【作者】 陈志华；

【导师】 顾平；

【作者基本信息】 苏州大学 ， 纺织材料与纺织品设计， 2012， 博士

【摘要】 紫外线是一种电磁波辐射线(Ultraviolet radiation—UVR)，按其波段可分为近紫外线（UVA）、远紫外线（UVB）和超短紫外线（UVC）三种，其波段分别为320－400nm、280－320nm、100－280nm。正常情况下，UVC能被大气层中臭氧层吸收，部分UVA及UVB也会被臭氧层吸收，只有很少一部分能到达地球表面。然而，近年来由于人类社会经济的高速发展，致使局部地区臭氧层变薄或出现臭氧层空洞。紫外线照射到织物上，一部分被织物自然吸收，另一部则被表面纤维反射，剩余的则透过织物，该部分紫外线能对皮肤产生影响，导致皮肤损伤，产生病变。紫外线的防护方法就是采用紫外线屏蔽剂或其它功能性助剂对纤维、纱线或织物进行改性处理，从而达到吸收或反射紫外线的目的。或利用抗紫外助剂进行织物后整理，单独或混合使用无机紫外线散射剂或有机紫外线吸收剂等，用浸渍法、印花法或吸尽法附着在合纤维或织物上，制得防紫外线纤维和织物。转光剂目前尚无统一定义，命名也不尽相同。通常认为，转光剂是一类能将日光中紫外光、绿光等转化为红光、蓝光的化学物质，其核心是稀土元素，如铕（Eu）、钐（Sm）等，其特有的f-f轨道电子跃迁，可以发出特征光，具有紫外转红、蓝或绿光的作用。另外，一些荧光惰性的稀土元素，如钇（Y），与荧光活性离子配合后，亦可起到荧光增强作用稀土有机转光剂是一类铕及杂核稀土元素的有机配合物，能吸收紫外光发射出可见光的光致发光材料，具有发光亮度高、光色单一性好、光热稳定性强、不易老化、易于分散于各种溶剂和有机材料中等优点，因此被用于制造各种有机荧光材料。利用转光剂的光转换机能，将紫外光进行有效转换可达到防紫外的效果，这对于拓展转光剂的应用领域，特别是开发功能性纺织品具有重要意义，然而尚无发现此类研究。本论文研究了转光剂应用于织物抗紫外的可行性，合成了新型转光剂，对不同配体、合成路线与合成工艺对转光剂转光能力的影响进行了研究。分析了新合成转光剂的分散性，并根据转光剂的吸收波段及其吸光能力差异，选定了具有宽频吸收紫外光并进行有效转换、能够应用于纺织抗紫外的转光剂。研究了不同转光剂的抗紫外整理工艺及整理后的织物性能变化。研究结果发现，市场上稀土有机配合物转光剂能吸收300-360nm紫外光，发射591.8，614.1，701.8nm红、黄光，经转光剂整理后，织物抗紫外能力明显提高，证明了其转光剂应用于织物抗紫外整理的可行性。但同时发现，市售转光剂存在着在水中不易溶解、分散性差、易于造成织物色差的现象。在合成新型转光剂的研究中发现，通过固相化学合成的方法能将碳酸铕与有机配体分别球磨合成Eu (sds)4、 Eu (q)4、 Eu (AcA)4、 Eu (DBM)4、Eu (TTA)3phen、 Eu (sal)3sds和Eu (DBM)3q配合物。首先制备氯化铕的无水乙醇溶液，铕与羟基喹啉和α噻吩-甲酰三氟丙酮能通过液相合成法，得到Eu (TTA)3phen稀土有机配合物的无水乙醇溶液。通过液相合成的Eu (TTA)3phen与固相合成法合成的Eu (TTA)3phen红外谱图的对比分析，发现在液相合成的Eu (TTA)3phen的红外谱图中的特征峰清晰，并且配体的特征峰在配合物中基本消失，表明通过固相方法在合成过程中配体与铕的结合不及液相合成方法充分。从合成的的稀土有机配合物的激发光谱看，在引入有机配体后，不同稀土配合物的吸收波段差异较大。但由于有机配体的π-π*电子转移的作用，配合物普遍能够吸收200-400nm的紫外光，最高的是碳酸铕与二苯甲酰甲烷合成的Eu (DBM)4配合物，其吸收波段可达到200-450nm。对比几种配合物的激发光谱，发现二元配体的配合物对紫外光的吸收能力要强于一元配体的配合物。二元有机配体的配合物Eu (TTA)3phen几乎能将200nm-400nm内的紫外光全部吸收，形成的吸收振动峰丰厚饱满，较一元配合物Eu (sds)4、 Eu (q)4、 Eu (AcA)4、 Eu (DBM)4的吸收能力都要强。对比六偏磷酸钠与聚丙烯酸钠两分散体系在相同条件下的分散情况，发现六偏磷酸钠的分散性明显优于聚丙烯酸钠。三种分散体系中，单一分散剂聚丙烯酸钠及六偏磷酸钠在浓度为1.5g/L时分散性最佳，二元分散剂（丙烯酸钠与六偏磷酸钠1:1配合）浓度在2.5g/L时分散性最佳。通过吸光度分析发现单一分散剂最佳分散效果优于二元分散剂，六偏磷酸钠对转光剂的分散效果好于聚丙烯酸钠。五种转光剂中，乙醇溶液转光剂A的分散性最佳，转光剂C最差。六偏磷酸钠、聚丙烯酸钠、二元分散剂的加入可不同程度地提高转光剂的分散性能，且随着分散剂浓度的增加分散体系的吸光度呈现先增加后减小的趋势。最佳分散工艺为：转光剂浓度1g/L，六偏磷酸钠浓度1.5g/L，高速搅拌下能获得较好的分散效果。单独使用转光剂时，1.0g/L的转光剂浓度抗紫外效果最佳。自然晾干、焙烘、浸轧三种整理工艺中，焙烘时织物的抗紫外防护系数最高，抗紫外效果最佳。加入分散剂六偏磷酸钠、聚丙烯酸钠可以大大提高织物的抗紫外性能，即六偏磷酸钠、聚丙烯酸钠1.5g/L，二元分散剂2.5g/L，加入六偏磷酸钠及适量转光剂时织物的转光效果最佳。本论文新合成的乙醇溶液转光剂抗紫外效果最优。经转光剂整理后，发现转光剂整理后织物的强伸度、折皱回弹性无显著变化，基本保持不变，整理后织物白度稍有下降，DATACOLOR SF-60测试发现转光剂整理后织物偏红光、绿光。综上所述，发现转光剂能用于织物的抗紫外整理，具有宽频高效吸收紫外光的能力，织物经整理后的抗紫外能力明显提高，且用量较少，这为织物抗紫外功能整理提供了一种新型助剂，有利于降低成本和减少工艺流程，同时为稀土的有效利用和拓宽其应用领域提供了重要的参考。更多还原

【Abstract】 Ultraviolet ray is an electromagnetic wave radiation (Ultraviolet radiation,UVR). According to the band, it can be divided into nearly Ultraviolet (UVA), farUltraviolet (UVB) and ultra short Ultraviolet (UVC), responding to the band320-400nm,280-320nm and100-280nm, respectively. Normally, UVC can be absorbed by theozone layer in the atmosphere, part of the UVA and UVB will also be absorbed bythe ozone layer, only a few Ultraviolet radiations can reach the surface of theearth. However, in recent years, due to the high speed development of economy inthe human society, the ozone layer is becoming thinner and thinner and the localarea appears ozone hole.Ultraviolet ray, which reaches to the fabrics, are absorbed partially by nature.Another one is reflected by fiber surface, the rest is through the fabric,undoubtedly, these ultraviolet rays have a disastrous effect on the skin, causingskin damage and producing lesions. UV protection method and principle are asfollows: the fiber, yarn and fabric were modified using UV shield agent or otherfunctional additives, so as to achieve the purpose of ultraviolet absorption orreflection. Or the fabrics are treated using inorganic ultraviolet lightscattering agent and/or organic ultraviolet ray absorber. By the immersion,printing or absorption process, the agents attach to the surface of the fabricsor yarns and then the ultraviolet prevention fiber and fabric can be produced.At present, there is no unifying definition for light conversion agent, thenaming are also different. Usually, light conversion agent is a kind of chemicalmaterial, which can transform ultraviolet light into red, green and blue light.Their core is the rare earth elements, such as Eu and Sm. Due to their unique f-frail electronic transition, they can send out features light, with the functionof conversion from ultraviolet to red, blue or green light. In addition, some fluorescence inert of rare earth elements, such as yttrium (Y), are bonded withfluorescence active ions, can play a fluorescence enhancement effect.Rare earth organic light conversion agent is a kind of organic complexconsisted of Eu or miscellaneous nuclear rare earth elements. They can absorbultraviolet light and launch out of visible light. Because they have the advantagessuch as high lighting brightness, excellent light color oneness, strong stability,good ageing resistance and easy to spread to all kinds of solvent and organicmaterials medium, it is especially suitable to make all kinds of organicfluorescent materials.Using the light conversion function of light conversion agent, ultravioletlight are conversed effectively, which can reach the purpose of preventingultraviolet ray. This will expand the application area of rare earth, especially,it has an important meaning for the development of functional textile, and yet.However, such researches have not been found. In this topic, we first studied thefeasibility of light conversion agent used as UV finishing agent of textiles, andthen the new light conversion agent were synthesized. Subsequently, the influenceof synthesis process such as the different ligands and synthetic route on theability of light conversion was then analyzed. Finally, the dispersion of the lightconversion agent was studied. According to the absorption capability of UV lightand the absorption wave band, we selected the ideal light conversion agent, whichcan absorb a broadband ultraviolet light effectively. Since then, the finishingprocess with different light conversion agent and the changes of the fabrics beforeand after finishing were studied.The results showed that the sold rare earth complexes light conversion agentcan absorb300-360nm ultraviolet light and launch591.8,614.1,701.8nm red,yellow light. The UV protection ability of the fabrics finished by the lightconversion agent obviously increased. This verified the feasibility of lightconversion agent used as fabric UV finishing agent. However, we also found thatlight conversion agent in the water was not easy to dissolve and disperse. Thiswill cause the color difference.In the synthesis of new light conversion agent, we found, through the solid phase synthesis methods, Eu carbonate and organic ligand could grinded togetherinto complexes such as Eu (sds)4、 Eu (q)4、 Eu (AcA)4、 Eu (DBM)4、 Eu (TTA)3phen、Eu (sal)3sds and Eu (DBM)3q, respectively. Chlorinated Eu was first dissolved inethanol, through the liquid