柔性UV固化材料的合成与应用研究
|
摘要
本论文在综述、分析了UV固化材料的研究状况和发展趋势的基础上，提出并研究了适用于皮革和纸印品等柔软基材的柔性UV固化材料。实验中合成了适合应用于柔软基材的三大类柔性UV固化预聚物：聚醚型聚氨酯、聚醚改性环氧丙烯酸酯、聚丙烯酸酯聚氨酯。用傅立叶红外光谱(FTIR)进行表征，证实了这三种预聚物的结构。对影响合成反应的诸多因素如加料方式、原料配比、反应温度、催化剂、阻聚剂等方面进行了研究，分别得到了适宜的合成条件，经过大量重复性实验，验证了这些合成条件的可靠性。对作为预聚物高分子主链柔性部分的聚醚进行的研究表明，采用分子量为1000的聚醚合成的预聚物，UV固化速度达到35m／min、固化后涂膜光泽度139.3％、涂膜断裂伸长率23.88％、拉伸强度4.475Mpa，综合性能优良。在合成聚丙烯酸酯聚氨酯的实验中选择丙烯酸丁酯为柔性单体，对聚内烯酸酯中间产物的研究表明，其粘度在800-1000 mPa·s时，合成的最终产物各方面性能良好。
应用实验中，本文对影响预聚物UV固化性能的稀释剂和光引发剂等助剂进行了筛选和研究，得到了适合的助剂种类及用量范围。根据研究的结果，进行大量的配方实验，研制了适合于皮革使用的UV上光油，经性能测试显示：光泽度＞110％、耐折性≥3万次、耐溶剂性＞200次、附着力合格，达到皮革上光油的使用要求。在研制纸印品UV上光油和油墨的应用实验中，讨论了颜料与引发剂的配伍性、颜料的用量对光固化速度的影响，并对PEA和BPUA两种树脂的共混比例进行了研究，结果显示PEA／BPUA=3／1-4／1时，固化后性能测试显示：附着力合格、光泽度≥100％，柔韧性1mm，综合性能良好。在此基础上研制的纸印品上光油综合性能良好，光泽度＞100％、附着力合格、耐溶剂性＞200次。研制的红、黄、蓝三种颜色的UV油墨，经性能测试表明：光泽度＞80％、附着力合格、耐溶剂性＞200次、油墨性能良好，柔韧性1mm，长时间老化实验后涂层没有出现发脆的现象，改善了现存油墨的脆性问题，油墨性能良好。
The research conditions and development trend of UV materials were reviewed and analyzed in this paper. The tender UV materials was brought forward and studied in UV leather based varnish and VU printing ink. Three kinds of tender UV-curing prepolymers were prepared. They are UV-curing polyurethane acrylate (PUA), soft UV-curing Epoxy acrylic resin (PEA) and UV-curing multiacrylate polyurethane acrylate (BPUA). The structures of these prepolymers were characterized by Fourier transform infrared (FTIR) spectra. Some influencing factors such as operation fashion, reaction temperature and catalyst on synthetic reactions were studied. Through some repeated experiment, the optimum conditions of synthetic reactions were got. As the tender part of polymer molecule, the poly (propylene glycol) (PPG) was studied. The result suggested that prepolymer which was prepared with the PPG (molecular weight is 1000) has good capability. It's UV-curing velocity is 35m/min, glossiness is 139.3%, tensibility is 23.88% and tensile strength is 4.475Mpa. Butyl acrylate was selected as the tender monomer in prepared BPUA, and when the viscosity of middle multipolymer is 800-1000mPa.s ,the last prepolymer had good capability.
