CN117925014A - 一种可烫金的哑光油及其制备方法 - Google Patents
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Abstract
本发明公开了一种可烫金的哑光油及其制备方法。该哑光油原料包括以下质量百分比的从成分：水性丙烯酸树脂20％～30％，丙烯酸成膜乳液15％～20％，丙烯酸不成膜乳液15％～25％，自交联丙烯酸乳液10％～20％，蜡乳液3％～6％，哑粉5％～10％，哑粉分散剂0.3％～0.5％，流平剂0.5％～1.5％，润湿剂0.5％～1％，消泡剂0.04％～0.1％，去离子水余量，所述蜡乳液为微晶蜡乳液；所述哑粉为无定型二氧化硅，其粒径为2μm～4.3μm；所述流平剂为吸附于二氧化硅上的改性聚丙烯酸酯。本发明的哑光油哑度低且烫金效果良好。
Description
技术领域
本发明涉及光油领域，具体涉及一种可烫金的哑光油及其制备方法。
背景技术
为了保护和装饰印刷品表面，常采用的印后加工工艺之一为覆膜工艺。经过覆膜的印刷品，不但增强印品美感效果，而且使印品表面更加平滑、耐污、耐水、耐油、耐磨、耐折等，保护印品在存储、运输、流通、使用环节不受破坏，提高其使用寿命。但是，塑料薄膜的使用会带来环保问题，采用水性光油代替覆膜工艺，既可减少“白色垃圾”的污染、处理，便于回收，且节约资源，减少能源浪费。
替塑哑光油是一种光泽度较低的水性光油，纸箱过哑光油后也常常伴随有烫金工艺，在logo、标识、或其他重点展示的部位采用烫金工艺，可使图案有凹凸变化，使图文呈现出金属浮雕般的质感，使烫金图文跳出平面，带来更强的视觉冲击力。这就要求哑光油除了满足基本的性能要求外，还应满足可烫金工艺的要求。
发明内容
本发明的目的提供一种可烫金的哑光油及其制备方法。本发明的哑光油哑度低且烫金效果良好。
为了实现以上目的，本发明采用以下技术方案：
本发明一方面提供一种可烫金的哑光油，其原料包括以下质量百分比的从成分：
水性丙烯酸树脂·····················20％～30％
丙烯酸成膜乳液·····················15％～20％
丙烯酸不成膜乳液····················15％～25％
自交联丙烯酸乳液····················10％～20％
蜡乳液·························3％～6％
哑粉··························5％～10％
哑粉分散剂·······················0.3％～0.5％
流平剂·························0.5％～1.5％
润湿剂·························0.5％～1％
消泡剂·························0.04％～0.1％
去离子水························余量
所述蜡乳液为微晶蜡乳液；
所述哑粉为无定型二氧化硅，其粒径为1μm～5μm；
所述流平剂为吸附于二氧化硅上的改性聚丙烯酸酯。
本发明的一个优选方案中所述哑光油的原料包括以下质量百分比的从成分：
水性丙烯酸树脂···················20％～25％
丙烯酸成膜乳液···················17％～20％
丙烯酸不成膜乳液··················20％～25％
自交联丙烯酸乳液··················13％～16％
蜡乳液·······················3％～5％
哑粉························5％～8％
哑粉分散剂·····················0.3％～0.5％
流平剂·······················0.7％～1％
润湿剂·······················0.7％～1％
消泡剂·······················0.05％～0.1％
去离子水······················余量。
优选地，所述水性丙烯酸树脂为苯丙树脂溶液，用以调节光油粘性，使得光油可以顺利转移。更优选地，所述苯丙树脂溶液的固含量为30％～36％，分子量为7000～10000。更优选地，所述苯丙树脂溶液采用Joncryl 61型苯丙树脂溶液(巴斯夫)。
优选地，所述丙烯酸成膜乳液为苯丙成膜乳液(苯丙树脂乳液)。其玻璃化温度(Tg)低，优选为-50℃至-30℃，室温下即可干燥成膜，具有一定的柔韧性，单独使用成膜后粘性较高，类似于胶的功能，防回粘差，同时因成膜太软，耐磨性能也不足。此外，其固含量优选为38％～45％。更优选地，所述苯丙成膜乳液采用Joncryl 1695型苯丙成膜乳液(巴斯夫)，其耐热性佳。
优选地，所述丙烯酸不成膜乳液为苯丙不成膜乳液(苯丙树脂乳液)。优选地，所述丙烯酸不成膜乳液的玻璃化温度(Tg)为50℃～100℃，其璃化温度高，室温干燥后不成膜，树脂硬度高，耐磨、防回粘效果好，故本发明将丙烯酸成膜乳液与丙烯酸不成膜乳液同时使用。此外，其固含量优选为40％～45％。更优选地，所述苯丙不成膜乳液采用Joncryl 1680型苯丙不成膜乳液(巴斯夫)。
所述自交联丙烯酸乳液可自交联形成三维网状结构薄膜，进一步提高耐磨性能、耐刮伤性能、柔韧性及抗回粘性。
