液态反应性防紫外线整理剂UVDHA的稳定性及应用研究
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摘要
上世纪20年代以来，由于碳氟系溶剂和氟利昂的大量使用，地球大气层中的臭氧层逐渐遭到破坏，致使地面上的紫外线辐射强度不断增加。适量的紫外线照射有助于人体健康，但过量的紫外线照射最直接的结果就是引起各种皮肤疾病，甚至导致皮肤癌。纯棉织物是夏季最常用的面料，但它对紫外线的屏蔽效果较差，因此对棉织物进行防紫外线整理是很有必要的。
棉用反应性防紫外线整理剂UVDH是实验室合成的均三嗪类紫外线吸收剂，适用于棉织物的防紫外线整理。它具有可与纤维素纤维发生反应的活性基团，整理过程类似于活性染料的染色，并在碱性条件下发生固着。UVDH在合成生产过程中往往要将其从液态烘干成固体并研磨成粉状，其间消耗大量的人力与能源，同时，以粉末状态使用时不仅使用不便，也容易对生产者造成一定的伤害；另外经UVDH整理后的棉织物具有很好的防紫外线效果，能够强烈地吸收UVB波段的紫外线，但对UVA波段的则吸收较少。本课题主要针对以上两个问题，通过对影响实验室合成的UVDH悬浮液体系的稳定性因素的研究，筛选出了2种有助于悬浮液体系稳定的分散剂IS和PEG20000，并确定了它们的总浓度为140g／L，其中IS与PEG20000的质量比为8：2。通过这个复合分散剂的加入，将液态的UVDH制成稳定的分散体系；另从一些吸收紫外线的物质中筛选出了合适的改进剂A，与液态的UVDH进行复配，得出UVDH与改进剂A的质量比为4：1的优化配方，并将其命名为UVDHA。该助剂在对UVB波段有较好吸收的同时，也对UVA波段产生较好的吸收效果，提高了防紫外线的能力。
液态的防紫外线整理剂UVDHA由于其自身反应活性基团存在，容易发生一定程度的水解。试验结果表明：水解的程度和速度受到存放时间，温度以及pH值等因素的影响。UVDHA应在中性或弱碱性条件下保存，且放置时间不宜超过3个月，放置温度不宜超过40℃。
本论文通过正交试验，确定了UVDHA对棉织物整理的优化工艺：其中元明粉浓度为90g／L，纯碱浓度为20g／L，吸附温度为60℃，固着温度为90℃。测定了经UVDHA整理后的棉织物的UPF值和紫外线透过率。坯布的UPF值可从4.17提高到30.1，而且UVA和UVB波段的紫外线透过率均有明显的降低，两者分别为3.04％，2.96％。将UVDHA分别与国内外同类产品进行对比，结果表明：经UVDHA处理后的织物不仅UVB波段的透过率较低，而且UVA波段的透过率也有明显降低，整体的防紫外线效果更佳。
本文还研究了UVDHA整理对染色布的防紫外线性能和染色性能的影响，同时也对其耐光色牢度、耐水色牢度、耐汗渍色牢度以及耐洗性等进行了测试。试验结果表明，经UVDHA整理后，染色织物的UPF值均比整理前有所提高，其中蓝色和黄色织物的UPF值增加较明显；同时，UVDHA对染色织物的整理会对织物的K／S值和有些色布耐光色牢度产生一定的影响，造成K／S值降低和耐光色牢度的升高。具体影响与染料和织物的颜色有关，有些红色和黄色织物的K／S值受到的影响较大，应用过程中应区别对待。此外，UVDHA的整理对它们的耐水、耐汗渍色牢度无明显影响，无色织物防紫外线整理效果的耐洗性优良，整理后的织物经20次水洗后，UPF值耐洗保持率在91.5％以上，经30次水洗后，仍保持在88.56％。因此UVDHA在棉织物防紫外线整理中应有良好的应用前景。
Since the 1920s last century, a large amount of application of thecarbon fluoride system solvent and the freon that caused the ozonospherein aerosphere thinner, which increased the amount of the ultraviolet thatreaches the earth. The moderate ultraviolet makes an importantcontribution to human's health. But too much ultraviolet will inducevarious skin diseases, even cancers. Cotton fabric is the most commonlyused materials in summer, but it was less effective shield to UV, so it isvery necessary to make the UV-protecting finishing on cotton fabrics.
