TWI623421B - 熱可塑性樹脂包覆金屬板及以此金屬板構成之罐體與罐蓋 - Google Patents
熱可塑性樹脂包覆金屬板及以此金屬板構成之罐體與罐蓋 Download PDFInfo
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- TWI623421B TWI623421B TW103121250A TW103121250A TWI623421B TW I623421 B TWI623421 B TW I623421B TW 103121250 A TW103121250 A TW 103121250A TW 103121250 A TW103121250 A TW 103121250A TW I623421 B TWI623421 B TW I623421B
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- Prior art keywords
- thermoplastic resin
- metal plate
- polyester
- resin
- coated metal
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Abstract
本發明係關於在金屬板的至少單面上隔著聚酯系底漆施加有熱可塑性樹脂包覆而成之熱可塑性樹脂包覆金屬板,藉由使前述聚酯系底漆為10μm厚的乾燥底漆片在1000mm/分鐘之拉伸速度中的斷裂伸長度為9~200%的範圍,且MEK萃取率為3~40%的範圍,在使用於成形罐體及罐蓋的情形,可不使用特殊的熱可塑性樹脂包覆或表面處理金屬板,即可防止成形中的胴體破損、或凸緣形成部分的熱可塑性樹脂包覆剝離,具有優異的加工密合性,並且提供耐凹性及經濟性優異的罐體及罐蓋。
Description
本發明係關於熱可塑性樹脂包覆金屬板及由該熱可塑性樹脂包覆金屬板構成之罐體與罐蓋,更詳而言之,係關於具有優異的加工密合性,並且可提供耐凹性及經濟性優異的罐體及罐蓋之熱可塑性樹脂包覆金屬板。
以往以來,已知有對預先在鋁板、鍍錫鐵板或非鍍錫鐵板等的金屬板包覆熱可塑性樹脂構成之樹脂包覆金屬板,賦予抽拉加工、彎曲伸展加工(拉伸加工)及/或打薄加工等而成形之無縫罐(側面無接縫罐)。 在從樹脂包覆金屬板成形無縫罐時,必須滿足樹脂包覆的加工密合性、耐衝擊性、香味性、或耐腐蝕性等,從如此之觀點,以往樹脂包覆金屬板係使用包覆以對苯二甲酸乙二酯單元為主體的熱可塑性聚酯樹脂構成之樹脂包覆金屬板(專利文獻1)。
然而,由熱可塑性樹脂包覆金屬板構成之無縫罐由於加工的程度高,所以會有在成形中發生胴體破損或凸緣形成部分之樹脂包覆剝離的情形。又會有具有從在無縫罐的罐胴受到衝擊時的凹陷部分產生腐蝕等問題的情形。作為對於受到衝擊之情形的凹陷(凹痕)之特性迄今已知有耐凹性(dent resistance),為了使耐凹性提升,作為樹脂包覆已有人提案含有離子聚合物之聚酯樹脂或含有二聚物酸之聚酯樹脂等(專利文獻2、3)。 又為了使熱可塑性樹脂包覆的加工密合性提升,亦有人提案塗布底漆作為熱可塑性樹脂的基底(專利文獻4)、或於使用的金屬板施加如在磷酸鋯系表面處理摻混酚系樹脂之有機無機表面處理般的特殊表面處理(專利文獻5)等。 【先前技術文獻】 【專利文獻】
【專利文獻1】日本特開2001-246695號公報 【專利文獻2】日本特開平7-195618號公報 【專利文獻3】日本特開2005-104146號公報 【專利文獻4】國際公開2007/91740號 【專利文獻5】日本特開2007-76012號公報
【發明所欲解決之課題】
