CN112406234A - 聚酯薄膜及其制造方法 - Google Patents
聚酯薄膜及其制造方法 Download PDFInfo
- Publication number
- CN112406234A CN112406234A CN201910976457.9A CN201910976457A CN112406234A CN 112406234 A CN112406234 A CN 112406234A CN 201910976457 A CN201910976457 A CN 201910976457A CN 112406234 A CN112406234 A CN 112406234A
- Authority
- CN
- China
- Prior art keywords
- resin material
- heat
- polyester film
- polyester
- resistant
- 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.)
- Pending
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- 238000000034 method Methods 0.000 title claims description 22
- 230000008569 process Effects 0.000 title description 10
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- 229920005989 resin Polymers 0.000 claims abstract description 127
- 239000011347 resin Substances 0.000 claims abstract description 127
- 229920001225 polyester resin Polymers 0.000 claims abstract description 92
- 239000004645 polyester resin Substances 0.000 claims abstract description 92
- 238000005452 bending Methods 0.000 claims abstract description 19
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- 239000000956 alloy Substances 0.000 claims description 41
- 229910045601 alloy Inorganic materials 0.000 claims description 41
- 238000012360 testing method Methods 0.000 claims description 29
- 239000004697 Polyetherimide Substances 0.000 claims description 20
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- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
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- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- XAAYMWLCUICVSL-UHFFFAOYSA-N anthracene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC3=CC(C(=O)O)=CC=C3C=C21 XAAYMWLCUICVSL-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- LNGJOYPCXLOTKL-UHFFFAOYSA-N cyclopentane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C1 LNGJOYPCXLOTKL-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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Abstract
