CN85109294A - 在聚酯容器上粘贴共聚酯阻挡层的方法 - Google Patents
在聚酯容器上粘贴共聚酯阻挡层的方法 Download PDFInfo
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Abstract
聚酯或共聚酯容器是用一种热活化的高阻挡性共聚酯标层粘贴在容器侧壁上制成的。生产高阻挡性容器的方法是:将一阻挡标层有效地贴附在中空聚酯或共聚酯壳体的外壁上,制造该容器的方法包括挤出吹塑法,注射吹塑法,取向吹塑或取向吹塑热定型法,以及利用一种可热活化的高阻挡性共聚酯树脂作粘合剂,通过“内模”(“in-mold”)技术把阻挡性标层贴上的方法。
Description
本发明是在聚酯容器的侧壁用一种高阻挡性共聚酯粘合剂粘合一个阻挡标层而制成高阻挡性容器的方法。更具体地说,本发明是把高阻挡性共聚酯阻挡标层粘贴在聚酯容器侧壁,采用高阻挡性共聚酯树脂作粘合剂,使标层和容器间形成有效的阻挡和牢固的粘合。
聚酯塑料容器的阻挡性质很重要。例如:如果氧气的渗透性可影响包装品的味道,颜色和/或者其他方面产品质量的话,那么氧气渗透性质可决定包装品的贮存期限。对于充碳酸氣的饮料,二氧化碳的渗透性决定着容器的碳酸氣损失率,因此也决定着产品的贮存期限。
自从聚对苯二甲酸乙二酯(PET)塑料饮料瓶进入市场以来,人们一直在努力改善PET容器的阻挡性能,以便在用小尺寸容器包装食品、酒类和碳化饮料方面扩大PET的使用。
改善聚酯容器的二氧化碳和氧气渗透性有几种不同的方法:即取向法、热定形法、阻挡涂层法以及阻挡贴标层法(barrierlabeling)。
什么是阻挡标层?阻挡标层的定义是“由低渗透或不渗透性的物质组成的标层,这种标层用一种高阻挡性粘合剂粘附在塑料容器上,使容器具有改善了的阻挡性能”。
为了更好的理解阻挡标层的概念,先看一个现有技术中采用的金属箔标层(图1所示)不太有效的例子。在这种情况下,对充碳酸氣的饮料,二氧化碳氣体从塑料容器内通过侧壁渗透,进入典型的粘合层和纸禙,这两者对二氧化碳的阻挡作用都很差。铝箔对气体是不可渗透的,但二氧化碳可透过粘合剂和纸扩散到瓶外。
另一方面,另一种能有效阻挡标层的实例示于图2。在此情况下把铝箔粘贴到容器侧壁的粘合剂形成牢固的粘合,它对CO2也是一种很好的阻挡层。因此,随着CO2从内部通过瓶壁渗透,缓慢地到达铝箔而停止。这样,CO2氣体损失率就明显降低。应该强调的是这种粘合剂应有足够的粘合强度,以经得住铝箔和粘附层之间聚集的CO2氣体的压力。如果这种粘结强度不够大,那么它将产生气泡,最终将标层剥离。
打算用于食品包装的阻挡层标层,除了应提供良好的氧气阻挡之外,还必须能经得起热充曝(hot fill exposure)而不致剥离。目前用于普通标层的热熔胶粘合剂,通常是在低温下(一般在70℃以下)活化,因此不适用于充热和蒸煮应用。所以对于充CO2饮料和食品使用可接受的的阻挡标层,粘结胶或粘合剂必须满足以下要求:
1、对气体特别是对CO2和O2具有低渗透性;
2、对于因CO2压力而产生气泡或剥离现象有抵抗作用;
3、在较高温度下稳定,以便能用于充热和蒸煮;
4、用商业上实用的方法,可容易地把阻挡标层粘贴在容器上。
本发明提供了生产塑料容器的多种方法和材料,这种容器实际上可克服前述的问题并满足上面规定的对有效阻挡标层的要求。本发明利用高阻挡性共聚酯作阻挡粘合剂。这种共聚酯树酯可显示宽范围的活化温度,这使它适合于各种不同的成型加工条件,如定向吹塑,定向吹塑热定型,挤出吹塑以及模内标定(in-mold labeling)。高阻挡性共聚酯与聚酯,特别是与聚对苯二甲酸乙二酯(PET)是相容的,因此,PET与高阻挡性粘结胶之间的粘合力强。本发明的细节如下:
本发明的目的在于提供一种生产高阻挡层容器的方法,这种容器为聚酯和共聚酯中空容器。其外侧壁带有有效的阻挡层标层。其制造方法包括挤出吹塑法,注塑吹塑法,定向吹塑法或者定向吹塑热定形法,并用热活化的高阻挡性共聚酯树脂作粘合剂,通过内模技术把阻挡标层贴附在容器上。