然而,由於如含有離子聚合物或二聚物酸等聚酯樹脂包覆的特殊聚酯樹脂包覆價格昂貴,所以在使用於通用無縫罐時於經濟性方面會有問題。又如上述所述,在塗布底漆或使用特殊的表面處理金屬板的情形,亦尚無充分滿足防止成形中的胴體破損、凸緣形成部分的樹脂剝離、或因罐胴的凹痕而導致腐蝕等全部發生者。
因此,本發明的目的係提供一種熱可塑性樹脂包覆金屬板,其可不使用特殊的熱可塑性樹脂包覆或表面處理金屬板,而有可防止成形中的胴體破損、或凸緣形成部分之熱可塑性樹脂包覆的剝離之優異的加工密合性,並且提供耐凹性及經濟性優異的罐體及罐蓋。 本發明的另一目的係提供一種熱可塑性樹脂包覆金屬板,其係無雙酚A,並且設置可提升熱可塑性樹脂包覆之加工密合性及耐凹性的底漆而構成。 【解決課題之手段】
根據本發明,可提供在金屬板的至少單面上隔著聚酯系底漆施有熱可塑性樹脂包覆而構成之熱可塑性樹脂包覆金屬板,其特徵在於:前述聚酯系底漆,當製成10μm厚的乾燥底漆片時,1000mm/分鐘之拉伸速度中的斷裂伸長度為9~200%的範圍,且MEK萃取率為3~40%的範圍。
在本發明的熱可塑性樹脂包覆金屬板中,較宜為: 1.聚酯系底漆係由含有芳香族二羧酸及碳數6~14的脂肪族二羧酸之聚酯樹脂、與硬化劑構成; 2.聚酯樹脂係含有癸二酸、與間苯二甲酸或對苯二甲酸之至少1者作為二羧酸成分,含有乙二醇、丙二醇、環己烷二甲醇之至少1者作為二醇成分,相對於聚酯樹脂全體,前述癸二酸之含量為8~25莫耳%的量; 3.聚酯樹脂係含有癸二酸、與間苯二甲酸或對苯二甲酸之至少1者作為二羧酸成分,相對於聚酯樹脂全體,前述癸二酸之含量為8~25莫耳%; 4.聚酯樹脂係含有環己烷二乙醇、與乙二醇或丙二醇之至少1者作為二醇成分,相對於聚酯樹脂全體,前述環己烷二乙醇之含量為15~40莫耳%; 5.硬化劑係前述聚酯樹脂每100質量份以5~43質量份的量摻合; 6.硬化劑為酚系硬化劑,尤其是由間甲酚所衍生之可溶酚醛樹脂型酚樹脂; 7.由聚酯系底漆構成之底漆層的厚度為0.1~4.5μm的範圍。 根據本發明,又可提供由上述熱可塑性樹脂包覆金屬板構成之罐體與罐蓋。 【發明效果】
本發明的熱可塑性樹脂包覆金屬板,熱可塑性樹脂包覆的加工密合性優異,能有效防止成形中的胴體破損、及在凸緣形成部分產生樹脂包覆的剝離。 又由本發明的熱可塑性樹脂包覆金屬板所形成的無縫罐耐衝擊性亦為優異,尤其是即使在內容物填充後受到衝擊而產生凹痕的情形,凹痕部分仍不會產生腐蝕,耐凹性優異。 再者,本發明的熱可塑性樹脂包覆金屬板由於使用不含有雙酚A的聚酯系底漆,所以衛生性亦為優異,可將該熱可塑性樹脂包覆適宜地使使用於內面樹脂包覆。
本發明的熱可塑性樹脂包覆金屬板的上述效果可由後述的實施例而明白清楚。 亦即,在本發明的熱可塑性樹脂包覆金屬板中,不發生胴體破損或凸緣形成部分的剝離,能以良好的成形性利用嚴苛的加工成形將無縫罐予以成形,而且所得之無縫罐的耐凹性亦為優異(實施例1~25)。 相對於此,在高速拉伸斷裂伸長度及MEK萃取率比上述範圍大的情形,即使得到優異的耐凹性,也會在凸緣形成部分產生樹脂包覆的剝離(比較例1),在高速拉伸斷裂伸長度及MEK萃取率比上述範圍小的情形,會發生胴體破損而無法成形無縫罐(比較例2及3)。又即使MEK萃取率滿足上述範圍,在高速拉伸斷裂伸長度比上述範圍小的情形,耐凹性變差(比較例4及5),無論是在怎樣的情形,都無法成形令人滿意的無縫罐。 【圖式簡單説明】
圖1用以說明本發明的熱可塑性樹脂包覆金屬板所使用的聚酯系底漆之高速拉伸斷裂伸長度的圖。 圖2表示本發明的熱可塑性樹脂包覆金屬板的剖面構造之一例的圖。
