較佳為80000~150000。若低於80000,則與乙烯基芳香族烴系共聚物的相溶性會降低,若高於150000,則與嵌段共聚物成分(II)的相溶性會降低,任一情形均會導致透明性惡化。
前述乙烯基芳香族烴的聚合嵌段,較佳乙烯
基芳香族烴含有率為90質量%以上。若低於90質量%,則與乙烯基芳香族烴系聚合物的相溶性會降低,透明性會惡化。更佳範圍係95質量%以上,再更佳為100質量%。
掌握乙烯基芳香族烴的聚合嵌段之存在的手
段之一,可舉出:依據文獻(記載於I.M.KOLTHOFF,et al.,Journal of Polymer Science,Volume 1,429(1946)之方法),從將該嵌段共聚物以鋨酸分解所得到之成分的分子量來判斷之方法。
前述嵌段共聚物成分(II)中的乙烯基芳香族
烴之聚合嵌段部分的分子量,較佳為5000~40000。在低於5000之情形,或高於40000之情形中的任一種情形,軍可能導致強度降低,而不佳。
本發明之嵌段共聚物組成物所含有之嵌段共
聚物成分(I)及嵌段共聚物成分(II),各自的乙烯基芳香族烴與共軛二烯之組成比,係含有自嵌段一邊末端往另一邊末端變化之錐形嵌段。各嵌段共聚物組成物中的主要之錐形嵌段全體所佔的單體質量比(乙烯基芳香族烴/乙烯基芳香族烴),沒有受到特別限制,較佳為相近,更佳為相等。各嵌段共聚物組成物的單體質量比之差異若變大,則相溶性會惡化,容易導致透明性降低。
錐形嵌段能藉由在該嵌段形成時,將乙烯基
芳香族烴與共軛二烯兩單體一次添加到聚合活性末端來得到。錐形嵌段的組成比之變化(梯度),可藉由一次添加時進料之乙烯基芳香族烴與共軛二烯的質量比、無規化劑之添加等來調整。
本發明之嵌段共聚物,為了實現前述結構上的特點,可採用下面列舉之結構中的任一種。
(a)A-C
(b)C-A
(c)A-C-A
(d)A-B-C
(e)B-C-A
(f)A-B-C-A
(g)A-C-C
(h)C-C-A
(i)A-C-C-A
(j)A-B-C-B-C-A
(k)A-B-C-C-A
(l)A-C-B-C-A
(m)A-C-X
(n)A-C-A-X
(o)A-B-C-X
(p)A-B-C-A-X
此處,A係乙烯基芳香族烴的聚合嵌段,B係共軛二烯的聚合嵌段,C係乙烯基芳香族烴與共軛二烯的共聚嵌段,表示從該嵌段的一末端,到另一邊的末端,連續地單調改變乙烯基芳香族烴與共軛二烯的組成比之錐形嵌段。又,X係表示偶合中心。本發明之嵌段共聚物成分(I)、(II)可取的結構之組合較佳為以下的任一種。
(甲)(I)A-C-A、(II)A-C
(乙)(I)A-C-A、(II)C-A
(丙)(I)A-B-C-A、(II)A-B-C
(丁)(I)A-B-C-A、(II)B-C-A
(戊)(I)A-C-C-A、(II)A-C-C
(己)(I)A-C-C-A、(II)C-C-A
(庚)(I)A-B-C-C-A、(II)A-B-C
(辛)(I)A-B-C-C-A、(II)C-A
(壬)(I)A-B-C-C-A、(II)C-C-A
(癸)(I)A-C-B-C-A、(II)A-C
(子)(I)A-C-B-C-A、(II)B-C-A
(丑)(I)A-C-X、(II)A-C
(寅)(I)A-C-A-X、(II)A-C-A
(卯)(I)A-B-C-X、(II)A-B-C
(辰)(I)A-B-C-A-X、(II)A-B-C-A
本發明之嵌段共聚物組成物的菲卡軟化溫度沒有受到特別限制,較佳為依據ISO306(JIS K7206),以10N負重所測定之菲卡軟化溫度為60~100℃。若低於60℃,除了嵌段共聚物組成物單體容易結塊以外,因還會導致成形加工性降低,故不佳。若高於100℃,除了會造成嵌段共聚物組成物的強度過度降低以外,因會變成高溫成形而導致成形加工性之降低,故不佳。菲卡軟化溫度的更佳範圍係70~90℃。
