CN105492529B - 发泡片用发泡性树脂组合物、发泡片、粒子状的聚乳酸树脂的制备方法及发泡片的制备方法 - Google Patents

发泡片用发泡性树脂组合物、发泡片、粒子状的聚乳酸树脂的制备方法及发泡片的制备方法 Download PDF

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CN105492529B
CN105492529B CN201480047646.3A CN201480047646A CN105492529B CN 105492529 B CN105492529 B CN 105492529B CN 201480047646 A CN201480047646 A CN 201480047646A CN 105492529 B CN105492529 B CN 105492529B
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foamed sheet
polylactic
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polylactic resin
resin
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CN105492529A (zh
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慎埈范
姜声蓉
李敏熙
权惠元
姜京旻
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Abstract

本发明提供发泡片用发泡性树脂组合物，上述发泡片用发泡性树脂组合物包含平均粒径为约1μm至约100μm的聚乳酸树脂粒子。上述粒子状的聚乳酸树脂的制备方法包括：投入聚乳酸树脂之后，形成熔融聚乳酸喷射液的步骤；以及一边利用熔融喷射法喷射上述熔融聚乳酸喷射液一边进行冷却，来获得粒子状的聚乳酸的步骤。并且，本发明提供发泡片的制备方法，上述发泡片的制备方法使用包含上述聚乳酸树脂的发泡片用发泡性树脂组合物。

