CN107848679A - 内表面由烯烃系树脂层形成的容器 - Google Patents
内表面由烯烃系树脂层形成的容器 Download PDFInfo
- Publication number
- CN107848679A CN107848679A CN201680040602.7A CN201680040602A CN107848679A CN 107848679 A CN107848679 A CN 107848679A CN 201680040602 A CN201680040602 A CN 201680040602A CN 107848679 A CN107848679 A CN 107848679A
- Authority
- CN
- China
- Prior art keywords
- container
- lubricant
- oil
- olefin
- based resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000000314 lubricant Substances 0.000 claims abstract description 99
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
本发明的容器特征在于,其内表面由烯烃系树脂层形成,并且有机系渗出性润滑剂和无机多孔剂配混在烯烃系树脂层中。
Description
技术领域
本发明涉及具有由烯烃系树脂层形成的内表面的容器。更具体地,本发明涉及具有包括有机系渗出性润滑剂的内层,由此提供相对于内容物优异的滑落性的容器。
背景技术
容纳流动性的内容物的容器,不管容器的材质如何,都要求具有相对于内容物的排出性。在容纳如水等的较低粘性的液体的情况下,基本上不需要考虑排出性。然而,在容纳如蛋黄酱和番茄酱等的粘度高的更粘稠的物质的情况下,排出性对塑料容器和玻璃容器两者会具有大的影响。更具体地,即使通过将容器倾斜,内容物也不会快速排出,并且会附着至容器壁。特别是相当大量的内容物不会排出,而是残留在容器的底部,因此不能将其用完。
在这种情况下,要求容器具有使得内容物从容器内表面快速排出的滑落性。
所提出的容器的实例包括在形成容器的内表面的烯烃系树脂层(内表面层)中共混有机系润滑剂(例如参见专利文献1、2)。由于容器的容器内表面的烯烃系树脂层适于润滑剂的渗出,所以润滑剂快速渗出以分布在容器的内表面上,由此改进相对于容器中的内容物的滑落性。
另一方面,近年来,提出改进相对于粘稠物质的滑落性的技术(例如参见专利文献3)。
现在,该技术由于与向形成成形体表面的合成树脂添加如润滑剂等的添加剂的情况相比能飞跃性地改进滑落性而引起注意。然而,该技术会引起一些问题。例如,形成液膜的液体会迁移至内容物,从而劣化内容物的风味,或者随着内容物的排出,滑落性会逐渐劣化。因此,仍然采用将润滑剂共混入形成容器内表面的树脂层中以改进相对于内容物的滑落性的传统技术。
此外,由本发明人的研究发现,在形成容器内表面的树脂层中共混润滑剂的情况下,内容物的风味也会劣化,尽管该劣化没有在表面上形成液膜的情况那么多。特别地,当使用包括脂肪酸的润滑剂时,或者当容器填充有如蛋黄酱样食品等的乳化物作为内容物时,风味性倾向于劣化更多。
现有技术文献
专利文献
专利文献1:JP-A-2008-222291
专利文献2:JP-A-2009-214914
专利文献3:WO2012/100099
发明内容
发明要解决的问题
因此,本发明的目的是提供具有由包括有机系渗出性润滑剂的烯烃系树脂层形成的内表面的容器。容器具有相对于内容物优异的滑落性,并且也具有相对于内容物优异的风味保持性。
本发明的另一目的是提供用于容纳特别是乳化物作为内容物的容器。
用于解决问题的方案
本发明提供具有由烯烃系树脂层形成的内表面的容器。烯烃系树脂层包括有机系渗出性润滑剂,并且共混有无机多孔剂。
在本发明的容器中,以下是合适的:
(1)有机系渗出性润滑剂是熔点为50℃以下的饱和或不饱和脂肪酸的至少一种;
(2)当通过用正庚烷填充容器而进行提取时,获得10~150μg/ml的提取液的蒸发残余物;
(3)无机多孔剂是二氧化硅/氧化铝比为80以上的高硅沸石;
(4)容器具有包括内表面的烯烃系树脂层的多层结构,并且无机多孔剂选择性地共混入内表面的烯烃系树脂层中;
(5)无机多孔剂以0.2~3.0质量%的量共混入形成容器内表面的烯烃系树脂层中;
(6)无机多孔剂的平均粒径在0.1~4.9μm的范围内;
(7)容器的内表面的平均表面粗糙度Ra(JIS-B-0601-1994)为0.3μm以下;和