本發明之嵌段共聚物組成物的彎曲強度沒有受到特別限制,但在依據ISO178(JIS K7171),以試驗速度2mm/min測定之情形,試驗片能承受之最大彎曲應力(
彎曲強度)為20~60MPa。若低於20MPa,則會造成剛性過度降低,導致對薄片熱成形時的成形加工性降低,若高於60MPa,因會導致成形品的柔軟性降低、強度降低,故不佳。彎曲強度的更佳範圍係30~50MPa。
本發明之嵌段共聚物組成物的霧值沒有受到
特別限制,但依據ISO14782(JIS K7136)所測定之霧值較佳為7以下。若高於7,則在將乙烯基芳香族系烴混合進嵌段共聚物組成物之情形,會造成透明性明顯降低,而不佳。霧值的更佳範圍係5以下。
本發明之嵌段共聚物組成物的光澤沒有受到
特別限制,較佳係依據JIS K7105所測定之光澤值為150以上。若低於150,因會導致巨觀上光澤感降低、透明性惡化、設計性降低,故不佳。光澤值的更佳範圍係160以上。
本發明之嵌段共聚物組成物,為了有效賦予
各種包裝材料所需要的防結塊性能及防堆疊性能,可使用單獨烴系蠟,或烴系蠟與由硬脂酸硬脂酯、硬脂酸單甘油酯、芥酸醯胺、蘿酸醯胺所選出的滑劑併用。前述烴系蠟以外的滑劑可單獨使用,也可2種類以上併用。前期滑劑的添加量,在嵌段共聚物組成物中,總添加量較佳為0.03~1.0質量%,更佳烴系蠟為0.03~0.5質量%,自硬脂酸硬脂酯、硬脂酸單甘油酯、芥酸醯胺、蘿酸醯胺所選出之滑劑的總量為0.03~0.5質量%。若低於0.03質量%,則無法充分展現防結塊性能、防堆疊性能、或其雙方,若高於0.5質量%,則滑劑對成形品表面的滲出容易
變得過剩,使外觀不良的危險性變高。
作為烴系蠟,除了前述聚乙烯蠟、費托蠟等合成蠟以外,可舉出以石蠟、微晶蠟等天然蠟為主者。較佳為石蠟、微晶蠟、合成蠟,更佳為微晶蠟、合成蠟、或其混合物。
本發明之嵌段共聚物組成物為了有效得到優良的防結塊性能,較佳含有烴系蠟。更佳為熔點為60~120℃之微晶蠟、合成蠟、微晶蠟與合成蠟之混合物中的任一種,再更佳為前述的烴系蠟之熔點為80~110℃。若熔點低於60℃,則得不到充分的防結塊性能,若高於120℃,因滑劑往成形品表面的移動性會降低,故不佳。
本發明之嵌段共聚物組成物為了有效得到優良的防堆疊性能,較佳使用由硬脂酸單甘油酯、硬脂酸硬脂酯、芥酸醯胺、蘿酸醯胺所選出之至少1種以上滑劑。前述的烴系蠟因能得到一定的防堆疊性能,雖能使用於泛用形狀之包裝材料用途,但在溝槽深或形狀複雜之包裝材料等特殊用途上,因成形品彼此的接觸面積增加,且要求高防堆疊性能,而變得難以使用。更佳為前述烴系蠟與由硬脂酸單甘油酯、硬脂酸硬脂酯、芥酸醯胺、蘿酸醯胺所選出之至少1種以上滑劑併用。
此外,本發明之嵌段共聚物組成物中,在不損害防結塊性能、防堆疊性能、外觀之範圍內,可依賦予抗靜電性能,及提升成形品彼此的分離性能之目的,而視需要使用前述的抗靜電劑。抗靜電劑之添加量,在
嵌段共聚物組成物中較佳含有0.03~3質量%。若小於0.03質量%,則得不到充分的抗靜電性能,而若高於3質量%,則抗靜電劑的滲出會變得過多,因容易導致外観惡化,故不佳。
如此進行所得到之嵌段共聚物組成物,視需
要可混合乙烯基芳香族烴系聚合物來使用,能混合之嵌段共聚物組成物/乙烯基芳香族烴系聚合物的質量比為30/70~100/0。該嵌段共聚物組成物的質量比若低於30,則會造成強度過度降低,無法供於實用。
能與本發明之嵌段共聚物組成物混合之乙烯
基芳香族烴系聚合物,可列舉出:乙烯基芳香族烴聚合物、乙烯基芳香族烴與丙烯酸酯的共聚物、乙烯基芳香族烴與甲基丙烯酸甲酯的共聚物等,代表性之物可列舉出:聚苯乙烯、苯乙烯/丙烯酸正丁酯共聚物、苯乙烯/甲基丙烯酸甲酯共聚物。其中,特別一般之物可舉出聚苯乙烯。
本發明之嵌段共聚物組成物,無論是單獨或
