CN103826846B - 容器用树脂被覆金属板 - Google Patents
容器用树脂被覆金属板 Download PDFInfo
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- CN103826846B CN103826846B CN201280047026.0A CN201280047026A CN103826846B CN 103826846 B CN103826846 B CN 103826846B CN 201280047026 A CN201280047026 A CN 201280047026A CN 103826846 B CN103826846 B CN 103826846B
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- resin
- polyester
- polyester resin
- container
- coated metal
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Abstract
本发明提供一种可应对食品罐头原材料所需的多种特性的容器用树脂被覆金属板。在金属板的至少单面,具有以聚酯树脂为主要成分的多层结构的树脂被覆层(A)。上述树脂被覆层(A)具有树脂层(a1),该树脂层(a1)与上述金属板面密合,含有(i)聚酯树脂、(ii)酚醛树脂、(iii)金属醇盐系化合物和/或金属螯合物、(iv)环氧树脂、(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上的成分,且以聚酯树脂为主要成分。优选在上述树脂层(a1)的上层形成聚酯膜(a2)。
Description
技术领域
本发明涉及例如用于食品罐头的罐身和盖等的容器用树脂被覆金属板。
背景技术
以往,以提高耐腐蚀性、耐久性、耐候性等为目的,对作为用于食品罐的金属罐头用原材料的无锡钢(TFS)、铝等金属板施行涂装。但是,施行该涂装的工序存在不仅烧结处理复杂,而且需要大量处理时间,进而排出大量溶剂的问题。
因此,为了解决这些问题,开发了在加热过的金属板上层压热塑性树脂膜而形成的膜层压金属板来代替涂装钢板,目前,在工业上作为食品罐头用原材料使用。
对于食品罐头用原材料,除了加工性、密合性等基本特性以外,若为2片罐用途,则还寻求深拉伸成型性、加工·蒸煮后密合性、耐腐蚀性、设计性等多种多样的功能。
作为使膜层压金属板多功能化的方法,可选择(1)在膜内加入具有欲附加的功能的改性剂,使膜自身多功能化的方法;(2)不对膜进行改性,在膜表面涂覆具有欲附加的功能的改性剂或包含改性剂的树脂的方法中的任一者。
对上述(1)的膜直接添加改性剂的方法是在大量地生产具有一定功能的膜时,生产效率高、收益性高的方法。但是,食品罐头的形状、内容物的种类多种多样,对每种罐头所要求的功能不同,因此该方法不适合。原因是,每当变更对膜赋予的功能,需要清洗树脂的挤出装置、流延鼓、冷却辊等,必须长时间停止生产线,生产效率显著下降。
另一方面,在上述(2)的膜的表面涂覆包含改性剂的树脂的方法容易变更对膜的附加功能,因此可以应对食品罐头的多种多样的需求。这是因为,可以将加入包含改性剂的涂覆液的罐通过清洗·交换而快速地应对。
作为这种在膜表面涂覆包含改性剂的树脂的方法,例如,可以举出专利文献1。专利文献1是在金属板与膜之间形成以环氧树脂为主要成分且包含三聚氰胺树脂、封闭型异氰酸酯化合物、着色剂的树脂层的方法。
然而,环氧树脂虽然富于反应性、与金属板的密合性优异,但存在深拉伸成型性差的缺点,因此无法得到能够作为2片罐用原材料使用的膜。即使欲将专利文献1的树脂被覆金属板成型为深拉伸罐(DRD罐),环氧树脂也无法追随罐高度方向的伸长变形,而约束了原材料的变形,在拉伸工序中原材料破裂。
专利文献2~5公开有以提高密合性为目的,对膜进行树脂涂覆的方法。专利文献2~5是以聚酯树脂与环氧树脂的复合系、或环氧树脂为主要成分的构成。因此,与专利文献1同样,深拉伸成型性有困难,不可应用于2片罐用途。此外,在专利文献2~5所记载的实施例中,没有公开对制罐加工性、深拉伸成型性进行评价的例子,由此也可明确,这些专利文献没有考虑需要深拉伸加工的2片罐用途。
专利文献
专利文献1:日本特开2007-185915号公报
专利文献2:日本特开平4-266984号公报
专利文献3:日本特开平8-199147号公报
专利文献4:日本特开平10-183095号公报
专利文献5:日本特开2002-206079号公报
发明内容
本发明鉴于上述情况,目的在于提供一种可应对食品罐原材料所要求的多种特性的容器用树脂被覆金属板。
本发明的发明人等为了解决课题而进行了深入研究,其结果,获得以下发现。
在金属板的至少单面,具有以聚酯树脂为主要成分的多层结构的树脂被覆层。而且,将包含(i)聚酯树脂、(ii)酚醛树脂、(iii)金属醇盐系化合物和/或金属螯合物、(iv)环氧树脂、(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上的树脂层制成与金属板的密合层,优选在它的上层层压聚酯膜,从而可以得到除优异的深拉伸成型性、加工后密合性等基本特性以外,还具有在蒸煮处理环境下的设计性等多种优异的功能的容器用树脂被覆金属板。
本发明是基于以上发现而完成的,其要旨如下所述。
[1]一种容器用树脂被覆金属板,其特征在于,在金属板的至少单面,具有以聚酯树脂为主要成分的多层结构的树脂被覆层(A),该树脂被覆层(A)具有树脂层(a1),所述树脂层(a1)与所述金属板面密合,含有下述(i)~(v)的成分,且以聚酯树脂为主要成分。
(i)聚酯树脂
(ii)酚醛树脂
(iii)金属醇盐系化合物和/或金属螯合物
(iv)环氧树脂
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上
[2]如[1]所述的容器用树脂被覆金属板,其特征在于,上述(iv)环氧树脂是除双酚A以外的环氧树脂。
[3]如上述[1]或[2]所述的容器用树脂被覆金属板,其特征在于,上述树脂被覆层(A)由上述树脂层(a1)和形成于该树脂层(a1)的上层的聚酯膜(a2)构成。