In the applied research, some influencing factors such as diluent, photoinitiator and photoinitiators that match to different pigments on the coating film were studied. Leather based varnish was prepared with self-prepared prepolymer. The capability testing suggested that glossiness is >110%,resistance to cracking is > 30000 times, resistance to acetone is >200 times and adhesion is well. In the study of UV printing ink suggested that when the PEA/BPUA(wt) is 3/1-4/1, the coating film had good capability: adhesion is well, glossiness is >110% and tenderness is 1mm. Self-prepared paper varnish with excellent comprehensive properties, adhesion is well, glossiness is >110% and resistance to acetone is >200 times. Self-prepared UV printing ink adhesion is well, glossiness is >80%, tenderness is 1mm and resistance to acetone is >200 times, and through aging testing, the coating film didn't become brittle.
应用实验中，本文对影响预聚物UV固化性能的稀释剂和光引发剂等助剂进行了筛选和研究，得到了适合的助剂种类及用量范围。根据研究的结果，进行大量的配方实验，研制了适合于皮革使用的UV上光油，经性能测试显示：光泽度＞110％、耐折性≥3万次、耐溶剂性＞200次、附着力合格，达到皮革上光油的使用要求。在研制纸印品UV上光油和油墨的应用实验中，讨论了颜料与引发剂的配伍性、颜料的用量对光固化速度的影响，并对PEA和BPUA两种树脂的共混比例进行了研究，结果显示PEA／BPUA=3／1-4／1时，固化后性能测试显示：附着力合格、光泽度≥100％，柔韧性1mm，综合性能良好。在此基础上研制的纸印品上光油综合性能良好，光泽度＞100％、附着力合格、耐溶剂性＞200次。研制的红、黄、蓝三种颜色的UV油墨，经性能测试表明：光泽度＞80％、附着力合格、耐溶剂性＞200次、油墨性能良好，柔韧性1mm，长时间老化实验后涂层没有出现发脆的现象，改善了现存油墨的脆性问题，油墨性能良好。
The research conditions and development trend of UV materials were reviewed and analyzed in this paper. The tender UV materials was brought forward and studied in UV leather based varnish and VU printing ink. Three kinds of tender UV-curing prepolymers were prepared. They are UV-curing polyurethane acrylate (PUA), soft UV-curing Epoxy acrylic resin (PEA) and UV-curing multiacrylate polyurethane acrylate (BPUA). The structures of these prepolymers were characterized by Fourier transform infrared (FTIR) spectra. Some influencing factors such as operation fashion, reaction temperature and catalyst on synthetic reactions were studied. Through some repeated experiment, the optimum conditions of synthetic reactions were got. As the tender part of polymer molecule, the poly (propylene glycol) (PPG) was studied. The result suggested that prepolymer which was prepared with the PPG (molecular weight is 1000) has good capability. It's UV-curing velocity is 35m/min, glossiness is 139.3%, tensibility is 23.88% and tensile strength is 4.475Mpa. Butyl acrylate was selected as the tender monomer in prepared BPUA, and when the viscosity of middle multipolymer is 800-1000mPa.s ,the last prepolymer had good capability.
In the applied research, some influencing factors such as diluent, photoinitiator and photoinitiators that match to different pigments on the coating film were studied. Leather based varnish was prepared with self-prepared prepolymer. The capability testing suggested that glossiness is >110%,resistance to cracking is > 30000 times, resistance to acetone is >200 times and adhesion is well. In the study of UV printing ink suggested that when the PEA/BPUA(wt) is 3/1-4/1, the coating film had good capability: adhesion is well, glossiness is >110% and tenderness is 1mm. Self-prepared paper varnish with excellent comprehensive properties, adhesion is well, glossiness is >110% and resistance to acetone is >200 times. Self-prepared UV printing ink adhesion is well, glossiness is >80%, tenderness is 1mm and resistance to acetone is >200 times, and through aging testing, the coating film didn't become brittle.