者是作為與乙烯基芳香族烴系聚合物的混合物,均適合使用於各種成形品。作為成形品之製造方法,可舉出:將用已知的T型模法、使用環狀模之吹塑法、流延法、延壓法等製成之薄片,用周知的真空成形法、壓空成形法、加壓成形法、熱板成形法等熱成形法,製成各種成形品之方法,或用周知的射出成形法來製成各種成形品之方法。此外,在將成形品重疊保管之用途也能使用。
使用本發明之由嵌段共聚物組成物與乙烯基
芳香族烴系聚合物所構成之樹脂組成物的薄片,厚度沒有特別限定,一般可在0.05mm~5mm之範圍使用。厚度若低於0.05mm,則會造成該薄片的剛性、強度過度降低,若高於5mm,則將該薄片熱成形為各種成形品會變困難,無法供於實用。更佳厚度為0.1mm~1.5mm。
本發明之由嵌段共聚物組成物與乙烯基芳香
族烴系聚合物所構成之樹脂組成物,主要係考慮包裝材料必須的強度、剛性、成本等的平衡,來選擇乙烯基芳香族烴系聚合物之添加量。作為不依附於乙烯基芳香族烴系聚合物的添加量,而所重視的物性,可舉出霧值、光澤等。
作為使用本發明之樹脂組成物的薄片的霧值
之較佳範圍的範例,0.6mm厚的薄片的霧值,較佳為7%以下,更佳為5%以下。霧值若高於7%,則因在巨觀上透明感明顯降低,設計性降低,而不佳。
另外,作為使用本發明之樹脂組成物的薄片
的光澤值之較佳範圍的範例,0.6mm厚的薄片的光澤值,較佳為150以上,更佳為160以上。光澤值若低於150,則因會導致巨觀上光澤感降低、透明性惡化、設計性降低,而不佳。
作為薄片之強度的指標,可舉出使用拉伸試
驗機的拉伸伸長率。作為使用本發明之樹脂組成物的薄片的拉伸伸長率之較佳範圍的範例,以拉伸速度10mm/min測定0.6mm厚的薄片,向薄片的生產方向之拉伸伸長率,較佳為20%以上。若低於20%,則薄片會缺乏
強度,供於實用會有困難。前述拉伸伸長率的更佳範圍為50%以上。
作為薄片的剛性之指標,可舉出以與前述拉
伸伸長率之測定同樣的方式得到之拉伸彈性率。使用本發明之樹脂組成物的薄片的拉伸彈性率之較佳範圍的範例,以拉伸速度10mm/min測定0.6mm厚的薄片,向薄片的生產方向之拉伸彈性率,較佳為500~2500MPa,更佳為1000~2000MPa。若低於500MPa,則會造成薄片的剛性、玻璃轉移溫度過度降低,導致成形加工性降低。若高於2500MPa,則會造成薄片強度過度降低,供於實用會有困難。
作為使用本發明之樹脂組成物的薄片的衝撃
強度之較佳範圍的範例,在0.6mm厚的薄片上,依據ASTM D-3420,使用半徑10mm之衝撃子的衝撃強度,較佳為2~10kJ/m。若低於2kJ/m,則會造成衝撃強度過度降低,若高於10kJ/m,則會造成薄片的剛性過度降低,並導致成形加工性降低。衝撃強度的更佳範圍為2~7kJ/m。
以下,基於實施例更詳細說明本發明,但本發明不受這些實施例所限定。
參考例1~15的嵌段共聚物(A)~(O)之製法
[參考例1]嵌段共聚物(A)之製法
(1)於反應容器中進料490kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加1640mL的正丁基鋰(10質量%環己烷溶液),添加12.0kg的苯乙烯單體,
加以升溫使其聚合。
(3)在內溫50℃下,添加36.5kg的丁二烯單體與49.6kg的苯乙烯單體,在不讓內溫大幅超過80℃之範圍內加以升溫使其聚合。
(4)在內溫60℃下,添加111.9kg的苯乙烯單體,加以聚合。
(5)在內溫75℃下,添加將33.7g的環氧化大豆油(ADEKA公司製ADK CIZER O-130P)以5L的環己烷稀釋而成的溶液,使其反應,結束聚合。
[參考例2]嵌段共聚物(B)之製法
(1)於反應容器中進料250kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加750mL的正丁基鋰(10質量%環己烷溶液),再添加34.0kg的苯乙烯單體,加以升溫使其聚合。