[4]如上述[1]~[3]中任一项所述的容器用树脂被覆金属板,其特征在于,形成上述树脂层(a1)的树脂成分的比率满足下述条件。
(i)聚酯树脂:50~89质量%
(ii)酚醛树脂:10~45质量%
(iii)金属醇盐系化合物和/或金属螯合物:0.01~10质量%
(iv)环氧树脂:0.5~20质量%
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上:0.1~10质量%
[5]如上述[1]~[4]中任一项所述的容器用树脂被覆金属板,其特征在于,上述(i)聚酯树脂的数均分子量为3000~100000,为下述(i-1)~(i-3)中的任一种以上。
(i-1)玻璃化转变温度为0℃以上且小于35℃的聚酯树脂
(i-2)玻璃化转变温度为35℃以上且小于65℃的聚酯树脂
(i-3)玻璃化转变温度为65℃以上且小于100℃的聚酯树脂
[6]如上述[5]所述的容器用树脂被覆金属板,其特征在于,形成上述(i)聚酯树脂的各聚酯树脂的比率满足下述条件。
玻璃化转变温度为0℃以上且小于35℃的聚酯树脂:30~70质量%
玻璃化转变温度为35℃以上且小于65℃的聚酯树脂:10~35质量%
玻璃化转变温度为65℃以上且小于100℃的聚酯树脂:10~35质量%
[7]如上述[1]~[6]中任一项所述的容器用树脂被覆金属板,其特征在于,上述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
[8]如上述[1]~[7]中任一项所述的容器用树脂被覆金属板,其特征在于,上述(iii)金属醇盐系化合物和/或金属螯合物是钛醇盐系化合物和/或钛螯合物。
[9]如上述[2]~[8]中任一项所述的容器用树脂被覆金属板,其特征在于,上述聚酯膜(a2)是聚酯树脂的构成单元的85质量%以上为对苯二甲酸乙二醇酯单元和/或萘二甲酸乙二醇酯单元的双轴拉伸聚酯膜,该双轴拉伸聚酯膜含有无机粒子和/或有机粒子。
根据本发明,可以得到可应对食品罐原材料所要求的多种特性的容器用树脂被覆金属板。而且,作为可以容易地附加食品罐所要求的多种功能的新的容器用树脂被覆金属板,是在产业上有益的发明。
附图说明
图1是表示金属板的层压装置的主要部分的图。(实施例1)
图2是表示膜层压金属板的截面结构的图。(实施例1)
图3是表示对罐身部赋予的横切损伤的位置的图。(实施例1)
图4是表示测定来自人工损伤的最大腐蚀宽度的方法的图。(实施例1)
具体实施方式
以下,对本发明的容器用树脂被覆金属板进行详细说明。
首先,对本发明中所使用的金属板进行说明。
作为本发明的金属板,可以使用作为罐用材料而广泛使用的铝板、软钢板等。尤其,最佳的是形成下层由金属铬构成、上层由氢氧化铬构成的二层皮膜的表面处理钢板(以下称为TFS)等。
对于TFS的金属铬层、氢氧化铬层的附着量,没有特别的限定,但是从加工后密合性、耐腐蚀性的观点出发,均以Cr换算计,优选金属铬层为70~200mg/m2,氢氧化铬层为10~30mg/m2的范围。
而且,本发明的容器用树脂被覆金属板在金属板的至少单面,具有以聚酯树脂为主要成分的多层结构的树脂被覆层(A)。作为该聚酯树脂,能够使用与下述树脂层(a1)中所说明的聚酯树脂同样的聚酯树脂。
而且,该树脂被覆层(A)具有与上述金属板面密合的树脂层(a1),进而,上述树脂层(a1)以聚酯树脂为主要成分且含有下述(i)~(v)的成分。如上所述,树脂被覆层(A)以聚酯树脂为主要成分,这里,主要成分是指在树脂被覆层(A)中包含50质量%以上的聚酯树脂。
(i)聚酯树脂
(ii)酚醛树脂
(iii)金属醇盐系化合物和/或金属螯合物
(iv)环氧树脂
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上
接着,对与金属板面密合的树脂层(a1)进行说明。
(i)聚酯树脂
本申请发明中,以聚酯树脂为主要成分,这里主要成分是指在树脂层(a1)中包含50质量%以上的聚酯树脂。
作为聚酯树脂,优选数均分子量为3000~100000,更优选为5000~30000,进一步优选为10000~25000的范围内。应予说明,数均分子量是凝胶渗透色谱分析中的利用与聚苯乙烯的比较而得的换算值。若数均分子量低于3000,则加工性变差,若高于100000,则有时涂料化时的粘度变高,无法适当的涂装。
聚酯树脂的玻璃化转变温度优选为0℃以上且小于100℃的范围内。通过将玻璃化转变温度设为0℃以上且小于100℃的范围,树脂的柔软性·加工性、耐粘连性会适度地平衡而适用于食品罐用途。
1种聚酯树脂有时难以满足多种性能要求。在单独使用时,例如,在聚酯树脂的玻璃化转变温度为0℃以上且小于35℃时,对树脂层赋予柔软性,因此加工性优异。但是,若在膜上涂覆树脂层后,直接以卷曲状态在大于玻璃化转变温度的温度下长时间保持,则有可能膜会粘连。此外,玻璃化转变温度低,且耐热性不足,因此耐蒸煮性会稍稍变差。
若玻璃化转变温度为35℃以上且小于65℃,则膜不会粘连,而不会损害膜的美观。若玻璃化转变温度为65℃以上且小于100℃,则虽然粘连性优异,但由于皮膜变硬,因此加工性稍稍变差。
因此,聚酯树脂优选并用玻璃化转变温度不同的多个树脂,发挥各聚酯树脂的良好性能,从而得到取得平衡的更优异的树脂层。
而且,并用玻璃化转变温度不同的多个树脂时,各聚酯树脂的比率优选如下所示。
玻璃化转变温度为0℃以上且小于35℃的聚酯树脂:30~80质量%
玻璃化转变温度为35℃以上且小于65℃的聚酯树脂:10~35质量%
玻璃化转变温度为65℃以上且小于100℃的聚酯树脂:10~35质量%
通过设为这种比率的范围,加工性与粘连性的平衡显著提高。
此外,聚酯树脂优选含有来源于双酚酸的重复单元。在作为用于制造聚酯树脂的原料成分的单体组合物中含有双酚酸时,与酚醛树脂的反应性提高,且固化速度提高,其结果,耐蒸煮白化性提高。此外,即使以高比率使用以双酚酸为必需单体的玻璃化转变温度为0℃以上且小于35℃的聚酯,固化性也提高。由此,具有即使玻璃化转变温度低,涂覆膜的粘连性也优异等特征,因此聚酯树脂优选含有来源于双酚酸的重复单元。
作为聚酯树脂(i),可以使用使多元酸成分与多元醇成分进行酯化反应而得的聚酯树脂。
作为多元酸成分,例如,可以使用邻苯二甲酸酐、间苯二甲酸、对苯二甲酸、琥珀酸、富马酸、己二酸、壬二酸、癸二酸、二聚酸等1种以上的二元酸以及这些酸的低级烷基酯化物,根据需要,可并用苯甲酸、巴豆酸等一元酸;偏苯三甲酸酐、甲基环己烯三羧酸等三元以上的多元酸等。