本发明的目的是提供一种加工方法,以及按此方法生产的制品。方法包括:用热活化的高阻挡性共聚酯材料把高阻挡性标层粘贴在聚酯和共聚酯容器上,用这种高阻挡性共聚酯材料容易而有效地将标层贴到容器侧壁上,生产方法包括热定型,制造容器时一次成型,或用挤出或注塑型坯定向吹塑法和内模塑贴标法制造容器。
本发明的目的是提供一种方法及用此法制造的产品,把高阻挡性标层加在聚酯和共聚酯容器如PET饮料瓶的侧壁上,使用高阻挡性共聚酯标层或其它阻挡性标层,并用高阻挡性共聚酯树脂粘贴标层,高阻挡性共聚酯树脂的粘合特性是在容器加工过程中能被加热活化,这种热活化能使阻挡标层和侧壁之间产生强而有效的高阻挡粘合层,并能降低容器侧壁的氧气和二氧化碳气的渗透性。
以上目的和其它目的,将可从下面的说明部分和图中看到,其中:
图1是按照现有技术,在容器侧壁上贴附标层的局部放大剖面图。
图2是根据本发明,利用高阻挡性共聚酯粘合剂把高阻挡标层粘贴到聚酯容器侧壁上的剖面放大图。
图3是PET瓶的正视图,在瓶体周围外粘贴高阻挡标层。
图4是透视图,表示出一个用热活性高阻挡共聚酯粘合剂粘贴的高阻挡性标层,它是在吹塑模中使瓶紧对着标层用内模塑法制得的。
本发明提供一种方法或生产高阻挡塑料容器的方法,这种聚酯中空容器的外部聚酯侧壁表面上贴附有阻挡性标层。此方法包含下面几步:
A,将涂有高阻挡性共聚酯的标层贴附到容器的聚酯外侧壁上并在此处形成标记层。
B,把标层和容器加热到合适的活化温度,使粘合剂软化到足以使标层粘附在聚酯侧壁上,并在标层和瓶壁之间边界区域形成有效的粘合。
在本发明的最佳实施方案中,高阻挡性标层由一个低渗透性膜和涂于膜上的高阻挡性共聚酯粘合剂组成。这种标层粘贴在取向的PET容器的壳体上,容器为一种饮料瓶,其壁厚约8到20密耳(mils),PET的I.V.为0.65~0.90。
如图1所示,低渗透性薄膜3由纸层6垫背粘结于容器侧壁4,用一个低阻挡粘结剂层5来代表已有技术制成的是一种典型的无效阻挡贴标层的容器。
图2中所示是根据本发明的一种有效的阻挡贴标层容器,它由一个取向的聚酯瓶9,瓶上带有高阻挡性标层20,用高阻挡热活化的共聚酯粘合层10粘贴到瓶侧壁14的外表面15上。作为例子,见图2,在瓶侧壁14和标层20之间有一边界层或边界区,外表面15和标层由热活化的高阻挡性共聚酯粘合剂10经热模塑牢固地粘合在一起,热模温度至少约100℃,该温度在粘合剂的玻璃化温度(Tg)以上,当然,一般说来瓶子的Tg较低。
阻挡性标层20由一般的印刷方法在其外表面加以装饰,以提供一个装饰的容器9,典型的带标层的瓶子如图3所示。另一种方法是瓶子可在标层20上附有一种非阻挡(可渗透)层,此层是纸的,塑料的(一般不取向),或者其它可印刷的容易使用的材料。
如图4所示,阻挡标层20可插入内壁26的吹塑模的局部,由此吹塑成型坯与壁26接触,在内模加工过程中形成一个贴标层的瓶子。
聚酯容器侧壁的厚度通常为10~30密耳,涂有高阻挡性共聚酯树脂粘合剂的低渗透性薄膜的标层通常厚1~6密耳,最好是2~4密耳厚。
共聚酯按美国专利第4,398,017号的例5所述方法制造是Santos W.Go(转让给Owens-Illinois,Inc.)的发明
例I
将以下物质加到装备有搅拌器、氮气入口和一个冷凝器的1-升的不锈钢反应器中:
332.3g 间苯二甲酸
180g 乙二醇
59.4g 1,3-双(2-羟基乙氧基)苯
0.7209g 1.1.1三(羟甲基)乙烷
0.1100g 钛氧基乙酰丙酮化合物
0.1458g Sb2O3
0.019g 乙二胺四乙酸钠
反应混合物在220℃加热1小时,然后,在N2氣下于240℃加热30分钟。在这一期间水被连续蒸出。然后将0.688g三(壬基苯基)亚磷酸酯加到反应混合物中,反应温度升高到250℃,在N2下维持40分钟。然后停止通N2,抽真空小于0.4mmHg。在低于0.4mmHg真空下于270℃继续反应
小时。所得共聚酯的特性粘度为0.82,玻璃化温度(Tg)为60℃,O2和CO2气体渗透率在白天气压下分别为1.6和6.6CC/mil/100in2。
本发明主要优点之一是使用一个高阻挡性共聚酯粘合剂,该粘合剂可在瓶子成型条件下(>90℃)活化,在模内把标层粘贴到PET瓶上得到一个高阻挡性容器。以下的表1将举例说明该方法所涉及的活化温度:
