CN104403552A - 一种户外用高性能蓄光-自发光膜的制备方法 - Google Patents

一种户外用高性能蓄光-自发光膜的制备方法 Download PDF

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CN104403552A
CN104403552A CN201410642082.XA CN201410642082A CN104403552A CN 104403552 A CN104403552 A CN 104403552A CN 201410642082 A CN201410642082 A CN 201410642082A CN 104403552 A CN104403552 A CN 104403552A
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CN104403552B (zh
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金闯
杨晓明
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Jiangsu Stick new materials Polytron Technologies Inc
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Suzhou Sidike New Material Science and Technology Co Ltd
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Abstract

本发明涉及膜技术领域，采用合适的方法将有机硅和聚氨酯丙烯酸树脂两种高分子材料进行复合，制备出兼具二者优异性能的成膜物，并将其应用于发光膜的制备中，从而明显提高了发光层涂料与基材的附着力，及发光膜的耐磨性、耐冲击性、柔韧性、耐水性、耐腐蚀性和耐老化性，户外使用寿命可达10年以上。该发光膜性能优越，使用灵活，尤其显著提升了其在户外长期应用的能力。

Description

一种户外用高性能蓄光-自发光膜的制备方法
技术领域
本发明涉及膜技术领域，特别涉及一种可于户外长期使用的自发光膜的制备方法。
背景技术
蓄光型-自发光材料是一类吸收激发光能并储存起来，光激发停止后，再把储存的能量以光的形式慢慢释放出来，并可持续几个甚至十几个小时的发光材料。目前，这种功能性光致发光材料已经以其优越的性能广泛的应用于在道路交通安全、消防紧急疏散、建筑工地等公共场所和民用建筑中，在光照后的黑暗中能清晰地起到警示或应急照明作用，在交通和安全领域起到了极为重要的作用。
现有软质塑料发光薄膜主要有丙烯酸、环氧树脂、羟基丙烯酸、聚酯树脂、氨基丙烯酸和聚氨酯丙烯酸等几种类型，背面含有压敏胶和离型纸，可贴于各种设备、物品表面。它除具有和硬板型发光板同样的应用外，还可以直接将其剪裁成各种发光图形，粘贴于所需之处。
其中，聚氨酯丙烯酸型以其优越的性能备受青睐，其兼备了聚氨酯和丙烯酸酯的优点，具有良好的透光性、耐寒性、耐溶剂性和耐候性，对极性和非极性表面均具有很强的附着力，但其耐水性、耐机械强度尤其耐老化性还是无法达到户外长期使用的要求，影响了其性能的发挥。
目前，蓄光-自发光膜在使用寿命也就在两年左右，尤其是在一些矿区、高岭土城市和道路上，上述产品的寿命可能还不到6个月，就会出现褪色、变色、龟裂、粉化和强度下降等问题。
发明内容
本发明所要解决的技术问题是提供一种耐热、耐冷、耐磨性、耐化学性，尤其是抗老化性能强的蓄光-自发光膜的制备方法，以提高其在户外的实际应用性能。
为解决上述问题，本发明采用的关键技术方案是：
有机硅树脂具有耐热性、耐候性、憎水性能、保光性和低表面张力等优点，本发明采用合适的方法将有机硅和聚氨酯丙烯酸树脂两种高分子材料进行复合，制备出兼具二者优异性能的成膜物，并将其应用于发光膜的制备中。
具体技术方案如下：
将质量分数分别为10-30％的聚已内酯二元醇、30-50％的异佛尔酮二异氰酸酯、10-50％丙烯酸预聚物及0.5-5％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应2-6h后，加入质量分数为20-50％的有机硅-硅溶胶和质量分数为0.2-2％的氧化二苯甲酰，85℃继续搅拌反应2-4h后，加入质量分数为10-50％(优选35％)的发光粉，混合均匀后，消泡，得到发光涂糊料。
将发光糊料涂布在透明基材上，80-120℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品。
其中，所述丙烯酸预聚物由质量分数分别为30-60％的甲基丙烯酸甲酯、5-20％的丙烯酸丁酯、2-8％的丙烯酸、0.5-2％的氧化二苯甲酰和30-60％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应2-3h后备用。
其中，所述有机硅-硅胶由质量分数分别为50～80％的γ-甲基丙烯酰氧基丙基三甲基硅烷、8-30％的正硅酸乙酯、5-20％的乙二醇和0.5-2％的过硫酸钾混合后，70℃加热搅拌反应3-6h后备用。
所述的发光粉是多种离子激活的硅酸盐、铝酸盐、硫化物发光材料或其混合物。
所述的发光粉的粒径在50-80um之间。
所述的透明基材为发光膜的保护层，由透明聚酯(PET)膜和其上有机硅改性聚氨酯丙烯酸树脂形成的5-20um的表面透光树脂层组成。
所述的白色基材为聚乙烯、聚丙烯、聚酯、聚碳酸酯或聚丙烯酸酯中的一种制成。
本发明与现有技术相比，其有益效果是：
本发明使用有机硅-硅溶胶对聚氨酯丙烯酸树脂进行改性，提高了聚氨酯丙烯酸分子链间的交联反应，形成了更致密的网状结构，另外有机硅分子嵌在聚氨酯丙烯酸酯主链中，得到的载体树脂兼具两者的优势，从而明显提高了发光层涂料与基材的附着力，及发光膜的耐磨性、耐冲击性、柔韧性、耐水性、耐腐蚀性和耐老化性，户外使用寿命可达10年以上。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步的详细说明。需要理解的是，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1：
将质量分数分别为12％的聚已内酯二元醇、50％的异佛尔酮二异氰酸酯、37.5％丙烯酸预聚物及0.5％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应3h后，加入质量分数为25％的有机硅-硅溶胶和质量分数为0.5％的氧化二苯甲酰，85℃继续搅拌反应2h后，加入质量分数为15％的发光粉(CaAl2O4：Eu，Nd)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为35％的甲基丙烯酸甲酯、5％的丙烯酸丁酯、5％的丙烯酸、1％的氧化二苯甲酰和54％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应2h后备用。
