CN114390977B - 激光诱导的转印法 - Google Patents
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Abstract
印刷方法,其中将承印基底布置在具有墨层的墨水载体对面,通过激光束区域性照射所述墨层,所述层通过吸收激光束而朝基底方向加速,其中为了激光吸收,所述墨层包含反射性粒子、溶剂和可溶性聚合物,其中所述反射性粒子具有>25的纵横比,纵横比被定义为平均粒度/平均粒子厚度。
Description
本发明涉及印刷方法和墨水的用途。
从例如US 6,241,344 B1中已知一种印刷基底的方法,其中将墨滴从涂有墨水的载体转移到承印基底上。为了转移墨水,在待印刷的基底位置,将能量透过载体引入载体上的墨水中。这造成一部分墨水汽化,因此墨水脱离载体。由于汽化的墨水的压力,由此离开的墨滴被推射到基底上。
通过以定向方式引入能量,有可能据此根据待印刷的图案将墨水转移到基底(substrate)上。例如通过激光引入转移墨水所需的能量。承载施加的墨水的载体(carrier)是例如循环条带(circulating ribbon),在印刷区前借助施加装置将墨水施加到其上。激光器位于循环条带的内部,因此激光器在背向墨水的一侧作用于载体。例如通过浸在储墨器中的辊实现将墨水施加到墨水载体上。
这种类型的印刷机也从例如US 5,021,808 A中获知。也根据这一文献的教导,使用施加装置将墨水从储存容器施加到循环条带上,在循环条带内存在激光器,借此在指定位置汽化墨水并相应地抛射到承印基底上。条带在这种情况下由对激光透明的材料制成。为了墨水的定向汽化,有可能用吸收层涂布循环条带,在其中吸收激光并转化成热,因此在暴露于激光的位置将墨水汽化。
还通过公开说明书DE 102 10 146 A1获知,通过使用小的激光吸收粒子(laser-absorbing particles),有可能增进激光诱导印刷法的效率。这是重要的,因为其能够显著提高所述方法的生产率。
使用吸收粒子时的一个缺点在于这些粒子经常也吸收可见波长光谱,造成待印刷的墨水(液体墨水)的强度或多或少的变色。
另一缺点在于激光诱导的粒子喷射可能伴随着许多破坏性的小得多的粒子(所谓附随物(satellites))的发射,这使印刷结果的品质变差。
与此相比,本发明的目的是至少减少现有技术的上述缺点。目标通常是实现良好的印刷结果。
已通过根据权利要求1的印刷方法实现本发明的目的。
由从属权利要求的主题以及说明书显而易见本发明的优选实施方案和扩展。
本发明涉及一种印刷方法,其中将承印基底布置在具有墨层的墨水载体对面,通过激光束区域性照射所述墨层,其特征在于所述墨层包含反射性粒子、溶剂和溶解在溶剂中的可溶性聚合物,其中所述反射性粒子具有>25的纵横比,其中纵横比被定义为平均粒度(average particle size)/平均粒子厚度(average particle thickness)。
在根据本发明的印刷方法的一个实施方案中,反射性粒子具有>50的纵横比。
在根据本发明的印刷方法的进一步实施方案中,反射性粒子具有平均粒子厚度PT<80+3PS,其中PT是以nm计的平均粒子厚度的绝对值,且PS是以μm计的平均粒度的绝对值。
因此,根据印刷方法的这一实施方案,反射性粒子具有>25的纵横比和PT<80+3PS。
可通过用包含反射性粒子、可溶性聚合物、染料和/或颜料和溶剂的墨水涂布墨带(ink ribbon)来形成墨层。可溶性聚合物是可溶于用作墨水组合物的溶剂的溶剂中的聚合物。
根据本发明,为了墨层部分的激光吸收,将用于本发明的方法的墨水与反射性粒子混合。
反射性粒子可能也对激光束具有吸附性质,尤其是在所用激光的波长范围内,更特别在300至3000nm的范围内。但是,不同于吸收粒子如炭黑粒子,反射性粒子也对可见波长光谱具有反射性质。
可使用对所用激光的波长,更特别对300至3000nm具有高反射的粒子。
