CN107446269B - 一种透明隔热的聚氯乙烯胶布及其制备方法 - Google Patents

一种透明隔热的聚氯乙烯胶布及其制备方法 Download PDF

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CN107446269B
CN107446269B CN201710729948.4A CN201710729948A CN107446269B CN 107446269 B CN107446269 B CN 107446269B CN 201710729948 A CN201710729948 A CN 201710729948A CN 107446269 B CN107446269 B CN 107446269B
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polyvinyl chloride
adhesive tape
insulating
transparent heat
heat
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CN107446269A (zh
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廖德超
黄英德
赖振和
林昭贤
袁敬尧
马登科
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Nan Ya Plastics Corp
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Nan Ya Plastics Corp
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Abstract

一种透明隔热的聚氯乙烯胶布,是以厚度0.02~2.0mm的透明软质或半硬质或硬质聚氯乙烯基材制成,且基材的内部均匀散布以特定配方制成粒径介于40~110nm的隔热浆料,具备优异耐候性,在符合ASTM G‑154规范下使用紫外线照射300小时后的性能衰退率(F)小于4%,衰退速度慢,长时间保留隔热效果的使用寿命,优于传统金属氧化物的隔热胶布。

Description

一种透明隔热的聚氯乙烯胶布及其制备方法
技术领域
本发明涉及一种具有高透明度及高隔热性的聚氯乙烯胶布及其制备方法,特别是所制得的聚氯乙烯胶布具备优异的耐候性,符合ASTM G-154规范下使用紫外线照射300小时后的耐候性衰退率小于4%。
背景技术
一般应用于贴在建筑物玻璃、汽车窗户、冷冻储藏展示柜上的聚氯乙烯胶布节能产品,除了必须具备视觉上透明的要求以外,还必须兼具阻隔红外光所产生的热能的功效,选用具备光波长选择性材料,要能有效滤除700nm~1800nm的红外光线,达到隔热功效,并让400nm~700nm的可见光线透过,以达到视觉上透明的要求。另外,太阳光中200nm~400nm的紫外光范围,会对人体造成某种程度的伤害,因此在建筑玻璃或汽车窗户用材料要具备UV遮蔽的能力,达到保护人体的功能。
传统上在塑料基材聚酯膜(PET)上以干式涂布或湿式涂布方法附加隔热功能,但此种经涂布加工制得的制品,却有使用寿命短及隔热功能衰退快的缺点。
如图1所示,以干式涂布加工制成的隔热透明胶膜10,是以真空溅镀或蒸镀方式,将金属或金属氧化物等无机材料12均匀附着在塑料基材11的上面而形成隔热膜。
如图2所示,以湿式涂布加工制成的隔热透明胶膜20,是将具隔热功能的无机颗粒22均匀分散在合适的树脂23及溶媒中,经配制成粘度合宜的涂布液后,再涂布在塑料基材21的上面;经干燥去除溶媒后,无机颗粒22及树脂23就形成附着在塑料基材21上面的隔热膜。
上述干式涂布或湿式涂布加工隔热透明胶膜10及20的制备工艺复杂,至少须经由两道程序,首先准备基材薄膜(胶布);其次于基材表面涂布或蒸镀具有红外线阻隔或紫外线遮蔽材料,所衍生的问题,包括:制备工艺中的溶剂挥发,导致污染空气;以及,制备工艺所产生的废溶剂处理,导致环保问题,为解决污染空气及环保问题,需使用高规格的工艺设备,导致加工成本偏高。
此外,传统隔热透明胶膜为提升隔热效果,借助添加锑锡氧化物(ATO)、锑锌氧化物(AZO)、类似金属氧化物以及六硼化物,包括添加六硼化镧(LaB6)或六硼化铈(CeB6)等隔热颗粒于传统隔热透明胶膜的组织中,从而确实提升隔热效果,但耐候性差的缺点,仍然未获得解决,隔热效果衰退的速度很快。
发明内容