本发明公开一种聚酯薄膜及其制造方法。所述聚酯薄膜包含有一耐热层,并且所述耐热层包含有一耐高温树脂材料及一聚酯树脂材料。所述耐高温树脂材料与所述聚酯树脂材料是借由一双螺杆造粒机彼此熔融及混炼。其中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,以使得所述耐高温树脂材料能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中。借此,最终制造的聚酯薄膜在不牺牲透明度的情况下、能具有良好的耐高温及耐弯折的特性,从而特别适合应用于折迭式手机的保护膜、或印刷电路板的高温制成用的保护膜。
Description
技术领域
本发明涉及一种聚酯薄膜,特别是涉及一种耐高温及耐弯折的透明聚酯薄膜。
背景技术
聚酯薄膜是一种高分子塑料薄膜,因其综合性能优良而越来越受到广大消费者的青睐。惟,现有的聚酯薄膜在某些物化特性(如:耐高温及耐弯折特性)上的表现仍不佳,以至于其无法应用于某一些特殊的应用领域 (如:折迭式手机的保护膜)。
举例来说,中国台湾专利第104137871申请号公开了一种双轴配向聚酯薄膜。该聚酯薄膜以PET及PEN掺混,得到大致落在40至80℃之间的结晶化参数(Tcg)。该聚酯薄膜具有优异的耐热性及耐湿热性,然而其玻璃转移温度(Tg)仅有80℃左右,因此,该聚酯薄膜在某些需耐高温的应用中仍然受到限制。
中国专利第99118718.0申请号所公开的聚酯薄膜则是以PET及PEI 进行掺混,虽然该聚酯薄膜的玻璃转移温度(Tg)可被提升至139℃左右,但是由于该聚酯薄膜的PEI添加量需在40wt%以上,其会造成PET及PEI 之间因膨胀系数差异太大而造成厚度不均(约11%)的情况发生。再者,该专利未提及其聚酯薄膜在高温230℃左右使用时的耐热情形。
中国专利第201080031380.5申请号所公开的聚酯薄膜则是借由将 PET与PSU、PEEK、PAI等耐高温树脂掺混,而得到尺寸安定性稳定的膜材。然而,该专利对于掺混后膜材的耐热性、玻璃转移温度、及透明度等均未作提及。
于是,本发明人有感上述缺陷可改善,乃特潜心研究并配合科学原理的运用,终于提出一种设计合理且有效改善上述缺陷的本发明。
发明内容
本发明所要解决的技术问题在于,针对现有技术的不足提供一种聚酯薄膜及其制造方法。
为了解决上述的技术问题,本发明所采用的其中一技术方案是,提供一种聚酯薄膜的制造方法,包括:实施一树脂合金母粒制备步骤,包含:以一双螺杆造粒机,将一耐高温树脂材料与一聚酯树脂材料,进行熔融及混炼,而后形成多个树脂合金母粒;其中,在所述树脂合金母粒制备步骤中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,以使得在多个所述树脂合金母粒中,所述耐高温树脂材料能以介于50纳米至200 纳米之间的粒径尺寸分散于所述聚酯树脂材料中;以及实施一薄膜成形步骤,包含:以一薄膜挤出机,将多个所述树脂合金母粒,进行熔融及挤出,以形成一聚酯薄膜;其中,所述聚酯薄膜包含有一耐热层,并且所述耐热层是由多个所述树脂合金母粒所形成,以使得所述耐热层包含有所述耐高温树脂材料与所述聚酯树脂材料。
优选地,所述耐高温树脂材料是选自由聚醚酰亚胺(polyetherimide, PEI)、聚砜(polysulfone,PSU)、液晶聚合物(liquid crystal polymer, LCP)、聚醚醚酮(polyetheretherketon,PEEK)、及聚酰胺酰亚胺 (polyamide-imide,PAI)所组成的材料群组中的至少其中一种材料。
优选地,所述耐高温树脂材料为一结晶性树脂材料、一半结晶性树脂材料或一非结晶性树脂材料,且所述耐高温树脂材料具有介于180℃至 400℃之间的一玻璃转移温度、一熔点或一热变形温度。
优选地,所述薄膜成形步骤进一步包含:将多个所述树脂合金母粒与另一聚酯树脂材料,以所述薄膜挤出机共同挤出,以使得所述聚酯薄膜包含有所述耐热层及一聚酯树脂基层;其中,所述耐热层是形成于所述聚酯树脂基层的一侧表面上。
优选地,所述薄膜成形步骤进一步包含:形成另一耐热层于所述聚酯树脂基层的另一侧表面上,以使得所述聚酯树脂基层被夹持于所述耐热层与另一所述耐热层之间;其中,另一所述耐热层也包含有所述耐高温树脂材料及所述聚酯树脂材料。
优选地,所述耐高温树脂材料于所述耐热层中的含量范围是介于10 wt%至80wt%之间,并且所述聚酯树脂材料于所述耐热层中的含量范围是介于20wt%至90wt%之间。
为了解决上述的技术问题,本发明所采用的另外一技术方案是,提供一种聚酯薄膜,包括:一耐热层,包含有一耐高温树脂材料及一聚酯树脂材料,并且所述耐高温树脂材料是以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中;其中,所述耐高温树脂材料于所述耐热层中的含量范围是介于10wt%至80wt%之间。
优选地,所述耐高温树脂材料是借由一双螺杆造粒机与所述聚酯树脂材料熔融及混炼;其中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至 500rpm之间,以使得所述耐高温树脂材料能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中。