(8)容器填充有乳化物作为内容物。
发明的效果
本发明的容器由于有机系渗出性润滑剂渗出以分布在容器的内表面上,因此显示相对于内容物优异的滑落性。此外,共混入烯烃系树脂层(内表面层)中的无机多孔剂使容器显示相对于内容物优异的风味保持性。
即,当渗出性润滑剂分布在表面上时,可以显著改进相对于内容物(特别是含水物质)的滑落性,但伴随有风味保持性的劣化。认为原因如下。有机系渗出性润滑剂在成形期间通过热部分地分解以产生低分子量组分,并且该组分会迁移至内容物。特别地,脂肪酸系润滑剂在成形过程期间会容易产生低分子量的醛和酮等,从而显著劣化风味。
相对地,在本发明中,由于在作为内层的烯烃系树脂层中共混的无机多孔剂吸附低分子量组分,所以可以有效地避免风味的劣化。
为了除去会劣化内容物的风味的气味组分,已知将如无机多孔剂等的吸附剂共混入形成容器的树脂层中。然而,就本发明人所知,将吸附剂共混入形成与内容物接触的容器内表面的树脂层(内表面层)中根本不为人所知,因为从常识的观点,不能采用在内表面层中共混可能影响内容物的风味的添加剂的措施,而且不知道有机系渗出性润滑剂可能劣化风味。
本发明的容器显示相对于粘稠物质优异的滑落性。例如,其显示即使相对于在25℃下的粘度为1260mPa·s以上的高粘性物质也优异的滑落性。该容器显示不仅相对于如以番茄酱为代表的非油性物质等的高粘性物质,而且相对于如蛋黄酱样食品和各种调料等的乳化物也优异的滑落性,因此有效地保持风味。
附图说明
[图1]为示出作为本发明的容器的优选实例的直接吹塑成形瓶的状态的图。
具体实施方式
本发明的容器具有由烯烃系树脂层形成的内表面。该烯烃系树脂层包括有机系渗出性润滑剂,并且进一步共混有无机多孔剂。
烯烃系树脂;
在本发明中,烯烃系树脂选自各种热塑性树脂以形成容器内表面。即,由于烯烃系树脂对于下述有机系润滑剂的渗出性优异,从而使有机系润滑剂容易分布在表面上而且容易制成挠性容器,因此烯烃系树脂可以适合用作用于容纳特别粘稠的内容物的直接吹塑成形瓶用的聚合物。
烯烃系树脂的实例包括如低密度聚乙烯、高密度聚乙烯、聚丙烯、聚(1-丁烯)、聚(4-甲基-1-戊烯)或乙烯、丙烯、1-丁烯和4-甲基-1-戊烯等的α-烯烃的无规或嵌段共聚物,以及环状烯烃共聚物。其中,从渗出性的观点,优选高密度聚乙烯或低密度聚乙烯,并且最优选密度在0.900~0.935g/cm3范围内的低密度聚乙烯。
有机系渗出性润滑剂;
在本发明中,上述烯烃系树脂层(容器的内表面层)中包括的有机系渗出性润滑剂(以下可简称为润滑剂)通过渗出而分布在烯烃系树脂的表面(容器内表面)上,从而赋予相对于粘稠的内容物的滑落性。
已知润滑剂的各种实例,并且典型的实例如下列出。
(a)如天然或合成石蜡、微晶蜡(micro wax)、聚乙烯蜡和氯化聚乙烯蜡等烃系蜡,以及如地蜡和石油蜡等矿物蜡;
(b)如棕榈酸、硬脂酸、月桂酸、油酸和芥酸等饱和或不饱和脂肪酸;
(c)如硬脂酸酰胺、棕榈酸酰胺、油酸酰胺、芥酸酰胺、亚甲基双硬脂酰胺(methylene bisstearoamide)和亚乙基双硬脂酰胺等饱和或不饱和脂肪族酰胺;
(d)如硬脂酸丁酯、硬化蓖麻油和乙二醇单硬脂酸酯等脂肪酸酯;
(e)如鲸蜡醇和硬脂醇等脂肪族醇;
(f)如硬脂酸锌和硬脂酸钙等金属皂;
(g)聚有机硅氧烷(硅油);
(h)如色拉油、精炼油(shirashime oil)(精炼菜籽油/大豆油)、玉米油、大豆油、芝麻油、菜籽油、红花油、葵花籽油、米油(rice oil)、米糠油(rice bran oil)、山茶油、棕榈油、椰子油、棉籽油、大麻籽油、葡萄油、罂粟籽油、蓖麻油、桐油、麻风树油、亚麻籽油、芥末油、小麦胚芽油、月见草油、紫苏(日本罗勒)油、杏仁油、木通油(Akebi oil)、茶梅油(Camellia sasanqua oil)、茶油、核桃油、白桦油、橄榄油、花生油、杏仁油、鳄梨油、榛子油、葡萄籽油、月桂油、澳洲坚果油、摩洛哥坚果油、南瓜籽油、山核桃坚果油、开心果油、霍霍巴油、白芒花油、咖啡豆油、马鲁拉果油、西兰花籽油、桃仁油、樱桃仁油、蔓越莓籽油、石榴籽油、夏威夷核果油、苦楝油、猕猴桃籽油、可可油脂、琉璃苣油、乳木果油、巴巴苏仁油、木棉油、瓜籽油、芒果脂、萨尔黄油、烛果油脂、玫瑰果油、蒙刚果油、沥青油、氧化锌油、加工的紫苏油、漆树蜡、小烛树蜡、巴西棕榈蜡和精油等的植物性油或植物性蜡;
(i)如蛋黄油、肝油、鲨鱼油、牛脚油、蜂蜡、猪油、牛脂、骨脂、骨油、鱼油、鸡油、鸭油、鹅油、蟹油、马油、鲸油、海豚油、羊毛脂、熟猪油(schmalz)、黄油、鸸鹋油、乳油、貂油和角鲨烯等的动物性油;和
(j)如液体石蜡、琥珀油和油页岩等的矿物性油。