作为多元醇成分,主要可以使用乙二醇、二乙二醇、丙二醇、1,4丁二醇、新戊二醇、3-甲基戊二醇、1,4-己二醇、1,6-己二醇、环己烷二甲醇等二元醇,进而,可以根据需要而并用丙三醇、三羟甲基乙烷、三羟甲基丙烷、季戊四醇等三元以上的多元醇。这些多元醇可以单独使用,或混合2种以上使用。
作为聚酯树脂(i)的市售品,例如,可以举出东洋纺织株式会社制造的Vylon300、500、560、600、630、650、670;Vylon GK130、140、150、190、330、590、680、780、810、890;UNITIKA株式会社制造的Elitel UE-3220、3500、3210、3215、3216、3620、3240、3250、3300;东亚合成株式会社制造的ARON MELT PES-310、318、334等。
(ii)酚醛树脂
通过添加酚醛树脂,会引起交联反应,形成三维网眼结构,因此可以得到使皮膜的耐腐蚀性、耐蒸煮性提高的效果。
在树脂层(a1)中进一步添加酚醛树脂作为成分(ii)。可以举出将苯酚、间甲酚、间乙基苯酚、3,5-二甲苯酚、间甲氧基苯酚等3官能酚化合物;或对甲酚、邻甲酚、对叔丁基苯酚、对乙基苯酚、2,3-二甲苯酚、2,5-二甲苯酚、间甲氧基苯酚等各种2官能性酚与甲醛在碱催化剂存在的条件下合成而得的树脂。这些酚化合物可以使用1种或混合使用2种以上。此外,可以使用将酚醛树脂中所含的羟甲基的一部分或全部利用碳原子数为1~12的醇类进行醚化而成的形式的树脂。
(iii)金属醇盐系化合物和/或金属螯合物
金属醇盐系化合物和/或金属螯合物与(i)聚酯树脂、(ii)酚醛树脂、(iv)环氧树脂发生反应。各树脂的官能团与金属醇盐系化合物和/或金属螯合物之间进行交联反应。该交联反应与没有金属醇盐系化合物和/或金属螯合物时相比,其皮膜的固化速度显著加快,因此,其结果,能够以极少的热能表现出优异的密合性、加工性、耐蒸煮性、耐腐蚀性。例如,现有的层压罐是将膜层压后以180℃以上施行数秒~数分钟的烧结,其后,利用后加热使树脂皮膜固化,确保上述各种性能要求。但是,就本发明中含有金属醇盐系化合物和/或金属螯合物时的树脂层而言,仅以进行热熔合层压时的1秒左右的短时间加热,树脂层就充分地固化,可以得到与施行了后加热的树脂层同等以上的性能。因此,不需要制造工艺中的后加热工序,格外提高制造效率。而且,也能够降低二氧化碳的排放,可成为在实用上极其有用的技术。进而,通过在皮膜中引入金属,提高皮膜的强度,其结果,大幅度地提高耐冲击性、耐腐蚀性。根据以上理由,上述树脂层(a1)含有金属醇盐系化合物和/或金属螯合物。
作为金属醇盐系化合物和/或金属螯合物,例如,可以举出铝、钛、锡、锆等的醇盐金属化合物、将乙酰乙酸配位于金属而得的金属螯合物等。其中,优选使用钛醇盐系化合物和/或钛螯合物。以下,对其理由进行说明。
通过将金属醇盐系化合物和/或金属螯合物与聚酯树脂和/或酚醛树脂连续地进行交联反应,在树脂层内形成分子链的三维网络。由此,能够最有效地抑制蒸煮处理环境下的水蒸气、热水的渗透所致的变色。
水蒸气所致的变色是指在蒸煮杀菌处理中以树脂层自身变得白浊的方式变色的现象,被称为蒸煮白化。由于罐外面的设计性受损,因此是能够使消费者的购买积极性减退的大问题。本发明的发明人等进行了深入研究,其结果认为原因是,水蒸气渗透于被覆罐体的树脂层内,从而在树脂层的界面以及界面附近形成液胞,在液胞部散射光。因此,为了改善特性,重要的是抑制在树脂层的界面以及界面附近的液胞形成。即,侵入树脂中的水蒸气在树脂中扩散而到达与金属板的界面。蒸煮处理刚刚开始后,填充于罐内的内容物处于接近常温的状态,因此从罐的外部至内部产生温度梯度。即,在树脂中扩散的水蒸气随着接近金属板而被冷却,从而在该界面以及界面附近液化,成为冷凝水而形成液胞。液胞在蒸煮处理后也残留于界面以及界面附近,从而导致光的散射,可以看到树脂表面产生白浊。因此,为了抑制蒸煮白化,只要抑制在界面以及界面附近的液胞的形成即可。
另一方面,蒸煮处理装置除了如上述地使用水蒸气作为加热介质的蒸煮处理装置以外,有使用热水作为加热介质的蒸煮装置。在使用热水作为加热介质的蒸煮装置的情况下,因与水蒸气所致的变色不同的机理,产生树脂层自身变色、设计性变差的问题。认为这是因为,在蒸煮处理的初期阶段,聚酯分子链的交联反应没有充分地进行时,渗透于树脂层内的水以聚酯的羰基末端基为催化剂而促进聚酯分子链的水解反应,从而在树脂层内形成大的液胞。
本发明的发明人等对上述2种变色现象进行了深入研究,其结果可知,使用钛醇盐系化合物和/或钛螯合物系化合物作为金属醇盐系化合物和/或金属螯合物时,在热熔合层压阶段能够充分地形成钛醇盐系化合物和/或钛螯合物系化合物、以及由聚酯树脂和/或酚醛树脂的交联反应得到的聚酯分子链的网络,其结果,可以最有效地抑制两者的变色现象。认为:聚酯分子链的网络可抑制水蒸气和热水渗透至树脂内且到达界面,并且可以通过提高树脂强度和弹性模量而抑制液胞的形成和生长。此外,通过分子链网络形成所伴随的羰基末端基量的减少,也可抑制剧烈的水解反应。因此,金属醇盐系化合物和/或金属螯合物优选为钛醇盐系化合物和/或钛螯合物。
(iv)环氧树脂
环氧树脂主要是使皮膜的密合性提高的树脂。特别优选为酚醛清漆型环氧树脂。作为酚醛清漆型环氧树脂的市售品,可以举出DIC株式会社制造的EPICLON N-665、670、673、680、690、695、730、740、770、865、870;Dow Chemical株式会社制造的XD-7855;AsahiKasei Epoxy株式会社制的ECN-1273、1299等。作为联苯型环氧树脂,可以举出三菱化学株式会社制造的YL6121H、YX7399。
此外,环氧树脂优选除双酚A以外的环氧树脂。原因是担心双酚A的内分泌扰乱作用。
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上
聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂与三聚氰胺树脂等相比,在固化速度快,可以形成强韧的皮膜方面优异。与由聚酯/三聚氰胺系、环氧/三聚氰胺系等构成的树脂组合物相比,固化特性优异,因此在层压钢板的耐蒸煮性、耐腐蚀性和加工性等方面,能够发挥特别优异的性能。