优选地，所述自交联丙烯酸乳液的玻璃化温度为-40℃至-20℃，固含量为50％～60％。更优选地，所述自交联丙烯酸乳液采用Neocryl A-1120丙烯酸树脂(帝斯曼)。
所述蜡乳液为微晶蜡乳液，提高哑光油的耐磨性能、耐刮伤性能，同时选择大粒径的蜡乳液，还具有一定的消光作用。优选地，所述蜡乳液的粒径为1μm～3μm。更优选地，所述蜡乳液采用Joncryl wax 22微晶蜡乳液(巴斯夫)，其耐磨擦性佳。
所述哑粉为无定型二氧化硅，其粒径为1μm～5μm。进一步优选地，所述哑粉采用ED-2型哑粉(格雷斯)。
优选地，所述哑粉分散剂为改性丙烯酸类聚合物，起分散哑粉、防止哑粉絮凝、沉降的作用。更优选地，所述哑粉分散剂采用Lencolo1109(蓝柯路)。
所述流平剂为吸附于二氧化硅上的改性聚丙烯酸酯，具有多功能性，除了具有流平效果，促使光油干燥成膜过程中形成一个平整、光滑、均匀的薄膜，还可以提高光油固化成膜后膜表面的表面张力，提高再涂性。优选地，所述流平剂中丙烯酸酯的含量为63％。进一步优选地，所述流平剂采用BYK-3933P多功能粉末状丙烯酸酯助剂(毕克化学)。
优选地，所述润湿剂为炔二醇类表面活性剂，可以降低光油表面张力，使其在基材上更好的润湿、铺展。更优选地，所述润湿剂采用Silok-8104E(斯洛柯)。
优选地，所述消泡剂为聚硅氧烷-聚醚共聚物，起消泡、抑泡作用。更优选地，所述消泡剂采用Tego 810(迪高)。
本发明另一方面提供一种以上哑光油的制备方法，该制备方法包括以下步骤：
1)将部分去离子水、水性丙烯酸树脂加入容器中，搅拌均匀(优选400rpm)后加入部分消泡剂，再次搅拌均匀后加入哑粉和哑粉分散剂，搅拌均匀后继续搅拌0.5h-1h(优选升速至1000rpm)；
2)将步骤1)所得混合物进行研磨，过滤除去研磨介质、杂质；
3)将步骤2)中研磨好的混合物转移至容器中，于搅拌中，依次缓慢加入流平剂、润湿剂和剩余消泡剂，搅拌均匀(优选搅拌10min)；
4)于搅拌中，依次加入丙烯酸酯成膜乳液、丙烯酸酯不成膜乳液、自交联丙烯酸乳液和蜡乳液，搅拌均匀(优选800rpm～1200rpm搅拌0.3h～1h)；
5)冷却至室温后加氨水或有机氨中和剂调节pH为8～9，加水调节粘度即得所述哑光油；优选调节粘度至40s～50s/25℃。
优选地，所述研磨的转速为2000rpm，时间为1h。
优选地，加水调节粘度后进行过滤并罐装。
在光油中，哑粉的添加是不利于烫金的，使用本发明多功能型的流平剂(既起流平作用，也提高光油膜表面的表面张力)才可烫金。而常规流平剂没有提高表面张力的作用。
本发明为了获得哑度低且可烫金的哑光油，需要考虑哑度和烫金性：
1)哑度：一般使用大粒径的哑粉，表面粗糙度高，消光能力强；但表面粗糙，不利于烫金，采用合适粒径的哑粉，同时提高哑粉的分散性，达到要求哑度时也适合烫金。
2)烫金：蜡乳液的添加会降低光油成膜后的表面张力，应尽量选用耐磨性好的蜡乳液，使其添加量最低，有利于烫金工艺。同时使用流平剂，作用是提高光油固化成膜后膜表面的表面张力，提高再涂性，即可烫金性。
具体实施方式
为了更清楚地说明本发明，下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解，下面所具体描述的内容是说明性的而非限制性的，不应以此限制本发明的保护范围。
以下实施例和对比例中的高光光油均通过以下步骤制备：
1)将部分去离子水、水性丙烯酸树脂依次倒入容器中，搅拌速度400rpm，搅拌均匀后加入1/3的消泡剂，搅拌均匀，加入哑粉和哑粉分散剂，搅拌均匀后提高搅拌速度至1000rpm，搅拌30min；
2)将步骤1)中的混合物转移至砂磨机中，转速2000rpm，研磨1h，过滤；
3)将步骤2)中研磨好的混合物转移至容器中，搅拌过程中，依次缓慢加入流平剂、润湿剂、剩余消泡剂，搅拌10min；
4)搅拌过程中，依次加入丙烯酸酯成膜乳液、丙烯酸酯不成膜乳液、自交联丙烯酸乳液、蜡乳液，搅拌速度1000rpm，搅拌1h；
5)冷却至室温，加氨水调节pH为8-9，加水调节粘度，过滤、罐装。
其中所涉及原料具体为：
水性丙烯酸树脂：Joncryl 61，巴斯夫；
丙烯酸成膜乳液：Joncryl 1695，巴斯夫；
丙烯酸不成膜乳液：Joncryl 1680，巴斯夫；
自交联丙烯酸乳液：Neocryl A-1120帝斯曼；
蜡乳液：JONCRYL WAX 22，2.5微米，巴斯夫；
哑粉：ED-2，格雷斯；
哑粉分散剂：Lencolo1109，蓝柯路；
流平剂：BYK-3933P，毕克化学；
润湿剂：Silok-8104E，斯洛柯；
消泡剂：Tego 810，迪高。
所涉及的性能测试包括：
1)粘度/25℃：
采用DIN 4#杯测试粘度，用手指堵住流出孔，将水性光油慢慢倒入杯内，直至液面凸出杯的上边缘，如有气泡，待气泡浮到表面上，用清洁的平玻璃板沿边缘平推一次，除去凸出的液面及气泡，使被测液的水平面与上边缘在一水平面上，将手指放开，水性光油垂直流出，同时开动秒表，水性光油流出成线条，断开时止动秒表，测得时间即为水性光油的粘度，单位为秒。
2)光泽度：
光泽度是指印刷样品在某一角度反射光线的能力，使用BYK光泽度仪测试光泽度，采用的角度为60°角。
