分散染料微胶囊合成工艺和超细聚酯仿麂皮染色的研究
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摘要
本论文从环保的角度出发，基于对分散染料微胶囊技术的进一步的研究，通过改变芯壁比来调节微胶囊的缓释速度，从而改变分散染料染色的上染速率，试图解决混合拼色中出现的由于不同染料上染速率不一样而导致竞染和色光出现偏差的问题，最终进一步改善了无助剂免水洗的分散染料微胶囊技术的应用性能。
本文分别选用分散蓝C．I．79染料，分散红C．I．167染料，分散黄C．I．211染料以及分散红C．I．60染料作为芯材，以三聚氰胺预聚体为壁材，采用原位聚合法结合双层造壁手段，相比为80：20，制得分散染料微胶囊。
首先，采用单因素实验讨论了芯壁比，乳化搅拌速度，系统调节剂用量各因素对微胶囊粒径大小，分布以及微胶囊包合率的影响，探索最佳的合成工艺：
其次，选用高中低温型分散染料微胶囊化，用制备的分散染料微胶囊高温高压无助剂方法染超细聚酯仿麂皮，从染色样品的染色牢度、染色废水吸光度大小以及匀染性等方面与传统分散染料染色工艺进行了比较；
再次，选用三种不同亲水性大小的分散染料，制得微胶囊，简要研究了由分散染料分子的极性基团引起亲水性大小的差异对分散染料微胶囊染色废水的影响；
最后，采用单因素实验，讨论了芯壁比对分散染料微胶囊上染速率的影响；并且选用高温型分散染料三原色微胶囊化，采用高温高压无助剂混合拼色，对分散染料微胶囊的混合拼色可行性进行了初步探讨。结果表明：芯壁比的选择对分散染料微胶囊的染色应用起到重要影响。芯壁比太大，壁材量不足以完全包覆住囊心；芯壁比太小，壁材过量，在胶囊表面产生许多聚合物。随着芯壁比的减小，壁材所占的比例增大，微胶囊的平均粒径随之相应减小，微胶囊的粒径分布也逐渐变窄，但当芯壁比小于一定程度时，胶囊粒径分布变化不大。另一方面，微胶囊的包合率随着芯壁比的减小，先增大，后减小，当壁材刚好完全包覆囊芯时，包合率最大，对于分散蓝79染料微胶囊化的最佳芯壁比为1：2。随着系统调节剂MS用量的增加，MS的粒径大小逐渐减小，粒径分布逐渐变窄；当MS用量过量时，制得的微胶囊结块状；MS用量过少，分布很宽，囊心没有被充分分散，制得的微胶囊粒径分布很宽，所以应该选择适量的MS用量。对于偶氮结构的分散染料一般选择0.3％，对于蒽醌结构的分散染料一般选择0.5％～0.7％。搅拌速度加快，微胶囊粒径逐渐变小，粒径分布逐渐变窄，微胶囊的包合率依次减小；考虑到产品性能和综合节能性，选择乳化搅拌速度5，000rpm／min较佳。
不同芯壁比的微胶囊染色速率有所不同。芯壁比减小，即壁材比例增大，对染料的初染速率有阻滞作用，以致使得初染速率相应减慢。同时，微胶囊的缓释性可以提高染色匀染性。而MS用量对染料的上染速率或许有一定影响，有待研究。
对于高中低温型分散染料微胶囊，高温高压无助剂染聚酯仿麂皮，由于囊壳沾附染样使得摩擦牢度偏低，比传统分散染料染色牢度低0.5级左右，这问题正待解决中。其他牢度均不低于分散染料传统染色工艺的染色牢度。分散染料微胶囊的染色牢度最主要还是取决于染料本身的性质。
当染料分子亲水性小，分散染料微胶囊的染色废水颜色比较浅，有的染色废水几乎呈无色；如果染料分子亲水性大，染料的溶解度也大，微胶囊化的染色废水吸光度相对变深，但分散染料微胶囊染色废水吸光度均比传统工艺分散染料染色废水小的多。
分散染料微胶囊用于配色，是切实可行的，而且仍然是环保节能的。
With an eye to environment-friendship, this thesis investigates the application of disperse dye microcapsules. It is studied how slow-releasing action of microcapsules could be adjusted by changing core/wall ration, as a result, the dyeing speed of disperse dyes could be controlled. The purpose of the study is to solve some problems on matching colors such as competing dyeing and different shade, thus improves the application performance of disperse dye microcapsules.