引文
[1] 金养智，洪啸吟．紫外光固化涂料的进展[J]．涂料工业，1999，29(12)：30-33
[2] 胡和丰．紫外光固化涂料的进展[J]．涂料工业，1991，36-37
[3] M.J.Dvorchak, B.H. Riberi. Water-reducible unsaturated polyesters as binders and clear coatings for UV curable furniture coatings[J]. Journal of Coatings Technology, 1992, 64(808): 43-56
[4] C.Decker. UV-curing chemistry: past, present, and future[J]. Journal of Coatings Technology, 1987, 59(751): 97
[5] 施文芳，黄宏．辐射固化涂层技术的最新发展[J]．化学通报，1997，60(4)：1-5
[6] 徐国财，刑宏龙，江棂．紫外光固化涂料进展[J]．涂料工业，1998，28(5)：36-38
[7] Chang-Sik Haetal. Properties of UV-Curable Polymerthane Acrylate Using Nonyellowing Polyisocyanate for Floor Coating [J]. Appl. Polym. Sci 1996. 62(7) p1001-1021.
[8] Bluestein, Photopolymerization of Surface Coatings, [J]. Polym Sci, 1982, 27.p 2361-2368.
[9] J.C.Padge. Polymers for water-based coatings-A thematic overview [J]. Journal of Coatings Technology, 1994,66(39):89-102
[10] P.Stenson. Radiation-curable water-borne urethanes for the wood industry[J]. Modern Paint and Coatings, 1990, 80(6): 44-48
[11] 唐承恒，董建华．辐射固化涂料[J]．涂料工业，1998，28(11)：34-35
[12] 洪啸吟，冯汉保．涂料化学[M]．北京：科学出版社，1997
[13] M.R.Sandet.Benzophenone Triethylamine-PhotoinitiatePolymerization of Methylacrylate[J].Polym. Sci.Polym. Chem., 1972,(10)31: 31-37
[14] Fouassier, J.P.Rabek,J. F. Radiation Curing in Polymer Science and Technology[M].Vol.3 Elserier Applied Science, London and New York, 1993
[15] Huilei Zhang, John L.Massingill. Low VOC, Low Viscosity UV Cationic Radiation-Cured Ink-Jet Ink System[J]. Journal of Coatings Technology, 2000, 72(6): 45～52
[16] M. E. Song,J.K.Kim, K.D.Suh. Preparation of UV-curable emulsions using
PEG-modified urethane acrylates and their coating properties[J]. Journal of Coatings Technology, 1996, 68(862): 43-50
[17] J.K.Kim, K.D.Suh. Synthesis of PEG-modified urethane acrylate and their soap-free emulsification[J]. Macromolecular Chem. Phys, 1996, 197(12): 2429-2438
[18] N.H.Park, K.D.Suh, J.Y.Kim et al. Preparation of UV-curable emulsions using PEG-modified urethane acrylates: the effect of china length of polyoxyethylene[J], Journal of Applied Polymer Science, 1997, 64(12): 2657-2664
[19] 沈百拴，杨进元，李新法，王可义．改性不饱和聚酯光固化涂料的研制[J]．涂料工业，1993，4：13-15
[20] 武利民．涂料技术基础[M]．化学工业出版社．1999
[21] 朱传启，段质美，王泳厚译．涂料助剂大全[M]．上海科学技术文献出版社．2000
[22] 朱惟德．紫外线固化涂料用光敏引发剂的进展[J]．涂料工业，1989，(3)：39-42
[23] C Decker. UV-radiation Curing of Vinyl Ether-based Coatings[J]. Surface Coatings International, 2000(4): 173～178
[24] 霍尔曼，奥尔德林著．徐茂均译．印刷油墨、涂料、色漆紫外光和电子束固化配方[M]．北京：原子能出版社．1994
[25] 郑耀臣，魏无际．光固化涂料用光引发剂的进展[J]．涂料工业，2002，(1)：31-34
[26] 林毅清，王金娣，祁国珍．水性光引发剂的进展[J]．现代化工，1998，18(8)：16-18