Description

发泡片用发泡性树脂组合物、发泡片、粒子状的聚乳酸树脂的 制备方法及发泡片的制备方法
技术领域
本发明涉及发泡片用发泡性树脂组合物、发泡片、粒子状的聚乳酸树脂的制备方法及发泡片的制备方法。
背景技术
多个使用聚乳酸的产品经过多次的热加工来生产。据报告，聚乳酸对热敏感，从而通过高温进行水解。由于这种聚乳酸的特性，在聚乳酸的产品的加工中因基于热的水解而发生分子量变化，其还对生产的完成品的状态产生影响。
发明内容
技术问题
本发明提供包含本发明的聚乳酸树脂，且可制备寿命得到提高的发泡片的发泡片用发泡性树脂组合物。
本发明的再一实例提供将包含于上述发泡片用发泡性树脂组合物的聚乳酸树脂制备成微粒子状的方法。
本发明的另一实例提供使用上述发泡片用发泡性树脂组合物来制备发泡片的方法。
解决问题的手段
在本发明的一实例中，提供发泡片用发泡性树脂组合物，上述发泡片用发泡性树脂组合物包含约1μm至约100μm的聚乳酸树脂粒子。
由上述发泡片用发泡性树脂组合物成型而成的发泡片可包含重均分子量为约100000至约200000的聚乳酸树脂。
上述发泡片用发泡性树脂组合物可以为在液态溶液中分散有上述粒子状的聚乳酸树脂的悬浮液。
在本发明的再一实例中，提供发泡片，上述发泡片包含约1μm至约100μm的聚乳酸树脂粒子。
上述发泡片可包含重均分子量为约100000至约200000的聚乳酸树脂。
在本发明的另一实例中，提供聚乳酸树脂粒子的制备方法，上述聚乳酸树脂粒子的制备方法包括：投入聚乳酸树脂后，形成熔融聚乳酸喷射液的步骤；以及一边利用熔融喷射法喷射上述熔融聚乳酸喷射液一边进行冷却，来获得粒子状的聚乳酸的步骤。
向挤压机投入上述聚乳酸树脂后，使上述聚乳酸树脂向喷嘴移动，来使上述聚乳酸树脂在上述喷嘴中加热，从而可形成上述熔融聚乳酸喷射液。
向上述挤压机可投入颗粒形状的聚乳酸树脂或粉末状的聚乳酸树脂。
向上述喷嘴一同注入空气，来可排出上述熔融聚乳酸喷射液。
向上述喷嘴注入的空气的温度可以为300至500℃，向上述喷嘴注入的空气的压力可以为约100至约1000psi，向上述喷嘴注入的空气的注入速度可以为约10至约50m/s。
上述喷嘴的温度可以为约200至约400℃。
上述喷嘴的压力可以为约10psi至约1000psi。
上述喷嘴的直径可以为约0.5至约3.0mm。
上述熔融聚乳酸喷射液可包含添加剂，上述添加剂包含选自由润滑剂、增塑剂及它们的组合组成的组中的至少一种。
在约250℃温度下，上述熔融聚乳酸喷射液的粘度可以为约1500至约2000cp。
可对上述喷嘴施加约2000V至约50000V的电压来执行熔融电喷射法。
上述粒子状的聚乳酸树脂的平均粒径可以为约1至约100μm。
在本发明的还一实例中，提供发泡片的制备方法，上述发泡片包括聚乳酸树脂层，上述发泡片的制备方法包括：混合平均粒径为约1至约100μm的粒子状的聚乳酸树脂、发泡树脂及添加剂，并涂敷发泡性树脂组合物来形成层的步骤；以及对由上述发泡性树脂组合物形成的层进行发泡来形成发泡层的步骤。
利用熔融喷射法来可获得上述粒子状的聚乳酸树脂。
通过上述发泡片的制备方法制备的发泡片可包含重均分子量为约100000至约200000的聚乳酸树脂。
发明的效果
使用上述微粒子状的聚乳酸树脂来制备的发泡片的耐久性、表面特性优秀，且寿命得到提高。
附图说明
图1简要表示本发明一实例的发泡片的制备方法的工序流程图。
图2简要表示发泡片的制备方法的工序流程图。
具体实施方式
以下，详细说明本发明的实例。但这仅作为例示而提出，本发明并不局限于此，本发明仅根据后述的发明要求保护范围的范围而定义。
在本发明的一实例中，提供平均粒径为约1μm至约100μm的聚乳酸树脂粒子。
具有上述大小范围的聚乳酸树脂粒子可通过熔融喷射法来制备具有。并且，当执行熔融喷射法时，向喷嘴一同放入高温高压的空气，从而可获得更均匀的聚乳酸粒子。上述熔融喷射法可通过执行熔融喷射法时施加电压的熔融电喷射法(melt ESD，meltElectrostatic Spray Deposition)来执行。
本发明的再一实例的聚乳酸树脂粒子的平均直径为约1至约100μm，上述聚乳酸树脂粒子的制备方法包括：投入聚乳酸树脂后，形成熔融聚乳酸喷射液的步骤；以及一边利用熔融喷射法喷射上述熔融聚乳酸喷射液一边进行冷却，来获得粒子状的聚乳酸的步骤。
在制备上述粒子状的聚乳酸树脂时，适用上述熔融喷射法，从而具有可容易调节聚乳酸树脂粒子大小，并使粒子大小的分布均匀的优点。例如，通过上述粒子状的聚乳酸树脂的制备方法，可制备平均粒径为约1至约100μm的聚乳酸树脂粒子。
为了执行上述熔融喷射法，首先，向具有喷嘴的挤压机(extruder)投入颗粒或粉末形态的聚乳酸，在高温的喷嘴中，熔融颗粒或粉末形态的聚乳酸被熔融而形成为熔融聚乳酸喷射液，上述熔融聚乳酸喷射液以高温的微大小的液滴形态喷射，并且，上述喷射在冷却室内进行，因而喷射的同时冷却上述液滴，从而形成聚乳酸树脂的微大小粒子。
选择性地，上述熔融喷射法可通过对上述喷嘴施加电压来执行熔融电喷射法。
向上述喷嘴一同注入空气，来排出上述熔融聚乳酸喷射液。
调节向上述喷嘴注入的空气的温度、压力及速度来可调节排出的熔融聚乳酸喷射液的液滴的大小及形状，由此可调节最终要形成的聚乳酸树脂的粒子的大小。
例如，向上述喷嘴注入的空气的温度可以为约300至约500℃，向上述喷嘴注入的空气的压力可以为约10至约1000psi，向上述喷嘴注入的空气的注入速度可以为约10至约50m/s。
在上述熔融喷射法中，为了使聚乳酸树脂以微大小的液滴喷射可调节上述熔融的聚乳酸的粘度。
调节上述熔融的聚乳酸树脂的粘度的方法有调节喷嘴的温度，或向上述挤压机中与聚乳酸树脂一同添加润滑剂或如增塑剂等添加剂来进行混合，或向投入于上述挤压机的颗粒形态的聚乳酸树脂注入如CO2之类的气体的方法等。