这些物质可以单独使用或作为其两种以上的混合物使用。特别地,用于工业应用的商购可得的润滑油通常以一定的比例包括碳原子数不同的物质,并且实际上,在大多数情况下将多种物质混合使用。
在本发明中,从良好的渗出性和特别是相对于乳化物的优异的滑落性的观点,在上述润滑剂中优选饱和或不饱和脂肪酸。特别地,优选熔点为50℃以下的饱和或不饱和脂肪酸的至少一种。例如,最优选使用C6-C12饱和脂肪酸和C16-C22不饱和脂肪酸。当熔点高于上述范围时,渗出量降低并且滑落性劣化。当碳数小于上述范围时,可能引起卫生问题;当碳数大于该范围时,可能提高熔点并降低渗出量。从风味的观点,适合使用饱和脂肪酸。
当内容物为食品时,可适合使用如天妇罗油(少精炼的色拉油)、色拉油、精炼油、辣椒油和韭葱油等的烹调油(食用油)。当内容物为蛋黄酱样食品时,特别适合使用色拉油或天妇罗油。
上述润滑剂需要渗出从而以适当的量分布在容器的内表面上,即烯烃系树脂层的表面上。渗出量(表面分布量)可以通过用作为提取液的正庚烷填充容器,并在25℃-60分钟的条件下提取在表面上渗出的润滑剂,由此作为提取物的蒸发残余物而获得其来计算。该试验方法规定于“Notification 370from Ministry of Health and Welfare datedDecember 28,1959”的蒸发残余物试验方法中。
在本发明中,优选以在使用正庚烷提取液的提取中获得的蒸发残余物的量为10~150μg/ml,特别是30~110μg/ml的量使用润滑剂。当蒸发残余物的量(渗出量)小于该范围时,滑落性可能劣化。当该量超过该范围时,由于过量使用润滑剂,成形性或风味保持性可能劣化。
只要稳定地保持渗出量,就不必需将润滑剂共混入形成容器内表面的烯烃系树脂层中,而是例如可以将润滑剂共混入与烯烃系树脂层相邻配置的层中。
无机多孔剂;
在本发明中,将无机多孔剂共混入形成容器内表面的烯烃系树脂层中。无机多孔剂用于防止由于使用上述润滑剂引起的内容物的风味性的劣化,从而维持内容物的风味性。
无机多孔剂的实例包括沸石、硅胶、活性氧化铝、硅酸镁、滑石、硅藻土和粘土。这些可以单独使用,或其以两种以上的组合使用。
在本发明中,优选沸石,因为当使用上述饱和或不饱和脂肪酸作为润滑剂时,其在不劣化滑落性的同时显示出良好的风味保持性。特别地,二氧化硅/氧化铝摩尔比(SiO2/Al2O3)为80以上的高硅沸石是最合适的。此类沸石是合适的,可能因为它具有有效地用于吸附在容器成形期间由饱和或不饱和脂肪酸产生的低分子量醛和酮的管状细孔。
上述无机多孔剂以通过激光衍射散射法测量的以体积计的平均粒径(D50)为约0.1μm~约4.9μm的粉末的状态使用,以使无机多孔剂均匀地分散在烯烃系树脂层中。当平均粒径小于该范围时,风味保持性可能不足。当该直径大于该范围时,透明性可能降低。
无机多孔剂在形成容器内表面的烯烃系树脂层中以0.2~3.0质量%,特别是0.5~2.0质量%的量共混。当该量不足时,风味保持性可能不令人满意。即使当使用过量的无机多孔剂时,也不能期望风味保持性的进一步改进,但可能引起透明性降低的缺点。
特别地,当使用二氧化硅/氧化铝摩尔比为80以上的无机多孔剂并且以0.5质量%以上的量共混时,以及当将正庚烷蒸发残余物控制在100μg/ml以下时,风味保持性特别有利于有效地减少来自容器的聚乙烯气味以及来自分解的润滑剂的气味。
在常规已知的技术中,为了使容器内表面粗糙化,由此改进相对于内容物的滑落性,将如上述无机多孔剂的无机颗粒共混入形成容器内表面的树脂层中。另一方面,在本发明中,将无机多孔剂共混不是为了使容器的内表面粗糙化,因此共混量减少。将用与该无机多孔剂共混的烯烃系树脂层形成的容器内表面设定为具有通常平均表面粗糙度Ra(JIS-B-0601-1994)为0.3μm以下的平滑面。即使当使容器的内表面粗糙化时,从滑落性的观点也没有问题发生。然而,在容器内表面与内容物之间可能夹入气泡,并且在容器的外部观察中,气泡可能降低容器的外观。
层构成;
本发明的上述容器,只要在形成容器内表面的烯烃系树脂层中共混无机多孔剂并进一步包括有机系渗出性润滑剂,则不限于具有仅由烯烃系树脂层形成的容器壁的单层结构,而是可以是包括层压在烯烃系树脂层上的任意其它树脂层的多层结构。
在本发明中,特别优选提供在形成容器外表面的外表面层和容器内表面的烯烃系树脂层之间具有起到润滑剂阻挡层作用的中间层的多层结构,以使有机系渗出性润滑剂可以在容器内表面上选择性地渗出。