不同于现有技术中已知的吸收粒子,例如炭黑,反射性粒子可能对墨层传达的色彩印象是基本中性的。
可用的粒子首先是例如金属粒子或金属涂布的载体材料的粒子。这些粒子基于镜面产生反射。特别有可能使用所谓的效果颜料,优选光泽颜料。
反射性粒子可特别以大于1和/或小于10重量%的量添加到用于墨层的墨水中。
此外,可使用利用全反射产生镜面效应的透明粒子。也可使用具有光学干涉涂层的粒子。
根据本发明的一个实施方案,使用具有0.1至25μm的平均粒度(mean particlesize)的粒子。对于一些应用,可能有利的是具有1至15μm的粒度。
由此可实现特别有效的吸收。
为了实现高反射效应,可使用具有大于50,优选大于70,更优选大于80的在L*a*b*颜色空间中的L*值的粒子。
此外,该粒子,特别是铝粒子,可为中性颜色。在一个实施方案中,该粒子在L*a*b*颜色空间中具有+/-30的a*和/或b*值。更特别可使用具有小于+/-5,优选+/-3的在L*a*b*颜色空间中的a*和/或b*值的粒子。
在根据本发明的方法中,可使用由金属和金属涂布的聚合物粒子组成的反射性材料。
本发明还涉及一种印刷方法,其中将承印基底布置在具有墨层的墨水载体对面,通过激光束区域性照射所述墨层,并且所述层通过吸收激光束而朝基底方向加速,其中通过粒子生成激光吸收。
根据本发明的一个方面,将具有大于250,000g/mol的分子量Mw的可溶性聚合物作为添加剂添加到用于墨层的墨水的溶剂中。
该墨水特别包含溶剂、染料,更特别是颜料,以及增进激光吸收的粒子,更特别是上述反射性粒子。
据发现,通过添加可溶于溶剂的聚合物,有可能显著降低附随物(喷溅物)的形成风险。
可溶性聚合物的比例根据本发明的一个实施方案为总墨水混合物的0.05-2重量%。可溶性聚合物的比例优选为总墨水混合物的大于0.05和/或小于1重量%,通常大于0.1和/或小于0.8重量%。
根据本发明的一个优选实施方案使用的可溶性聚合物包括纤维素酯、硝酸纤维素、纤维素醚,更特别是羟丙基纤维素,聚氨酯或乙烯基聚合物。特别地,羟丙基纤维素,换言之,其中一些羟基作为醚与羟丙基连接的纤维素醚,看起来特别适合于本发明的效果。
在本发明中使用的墨水组合物中使用的组合物中可用的合适溶剂包括二醇醚、醇、酯、芳烃、二烷基醚、二醇酯和二醇醚。
据发现,当改变印刷墨水的流变学时,破坏性的喷溅物完全没有形成或仅在极大减少的程度上形成。据发现,在大约Mw:250,000g/mol至大约1,500,000g/mol的平均分子量范围内的可溶性聚合物的低量混入对墨水的印刷行为具有正面影响。
这些外加剂(admixtures)改变墨水的所谓弹性。Mw小于250,000g/mol的可溶性聚合物的外加剂只有增稠作用并表现出清晰的喷溅性质。与此相比,具有更高Mw值(>1,500,000g/mol)的聚合物没有带来防喷溅性质的进一步改进,而是仅进一步阻碍可溶性。因此优选使用具有低于2,500,000g/mol,更优选低于1,500,000g/mol的分子量(Mw)的聚合物。
表1与印刷工业内常规的各种溶剂一起的合适的可溶性聚合物外加剂的实例,和表现出良好防喷溅性质的在总墨水混合物中常用的量(以重量%计):
表1
本发明进一步涉及具有纵横比>25的反射性粒子和可溶性聚合物的墨水用于如上所述的印刷方法的用途。
附图简述
下面参考图1更详细阐释本发明的主题。
图1是用于本发明的方法的印刷机的图解视图。
附图详述
图1是本发明的印刷机(1)的一个示例性实施方案的图解视图。
印刷机(1)包含循环墨带作为墨水载体(4)。
通过上墨单元(8)均匀地和在其整个面积上为墨带涂布墨水(2)。墨带随后朝箭头方向移动到印刷压区(printing nip)(10)。墨水载体(4)与承印基底(6)相距一定的间隙。间隙宽度优选可调和/或连续调整。这可借助例如适应性间隔辊(5)实现。
在印刷压区(10)中,使用激光扫描器(11)将激光束(3)透过激光可透的墨水载体(4)聚焦到墨水(2)中。借助激光束(3)局部和定向加热部分墨水(2)造成墨水(2)的小区域的爆炸性汽化(explosive vaporization),因此一部分印刷墨水(2)从墨带转移到对面的基底(6)上。