如表1所示,对于定向吹塑,使用高阻挡性热稳定共聚酯材料作为阻挡标层薄膜,它本身与作为粘合剂的适宜热活化高阻挡性共聚酯树脂连接是行得通的。在这种情况下,可制得热稳定高阻挡性共聚酯材料和热活化高阻挡性共聚酯树脂共挤出物,标层的长度从共挤出的片材按要求裁出。
表1
共聚酯粘合剂的活化温度(瓶料) 标层材料 高阻挡性共聚 其它标 瓶温度加工 酯标层材料 层材料定向吹塑 (PET) <100℃ <100℃ 瓶在90~100℃定向吹塑
<100℃ 瓶模冷却
(PET) 不用/热定形 >100℃ 90~100℃
200~240℃注射—吹塑
(共聚酯) 不能用 >100℃ 瓶在150~200℃或挤出吹塑
如PETG(未取向)
标层可用烧瓶缠绕的方法贴于瓶侧壁上,或通过把共聚酯依次进入标层套,瓶从下往上进入适当位置,通过在模内吹塑瓶子,使定位在内模法模具内部的标层粘贴在瓶子侧壁上。
以下热定形实例可说明本发明:
例II
标层插入吹塑模内,并在真空条件下保持在适当位置。例如,把该模加热到230℃。聚酯预成型品或聚酯瓶对着热模吹塑,与模保持接触,以达到聚酯瓶容器热定型的目的,并使阻挡标层活化,此后,开模,取出瓶子,冷却。用这种方法,阻挡标层和聚酯容器之间可形成很强的粘合。
Claims (15)
1、提供一种在外部为聚酯表面的聚酯空容器上粘贴一种高阻挡性标层的方法,该方法包括以下三步:
A,在低渗透性贴标层薄膜的内表面上形成一个可热活化的高阻挡性共聚酯粘合剂层以制得标层。
B,制得带外壳和聚酯外壁表面的聚酯容器。
C,把标层和容器加热使共聚酯层充分软化,足以把共聚酯层粘附在聚酯壁上,在共聚酯层与聚酯壁之间的边界区域形成粘合剂粘结。
2、根据权利要求1所定义的方法,制成一种可有效阻挡的贴标层的容器,在这种方法中,当容器吹塑时,共聚酯粘合剂层被活化。
3、按照权利要求1定义的方法,其中容器由挤压吹塑方法制成。
4、按照权利要求1定义的方法,其中容器用注射吹塑制成。
5、按照权利要求1定义的方法,其中高阻挡层是在型坯上形成,随后制成为容器。
6、将高阻挡塑料标层贴到PET容器壳体的侧壁上,所用方法包括以下步骤:
A,围绕容器的外壳侧壁生成一个固体热塑性共聚酯标定,标层含有一个共聚酯层,共聚酯层与容器的侧壁相接触,共聚酯是下列的反应产物:
(1)二羧苯二甲酸及其衍生物;
(2)乙二醇和1,3-双(2-羟基乙氧基)苯,共聚酯的I.V.至少约为0.6,玻璃化温度Tg约60~75℃,O2和CO2渗透率分别约为(白天气压)1~6和和5~10厘米3/密尔/100吋2;
B、标层和容器至少加热到大约100℃,使标层软化、在标层和容器侧壁之间形成粘结界面层。
7、按照权利要求6定义的方法,其步骤是在共聚酯上形成一个能透过的外层,此层变为环绕容器形成的标层膜的外层。
8、按照权利要求1定义的方法,其中步骤B的加热温度约100~250℃。
9、按照权利要求1定义的方法,其中加热步骤B是使共聚酯软化,同时使聚酯侧壁热定形。
10、按照权利要求1所述的方法生产的产品。
11、按照权利要求1所述方法生产的产品,其中聚酯是PET.共聚酯是间苯二甲酸,乙二醇和1,3-双(2-羟基乙氧基)苯的反应产物。
12、按照权利要求1所述方法生产的产品,其中,聚酯侧壁厚约为15~30密耳,共聚酯厚为1/10~1密耳。
13、对双轴取向的聚对苯二甲酸乙二醇酯中空容器提供一个高阻挡性多层塑料标层的方法,该PET容器的壳体围绕着一层侧壁,并有一个不可渗透性共聚酯层标层以及适合于印刷标记可渗透层。共聚酯是一种固体热塑性共聚酯,主要由下列聚合反应产物组成
A、反应物选自间苯二甲酸,对苯二甲酸和它们的C1到C4的烷基酯,和按任何比例得到的任何混合物。
B、反应物,1,3-双(2-羟基乙氧基)苯加乙二醇,和任意一种或多种能生成二羟基有机碳氢化合物的其它酯的反应物。
C、反应物,双(4-B羟基乙氧基苯基)砜,其中
(1)所说的1,3-双(2-羟基乙氧基)苯的用量为反应物A用量的5~90mol%。
(2),反应物B和C的总用量约为反应物A用量的110~300mol%,