作为聚胺树脂,若例示特别具有代表性的聚胺树脂,则作为脂肪族胺,可以举出二亚乙基三胺、三亚乙基三胺、三亚乙基五胺,作为脂环式聚胺,可以举出异佛尔酮二胺等。此外,为了改善作业性、低刺激化、提高机械物性,也可以举出使脂肪族聚胺与环氧树脂、丙烯腈加成,或使甲醛与苯酚反应而改性的聚胺树脂。作为芳香族聚胺,可以举出间苯二胺、二氨基二苯基磺酸、二氨基二苯基甲烷等。作为市售品,可以举出DIC株式会社制造的EPICLONEXB-353、Air Products Japan株式会社制造的ANCAMINE2596、ANCAMINE2605等。
聚酰胺-胺树脂、聚酰胺树脂是例如通过油脂脂肪酸与聚胺的脱水缩合反应而合成的化合物。作为市售品,可以举出三洋化成的POLYMIDE L-15-3、POLYMIDE L-45-3、AirProducts Japan株式会社制ANCAMIDE2137、SUNMIDE330、SUNMIDE X-2000等。
树脂层(a1)的组成(质量%)
形成树脂层(a1)的树脂成分的比率优选满足下述条件。
(i)聚酯树脂:50~89质量%
(ii)酚醛树脂:10~45质量%
(iii)金属醇盐系化合物和/或金属螯合物:0.01~10质量%
(iv)环氧树脂:0.5~20质量%
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上:0.1~10质量%
若(i)聚酯树脂的比率低于50质量%,则加工性变差,若大于89质量%,则有时固化性不足且耐蒸煮性下降。更优选为55~85质量%的范围。
若(ii)酚醛树脂的比率低于10质量%,则固化性不足且耐蒸煮性差,若大于45质量%,则有时加工性变差。更优选为20~40质量%。
若(iii)金属醇盐系化合物和/或金属系螯合物的比率低于0.01质量%,则无法得到所期待的快速固化性等效果,此外,若大于10质量%,则树脂皮膜变硬且加工性变差,此外,有时在涂覆液制作时引起凝胶化。更优选为0.1~7质量%。
若(iv)环氧树脂的比率低于0.5质量%,则密合性下降,其结果,耐腐蚀性变差,若大于20质量%,则有时耐蒸煮白化性下降。更优选为2~7质量%。
若(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上的比率低于0.1质量%,则固化性不足且耐蒸煮性差,若大于10质量%,则有时加工性变差。更优选为1~4质量%。
树脂层(a1)的附着量
树脂层(a1)的附着量优选规定为0.1g/m2以上5.0g/m2以下的范围。小于0.1g/m2时,有时无法均匀地被覆金属板表面,膜厚变得不均匀。另一方面,若大于5.0g/m2,则有可能树脂的凝聚力变得不充分,树脂层的强度下降。其结果,在制罐加工时,树脂层发生凝聚破坏而膜剥离,以此为起点,罐身部断裂。
根据以上,附着量优选为0.1~5.0g/m2,进一步优选为0.1~3.0g/m2,更进一步优选为0.5~2.5g/m2。
着色剂
进而,通过在树脂层(a1)中添加染料、颜料等着色剂,可以遮盖基底金属板,赋予树脂独特的多种多样的色调。例如,通过添加炭黑作为黑色颜料,可以遮盖基底的金属色,而且对食品罐头赋予黑色所具有的高级感。
作为炭黑的粒径,可以使用5~50nm的范围的粒径,但是若考虑在聚酯树脂中的分散性、发色性,则优选为5~30nm的范围。
除黑色颜料以外,通过添加白色颜料,可以遮盖基底的金属光泽,并且使印刷面鲜明化,可以得到良好的外观。作为所添加的颜料,需要在容器成型后可发挥优异的设计性,从该观点出发,可以使用二氧化钛等无机系颜料。由于着色力强,还富有延展性,容器成型后也可以确保良好的设计性,因此优选。
在期望容器表面有明亮色时,优选使用黄色的有机系颜料。由于透明性优异且着色力强、富有延展性,因此容器成型后也可以得到具有明亮色的外观。若例示本发明中可使用的有机系颜料,则可以举出颜色索引(简称:C.I.)颜料黄12、13、14、16、17、55、81、83、139、180、181、183、191、214中的至少1种。尤其,从色调(明亮色)的鲜明性、耐热水变色性等观点出发,更优选使用C.I.颜料黄180、214。
此外,作为红色颜料,可以举出C.I.颜料红101、177、179、187、220、254、作为蓝色颜料,可以举出C.I.颜料蓝15、15:1、15:2、15:3,作为紫色颜料,可以举出C.I.颜料紫19,作为橙色颜料,可以举出C.I.颜料橙64,作为绿色颜料,可以举出C.I.颜料绿7等。
以上的着色剂的配合比率优选为在构成树脂层(a1)的树脂层的全部固体成分中含有0.1~70质量%。
固化催化剂
在树脂层(a1)中除了上述成分(i)~(v)以及着色剂以外,还可以添加促进交联的固化催化剂。例如,可以使用磷酸等无机酸、十二烷基苯磺酸、甲苯磺酸等有机酸以及将它们用胺等进行封闭而得的化合物。固化催化剂的配合比率优选在构成树脂层(a1)的树脂层的全部固体成分中为0.01~5质量%。
此外,树脂层(a1)中能够添加以往公知的润滑剂、消泡剂、流平剂、颜料、二氧化硅等抗粘连剂等。此外,作为固化助剂,可以并用三聚氰胺树脂、苯代三聚氰胺树脂、异氰酸酯树脂等其它固化剂,对于它们,能够根据膜的干燥条件、层压条件而并用适当的固化剂。
接下来,对形成于树脂层(a1)上层的树脂层(聚酯膜)(a2)进行说明。
树脂被覆层(A)优选在树脂层(a1)的上层形成以聚酯树脂为主要成分的树脂层(a2)作为最上层,更优选以聚酯膜(a2)为树脂层(a2)。
聚酯膜(a2)组成
本发明中所使用的聚酯膜从蒸煮后的味道特性良好方面、抑制制罐工序中的磨耗粉产生的方面考虑,优选以对苯二甲酸乙二醇酯和/或萘二甲酸乙二醇酯为主要构成成分。以对苯二甲酸乙二醇酯和/或萘二甲酸乙二醇酯为主要构成成分的聚酯是聚酯的85质量%以上为以对苯二甲酸乙二醇酯和/或萘二甲酸乙二醇酯为构成成分的聚酯。进一步优选为90质量%以上,若如此,则即使将饮料长期填充在金属罐中,味道特性也良好,因此优选。
另一方面,在不损害味道特性的范围内,可将其它二羧酸成分、二醇成分共聚,作为二羧酸成分,例如,可以举出二苯基羧酸、间苯二甲酸5-磺酸钠、邻苯二甲酸等芳香族二羧酸;草酸、琥珀酸、己二酸、癸二酸、二聚酸、马来酸、富马酸等脂肪族二羧酸;环己烷二甲酸等脂环族二羧酸;对羟基苯甲酸等羟基羧酸等。