通过间隔辊(5)和偏转辊(7)的控制,墨带随后朝上墨单元(8)的方向向回移动。在上墨单元(8)和墨带之间接触时,补充已消耗的墨水(2)。
上墨单元(8)中的过量墨水(2)收集在底部的墨槽(9)中并连续反复添加到印刷操作中。
测量方法
平均粒度:通过使用Helos/BR Multirange(Sympatec)装置根据制造商指示和根据ISO 13320-1的激光散射粒度测定法测量粒度分布。在测量粒度分布前将粒子在搅拌下溶解在异丙醇中。在Fraunhofer-近似(Fraunhofer-approximation)中作为等效球体的体积加权累积频率分布计算粒度函数。中值d50是指测量粒子的50%低于这一值(在体积平均分布中)。取d50值作为平均粒度。
平均粒子厚度:使用反射式电子显微镜(REM)测定粒径。将常规用于电子显微术的树脂,例如TEMPFIX(Gerhard Neubauer Chemikalien,D-48031Munster,Germany)施加到样品板上并在热板上加热到软化。随后,从热板上取下样品板并将要测量的样品散布到软化树脂上。在厚度的测量中,相对于垂直于表面的平面估算颜料的方位角α并在根据公式Heff=Hmes/cosα评估厚度时虑及。
由Heff值借助相对出现频率绘制累积频率曲线。计数至少大约100个粒子并取Heff的平均值作为平均粒子厚度。
L*a*b值:使用DTM 分光光度计在15至25°的角度下测定在L*a*b*颜色空间中的值。
分子量:根据DIN 55672-2:2016-3测定可溶性聚合物的重均(Mw)分子量。
实施例
制备包含不同的反射性铝粒子的各种墨水组合物。使用US 6,241,344 B1中描述的方法,测量铝粒子转移到基底上。通过混合下列成分制备墨水组合物:
43重量%的乙醇
32重量%的甲氧基丙醇
10重量%的羟丙纤维素(klucel)在水中的3%溶液
1,5重量%的乙基纤维素
1,5重量%的聚乙烯醇缩丁醛
12重量%的反射性铝颜料
结果显示在表2中。
表2
为了测试可溶性聚合物的分子量对喷溅行为的影响,进行各种实验。在墨水组合物中,与反射性铝粒子结合,使用3-乙氧基-1-丙醇作为溶剂。实验概括在表3中。
这些实验清楚表明,Mw>100,000的可溶性聚合物显著减少喷溅。
表3
实施例 | 纤维素醚Mw | 总比例 | 散布的喷溅物% |
Ex.5* | 无聚合物 | 100% | |
Ex.6* | 100,000 | 1% | ca.90% |
Ex.7 | 300,000 | 1% | ca.70% |
Ex.8 | 800,000 | 1% | ca.10% |
Ex.9 | 1,200,000 | 1% | ca.10% |
*对比例
关于图1的附图标记单
1.印刷机
2.墨水
3.激光束
4.墨水载体
5.间隔辊
6.基底
7.偏转辊
8.上墨单元
9.墨槽
10.印刷压区
11.激光扫描器
Claims (26)
1.印刷方法,其中将承印基底布置在具有墨层的墨水载体对面,通过激光束区域性照射所述墨层,其中所述墨层包含反射性粒子、溶剂和溶解在溶剂中的可溶性聚合物,其特征在于所述反射性粒子具有>25的纵横比,其中纵横比被定义为平均粒度/平均粒子厚度,并且其中所述反射性粒子由金属或金属涂布的载体材料组成。
2.根据权利要求1的印刷方法,其中对于所述反射性粒子,PT<80+3PS,其中PT是以nm计的平均粒子厚度的绝对值,且PS是以μm计的平均粒度的绝对值。
3.根据权利要求1的印刷方法,其特征在于所述反射性粒子具有0,1-25μm的平均粒度。
4.根据权利要求2的印刷方法,其特征在于所述反射性粒子具有0,1-25μm的平均粒度。
5.根据权利要求1至4任一项的印刷方法,所述可溶性聚合物具有大于250,000g/mol的重均(Mw)分子量,其中根据DIN 55672-2:2016-3测定可溶性聚合物的重均(Mw)分子量。