[27] 林毅清，王金娣，祁国珍．新型水性硫杂蒽酮类光引发剂的合成及性质[J]．应用化学，1999，16(5)：25-29
[28] 吕九琢，徐亚贤，袁光等．紫外线固化涂料用光敏引发剂的研究进展[J]．石油化工高等学校学报，2001，14(2)：47-48
[29] 吕九琢，徐亚贤，袁光等．紫外线固化涂料用光敏引发剂的研究进展[J]．石油化工高等学校学报，2001，14(2)：47-48
[30] J.P.Fouassier, J. F. Rabek. Radiation curing in polymer science and technology[M]. London and New York: Elsevier applied science, 1993
[31] 戴洪义，石守衡，王美君．辐射固化市场的主要障碍及开发热点[J]．化学推进剂与高分子材料，1998(3)：38-40
[32] Lausonk. Status of The North American UV/EB Market[J]. Industrial Paint & Powder, 1996(11): 22
[33] 戴洪义，王少君，高学明，王美君．用于辐射固化的特种丙烯酸酯单体及其发展动向[J]，山东化工 2002(29)：5-7
[34] 杨爱军．我国辐射固化用活性稀释剂和齐聚物现状[J]．精细与专用化学品，1999，7(9)：13-14
[35] 王泳厚．聚氨酯涂料用助剂[M]．涂料工业，1994，(5)：49-51
[36] 陆玮洁，孙镛．浅谈UV光敏涂料的发展状况[J]．山东化工，1996，2：36-38
[37] 丁年生．涂料用消泡剂[J]．涂料工业，1992，(3)：51-55
[38] 朱妹，黄之祥．水性涂料助剂的功能与应用[J]．涂料工业，1999，39(8)：34-35
[39] 朱骥良，吴申年．颜料工艺学[M]．北京：化学工业出版社，1989
[40] C. Decker, K. Moussa. Recent advanced in UV curing chemistry[J]. Journal of Coatings Technology, 1993, 65(819): 49
[41] J.C.Padge. Polymers for water-based coatings-A thematic overview [J].Journal of Coatings Technology, 1994, 66(39): 89-102
[42] 杨永源．UV固化材料进展[J]．精细与专用化学品，2001，9(7)：9-13
[43] 朱晔．皮革涂饰技术的进展[J]．中国皮革，2002，31(7)：1-3
[44] A.D.P.Harbourne. The Invisible Technology That's Almost Every Where. Symposium on Radiation Curing Technology and Market Development in China for the 21st Century, 2000, 10: 16
[45] 谭俊峤．国内外柔性版印刷现状与发展[J]．印刷杂志，2002增刊，9-15
[46] 熊贵志，于伟龙，储伟．一种碘／氯摩尔比等于1的韦氏试剂的制备方法和用与碘值的测定[J]．分析化学研究简报，1999，27(8)：949-951
[47] 张传芳，王小燕．脂肪酸碘值的快速测定[J]．齐鲁石油化工，1995，24(2)：148-149
[48] 山西省化工研究所编．聚氨酯弹性体手册[M]．北京：化学工业出版社，2001
[49] 李绍雄，朱吕明．聚氨酯树脂[M]．江苏：科学技术出版社，1992
[50] 涂料工艺编委会编．涂料工艺[M]．北京：化学工业出版社，1997
[51] D. H. Solomon: The Chemiary of Formers[M]. Published by R. Krilger Publishing Co. 1977
[52] 大森英三．丙烯酸树脂及其聚物[M]化学工业出版社．1985．3
[53] 栾寿亭．皮化产品的回顾与展望[J]．．皮革化工，1997，Vol3 Nol．1-3
[54] 林尚安，陆耘，梁兆熙．高分子化学[M]．北京：科学出版社，1984
[55] 武汉大学主编．分析化学[M]．北京：高等教育出版社，1992
[56] 邢宏龙．紫外光固化油墨的进展[J]．精细与专用化学品．2000(7)：8
[2] 胡和丰．紫外光固化涂料的进展[J]．涂料工业，1991，36-37
[3] M.J.Dvorchak, B.H. Riberi. Water-reducible unsaturated polyesters as binders and clear coatings for UV curable furniture coatings[J]. Journal of Coatings Technology, 1992, 64(808): 43-56
[4] C.Decker. UV-curing chemistry: past, present, and future[J]. Journal of Coatings Technology, 1987, 59(751): 97
[5] 施文芳，黄宏．辐射固化涂层技术的最新发展[J]．化学通报，1997，60(4)：1-5
[6] 徐国财，刑宏龙，江棂．紫外光固化涂料进展[J]．涂料工业，1998，28(5)：36-38
[7] Chang-Sik Haetal. Properties of UV-Curable Polymerthane Acrylate Using Nonyellowing Polyisocyanate for Floor Coating [J]. Appl. Polym. Sci 1996. 62(7) p1001-1021.