(3)在內溫40℃下,添加12.0kg的丁二烯單體,加以聚合。
(4)在內溫50℃下,添加54.0kg的苯乙烯單體,結束聚合。
參考例4(嵌段共聚物(D))、參考例11(嵌段共聚物(K))係參考參考例2之製法製作。各原料的進料量記於表1。
[參考例3]嵌段共聚物(C)之製法
(1)反應容器中進料518kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加1360mL的正丁基鋰(10質量%環己烷溶液),再添加9.1kg的苯乙烯單體
,加以升溫使其聚合。
(3)在內溫65℃下,添加3.6kg的丁二烯單體,加以升溫使其聚合。
(4)在內溫40℃下,一次添加27.3kg的丁二烯單體與23.3kg的苯乙烯單體,在不讓內溫大幅超過80℃之範圍內,加以升溫使其聚合。
(5)在內溫40℃下,添加118.7kg的苯乙烯單體,結束聚合。
參考例7(嵌段共聚物(G))、參考例8(嵌段共聚物(H))係參考參考例3之製法製作。各原料的進料量記於表1。
[參考例5]嵌段共聚物(E)之製法
(1)將反應容器中進料367.5kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加780mL的正丁基鋰(10質量%環己烷溶液),添加5.5kg的苯乙烯單體,加以升溫使其聚合。
(3)在內溫40℃下,一次添加16.9kg的丁二烯單體與22.8kg的苯乙烯單體,在不讓內溫大幅超過70℃之範圍內,加以升溫使其聚合。
(5)在內溫40℃下,添加112.3kg的苯乙烯單體,結束聚合。
[參考例6]嵌段共聚物(F)之製法
(1)於反應容器中進料450kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加990mL的正丁基鋰(10質量%環己烷溶液),再添加3.6kg的苯乙烯單體
,加以升溫使其聚合。
(3)一邊將內溫保持在80℃,一邊將總量156.6kg的苯乙烯單體、及總量16.2kg的丁二烯單體,一邊分別以96.7kg/h、10.0kg/h之一定添加速度,同時添加二者,在添加結束後,亦在此狀態下保持充分的時間。
(4)讓內溫為78℃,添加3.6kg的苯乙烯單體,結束聚合。
[參考例9]嵌段共聚物(I)之製法
(1)於反應容器中進料259kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加2020mL的正丁基鋰(10質量%環己烷溶液),添加9.1kg的苯乙烯單體,加以升溫使其聚合。
(3)在內溫60℃下,添加2.7kg的丁二烯單體,使其聚合。
(4)在內溫40℃下,一次添加42.8kg的丁二烯單體與36.4kg的苯乙烯單體,在不讓內溫大幅超過70℃之範圍內升溫,結束聚合。
參考例15(嵌段共聚物(O))係參考參考例9之製法製作。各原料之進料量記於表1。
[參考例10]嵌段共聚物(J)之製法
(1)於反應容器中進料270kg的環己烷。
(2)在內溫30℃下一邊攪拌,一邊添加3980mL的正丁基鋰(10質量%環己烷溶液),再添加22.0kg的苯乙烯單體,加以升溫使其聚合。
(3)在內溫40℃下,一次添加45.0kg的丁二烯單體與
33.0kg的苯乙烯單體,在不讓內溫大幅超過65℃之範圍內升溫,結束聚合。
參考例12(嵌段共聚物(L))、參考例13(嵌段共聚物(M))、參考例14(嵌段共聚物(N))係參考參考例10之製法製作。各原料之進料量記於表1。
如此進行所得到之嵌段共聚物A~O的構造上之特徵示於表1。關於表1中的嵌段共聚物之構造,A1、及A2係表示聚苯乙烯嵌段,B係表示聚丁二烯嵌段,C係表示由苯乙烯與丁二烯所構成之錐形嵌段,Cr係表示由苯乙烯與丁二烯所構成之無規嵌段,X係表示偶合中心。各嵌段共聚物之分子量、嵌段共聚物中所佔的共軛二烯之比例、乙烯基芳香族烴的聚合嵌段部分之分子量,係依據後述方法測定。