在本發明的熱可塑性樹脂包覆金屬板中,滿足下列特性係其重要特徵:位在熱可塑性樹脂包覆及金屬板之間的聚酯系底漆,當製成10μm厚的乾燥底漆片時,1000mm/分鐘的拉伸速度的斷裂伸長度為9~200%的範圍,尤其是9~80%的範圍,及MEK萃取率為3~40%的範圍,尤其是4~25%的範圍。 在本發明中,發現:藉由使聚酯系底漆滿足上述特性,發現不會發生在以往對熱可塑性樹脂包覆金屬板施予抽拉加工、彎曲伸展加工(拉伸加工)及/或打薄加工等嚴苛的成形加工時所產生的胴體破損或凸緣形成部的樹脂包覆的剝離,而且施加該嚴苛的成形加工構成之無縫罐能展現優異的耐凹性。 亦即,斷裂伸長度為比上述範圍小的情形,會有耐凹性下降之虞,在比上述範圍大的情形,會有凸緣形成部發生剝離之虞。又MEK萃取率為比上述範圍小的情形,會有底漆的伸長不足,而有胴體破損之虞,在比上述範圍大的情形,會有凸緣形成部發生剝離之虞。
圖1係表示本發明的聚酯系底漆當製成10μm厚的乾燥底漆片時, 1000mm/分鐘的拉伸速度的負荷-伸長度曲線,從圖1可知由本發明使用的聚酯系底漆構成之層,相較於內面包覆樹脂(實施例1的內面聚酯樹脂)或以往的聚酯系底漆(比較例5),斷裂伸長度較大。為此,由本發明使用的聚酯系底漆構成之層係耐衝擊性或加工密合性優異,即使在使用通用的熱可塑性樹脂包覆且因衝擊而在該包覆產生龜裂,底漆層仍不會產生缺損而可保護金屬板,即使在填充酸性飲料等腐蝕性高的內容物的情形,仍可維持優異的耐腐蝕性。 又藉由使由本發明使用的聚酯系底漆構成之層的MEK萃取率為上述範圍內,底漆層在能得到上述斷裂伸長度之範圍充分地硬化,即使在接受嚴苛的成形加工之情形,亦可防止胴體破損或凸緣形成部的樹脂包覆的剝離。
(聚酯系底漆) 用於本發明的熱可塑性樹脂包覆金屬板之聚酯系底漆,其重要的是具有前述之範圍的斷裂伸長度及MEK萃取率,就具有如此特性的聚酯系底漆而言,並不限定於此,可列舉由含有芳香族二羧酸及碳數6~14、尤其是碳數8~12的脂肪族二羧酸之聚酯樹脂、與硬化劑而構成者。
[聚酯樹脂] 就芳香族二羧酸而言,可列舉對苯二甲酸、間苯二甲酸、鄰苯二甲酸、萘二羧酸等,就碳數6~14的脂肪族二羧酸而言,可列舉己二酸、庚二酸、辛二酸、壬二酸、癸二酸等。上述碳數6~14的脂肪族二羧酸,相對於聚酯樹脂全體,含量為8~25莫耳%的範圍較理想。在脂肪族二羧酸含量較上述範圍少的情形,拉伸斷裂伸長度變小,無法提升耐凹性,在脂肪族二羧酸含量較上述範圍多的情形,拉伸斷裂伸長度變得過大,而會有凸緣形成部的剝離發生之虞。 在本發明中,就二羧酸成分而言,含有癸二酸、與間苯二甲酸或對苯二甲酸之至少一者為適宜。 癸二酸係相對於聚酯樹脂全體,含量為8~25莫耳%、尤其是9~17莫耳%的量為特別適宜。 又含有上述含量的癸二酸的同時,相對於聚酯樹脂全體(將二羧酸成分的總量設為50莫耳%的情形),含有對苯二甲酸0~42莫耳%、尤其是0~20莫耳%、含有間苯二甲酸0~42莫耳%、尤其是13~41莫耳%為適宜。 尤其是在本發明中,二羧酸係由癸二酸、對苯二甲酸、間苯二甲酸的3成分構成為最適宜,相對於聚酯樹脂全體(將二羧酸成分的總量設為50莫耳%的情形),含量為癸二酸9~17莫耳%、對苯二甲酸1~20莫耳%、間苯二甲酸13~40莫耳%的範圍的量為適宜。
就二醇成分而言,並未特別限定,可為從乙二醇、丙二醇(1,2-丙二醇)、1,3-丙二醇、1,4-丁二醇、1,2-丁二醇、1,3-丁二醇、2-甲基-1,3-丙二醇、新戊二醇、1,5-戊二醇、1,6-己二醇、3-甲基-1,5-戊二醇、2-乙基-2-丁基-1,3-丙二醇、2,4-二乙基-1,5-戊二醇、1-甲基-1,8-辛二醇、3-甲基-1,6-己二醇、4-甲基-1,7-庚二醇、4-甲基-1,8-辛二醇、4-丙基-1,8-辛二醇、1,9-壬二醇等的脂肪族二醇、二乙二醇、三乙二醇、聚乙二醇、聚丙二醇、聚伸丁二醇等的醚二醇類;1,4-環己烷二甲醇、1,3-環己烷二甲醇、1,2-環己烷二甲醇、三環癸烷二醇類、氫化雙酚類等的脂環族多元醇;三羥甲基丙烷、三羥甲基乙烷、季戊四醇等的3元以上的多元醇等之1種、或組合2種以上而使用。 在本發明中,二醇成分係含有環己烷二乙醇、與乙二醇或丙二醇之至少一者為適宜。 