优选地,所述耐高温树脂材料是选自由聚醚酰亚胺(polyetherimide, PEI)、聚砜(polysulfone,PSU)、液晶聚合物(liquid crystal polymer, LCP)、聚醚醚酮(polyetheretherketon,PEEK)、及聚酰胺酰亚胺 (polyamide-imide,PAI)所组成的材料群组中的至少其中一种材料。
优选地,所述耐高温树脂材料为一结晶性树脂材料、一半结晶性树脂材料、或一非结晶性树脂材料,并且所述耐高温树脂材料具有介于180℃至400℃之间的一玻璃转移温度、一熔点、或一热变形温度。
优选地,所述聚酯薄膜进一步包括:一聚酯树脂基层,并且所述耐热层是形成于所述聚酯树脂基层的一侧表面上。
优选地,所述聚酯薄膜进一步包括:另一耐热层,并且另一所述耐热层是形成于所述聚酯树脂基层的另一侧表面上,以使得所述聚酯树脂基层被夹持于所述耐热层与另一所述耐热层之间;其中,另一所述耐热层也包含有所述耐高温树脂材料及所述聚酯树脂材料;其中,所述聚酯树脂基层具有介于15微米至350微米之间的一厚度,所述耐热层具有介于0.5微米至70微米之间的一厚度,并且另一所述耐热层具有介于0.5微米至70 微米之间的一厚度。
优选地,所述聚酯薄膜的整体具有介于110℃至150℃之间的一玻璃转移温度、不小于80%的一透明度、及不大于5%的一雾度。
优选地,所述聚酯薄膜符合以下条件:(1)所述聚酯薄膜在经过一热压试验或一耐热试验后,所述聚酯薄膜的一翘曲变形量不大于3mm,并且所述聚酯薄膜不产生裂化;其中,所述热压试验包含:将所述聚酯薄膜置放于220℃至240℃的一温度环境下;接着,对所述聚酯薄膜施予 40公斤至50公斤的一荷重、且持续2.5小时至3.5小时;其中,所述耐热试验包含:将所述聚酯薄膜置放于220℃至240℃的一温度环境下进行加热;接着,将所述聚酯薄膜置放于一室温环境下进行冷却;并且,上述加热步骤及冷却步骤重复循环五次;及(2)所述聚酯薄膜在经过一耐弯折试验后,所述聚酯薄膜不产生裂化;其中,所述耐弯折试验包含:以一耐弯折试验机、对所述聚酯薄膜不间断地弯折25,000次至30,000次。
优选地,所述聚酯薄膜为仅包含有一个所述耐热层的单层薄膜结构,并且所述耐热层具有介于15微米至350微米之间的一厚度。
优选地,所述聚酯薄膜进一步包括:混合至所述耐高温树脂材料与所述聚酯树脂材料1中的一相容剂,并且所述相容剂为聚碳酸酯及聚苯醚树脂的至少其中之一。
本发明的其中一有益效果在于,本发明所提供的聚酯薄膜及其制造方法,其能通过“所述耐高温树脂材料是以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中”以及“在所述树脂合金母粒制备步骤中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,以使得所述耐高温树脂材料能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中”的技术方案,以使得最终制造的聚酯薄膜在不牺牲透明度的情况下、能具有良好的耐高温及耐弯折的特性,从而特别适合应用于折迭式手机的保护膜、或印刷电路板的高温制成用的保护膜。
为使能更进一步了解本发明的特征及技术内容,请参阅以下有关本发明的详细说明与图式,然而所提供的图式仅用于提供参考与说明,并非用来对本发明加以限制。
附图说明
图1为本发明实施例的聚酯薄膜的制造方法流程图。
图2为本发明实施例的聚酯薄膜的示意图。
图3为本发明的一变化态样实施例的聚酯薄膜的示意图。
图4为本发明的另一变化态样实施例的聚酯薄膜的示意图。
图5为本发明的又一变化态样实施例的聚酯薄膜的示意图。
图6为本发明的再一变化态样实施例的聚酯薄膜的示意图。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开的实施方式,本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用,本说明书中的各项细节也可基于不同观点与应用,在不悖离本发明的构思下进行各种修改与变更。另外,本发明的附图仅为简单示意说明,并非依实际尺寸的描绘,事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容,但所公开的内容并非用以限制本发明的保护范围。
[聚酯薄膜的制造方法]
如图1及图2所示,本实施例公开一种聚酯薄膜的制造方法。所述聚酯薄膜的制造方法包含步骤S110、步骤S120、步骤S130、及步骤S140。必须说明的是,本实施例所载之各步骤的顺序与实际的操作方式可视需求而调整,并不限于本实施例所载。
步骤S110为实施一选材步骤。所述选材步骤包含:提供一耐高温树脂材料11及一聚酯树脂材料12。