本发明的主要目的在于提供一种透明隔热的聚氯乙烯胶布,以厚度0.02~2.0mm的透明软质或半硬质或硬质聚氯乙烯基材制成,且基材的内部组织中均匀散布以特定配方制成粒径介于40~110nm的隔热浆料,具备优异耐候性,聚氯乙烯胶布拥有的可见光透过率(VLT%)及与红外线阻隔率(IR cut%)特性,衰退速度慢,长时间保留隔热效果的使用寿命,优于传统金属氧化物的隔热胶布。
本发明的另一主要目的在于提供一种透明隔热的聚氯乙烯胶布,在符合ASTM G-154规范下使用紫外线照射300小时后的性能衰退率(F)小于4%,且由100重量份的聚氯乙烯、0.1~60重量份的增塑剂、1~10重量份的环氧大豆油、0.1~10重量份的稳定剂、0.05~5.0重量份的紫外线吸收剂、0.05~0.2重量份的偶合剂、及5.5~7.5重量份的隔热浆料制成;而且,所述隔热浆料由下列组分g1)~g3)的总和为100wt%调制而成,且均匀散布于聚氯乙烯胶布的聚氯乙烯基材内部:
g1)钨铯粉(WCs),化学式为CsxNyWO3-zClc,占10~18wt%,其中,Cs为铯;N为锡、锑或铋;W为钨;O为氧;Cl为氯;x、y、z、c均为正数,且符合x≤1.0;y≤1.0;y/x≤1.0;z≤0.6;及c≤0.1的条件;
g2)分散剂,占2~5wt%;及
g3)增塑剂,占77~88wt%。
本发明的又一主要目的在于提供制备透明隔热的聚氯乙烯胶布的方法,包括以下步骤:
1)取100重量份的聚氯乙烯、0.1~60重量份的增塑剂1~10重量份的环氧大豆油、0.1~10重量份的稳定剂、0.05~5.0重量份的紫外线吸收剂、0.05~0.2重量份的偶合剂、及5.5~7.5重量份的隔热浆料为原料,使用搅拌机混合均匀后,引入至密炼机中均匀混炼;
2)料温控制在150~190℃,经辊轮机(roller machine)制成充分胶化反应的混合料;选择引入步骤3)或步骤4)或步骤5)的其中一个步骤进行加工;
3)以压延加工制成厚度介于0.05~1.0mm的热熔胶布,成型后选择引入步骤6)或直接引入步骤7)
4)以T型模(T-Die)加工制成厚度介于0.05~2.0mm的热熔胶布,成型后直接引入步骤7);
5)以吹塑成型制成厚度介于0.02~0.8mm的热熔胶布,成型后直接引入步骤7);
6)引入温度介于20~85℃的水中冷却硬化,再经过除水后,引入步骤7);
7)将胶布冷却定型及卷取后,制成所述透明隔热聚氯乙烯胶布。
作为优选实施例,所述偶合剂选自有机硅烷化合物偶合剂、有机锆铝化合物偶合剂或有机钛铝化合物偶合剂。
作为优选实施例,所述隔热浆料的分散剂,选自高分子型的共聚物分散剂、含硅成份分散剂或含氟成份分散剂中的一种以上。
作为优选的实例,所述增塑剂选自邻苯二甲酸二(C9~C11烷基)酯、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异癸酯(DIDP)、对苯二甲酸二异辛酯(DOTP)、己二酸二异壬酯(DINA)、己二酸二(2-乙基己基)酯(DOA)、偏苯三酸三辛酯(TOTM)、1,2-环己烷二羧酸二异壬酯(DHIN)或1,2-环已烷二羧酸异辛酯(DHEH)中的一种或以上
作为优选的实例,所述紫外线吸收剂选自羟基苯基苯并三唑类紫外线吸收剂或羟基二苯甲酮类紫外线吸收剂中的一种或以上。
作为优选的实例,本发明的透明隔热聚氯乙烯胶布,是以二片或二片以上单层结构的透明隔热聚氯乙烯胶布叠合一起构成。
作为优选的实例,本发明的透明隔热聚氯乙烯胶布,是由一片单层结构透明隔热的聚氯乙烯胶布与其它种类塑料基材叠合一起构成。
本发明的聚氯乙烯胶布,具备以下有益的效果,包括:
1)使用特定配方的隔热浆料,且填加于聚氯乙烯胶布中,促进聚氯乙烯胶布具有高透明、高隔热的效果;
2)隔热浆料在聚氯乙烯胶布加工工艺中没有析出的问题;
3)制得的聚氯乙烯胶布耐候隔热效果佳,具有长久保持的隔热功能,隔热效果衰退慢,尤其是,在符合ASTM G-154规范下使用紫外线照射300小时后的性能衰退率(F)小于4%;优于传统金属氧化物的隔热胶布;
4)具有自粘性,适合家庭自行组装。
附图说明
图1是传统干式涂布加工制得的透明隔热胶膜的断面放大图。
图2是传统湿式涂布加工制得的透明隔热胶膜的断面放大图。
图3是本发明透明隔热聚氯乙烯胶布的断面放大图,呈现单层结构且隔热浆料均匀散布于聚氯乙烯基材中。
图4是本发明的另一种透明隔热聚氯乙烯胶布的断面放大图,呈现复层结构,由二片单层结构透明隔热聚氯乙烯胶布叠合一起构成。
图5是本发明的另一种复合异质结构透明隔热的聚氯乙烯胶布的断面放大图,呈现异质复层结构,由一片单层结构透明隔热聚氯乙烯胶布与其它种类的塑料基材叠合一起构成。