環己烷二乙醇係相對於聚酯樹脂全體(將二醇成分的總量設為50莫耳%的情形),含量為15~40莫耳%、尤其是23~37莫耳%的量為特別適宜。 又含有上述含量的環己烷二乙醇的同時,相對於聚酯樹脂全體(將二醇成分的總量設為50莫耳%的情形),含有乙二醇0~35莫耳%、丙二醇0~35莫耳%為適宜。 尤其是在本發明中,二醇成分係由乙二醇、丙二醇、環己烷二乙醇的3成分構成為最適宜,相對於聚酯樹脂全體(將二醇成分的總量設為50莫耳%的情形),含量為環己烷二甲醇15~40莫耳%、乙二醇1~20莫耳%、丙二醇1~20莫耳%範圍的量為適宜。 聚酯樹脂係數平均分子量為3000~100000、酸價為0~50mgKOH/g、玻璃轉移溫度為-20~100℃的範圍為佳。
[硬化劑] 就用於本發明之聚酯系底漆中使用的硬化劑而言,可使用由使用具有能與聚酯樹脂的官能基例如羧基、或進一步能與氫氧基反應之官能基的硬化性樹脂,例如酚系樹脂、異氰酸酯化合物、胺基系樹脂等構成之硬化劑。此等樹脂可單獨或亦可組合2種以上的使用。 在本發明,上述硬化劑之中亦可適當使用由間甲酚所衍生之可溶酚醛樹脂型酚樹脂。 由間甲酚所衍生之可溶酚醛樹脂型酚樹脂,較佳係含有50質量%以上之間甲酚的酚化合物與甲醛的共聚物。 除了前述酚化合物外,由間甲酚所衍生之酚醛樹脂可於原料中,以小於50質量%的範圍添加至不使性能降低的程度,就酚化合物而言,例如可列舉:鄰甲酚、對甲酚、對第三丁基苯酚、對乙基苯酚、2,3-二甲苯酚、2,5-二甲苯酚等的2官能的酚化合物。 酚醛樹脂可藉由以福馬林、多聚甲醛甲醛或三□烷等將含有酚化合物50質量%以上之酚醛樹脂予以羥甲基化而得到。
[底漆的調製] 用於本發明之聚酯系底漆,可藉由聚酯樹脂每100質量份,使硬化劑以5~43質量份、尤其是10~25質量份的量溶解於有機溶劑中進行摻混而調製。 此時,作為硬化觸媒之酸觸媒,宜相對於全部樹脂成分(合併聚酯樹脂與硬化劑者)100質量份之含量為0.01質量份~3質量份較佳。就酸觸媒而言,例如可列舉:硫酸、對甲苯磺酸、十二基苯磺酸、萘磺酸、二壬基萘磺酸、二壬基萘二磺酸、樟腦磺酸、磷酸、及將此等予以胺中和 (以胺化合物中和一部分或全部)而成者等,可使用來自此等之中的一種或併用二種以上。此等酸觸媒之中,從與樹脂的相溶性、衛生性之面來看,十二基苯磺酸、及將十二基苯磺酸予以胺中和而成者為特佳。
就有機溶劑而言,具有聚酯樹脂的可塑效果且具有兩親媒性者為佳,例如可列舉:乙醇、正丙醇、異丙醇、正丁醇、異丁醇、第二丁醇、第三丁醇、異戊醇、第二戊醇、第三戊醇、正己醇、環己醇等的醇類;甲基乙基酮、甲基異丁基酮、乙基丁基酮等的酮類;四氫呋喃、二□烷、1,3-二氧戊環等的環狀醚類;乙二醇、乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丁基醚、乙二醇單乙基醚乙酸酯、二乙二醇、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、二乙二醇乙基醚乙酸酯、丙二醇、丙二醇單甲基醚、丙二醇單丁基醚、丙二醇甲基醚乙酸酯等的二醇衍生物;3-甲氧基-3-甲基丁醇、3-甲氧基丁醇、乙腈、二甲基甲醯胺、二甲基乙醯胺、二丙酮醇、乙醯乙酸乙酯等。 又,然後,可按照需要將溶解聚酯樹脂時所使用的有機溶劑進行加熱餾去、或減壓餾去。就餾去有機溶劑的方法而言,為了抑制酚樹脂因有機溶劑餾去中的熱而縮合,宜在100℃以下的減壓餾去,進一步較佳為80℃以下的減壓餾去。在該情形,若將有機溶劑全量餾去,可得到完全水系的樹脂組成物,但考量分散體的安定性、成膜性等,宜含有3質量%~20質量%的有機溶劑。