[分子量之測定]
嵌段共聚物之分子量係以下述GPC測定裝置、及條件測定。
裝置名:高速GPC裝置 HLC-8220(Tosoh股份有限公司製)
管柱:將3支PL gel MIXED-B串聯
溫度:40℃
檢測:微差折射率
溶媒:四氫呋喃
濃度:2質量%
檢量線:使用標準聚苯乙烯(PL社製)製作,測定以聚苯乙烯換算值在分子量70000~150000之範圍,與150000~350000之範圍有分子量峰之主要成分的峰分子量。另外對於重量平均分子量,也依照相同測定條件測定,以聚苯乙烯換算值測定。
[共軛二烯含有比例之測定]
嵌段共聚物中的共軛二烯的含有質量%之測定,係依下述方法測定。
(1)將0.1g的試料溶解於氯仿50mL。
(2)添加25mL的氯化碘/四氯化碳溶液並充分混合後,在暗處放置1小時。
(3)添加75mL的2.5%碘化鉀溶液,充分混合。
(4)一邊充分攪拌,一邊添加20%硫代硫酸鈉/乙醇溶液直至溶液顏色變成淡黃色程度。
(5)加入約0.5mL的1%澱粉指示劑,再以20%硫代硫
酸鈉/乙醇溶液滴定至變成無色為止。
(6)滴定結束後,計測消耗掉的硫代硫酸鈉/乙醇溶液量a[mL]。
為了實施以空白試驗之測定進行校正,以單獨氯仿實施(1)~(6)的操作,測定消耗掉的硫代硫酸鈉/乙醇溶液量b[mL]。
共軛二烯的含有率係依據下式由測定值算出。
共軛二烯的含有率(%)=[(b-a)×0.1×c×27/1000]/W×100
c:20%硫代硫酸鈉/乙醇溶液的滴定量
W:試料量[g]
[乙烯基芳香族烴的聚合嵌段部分之分子量測定]
嵌段共聚物中的乙烯基芳香族烴的聚合嵌段部分之分子量,係經由前述的鋨酸分解法,藉由GPC測定裝置測定所得到之乙烯基芳香族烴嵌段成分。而關於低分子量成分,係以使用低分子量管柱之GPC測定裝置測定。
前述嵌段共聚物(A)~(O)係在聚合後,以聚合液之狀態將2種以上溶液摻和後,使用直脫式的擠出機進行除去溶劑,得到嵌段共聚物組成物。關於嵌段共聚物組成物的一般物性,係歸納於表2及表3。嵌段共聚物組成物中所佔的共軛二烯之比例,係依據前述方法,而霧值、產生拉伸破裂之應變、彎曲彈性率、菲卡軟化溫度、彎曲強度係依據以下方法測定。
[菲卡軟化溫度之測定]
嵌段共聚物組成物之菲卡軟化溫度係使用148 HDA Heat Distortion Tester(安田精機製作所股份有限公司製),依據ISO306(JIS K7206),以10N負重來測定。
[彎曲強度之測定]
嵌段共聚物組成物之彎曲強度係使用BENDOGRAPH II(東洋精機股份有限公司製),依據ISO178(JIS K7171),測定以試驗速度2mm/min測定之情形的試驗片所能承受的最大彎曲應力(彎曲強度)。
[伸長率(產生拉伸破裂之應變)之測定]
嵌段共聚物組成物的伸長率(產生拉伸破裂之應變)係使用拉伸試驗機(TSE股份有限公司製),依據ISO527-2(JIS K7161、7162)進行測定。
[霧值之測定]
嵌段共聚物組成物的霧值係使用Haze Meter NDH300A(日本電色工業股份有限公司製),依據ISO14782(JIS K7136)進行測定。
[光澤之測定]
薄片之光澤係使用Gloss Meter VG2000(日本電色工業股份有限公司製),依據ISO2813(JIS Z8741),測定入射角60°的光澤值。
接下來,對表2及表3之嵌段共聚物組成物,將各嵌段共聚物組成物與聚苯乙烯(東洋苯乙烯股份有限公司製TOYO Styrol GP級名:G200C)加以充分摻和為丸粒後,使用田邊PLASTICS機械股份有限公司製薄片