In the study, C.I.disperse blue 79, C.I.disperse red 167, C.I.disperse yellow211 and C.I.disperse red 60 had been chosen as the core materials, and melamine performed polymer had been chosen as the wall-former. Disperse dye microcapsules with double-layed wall were prepared by means of in-situ polymerization method, operating in phase ration 80:20.
First, the impacts on particle size, and particle distribution as well as the content of microcapsules were studied and ensured by monofactorial experiments. The best techniques for synthesizing were explored in the operating conditions as follows: core/wall ration, milling speed of emulsification, concentration of MS.
Second, choosing S, SE and E types disperse dye microencapsulated in that manner, these disperse dye microcapsules were used to dye polyester suede-like under high temperature press condition without auxiliaries, by comparing dyeing grades, wastewater absorbance and level-dyeing property with traditional disperse dyes.
Moreover, choosing 3 different kinds hydrophilic property of disperse dye molecule microencapsulated, the impacts on dyeing wastewater with respect to different kinds of hydrophilic property were discussed.
Finally, the paper discussed the influence on the dyeing speed of microcapsules because of different core/wall rations by monofactorial experiments. The possibility of matching colors with 3 S type primary colors disperse dyes microencapsulated was also studied.
本文分别选用分散蓝C．I．79染料，分散红C．I．167染料，分散黄C．I．211染料以及分散红C．I．60染料作为芯材，以三聚氰胺预聚体为壁材，采用原位聚合法结合双层造壁手段，相比为80：20，制得分散染料微胶囊。
首先，采用单因素实验讨论了芯壁比，乳化搅拌速度，系统调节剂用量各因素对微胶囊粒径大小，分布以及微胶囊包合率的影响，探索最佳的合成工艺：
其次，选用高中低温型分散染料微胶囊化，用制备的分散染料微胶囊高温高压无助剂方法染超细聚酯仿麂皮，从染色样品的染色牢度、染色废水吸光度大小以及匀染性等方面与传统分散染料染色工艺进行了比较；
再次，选用三种不同亲水性大小的分散染料，制得微胶囊，简要研究了由分散染料分子的极性基团引起亲水性大小的差异对分散染料微胶囊染色废水的影响；
最后，采用单因素实验，讨论了芯壁比对分散染料微胶囊上染速率的影响；并且选用高温型分散染料三原色微胶囊化，采用高温高压无助剂混合拼色，对分散染料微胶囊的混合拼色可行性进行了初步探讨。结果表明：芯壁比的选择对分散染料微胶囊的染色应用起到重要影响。芯壁比太大，壁材量不足以完全包覆住囊心；芯壁比太小，壁材过量，在胶囊表面产生许多聚合物。随着芯壁比的减小，壁材所占的比例增大，微胶囊的平均粒径随之相应减小，微胶囊的粒径分布也逐渐变窄，但当芯壁比小于一定程度时，胶囊粒径分布变化不大。另一方面，微胶囊的包合率随着芯壁比的减小，先增大，后减小，当壁材刚好完全包覆囊芯时，包合率最大，对于分散蓝79染料微胶囊化的最佳芯壁比为1：2。随着系统调节剂MS用量的增加，MS的粒径大小逐渐减小，粒径分布逐渐变窄；当MS用量过量时，制得的微胶囊结块状；MS用量过少，分布很宽，囊心没有被充分分散，制得的微胶囊粒径分布很宽，所以应该选择适量的MS用量。对于偶氮结构的分散染料一般选择0.3％，对于蒽醌结构的分散染料一般选择0.5％～0.7％。搅拌速度加快，微胶囊粒径逐渐变小，粒径分布逐渐变窄，微胶囊的包合率依次减小；考虑到产品性能和综合节能性，选择乳化搅拌速度5，000rpm／min较佳。
不同芯壁比的微胶囊染色速率有所不同。芯壁比减小，即壁材比例增大，对染料的初染速率有阻滞作用，以致使得初染速率相应减慢。同时，微胶囊的缓释性可以提高染色匀染性。而MS用量对染料的上染速率或许有一定影响，有待研究。
对于高中低温型分散染料微胶囊，高温高压无助剂染聚酯仿麂皮，由于囊壳沾附染样使得摩擦牢度偏低，比传统分散染料染色牢度低0.5级左右，这问题正待解决中。其他牢度均不低于分散染料传统染色工艺的染色牢度。分散染料微胶囊的染色牢度最主要还是取决于染料本身的性质。
当染料分子亲水性小，分散染料微胶囊的染色废水颜色比较浅，有的染色废水几乎呈无色；如果染料分子亲水性大，染料的溶解度也大，微胶囊化的染色废水吸光度相对变深，但分散染料微胶囊染色废水吸光度均比传统工艺分散染料染色废水小的多。
分散染料微胶囊用于配色，是切实可行的，而且仍然是环保节能的。
With an eye to environment-friendship, this thesis investigates the application of disperse dye microcapsules. It is studied how slow-releasing action of microcapsules could be adjusted by changing core/wall ration, as a result, the dyeing speed of disperse dyes could be controlled. The purpose of the study is to solve some problems on matching colors such as competing dyeing and different shade, thus improves the application performance of disperse dye microcapsules.