例如，上述喷嘴的直径可以为约0.5至约3.0mm。
具体地，在约250℃温度下，上述熔融聚乳酸喷射液的粘度可以为约1500至约2000cp。以上述范围的粘度形成涂覆液来可形成微粒子状的聚乳酸树脂。
上述熔融喷射法的工序条件并没有特别限制，可将公知的工序条件，例如，上述喷嘴的压力设定为约100psi至约1000psi来执行。
但是，上述熔融喷射法应在聚乳酸熔融的温度范围内执行。例如，上述喷嘴的温度可以为约200至约400℃。
并且，如上所述，为了形成微粒子状的聚乳酸树脂，可将喷嘴的直径可设定为约0.5mm至约3.0mm。
例如，上述熔融喷射法可对上述喷嘴施加约2000V至约50000V的电压来执行熔融电喷射法。
可通过上述方法制备的微粒子状的聚乳酸树脂可有用地适用于发泡片的制备。
在本发明的还一实例中，提供发泡片，上述发泡片包含约1μm至约100μm的聚乳酸树脂粒子。使用具有上述微大小的小粒径的聚乳酸树脂粒子，通过后述的发泡片的制备方法可制备发泡片，根据如上所述的方法制备的发泡片最小化基于热的加工工序次数，来最小化聚乳酸树脂的劣化，从而可维持更高的分子量。具体地，上述发泡片可包含重均分子量为约100000至约200000的聚乳酸树脂。
图2简要表示制备示例性发泡片的工序流程图。一般，适用聚乳酸树脂的发泡片通过多种工序来生产。进行具体地说明，首先，向粉末或颗粒的聚乳酸树脂添加润滑剂、添加剂、稳定剂等并进行搅拌及捏合(kneading)来进行T模(T-die)挤压加工之后，执行与纸贴合(Lamination)及发泡工序。通过上述工序，通常制备发泡片，至少经过三四次左右的热加工工序。
但是，聚乳酸树脂在高温条件下进行水解，因而众所周知，其对热处理敏感。根据这种聚乳酸树脂的特性，适用聚乳酸树脂的发泡片由于加工中基于热的水解，对聚乳酸树脂的分子量产生影响，而这导致产品的劣化。
在本发明的又一实例中，提供发泡片的制备方法，在制备发泡片时使用上述微粒子状的聚乳酸树脂，从而可减少基于热的加工工序次数。
在一实例中，提供发泡片的制备方法，上述发泡片包括聚乳酸树脂发泡层，上述发泡片的制备方法包括：混合平均粒径为约1至约100m的粒子状的聚乳酸树脂、发泡树脂及添加剂，并涂敷发泡性树脂组合物来形成层的步骤；以及对由上述发泡性树脂组合物形成的层进行发泡来形成发泡层的步骤。
上述发泡性树脂组合物可通过混合微大小聚乳酸树脂来形成悬浮液。具体地，对溶胶-凝胶形态的上述发泡性树脂组合物进行发泡来可形成聚乳酸发泡层。
图1为本发明的一实例的发泡片的制备方法的工序流程图。首先，适用熔融喷射法来制备微大小的聚乳酸粒子粉末(图1的熔融电喷射法步骤)，接着，混合包含具有微大小的上述聚乳酸粒子粉末的发泡性树脂组合物来准备悬浮溶液(图1的混合(溶胶(Sol)制备步骤)，并将其涂敷于基材上来形成涂敷层之后(图1的涂敷溶胶的步骤)，进行发泡(图1的发泡步骤)并形成发泡层，从而可制备发泡片。
通过上述发泡片的制备方法可制备发泡片，上述发泡片包括聚乳酸发泡层，上述聚乳酸发泡层包含平均粒径为约1μm至约100μm的聚乳酸树脂粒子。
上述发泡树脂可没有限制地使用用于制备发泡片的发泡层的材料，例如，上述材料可以为聚氯乙烯(PVC)、聚氨酯等。
以上述方法形成的发泡层均匀分散上述聚乳酸树脂的微粒子。如上所述，聚乳酸树脂均匀地分散而存在，因而可提高最终生成的发泡片的产品表面特性，还提高发泡片的耐久性。
上述发泡片的制备方法与一般公知的发泡片的制备工序相比，减少基于热的加工次数，从而可明显减少根据聚乳酸树脂的水解所产生的损伤，因此，可抑制根据聚乳酸树脂的水解的分子量的下降。由此，根据上述发泡片的制备方法制备的发泡片明显改善基于热的加工工序的产品的劣化，从而提高寿命。
根据上述发泡片的制备方法制备的发泡片不根据所使用的微粒子状的聚乳酸树脂的分子量水解大大减少而可维持。例如，根据上述发泡片的制备方法制备的发泡片可包含重均分子量为约100000至约200000的聚乳酸树脂。
尤其，根据上述发泡片的制备方法制备的发泡片能够以包含重均分子量为约100000以上的聚乳酸树脂的方式制备。
以下，记载本发明的实施例及比较例。这种实施例只是本发明的一实施例，本发明不局限于以下实施例。
实施例
实施例1
利用颗粒形态的聚乳酸树脂，并通过熔融电喷射法来制备了平均大小为50μm的粒子。当执行熔融电喷射法时，喷嘴的温度为250℃，喷嘴的压力为500psi，喷嘴的直径为1mm，对喷嘴施加20000V的电压，在250℃温度下，熔融聚乳酸喷射液的粘度为2000cp。
放入制备的上述聚乳酸粒子和增塑剂、稳定剂、润滑剂等的添加剂，并搅拌来制备了含有聚乳酸树脂的溶胶。将制备的含有聚乳酸树脂溶胶以溶胶-凝胶的方式涂敷后，进行干燥(发泡)，从而制备了厚度为约0.5mm的发泡片样品。
比较例1
在与实施例1相同的颗粒形态的聚乳酸树脂中放入增塑剂、稳定剂、润滑剂等的添加剂并进行混合，从而制备了含有聚乳酸树脂混合组合物。在150℃温度下，使用密炼机来对含有上述聚乳酸树脂的混合组合物进行混炼，并使用150℃温度的二辊机进行第一次混合、第二次混合。由此，对以这种方式制备的混合原料进行压延加工并发泡，来制备了厚度为0.5mm的发泡片样品。
评价
实验例1：聚乳酸的分子量测定
针对在上述实施例1及比较例1中制备的发泡片样品，使用凝胶渗透色谱法(GPC，gel permeation chromatography)(e2695，Waters制备)来测定重均分子量，并记载在下列表1中。
实验例2：耐久性评价
根据ASTM D256方式，测定在上述实施例1及比较例1中制备的薄片的耐冲击强度，并记载在下列表1中。
实验例3：表面特性评价
通过肉眼对在上述实施例1及比较例1中制备的薄片的表面特性进行评价，并记载在下列表1中。评价基准通过肉眼来判定，采用5分制，判定为5分(优秀)～1分(NG)。
表1