底漆可藉由輥塗法、噴塗法、浸漬法、刷毛塗抹法等的以往眾所周知的方法而適用,底漆塗膜的烙印條件係100~300℃、5秒~30分鐘為佳,更佳為在150~270℃、15秒~15分鐘。 又底漆塗膜的膜厚係以乾燥膜厚為0.1~4.5μm、尤其是在0.4~2.7μm的範圍為佳。在底漆塗膜的厚度比上述範圍薄的情形,會有無法得到所期望的耐凹性之虞,另一方面,在比上述範圍厚的情形,底漆的烙印所需要的時間變長且生產性變差,並且烙印變得不充分地時,會有MEK萃取率變大、凸緣形成部的剝離發生之虞。 此外,當底漆塗膜較厚實,由於耐腐蝕性提升,所以藉由在上述範圍內控制底漆塗膜,例如即使是以高濃度含有食鹽的高腐蝕性酸性飲料也可以應付。
(熱可塑性樹脂包覆) 在本發明的熱可塑性樹脂包覆金屬板中,就隔著上述的底漆對金屬板所施用的熱可塑性樹脂而言,並未特別限定,例如可列舉:由結晶性聚丙烯、結晶性丙烯-乙烯共聚物、結晶性聚丁-1-烯、結晶性聚4-甲基戊-1-烯、低-、中-、或高密度聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、乙烯-丙烯酸乙酯共聚物(EEA)、離子交聯烯烴共聚物(離子聚合物)等的聚烯烴類;聚苯乙烯、苯乙烯-丁二烯共聚物等的芳香族乙烯共聚物;聚氯乙烯、偏二氯乙烯樹脂等的鹵化乙烯聚合物;如丙烯腈-苯乙烯共聚物、丙烯腈-苯乙烯-丁二烯共聚物的腈聚合物;如耐綸6、耐綸66、鄰或對苯二甲基己二醯胺的聚醯胺類;聚對苯二甲酸乙二酯(PET)、聚對苯二甲酸伸丁酯等的聚酯類;各種聚碳酸酯;聚甲醛等聚縮醛類等的熱可塑性樹脂構成的塑膠膜。
在本發明,上述熱可塑性樹脂之中,尤其可適宜使用聚酯樹脂。 就可適宜使用的聚酯樹脂而言,可為均聚對苯二甲酸乙二酯,可為以酸成分為基準含有30莫耳%以下的量的對苯二甲酸以外的酸成分,又可以醇成分為基準含有30莫耳%以下的量的乙二醇以外的醇成分之共聚合聚酯單體或彼等的摻混物。 就對苯二甲酸以外的酸成分而言,可列舉間苯二甲酸、萘二羧酸、環己烷二羧酸、P-β-氧基乙氧基苯甲酸、二苯氧基乙烷-4,4’-二羧酸、5-磺基間苯二甲酸鈉、六氫對苯二甲酸、丁二酸、己二酸、癸二酸、十二烷二酸、二聚物酸、偏苯三甲酸、苯均四酸等。 又就乙二醇以外的醇成分而言,可列舉丙二醇、1,4-丁二醇、新戊二醇、1,6-己二醇、二乙二醇、三乙二醇、環己烷二甲醇、雙酚A的環氧乙烷加成物、三羥甲基丙烷、季戊四醇等的二醇成分。 特佳為聚對苯二甲酸乙二酯、間苯二甲酸共聚合聚對苯二甲酸乙二酯、萘二羧酸共聚合聚對苯二甲酸乙二酯、聚對苯二甲酸乙二酯/聚對苯二甲酸丁二酯的摻混物之任一者。
聚酯樹脂應具有薄膜形成範圍的分子量,作為溶劑,使用酚/四氯乙烷混合溶劑所測定的固有黏度[η]為0.5以上、尤其是在0.52~0.70的範圍的話,從對於腐蝕成分的隔絕性或機械性質之觀點而言為佳,又玻璃轉移點為50℃以上、尤其是在60℃~80℃的範圍為佳。 聚酯薄膜中,可藉由眾所周知的配方摻混其本身眾所周知的薄膜用摻混劑、潤滑劑、抗結塊劑、顏料、各種抗靜電劑、抗氧化劑等。
熱可塑性樹脂可為形成薄膜後,以熱接著法包覆於金屬板者,亦可為藉由使用擠壓機將經加熱熔融之熱可塑性樹脂擠壓成薄膜狀,直接包覆於金屬板上之擠壓疊層法得到者。 又在形成熱可塑性樹脂薄膜後進行包覆的情形,薄膜可被延伸,但從成形加工性及耐凹性之觀點而言,未延伸薄膜為佳。 聚酯薄膜的厚度一般係在5~40μm的範圍為佳。 熱可塑性樹脂包覆可為二層構成,在該情形,下層係以對苯二甲酸乙二酯單元作為主體,含有1~30莫耳%的量的間苯二甲酸、萘二羧酸等的至少一種且在作為上層之聚酯薄膜中由其量比上述酸成分的摻合量多的聚酯樹脂形成的話,從加工密合性、耐凹性等之觀點而言為特別適宜。