图6是本发明的又一种复合异质结构透明隔热的聚氯乙烯胶布的断面放大图,呈现异质复层结构,由一片其它种类的塑料基材叠合夹置在二片单层结构透明隔热聚氯乙烯胶布中间一起构成。
附图标记
10 隔热透明胶膜
11 塑料基材
12 无机材料
20 隔热透明胶膜
21 塑料基材
22 无机颗粒
23 树脂
30 透明隔热的聚氯乙烯胶布或PVC胶布
31 聚氯乙烯基材或PVC基材
32 隔热浆料
40 复层结构PVC胶布
50 复合异质结构PVC胶布
60 异质夹层结构PVC胶布
具体实施方式
如图3所示,本发明的透明隔热的聚氯乙烯胶布30(下称PVC胶布30),是厚度介于0.02~2.0mm的透明软质或半硬质或硬质胶布,兼具透明性以及遮蔽红外线及紫外线的特性。
所述PVC胶布30的透明性,是以所述PVC胶布30的可见光透过率(VLT%)评估所述PVC胶布30可以让可见光穿透的能力,可见光透过率(VLT%)的数值越高,代表所述PVC胶布30的透明性越佳。
所述PVC胶布30的遮蔽红外线特性,是以所述PVC胶布30的红外线阻隔率(IRcut%)评估所述PVC胶布30隔绝红外线穿透的能力以及达到的隔热效果,红外线阻隔率(IRcut%)的数值越高,代表所述PVC胶布30的隔热效果越佳。
所述PVC胶布30的透明隔热性能指数(Q),是指所述PVC胶布30的可见光透过率(VLT%)与红外线阻隔率(IR cut%)两者数值的总和,再乘以100的乘积值,也就是,(VLT%+IR cut%)*100的数值。
所述PVC胶布30的性能衰退率(F),是指经过一段使用时间(T)后,所述PVC胶布30的透明隔热性能指数(Q),随着使用时间(T)衰退的衰退程度,是评估所述PVC胶布30的使用寿命或耐候性的依据。例如,使用前,所述PVC胶布30的透明隔热性能指数为Q1,经过一段使用时间(T)后,所述PVC胶布30的透明隔热性能指数衰退为Q2。此刻,经过一段使用时间(T)后,所述PVC胶布30的性能衰退率(F),为[(Q1-Q2)/Q1]*100%的数值。
所述PVC胶布30的性能衰退率(F)值越小,表示经过一段使用时间(T)后,所述PVC胶布30使用前后的透明隔热性能指数Q1及Q2差异越小,也代表所述PVC胶布30的耐候性越佳,长久保持具备隔热功能的使用寿命越长。
如图3所示,本发明的PVC胶布30的结构特征,是在0.02~2.0mm厚度的聚氯乙烯基材31(下称PVC基材31)的组织中,均匀散布有直径介于40~110nm的隔热浆料32。
更具体而言,本发明的PVC胶布30,是具优异耐候性的透明隔热聚氯乙烯胶布,厚度介于0.02~2.0mm,且使用下列组分a)~g)制成,且其内部均匀散布有隔热浆料32:
a)聚氯乙烯(PVC)树脂:100重量份;
b)增塑剂:0.1~60重量份;
c)环氧大豆油:1~10重量份;
d)稳定剂:0.1~10重量份;
e)紫外线(UV)吸收剂:0.05~5.0重量份;
f)偶合剂:0.05~0.2重量份;及
g)隔热浆料:5.5~7.5重量份。
而且,所述隔热浆料32或g)的成分组成,是由下列组分g1)~g3)构成,且各组分的总和为100wt%:
g1)钨铯粉(WCs),化学式为CsxNyWO3-zClc,占10~18wt%,其中,Cs为铯;N为锡、锑或铋;W为钨;O为氧;Cl为氯;x、y、z、c均为正数,且符合x≤1.0;y≤1.0;y/x≤1.0;z≤0.6;及c≤0.1的条件;
g2)分散剂,占2~5wt%;及
g3)增塑剂,占77~88wt%。
所述隔热浆料32的粒径大小,介于50nm~110nm,是采用以下两种研磨条件:
1.单一阶段研磨:将所述隔热浆料32的粒径研磨至平均粒径约90~110nm,研磨条件如下:
研磨珠:直径介于0.2-0.6mm;填充率:介于80%~95%;筛网孔目大小:介于15~100μm;温控:50℃以下;研磨时间:6~12小时。
2.两阶段研磨(包括粗磨及细磨):将所述隔热浆料32的粒径研磨至平均粒径约40~60nm,研磨条件如下:
1)粗磨段同上述单一阶段研磨的研磨条件。
2)细磨段:研磨珠:直径介于0.05~0.2mm;填充率:介于80%~95%;筛网孔目大小:介于15~100μm;温控:50℃以下;研磨时间:4~8小时。
基于所述PVC胶布30的结构特征,本发明的PVC胶布30具备优异耐候性,在符合ASTM G-154规范下,使用紫外线加速老化设备(QUV weathering tester)进行耐候测试照射300小时(简称QUV-300耐候测试)后,所述PVC胶布30的性能衰退率(F)小于5%,优选为小于4%。
本发明的PVC胶布30的制法,是由下列步骤制得:
