PET基材纳米吸墨材料的制备及性能研究

发布时间：2018-10-31 20:21

【摘要】：纳米吸墨材料以其鲜明的色彩表达能力、优良的色彩打印效果等优点近年来得到迅猛发展。吸墨材料最终质量的好坏很大程度上由吸墨材料中吸墨层的性能决定。然而,目前产业化的吸墨材料存在吸收性差,印刷性不好等缺点,限制了其应用。本文的目的是构建性能优异可控的纳米吸墨材料。在本文中首先对基材改性进行了研究,接着对不同种类的纳米粒子对吸墨材料性能的影响进行了探讨,并以不同粒径和比表面积的纳米二氧化硅为研究对象,研究了同种纳米组分对吸墨材料性能的影响及性能增强机理,最后考察了胶粘剂用量对纳米吸墨材料的性能影响。PET薄膜是弱极性的高分子材料,其亲水性能比较差,因而须对其在涂装前进行预处理。利用低温等离子体处理技术对吸墨材料所用PET薄膜进行表面改性,通过变化不同的处理时间与处理功率来改善PET表面的润湿性,从而为得到高品质的纳米吸墨材料奠定坚实的基础。通过对低温等离子体处理后基材PET表面粗糙度、表面元素、表面形貌、表面接触角和表面能等的表征发现,低温等离子体改性通过改变PET薄膜表面的含氧量,极性官能团增加,表面粗糙度变大,增加了PET界面处的空间机械锁合作用,提高了PET与胶粘剂间的界面粘结性能。改性之前C=O官能团的含量为零,在改性时间为20s时其含量增加到13.37%。另通过测试发现低温等离子对PET改性具有时效性,且其力学性能在改性前后发生微小的变化。从表3-5中可以看出,PET薄膜在改性之前,在对C1s谱图进行分峰时,在谱图中C-C(284.80e V)、C-O(C-OH)(285.78e V)、O=C-O(COOH)(286.90e V)这些官能团几乎不存在。对经过等离子体改性的PET进行分峰,C-C、C-O(C-OH))、O=C-O(COOH)这几个官能团的含量均有增加,尤其是C=O官能团和O=C-O官能团,未改性之前它们的含量为零。改性后C=O官能团在改性时间为10s时其含量增加到12.83%,在其改性时间为20s时其含量增加到13.37%。而改性后O=C-O官能团在改性时间为10s时其含量增加到14.01%,在其改性时间为20s时其含量增加到17.46%。改性后PET表面C=O官能团的增加,也表明PET的极性得到了改善。极性的改善将直接影响到PET与吸墨层之间的粘结性能及界面间的结合能力。对不同种类的颜料构成的纳米吸墨材料的吸墨层结构进行表征,纳米吸墨材料加入了这几种纳米粒子后,其本体性能、表面强度,印刷性和稳定性均有所提高。纳米二氧化硅均匀分散在胶粘剂中,其分散性好于纳米二氧化钛和纳米碳酸钙。纳米二氧化硅构成的吸墨材料对墨水的吸收曲线波动幅度较小,墨水渗透最深处的深度值为16.6μm,渗透最浅处的深度值为13.6μm。纳米二氧化硅构成的吸墨材料印刷性最好,含纳米二氧化钛的吸墨材料的稳定性提高的最多。对于纳米吸墨材料而言,由较小粒径的二氧化硅构成的吸墨材料的吸墨层表面颗粒堆积较为密实(但是表面有裂纹),而较大粒径的纳米二氧化硅粒子构成的吸墨层则粒子排列松散。随着纳米二氧化硅粒径的增加,吸墨层表面的孔隙也不断增大。吸墨材料的孔隙率、吸墨层孔径、孔面积和孔体积都随纳米粒子粒径的增加而增加。通过测试分析表明,粒径在12nm的二氧化硅粒子制得的吸墨材料的白度、平滑度、光泽度、吸收效率较另外两种纳米二氧化硅粒子制得的吸墨材料的的相应值大,而粗糙度、浸润性、浸润深度、表面强度、密度差值则颜料粒径越小这些值越小。吸墨材料由于加入了纳米粒子,其耐热稳定性和耐紫外稳定性均有所提高,纳米粒子的加入起到了对吸墨材料的保护作用,提高了其使用年限。当胶粘剂用量从10%增加到25%时,吸墨材料的孔隙体积减小,平均孔径下降,透气性减弱,吸墨层表面的宏观粗糙度变小,吸墨材料的表面自由能降低,油墨吸收性随之减小。增加胶粘剂的用量,吸墨层表面成膜性增强,吸墨材料热稳定性降低。因而,考虑成本、胶粘剂对纳米复合吸墨材料性能影响等因素,在本论文中,制备纳米吸墨材料的胶粘剂用量一般不超过20%。
[Abstract]:The nano ink absorbing material has the advantages of vivid color expression ability, excellent color printing effect and the like, and has been developed rapidly in recent years. The final quality of the ink-receptive material is largely determined by the performance of the ink-receptive layer in the ink-receptive material. However, at present, the ink-absorbing material of the industrialization has the defects of poor absorption, poor printability and the like, and the application thereof is limited. The purpose of this paper is to build a nanometer ink-absorbing material with excellent properties. The effects of different kinds of nano-particles on the properties of ink-absorbing materials were studied in this paper, and nano-silica with different particle size and specific surface area was studied. The effect of the same nano-component on the properties of ink-absorbing material and the mechanism of performance enhancement were studied, and the effect of the amount of adhesive on the properties of the nano-ink-absorbing material was investigated. The PET film is a weakly polar polymer material, and the hydrophilicity of the PET film is poor, so it is necessary to pre-treat the PET film before coating. the surface modification of the PET film used for the ink-absorbing material is carried out by utilizing the low-temperature plasma processing technology, and the wettability of the PET surface is improved by changing different treatment time and processing power so as to lay a solid foundation for obtaining the high-quality nano ink-absorbing material. Through characterization of the surface roughness, surface elements, surface morphology, surface contact angle and surface energy of the substrate after the low temperature plasma treatment, the low temperature plasma modification can change the oxygen content of the surface of the PET film, the polar functional group is increased, and the surface roughness becomes large, and the interfacial bonding property between the PET and the adhesive is improved. The content of C = O functional group before modification was zero, and its content increased to 13.37% when the modification time was 20s. It was found that the modification of PET by low-temperature plasma was time-sensitive and its mechanical properties changed slightly before and after modification. As can be seen from Table 3-5, the functional groups of C-C (284. 80e V), C-O (C-OH) (285. 78e V), O = C-O (COOH) (286. 