synthesis process, Eu and TTA, phen can get rareearth Eu (TTA)3phen complex. Compared with Eu (TTA)3phen complex synthesizedthrough the solid phase, the characteristic peak of the complex synthesized inthe liquid phase was clearer. Additionally, the characteristic peak of the liganddisappeared, suggesting that the bonding between Eu and the ligand in the liquidwas tighter than the one in the solid phase. From the excitation spectra of newsynthetic rare earth organic complexes, due to the introduction of organic ligand,the absorption band was not similar for different complexes. However, because ofelectron transfer function of organic ligands, these complexes generally couldabsorb200-400nm UV ray. The absorption band could be up to200-450nm forEu (DBM)4complexes. In comparison of the excitation spectrum of severalcomplexes, we could find that the UV absorption of the complex with two ligandswas higher than the complex with one ligand. Eu (TTA)3phen, which had two ligands,could absorb UV ray with the band from200nm-400nm. Furthermore, the absorptionvibrating peak of Eu (TTA)3phen was wider and higher than the complexes such asEu (sds)4、 Eu (q)4、 Eu (AcA)4、 Eu (DBM)4, suggesting that it had a strongerabsorption capability.In the analysis of dispersion, we found that the dispersion ability of sodiumhexametaphosphate was significantly better than sodium polyacrylate. Three kindsof decentralized system, the better concentration was1.5g/L for sodiumhexametaphosphate and sodium polyacrylate, but the concentration of2.5g/L wasideal for the composite dispersant (sodium hexametaphosphate to sodiumpolyacrylate was1:1). Through the absorbency analysis, we could also obtain thesame results. We found that, type A light conversion agent that could dissolvein the ethanol had the best dispersion, Type C was the worst. The addition ofdispersant improved the dispersion performance in varying degrees, and with theincrease of the concentration of dispersant, the absorbency first increased and then decreased. The best decentralized process was follows: the concentration oflight conversion agent1g/L, the concentration of sodium hexametaphosphate1.5g/L, and stirring in high speed.When light conversion agent was used alone, the concentration1.0g/L couldobtain the best ultraviolet protection effect. The finishing process of bakingwas better than the other processes such as natural drying and padding. The additionof dispersant could increase the UV protection ability. The concentration of thedispersant in the finishing process was similar with the one in the dispersionresearches. The ultraviolet protection effect of Eu (TTA)3phen was the best. Afterfinishing by light conversion agent, the wrinkle recovery and the strength hadno significant change, but the white degree demonstrated a slight decline,additionally, DATACOLOR SF-60testing results showed that the fabric finished bylight conversion agent turned red and green light.To sum up, we can find that light conversion agent can be used as fabric UVprotection finishing agent. They have the absorption ability of broad bandultraviolet light. The UV resistance of the fabric finished by light conversionagent obviously improved, but it just needs less dosage, which provides a newassistant for the UV protection finishing. This can reduce the cost and the process.In addition, this provides important reference for the effective use of rare earthand its application expansion.更多还原