1)取前面所述的组分a)~g)为原料,使用搅拌机混合均匀后,引入至密炼机均匀混炼;
2)料温控制在150~190℃,经辊轮机制成充分胶化反应的混合料;选择引入步骤3)或步骤4)或步骤5)的其中一个步骤进行加工;
3)以压延加工制成厚度介于0.05~1.0mm的热熔胶布,成型后选择引入步骤6)或直接引入步骤7)
4)以T性模加工制成厚度介于0.05~2.0mm的热熔胶布,成型后直接引入步骤7);
5)以吹塑成型制成厚度介于0.02~0.8mm的热熔胶布,成型后直接引入步骤7);
6)引入温度介于20~85℃的水中冷却硬化,再经过除水后,引入步骤7);
7)将胶布冷却定型及卷取后,制成所述透明隔热聚氯乙烯胶布。
制备本发明的PVC胶布30的过程中,所使用的聚氯乙烯(PVC)树脂a),可选自以本体聚合(Bulk Polymerization)、溶液聚合(Solution Polymerization)、悬浮聚合(Suspension Polymerization)或乳液聚合(Emulsion Polymerization)制得的聚氯乙烯聚合物或共聚物中的一种以上的组合物。
制备本发明的PVC胶布30的过程中,所使用的增塑剂b)或g3),选自磷酸酯类、酞酸酯类、苯三酸酯类、环氧类、聚酯类、氯化烃类或脂肪族二酸酯类增塑剂中的一种以上。
其中,所述酞酸酯类增塑剂选自邻苯二甲酸二(C9~C11烷基)酯((C9-C11)dialkyl phthalate,例如,南亚塑胶工业股份有限公司制品911P)、邻苯二甲酸二异壬酯(di-isononyl phthalate,DINP)、邻苯二甲酸二(2-乙基己基)酯(di-2-ethylhexylphthalate,DEHP)、邻苯二甲酸二丁酯(Di-Butyl Phthalate,DBP)、邻苯二甲酸二异癸酯(di-iso-decyl phthalate,DIDP)、对苯二甲酸二异辛酯(di-2-ethylhexylterephthalate,DOTP)中的一种以上。
所述脂肪族二酸酯类增塑剂选自己二酸二异壬酯(di-isononyl adipate,DINA)或己二酸二(2-乙基己基)酯(dioctyl adipate,DOA)中的一种以上。
所苯三酸酯类增塑剂选自偏苯三酸三辛酯(tris(2-ethylhexyl)trimellitate,TOTM)。所述聚酯类增塑剂选自1,2-环己烷二羧酸二异壬酯(1,2-cyclohexandicarbonsurediisononylester,DHIN)或1,2-环已烷二羧酸异辛酯(bis(2-ethylhexyl)cyclohexane-1,2-dicarboxylate,DHEH)中的一种以上。
制备本发明的PVC胶布30的过程中,所使用的隔热浆料32或g),粒径界于40~110nm,视透明度、雾度等不同物性的需求,可选自纳米复合钨氧氯化物中的一种以上。
制备本发明的PVC胶布30的过程中,所使用的稳定剂d),可选自Ba-Zn系稳定剂或Ca-Zn系稳定剂或有机锡稳定剂。
制备本发明的PVC胶布30的过程中,可以添加使用助剂,可选自改性剂、分散剂、或紫外线吸收剂中的一种以上搭配而成。添加助剂的目的,在于促使PVC基材31的组织中的隔热浆料32达到均匀分散的目的。
制备本发明的PVC胶布30的过程中,所使用的偶合剂f),选自有机硅烷化合物偶合剂、有机锆铝化合物偶合剂或有机钛铝化合物中的一种以上,利于加工,防止析出。
制备本发明的PVC胶布30的过程中,所使用的紫外线(UV)吸收剂e),可选自羟基苯基苯并三唑类紫外线吸收剂或羟基二苯甲酮类紫外线吸收剂中的一种或以上。
在使用上,本发明的PVC胶布30,可以如图3所示呈现单层结构,或如图4所示为了提高厚度取代玻璃而呈现以多片单层结构PVC胶布30叠合一起构成复层结构PVC胶布40。
本发明的PVC胶布30也可以与其它种类的塑料基材40叠合在一起使用,例如,可以如图5所示呈现以单层结构PVC胶布30与其它种类的塑料基材40叠合一起构成复合异质结构PVC胶布50,或如图6所示呈现其它种类塑料基材40叠合夹置在二片单层结构的PVC胶布30中间一起构成异质夹层结构PVC胶布60。其它种类的塑料基材40可以作为补强用,视用途决定贴合层数与塑料材质。
以下,列举实施例进一步说明本发明的PVC胶布30具备优异耐候性,在符合ASTMG-154规范下进行QUV-300耐候测试后,所述PVC胶布30的性能衰退率(F)小于5%。而且,本发明的PVC胶布30各项物性的评估方式,是依据下列的测试方法。
1、可见光透过率(VLT%)及雾度测试:
