CN115181526B - 一种无溶剂型耐水洗反光材料胶黏剂及其制备方法 - Google Patents
一种无溶剂型耐水洗反光材料胶黏剂及其制备方法 Download PDFInfo
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Abstract
本发明涉及反光布制备技术领域,所属IPC分类号为C09J175/06,尤其涉及一种无溶剂型耐水洗反光材料胶黏剂及其制备方法。所述胶黏剂的原料包括,聚醚多元醇10~40份、聚酯多元醇5~35份、多异氰酸酯类单体10~35份、丙烯酸酯树脂10~35份、抗氧剂0.5~3份、水解稳定剂0.5~3份、硅烷偶联剂1~5份、催化剂0.1~1份。本发明弥补国内PUR反光材料胶黏剂方面专利的空白,本发明提供的反光材料胶黏剂具有良好的耐水洗效果,性能满足国标GB20653‑2006要求,同时,在生产过程中不使用任何有机溶剂,无VOC排放,材料来源广泛,生产工艺简单,适宜工业化生产。
Description
技术领域
本发明涉及反光布制备技术领域,所属IPC分类号为C09J175/06,尤其涉及一种无溶剂型耐水洗反光材料胶黏剂及其制备方法。
背景技术
反光材料的主要结构是表层涂覆一种只有数十微米直径的玻璃珠与固着剂及色浆,而在玻璃微珠内层有一层极薄的镀铝层。射入的光束由于玻璃与空气折射率不同,光线通过玻璃珠后聚焦于珠后的镀铝层上,镀铝层将射入的光束沿入射方向反射出来。
专利CN104927745B制备了一种反光弹力布用的胶黏剂,但是制备得到的胶黏剂中使用了有机溶剂,并且市面上现有反光材料均为溶剂型胶黏剂,含有大量有机溶剂,固化过程中释放大量VOC,这与我国现有的环保理念相悖。
本发明提供的一种无溶剂型耐水洗反光材料胶黏剂,合成过程中不添加任何溶剂,同时在固化过程中是通过与空气中的水汽反应,不释放任何有害物质。
发明内容
为了能够更好的理解本发明的技术内容,结合以下本发明的优选实施方法的详述。
为了解决上述技术问题,本发明的第一个方面提供了一种无溶剂型耐水洗反光材料胶黏剂,所述胶黏剂的原料包括,聚醚多元醇10~40份、聚酯多元醇5~35份、多异氰酸酯类单体10~35份、丙烯酸酯树脂10~35份、抗氧剂0.5~3份、水解稳定剂0.5~3份、硅烷偶联剂1~5份、催化剂0.1~1份。
优选的,所述胶黏剂的原料包括,按重量份计,聚醚多元醇5~35份、聚酯多元醇30~45份、多异氰酸酯类单体10~30份、丙烯酸酯树脂15~25份、抗氧剂0.8~1.5份、水解稳定剂0.8~2份、硅烷偶联剂1~2.5份、催化剂0.2~0.5份。
所述聚醚多元醇至少包括含有一种三官能度聚醚多元醇。
所述三官能度聚醚多元醇的重均分子量为1000~6000;可以列举的三官能度聚醚多元醇有聚氧化丙烯三醇。
所述聚氧化丙烯三醇的购买厂家包括但不限于上海华大。
优选的,所述聚醚多元醇还包括二官能度聚醚多元醇。
所述二官能度聚醚多元醇的重均分子量为650~6000。
所述二官能度聚醚多元醇选自聚氧化乙烯二醇、聚氧化丙烯二醇、聚四氢呋喃二醇中的至少一种。
所述二官能度聚醚多元醇的购买厂家包括但不限于韩国晓星和科思创。
所述三官能度聚醚多元醇与二官能度聚醚多元醇的重量比为(0.4-0.88):1。
在研究中发现,在本发明体系中未选用三官能度聚醚多元醇时,得到的材料制品的耐水解效果较差,胶黏剂的使用价值不高,可能是因为当不含三官能度聚醚多元醇时体系的交联程度低,强度低。但是当体系中只有三官能度聚醚多元醇导致在水洗过程中会出现开裂玻璃现象,可能是因为当体系中的胶黏剂固化后的硬度较高,导致在水洗过程中,过硬的胶层容易出现开裂剥离等现象。在本发明中通过特定的三官能度聚醚多元醇与二官能度聚醚多元醇相互协同作用能够很好的控制胶黏剂的硬度和附着力。