[8] Bluestein, Photopolymerization of Surface Coatings, [J]. Polym Sci, 1982, 27.p 2361-2368.
[9] J.C.Padge. Polymers for water-based coatings-A thematic overview [J]. Journal of Coatings Technology, 1994,66(39):89-102
[10] P.Stenson. Radiation-curable water-borne urethanes for the wood industry[J]. Modern Paint and Coatings, 1990, 80(6): 44-48
[11] 唐承恒，董建华．辐射固化涂料[J]．涂料工业，1998，28(11)：34-35
[12] 洪啸吟，冯汉保．涂料化学[M]．北京：科学出版社，1997
[13] M.R.Sandet.Benzophenone Triethylamine-PhotoinitiatePolymerization of Methylacrylate[J].Polym. Sci.Polym. Chem., 1972,(10)31: 31-37
[14] Fouassier, J.P.Rabek,J. F. Radiation Curing in Polymer Science and Technology[M].Vol.3 Elserier Applied Science, London and New York, 1993
[15] Huilei Zhang, John L.Massingill. Low VOC, Low Viscosity UV Cationic Radiation-Cured Ink-Jet Ink System[J]. Journal of Coatings Technology, 2000, 72(6): 45～52
[16] M. E. Song,J.K.Kim, K.D.Suh. Preparation of UV-curable emulsions using
PEG-modified urethane acrylates and their coating properties[J]. Journal of Coatings Technology, 1996, 68(862): 43-50
[17] J.K.Kim, K.D.Suh. Synthesis of PEG-modified urethane acrylate and their soap-free emulsification[J]. Macromolecular Chem. Phys, 1996, 197(12): 2429-2438
[18] N.H.Park, K.D.Suh, J.Y.Kim et al. Preparation of UV-curable emulsions using PEG-modified urethane acrylates: the effect of china length of polyoxyethylene[J], Journal of Applied Polymer Science, 1997, 64(12): 2657-2664
[19] 沈百拴，杨进元，李新法，王可义．改性不饱和聚酯光固化涂料的研制[J]．涂料工业，1993，4：13-15
[20] 武利民．涂料技术基础[M]．化学工业出版社．1999
[21] 朱传启，段质美，王泳厚译．涂料助剂大全[M]．上海科学技术文献出版社．2000
[22] 朱惟德．紫外线固化涂料用光敏引发剂的进展[J]．涂料工业，1989，(3)：39-42
[23] C Decker. UV-radiation Curing of Vinyl Ether-based Coatings[J]. Surface Coatings International, 2000(4): 173～178
[24] 霍尔曼，奥尔德林著．徐茂均译．印刷油墨、涂料、色漆紫外光和电子束固化配方[M]．北京：原子能出版社．1994
[25] 郑耀臣，魏无际．光固化涂料用光引发剂的进展[J]．涂料工业，2002，(1)：31-34
[26] 林毅清，王金娣，祁国珍．水性光引发剂的进展[J]．现代化工，1998，18(8)：16-18