(3),所说的可形成二羟基有机碳氢化合物的反应物的其他酯的用量是反应物A用量的0~20mol%,
(4)反应物C加1,3-双(2-羟基乙氧基)苯和上述可形成二羟基有机碳氢反应物的其它酯的总用量不超过反应物A的90mol%;制造方法包括以下几步:
(a),把标层贴附在带共聚酯层的容器侧壁上,共聚酯层紧挨着容器壁,
(b),把标层的共聚酯层和侧壁加热到至少在共聚酯的玻璃化温度以上25℃,使共聚酯层和侧壁软化,在它们之间的边界层区形成牢固的粘结。
14、一种带有外侧壁表面的中空聚酯或共聚酯容器,一个高阻挡性共聚酯材料的标层通过容器侧壁和标层间的边界层粘结在外侧壁表面,标层的共聚酯层和侧壁表面相接触并粘合在一起。共聚酯层材料是间苯二甲酸,乙二醇和1,3-双(2-羟基乙氧基)苯的反应产物。
15,一个取向的PET中空瓶,通常带有一个筒形侧壁,该筒形侧壁具有外表面,共聚酯标层粘附在侧壁上,标层包括粘附在侧壁上的共聚酯粘合剂层,在侧壁外表面和标层之间有一边界层,共聚酯是一个固体热塑性共聚酯,主要含有以下几种聚合反应产物:
A,反应物,选自间苯二甲酸,对苯二甲酸,和它们的C1到C4烷基酯以及它们以任何比例混合的任何混合物。
B,反应物,1,3-双(2-羟基乙氧基)苯加乙二醇和任意一种或多种能形成二羟基有机碳氢化合物的其他酯反应物。
C,反应物,双(4-B-羟基乙氧基苯基)砜,其中
(1)所说的双(2-羟基乙氧基)苯的用量为反应物A用量的5~90mol%,
(2)反应物B和C的总用量约为反应物A用量的110~300mol%,
(3)上述可形成二羟基有机碳氢化合物反应物的其它酯的用量是反应物A用量的0~20mol%,
(4)反应物C加1,3-双(2-羟基乙氧基)苯和上述可形成二羟基有机碳氢反应物的其它酯的总用量不起过反应物A的90mol%。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/694,375 US4601926A (en) | 1985-01-24 | 1985-01-24 | Process for applying copolyester barrier layer on polyester container |
US694,375 | 1991-05-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN85109294A true CN85109294A (zh) | 1986-08-27 |
Family
ID=24788567
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN198585109294A Pending CN85109294A (zh) | 1985-01-24 | 1985-12-26 | 在聚酯容器上粘贴共聚酯阻挡层的方法 |
Country Status (13)
Country | Link |
---|---|
US (1) | US4601926A (zh) |
EP (1) | EP0190009B1 (zh) |
JP (1) | JPS61169233A (zh) |
CN (1) | CN85109294A (zh) |
AT (1) | ATE59400T1 (zh) |
AU (1) | AU568786B2 (zh) |
BR (1) | BR8600263A (zh) |
CA (1) | CA1258614A (zh) |
DE (1) | DE3676511D1 (zh) |
IN (1) | IN166337B (zh) |
MX (1) | MX170902B (zh) |
NZ (1) | NZ214325A (zh) |
ZA (1) | ZA859874B (zh) |
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-