采用日本的Tokyo Denshoku Co.,Ltd.制造的型号为TC-HⅢ的光透过率及雾度测试机(Haze Meter),依JIS K7705测试标准,测试聚氯乙烯胶布的光透过率及雾度值。
测试结果为可见光透过率越高、雾度值越低,则代表聚氯乙烯胶布的透明性越佳。
2、红外线阻隔率(IR cut%)测试:
采用日本的HOYA制造的型号为LT-3000红外线及紫外线阻隔率测试机,依JISR3106测试标准,测试聚氯乙烯胶布的红外线阻隔率。
测试结果为红外线阻隔率愈高,代表聚氯乙烯胶布的隔热效果越佳。
3、紫外线阻隔率测试:
采用日本的HOYA制造的型号为LT-3000红外线及紫外线阻隔率测试机,依JISR3106测试标准,测试聚氯乙烯胶布的紫外线阻隔率。
测试结果为紫外线穿透率愈低,代表聚氯乙烯胶布的阻隔紫外线(UV)效果越佳。
4、QUV-300小时耐候(老化)测试:
采用台湾联宙科技股份有限公司(ATLAS TECHNOLOGY Co.)制造的型号为ATLASUV TEST紫外线加速老化设备(耐候试验机),依ASTM G-154测试标准,测试聚氯乙烯胶布经过照射300小时后的耐候性,包括可见光透过率(VLT%)及红外线阻隔率(IR cut%)。耐候试验条件如下:
灯管波长:UVB 313nm;
试验温度:50~60℃;
照射周期:每周期包括照射4小时,接着蒸湿4小时;
试验时间300小时;及
照射能量:0.71w/m2
试品经过QUV耐候试验300小时后,再次根据上述(1)可见光穿透率及雾度测试,以及(2)红外线阻隔率测试,进行(1)及(2)的测试,获得试片经过QUV耐候试验300小时后的VLT+IR cut(%)数值。
5、评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F):
PVC胶布的性能衰退率(F),或称耐PVC胶布的耐候性衰退率,是指PVC胶布的可见光透过率(VLT%)与红外线阻隔率(IR cut%)的总和,在未经过QUV-300小时耐候测试前,与经过QUV-300小时耐候测试后的衰退百分比例。
测试前后的VLT+IR cut(%)值差异越小,代表PVC胶布的性能衰退率(F)或耐候性衰退率越小,PVC胶布的耐候越佳。
6、评估PVC胶布的软硬度:
PVC胶布的软硬度,是通过加入一定数量的增塑剂来调整,添加的增塑剂量越多,PVC胶布的硬度越软。
评估PVC胶布软硬度的表述方法,是以PVC胶布添加的增塑剂的含量PHR来表述,PHR(重量份)越大,代表材料硬度越软。例如,软度40PHR或软度60PHR的PVC胶布,各分别代表添加增塑剂40重量份或60重量份的PVC胶布,且软度60PHR的PVC胶布的硬度更软。
【制备隔热浆料样品WCs1~WCs6】
【样品WCs1】
参照表1的隔热浆料配方,取10重量份钨铯粉(WCs)投入88重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入2重量份高分子型分散剂。按照下面研磨条件,利用1mm钇锆珠进行单一阶段研磨,制得平均粒径为100nm的隔热浆料WCs1。
研磨条件:研磨珠直径介于0.2-0.6mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:6-12小时。
【样品WCs2】
参照表1的隔热浆料配方,取15重量份钨铯粉(WCs)投入83重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入2重量份高分子型分散剂。进行两阶段研磨,第一阶段粗磨段同上述样品WCs1的研磨条件;第二阶段细磨段的研磨条件为,研磨珠直径:0.05-0.2mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:4-8小时,研磨至平均粒径约55nm,即为WCs2。
【样品WCs3】
参照表1的隔热浆料配方,取15重量份钨铯粉(WCs)投入82重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入3重量份高分子型分散剂。按照下面研磨条件,进行单一阶段研磨,制得平均粒径为100nm的隔热浆料WCs3。
研磨条件:研磨珠直径介于0.2-0.6mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:6-12小时。
【样品WCs4】