In the study, C.I.disperse blue 79, C.I.disperse red 167, C.I.disperse yellow211 and C.I.disperse red 60 had been chosen as the core materials, and melamine performed polymer had been chosen as the wall-former. Disperse dye microcapsules with double-layed wall were prepared by means of in-situ polymerization method, operating in phase ration 80:20.
First, the impacts on particle size, and particle distribution as well as the content of microcapsules were studied and ensured by monofactorial experiments. The best techniques for synthesizing were explored in the operating conditions as follows: core/wall ration, milling speed of emulsification, concentration of MS.
Second, choosing S, SE and E types disperse dye microencapsulated in that manner, these disperse dye microcapsules were used to dye polyester suede-like under high temperature press condition without auxiliaries, by comparing dyeing grades, wastewater absorbance and level-dyeing property with traditional disperse dyes.
Moreover, choosing 3 different kinds hydrophilic property of disperse dye molecule microencapsulated, the impacts on dyeing wastewater with respect to different kinds of hydrophilic property were discussed.
Finally, the paper discussed the influence on the dyeing speed of microcapsules because of different core/wall rations by monofactorial experiments. The possibility of matching colors with 3 S type primary colors disperse dyes microencapsulated was also studied.
引文
[1] Nixon J R. Preparation ofmicrocapsules with possible pharmaceutical use [J]. Endeavour, 1985, 9(3): 123-128;
[2] Hunkeler D. Polymer for bioartificial organs [J]. Trend Polym. Sci., 1997, 5(9): 286-293;
[3] Finch C A.Polymers for microcapsule wall [J]. Chemy Ind, 1985, 22: 752-756;
[4] Latyshev V N, Naumov A G, Chirkin S A. Mechanisms releasing coolant lubricants from microcapsules during friction between metallic surfaces [J]. Trenie Iznos, 1999, 20(4): 433-438;
[5] Thies C. Microcapsulation [J]. Encyclopedia of Polym Sci & Engng, 1987, 9: 724-725;
[6] 梅望平．微胶囊包覆技术在染整工业的应用．纺织中心期刊，1995，5(3)：188-200；
[7] 纳富泰子．用及用[P]．日本专利：特开平8-52939，1996-02-27；
[8] Zhony Yi,Chen Shuilin.Dying of polyester using microencapsulated disperse dyes in the absence of auxiliaries.Colorage Technology,2005,121:76～80;
[9] 冯继红，钟毅，罗艳等．不同分散染料微胶囊的制备和应用．染料与染色，2004，5：264～266；
[10] 陈水林，李卓．CN1443807A，2003；
[11] Finch C. A..Chem. Ind.,London,1985, 752～756;
[12] Finch C. A..Ullman Encylopedia of Science, Vol. 16:575;
[13] 张可达，徐冬梅，王平．微胶囊化方法[J]．功能高分子学报，2001，14(12)：474-480；
[14] Kruyt H. R..Colloid Science, Vol.2, Elsevier, New York, 1949, 216;
[15] Evreinova T. N., Karaukov W. N., Marmontova T. W., etc. J. Colloid Interface Sci. 1971, 36: 18;
[16] Green B. K..US Pat. 2 800 457,1957;
[17] Green B. K., Schleicher L. S..US Pat. 2 800 458,1957;
[18] N. Zydowicz, E. Nzimba-Ganyanad, Polymer Bulletin, 2002,47: 457-463;