作为二醇成分,例如,可以举出乙二醇、丙二醇、丁二醇、戊二醇、己二醇、新戊二醇等脂肪族二醇;环己烷二甲醇等脂环族二醇;双酚A、双酚S等芳香族二醇;二乙二醇、聚乙二醇等。另外,由于担心芳香族二醇中的双酚A的内分泌扰乱作用,优选不将其用作二醇成分。此外,这些二羧酸成分、二醇成分也可以并用2种以上。
此外,只要不阻碍本发明的效果,也可以共聚偏苯三酸、均苯三酸、三羟甲基丙烷等多官能化合物。
粒子
本发明中所使用的聚酯膜可以含有无机粒子和/或有机粒子。本发明中所使用的聚酯膜中的粒子在组成上,有机、无机均可,没有特别的限制,但是从成型为膜时的突起形状、耐磨性、加工性、味道特性的观点出发,体积换算平均粒径优选为0.005~5.0μm,特别优选为0.01~3.0μm。此外,从耐磨性等方面出发,下述式所示的相对标准偏差优选为0.5以下,进一步优选为0.3以下。
[数1]
[数1]
其中,
σ:相对标准偏差
D:数均粒径(μm)
Di:粒径(pm)
n:粒子个数(个)。
作为粒子的长径/短径比,优选为1.0~1.2。作为莫氏硬度,从突起硬度、耐磨性等方面出发,优选为小于7。
此外,为了充分地表现这些效果,优选含有0.005~10质量%的由上述构成的粒子。
具体而言,作为无机粒子,可以举出湿式及干式二氧化硅、胶体二氧化硅、硅酸铝、氧化钛、碳酸钙、磷酸钙、硫酸钡、氧化铝、云母、高岭土、粘土等。其中,优选为粒子表面的官能团与聚酯反应而生成羧酸金属盐的粒子,具体而言,从与聚酯的亲合性、耐磨耗性等方面考虑,优选为相对于1g粒子具有10-5mol以上的官能团的粒子,进一步优选为2×10-5mol以上。
此外,作为有机粒子,可以使用各种各样的有机高分子粒子,作为其种类,若至少一部分为对聚酯不溶的粒子,则可以是任意组成的粒子。此外,作为这种粒子的原材料,可以使用聚酰亚胺、聚酰胺-酰亚胺、聚甲基丙烯酸甲酯、甲醛树脂、酚醛树脂、交联聚苯乙烯、有机硅树脂等各种原材料。其中,特别优选为容易得到耐热性高且粒度分布均匀的粒子的乙烯系交联高分子粒子。
这种无机粒子和有机高分子粒子可以单独使用,优选并用2种以上而使用,但是通过将粒度分布、粒子强度等物性不同的粒子进行组合,可以得到功能性更高的聚酯树脂。
此外,在不妨碍本发明的效果的范围内,可以使用其它粒子,例如各种不定形的外部添加型粒子、以及内部析出型粒子,或各种表面处理剂。进而,若聚酯膜为双轴拉伸聚酯膜,则从耐热性、味道特性的观点出发,为优选。作为双轴拉伸的方法,同时双轴拉伸、逐次双轴拉伸均可,但是从使层压性、成型性良好的方面考虑,优选使拉伸条件、热处理条件特定化,且膜的厚度方向的折射率为1.50以上。进而,若厚度方向的折射率为1.51以上,尤其是1.52以上,则即使层压时稍有差异,也兼具成型性、耐冲击性,而且能够将面取向系数控制在特定的范围,因此为优选。
此外,双轴拉伸聚酯膜在制罐工序中拉深成型后受到200~230℃左右的热历程后加工颈部时的加工性、耐冲击性方面,优选利用固体高分辨率NMR的结构解析中的羰基部的缓和时间为270毫秒(msec)以上。进一步优选为280毫秒以上,特别优选为300毫秒以上。在不妨碍本发明的效果的范围内,可以使用其它粒子,例如各种不定形的外部添加粒子、以及内部析出型粒子,或各种表面处理剂。
聚酯膜(a2)的厚度
本发明中所使用的聚酯膜的厚度优选为5~100μm。聚酯膜的厚度小于5μm时,被覆性不充分,无法确保耐冲击性和成型性。另一方面,若大于100μm,则上述特性饱和,不仅无法得到任何改善效果,而且对金属表面进行热熔合时所需的热能增大,因此经济性受损。从这种观点出发,更优选聚酯膜的厚度为8~50μm,进一步优选为10~25μm。
接下来,对本发明的容器用树脂被覆金属板的制造方法进行说明。
以聚酯为主要成分的树脂层(a1)的形成方法
作为一个例子,对在聚酯膜(a2)表面形成聚酯树脂层(a1)的方法进行叙述。
使成为主要成分的聚酯树脂溶解于有机溶剂中,并且使本发明所规定的树脂层(a1)的添加成分以及任意添加成分溶解或分散于有机溶剂中而制备涂覆液。将该涂覆液在聚酯膜(a2)制膜时或制膜后涂布于膜表面且干燥,从而形成树脂层(a1)。
作为用于使聚酯树脂溶解的有机溶剂,可以举出甲苯、二甲苯等芳香族烃溶剂;甲基乙基酮、环己酮等酮溶剂、乙酸乙酯、乙二醇单乙醚乙酸酯等酯系溶剂等,可以适当选定它们中的1种以上而使用。
在上述涂覆液中能够添加以往公知的润滑剂、消泡剂、流平剂、颜料、二氧化硅等抗粘连剂等。此外,作为固化助剂,可以并用三聚氰胺树脂、苯代三聚氰胺树脂、异氰酸酯树脂等其它固化剂,对于它们,能够根据膜的干燥条件、层压条件而并用适当的固化剂。
此外,也可以使本发明中所规定的交联剂、固化催化剂、作为着色剂的炭黑、偶氮系颜料等添加剂分散于有机溶剂中而使用。此时,若并用分散剂,则可以赋予添加剂均匀性,因此为优选。
作为将涂覆液涂布于聚酯膜的方法,可以应用辊涂机方式、模涂机方式、凹版方式、凹版胶印方式、喷涂方式等已知的涂装方法,最优选为凹版辊涂法。作为涂覆液涂布后的干燥条件,优选为80℃~170℃下1~30秒钟,特别优选为100℃~130℃下5~30秒钟。干燥后的树脂层(a1)的附着量优选为0.1~5.0g/m2的范围内。若为0.1~5.0g/m2的范围内,则连续均匀涂布性优异,也没有设计性的问题,可以确保耐蒸煮性、密合性,也可消除卷绕膜时的粘连性。小于0.1g/m2时,有时皮膜的连续性容易产生难点,难以表现物性和设计性。此外,在蒸煮杀菌处理中,对水蒸气的阻隔性差,在树脂层(a1)/聚酯膜(a2)的界面容易滞留水分,能够引起蒸煮白化。另一方面,若大于5.0g/m2,则涂覆后的溶剂脱离性下降,作业性显著下降,而且,容易产生残留溶剂的问题,从而有时卷绕膜时的粘连性显著下降。作为优选的范围,为0.5~2.5g/m2的范围。
将涂覆树脂层(a1)后的聚酯膜(a2)层压于金属板表面的方法
将涂覆了树脂层(a1)的聚酯膜(a2)以树脂层(a1)与金属板面密合的方式层压于金属板表面。例如,可以使用将金属板以大于膜的熔点的温度加热,使用压接辊(以下称为层压辊),使涂覆了树脂层(a1)的聚酯膜(a2)与其表面接触而热熔合的方法。另外,此时,如上所述,需要使用层压辊使涂覆了树脂层(a1)的聚酯膜面与金属板接触而使之热熔合。