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- 1985-01-24 US US06/694,375 patent/US4601926A/en not_active Expired - Lifetime
- 1985-11-26 CA CA000496263A patent/CA1258614A/en not_active Expired
- 1985-11-26 NZ NZ21432585A patent/NZ214325A/xx unknown
- 1985-11-28 IN IN959/MAS/85A patent/IN166337B/en unknown
- 1985-12-20 AU AU51508/85A patent/AU568786B2/en not_active Ceased
- 1985-12-26 CN CN198585109294A patent/CN85109294A/zh active Pending
- 1985-12-30 ZA ZA859874A patent/ZA859874B/xx unknown
-
1986
- 1986-01-03 MX MX001149A patent/MX170902B/es unknown
- 1986-01-23 EP EP19860300446 patent/EP0190009B1/en not_active Expired - Lifetime
- 1986-01-23 DE DE8686300446T patent/DE3676511D1/de not_active Expired - Fee Related
- 1986-01-23 BR BR8600263A patent/BR8600263A/pt unknown
- 1986-01-23 AT AT86300446T patent/ATE59400T1/de not_active IP Right Cessation
- 1986-01-23 JP JP61011235A patent/JPS61169233A/ja active Granted
Cited By (2)
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CN102189672A (zh) * | 2010-01-25 | 2011-09-21 | 克朗斯股份公司 | 对旋转吹塑成型机的吹塑模具中塑料容器贴标签的贴标签机和贴标签方法 |
CN102189672B (zh) * | 2010-01-25 | 2014-05-07 | 克朗斯股份公司 | 对旋转吹塑成型机的吹塑模具中塑料容器贴标签的贴标签机和贴标签方法 |
Also Published As
Publication number | Publication date |
---|---|
JPS61169233A (ja) | 1986-07-30 |
EP0190009B1 (en) | 1990-12-27 |
CA1258614A (en) | 1989-08-22 |
US4601926A (en) | 1986-07-22 |
MX170902B (es) | 1993-09-22 |
BR8600263A (pt) | 1986-10-07 |
AU5150885A (en) | 1986-07-31 |
DE3676511D1 (de) | 1991-02-07 |
NZ214325A (en) | 1988-10-28 |
IN166337B (zh) | 1990-04-14 |
JPH0524819B2 (zh) | 1993-04-09 |
AU568786B2 (en) | 1988-01-07 |
ATE59400T1 (de) | 1991-01-15 |
ZA859874B (en) | 1986-09-24 |
EP0190009A3 (en) | 1987-07-01 |
EP0190009A2 (en) | 1986-08-06 |
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