其中,为了使得最终制造的聚酯薄膜100具有耐高温及耐弯折的特性,所述耐高温树脂材料11是选自由聚醚酰亚胺(polyetherimide,PEI)、聚砜(polysulfone,PSU)、液晶聚合物(liquid crystal polymer,LCP)、聚醚醚酮(polyetheretherketon,PEEK)、及聚酰胺酰亚胺(polyamide-imide, PAI)所组成的材料群组中的至少其中一种材料。
在上述耐高温树脂材料11中,聚醚酰亚胺为非结晶性树脂材料、且具有大致为215℃的玻璃转移温度。聚砜为非结晶性树脂材料、且具有大致为185℃的玻璃转移温度、及大致为280℃的熔点。液晶聚合物为结晶性树脂材料、且具有大致介于180℃至260℃之间的热变形温度。聚醚醚酮为半结晶性树脂材料、且具有大致为340℃的玻璃转移温度。聚酰胺酰亚胺为非结晶性树脂材料、且具有大致介于280℃至290℃之间的玻璃转移温度。
也就是说,上述耐高温树脂材料11可以例如是一结晶性树脂材料、一半结晶性树脂材料、或一非结晶性树脂材料,并且该些耐高温树脂材料 11可以例如是具有介于180℃至400℃之间的一玻璃转移温度、一熔点、或一热变形温度。
进一步地说,所述聚酯树脂材料12是由二元酸与二元醇或其衍生物通过缩合聚合反应而获得的高分子聚合物。优选地,所述聚酯树脂材料 12为聚对苯二甲酸乙二酯(PET)或聚萘二甲酸乙二醇酯(PEN),但本发明不受限于此。
值得一提的是,上述形成聚酯树脂材料12中的原料二元酸为对苯二甲酸、间苯二甲酸、1,5-萘二甲酸、2,6-萘二甲酸2,6-萘二甲酸、1,4-萘二甲酸、联苯甲酸、二苯基乙烷二羧酸、二苯基砜二羧酸、蒽-2,6-二羧酸、 1,3-环戊烷二甲酸、1,3-环己烷二甲酸、1,4-环己烷二甲酸、丙二酸、二甲基丙二酸、丁二酸、3,3-丁二酸二乙酯、戊二酸、2,2-二甲基戊二酸、己二酸、2-甲基己二酸、三甲基己二酸、庚二酸、壬二酸、癸二酸、辛二酸、及十二烷二酸中的至少其中一种。再者,上述形成聚酯树脂材料12中的原料二元醇为乙二醇、丙二醇、六亚甲二醇、新戊二醇、1,2-环己二甲醇、 1,4-环己二甲醇、1,10-癸二醇、1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、1,6- 己二醇、及2,2-双(4-羟苯基)丙烷或双(4-羟苯)砜中的至少其中一种。
步骤S120为实施一树脂合金母粒制备步骤。所述树脂合金母粒制备步骤包含:以一双螺杆造粒机,将所述耐高温树脂材料11与聚酯树脂材料12、依据一预定重量比例范围,进行熔融及混炼,而后形成多个树脂合金母粒(resin alloy master batches)。
其中,在所述树脂合金母粒制备步骤中,所述耐高温树脂材料11的用量范围优选为10重量份至90重量份之间,并且所述聚酯树脂材料12 的用量范围优选为10重量份至90重量份之间。再者,所述耐高温树脂材料11的用量范围特优选为5重量份至60重量份之间,而所述聚酯树脂材料12的用量范围特优选为40重量份至95重量份之间。其中,上述各成份的用量总和为100重量份。
进一步地说,为了使得最终制造的聚酯薄膜100能具有良好的耐高温及耐弯折的特性,在本实施例中,所述耐高温树脂材料11是以纳米级的尺寸分散于聚酯树脂材料12中。
为了达成上述目的,在所述树脂合金母粒制备步骤中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间、且优选是介于280℃至 300℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800 rpm之间、且优选是介于400rpm至600rpm之间,以使得在多个所述树脂合金母粒中,所述耐高温树脂材料11能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料12中。
也就是说,所述耐高温树脂材料11主要是通过上述双螺杆温度及双螺杆转速的制程条件,而能以纳米级的尺寸分散于聚酯树脂材料12中。借此,所述耐高温树脂材料11不仅能在聚酯薄膜100中发挥它的材料特性,并且仍能让聚酯薄膜100维持其所需的透明度。
另外,值得一提的是,为了增加所述耐高温树脂材料11(如:PEI、 PSU、LCP、PEEK、PAI)与聚酯树脂材料12(如:PET、PEN)之间的相容性,本实施例的树脂合金母粒制备步骤(步骤S120)可以进一步包含将一相容剂混合至上述耐高温树脂材料11与聚酯树脂材料12中,并且与该些树脂材料一同进行熔融及混炼。其中,所述相容剂可以例如是聚碳酸酯及聚苯醚树脂的至少其中之一,并且所述相容剂于树脂合金母粒中的用量范围是介于0.01重量份至1重量份之间。
步骤S130为实施一薄膜成形步骤。所述薄膜成形步骤包含:以一薄膜挤出机(或称薄膜押出机),将多个所述树脂合金母粒,进行熔融及挤出,以使得多个所述树脂合金母粒形成为一耐热层1(如图2所示)。由于所述耐热层1是由多个树脂合金母粒所形成,因此所述耐热层1包含有上述耐高温树脂材料11及聚酯树脂材料12。其中,所述耐高温树脂材料 11是以多个颗粒状的方式分散于聚酯树脂材料12中,并且所述耐高温树脂材料11在耐热层1中的粒径尺寸是介于50纳米至200纳米之间。