对于层压条件,以可以得到本发明所规定的树脂层的方式适当设定。例如,优选将层压开始时的温度至少设为膜的熔点以上,作为层压时膜所受到的温度历程,将以膜的熔点以上的温度接触的时间设为1~35毫秒的范围。为了达成这样的层压条件,除了在高速下的层压以外,也需要熔合中的冷却。层压时的加压没有特别的规定,作为表面压力,优选为9.8~294N/cm2(1~30kgf/cm2)。若该值过低,则即使到达树脂界面的温度为熔点以上,时间也是短时间,因此熔融不充分,难以得到充分的密合性。此外,若加压较大,则虽然在层压金属板的性能上没有不妥,但施加于层压辊的力较大,需要设备上的强度,导致装置的大型化,因此不经济。
实施例1
以下,对本发明的实施例进行说明。
金属板的制造
作为金属板,使用镀铬钢板。对施行了冷轧、退火、调质压延的厚度0.18mm、宽度977mm的钢板在脱脂、酸洗后,进行镀铬处理,制造镀铬钢板。镀铬处理是在包含CrO3、F-、SO4 2-的镀铬浴中镀铬、中间冲洗后,在包含CrO3,F-的化学转化处理液中电解。此时,调整电解条件(电流密度·电量等)而将金属铬附着量和氢氧化铬附着量以Cr换算计分别调整为120mg/m2、15mg/m2。
罐内面侧的树脂被覆用膜的制造
以表2所示的比率将表2所示的酸成分和二醇成分聚合而得的聚酯树脂中,配合表2所示的粒子而制成树脂组合物,将该树脂组合物根据常法干燥、熔融、挤出,在冷却滚筒上冷却固化,得到未拉伸膜后,进行双轴拉伸·热固定,得到双轴取向聚酯膜(a2)。
接下来,将表1(表1-1和表1-2。以下相同)所示的各聚酯树脂、酚醛树脂、金属醇盐系化合物和/或金属螯合物、环氧树脂、聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂以表1所示的比例,溶解于甲苯和甲基乙基酮的混合溶剂中而制作涂覆液。
这里,示出包含来源于双酚酸的重复单元的聚酯树脂(i-1)的合成例。将作为酸成分的50质量份的对苯二甲酸、112质量份的间苯二甲酸、4.9质量份的双酚酸,作为多元醇成分的50质量份的2-乙基-2-丁基-1,3-丁二醇、99质量份的1,4-丁二醇、48质量份的1,4-环己烷二甲醇,0.07质量份的四丁醇钛装入2L烧瓶中,用4小时缓缓升温至220℃,使水馏出,进行酯化。使规定量的水馏出后,用30分钟进行减压聚合,直至10mmHg为止,并且将温度升温至250℃,进而,直接在1mmHg以下进行50分钟的后期聚合。接着,停止减压聚合,在氮气流下冷却至220℃,添加1.9质量份的偏苯三甲酸酐,以220℃搅拌30分钟,进行羧基改性(后加成)后,取出树脂,得到数均分子量22000、酸价5(mgKOH/g)、玻璃化转变温度30℃的聚酯树脂(i-1)。其后,冷却至60℃以下,以甲基乙基酮/甲苯=50/50的混合溶液进行稀释,得到不挥发成分为40%的聚酯树脂(i-1)溶液。
对于聚酯树脂(i-2),例如可以使用市售的聚酯树脂Vylon GK-250(数均分子量:10000,玻璃化转变温度:60℃,东洋纺织制)。在甲基乙基酮/甲苯=50/50的混合溶剂中,使Vylon GK-250混合,得到不挥发成分为40%的聚酯树脂(i-2)溶液。
对于聚酯树脂(i-3),例如可以使用市售的聚酯树脂Vylon GK-640(数均分子量:18000,玻璃化转变温度:79℃,东洋纺织制)。在甲基乙基酮/甲苯=50/50的混合溶剂中,使Vylon GK-640混合,得到不挥发成分为40%的聚酯树脂(i-3)溶液。
此外,对于酚醛树脂,可以使用市售品TD2495(对甲酚型酚醛树脂,50%正丁醇溶液,DIC株式会社制)等。
作为金属螯合物,使用市售的TC-200(辛二醇钛螯合物,Matsumoto FineChemical株式会社)等,作为金属醇盐化合物,使用市售的ZA-65(丁醇锆,Matsumoto FineChemical株式会社)。
作为环氧树脂,使用市售的EPICLON N-660(甲酚酚醛清漆型环氧树脂,50%甲基乙基酮溶液,DIC株式会社制)和市售的YL6121H(联苯型环氧树脂,三菱化学株式会社制)。
此外,作为聚胺树脂,使用市售品的EPICLON EXB-353(DIC株式会社制)。作为聚酰胺-胺树脂,使用市售品的SUNMIDE328A(Air Products Japan制)。作为聚酰胺树脂,使用市售品的POLYMIDE L-15-3(三洋化成制)。
将该涂覆液在以上述方式得到的双轴取向聚酯膜(a2)的单侧的表面,利用凹版辊涂机以成为规定的干燥膜厚的方式涂布、干燥,调整干燥后的树脂层(a1)的膜厚。干燥温度设为80~120℃的范围。
[表1-1]
[表1-2]
[表2]
罐外面侧的树脂被覆用膜的制造
以表4所示的比率将表4所示的酸成分和二醇成分聚合而得的聚酯树脂中,配合表4所示的粒子而制成树脂组合物,将该树脂组合物根据常法干燥、熔融、挤出,在冷却滚筒上冷却固化,得到未拉伸膜后,进行双轴拉伸·热固定,得到双轴取向聚酯膜(a2)。
接下来,将表3(表3-1和表3-2。以下相同)所示的各聚酯树脂、酚醛树脂、金属醇盐系化合物和/或金属螯合物、环氧树脂、聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂和着色剂以表3所示的比例,溶解于甲苯和甲基乙基酮的混合溶剂中而制作涂覆液。
这里,示出含有来源于双酚酸的重复单元的聚酯树脂(i-1)的合成例。将作为酸成分的50质量份的对苯二甲酸、112质量份的间苯二甲酸、4.9质量份的双酚酸、作为多元醇成分的50质量份的2-乙基-2-丁基-1,3-丁二醇、99质量份的1,4-丁二醇、48质量份的1,4-环己烷二甲醇,四丁醇钛0.07质量份装入2L烧瓶,用4小时缓缓升温至220℃,使水馏出,进行酯化。使规定量的水馏出后,用30分钟进行减压聚合,直至10mmHg为止,并且将温度升温至250℃,进而,直接在1mmHg以下进行50分钟的后期聚合。接着,停止减压聚合,在氮气流下冷却至220℃,添加1.9质量份的偏苯三甲酸酐,以220℃搅拌30分钟,进行羧基改性(后加成)后,取出树脂,得到数均分子量22000、酸价5(mgKOH/g)、玻璃化转变温度30℃的聚酯树脂(i-1)。其后,冷却至60℃以下,以甲基乙基酮/甲苯=50/50的混合溶液进行稀释,得到不挥发成分为40%的聚酯树脂(i-1)溶液。
对于聚酯树脂(i-2),可以使用例如市售的聚酯树脂Vylon GK-250(数均分子量:10000,玻璃化转变温度:60℃,东洋纺织制)。在甲基乙基酮/甲苯=50/50的混合溶剂中,使Vylon GK-250混合,得到不挥发成分为40%的聚酯树脂(i-2)溶液。