[27] 林毅清，王金娣，祁国珍．新型水性硫杂蒽酮类光引发剂的合成及性质[J]．应用化学，1999，16(5)：25-29
[28] 吕九琢，徐亚贤，袁光等．紫外线固化涂料用光敏引发剂的研究进展[J]．石油化工高等学校学报，2001，14(2)：47-48
[29] 吕九琢，徐亚贤，袁光等．紫外线固化涂料用光敏引发剂的研究进展[J]．石油化工高等学校学报，2001，14(2)：47-48
[30] J.P.Fouassier, J. F. Rabek. Radiation curing in polymer science and technology[M]. London and New York: Elsevier applied science, 1993
[31] 戴洪义，石守衡，王美君．辐射固化市场的主要障碍及开发热点[J]．化学推进剂与高分子材料，1998(3)：38-40
[32] Lausonk. Status of The North American UV/EB Market[J]. Industrial Paint & Powder, 1996(11): 22
[33] 戴洪义，王少君，高学明，王美君．用于辐射固化的特种丙烯酸酯单体及其发展动向[J]，山东化工 2002(29)：5-7
[34] 杨爱军．我国辐射固化用活性稀释剂和齐聚物现状[J]．精细与专用化学品，1999，7(9)：13-14
[35] 王泳厚．聚氨酯涂料用助剂[M]．涂料工业，1994，(5)：49-51
[36] 陆玮洁，孙镛．浅谈UV光敏涂料的发展状况[J]．山东化工，1996，2：36-38
[37] 丁年生．涂料用消泡剂[J]．涂料工业，1992，(3)：51-55
[38] 朱妹，黄之祥．水性涂料助剂的功能与应用[J]．涂料工业，1999，39(8)：34-35
[39] 朱骥良，吴申年．颜料工艺学[M]．北京：化学工业出版社，1989
[40] C. Decker, K. Moussa. Recent advanced in UV curing chemistry[J]. Journal of Coatings Technology, 1993, 65(819): 49
[41] J.C.Padge. Polymers for water-based coatings-A thematic overview [J].Journal of Coatings Technology, 1994, 66(39): 89-102
[42] 杨永源．UV固化材料进展[J]．精细与专用化学品，2001，9(7)：9-13
[43] 朱晔．皮革涂饰技术的进展[J]．中国皮革，2002，31(7)：1-3
[44] A.D.P.Harbourne. The Invisible Technology That's Almost Every Where. Symposium on Radiation Curing Technology and Market Development in China for the 21st Century, 2000, 10: 16
[45] 谭俊峤．国内外柔性版印刷现状与发展[J]．印刷杂志，2002增刊，9-15
[46] 熊贵志，于伟龙，储伟．一种碘／氯摩尔比等于1的韦氏试剂的制备方法和用与碘值的测定[J]．分析化学研究简报，1999，27(8)：949-951
[47] 张传芳，王小燕．脂肪酸碘值的快速测定[J]．齐鲁石油化工，1995，24(2)：148-149
[48] 山西省化工研究所编．聚氨酯弹性体手册[M]．北京：化学工业出版社，2001
[49] 李绍雄，朱吕明．聚氨酯树脂[M]．江苏：科学技术出版社，1992
[50] 涂料工艺编委会编．涂料工艺[M]．北京：化学工业出版社，1997
[51] D. H. Solomon: The Chemiary of Formers[M]. Published by R. Krilger Publishing Co. 1977
[52] 大森英三．丙烯酸树脂及其聚物[M]化学工业出版社．1985．3
[53] 栾寿亭．皮化产品的回顾与展望[J]．．皮革化工，1997，Vol3 Nol．1-3
[54] 林尚安，陆耘，梁兆熙．高分子化学[M]．北京：科学出版社，1984
[55] 武汉大学主编．分析化学[M]．北京：高等教育出版社，1992
[56] 邢宏龙．紫外光固化油墨的进展[J]．精细与专用化学品．2000(7)：8