在本发明的一实施例中,多个所述树脂合金母粒优选地是在280℃至300℃的操作温度范围下,以所述薄膜挤出机熔融且挤出,以形成所述耐热层1。
另外,值得一提的是,本实施例的耐热层1是以多个树脂合金母粒直接熔融及挤出而形成,但本发明不受限于此。举例来说,若所述耐高温树脂材料11于树脂合金母粒中的的含量较低(如:低于40wt%),则该些树脂合金母粒可以如同上述实施例、直接被熔融挤出、而形成所述耐热层 1。
然而,若所述耐高温树脂材料11于树脂合金母粒中的的含量较高(如:高于50wt%),则该些树脂合金母粒需再与额外的聚酯树脂材料12一起进行熔融及挤出,而后形成所述耐热层1,以降低耐高温树脂材料11于耐热层1中的浓度。借此,所述耐高温树脂材料11于耐热层1中可以具有合适的含量范围,以使得最终制造的聚酯薄膜100在不牺牲透明度的情况下、能具有良好的耐高温及耐弯折的特性。
为了达成上述目的,在本发明的一实施例中,所述耐高温树脂材料 11于耐热层1中的含量范围优选是介于10wt%至80wt%之间、且特优选是介于15wt%至70wt%之间,并且所述聚酯树脂材料12于耐热层1中的含量范围优选是介于20wt%至90wt%之间、且特优选是介于30wt%至 85wt%之间。
更具体的说,在本实施例中,步骤S130的薄膜成形步骤为:将多个所述树脂合金母粒与另一聚酯树脂材料21(如:PET、PEN),以所述薄膜挤出机、通过一共挤押出(Co-Extrusion)技术、共同挤出,以同时形成两个耐热层1、1’及一个聚酯树脂基层2。其中,两个所述耐热层1、1’是分别形成于聚酯树脂基层2的位于相反侧的两个表面上,以使得所述聚酯树脂基层2被夹持于两个所述耐热层1、1’之间。
其中,两个所述耐热层1、1’皆是对应地由多个所述树脂合金母粒所形成,而所述聚酯树脂基层2则是单纯由另一所述聚酯树脂材料21所形成(如图2及图3)、或者也可以由多个所述树脂合金母粒所形成(如图 5及图6)。
其中,两个所述耐热层1、1’的耐高温树脂材料11及聚酯树脂材料 12的材料种类及含量范围可以完全相同或不同,并且两个所述耐热层1、1’与聚酯树脂基层2的聚酯树脂材料的材料种类也可以完全相同或不同,本发明并不予以限制。
如图2所示,根据本实施例的上述制造方法,本实施例最终制造的聚酯薄膜100为具有由上至下依序堆栈一耐热层1、一聚酯树脂基层2、及另一耐热层1’的三层结构。
再者,上述聚酯薄膜100在被薄膜挤出机挤出后,可再经由一冷却鼓轮(如:冷却至15℃至50℃的鼓轮)进行急速冷却,但本发明不受限于此。
步骤S140为实施一双轴延伸步骤。所述双轴延伸步骤包含:将上述具有三层结构的聚酯薄膜100进行双轴延伸,以形成一经过双轴延伸的聚酯薄膜100。
其中,上述双轴延伸的方式可以例如是采用纵单轴延伸法、横单轴延伸法、纵轴逐次双轴延伸法、或纵轴同时双轴延伸法,本发明并不予以限制。再者,上述双轴延伸的方式可以例如是于延伸温度50℃至150℃下对未经延伸的聚酯薄膜100进行预热,并且依照不同的延伸比例对未经延伸的聚酯薄膜100的宽度方向(或称,纵向方向,MD)施予2.0倍至5.0倍的延伸加工、且优选为施予3.0倍至4.5倍的延伸加工,并且进一步再对该聚酯薄膜100的长度方向(或称,横向方向,TD)施予2.0倍至5.0 倍的延伸加工、且优选为施予3.0倍至4.5倍的延伸加工。
[聚酯薄膜]
如图2所示,本实施例也公开一种聚酯薄膜100。所述聚酯薄膜100 可以是通过上述聚酯薄膜的制造方法所制得,但本发明不受限于此。
具体来说,所述聚酯薄膜100包含有一聚酯树脂基层2及两个耐热层 1、1’。其中,所述聚酯树脂基层2的材料是以聚酯树脂材料21为主(如图2及图3)、但也可以选择性地混掺有耐高温树脂材料11(如图5及图 6)。两个所述耐热层1、1’是分别形成于聚酯树脂基层2的位于相反侧的两个表面上,以使得所述聚酯树脂基层2被夹持于两个所述耐热层1、1’之间。两个所述耐热层1、1’各自包含有一耐高温树脂材料11及一聚酯树脂材料12,并且所述耐高温树脂材料11是以介于50纳米至200纳米之间的粒径尺寸分散于聚酯树脂材料12中。其中,所述耐高温树脂材料11 于耐热层1、1’中的含量范围是介于10wt%至80wt%之间。需说明的是,当所述聚酯树脂基层2也混掺有耐高温树脂材料11时(如图5及图6),所述聚酯树脂基层2的耐高温树脂材料11的含量范围是介于5至50wt%,而所述耐热层1、1’的耐高温树脂材料11的含量范围是介于5至80wt%。
请继续参阅图1所示,在本实施例中,为了让聚酯薄膜100具有良好的耐高温及耐弯折特性、且能同时维持良好的透明度。所述聚酯薄膜100 的每一层结构皆具有一优选的厚度范围。具体来说,所述聚酯树脂基层2 具有介于15微米至350微米之间的一厚度D1,所述耐热层1具有介于 0.5微米至70微米之间的一厚度D2,并且另一所述耐热层1具有介于0.5 微米至70微米之间的一厚度D3。