Claims (14)

1.一种发泡片用发泡性树脂组合物，其特征在于，包含粒径1μm至100μm的聚乳酸树脂粒子，且粒子状的聚乳酸树脂由熔融喷射法得到；
由所述发泡片用发泡性树脂组合物成型而成的发泡片包含重均分子量为100000至200000的聚乳酸树脂；
所述发泡片用发泡性树脂组合物为在液态溶液中分散有所述粒子状的聚乳酸树脂的悬浮液。
2.根据权利要求1所述的发泡片用发泡性树脂组合物，其中所述粒子的粒径为1μm至50μm。
3.一种粒子状的聚乳酸树脂的制备方法，其特征在于，包括：
投入聚乳酸树脂后，形成熔融聚乳酸喷射液的步骤；以及
利用熔融喷射法喷射所述熔融聚乳酸喷射液的同时进行冷却，来获得粒子状的聚乳酸的步骤；向喷嘴一同注入空气，来排出所述熔融聚乳酸喷射液；
在250℃温度下，所述熔融聚乳酸喷射液的粘度为1500至2000cp。
4.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，向挤压机投入所述聚乳酸树脂后，使所述聚乳酸树脂向喷嘴移动，在所述喷嘴中加热所述聚乳酸树脂，从而形成所述熔融聚乳酸喷射液。
5.根据权利要求4所述的粒子状的聚乳酸树脂的制备方法，其特征在于，向所述挤压机投入颗粒形状的聚乳酸树脂或粉末状的聚乳酸树脂。
6.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，向所述喷嘴注入的空气的温度为300至500℃，向所述喷嘴注入的空气的压力为100至1000psi，向所述喷嘴注入的空气的注入速度为10至50m/s。
7.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，所述喷嘴的温度为200至400℃。
8.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，所述喷嘴的压力为10psi至1000psi。
9.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，所述喷嘴的直径为0.5至3.0mm。
10.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，所述熔融聚乳酸喷射液包含添加剂，所述添加剂包含选自由润滑剂、增塑剂及它们的组合组成的组中的至少一种。
11.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，对所述喷嘴施加2000V至50000V的电压来执行熔融电喷射法。
12.根据权利要求3所述的粒子状的聚乳酸树脂的制备方法，其特征在于，所述粒子状的聚乳酸树脂的平均粒径为1至100μm。
13.一种发泡片的制备方法，所述发泡片包括聚乳酸发泡层，所述发泡片的制备方法的特征在于，包括：
利用熔融喷射法获得平均粒径为1至100μm的粒子状的聚乳酸树脂；
混合所述聚乳酸树脂、发泡树脂及添加剂，并涂敷发泡性树脂组合物来形成层的步骤；以及
对由所述发泡性树脂组合物形成的层进行发泡来形成发泡层的步骤；
其中所述发泡性树脂组合物是悬浮液并且通过所述制备方法制备的发泡片包含重均分子量为100000至200000的聚乳酸树脂。
14.一种由权利要求13所述的制备方法制备的发泡片。
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