参照表1的隔热浆料配方,取15重量份钨铯粉(WCs)投入82重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入3重量份高分子型分散剂。进行两阶段研磨,第一阶段粗磨段同上述样品WCs3的研磨条件;第二阶段细磨段的研磨条件为,研磨珠直径:0.05-0.3mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:4-8小时,研磨至平均粒径约55nm,即为WCs4。
【样品WCs5】
参照表1的隔热浆料配方,取15重量份钨铯粉(WCs)投入80重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入5重量份高分子型分散剂。按照下面研磨条件,进行单一阶段研磨,制得平均粒径为100nm的隔热浆料WCs5。
研磨条件:研磨珠直径介于0.2-0.6mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:6-12小时。
【样品WCs6】
参照表1的隔热浆料配方,取18重量份钨铯粉(WCs)投入77重量份增塑剂(DHIN)中,配制成钨铯粉的溶液,并加入5重量份高分子型分散剂。进行两阶段研磨,第一阶段粗磨段同上述样品WCs5的研磨条件;第二阶段细磨段的研磨条件为,研磨珠直径:0.05-0.2mm;填充率80-95%;筛网:15-100μm;温控:50℃以下;研磨时间:4-8小时,研磨至平均粒径约55nm,即为WCs6。
表1隔热浆料制备
Figure BDA0001386879530000111
【实施例及比较例】
【实施例1】
生产厚度0.2mm软度40PHR的透明隔热聚氯乙烯胶布30,其制法为:
(1)依表2的特定配方,先制备隔热浆料WCs 1,然后取隔热浆料65重量份、紫外线吸收剂1重量份、增塑剂40重量份投入混合机,搅拌均匀,再次依序投入聚氯乙烯树脂100重量份、环氧大豆油1重量份、稳定剂4重量份及偶合剂0.1重量份进行混合后,引入至密炼机均匀混炼;
(2)料温控制在150~190℃,经辊轮机胶化后,以压延加工将充分反应的混合料制成厚度0.2mm的热熔胶布。于成型后,随即引入冷却轮;
(3)将热熔胶布引入冷却轮组冷却定型,经卷取即制得厚度0.2mm软度40PHR的隔热聚氯乙烯透明胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.2mm软度40PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于1.2%。
【实施例2~3】
依表2的特定配方,除隔热浆料采用WCs2及WCs3,不同于实施例1外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同。
进行QUV-300小时的耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.2mm软度40PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于1.2%。
【实施例4~5】
依表2的特定配方,除隔热浆料采用WCs4及WCs5,不同于实施例1外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法与实施例1相同,分别制得厚度0.1mm及0.3mm,软度40PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时的耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.1mm或0.3mm软度40PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估实施例4及5的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),实施例4的PVC胶布小于2.4%。实施例5的PVC胶布小于1.2%。
【实施例6】
依表2的特定配方,除隔热浆料采用WCs6及增塑剂DHIN用量高达60重量份外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同,制得厚度0.5mm,软度60PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.5mm软度60PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,惟胶布厚度薄,红外线遮蔽率稍低,且加工过程中隔热浆料不会有析出的现象。
评估实施例6的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于0.6%。