(金屬板) 本發明中,就隔著前述聚酯系底漆而形成熱可塑性樹脂包覆之金屬板而言,可使用以往樹脂包覆金屬板中所使用的冷間壓延鋼板、表面處理鋼板、純鋁板及鋁合金板等的鋁板、或對此等施加各種表面處理構成之表面處理鋁板。 就表面處理鋼板而言,可列舉為將冷間壓延鋼板進行退火後調質壓延或經二次冷間壓延之鋼板,亦即對SR材或DR材進行鍍鋅、鍍錫、鍍鎳、電解鉻酸處理、鉻酸處理、磷酸處理等的表面處理之一種或二種以上者。 又就表面處理鋁板而言,可列舉對鋁板的表面進行磷酸鉻酸鹽處理、磷酸鋯處理、磷酸處理等的無機表面處理、或聚丙烯酸、酚樹脂、鞣酸、伊康酸、膦酸等的有機表面處理、及組合此等之有機無機複合表面處理。 在本發明,尤其適宜使用施加有組合磷酸鋯處理、磷酸鉻酸鹽處理、酚醛樹脂與磷酸鋯處理之處理的表面處理鋁板、或未施加表面處理的鋁板。 金屬板的厚度係因金屬的種類、疊層材料的用途或尺寸而不同,但一般係具有0.10至0.50mm的厚度為佳,其中在表面處理鋼板的情形具有0.10至0.30mm的厚度為佳,又在鋁板的情形具有0.15至0.40mm的厚度為佳。
(熱可塑性樹脂包覆金屬板及其製法) 在本發明的熱可塑性樹脂包覆金屬板中,於金屬板形成熱可塑性樹脂包覆可以任意的手段來進行,例如可預先用以往眾所周知的方法作成熱可塑性樹脂薄膜,將其疊層於塗佈有聚酯系底漆之金屬板,或可將底漆塗佈於熱可塑性薄膜後疊層於金屬板,或可藉由在塗佈有聚酯系底漆的金屬板上,利用擠壓塗布直接形成熱可塑性樹脂薄膜而進行疊層。
圖2係表示本發明的熱可塑性樹脂包覆金屬板的剖面構造之一例,該熱可塑性樹脂包覆金屬板1係由金屬板2、由作成容器時設置在內面側之側的聚酯系底漆構成之層3a、熱可塑性樹脂層4a構成。圖2所示之具體例中,可在金屬板2的容器外面側,隔著由聚酯系底漆構成之層3b形成有熱可塑性樹脂層4b,但在本發明的熱可塑性樹脂包覆金屬板中,熱可塑性樹脂包覆只要形成在至少應為罐體或罐蓋的內面之面即可。
(罐體及其製法) 本發明的由熱可塑性樹脂包覆金屬板構成之罐體可藉由以往眾所周知的成形法,以上述的熱可塑性樹脂包覆面為罐內面側的方式進行製罐。 本發明的熱可塑性樹脂包覆金屬板中,由於熱可塑性樹脂包覆具有優異的加工密合性,所以能不產生胴體破損或凸緣形成部的樹脂包覆的剝離而成形藉由抽拉加工、拉伸/深拉伸加工、拉伸/打薄加工、拉伸/彎曲伸展加工・打薄加工等的嚴苛加工所成形的無縫罐。 無縫罐的側壁部係藉由熱可塑性樹脂包覆金屬板的抽拉-再抽拉加工所致的彎曲伸展或進一步藉由打薄加工,而被薄化成熱可塑性樹脂包覆金屬板的原來厚度的20至95%、尤其是25至85%的厚度為佳。 所得到的無縫罐係賦予至少一段的熱處理,除去因加工所產生的薄膜的殘留變形,並使加工時所使用的滑劑從表面揮散,並進一步使印刷於表面的印刷印墨乾燥硬化。熱處理後的容器經急冷或放冷後,根據希望,賦予一段或多段的縮幅加工並進行凸緣加工,而作成捲封用的罐。
(罐蓋及其製法) 由本發明的熱可塑性樹脂包覆金屬板構成之罐蓋係除了上述的成形為熱可塑性樹脂包覆面為罐蓋內面側以外,可藉由以往眾所周知的罐蓋製法而進行成形。 又罐蓋的形狀可採用設置有為了形成內容物注出用開口的刻痕(score)及開啟用的拉環(tab)之易開罐(easy open ends)等的以往眾所周知的形狀。 【實施例】
(實施例1) [底漆的調製] 以下表示本發明的聚酯系底漆及比較用底漆的調製例。文中及表1中的「份」係表示「質量份」。 ・聚酯樹脂的調製 將對苯二甲酸110份、間苯二甲酸194份、癸二酸115份、乙二醇34份、丙二醇62份、環己烷二甲醇265份、四丁氧鈦0.16份進料至2L的四口燒瓶,歷時4小時緩緩地升溫至220℃,一邊使水餾去一邊進行酯化反應。餾去規定量的水後,歷時30分鐘進行減壓初期聚合至10mmHg並且將溫度升溫至250℃,進一步直接在1mmHg以下進行50分鐘後期聚合,停止減壓聚合,取出樹脂而得到聚酯樹脂。將所得到的聚酯樹脂成分的莫耳比示於表1。 ・硬化劑的調製 加入間甲酚100份、37質量%福馬林水溶液180份、及氫氧化鈉1份,在60℃反應3小時後,於減壓下在50℃脫水1小時。接著,加入正丁醇100份,在110℃進行4小時反應,在反應結束後,過濾所得到的溶液,以調製由間甲酚所衍生之可溶酚醛樹脂型酚樹脂。 ・底漆的調製 將所得到的聚酯樹脂100份與溶劑加入燒瓶,進行加溫,在100℃以下一邊充分攪拌一邊使之溶解。在完全溶解後冷卻至室溫,一邊充分攪拌一邊添加規定的可溶酚醛樹脂型酚樹脂15份、與硬化觸媒2份,以調製聚酯系底漆。硬化觸媒係使用(日本CYTECH Industries(股)製Cycat 602)。