其中，所述有机硅-硅胶由质量分数分别为60％的γ-甲基丙烯酰氧基丙基三甲基硅烷、25％的正硅酸乙酯、14％的乙二醇和1％的过硫酸钾混合后，70℃加热搅拌反应3h后备用。
将发光糊料涂布在透明基材上，100℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为蓝紫色，10min内余辉亮度为460mcd/m2，余辉时间为1000min，发光膜的其它性能参数见表1。
实施例2：
将质量分数分别为25％的聚已内酯二元醇、45％的异佛尔酮二异氰酸酯、27％丙烯酸预聚物及3％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应5h后，加入质量分数为50％的有机硅-硅溶胶和质量分数为2％的氧化二苯甲酰，85℃继续搅拌反应4h后，加入质量分数为45％的发光粉(SrAl2O4：Eu，Dy)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为60％的甲基丙烯酸甲酯、5％的丙烯酸丁酯、4％的丙烯酸、1％的氧化二苯甲酰和30％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应3h后备用。
其中，所述有机硅-硅胶由质量分数分别为70％的γ-甲基丙烯酰氧基丙基三甲基硅烷、20％的正硅酸乙酯、8％的乙二醇和2％的过硫酸钾混合后，70℃加热搅拌反应6h后备用。
将发光糊料涂布在透明基材上，110℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为黄绿色，10min内余辉亮度为660mcd/m2，余辉时间为3600min，发光膜的其它性能参数见表1。
实施例3：
将质量分数分别为20％的聚已内酯二元醇、40％的异佛尔酮二异氰酸酯、39％丙烯酸预聚物及1％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应4h后，加入质量分数为30％的有机硅-硅溶胶和质量分数为1％的氧化二苯甲酰，85℃继续搅拌反应3h后，加入质量分数为35％的发光粉(Sr4Al14O25：Eu，Dy)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为40％的甲基丙烯酸甲酯、10％的丙烯酸丁酯、6％的丙烯酸、1％的氧化二苯甲酰和43％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应3h后备用。
其中，所述有机硅-硅胶由质量分数分别为70％的γ-甲基丙烯酰氧基丙基三甲基硅烷、20％的正硅酸乙酯、9％的乙二醇和1％的过硫酸钾混合后，70℃加热搅拌反应5h后备用。
将发光糊料涂布在透明基材上，100℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为蓝绿色，10min内余辉亮度为620mcd/m2，余辉时间为4100min，发光膜的其它性能参数见表1。
实施例4：
将质量分数分别为15％的聚已内酯二元醇、50％的异佛尔酮二异氰酸酯、32％丙烯酸预聚物及3％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应5h后，加入质量分数为40％的有机硅-硅溶胶和质量分数为0.2％的氧化二苯甲酰，85℃继续搅拌反应2.5h后，加入质量分数为30％的发光粉(Sr2MgSi2O7：Eu，Dy)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为35％的甲基丙烯酸甲酯、15％的丙烯酸丁酯、8％的丙烯酸、2％的氧化二苯甲酰和40％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应2.5h后备用。
其中，所述有机硅-硅胶由质量分数分别为60％的γ-甲基丙烯酰氧基丙基三甲基硅烷、25％的正硅酸乙酯、14％的乙二醇和1％的过硫酸钾混合后，70℃加热搅拌反应5h后备用。
将发光糊料涂布在透明基材上，85℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为蓝色，10min内余辉亮度为220mcd/m2，余辉时间为800min，发光膜的其它性能参数见表1。
实施例5：
将质量分数分别为25％的聚已内酯二元醇、45％的异佛尔酮二异氰酸酯、27.5％丙烯酸预聚物及2.5％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应5h后，加入质量分数为30％的有机硅-硅溶胶和质量分数为0.5％的氧化二苯甲酰，85℃继续搅拌反应3h后，加入质量分数为35％的发光粉(ZnS：Cu，Co)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为32％的甲基丙烯酸甲酯、18.5％的丙烯酸丁酯、3％的丙烯酸、1.5％的氧化二苯甲酰和45％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应2h后备用。
其中，所述有机硅-硅胶由质量分数分别为60％的γ-甲基丙烯酰氧基丙基三甲基硅烷、25％的正硅酸乙酯、14.5％的乙二醇和0.5％的过硫酸钾混合后，70℃加热搅拌反应4h后备用。
将发光糊料涂布在透明基材上，115℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为黄绿色，10min内余辉亮度为180mcd/m2，余辉时间为260min，发光膜的其它性能参数见表1。
对比例：
将质量分数分别为25％的聚已内酯二元醇、40％的异佛尔酮二异氰酸酯、33％丙烯酸预聚物及2％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应4h后，加入质量分数为35％的发光粉(Sr4Al14O25：Eu，Dy)，混合均匀后，消泡，得到发光涂糊料。
其中，所述丙烯酸预聚物由质量分数分别为40％的甲基丙烯酸甲酯、15％的丙烯酸丁酯、4％的丙烯酸、1％的氧化二苯甲酰和40％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应3h后备用。
将发光糊料涂布在透明基材上，100℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品，发光颜色为蓝绿色，10min内余辉亮度为540mcd/m2，余辉时间为3200min，发光膜的其它性能参数见表1。
表1发光膜性能参数