【实施例7~8】
依表2的特定配方,除偶合剂、隔热浆料用量不同外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同,制得厚度0.2mm,软度40PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时的耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.2mm软度40PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估实施例7及8的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时的耐候测试后的性能衰退率(F),实施例7的PVC胶布小于1.2%。实施例8的PVC胶布小于3.6%。
【实施例9】
依表2的特定配方,除增塑剂、稳定剂用量不同外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同,制得厚度0.2mm,软度0.1PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.2mm软度0.1PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估实施例9的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于2.3%。
【实施例10】
依表2的特定配方,除增塑剂使用DHIN及DINP两种组合各30重量份以及紫外线吸收剂0.05重量份及环氧大豆油2重量份外,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同,制得厚度0.3mm,软度60PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.3mm软度60PHR的透明隔热聚氯乙烯胶布30具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估实施例10的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于0.6%。
【实施例11】
依表2的特定配方,配方组分与实施例6相同,取实施例6的0.5mm隔热胶布四层,加热180℃,加压5KG/M2贴合成厚度2.0mm,软度60PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的2.0mm软度60PHR的透明隔热聚氯乙烯胶布具备良好的透明性、红外线阻隔率及紫外线阻隔率,且加工过程中隔热浆料不会有析出的现象。
评估实施例11的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),小于1.2%。
【比较例1】
依表2的特定配方,使用ATO隔热颗粒,生产厚度0.3mm软度40PHR的透明隔热聚氯乙烯胶布30。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.3mm软度40PHR的透明隔热聚氯乙烯胶布,仍具备透明性、红外线阻隔率及紫外线阻隔率,但劣于各实施例1-11,且经Quv300小时照射后,透明度及隔热效果大幅衰退。
评估比较例1的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),大于10%。
【比较例2】
依表2的特定配方,除厚度为0.2mm外,使用ATO并配合六硼化镧(LaB6)隔热颗粒,生产厚度0.2mm软度40PHR的透明隔热的聚氯乙烯胶布。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的透明隔热聚氯乙烯胶布30仍具备透明性、红外线阻隔率及紫外线阻隔率,优于比较例1,但劣于各实施例1-11,且经Quv300小时照射后,透明度及隔热效果更大幅衰退。
评估比较例2的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),大于28%。
【比较例3】
依表2的特定配方,除不使用偶合剂外,与实施例1的配方相同,且使用实施例1的制法生产厚度0.2mm软度40PHR的透明隔热聚氯乙烯胶布30。
经加工过程中隔热颗粒会有析出的现象,其成品质量不稳定,因此各物性不测试。
【比较例4】