[熱可塑性樹脂包覆金屬板的製造] 使用Nihon Parkerizing公司製「Alodine N-405」對鋁合金JIS3104的厚度0.28mm板的兩面進行化成處理,形成由磷酸鋯構成之表面處理皮膜,以製作表面處理金屬板。在該表面處理金屬板成為罐內面側之面,輥塗上述聚酯系底漆,且在250℃進行烙印,形成0.9μm的厚度的底漆後將其捲繞。 一邊回捲該底漆包覆表面處理金屬板,一邊以擠壓塗布法將熱可塑性樹脂熱疊層於兩面。此外,罐內面側的熱可塑性樹脂包覆係使用由下層為8μm厚的含有15莫耳%間苯二甲酸的聚對苯二甲酸乙二酯(以下,標示記載為「PET/IA15」)及上層為8μm厚的PET/IA2構成之二層構造的熱可塑性樹脂包覆。罐外面側的熱可塑性樹脂包覆係作成下層為7μm厚的PET/IA15及上層為3μm厚的PET/IA7.5的二層構造之熱可塑性樹脂包覆。然後,在內外面塗佈噴蠟(Glamour Wax)後捲繞,以製作熱可塑性樹脂包覆金屬板。
[無縫罐的成形] 切料該熱可塑性樹脂包覆金屬板,進行抽拉打薄加工,將開口端修整成規定尺寸,在200℃以30秒進行熱定型、印刷、塗布精面清漆,在200℃以40秒進行烙印、將開口端縮頸並進行凸緣化,以製作罐胴211徑且頸部206徑的容量為500ml之無縫罐。
(實施例2~24、比較例1~5) 除了將底漆的組成、底漆膜厚、及使用的金屬板(表面處理物質)變更為如表1所示以外,與實施例1同樣地製作熱可塑性樹脂包覆金屬板及無縫罐。 針對實施例2~24、比較例1~5的底漆,與前述的合成例同樣地,藉由變更聚酯樹脂成分的單體的量,以調製表1所示之各種聚酯樹脂。又,以成為表1所示之聚酯樹脂與硬化劑比的方式來調製底漆。實施例23的硬化劑係使用封端異氰酸酯化合物(EPOCK Degussa Japan公司製VESTANAT B1370),實施例24的硬化劑係使用胺基系樹脂(日本CYTECH Industries公司製Mycoat 506)。 又,實施例21的磷酸鉻酸鹽系表面處理係以Nihon Parkerizing公司製ALKROM K702進行化成處理,實施例22則並無進行表面處理。
(實施例25) 除了以常用方法的陰極電解法對厚度0.185mm的冷間壓延低碳鋼板的兩面進行鉻酸處理以外,與實施例1同樣地製作熱可塑性樹脂包覆金屬板,使用與實施例1同樣的方法製作罐胴202徑、頸部200徑之容量為200ml的無縫罐,並與實施例1同樣地進行評價。
(評價方法) [成形性(耐胴體破損性)] 以上述抽拉打薄加工成形500罐,胴體破損發生1罐以上的情形評為×,無胴體破損的情形評為○。
[凸緣相當部剝離性(加工密合性)] 針對上述的熱定型後無縫罐的內面調查開口端(修整部),以放大鏡測定從開口端起的金屬露出長度(剝離部長度)。調查20罐,就20罐中的最大剝離長度,用以下的基準來賦予評分。 ◎:最大剝離長度為零。 ○:最大剝離長度小於0.1mm。 △:最大剝離長度為0.1mm~小於0.5mm。 ×:最大剝離長度為0.5mm以上。
[下部凹痕耐腐蝕性] 在所得到的無縫罐中,於5℃將市售的可口可樂(註冊商標)重新包裝,二重捲封(double seaming)留置式拉環蓋,以35℃的熱水加熱至室溫,在5℃保管庫保管1天,並且於5℃對於罐緣上端起2mm上的罐胴落下塊件而賦予罐周方向長度約15mm的凹陷。然後,在37℃正立保管6個月後開罐,從罐內面側調查凹痕部的腐蝕狀態。用以下的基準來賦予評分。 ◎:凹痕部無腐蝕。 ○:凹痕部腐蝕為斑點的,斑點為2個以下。 △:斑點腐蝕為3個以上。 ×:凹痕部為全面腐蝕。