所述聚酯多元醇选自聚间苯二甲酸-己二酸-3-甲基-1,5-戊二醇酯二醇、聚邻苯二甲酸-己二酸-3-甲基-1,5-戊二醇酯二醇、聚邻苯二甲酸-3-甲基-1,5-戊二醇酯二醇、聚间苯二甲酸-3-甲基-1,5-戊二醇酯二醇中的一种或多种。
所述聚酯多元醇的重均分子量为1000~4000。所述聚酯多元醇可通过市售得到,比如说旭川化学、赢创、上海华大等。
所述多异氰酸酯类单体选自六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(MDI)、苯二亚甲基二异氰酸酯(XDI)、异佛尔酮二异氰酸酯(IPDI)或四甲基苯二甲基二异氰酸酯(TMXDI)中的一种或多种,其中多异氰酸酯类单体的来源并没有限定。
所述丙烯酸酯树脂的玻璃化转变温度为0-60℃。
所述丙烯酸树脂选自MMA-BMA共聚高分子、MMA-BMA-MA共聚高分子、MMA-BMA-HEMA共聚高分子、MMA-BA共聚高分子、MMA-EMA共聚高分子中的一种或两种。
所述丙烯酸树脂的厂家包括但不限于日本三菱或中国上海博立尔实业有限公司的产品。
所述抗氧剂选自氧化剂232、抗氧化剂264、抗氧化剂1010、抗氧化剂1135中的至少一种或其它通用聚氨酯抗氧剂。
所述水解稳定剂为含有碳化二亚胺官能团的化合物,比如说碳化二亚胺。
所述硅烷偶联剂选自KH-550、KH-560、KH-570、KH-792、DL602中的一种或几种。在本发明中加入硅烷偶联剂能够在一定程度上提高反光玻璃微珠机镀铝膜的附着力。
所述催化剂选自双吗啉基二乙基醚(DMDEE)、胺类催化剂、有机锡类催化剂中的至少一种
可以列举的胺类催化剂三乙醇胺、二甲基乙醇胺等;可以列举的有机锡类催化剂有辛酸亚锡、二月桂酸二丁基锡等。
本发明的第二个方面提供了一种无溶剂型耐水洗反光材料胶黏剂的制备方法,包括以下步骤:
步骤一,在密闭反应器中加入聚醚多元醇、聚酯多元醇、丙烯酸酯树脂、抗氧剂、水解稳定剂,在110~140℃条件下完全溶解,真空干燥45-90分钟至水分含量低于200ppm;
步骤二,将体系降温至70~90℃,加入异氰酸酯单体,控制温度在90~140℃反应1.5~3.5h,然后加入催化剂高速搅拌10~20min,随后加入硅烷偶联剂高速搅拌10~20min得到无溶剂型耐水洗反光材料胶黏剂。
在一些实施方式中,所述密闭反应器装有搅拌装置、温敏装置并通有氮气保护。
本发明的第三个方面提供了一种无溶剂型耐水洗反光材料胶黏剂的使用方法,包括以下步骤:
(1)将胶黏剂均匀涂覆在压有玻璃微珠和镀铝层的PET、PVC或聚乙烯薄膜上,胶黏剂涂层厚度为0.5~5μm;此处的涂层为预涂层,是临时性涂布在PETPET、PVC或聚乙烯薄膜上,称之为反光材料膜材或烫金材料膜材;
(2)将涂有胶黏剂的薄膜与反光基材压合,在50~90℃,相对湿度≥40-85%的条件下固化24h以上,分离基材与薄膜即可;此时预涂层从PET、PVC或聚乙烯薄膜上分离。
步骤(2)中压合的条件为:2~5MPa。
所述反光基材包括尼龙、针织、涤纶纺织材料中的任意一种,为针织布或无纺布。
本发明至少包括下述有益效果:
1.在本发明中以特定的聚醚多元醇和聚酯多元醇为软段、异氰酸酯单体为硬段,通过丙烯酸酯树脂和硅烷偶联剂的多重改性,增加了产品耐水洗的效果,现有技术中聚氨酯材料存在易水解与镀铝层粘接强度低的缺陷,在本发明中通过对软硬段比例的调整及不同改性材料的搭配,克服了反应型聚氨酯材料易水解、与镀铝层粘接强度等缺陷;同时,本发明生产过程中不使用任何有机溶剂,使用过程中,与溶剂型聚氨酯粘结剂超过60%的VOC产品相比,有着本质差别,属于近于零排放的产品,是一种环境友好型胶黏剂;这类胶粘剂的使用会使得反光材料及烫金材料的复合生产实现环保生产、节能生产及高效生产。