换一个角度来说,所述聚酯薄膜100的整体具有介于15微米至350 微米之间的一厚度,并且所述耐热层1、所述聚酯树脂基层2、及另一所述耐热层1’的厚度比例范围优选是介于1:98:1至20:60:20之间。
根据上述配置,本实施例的聚酯薄膜100具有良好的耐高温及耐弯折特性、且能同时维持良好的透明度。具体而言,本实施例聚酯薄膜100的整体具有介于110℃至150℃之间的一玻璃转移温度、不小于80%的一透明度、及不大于5%的一雾度。优选地,所述聚酯薄膜100的玻璃转移温度是介于120℃至140℃之间,所述聚酯薄膜100的透明度是不小于 88%,并且所述聚酯薄膜100的雾度是不大于3%。
再者,本实施例的聚酯薄膜100能符合以下测试条件:(1)所述聚酯薄膜100在经过一热压试验或一耐热试验后,所述聚酯薄膜100于A4 大小下的一翘曲变形量不大于3mm,并且所述聚酯薄膜100不产生裂化 (不裂化是指膜面完整不产生裂纹);其中,所述热压试验包含:将所述聚酯薄膜100置放于220℃至240℃的一温度环境下;接着,对所述聚酯薄膜100施予40公斤至50公斤的一荷重、且持续2.5小时至3.5小时;其中,所述耐热试验包含:将所述聚酯薄膜100置放于220℃至240℃的一温度环境下进行加热;接着,将所述聚酯薄膜100置放于一室温环境下进行冷却;并且,上述加热步骤及冷却步骤重复循环五次;及(2)所述聚酯薄膜100在经过一耐弯折试验后,所述聚酯薄膜100不产生裂化;其中,所述耐弯折试验包含:以一耐弯折试验机、对所述聚酯薄膜100不间断地弯折25,000次至30,000次。
值得一提的是,本实施例的聚酯薄膜100在经过上述热压试验或耐热试验后,该聚酯薄膜100的色差ΔE(或称色像差)不小于2。
在机械特性方面,本实施例的聚酯薄膜100根据ASTM D882的国际标准测试方法进行测试,可以得到该薄膜的长度方向(MD)的断裂强度不小于20kgf/mm2、该薄膜的宽度方向(TD)的断裂强度不小于25kgf/mm2、该薄膜的长度方向(MD)的伸长率不小于230%、且该薄膜的宽度方向 (TD)的伸长率不小于160%。
本实施例的聚酯薄膜100根据ASTM D1204的国际标准测试方法进行测试,可以得到该薄膜的长度方向(MD)于室温下的收缩率介于0.35%至0.4%之间,并且该薄膜的宽度方向(TD)于室温下的收缩率介于0.05 %至0.15%之间。再者,该薄膜的长度方向(MD)于220℃至240℃的温度环境下的收缩率不大于2.5%,并且该薄膜的宽度方向(TD)于220 ℃至240℃的温度环境下的收缩率不大于4.5%。
由于本实施例的聚酯薄膜100具有良好的耐高温及耐弯折的特性、且具有良好的透明度,因此本实施例的聚酯薄膜100特别适合应用于折迭式手机的保护膜、或印刷电路板的高温制成用的保护膜。
值得一提的是,本实施例虽然是以具有三层结构的聚酯薄膜100(包含一聚酯树脂基层2及两个耐热层1)为例作说明,但本发明不受限于此。
举例而言,如图3所示,在本发明的一变化态样实施例中,所述聚酯薄膜100’也可以为具有双层结构聚酯薄膜100’(包含一聚酯树脂基层2 及形成于该聚酯树脂基层2的一侧表面上的一个耐热层1)。
或者,如图4所示,在本发明的另一变化态样实施例中,所述聚酯薄膜100”也可以为仅具有单层结构的聚酯薄膜100”。也就是说,所述聚酯薄膜100”仅包含有一个耐热层1、并且所述耐热层1具有介于15微米至 350微米之间的一厚度。借此,所述聚酯薄膜100”可以在为单层结构的情况下,仍然具有良好的耐高温及耐弯折的特性、且维持一定透明度。
再者,如图5及图6所示的三层结构及双层结构的聚酯薄膜100”’、 100””,所述聚酯树脂基层2也可以混掺有耐高温树脂材料11。其中,所述聚酯树脂基层2的耐高温树脂材料11的含量范围是介于5至50wt%,而所述耐热层1、1’的耐高温树脂材料11的含量范围是介于5至80wt%。
[实验数据测试]
以下,参照示范例1至3与比较例1至3详细说明本发明之内容。然而,以下示范例仅作为帮助了解本发明,本发明的范围并不限于这些示范例。
示范例1:将50重量份的耐高温树脂材料PEI(购自Sabic公司,产品名称UltemXH6050-1000)与50重量份的聚脂材料PET(由南亚塑料公司提供),在螺杆长度比上螺杆直径的比值为48的双螺杆造粒机中进行混练,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,从而得到PEI-PET的混和比率为50/50的耐高温树脂合金母粒,而后在140℃、 240min的条件下结晶干燥。
将聚酯树脂与上述耐高温树脂合金母粒依不同的比例混练、且进行 A/B/A层的三层共押出,其中A层含30wt%的PEI、B层含30wt%的PEI, A/B/A层的厚度比例为10/80/10,其中,在双轴延伸的步骤中,纵延伸的预热温度为95℃,纵延伸的倍率为3.0;横延伸的预热温度为120℃,横延伸的倍率为4.5;热定型温度为235℃,借以制得耐高温耐曲折的透明聚酯薄膜。