[19] Hong K, Park S. Preparation of Polyurea Microcapsules with Different Composition Ratio: Strutures and Thermal Properties [J]. Mater Sci Engng, 1999, A272: 418-421;
[20] Hong K, Park S. Preparation ofPolyurea Microcapsules Containing Ovalbumin [J]. Mater Chem Phys, 2000, 64: 20-24;
[21] Hong K, Park S. Preparation of Polyurethane Microcapsules with Different Soft Segment and Their Characteristics [J]. Reactive & Func Polym, 1999, 42:193-200;
[22] Kimiko Kakino, Mebae Umetsu, Yuko Goto, etc. Two-layer Structures of Microcapsule Membrane as Predicted from Electrophoretic Studies [J]. J Colloid Interface, 1999, 218:275-281;
[23] Hong K, Park S. Melamine resin microcapsules containing fragrant oil. Synthesis and Characterization [J]. Mater Chemy Phys, 1999, 58: 128-131;
[24] Chol H J, Lee Y H, Kim C A. Mierocapsulated Polyaniline Partial for Electroeological Materials [J]. J. Mater Sci Lett, 2000, 19: 533,535;
[25] 宋心远，沈煜如．新型染整技术．北京：中国纺织出版社，1999：130～143；
[26] Mei W. P.. J. China Tex. Inst., 1995, 5(3):188;
[27] Lewis. et al. Microencapsulated System for Thermal Paper [P] USP 5741592, 998-04-21;
[28] Sakaoka H., Nakano T.,Japan Text. New, May, 1974, 41-43;
[29] Sakaoka H., US Pat. 3 948 597,1976;
[30] Marabella C. P.,E.Pat.0232001,1987;
[31] Sandoz Ltd., Goorhuis H ,US Pat. 3 782 895, 1974;
[32] Yasunari Sawanoi, Teruo Hori. Dyeing Properties of Capsules Containing Disperse Dyes into Polyester Fabrics [J] .Sen'i Gakkaishi, 2002, 58: 68-72;
[33] Sakaoka H. ,Nakano T..Sen'i Kako, 1973,25(10): 670;
[34] D Aitken, S M Burkinshaw, J Griffiths ,etc.Rev. Prog. Color., 1996, 26: 1;
[35] Y Kitagawa ,R Hoshikawa. Matsui Shikiso Chemical, GB 2 270 321A ,1994;
[36] L D Small ,G Highberger. Chromatic Technologies, US Pat. 5 997 849,1999;
[37] K H Park,M Casetta, V Koncar. Diffusion of disperse dyes into microfibers and conventional polyester fibers. Color Technology, 2002,118:319-324;
[38] 冯继红，钟毅，罗艳，陈水林等．分散染料微胶囊高温高压无助剂染色，印染，2004(21)：9～11；
[39] 宋心远，印染，1984(1)：50：
[40] 董振礼．聚酯超细纤维碱性浴染色性能研究，印染，1998(12)：8～11；
[41] 王晶．聚酯超细纤维染色匀染性的研究．天津纺织工学院硕士论文，1998；
[42] 罗艳．缓释性微胶囊的研制及在纺织上的应用．东华大学化学与化工学院博士论文，2002；
[43] 潘祖仁．高分子化学，北京，化学工业出版社，1994：76～77；
[44] 黑木宣彦著，陈水林译，染色理论化学．北京，纺织工业出版社，1981：212；
[45] 钱蕾，陈水林．中国纺织大学学报，1997，23(2)：27～33；
[46] 钱蕾，陈水林．中国纺织大学学报，1996，22(5)：1～7；
[47] Li Zhuo,Chen Shuilin,Zhou Shizhou.Factors affecting the particle size and size distribution polyurea microcapsules by interfacial polymerization of polyisocyanates. International Journal of Polymeric Materials,2004,53:21～31;
[48] Chen Shuilin, Zhong Yi and Feng Jihong .Microcapsules disperse dye dyeing polymer in the absence of auxiliaries .Coloration Technology, 2005,121:76-80;
[2] Hunkeler D. Polymer for bioartificial organs [J]. Trend Polym. Sci., 1997, 5(9): 286-293;
[3] Finch C A.Polymers for microcapsule wall [J]. Chemy Ind, 1985, 22: 752-756;
[4] Latyshev V N, Naumov A G, Chirkin S A. Mechanisms releasing coolant lubricants from microcapsules during friction between metallic surfaces [J]. Trenie Iznos, 1999, 20(4): 433-438;