2.本发明中的一种无溶剂型耐水洗反光材料胶黏剂的制备方法,该方法属于一步法,其工艺简单,合成条件易于达成,降低了工业化生产的难度,生产过程中原料以熔融状态聚合,不用水也未使用有机溶剂,不会污染环境。
具体实施方式
以下给出本发明的具体实施例,但本发明不受实施例的限制;另外,如果没有特殊说明,本发明中的原料均可由市售得到。
实施例1:在装有搅拌装置、温敏装置并通有氮气保护的密闭反应器中加入170g聚氧化丙烯三醇(重均分子量为2000,购自上海华大)、200g聚四氢呋喃二醇(重均分子量为2000,购自韩国晓星)、103g聚邻苯二甲酸-3-甲基-1,5-戊二醇酯二醇(重均分子量为3000,购自旭川化学)、200g丙烯酸酯树脂MB775(购自中国上海博立尔实业有限公司,重均分子量为28000,玻璃化转变温度为49℃)、11g抗氧剂1010、10g碳化二亚胺,在140℃条件下完全溶解,真空干燥60min至水分含量低于20ppm;随后,将体系降温至80℃,加入193gMDI控制温度在115℃反应3h,然后加入3g双吗啉基二乙基醚并高速搅拌20min,随后加入15g KH570高速搅拌12min得到无溶剂型耐水洗反光材料胶黏剂。
实施例2:在装有搅拌装置、温敏装置并通有氮气保护的密闭反应器中加入470g聚氧化丙烯三醇(同实施例1)、76g聚间苯二甲酸-3-甲基-1,5-戊二醇酯二醇(同实施例1)、139g丙烯酸酯树脂AC25K(购自中国上海博立尔实业有限公司尔,重均分子量为25000,玻璃化转变温度为52℃)、11g抗氧剂1010、10g碳化二亚胺,在135℃条件下完全溶解,真空干燥60min至水分含量低于20ppm;随后,将体系降温至75℃,加入270g MDI控制温度在115℃反应3h,然后加入3g双吗啉基二乙基醚并随后加入20gKH570高速搅拌12min得到无溶剂型耐水洗反光材料胶黏剂。
在本实施例中体系中配方R值接近7,其中R值指的是体系中总NCO的摩尔数比体系中总OH的摩尔;经测定胶黏剂的NCO含量约为9.5%。
实施例3:在装有搅拌装置、温敏装置并通有氮气保护的密闭反应器中加入98g聚氧化丙烯三醇(同实施例1)、200g聚氧化乙烯二醇(重均分子量为3000,购自科思创)、187g聚间苯二甲酸-3-甲基-1,5-戊二醇酯二醇(同实施例1)、240g丙烯酸酯树脂(三菱MB2876)、11g抗氧剂1010、19g碳化二亚胺,在135℃条件下完全溶解,真空干燥60min至水分含量低于20ppm;随后,将体系降温至90℃,加入198gHDI控制温度在130℃反应3.5h,然后加入3g双吗啉基二乙基醚高速搅拌20min,随后加入20gKH570高速搅拌20min得到无溶剂型耐水洗反光材料胶黏剂。
性能测试
样品的制备:(1)分别将实施例1~3胶黏剂均匀涂覆在压有玻璃微珠和镀铝层的聚乙烯薄膜上,厚度为1μm;(2)将涂有胶黏剂的薄膜与尼龙压合,在90℃,相对湿度≥40-85%的条件下固化24h以上,分离基材与薄膜即可;步骤(2)中压合的条件为:90℃,3MPa。
按照本领域公知的测试方法将样品水洗0~25次(65℃,pH=11,每一环化2小时)后测试样品的反光度,测试结果如表1所示:
表1