擠出機(螺桿直徑:40mm、螺桿構成:全程型),一邊以200℃加以熔融混合,一邊自模間隙0.65mm之T型模擠出成薄片狀。擠出之薄片,係以施加過鏡面加工之50℃的2支輥進行拉取並冷卻,以生產速度0.9m/min採取平均厚度0.60mm之薄片。對嵌段共聚物組成物與聚苯乙烯的混合比(嵌段共聚物組成物之質量%/聚苯乙烯之質量%)之薄片物性的測定結果,係合併歸納於表2及表3。薄片的拉伸彈性率、伸長率、薄片衝擊度、霧值、光澤係依據以下方法測定。
[拉伸彈性率、伸長率之評價]
薄片的拉伸彈性率係使用TENSILON萬能試驗機RTG-1210(A&D股份有限公司製),以薄片的生產方向(以下簡稱為MD。)與拉伸方向一致的方式,衝壓成啞鈴狀,以拉伸速度10mm/min、夾頭間距離50mm測定。另外,薄片的伸長率(到破裂之伸長率),係在前述拉伸彈性率之測定時一併測定。
[薄片衝擊度之評價]
薄片衝擊度(薄片衝撃強度)係使用衝擊試驗機(TESTER SANGYO股份有限公司製),依據ASTM D-3420,進行使用直徑10mm的衝撃子之衝壓來測定。
[霧值之評價]
薄片之霧值,係使用Haze Meter NDH2000(日本電色工業股份有限公司製),依據ISO14782(JIS K7136)測定。
[光澤之評價]
薄片之光澤係使用Gloss Meter VG2000(日本電色工
業股份有限公司製),依據ISO2813(JIS Z8741),測定入射角60°的光澤值。
接下來,將任意滑劑混合進前述嵌段共聚物
組成物,製作記載於表4之實施例5~10,與記載於表5之比較例6~10的嵌段共聚物組成物。將前述嵌段共聚物組成物與聚苯乙烯(東洋苯乙烯股份有限公司製TOYO Styrol GP級名:G200C)以混合比(嵌段共聚物組成物之質量%/聚苯乙烯之質量%)70質量%/30質量%加以充分摻和為丸粒後,使用田邊PLASTICS機械股份有限公司製薄片擠出機(螺桿直徑:40mm、螺桿構成:全程型),一邊以200℃加以熔融混合,一邊自模間隙0.65mm之T型模擠出成薄片狀。擠出之薄片,係以施加過鏡面加工之50℃的2支輥進行拉取並冷卻,以生產速度1.9m/min製作平均厚度0.30mm之薄片。製成之薄片的防結塊性能,係依據以下進行評價。
[防結塊性能之評價]
製作平均厚度0.30mm之薄片後,5分鐘連續捲取到直徑90mm的紙管上成為輥狀。使用相同方式,各製作2支輥,在23℃之環境下與40℃之環境下,分別保管1支。在前述既定溫度環境下保管24小時後,取出,依據以下基準評價自輥將薄片剝下時的剝離性,結果示於表4及表5。
良:能容易地將薄片剝離,且剝離薄片外觀無異常。
可:雖然能將薄片剝離,但剝離時伴隨著抵抗感,或剝離時伴隨著異音。
不可:薄片結塊,剝離時伴隨著傷痕或破裂等外觀異常。
接下來,在製作實施例5~10、比較例6~12之
嵌段共聚物組成物後,將前述嵌段共聚物組成物與聚苯乙烯(東洋苯乙烯股份有限公司製TOYO Styrol GP級名:G200C)以混合比(嵌段共聚物組成物之質量%/聚苯乙烯之質量%)60質量%/40質量%加以充分摻和為丸粒,使用田邊PLASTICS機械股份有限公司製薄片擠出機(螺桿直徑:40mm、螺桿構成:全程型),一邊以200℃加以熔融混合,一邊自模間隙0.65mm的T型模擠出成薄片狀。擠出的薄片係以施加過鏡面加工之50℃的2支輥進行拉取並冷卻,以生產速度0.9m/min製成平均厚度0.60mm之薄片。製成之薄片,係以淺野研究所股份有限公司製作的研究開發用壓空真空成形機,使用托盤深度19mm的零件托盤用模具,於110℃真空成形。製成之成形品的防堆疊性能係依據以下進行評價。
[防堆疊性能之評價]
作為防堆疊性能之評價,真空成形之托盤係在5片重疊之狀態下,於23℃的環境下保管24小時,測定將以自身重量重疊之托盤,以人力個別分離所需要的時間[秒]。接下來,對在23℃的環境下成形後保管7天之零件托盤的分離秒數,依據以下基準判定防堆疊性能之優劣。測定結果示於表4及表5。
良:分離秒數為7秒以下
可:分離秒數為10秒以下
不可:分離秒數為11秒以上