[5] Thies C. Microcapsulation [J]. Encyclopedia of Polym Sci & Engng, 1987, 9: 724-725;
[6] 梅望平．微胶囊包覆技术在染整工业的应用．纺织中心期刊，1995，5(3)：188-200；
[7] 纳富泰子．用及用[P]．日本专利：特开平8-52939，1996-02-27；
[8] Zhony Yi,Chen Shuilin.Dying of polyester using microencapsulated disperse dyes in the absence of auxiliaries.Colorage Technology,2005,121:76～80;
[9] 冯继红，钟毅，罗艳等．不同分散染料微胶囊的制备和应用．染料与染色，2004，5：264～266；
[10] 陈水林，李卓．CN1443807A，2003；
[11] Finch C. A..Chem. Ind.,London,1985, 752～756;
[12] Finch C. A..Ullman Encylopedia of Science, Vol. 16:575;
[13] 张可达，徐冬梅，王平．微胶囊化方法[J]．功能高分子学报，2001，14(12)：474-480；
[14] Kruyt H. R..Colloid Science, Vol.2, Elsevier, New York, 1949, 216;
[15] Evreinova T. N., Karaukov W. N., Marmontova T. W., etc. J. Colloid Interface Sci. 1971, 36: 18;
[16] Green B. K..US Pat. 2 800 457,1957;
[17] Green B. K., Schleicher L. S..US Pat. 2 800 458,1957;
[18] N. Zydowicz, E. Nzimba-Ganyanad, Polymer Bulletin, 2002,47: 457-463;
[19] Hong K, Park S. Preparation of Polyurea Microcapsules with Different Composition Ratio: Strutures and Thermal Properties [J]. Mater Sci Engng, 1999, A272: 418-421;
[20] Hong K, Park S. Preparation ofPolyurea Microcapsules Containing Ovalbumin [J]. Mater Chem Phys, 2000, 64: 20-24;
[21] Hong K, Park S. Preparation of Polyurethane Microcapsules with Different Soft Segment and Their Characteristics [J]. Reactive & Func Polym, 1999, 42:193-200;
[22] Kimiko Kakino, Mebae Umetsu, Yuko Goto, etc. Two-layer Structures of Microcapsule Membrane as Predicted from Electrophoretic Studies [J]. J Colloid Interface, 1999, 218:275-281;
[23] Hong K, Park S. Melamine resin microcapsules containing fragrant oil. Synthesis and Characterization [J]. Mater Chemy Phys, 1999, 58: 128-131;
[24] Chol H J, Lee Y H, Kim C A. Mierocapsulated Polyaniline Partial for Electroeological Materials [J]. J. Mater Sci Lett, 2000, 19: 533,535;
[25] 宋心远，沈煜如．新型染整技术．北京：中国纺织出版社，1999：130～143；
[26] Mei W. P.. J. China Tex. Inst., 1995, 5(3):188;
[27] Lewis. et al. Microencapsulated System for Thermal Paper [P] USP 5741592, 998-04-21;
[28] Sakaoka H., Nakano T.,Japan Text. New, May, 1974, 41-43;
[29] Sakaoka H., US Pat. 3 948 597,1976;
[30] Marabella C. P.,E.Pat.0232001,1987;
[31] Sandoz Ltd., Goorhuis H ,US Pat. 3 782 895, 1974;
[32] Yasunari Sawanoi, Teruo Hori. Dyeing Properties of Capsules Containing Disperse Dyes into Polyester Fabrics [J] .Sen'i Gakkaishi, 2002, 58: 68-72;
[33] Sakaoka H. ,Nakano T..Sen'i Kako, 1973,25(10): 670;
[34] D Aitken, S M Burkinshaw, J Griffiths ,etc.Rev. Prog. Color., 1996, 26: 1;
[35] Y Kitagawa ,R Hoshikawa. Matsui Shikiso Chemical, GB 2 270 321A ,1994;
[36] L D Small ,G Highberger. Chromatic Technologies, US Pat. 5 997 849,1999;
[37] K H Park,M Casetta, V Koncar. Diffusion of disperse dyes into microfibers and conventional polyester fibers. Color Technology, 2002,118:319-324;
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