不用说,在起到润滑剂阻挡层作用的中间层中没有共混润滑剂。为了起到润滑剂阻挡层的作用,要求该中间层由密度为1.00g/cm3以上并且玻璃化转变点(Tg)为35℃以上的树脂形成。结果,由树脂形成的中间层变成致密层,从而有效地起到润滑剂阻挡层的作用,以有效地防止或减少共混在容器内表面侧的层而不是中间层中的润滑剂向外表面层的迁移。结果,通过渗出分布在容器内表面上的润滑剂的量(上述正庚烷提取液的蒸发残余物的量)可以容易地设定在预定的范围内。
例如,在通过使用密度或玻璃化转变点(Tg)低于上述范围的树脂而形成中间层的情况下,中间层可能粗糙,并且不能显示起到润滑剂阻挡层的作用。结果,不能防止配置在中间层内侧的层中共混的润滑剂向外表面侧的迁移,使得难以控制在容器内表面上渗出的润滑剂的量。
用于形成中间层的树脂没有特别限制,只要密度和玻璃化转变点(Tg)两者在上述范围内即可,并且可以使用任意适当的可成形的热塑性树脂。通常,优选使用如乙烯乙烯醇共聚物(皂化乙烯乙酸乙烯酯共聚物)和芳香族聚酰胺等的阻气性树脂,并特别优选使用乙烯乙烯醇共聚物。通过使用阻气性树脂作为用于形成中间层的树脂,可以赋予中间层以润滑剂阻挡性,并且进一步赋予氧阻挡性。由于乙烯乙烯醇共聚物显示特别优异的氧阻挡性,因此可以有效地防止或控制由氧渗透引起的油性内容物的氧化劣化。结果,可以维持优异的滑落性,同时可以确保优异的内容物保存性。
对于上述乙烯乙烯醇共聚物,通常适合使用通过使含有20~60mol%乙烯、特别优选25~50mol%的乙烯的乙烯-乙酸乙烯酯共聚物皂化以使皂化度变为96mol%以上、特别优选为99mol%以上而获得的皂化共聚物。在此类共聚物中,选择性地使用密度和玻璃化转变点(Tg)在上述范围内的共聚物。
此外,起到润滑剂阻挡层作用的中间层的厚度通常优选在1~50μm的范围内,适合在9~40μm的范围内。当该层过度薄时,其润滑剂阻挡性可能劣化,因此,在比中间层更靠近容器内表面的层中共混的润滑剂可能迁移至容器外表面侧,从而导致内表面层中的润滑剂的缺乏。即使当该层过度厚时,也不能再改进润滑剂阻挡性,但可能引起一些缺点,例如容器壁的厚度可能超过必要地增加,或者成本可能增加。
当阻气性树脂用作中间层时,为了增强与内层和外层的粘接性并防止分层,优选介由粘接层设置中间层。由此,中间层可以牢固地粘接并固定至内层和外层。用于形成粘接层的粘接剂树脂本身是已知的,例如,它们是以1~100meq/100g树脂、特别是10~100meq/100g树脂的量在主链或侧链中含有羰基(>C=O)的树脂。用作粘接剂树脂的此类树脂的具体实例包括:用如马来酸、衣康酸或富马酸等的羧酸或其酸酐、或用酰胺或酯接枝改性的烯烃树脂;乙烯-丙烯酸共聚物;离子交联的烯烃系共聚物;和乙烯-乙酸乙烯酯共聚物。粘接剂树脂层可以具有获得适当程度的粘接力的厚度,并且厚度通常为0.5~20μm,并且适当地为约1~约8μm。如果粘接层满足上述密度和玻璃化转变点的条件,则其也可以起润滑剂阻挡层的作用。
此外,在设置有润滑剂阻挡性中间层的多层结构中,用于形成容器外表面的外表面层可以用各种热塑性树脂(例如,如聚对苯二甲酸乙二醇酯等的聚酯树脂)形成。为了赋予容器以挤压性以使内容物能从容器中挤出,外表面层优选由与容器内表面同样的烯烃系树脂层形成。
不用说,在外表面层中可以共混各种渗出性添加剂,以防止容器粘附至另一个容器或输送带,从而改进输送性能。换句话说,由于起到润滑剂阻挡层作用的中间层的存在,在外表面层中共混的渗出性添加剂不会渗出至容器内表面上,因此,添加剂不会影响容器内表面的滑落性。
此外,在根据本发明的设置有上述中间层的多层结构中,由在容器成形期间产生的废料树脂形成并与未用过的烯烃系树脂共混的回用料层可以设置在起到润滑剂阻挡层作用的中间层和容器内表面层或容器外表面层之间。在这种情况下,从在维持成形性的同时再利用资源的观点,废料树脂的量相对于100质量份未用过的聚烯烃系树脂优选在约10质量%~约60质量%的范围内。
上述废料树脂可以是在本发明的容器的成形期间产生的废料树脂,或者是在包括烯烃系树脂的任意其它容器的成形期间产生的废料树脂。
此外,回用料层与形成容器内表面的烯烃系树脂层同样地显示高渗出性。因此,在将回用料层设置在具有润滑剂阻挡性的中间层和容器内表面(烯烃系树脂层)之间的情况下,可以将上述渗出性润滑剂共混入回用料层中。即,共混在回用料层中的润滑剂可以通过形成容器内表面的烯烃系树脂渗出至容器内表面上。结果,即使在容器内表面的烯烃系树脂层中没有共混润滑剂,容器内表面的烯烃系树脂层也可以包括润滑剂,由此润滑剂可以渗出以分布在容器内表面上。
因此,在形成内表面或回用料层的任意烯烃系树脂层中共混润滑剂的情况下,设定共混的润滑剂的量以使上述正庚烷提取液中的蒸发残余物在预定的范围内。在上述渗出量的控制中,通常,润滑剂的渗出量根据例如共混有润滑剂的层的种类或形成层的树脂的种类而变化,并且难以一概而论地规定。然而,通常,在内表面的烯烃系树脂层或回用料层中共混润滑剂的任意情况中,润滑剂的共混量可以为约0.1~20质量%。