90e V) are hardly present in the spectrogram prior to modification of the PET film. The content of the functional groups of C-C, C-O (C-OH), O = C-O (COOH) was increased, especially C = O functional group and O = C-O functional group, and their content was zero before modification. After modification, the content of C = O functional group increased to 12.83% when the modification time was 10s, and its content increased to 13.37% when its modification time was 20s. The modified O = C-O functional group increased to 14.01% when the modification time was 10s, and its content increased to 17. 46% when its modified time was 20s. The addition of the modified PET surface C = O functional group also shows that the polarity of PET is improved. The improvement of polarity will directly affect the bonding energy between PET and ink absorbing layer and the bonding ability between interfaces. the ink receptive layer structure of the nano ink-absorbing material composed of different kinds of pigments is characterized, and after the nano ink-absorbing material is added with the nano-particles, the bulk property, the surface strength, the printing property and the stability of the nano ink-absorbing material are improved. the nano silicon dioxide is uniformly dispersed in the adhesive, and the dispersibility is good for the nano titanium dioxide and the nano calcium carbonate. The ink absorbing material composed of nano silicon dioxide has small fluctuation range of the absorption curve of the ink, the depth value at the deepest depth of the ink is 16. 6. m u.m, the depth value at the deepest part of the penetration is 13. 6. m u.m. The printing property of the ink-absorbing material composed of nano silicon dioxide is the best, the stability of the ink-receptive material containing the nano-titanium dioxide is improved. In the case of the nano-ink-absorbing material, the surface particles of the ink-absorbing layer of the ink-absorbing material composed of silica having a smaller particle diameter are densely packed (but there are cracks on the surface), and the ink-absorbing layer composed of the nano-silica particles having a larger particle size is loosely arranged. With the increase of the size of the nano-silica, the porosity of the surface of the ink-absorbing layer also increases. The porosity of the ink-absorbing material, the pore size of the ink-absorbing layer, the pore area and the pore volume increase with the increase of the particle size of the nanoparticles. According to the test analysis, the whiteness, smoothness, glossiness and absorption efficiency of the ink-absorbing material prepared by the silica particles with the particle size of 12nm are large, and the corresponding values of the ink-absorbing material prepared by the two kinds of nano-silica particles are large, and the roughness, the wettability, the wetting depth and the surface strength are large, The smaller the density difference, the smaller these values the smaller the pigment particle size. As the ink absorbing material is added with nano particles, the heat-resistant stability and the ultraviolet-resistant stability of the ink-absorbing material are improved, the addition of the nano-particles plays a protective role on the ink-absorbing material, and the service life of the ink-absorbing material is improved. When the amount of the adhesive is increased from 10% to 25%, the pore volume of the ink-absorbing material is reduced, the average pore diameter is reduced, the air permeability is weakened, the macro-roughness of the surface of the ink-absorbing layer becomes small, the surface free energy of the ink-absorbing material can be reduced, and the ink absorption is reduced. the amount of the adhesive is increased, the film forming property of the ink-absorbing layer is enhanced, and the thermal stability of the ink-absorbing material is reduced. Therefore, in this paper, the amount of adhesive used to prepare the nano-ink-absorbing material is generally not more than 20% considering the factors such as cost and the influence of the adhesive on the performance of the nano composite ink-absorbing material.
【学位授予单位】：哈尔滨工业大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：TB383.1

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