对于聚酯树脂(i-3),可以使用例如市售的聚酯树脂Vylon GK-640(数均分子量:18000,玻璃化转变温度:79℃,东洋纺织制)。在甲基乙基酮/甲苯=50/50的混合溶剂中,使Vylon GK-640混合,得到不挥发成分为40%的聚酯树脂(i-3)溶液。
此外,对于酚醛树脂(ii),使用市售品TD2495(对甲酚型酚醛树脂,50%正丁醇溶液,DIC株式会社制)等。
作为金属螯合物,使用市售的TC-200(辛二醇钛螯合物,Matsumoto FineChemical株式会社)等,作为金属醇盐化合物,使用市售的ZA-65(丁醇锆,Matsumoto FineChemical株式会社)。
作为环氧树脂,使用市售的EPICLON N-660(甲酚酚醛清漆型环氧树脂,50%甲基乙基酮溶液,DIC株式会社制)和市售的YL6121H(联苯型环氧树脂,三菱化学株式会社制)。
此外,作为聚胺树脂,使用市售品EPICLON EXB-353(DIC株式会社制)。作为聚酰胺-胺树脂,使用市售品SUNMIDE328A(Air Products Japan制)。作为聚酰胺树脂,使用市售品POLYMIDE L-15-3(三洋化成制)。
将该涂覆液在以上述方式得到的双轴取向聚酯膜(a2)的单侧的表面,利用凹版辊涂机以成为规定的干燥膜厚的方式涂布、干燥,调整干燥后的树脂层(a1)的膜厚。干燥温度设为80~120℃的范围。
[表3-1]
[表3-2]
[表4]
容器用树脂被覆金属板的制造
使用图1所示的金属带的层压装置,将上述所得的镀铬钢板1用金属带加热装置2加热,利用层压辊3,在镀铬钢板1的一面,层压(热熔合)罐内面侧的树脂被覆层(A),并且,在另一面层压(热熔合)罐外面侧的树脂被覆层(A)。其后,以金属带冷却装置5进行水冷,制造聚酯树脂被覆金属板。上述层压辊3设为内部水冷式,在层压中强制循环冷却水,进行膜接合中的冷却。将树脂膜层压于金属板时,将与金属板接触的界面的膜温度成为膜的熔点以上的时间设为1~35毫秒的范围内。
将根据以上方式而制造的容器用树脂被覆金属板(本发明例)的单面侧的被膜截面结构示于图2。
容器用树脂被覆金属板的评价
对于根据以上方式而制造的容器用树脂被覆金属板的特性,通过下述(1)~(7)的方法分别进行测定、评价。
(1)成型性
在容器用树脂被覆金属板涂布蜡后,冲裁直径200mm的圆板,以拉深比2.00得到浅拉深罐。接下来,对该拉深罐,以拉深比2.50进行再拉深加工。此后,根据常法进行成拱成型后,进行修整,接下来,施行缩颈-凸缘加工,将深拉伸罐成型。着眼于由此而得的深拉伸罐的缩颈部,目视观察膜的损伤程度。评价对象是罐的内外面。
(关于评分)
◎:成型后膜上未发现损伤也未发现白化的状态
○:成型后膜上未发现损伤,但发现部分白化的状态
×:罐身破裂,无法成型
(2)耐蒸煮白化性
以上述(1)的成型性评价中可成型(○以上)的罐的底部(罐外面侧)为对象。在罐内充满常温的自来水后,拧紧盖而密封。其后,将罐底部朝下,配置于蒸汽式蒸煮杀菌炉中,以125℃进行90分钟的蒸煮处理。处理后,以目视观察罐底部外面的外观变化。
(关于评分)
◎:外观无变化
○:外观产生略微的浑浊
×:外观白浊(产生白化)
(3)耐热水变色性
以上述(1)的成型性评价中可成型(○以上)的罐的底部(罐外面侧)为对象。在罐内充满常温的自来水后,拧紧盖而密封。其后,将罐底部朝下,配置于热水式蒸煮杀菌炉中,以125℃进行90分钟的蒸煮处理。处理后,以目视观察罐底部外面的外观变化。
(关于评分)
◎:外观无变化
○:外观稍有变化(产生变色)
×:外观产生变化(产生显著的变色)
(4)成型后密合性1
以上述(1)的成型性评价中可成型(○以上)的罐为对象。从罐身部切出剥离试验用的样品(宽度15mm、长度120mm)。从所切出的样品的长边侧端部起剥离膜的一部分。将剥离的膜在与剥离的方向相反的方向(角度:180°)打开,使用拉伸试验机,以30mm/min.的拉伸速度进行剥离试验,评价每15mm宽度的密合力。评价对象是罐外面的罐身部。
(评分)
◎:10.0(N)/15(mm)以上
○:5.0(N)/15(mm)以上且小于10.0(N)/15(mm)
×:小于5.0(N)/15(mm)
(5)成型后密合性2
以上述(1)的成型性评价中可成型(○以上)的罐为对象。在罐的内部填充自来水后,拧紧盖而密封。接下来,在130℃、90分钟的条件下实施蒸煮杀菌处理,从罐身部切出剥离试验用的样品(宽度15mm、长度120mm)。从所切出的样品的长边侧端部起剥离膜的一部分。将剥离的膜在与剥离的方向相反的方向(角度:180°)打开,使用拉伸试验机,以30mm/min.的拉伸速度进行剥离试验,评价每15mm宽度的密合力。评价对象是罐内面的罐身部。
(评分)
◎:10.0(N)/15(mm)以上
○:5.0(N)/15(mm)以上且小于10.0(N)/15(mm)
×:小于5.0(N)/15(mm)
(6)损伤部耐腐蚀性评价1
以上述(1)的成型性评价中可成型(○以上)的罐为对象。如图3所示,在罐外面的罐身部的2个部位,切入到达基底钢板的横切损伤。接着,对赋予了横切损伤的罐,进行300小时的按照JISZ2371的盐水喷雾试验,测定来自损伤部的单侧最大腐蚀宽度。测定方法如图4所示。评价对象是罐外面的罐身部。
(关于评分)
◎:单侧最大腐蚀宽度小于0.5mm
○:单侧最大腐蚀宽度为0.5mm以上且小于1.0mm
×:单侧最大腐蚀宽度为1.0mm以上
(7)损伤部耐腐蚀性评价2
以上述(1)的成型性评价中可成型(○以上)的罐为对象。如图3所示,在罐内面的罐身部的2个部位,切入到达基底钢板的横切损伤。接着,在罐的内部填充1.5%NaCl+1.5%柠檬酸钠的混合液后,拧紧盖而密封。接着,在130℃、90分钟的条件下实施蒸煮杀菌处理后,在温度38℃的恒温槽内,经过20天。其后,切开罐,测定来自横切损伤部的单侧最大腐蚀宽度。测定方法与(6)损伤部耐腐蚀性评价1同样。此外,评价对象是罐内面的罐身部。
(关于评分)
◎:单侧最大腐蚀宽度小于1.0mm
○:单侧最大腐蚀宽度为1.0mm以上且小于3.0mm
×:单侧最大腐蚀宽度为3.0mm以上
根据以上方式而得到的结果示于表5和表6。
[表5]
[表5]
罐内面侧的性能评价结果
[表6]