只要将预定量的无机多孔剂仅共混在内表面的烯烃系树脂层(内表面层)中,则没有必要将无机多孔剂另外地共混在回用料层中。
在本发明中,作为回用料层的替代或与回用料层一起,没有与无机多孔剂共混的烯烃系树脂层可以与内表面层相邻设置。同样地在这种情况下,在烯烃系树脂层中可以包括润滑剂。然而,由于无机多孔剂选择性地共混在内表面层中,因此可以减少无机多孔剂的使用量以使防止风味劣化的效果最大化。
如上所述,本发明的容器可以具有各种的层构成。最简单的层结构的实例由以下组分组成,其中AD表示粘接层。
(A)单层烯烃系树脂(包含无机多孔剂和润滑剂)
(B)内表面层(包含无机多孔剂和润滑剂)/AD/润滑剂阻挡层/AD/外表面层
(C)内表面层(包含无机多孔剂)/回用料层(包含润滑剂)/AD/润滑剂阻挡层/AD/外表面层
在上述层结构中,内表面层是由烯烃系树脂形成的层,而外表面层优选为由与内表面层同样的烯烃系树脂形成的层。
在上述层构成中,没有与无机多孔剂共混的烯烃系树脂层可以与内表面的烯烃系树脂层相邻设置。
在上述各层中,在不劣化各层所需的性质的范围内,可以根据需要共混如颜料和紫外线吸收剂等本身已知的各种配混剂。
各层的厚度可以在不劣化润滑剂在容器内表面上的渗出性的范围内,在有效地显示各层的功能的同时,确定为不超过所需的厚度。
在本发明中,由包括润滑剂并且其中共混有无机多孔剂的烯烃系树脂层形成的内表面层,尽管共混有无机多孔剂,但是其平均表面粗糙度Ra(JIS-B-0601-1994)设定为0.3μm以下,因为如上所述无机多孔剂不用作粗糙化剂。
特别地,当具有高渗出性的低密度聚乙烯用作形成内表面层的烯烃系树脂时,在容器的成形期间容易产生熔体破裂,这容易在表面上引起称为鲨鱼皮的粗糙皮。例如,经过模具的镜面研磨步骤,通过将表面粗糙度调整在该范围内,可以有效地避免这种外观不良。
<容器的形态>
本发明的容器可以制备为例如用于形成膜、片、瓶、盖和管的型坯,或者制备为用于形成导管、瓶或管的预制品,并且也可以以本身已知的任意方法生产。
例如,可以使用与各层相对应的数量的挤出机或注射成形机,通过共挤出成形法、共注射法和顺序注射法等,生产用于形成膜、片、盖和管的型坯,或者用于成形导管、瓶或管的预制品。此外,如此获得的膜可以双轴拉伸以制成拉伸膜。
例如,可以通过用一对分型模将挤出物挤出并向内部吹送流体而容易地进行从型坯、管或预制品的瓶形成。
可以通过冷却导管或预制品,然后将其加热至拉伸温度以沿轴向拉伸,并且在流体压力下沿圆周方向吹塑拉伸获得拉伸瓶等。
此外,使膜或片进行真空成形、加压成形、拉伸膨胀成形和模塞助压成形等的任意手段,以获得像杯或托盘等的形状的包装容器。
在此成形过程中,用于确定内表面层的模具的表面预先镜面加工,使得容器内表面层的平均表面粗糙度Ra可以设定为0.3μm以下。
图1示出作为本发明的容器的最适合形态的直接吹塑成形瓶。
在图1中,作为整体表示为数字10的瓶具有带有螺纹的颈部11、通过肩部13延伸至颈部11的主体部壁15以及将主体部壁15的下端封闭的底壁17。容纳在瓶10中的粘稠物质可以通过在主体部壁15处挤压该瓶而排出。瓶10用如铝箔等的密封箔19在口部密封,进一步安装盖20以进入市场。
在本发明的瓶10中,上述有机系渗出性润滑剂渗出以分布在瓶的内表面上,由此该瓶显示相对于内容物优异的滑落性。此外,由于在容器内表面的烯烃系树脂层中共混无机多孔剂,所以相对于内容物的风味保持性良好。
因此,以瓶10为代表的本发明的容器适合用于容纳粘稠的内容物。
由于本发明的容器显示相对于内容物优异的滑落性,因此例如适合用作容纳在25℃下的粘度为1260mPa·s以上的高粘性物质的容器。虽然对于乳化物,特别是仅含有少量油(脂)的乳化物,滑落性倾向于劣化,但是即使相对于含有较少量油的乳化物,本发明的容器也显示优异的滑落性。此外,由于可以保持内容物的风味,因此适合用于容纳食品。该容器特别适合用于如番茄酱等的非油性物质和其它蛋黄酱样食品、各种调料、和特别是如低卡路里蛋黄酱等的乳化物。
实施例
以下将参照实施例描述本发明。
实施例和比较例中各种性质的测量和评价按照以下方式进行。
<正庚烷提取蒸发残余物测量>
由此获得的瓶按照Ministry of Health and Welfare的Notification No.370通过使用正庚烷作为提取液在25℃-60分钟的溶出条件下进行蒸发残余物的测量。
<滑落性评价>