3)耐磨擦性能：
根据GB/T 7706-2008《凸版装潢印刷品》中的6.8墨层耐磨性的测试条件进行测试，并以墨层颜色是否摩掉为标准评判环保型水性光油的耐磨性，并能记录墨层颜色刚开始被摩掉时的摩擦次数。
4)爽滑度：
采用滑度角设备，将过油的其中一个试样(过油面向上)，平整的固定在水平试验台上，试样与试验台的长度方向平行，将另一过油试样光油面向下，黏贴在1kg重的滑块上，然后将固定有试样的滑块放在第一个试样中央，开始测试，滑块滑下时停止测试，记录试验台倾斜的角度。
5)烫金工艺：利用热压转移原理，将电化铝中的铝层转印到承印物表面以形成特殊的金属效果。
优：文字图案清晰完整、边缘整齐，用纸张底面对烫金处来回摩擦3次，烫印层不脱落；
良：文字图案清晰，但残缺或断线距离小于等于0.5mm不超过2处，用纸张底面对烫金处来回摩擦3次，烫印层不脱落；
中：文字图案模糊或文字图案清晰，但残缺或断线面积较大且大于2处，用纸张底面对烫金处来回摩擦3次，烫印层部分脱落；
差：文字图案模糊或未烫印上。
各实施例和对比例的原料配方如下(每1000克产品中含)：
实施例1
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例2
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························60g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例3
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························80g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例4
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························30g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例5
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························50g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例6
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························6g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
实施例7
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························12g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
对比例1
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························70g
哑粉分散剂·······················0g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
对比例2
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························0g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························9g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
对比例3
水性丙烯酸树脂·····················220g
丙烯酸成膜乳液·····················190g
丙烯酸不成膜乳液····················220g
自交联丙烯酸乳液····················150g
蜡乳液·························40g
哑粉··························70g
哑粉分散剂·······················3g
流平剂·························0g
润湿剂·························8g
消泡剂·························0.8g
去离子水························余量
将以上实施例和对比例所得光油进行成膜测试，性能测试结果如下表1所示。
表1
实施例1、2、3的区别为哑光粉含量不同，分别为7％、6％、8％，由表1可知，哑粉含量越高，其哑油成膜后的光泽度越低，即哑光效果越好，同时其耐磨性能也减弱，主要是因为哑粉颗粒大，因而哑油的摩擦系数高，易磨损，故其耐磨性能降低；也因为哑粉含量越高，其表面能也逐渐降低，其烫金性能减弱。保证光泽度及烫金性能情况下，本发明中哑粉的最佳含量为7％