[表6]
罐外面侧的性能评价结果
由表5、表6可知,本发明例对于食品罐原材料所需的成型性、耐蒸煮白化性、耐热水变色性、成型后密合性、损伤部耐腐蚀性而言,具有良好的性能。与此相对,在本发明的范围之外的比较例的特性均差。产业上的可利用性
能够作为食品罐头原材料,以食品罐头的罐身和盖等为中心,在世界的所有市场上使用。
符号说明
1 金属板(镀铬钢板)
2 金属带加热装置
3 层压辊
4a、4b 膜
5 金属带冷却装置
Claims (17)
1.一种容器用树脂被覆金属板,其特征在于,在金属板的至少单面,具有以聚酯树脂为主要成分的多层结构的树脂被覆层(A),该树脂被覆层(A)具有树脂层(a1),该树脂层(a1)与所述金属板面密合,含有下述(i)~(v)的成分,且以聚酯树脂为主要成分;
(i)聚酯树脂:50~89质量%,
(ii)酚醛树脂:10~45质量%,
(iii)金属醇盐系化合物和/或金属螯合物:0.01~10质量%,
(iv)环氧树脂:0.5~20质量%,
(v)选自聚胺树脂、聚酰胺-胺树脂、聚酰胺树脂中的任一种以上:0.1~10质量%,
所述聚酯树脂的玻璃化转变温度在0℃以上、小于100℃。
2.如权利要求1所述的容器用树脂被覆金属板,其特征在于,所述(iv)环氧树脂是除双酚A以外的环氧树脂。
3.如权利要求1所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂的数均分子量为3000~100000,为下述(i-1)~(i-3)中的任一种以上:
(i-1)玻璃化转变温度为0℃以上且小于35℃的聚酯树脂,
(i-2)玻璃化转变温度为35℃以上且小于65℃的聚酯树脂,
(i-3)玻璃化转变温度为65℃以上且小于100℃的聚酯树脂。
4.如权利要求2所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂的数均分子量为3000~100000,为下述(i-1)~(i-3)中的任一种以上:
(i-1)玻璃化转变温度为0℃以上且小于35℃的聚酯树脂,
(i-2)玻璃化转变温度为35℃以上且小于65℃的聚酯树脂,
(i-3)玻璃化转变温度为65℃以上且小于100℃的聚酯树脂。
5.如权利要求3所述的容器用树脂被覆金属板,其特征在于,形成所述(i)聚酯树脂的各聚酯树脂的比率满足下述条件:
玻璃化转变温度为0℃以上且小于35℃的聚酯树脂:30~70质量%,
玻璃化转变温度为35℃以上且小于65℃的聚酯树脂:10~35质量%,
玻璃化转变温度为65℃以上且小于100℃的聚酯树脂:10~35质量%。
6.如权利要求4所述的容器用树脂被覆金属板,其特征在于,形成所述(i)聚酯树脂的各聚酯树脂的比率满足下述条件:
玻璃化转变温度为0℃以上且小于35℃的聚酯树脂:30~70质量%,
玻璃化转变温度为35℃以上且小于65℃的聚酯树脂:10~35质量%,
玻璃化转变温度为65℃以上且小于100℃的聚酯树脂:10~35质量%。
7.如权利要求1所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
8.如权利要求2所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
9.如权利要求3所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
10.如权利要求4所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
11.如权利要求5所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
12.如权利要求6所述的容器用树脂被覆金属板,其特征在于,所述(i)聚酯树脂是含有来源于双酚酸的重复单元的聚酯树脂。
13.如权利要求1~12中任一项所述的容器用树脂被覆金属板,其特征在于,所述(iii)金属醇盐系化合物和/或金属螯合物是钛醇盐系化合物和/或钛螯合物。
14.如权利要求1~12中任一项所述的容器用树脂被覆金属板,其特征在于,所述树脂被覆层(A)由所述树脂层(a1)和形成于该树脂层(a1)的上层的聚酯膜(a2)构成。
15.如权利要求13所述的容器用树脂被覆金属板,其特征在于,所述树脂被覆层(A)由所述树脂层(a1)和形成于该树脂层(a1)的上层的聚酯膜(a2)构成。
16.如权利要求14所述的容器用树脂被覆金属板,其特征在于,所述聚酯膜(a2)是聚酯树脂的构成单元的85质量%以上为对苯二甲酸乙二醇酯单元和/或萘二甲酸乙二醇酯单元的双轴拉伸聚酯膜,该双轴拉伸聚酯膜含有无机粒子和/或有机粒子。
17.如权利要求15所述的容器用树脂被覆金属板,其特征在于,所述聚酯膜(a2)是聚酯树脂的构成单元的85质量%以上为对苯二甲酸乙二醇酯单元和/或萘二甲酸乙二醇酯单元的双轴拉伸聚酯膜,该双轴拉伸聚酯膜含有无机粒子和/或有机粒子。
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EP2762304A1 (en) | 2014-08-06 |
US20140227529A1 (en) | 2014-08-14 |
EP2762304B1 (en) | 2016-06-08 |
CN103826846A (zh) | 2014-05-28 |
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JP5541420B2 (ja) | 2014-07-09 |
US9751283B2 (en) | 2017-09-05 |
AU2012313653A1 (en) | 2014-04-24 |
MY168765A (en) | 2018-12-04 |
AU2012313653B2 (en) | 2015-01-22 |
JPWO2013046687A1 (ja) | 2015-03-26 |
WO2013046687A1 (ja) | 2013-04-04 |
TWI483843B (zh) | 2015-05-11 |
EP2762304A4 (en) | 2015-06-03 |
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