将由此获得的塑料瓶(容器)在室温(23℃)下用规定量(500g)的低卡路里蛋黄酱填充。在填充后即刻和在23℃下贮存一个月(经时)后在主体部挤压该瓶以通过瓶口部挤出而排出内容物,然后将空气引入瓶中以恢复形状。
然后,将该瓶在冰箱中倒置(口部朝下)贮存一天以测量该瓶主体部的内容物的滑落程度,从而通过以下等式计算内容物滑落率:
内容物滑落率(%)=(‘内容物滑落的表面积’/‘瓶主体部壁表面积’)×100
基于以上述方式测量的内容物滑落率,根据以下标准评价滑落性。
◎:内容物滑落率为90%以上
○:内容物滑落率为70%以上且低于90%
△:内容物滑落率为50%以上且低于70%
×:内容物滑落率为低于50%
<风味性评价>
将由此获得的瓶在口部用铝箔热封,并在23℃贮存一个月。然后,将铝箔从瓶剥离以功能性地评价瓶内的气味。基于以下标准评价。
◎:该瓶没有分解的润滑剂的气味,并且没有容器的聚乙烯的气味
○:该瓶没有分解的润滑剂的气味,并且有容器的聚乙烯的气味
△:该瓶在允许的范围内有轻微的分解的润滑剂的气味,并且有容器的聚乙烯的气味
×:该瓶有分解的润滑剂的气味,并且有容器的聚乙烯的气味
<透明性评价>
从所得各瓶的主体部切出长度40mm×宽度40mm的试验片。使用由NIPPONDENSHOKU INDUSTRIES Co.,LTD.制造的浊度计NDH1001对试验片进行雾度(%)的测量。基于以下标准评价。
◎:小于20%
○:20%以上且小于30%
△:30%以上且小于40%
×:40%以上
<表面粗糙度测量>
从所得各瓶的主体部切出长度40mm×宽度40mm的试验片。对于该试验片的瓶内表面侧,根据JIS-B-0601-1994,通过使用由TOKYO SEIMITSU CO.,LTD.制造的SURFCOM2000SD3,以0.3mm/s的测量速度测量算术平均表面粗糙度Ra。
<有机系渗出性润滑剂熔点测量>
有机系渗出性润滑剂的熔点用差示扫描量热计(DSC)测量。在熔融峰宽的情况下,采用最大峰值的温度。
<无机多孔剂的平均粒径的测量>
无机多孔剂的平均粒径为通过激光衍射散射法测量的以体积计的平均粒径(D50)。
<实施例1>
通过使用五台挤出机成形包括五种六层的多层型坯。使该多层型坯进行直接吹塑成形以获得由具有图1所示的形状的五种六层构成的塑料瓶(内容积:500ml)。在挤出之前通过将以下树脂粒料、有机系渗出性润滑剂和无机多孔剂混合来制备内表面层的材料。
外表面层(75μm)/粘接层(2.4μm)/阻气层(10μm)/粘接层(2.4μm)/主层(180.2μm)/内表面层(30μm)
以下描述各层的材料。
低密度聚乙烯缩写为LDPE。此处,主层表示其中无机多孔剂和润滑剂都不共混的烯烃系树脂层。
外表面层;
LDPE(密度:0.921g/cm3)
粘接层;
酸改性聚乙烯
阻气层;
EVOH共聚物
主层;
LDPE(密度:0.921g/cm3)
内表面层;
LDPE(密度:0.921g/cm3)
有机系渗出性润滑剂:
色拉油(熔点=-20℃)
共混量=5.0质量%
无机多孔剂:
高硅沸石
二氧化硅/氧化铝比=80
平均粒径=4.5μm
共混量=1.0质量%
使该瓶进行正庚烷提取蒸发残余物量、滑落性、风味性、透明性和内表面的表面粗糙度Ra的评价。瓶内表面层的规格和评价结果示于表1和2中。
<实施例2>
除了将内表面层的润滑剂替换为芥酸(熔点=34℃),并将共混量改变为10.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例3>
除了将内表面层的润滑剂替换为月桂酸(熔点=45℃),并将共混量改变为10.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例4>
除了将内表面层的润滑剂替换为作为脂肪酸酯的中链脂肪酸甘油三酯(熔点=-6℃以下)以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例5>
除了将内表面层中的润滑剂的共混量改变为10.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例6>
除了将内表面层中的润滑剂的共混量改变为7.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例7>
除了将内表面层中的润滑剂的共混量改变为2.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例8>
除了将内表面层中的润滑剂的共混量改变为0.5质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例9>