The ultraviolet absorber UVDH is suitable for cotton fabrics whichbelong to the type of s-triazine ramification. It has a reactive group andcould react to the cellulose, the process same to the dyeing of the reactivedyestuffs, fixing in alkaline condition. In the process of synthesisproduction, UVDH was dried from liquid to solid and grinded to powder.Much energy and manpower were wasted. At the same time, it will notonly be inconvenience in using process but also damage the workers'health, because the power could easy go into their bodies. In addition, the fabrics finished by UVDH would get good. effectiveness foranti-ultraviolet, the transmittance of the UVB band is very low, but theUVA band is still high. This paper mainly aims at these two aspects.Through selecting the dispersants, IS and PEG20000 were proved thatthey could keep the stability of liquid UVDH when their totalconcentration was 140g/L, in which the mass ratio oflS and PEG20000 is8:2. As the compound dispersants added, the stability of the liquid UVDHimproved prominently. On the other hand, improver A was chosen fromsome substances that can absorb the ultraviolet. The mixture was fixed byimprover A and UVDH, the mass ratio is 1:4, and dispersant. It wasnamed UVDHA. This auxiliary could absorb the radiation of UVB bandand also UVA band and improve the ability of anti-UV.
The liquid ultraviolet absorber UVDHA was prone to hydrolyze asits reactive group. Through some tests, the results show that the degreeand velocity of hydrolyzation were infected by storage time and storagetemperature and pH value etc of the UVDHA. The UVDHA should bedeposited in a neuter environment and lower than 40℃and no more than3 months.
The optimized process of the UVDHA was obtained through theorthogonal tests which was Na_2SO_4 90g/L., Na_2CO_3 20g/L, adsorptiontemperature 60℃, fixing temperature 90℃. After test, the UPF value ofthe cotton sample rise from 4.17 to 30.1, and UV transmittances of the UVA band and the UVB band were only 3.04％and 2.96％. Comparedwith the other domestic and overseas absorbers, not only the UVtransmittance ofUVB band of the cotton fabrics finished by UVHDA waslower than the fabrics finished by the other absorbers,, but also the UVtransmittance of UVA band.
This paper also discussed the effect on the UV-protecting and thedyeing properties of dyed fabrics which are finished by UVDHA. Thefastness to light, fastness to water, fastness to perspiration and fastness towashing of the fabrics also were tested. The results show that the UPFvalues of the fabrics rose prominently, especially the yellow and bluefabrics. The UVDHA could affect the light fastness and reduce the K/Svalue of the fabrics. According to different colors of the dyestuffs and thefabrics, the effects of their fastness to light were different. But the K/Svalues of the red and yellow fabrics were affected more obviously.Furthermore, the fastness to water and fastness to perspiration of thefabrics were affected rarely. Meanwhile, the washing fastness of thecolorless fabrics was excellent, the UPF value retain rate still more than91.5％after washing 20times and 88.56％after washing 30times. SoUVDHA should have a good prospect in UV-protecting finishing oncotton thbrics.
棉用反应性防紫外线整理剂UVDH是实验室合成的均三嗪类紫外线吸收剂，适用于棉织物的防紫外线整理。它具有可与纤维素纤维发生反应的活性基团，整理过程类似于活性染料的染色，并在碱性条件下发生固着。UVDH在合成生产过程中往往要将其从液态烘干成固体并研磨成粉状，其间消耗大量的人力与能源，同时，以粉末状态使用时不仅使用不便，也容易对生产者造成一定的伤害；另外经UVDH整理后的棉织物具有很好的防紫外线效果，能够强烈地吸收UVB波段的紫外线，但对UVA波段的则吸收较少。本课题主要针对以上两个问题，通过对影响实验室合成的UVDH悬浮液体系的稳定性因素的研究，筛选出了2种有助于悬浮液体系稳定的分散剂IS和PEG20000，并确定了它们的总浓度为140g／L，其中IS与PEG20000的质量比为8：2。通过这个复合分散剂的加入，将液态的UVDH制成稳定的分散体系；另从一些吸收紫外线的物质中筛选出了合适的改进剂A，与液态的UVDH进行复配，得出UVDH与改进剂A的质量比为4：1的优化配方，并将其命名为UVDHA。该助剂在对UVB波段有较好吸收的同时，也对UVA波段产生较好的吸收效果，提高了防紫外线的能力。
液态的防紫外线整理剂UVDHA由于其自身反应活性基团存在，容易发生一定程度的水解。试验结果表明：水解的程度和速度受到存放时间，温度以及pH值等因素的影响。UVDHA应在中性或弱碱性条件下保存，且放置时间不宜超过3个月，放置温度不宜超过40℃。
本论文通过正交试验，确定了UVDHA对棉织物整理的优化工艺：其中元明粉浓度为90g／L，纯碱浓度为20g／L，吸附温度为60℃，固着温度为90℃。测定了经UVDHA整理后的棉织物的UPF值和紫外线透过率。坯布的UPF值可从4.17提高到30.1，而且UVA和UVB波段的紫外线透过率均有明显的降低，两者分别为3.04％，2.96％。将UVDHA分别与国内外同类产品进行对比，结果表明：经UVDHA处理后的织物不仅UVB波段的透过率较低，而且UVA波段的透过率也有明显降低，整体的防紫外线效果更佳。