示范例2:将50重量份的耐高温树脂材料PSU(购自Solvay公司,产品名称P-3900)与50重量份的聚脂材料PET(由南亚塑料公司提供),在螺杆长度比上螺杆直径的比值为48的双螺杆造粒机中进行混练,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,从而得到 PSU-PET的混和比率为50/50的耐高温树脂合金母粒,而后在140℃、 240min的条件下结晶干燥。
示范例3:将50重量份的耐高温树脂材料PAI(购自Solvay公司,产品名称Toron4000T)与50重量份的聚脂材料PET(由南亚塑料公司提供),在螺杆长度比上螺杆直径的比值为48的双螺杆造粒机中进行混练,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,从而得到PAI-PET的混和比率为50/50的耐高温树脂合金母粒,而后在140℃、 240min的条件下结晶干燥。其中,示范例2及3的双轴延伸的制备条件与示范例1相同,在此不再赘述。
比较例1:聚酯薄膜的制备方式与示范例1相同,不同之处在于比较例1的双螺杆转速为200rpm。
比较例2:聚酯薄膜的制备方式与示范例1相同,不同之处在于在比较例2的A/B/A层中,A层的PEI含量为5%,且B层的PEI含量也为5%。
比较例3:聚酯薄膜的制备方式与示范例1相同,不同之处在于比较例3的A/B/A层的整体厚度较薄(不大于15微米)。
其中,各成分的制程参数条件整理如下表1。
接着,将示范例1至3与比较例1至3所制得的聚酯薄膜进行物化特性的测试,以得到该些聚酯薄膜的物化特性,诸如:玻璃转移温度(℃),透明度(%)、及雾度(%)。相关测试方法说明如下,并且相关测试结果整理如表1。
玻璃转移温度测试:以示差扫描热量分析仪(DSC)TA Q20量测基板一次熔融热焓。
透明度及雾度测试:采用Tokyo Denshoku公司的Haze Meter(型号为TC-HⅢ),测试下面实施例聚酯薄膜的透明度(或称光透过率)及雾度值,其方法符合JIS K7705规范。
烘烤后翘曲变形量测试:将聚酯薄膜置于220℃下1hr,循环10次,以A4大小的薄膜观察其翘曲变形量(mm)。
薄膜裂化测试(耐热性):将聚酯薄膜以热压实验220℃荷重45Kg、 3hr,评价指标:膜面平整无劣化评价为◎、膜面破裂评价为×。
[表1示范例与比较例的制程条件与物化特性测试]
[测试结果讨论]
在示范例1至3中,其聚酯薄膜的各种物化特性皆达到需求。比较例 1因螺杆转速太低,无法使得耐高温树脂材料达到均匀分散的效果。比较例2的耐高温树脂材料的添加量太少,导致聚酯薄膜整体的耐热性不足,且烘烤后翘曲变形量偏高。比较例3的整体薄膜厚度较薄,导致薄膜劣化测试的效果不佳。
[实施例的有益效果]
本发明的其中一有益效果在于,本发明所提供的聚酯薄膜及其制造方法,其能通过“所述耐高温树脂材料11是以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料12中”以及“在所述树脂合金母粒制备步骤中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至500rpm之间,以使得所述耐高温树脂材料11能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料12中”的技术方案,以使得最终制造的聚酯薄膜 100在不牺牲透明度的情况下、能具有良好的耐高温及耐弯折的特性,从而特别适合应用于折迭式手机的保护膜、或印刷电路板的高温制成用的保护膜。
以上所公开的内容仅为本发明的优选可行实施例,并非因此局限本发明的申请专利范围,所以凡是运用本发明说明书及图式内容所做的等效技术变化,均包含于本发明的申请专利范围内。
Claims (16)
1.一种聚酯薄膜的制造方法,其特征在于,所述聚酯薄膜的制造方法包括:
实施一树脂合金母粒制备步骤,包含:以一双螺杆造粒机,将一耐高温树脂材料与一聚酯树脂材料,进行熔融及混炼,而后形成多个树脂合金母粒;其中,在所述树脂合金母粒制备步骤中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至800rpm之间,以使得在多个所述树脂合金母粒中,所述耐高温树脂材料能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中;以及
实施一薄膜成形步骤,包含:以一薄膜挤出机,将多个所述树脂合金母粒,进行熔融及挤出,以形成一聚酯薄膜;其中,所述聚酯薄膜包含有一耐热层,并且所述耐热层是由多个所述树脂合金母粒所形成,以使得所述耐热层包含有所述耐高温树脂材料与所述聚酯树脂材料。
2.根据权利要求1所述的聚酯薄膜的制造方法,其特征在于,所述耐高温树脂材料是选自由聚醚酰亚胺(polyetherimide,PEI)、聚砜(polysulfone,PSU)、液晶聚合物(liquidcrystal polymer,LCP)、聚醚醚酮(polyetheretherketon,PEEK)、及聚酰胺酰亚胺(polyamide-imide,PAI)所组成的材料群组中的至少其中一种材料。