除了将内表面层中的无机多孔剂替换为二氧化硅/氧化铝摩尔比为33的高硅沸石以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例10>
除了将内表面层中的无机多孔剂的共混量改变为3.0质量%以外,以与实施例1相同的方式制作塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例11>
除了将内表面层中的无机多孔剂的共混量改变为0.2质量%以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例12>
除了将内表面层中的无机多孔剂替换为平均粒径为0.5μm的高硅沸石以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例13>
除了将内表面层中的无机多孔剂替换为平均粒径为0.5μm的高硅沸石,并将共混量改变为0.2质量%以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例14>
除了将内表面层的树脂替换为密度为0.903g/cm3的线性低密度聚乙烯(LLDPE)以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例15>
除了将内表面层的树脂替换为密度为0.935g/cm3的线性低密度聚乙烯(LLDPE)以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例16>
除了将内表面层中的无机多孔剂替换为平均粒径为5.0μm的A型合成沸石(二氧化硅/氧化铝比=2)以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<实施例17>
除了将内表面层中的无机多孔剂替换为平均粒径为5.0μm的天然二氧化硅以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<比较例1>
通过使用五台挤出机成形包括五种七层的多层型坯。然后使该多层型坯进行直接吹塑成形以获得具有图1所示的形状的由下述五种七层构成的塑料瓶(内容积:500ml)。在挤出之前通过将以下树脂粒料、有机系渗出性润滑剂和无机多孔剂混合来制备内表面层的材料。
外表面层(75μm)/粘接层(2.4μm)/阻气层(10μm)/粘接层(2.4μm)/主层(177.8μm)/粘接层(2.4μm)/内表面层(30μm)
以下描述各层的材料。
外表面层;
LDPE(密度:0.921g/cm3)
粘接层;
酸改性聚乙烯
阻气层;
EVOH共聚物
主层;
LDPE(密度:0.921g/cm3)
内表面层;
非晶性聚酯(PETG)(密度:1.27g/cm3)
有机系渗出性润滑剂:
色拉油(熔点=-20℃)
共混量=5.0质量%
无机多孔剂:
高硅沸石
二氧化硅/氧化铝比=80
平均粒径=4.5μm
共混量=1.0质量%
<比较例2>
除了在内表面层中没有共混有机系渗出性润滑剂以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
<比较例3>
除了在内表面层中没有共混无机多孔剂以外,以与实施例1相同的方式形成塑料瓶,并进行各评价。评价结果示于表1和2中。
表中的缩写如下
Ex:实施例
Com:比较例
润滑剂A:色拉油
润滑剂B:芥酸
润滑剂C:月桂酸
润滑剂D:中链脂肪酸甘油三酯
HSZ:高硅沸石
SZ:合成沸石
NS:天然二氧化硅
[表2]
附图标记说明
10:直接吹塑成形瓶
11:颈部
13:肩部
15:主体部壁
17:底壁
Claims (9)
1.一种容器,其具有由烯烃系树脂层形成的内表面,其中所述烯烃系树脂层包括有机系渗出性润滑剂并且共混有无机多孔剂。
2.根据权利要求1所述的容器,其中所述有机系渗出性润滑剂是熔点为50℃以下的饱和或不饱和脂肪酸的至少一种。
3.根据权利要求1所述的容器,其中当通过用正庚烷填充所述容器进行提取时,获得10~150μg/ml所述提取液的蒸发残余物。
4.根据权利要求1所述的容器,其中所述无机多孔剂是二氧化硅/氧化铝比为80以上的高硅沸石。
5.根据权利要求4所述的容器,其中所述容器具有包括所述内表面的所述烯烃系树脂层的多层结构,并且所述无机多孔剂选择性地共混入所述内表面的所述烯烃系树脂层中。
6.根据权利要求1所述的容器,其中所述无机多孔剂以0.2~3.0质量%的量共混入形成容器内表面的所述烯烃系树脂层中。
7.根据权利要求1所述的容器,其中所述无机多孔剂的平均粒径在0.1~4.9μm的范围内。