实施例1、4、5的区别为蜡乳液含量不同，分别为4％、3％、5％，由表1数据可以看出，随蜡乳液含量增加，其哑油成膜后的光泽度降低，是因为蜡乳液也具有消光效果，同时因蜡乳液主要提高哑油的耐磨性能，故实施例4较实施例1减少蜡乳液含量，成膜后的光泽度增加，耐磨擦性能也降低；实施例5较实施例1增加蜡乳液含量，成膜后的哑光效果较好，耐磨擦性能提高，蜡乳液与哑粉一样，表面能低，加入量多，其烫金性能变差；故本发明中蜡乳液最佳含量为4％。
实施例1、6、7的区别为流平剂含量不同，分别为0.9％、0.6％、1.2％，由表1数据可以看出，流平剂在哑油成膜过程中上浮至光油膜表面，其表面张力高，其含量增加，可提高光油表面的表面能，其烫金效果好，但过量容易引起体系不稳定，性能下降，因此实施例6较实施例1减少流平剂含量，成膜后的烫金性减弱，实施例7较实施例1增加流平剂含量，成膜后的烫金性未变弱，但耐磨性有所下降，本发明中流平剂的最佳含量为0.9％。
与实施例1相比，对比例1无哑粉分散剂，整个体系哑光粉分散不匀，其哑光效果变差，烫金性下降，且耐磨性也有所下降。对比例2无蜡乳液，其耐磨性变差，哑光效果也有所变差。对比例3无流平剂，其烫金性很差。
光油成膜后，蜡乳液、哑粉、哑粉分散剂、流平剂上浮至光油膜表面，蜡乳液粒径相对较大，可极大提高其耐磨性能，同时具有消光性能；蜡乳液与哑粉一起形成较低哑度的光油，哑粉分散剂、流平剂同为改性的聚丙烯酸酯，相容性较好，在光油膜的表面，提高表面的表面张力，提高其可烫金性。因此，蜡乳液、哑粉、哑粉分散剂、流平剂之间互相配合及精确的配比，其综合性能才能完美的呈现。
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定，对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无法对所有的实施方式予以穷举，凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
1.一种可烫金的哑光油，其特征在于，其原料包括以下质量百分比的从成分：
水性丙烯酸树脂······················20％～30％
丙烯酸成膜乳液······················15％～20％
丙烯酸不成膜乳液·····················15％～25％
自交联丙烯酸乳液·····················10％～20％
蜡乳液··························3％～6％
哑粉···························5％～10％
哑粉分散剂························0.3％～0.5％
流平剂··························0.5％～1.5％
润湿剂··························0.5％～1％
消泡剂··························0.04％～0.1％
去离子水·························余量
所述蜡乳液为微晶蜡乳液；
所述哑粉为无定型二氧化硅，其粒径为1μm～5μm；
所述流平剂为吸附于二氧化硅上的改性聚丙烯酸酯。
2.根据权利要求1所述的哑光油，其特征在于，所述水性丙烯酸树脂为苯丙树脂溶液。
3.根据权利要求2所述的哑光油，其特征在于，所述苯丙树脂溶液的固含量为30％～36％，分子量为7000～10000。
4.根据权利要求1所述的哑光油，其特征在于，所述丙烯酸成膜乳液为苯丙成膜乳液，其玻璃化温度为-50℃至-30℃，固含量为38％～45％。
5.根据权利要求1所述的哑光油，其特征在于，所述丙烯酸不成膜乳液为苯丙不成膜乳液，其玻璃化温度为50℃～100℃，固含量为40％～45％。
6.根据权利要求1所述的哑光油，其特征在于，所述自交联丙烯酸乳液的玻璃化温度为-40℃至-20℃，固含量为50％～60％。
7.根据权利要求1所述的哑光油，其特征在于，所述蜡乳液的粒径为1μm～3μm。
8.根据权利要求1所述的哑光油，其特征在于，所述哑粉分散剂为改性丙烯酸类聚合物。
9.根据权利要求1所述的哑光油，其特征在于，所述润湿剂为炔二醇类表面活性剂，所述消泡剂为聚硅氧烷-聚醚共聚物。
10.一种权利要求1-9任一项所述哑光油的制备方法，其特征在于，该制备方法包括以下步骤：
1)将部分去离子水、水性丙烯酸树脂加入容器中，搅拌均匀；后加入部分消泡剂，再次搅拌均匀后加入哑粉和哑粉分散剂，搅拌均匀后继续搅拌0.5h～1h；
2)将步骤1)所得混合物进行研磨，过滤；
3)将步骤2)中研磨好的混合物转移至容器中，于搅拌中，依次缓慢加入流平剂、润湿剂和剩余消泡剂，搅拌均匀；
4)于搅拌中，依次加入丙烯酸酯成膜乳液、丙烯酸酯不成膜乳液、自交联丙烯酸乳液和蜡乳液，搅拌均匀；
5)冷却至室温后加氨水或有机氨中和剂调节pH为8～9，加水调节粘度即得所述哑光油。
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