3.根据权利要求1所述的聚酯薄膜的制造方法,其特征在于,所述耐高温树脂材料为一结晶性树脂材料、一半结晶性树脂材料或一非结晶性树脂材料,且所述耐高温树脂材料具有介于180℃至400℃之间的一玻璃转移温度、一熔点或一热变形温度。
4.根据权利要求1所述的聚酯薄膜的制造方法,其特征在于,所述薄膜成形步骤进一步包含:将多个所述树脂合金母粒与另一聚酯树脂材料,以所述薄膜挤出机共同挤出,以使得所述聚酯薄膜包含有所述耐热层及一聚酯树脂基层;其中,所述耐热层是形成于所述聚酯树脂基层的一侧表面上。
5.根据权利要求4所述的聚酯薄膜的制造方法,其特征在于,所述薄膜成形步骤进一步包含:形成另一耐热层于所述聚酯树脂基层的另一侧表面上,以使得所述聚酯树脂基层被夹持于所述耐热层与另一所述耐热层之间;其中,另一所述耐热层也包含有所述耐高温树脂材料及所述聚酯树脂材料。
6.根据权利要求5所述的聚酯薄膜的制造方法,其特征在于,所述耐高温树脂材料于所述耐热层中的含量范围是介于10wt%至80wt%之间,并且所述聚酯树脂材料于所述耐热层中的含量范围是介于20wt%至90wt%之间。
7.一种聚酯薄膜,其特征在于,所述聚酯薄膜包括:
一耐热层,包含有一耐高温树脂材料及一聚酯树脂材料,并且所述耐高温树脂材料是以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中;其中,所述耐高温树脂材料于所述耐热层中的含量范围是介于10wt%至80wt%之间。
8.根据权利要求7所述的聚酯薄膜,其特征在于,所述耐高温树脂材料是借由一双螺杆造粒机与所述聚酯树脂材料熔融及混炼;其中,所述双螺杆造粒机的双螺杆温度是介于250℃至320℃之间,并且所述双螺杆造粒机的双螺杆转速是介于300rpm至500rpm之间,以使得所述耐高温树脂材料能以介于50纳米至200纳米之间的粒径尺寸分散于所述聚酯树脂材料中。
9.根据权利要求7所述的聚酯薄膜,其特征在于,所述耐高温树脂材料是选自由聚醚酰亚胺(polyetherimide,PEI)、聚砜(polysulfone,PSU)、液晶聚合物(liquid crystalpolymer,LCP)、聚醚醚酮(polyetheretherketon,PEEK)、及聚酰胺酰亚胺(polyamide-imide,PAI)所组成的材料群组中的至少其中一种材料。
10.根据权利要求7所述的聚酯薄膜,其特征在于,所述耐高温树脂材料为一结晶性树脂材料、一半结晶性树脂材料、或一非结晶性树脂材料,并且所述耐高温树脂材料具有介于180℃至400℃之间的一玻璃转移温度、一熔点、或一热变形温度。
11.根据权利要求7所述的聚酯薄膜,其特征在于,所述聚酯薄膜进一步包括:一聚酯树脂基层,并且所述耐热层是形成于所述聚酯树脂基层的一侧表面上。
12.根据权利要求11所述的聚酯薄膜,其特征在于,所述聚酯薄膜进一步包括:另一耐热层,并且另一所述耐热层是形成于所述聚酯树脂基层的另一侧表面上,以使得所述聚酯树脂基层被夹持于所述耐热层与另一所述耐热层之间;其中,另一所述耐热层也包含有所述耐高温树脂材料及所述聚酯树脂材料;其中,所述聚酯树脂基层具有介于15微米至350微米之间的一厚度,所述耐热层具有介于0.5微米至70微米之间的一厚度,并且另一所述耐热层具有介于0.5微米至70微米之间的一厚度。
13.根据权利要求12所述的聚酯薄膜,其特征在于,所述聚酯薄膜的整体具有介于110℃至150℃之间的一玻璃转移温度、不小于80%的一透明度、及不大于5%的一雾度。
14.根据权利要求12所述的聚酯薄膜,其特征在于,所述聚酯薄膜符合以下条件:
(1)所述聚酯薄膜在经过一热压试验或一耐热试验后,所述聚酯薄膜的一翘曲变形量不大于3mm,并且所述聚酯薄膜不产生裂化;其中,所述热压试验包含:将所述聚酯薄膜置放于220℃至240℃的一温度环境下;接着,对所述聚酯薄膜施予40公斤至50公斤的一荷重、且持续2.5小时至3.5小时;其中,所述耐热试验包含:将所述聚酯薄膜置放于220℃至240℃的一温度环境下进行加热;接着,将所述聚酯薄膜置放于一室温环境下进行冷却;并且,上述加热步骤及冷却步骤重复循环五次;及
(2)所述聚酯薄膜在经过一耐弯折试验后,所述聚酯薄膜不产生裂化;其中,所述耐弯折试验包含:以一耐弯折试验机、对所述聚酯薄膜不间断地弯折25,000次至30,000次。
15.根据权利要求7所述的聚酯薄膜,其特征在于,所述聚酯薄膜为仅包含有一个所述耐热层的单层薄膜结构,并且所述耐热层具有介于15微米至350微米之间的一厚度。
16.根据权利要求7所述的聚酯薄膜,其特征在于,所述聚酯薄膜进一步包括:混合至所述耐高温树脂材料与所述聚酯树脂材料1中的一相容剂,并且所述相容剂为聚碳酸酯及聚苯醚树脂的至少其中之一。
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