8.根据权利要求1所述的容器,其中所述容器的内表面的平均表面粗糙度Ra为0.3μm以下。
9.根据权利要求1所述的容器,其填充有乳化物作为内容物。
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JP2015137436A JP6069426B2 (ja) | 2015-07-09 | 2015-07-09 | 内面がオレフィン系樹脂層により形成されている容器 |
JP2015-137436 | 2015-07-09 | ||
PCT/JP2016/069775 WO2017006906A1 (ja) | 2015-07-09 | 2016-07-04 | 内面がオレフィン系樹脂層により形成されている容器 |
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US (2) | US20180162595A1 (zh) |
EP (1) | EP3321208B1 (zh) |
JP (1) | JP6069426B2 (zh) |
KR (1) | KR102140027B1 (zh) |
CN (1) | CN107848679B (zh) |
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CN110177689A (zh) * | 2017-01-18 | 2019-08-27 | 东洋制罐株式会社 | 表面上具有油膜的结构体 |
JP6776983B2 (ja) * | 2017-03-31 | 2020-10-28 | 日本ポリエチレン株式会社 | 低味低臭フィルム |
JP7180969B2 (ja) * | 2017-08-10 | 2022-11-30 | 東洋製罐グループホールディングス株式会社 | 包装用多層構造体の製造方法 |
JP2020001773A (ja) * | 2018-06-29 | 2020-01-09 | 東洋製罐株式会社 | 内面に潤滑液コーティング層を備えたダイレクトブロー空ボトルおよびボトル詰め水中油型乳化食品 |
JP7304690B2 (ja) * | 2018-12-05 | 2023-07-07 | 東洋製罐グループホールディングス株式会社 | 包装用多層構造体 |
JP7292629B2 (ja) | 2019-01-24 | 2023-06-19 | キョーラク株式会社 | プラスチック容器及びその製造方法 |
JP7356803B2 (ja) * | 2019-02-13 | 2023-10-05 | 東洋製罐グループホールディングス株式会社 | 液状滑剤を含む包装用構造体 |
JP2021070497A (ja) * | 2019-10-31 | 2021-05-06 | 大和製罐株式会社 | キャップ |
WO2024034519A1 (ja) * | 2022-08-08 | 2024-02-15 | 住友化学株式会社 | ポリオレフィン系樹脂組成物、成形体および積層体 |
US20240199295A1 (en) * | 2022-12-15 | 2024-06-20 | Colgate-Palmolive Company | Packaging Article with Surface Coating |
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EP3321208A1 (en) | 2018-05-16 |
US20180162595A1 (en) | 2018-06-14 |
MY186967A (en) | 2021-08-26 |
JP2017019516A (ja) | 2017-01-26 |
US11820553B2 (en) | 2023-11-21 |
WO2017006906A1 (ja) | 2017-01-12 |
KR102140027B1 (ko) | 2020-07-31 |
CN107848679B (zh) | 2019-12-13 |
KR20180012315A (ko) | 2018-02-05 |
EP3321208A4 (en) | 2019-03-06 |
JP6069426B2 (ja) | 2017-02-01 |
EP3321208B1 (en) | 2020-12-30 |
US20220033142A1 (en) | 2022-02-03 |
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