6.根据权利要求5的印刷方法,其特征在于所述可溶性聚合物具有250,000g/mol至2,500,000g/mol的重均(Mw)分子量。
7.根据权利要求6的印刷方法,其特征在于所述可溶性聚合物具有250,000g/mol至1,500,000g/mol的重均(Mw)分子量。
8.根据权利要求1至4、6至7之一的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.05至2重量%。
9.根据权利要求5的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.05至2重量%。
10.根据权利要求8的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.05至1重量%。
11.根据权利要求9的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.05至1重量%。
12.根据权利要求8的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.1至0.8重量%。
13.根据权利要求9的印刷方法,其特征在于可溶性聚合物的比例为总墨水混合物的0.1至0.8重量%。
14.根据权利要求1至4、6至7、9至13之一的印刷方法,其特征在于所用可溶性聚合物包含纤维素酯、硝酸纤维素、纤维素醚,聚氨酯或乙烯基聚合物。
15.根据权利要求14的印刷方法,其特征在于纤维素醚是羟丙基纤维素。
16.根据权利要求5的印刷方法,其特征在于所用可溶性聚合物包含纤维素酯、硝酸纤维素、纤维素醚,聚氨酯或乙烯基聚合物。
17.根据权利要求16的印刷方法,其特征在于纤维素醚是羟丙基纤维素。
18.根据权利要求8的印刷方法,其特征在于所用可溶性聚合物包含纤维素酯、硝酸纤维素、纤维素醚,聚氨酯或乙烯基聚合物。
19.根据权利要求18的印刷方法,其特征在于纤维素醚是羟丙基纤维素。
20.根据权利要求1至4、6至7、9至13、15至19之一的印刷方法,其特征在于所用反射性粒子是具有大于50的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-5的在L*a*b*颜色空间中的a*和/或b*值的粒子。
21.根据权利要求20的印刷方法,其特征在于所用反射性粒子是具有大于70的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-5的在L*a*b*颜色空间中的a*和/或b*值的粒子。
22.根据权利要求20的印刷方法,其特征在于所用反射性粒子是具有大于80的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-5的在L*a*b*颜色空间中的a*和/或b*值的粒子。
23.根据权利要求20的印刷方法,其特征在于所用反射性粒子是具有大于50的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-3的在L*a*b*颜色空间中的a*和/或b*值的粒子。
24.根据权利要求20的印刷方法,其特征在于所用反射性粒子是具有大于70的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-3的在L*a*b*颜色空间中的a*和/或b*值的粒子。
25.根据权利要求20的印刷方法,其特征在于所用反射性粒子是具有大于80的在L*a*b*颜色空间中的L*值的粒子,并且是具有小于+/-3的在L*a*b*颜色空间中的a*和/或b*值的粒子。
26.包含反射性粒子和可溶性聚合物的墨水在根据权利要求1至25之一的印刷方法中的用途。
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