本文还研究了UVDHA整理对染色布的防紫外线性能和染色性能的影响，同时也对其耐光色牢度、耐水色牢度、耐汗渍色牢度以及耐洗性等进行了测试。试验结果表明，经UVDHA整理后，染色织物的UPF值均比整理前有所提高，其中蓝色和黄色织物的UPF值增加较明显；同时，UVDHA对染色织物的整理会对织物的K／S值和有些色布耐光色牢度产生一定的影响，造成K／S值降低和耐光色牢度的升高。具体影响与染料和织物的颜色有关，有些红色和黄色织物的K／S值受到的影响较大，应用过程中应区别对待。此外，UVDHA的整理对它们的耐水、耐汗渍色牢度无明显影响，无色织物防紫外线整理效果的耐洗性优良，整理后的织物经20次水洗后，UPF值耐洗保持率在91.5％以上，经30次水洗后，仍保持在88.56％。因此UVDHA在棉织物防紫外线整理中应有良好的应用前景。
Since the 1920s last century, a large amount of application of thecarbon fluoride system solvent and the freon that caused the ozonospherein aerosphere thinner, which increased the amount of the ultraviolet thatreaches the earth. The moderate ultraviolet makes an importantcontribution to human's health. But too much ultraviolet will inducevarious skin diseases, even cancers. Cotton fabric is the most commonlyused materials in summer, but it was less effective shield to UV, so it isvery necessary to make the UV-protecting finishing on cotton fabrics.
The ultraviolet absorber UVDH is suitable for cotton fabrics whichbelong to the type of s-triazine ramification. It has a reactive group andcould react to the cellulose, the process same to the dyeing of the reactivedyestuffs, fixing in alkaline condition. In the process of synthesisproduction, UVDH was dried from liquid to solid and grinded to powder.Much energy and manpower were wasted. At the same time, it will notonly be inconvenience in using process but also damage the workers'health, because the power could easy go into their bodies. In addition, the fabrics finished by UVDH would get good. effectiveness foranti-ultraviolet, the transmittance of the UVB band is very low, but theUVA band is still high. This paper mainly aims at these two aspects.Through selecting the dispersants, IS and PEG20000 were proved thatthey could keep the stability of liquid UVDH when their totalconcentration was 140g/L, in which the mass ratio oflS and PEG20000 is8:2. As the compound dispersants added, the stability of the liquid UVDHimproved prominently. On the other hand, improver A was chosen fromsome substances that can absorb the ultraviolet. The mixture was fixed byimprover A and UVDH, the mass ratio is 1:4, and dispersant. It wasnamed UVDHA. This auxiliary could absorb the radiation of UVB bandand also UVA band and improve the ability of anti-UV.
The liquid ultraviolet absorber UVDHA was prone to hydrolyze asits reactive group. Through some tests, the results show that the degreeand velocity of hydrolyzation were infected by storage time and storagetemperature and pH value etc of the UVDHA. The UVDHA should bedeposited in a neuter environment and lower than 40℃and no more than3 months.
The optimized process of the UVDHA was obtained through theorthogonal tests which was Na_2SO_4 90g/L., Na_2CO_3 20g/L, adsorptiontemperature 60℃, fixing temperature 90℃. After test, the UPF value ofthe cotton sample rise from 4.17 to 30.1, and UV transmittances of the UVA band and the UVB band were only 3.04％and 2.96％. Comparedwith the other domestic and overseas absorbers, not only the UVtransmittance ofUVB band of the cotton fabrics finished by UVHDA waslower than the fabrics finished by the other absorbers,, but also the UVtransmittance of UVA band.
This paper also discussed the effect on the UV-protecting and thedyeing properties of dyed fabrics which are finished by UVDHA. Thefastness to light, fastness to water, fastness to perspiration and fastness towashing of the fabrics also were tested. The results show that the UPFvalues of the fabrics rose prominently, especially the yellow and bluefabrics. The UVDHA could affect the light fastness and reduce the K/Svalue of the fabrics. According to different colors of the dyestuffs and thefabrics, the effects of their fastness to light were different. But the K/Svalues of the red and yellow fabrics were affected more obviously.Furthermore, the fastness to water and fastness to perspiration of thefabrics were affected rarely. Meanwhile, the washing fastness of thecolorless fabrics was excellent, the UPF value retain rate still more than91.5％after washing 20times and 88.56％after washing 30times. SoUVDHA should have a good prospect in UV-protecting finishing oncotton thbrics.
引文
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[5] 周秀会，曹晓英．防紫外线织物新进展[J]．国外纺织技术，2000，(2)：30-33．
[6] 宋心远，沈煜如．新型染整技术[M]．北京：中国纺织出版社，1999：269-275．
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