从表1的测试结果可知实施例1(三官聚醚与二官聚醚的重量比为0.85:1)中制备得到的胶黏剂粘结的反光材料经过25轮水洗,无明显脱落(明显脱落指的是玻璃微珠开始出现大于1mm直径大小斑块完全从镀铝层脱落的现象),反射强度无明显下降,达到GB20653-2006要求;实施例2中制备得到胶黏剂粘结的反光材料经过25轮水洗,出现大量龟裂(龟裂指的是在水洗反光材料表面出现裂纹),同时反射强度下降明显(实施例2中聚醚多元醇聚氧化丙烯三醇为100%三官聚醚),说明该产品不适用于工业生产;实施例3中的的胶黏剂粘(三官聚醚与二官聚醚的重量比为0.49:1),其粘接结的反光材料经过25轮水洗,反射略微但无明显下降。
Claims (7)
1.一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述胶黏剂的原料包括,聚醚多元醇10~40份、聚酯多元醇5~35份、多异氰酸酯类单体10~35份、丙烯酸酯树脂10~35份、抗氧剂0.5~3份、水解稳定剂0.5~3份、硅烷偶联剂1~5份、催化剂0.1~1份;
所述聚醚多元醇包括二官能度聚醚多元醇和三官能度聚醚多元醇,所述二官能度聚醚多元醇和三官能度聚醚多元醇的重量比为1:(0.4-0.88);
所述丙烯酸酯树脂的玻璃化转变温度为0-60℃;
所述丙烯酸酯树脂选自MMA-BMA-MA共聚高分子、MMA-BMA-HEMA共聚高分子中的一种或两种。
2.根据权利要求1所述的一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述三官能度聚醚多元醇的重均分子量为1000~6000。
3.根据权利要求1所述的一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述聚酯多元醇选自聚间苯二甲酸-己二酸-3-甲基-1,5-戊二醇酯二醇、聚邻苯二甲酸-己二酸-3-甲基-1,5-戊二醇酯二醇、聚邻苯二甲酸- 3-甲基-1,5-戊二醇酯二醇、聚间苯二甲酸-3-甲基-1,5-戊二醇酯二醇中的一种或多种。
4.根据权利要求1或2所述的一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述多异氰酸酯类单体选自六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯、苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯或四甲基苯二甲基二异氰酸酯中的一种或多种。
5.根据权利要求1所述的一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述硅烷偶联剂选自KH-550、KH-560、KH-570、KH-792、DL602中的一种或几种。
6.根据权利要求1所述的一种无溶剂型耐水洗反光材料胶黏剂,其特征在于,所述胶黏剂的使用方法包括步骤:
(1)将胶黏剂均匀涂覆在压有玻璃微珠和镀铝层的PET、 PVC或聚乙烯薄膜上厚度为0.5~5μm;
(2)将涂有胶黏剂的薄膜与反光基材压合,在50~90℃,相对湿度≥40-85%的条件下固化24h以上,分离基材与薄膜即可。
7.一种根据权利要求1-5任一项所述的一种无溶剂型耐水洗反光材料胶黏剂的制备方法,其特征在于,包括以下步骤:
步骤一,在密闭反应器中加入聚醚多元醇、聚酯多元醇、丙烯酸酯树脂、抗氧剂、水解稳定剂,在110~140℃条件下完全溶解,真空干燥45-90分钟至水分含量低于200ppm;
步骤二,将体系降温至70~90℃,加入异氰酸酯单体,控制温度在90~140℃反应1.5~3.5h,然后加入催化剂高速搅拌10~20min,随后加入硅烷偶联剂高速搅拌10~20min得到无溶剂型耐水洗反光材料胶黏剂。
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