Claims (7)

1.一种户外用高性能蓄光-自发光膜的制备方法，其特征在于将质量分数分别为10-30％的聚已内酯二元醇、30-50％的异佛尔酮二异氰酸酯、10-50％丙烯酸预聚物及0.5-5％二月桂酸二丁基锡进行混合，在氮气保护下，80℃保温搅拌反应2-6h后，加入质量分数为20-50％的有机硅-硅溶胶和质量分数为0.2-2％的氧化二苯甲酰，85℃继续搅拌反应2-4h后，加入质量分数为10-50％的发光粉，混合均匀后，消泡，得到发光涂糊料；
将发光糊料涂布在透明基材上，80-120℃烘干后，与白色基材复合即可成膜。然后，将压敏胶涂布在离型纸上与发光膜的白色基材覆合，即得发光膜的成品；
其中，所述丙烯酸预聚物由质量分数分别为30-60％的甲基丙烯酸甲酯、5-20％的丙烯酸丁酯、2-8％的丙烯酸、0.5-2％的氧化二苯甲酰和30-60％的二甲苯混合后，在氮气保护下，85℃加热搅拌反应2-3h后备用；
其中，所述有机硅-硅胶由质量分数分别为50-80％的γ-甲基丙烯酰氧基丙基三甲基硅烷、8-30％的正硅酸乙酯、5-20％的乙二醇和0.5-2％的过硫酸钾混合后，70℃加热搅拌反应3-6h后备用。
2.根据权利要求1所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于所述的发光粉是多种离子激活的硅酸盐、铝酸盐、硫化物发光材料或其混合物。
3.根据权利要求2所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于所述的发光粉的粒径在50-80um之间。
4.根据权利要求1所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于发光粉的质量分数加入量是35％。
5.根据权利要求1所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于所述的透明基材为发光膜的保护层，由透明聚酯(PET)膜和其上有机硅改性聚氨酯丙烯酸树脂形成的表面透光树脂层组成。
6.根据权利要求5所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于所述的表面透光树脂层的厚度为5-20um。
7.根据权利要求1所述的户外用高性能蓄光-自发光膜的制备方法，其特征在于所述的白色基材为聚乙烯、聚丙烯、聚酯、聚碳酸酯或聚丙烯酸酯中的一种制成。
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