[高速拉伸斷裂伸長度] 以刮棒塗佈機將所得到的聚酯系底漆塗佈於由Teflon(註冊商標)構成之片,使乾燥後的底漆厚度成為10μm,在185℃進行10分鐘的烙印。從由Teflon(註冊商標)構成之片剝離其底漆膜,以製作乾燥底漆片。將此片切出長度35mm寬15mm的條,卡緊在拉伸試驗機上,使測定部長度成為25mm。拉伸速度係以1000mm/分鐘的高速進行。進行測定3次並求得斷裂伸長度(%)的平均値。測定係在25℃的恆溫室進行。斷裂伸長度(%)的計算式係如下所示。 斷裂伸長度(%)=(斷裂時的伸長量(mm)×100)/測定部長度(mm)
[MEK萃取率] 對形成熱可塑性樹脂包覆之前的底漆包覆表面處理金屬板,以下述的方式測定MEK萃取率(%)。 從底漆包覆表面處理金屬板切出10cm×10cm尺寸的試驗板,測定重量(A),浸漬在煮沸的甲基乙基酮(MEK)中60分鐘後,取出底漆包覆表面處理金屬板並乾燥,測定重量(B)。然後,以濃硫酸脫膜底漆層,測定表面處理金屬板的重量(C)。將以下的計算値當作MEK萃取率(%)。 MEK萃取率(%)=(A ― B)×100/(A ― C)
【產業利用性】
本發明的熱可塑性樹脂包覆金屬板由於即使被賦予拉伸/打薄加工、拉伸/彎曲伸展加工・打薄加工等的嚴苛加工,也不會產生胴體破損或樹脂包覆的剝離等,所以可適合利用於藉由此等加工所成形之無縫罐的成形。 而且本發明的熱可塑性樹脂包覆金屬板中,隔著高速拉伸時的斷裂伸長度高的聚酯系底漆塗膜形成有熱可塑性樹脂包覆,且藉由通用的熱可塑性樹脂形成包覆,即使受到衝擊而在該包覆產生龜裂的情形,由於底漆塗膜無缺損,具有優異的耐凹性及耐腐蝕性,所以可適合利用於填充酸性飲料等腐蝕性高的內容物之罐體及罐蓋。
1‧‧‧熱可塑性樹脂包覆金屬板
2‧‧‧金屬板
3a、3b‧‧‧聚酯系底漆層
4a、4b‧‧‧熱可塑性樹脂層
2‧‧‧金屬板
3a、3b‧‧‧聚酯系底漆層
4a、4b‧‧‧熱可塑性樹脂層
Claims (7)
- 一種熱可塑性樹脂包覆金屬板,係在金屬板的至少單面上隔著聚酯系底漆施有熱可塑性樹脂包覆而構成,其特徵係:該聚酯系底漆係由聚酯樹脂、與硬化劑構成,該聚酯樹脂含有癸二酸、與間苯二甲酸或對苯二甲酸之至少1者作為二羧酸成分,且相對於聚酯樹脂全體,該癸二酸之含量為8~25莫耳%,該硬化劑,就該聚酯樹脂每100質量份以5~43質量份的量摻合;該熱可塑性樹脂包覆係聚酯樹脂包覆;該聚酯系底漆,當製成10μm厚的乾燥底漆片時,1000mm/分鐘之拉伸速度的斷裂伸長度為9~200%的範圍,且MEK萃取率為3~40%的範圍。
- 如申請專利範圍第1項之熱可塑性樹脂包覆金屬板,其中該聚酯樹脂係含有環己烷二乙醇、與乙二醇或丙二醇之至少1者作為二醇成分,且相對於聚酯樹脂全體,該環己烷二乙醇之含量為15~40莫耳%。
- 如申請專利範圍第1或2項之熱可塑性樹脂包覆金屬板,其中該硬化劑為酚系硬化劑。
- 如申請專利範圍第1或2項之熱可塑性樹脂包覆金屬板,其中該硬化劑係由間甲酚所衍生的可溶酚醛樹脂型酚樹脂。
- 如申請專利範圍第1或2項之熱可塑性樹脂包覆金屬板,其中由該聚酯系底漆構成之底漆層的厚度為0.1~4.5μm的範圍。
- 一種罐體,其係由如申請專利範圍第1~5項中任一項之熱可塑性樹脂包覆金屬板構成。
- 一種罐蓋,其係由如申請專利範圍第1~5項中任一項之熱可塑性樹脂包覆金屬板構成。
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EP3012100A1 (en) | 2016-04-27 |
JP2015003450A (ja) | 2015-01-08 |
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