由表2、表3的結果可知,藉由使用本發明之
嵌段共聚物組成物,除了展現平衡良好的透明性、光澤、剛性、強度、成形加工性以外,在製成與乙烯基芳香族烴聚合物的樹脂組成物之情形,也不會引起透明性、光澤的明顯降低,能適當地使用。此外,由表4、表5的結果可知,藉由使用特定的滑劑,可實現更優良的防結塊性能與防堆疊性能。藉此,藉由使用本發明之嵌段共聚物組成物,讓各種形狀之包裝材料的製造及使用變容易。
本發明之嵌段共聚物組成物係適合各種形狀之各種包裝材料的製造及使用之材料,使用此材料之薄片,可使用於食品容器、飲料容器、工業用容器、泡鼓包裝等。此外,也適合使用於如實施射出成形、異模擠出之用途。
Claims (13)
- 一種嵌段共聚物組成物,其係由乙烯基芳香族烴與共軛二烯所構成之嵌段共聚物組成物,其特徵為:於在分子量180000~290000之範圍具有分子量峰(peak),且含有錐形嵌段之嵌段共聚物成分(I)中之共軛二烯的含有率為10~20質量%;於在分子量50000~140000之範圍具有分子量峰,且含有錐形嵌段之嵌段共聚物成分(II)中之共軛二烯含有率為30~50質量%;且嵌段共聚物組成物中所佔的嵌段共聚物成分(I)與嵌段共聚物成分(II)之分子量峰面積的比(I)/(II)為20/80~80/20。
- 如申請專利範圍第1項之嵌段共聚物組成物,其中嵌段共聚物成分(I)係在分子量180000~290000之範圍具有分子量峰,且共軛二烯的含有率為10~15質量%,嵌段共聚物成分(II)係在分子量60000~100000之範圍具有分子量峰,且共軛二烯含有率為30~40質量%,嵌段共聚物組成物中所佔的嵌段共聚物成分(I)與嵌段共聚物成分(II)之分子量峰的面積比(I)/(II)為40/60~60/40。
- 如申請專利範圍第1或2項之嵌段共聚物組成物,其中嵌段共聚物成分(I)包含滿足分子量80000~150000之範圍的乙烯基芳香族烴之聚合嵌段部分,嵌段共聚物成分(II)包含滿足5000~40000之分子量範圍的乙烯基芳香族烴之聚合嵌段部分。
- 如申請專利範圍第1項之嵌段共聚物組成物,其係在嵌段共聚物組成物中,含有總量0.03~1.0質量%之單獨烴系蠟,或烴系蠟與由硬脂酸硬脂酯、硬脂酸單甘油 酯、芥酸醯胺、蘿酸醯胺所選出的一種以上。
- 如申請專利範圍第4項之嵌段共聚物組成物,其中烴系蠟係熔點60~120℃之微晶蠟、合成蠟、微晶蠟與合成蠟的混合物中的任一種,且在嵌段共聚物組成物中,含有0.03~0.5質量%。
- 如申請專利範圍第5項之嵌段共聚物組成物,其中烴系蠟係熔點80~110℃。
- 如申請專利範圍第4至6項中任一項之嵌段共聚物組成物,其係在嵌段共聚物組成物中,含有總量0.03~0.5質量%之由硬脂酸硬脂酯、硬脂酸單甘油酯、芥酸醯胺、蘿酸醯胺所選出的滑劑。
- 一種樹脂組成物,其係由如申請專利範圍第1至7項中任一項之嵌段共聚物組成物與乙烯基芳香族烴系聚合物所構成,且相對於該嵌段共聚物組成物與該乙烯基芳香族烴系聚合物的總質量份,該嵌段共聚物組成物的含量為30質量份以上且小於100質量份。
- 一種薄片,其使用如申請專利範圍第1至7項中任一項之嵌段共聚物組成物。
- 一種薄片,其使用如申請專利範圍第8項之樹脂組成物。
- 一種容器,其使用如申請專利範圍第1至7項中任一項之嵌段共聚物組成物。
- 一種容器,其使用如申請專利範圍第8項之樹脂組成物。
- 一種容器,其使用如申請專利範圍第9或10項之薄片。
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KR (1) | KR102036541B1 (zh) |
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KR102362986B1 (ko) * | 2014-06-06 | 2022-02-16 | 덴카 주식회사 | 블록 공중합체 함유 수지 조성물 |