与实施例1相同,但降低隔热浆料用量为4.5重量份,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同。
进行QUV-300小时耐候(老化)测试进行测试,结果如表2所示,显示所制得的0.2mm透明隔热聚氯乙烯胶布30的红外线阻隔率明显降低。
评估比较例4的PVC胶布的耐候性衰退率,也就是,评估PVC胶布经过QUV-300小时耐候测试后的性能衰退率(F),大于7%。
【比较例5】
与实施例1相同,但大幅提高隔热浆料用量为8.5重量份,所制得的透明隔热聚氯乙烯胶布30的原物料配方及制法皆与实施例1相同。
经加工过程中隔热颗粒会有析出的现象,其成品质量不稳定,因此各物性不测试。
表2 PVC胶布加工配方及物性 用量单位为:重量份
Figure BDA0001386879530000151
注:1.PVC为市售聚氯乙烯塑料粉,商品名S70
2.耐候性衰退率的数值越小,PVC胶布的耐候越佳。

Claims (10)

1.一种透明隔热的聚氯乙烯胶布,厚度介于0.02~2.0mm,且符合ASTMG-154规范下使用紫外线照射300小时后的性能衰退率(F)小于4%,其特征在于,所述聚氯乙烯胶布是使用下列组分a)~g)制成且所述聚氯乙烯胶布的内部均匀散布有组分g):
a)聚氯乙烯:100重量份;
b)增塑剂:0.1~60重量份;
c)环氧大豆油:1~10重量份;
d)稳定剂:0.1~10重量份;
e)紫外线吸收剂:0.05~5.0重量份;
f)偶合剂:0.05~0.2重量份;及
g)隔热浆料:5.5~7.5重量份;由下列组分g1)~g3)的总和为100wt%调制而成:
g1)钨铯粉(WCs),化学式为CsxNyWO3-zClc,占10~18wt%,其中,Cs为铯;N为锡、锑或铋;W为钨;O为氧;Cl为氯;x、y、z和c均为正数,且符合以下条件:
x≤1.0;y≤1.0;y/x≤1.0;z≤0.6;及c≤0.1;
g2)分散剂,占2~5wt%;及
g3)增塑剂,占77~88wt%。
2.如权利要求1所述的透明隔热的聚氯乙烯胶布,其制备方法为:
1)取权利要求1所述的组分a)~g)为原料,使用搅拌机混合均匀后,引入至密炼机均匀混炼;
2)料温控制在150~190℃,经辊轮机制成充分胶化反应的混合料;选择引入步骤3)或步骤4)或步骤5)的其中一个步骤进行加工;
3)以压延加工制成厚度介于0.05~1.0mm的热熔胶布,成型后选择引入步骤6)或直接引入步骤7)
4)以T型模加工制成厚度介于0.05~2.0mm的热熔胶布,成型后直接引入步骤7);
5)以吹塑成型制成厚度介于0.02~0.8mm的热熔胶布,成型后直接引入步骤7);
6)引入温度介于20~85℃的水中冷却硬化,再经过除水后,引入步骤7);
7)将胶布冷却定型及卷取后,制成所述透明隔热聚氯乙烯胶布。
3.如权利要求1或2所述的透明隔热的聚氯乙烯胶布,其特征在于,所述隔热浆料的粒径介于40~110nm。
4.如权利要求1或2所述的透明隔热的聚氯乙烯胶布,其特征在于,所述钨铯粉(WCs)的粒径介于0.005~2μm。
5.如权利要求1或2所述的透明隔热的聚氯乙烯胶布,其特征在于,所述偶合剂f)选自有机硅烷化合物偶合剂、有机锆铝化合物偶合剂或有机钛铝化合物偶合剂。
6.如权利要求1或2所述的透明隔热的聚氯乙烯胶布,其特征在于,所述隔热浆料的分散剂g2)选自高分子型的共聚物分散剂、含硅成份分散剂或含氟成份分散剂的中的一种以上。
7.如权利要求1或2所述的透明隔热聚氯乙烯胶布,其特征在于,所述增塑剂b)及g3)选自邻苯二甲酸二(C9~C11烷基)酯、邻苯二甲酸二异壬酯(DINP)、邻苯二甲酸二(2-乙基己基)酯(DEHP)、邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二异癸酯(DIDP)、对苯二甲酸二异辛酯(DOTP)、己二酸二异壬酯(DINA)、己二酸二(2-乙基己基)酯(DOA)、偏苯三酸三辛酯(TOTM)、1,2-环己烷二羧酸二异壬酯(DHIN)或1,2-环已烷二羧酸异辛酯(DHEH)中的一种以上
8.如权利要求1或2所述的透明隔热的聚氯乙烯胶布,其特征在于,所述紫外线吸收剂e)选自羟基苯基苯并三唑类紫外线吸收剂或羟基二苯甲酮类紫外线吸收剂中的一种以上。
9.一种透明隔热的聚氯乙烯胶布,其具有以二片以上的权利要求1所述的透明隔热的聚氯乙烯胶布构成叠层结构。
10.一种透明隔热的聚氯乙烯胶布,其具有以一片以上的权利要求1所述的透明隔热的聚氯乙烯透明胶布与一片以上的塑料基材构成叠层结构。
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