JP7164933B2 (ja) * | 2014-09-30 | 2022-11-02 | 日本ゼオン株式会社 | ブロック共重合体組成物およびフィルム |
CN107531835A (zh) | 2015-03-30 | 2018-01-02 | 科腾聚合物美国有限责任公司 | 可硫化的透明橡胶组合物、由其制造的硫化的透明橡胶组合物以及制造方法 |
JP6513488B2 (ja) * | 2015-06-01 | 2019-05-15 | デンカ株式会社 | シュリンクフィルム用樹脂組成物、シュリンクフィルム及びシュリンクフィルムを装着した容器 |
BR112018015146B1 (pt) | 2016-01-26 | 2022-12-06 | Dynasol Elastómeros, S.A. De C.V. | Copolímero dibloco contra-cônico, composição de elastômero termoplástico contra- cônico (ctte), processo para fabricação destes, composições de asfalto modificado por polímero (pma), adesiva, selante e plástica |
JP6785065B2 (ja) * | 2016-05-27 | 2020-11-18 | デンカ株式会社 | 成形体 |
US11220594B2 (en) | 2017-07-26 | 2022-01-11 | Ineos Styrolution Group Gmbh | Scratch-resistant styrene copolymer composition containing amide wax |
KR102066260B1 (ko) * | 2018-07-25 | 2020-02-11 | 금호석유화학 주식회사 | 공중합체, 그 제조방법, 및 이를 포함하는 접착제 조성물 |
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SG11201407159PA (en) | 2014-12-30 |
KR20150012273A (ko) | 2015-02-03 |
EP2848650B1 (en) | 2017-11-08 |
TW201350514A (zh) | 2013-12-16 |
EP2848650A1 (en) | 2015-03-18 |
EP2848650B2 (en) | 2020-05-27 |
CN104271666A (zh) | 2015-01-07 |
WO2013168679A1 (ja) | 2013-11-14 |
IN2014DN10034A (zh) | 2015-08-14 |
US9732215B2 (en) | 2017-08-15 |
JPWO2013168679A1 (ja) | 2016-01-07 |
US20150152257A1 (en) | 2015-06-04 |
MX362954B (es) | 2019-02-27 |
CN104271666B (zh) | 2018-11-13 |
MX2014013421A (es) | 2015-04-14 |
KR102036541B1 (ko) | 2019-10-25 |
EP2848650A4 (en) | 2015-12-30 |
JP6099637B2 (ja) | 2017-03-22 |
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