UV固化聚氨酯丙烯酸酯水性乳液的合成及应用
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摘要
为响应二十一世纪高效、节能、绿色和环保的时代主题,水性紫外光固化体系以其无毒性、无污染、无刺激性和生产安全等优点,在众多的固化体系中脱颖而出,是目前较为活跃的研究和开发领域。
本文以甲苯二异氰酸酯(MDI)、聚醚二元醇(PO3114)、二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA)和三乙胺(TEA)为原料,通过三步法合成了亲水性优异,能进行紫外光固化的阴离子型水性聚氨酯丙烯酸酯(WPUA),并将其乳化制得水性PUA乳液。
研究了水性聚氨酯丙烯酸酯树脂及其乳液的合成,确定了水性上光油和油墨的配方。讨论了光引发剂的种类和用量、中和剂种类、中和度、固含量以及反应物配比对光固化速度的影响,同时对光固化膜的性能进行了测定,并讨论了亲水基团含量、中和度、固含量和异氰酸指数(R值)对乳液性能的影响。
结果表明:随亲水基团含量和中和度的提高,分子链亲水性增强,乳液粒径下降,乳液的分散性、稳定性均得到提高;在光固化性能方面,光引化剂优选Darocur4265,最佳用量为2%,中和度为80%时光固化速度最快;用NaOH作为中和剂时光固化速度快于三乙胺(TEA),但乳化不完全。反应物的最佳配比为n(TDI):n(PO3114):n(HEA): n(DMPA)=6:2:4:3;合成树脂的固化膜具有良好的耐水、耐溶剂和耐酸性,但耐强碱性较差。
在上光油配方的合成中,随固含量的提高,粘度上升,固化膜的光泽度先增加,后略微下降,光固化时间先增加后减小,固含量在70%-80%之间最为合适;pH值太高,粘度降低,光泽度降低,pH值太低,碱性太弱,粘度太高,光泽度降低,pH值在8-9最为合适;在油墨配方的合成中,固含量越高,固化速度越快;颜料对光引发剂存在屏蔽作用;比热容较小的基材会加快光固化速度。
In response to the 21st century high efficiency,energy saving,green and environmental protection,water-borne UV curable system stands out in numerous curing system,with non- toxic,non-polluting,without excitant and production safety advantages,which is relatively active research and development fields.
This paper introduce that an excellent hydrophilic and ionic UV-curing water-borne polyurethane acrylates (WPUA) was synthesized through the three-step synthesis method, with toluene disocyanate(TDI),polyether glycol(PO3114),dimethylol propionic acid(DMPA), hydroxyethyl acrylate(HEA) and triethylamine(TEA),which was made the water-borne poly- urethane acrylate emulsion.
The water-borne polyurethane acrylates emulsion(WPUA),water-based polish oil and ink formulations were studied. Photoinitiators’type and dosage,neutralizer’s type,neutralization degree,solid content and the ratio of reactants were discussed on the speed of light curing, meanwhile the performance of light curing film was studied,and the content of hydrophilic groups,neutralization degree,solid content and the isocyanate index (R value) were discussed on the properties of emulsion.
The results showed that:the molecular chain hydrophilic enhanced,emulsion particle size declined,the dispersion and stability improved with hydrophilic groups content and neu- tralization degree rising;In light-cured properties,Darocur4265 is the best photoinitiator,and optimum dosage is 2%,the light-cured speed is the fastest when neutralization degree is 80%;The light-cured speed with NaOH as neutralizer is faster than triethylamine (TEA), But not emulsified completely.For the best ratio of reactants is that:n(TDI):n(PO3114):n(HEA): n(DMPA)=6:2:4:3.The cured film of synthetic resin has good water, solvent and acid resis- tance,but alkali resistant is bad.
In the determination of the polish oil formulation,when the solid content increased,the viscosity increased,the gloss of the cured film first increased,then decreased slightly,the light curing time increases firstly and then decreased,and solid content in the most appropriate is between 70 to 80 percent;The pH value is too high,viscosity reduced,gloss reduced,while pH value too low,alkaline weaken,viscosity higher,gloss reduced,The most appropriate pH value is 8-9.In the determination of ink formulations, the higher the solid content,the faster the cure; The pigment exist shield effect on light initiator;The base material that have smaller heat capacity will speed up the light-curing rate.
本文以甲苯二异氰酸酯(MDI)、聚醚二元醇(PO3114)、二羟甲基丙酸(DMPA)、丙烯酸羟乙酯(HEA)和三乙胺(TEA)为原料,通过三步法合成了亲水性优异,能进行紫外光固化的阴离子型水性聚氨酯丙烯酸酯(WPUA),并将其乳化制得水性PUA乳液。
研究了水性聚氨酯丙烯酸酯树脂及其乳液的合成,确定了水性上光油和油墨的配方。讨论了光引发剂的种类和用量、中和剂种类、中和度、固含量以及反应物配比对光固化速度的影响,同时对光固化膜的性能进行了测定,并讨论了亲水基团含量、中和度、固含量和异氰酸指数(R值)对乳液性能的影响。
结果表明:随亲水基团含量和中和度的提高,分子链亲水性增强,乳液粒径下降,乳液的分散性、稳定性均得到提高;在光固化性能方面,光引化剂优选Darocur4265,最佳用量为2%,中和度为80%时光固化速度最快;用NaOH作为中和剂时光固化速度快于三乙胺(TEA),但乳化不完全。反应物的最佳配比为n(TDI):n(PO3114):n(HEA): n(DMPA)=6:2:4:3;合成树脂的固化膜具有良好的耐水、耐溶剂和耐酸性,但耐强碱性较差。
在上光油配方的合成中,随固含量的提高,粘度上升,固化膜的光泽度先增加,后略微下降,光固化时间先增加后减小,固含量在70%-80%之间最为合适;pH值太高,粘度降低,光泽度降低,pH值太低,碱性太弱,粘度太高,光泽度降低,pH值在8-9最为合适;在油墨配方的合成中,固含量越高,固化速度越快;颜料对光引发剂存在屏蔽作用;比热容较小的基材会加快光固化速度。
In response to the 21st century high efficiency,energy saving,green and environmental protection,water-borne UV curable system stands out in numerous curing system,with non- toxic,non-polluting,without excitant and production safety advantages,which is relatively active research and development fields.
This paper introduce that an excellent hydrophilic and ionic UV-curing water-borne polyurethane acrylates (WPUA) was synthesized through the three-step synthesis method, with toluene disocyanate(TDI),polyether glycol(PO3114),dimethylol propionic acid(DMPA), hydroxyethyl acrylate(HEA) and triethylamine(TEA),which was made the water-borne poly- urethane acrylate emulsion.
The water-borne polyurethane acrylates emulsion(WPUA),water-based polish oil and ink formulations were studied. Photoinitiators’type and dosage,neutralizer’s type,neutralization degree,solid content and the ratio of reactants were discussed on the speed of light curing, meanwhile the performance of light curing film was studied,and the content of hydrophilic groups,neutralization degree,solid content and the isocyanate index (R value) were discussed on the properties of emulsion.
The results showed that:the molecular chain hydrophilic enhanced,emulsion particle size declined,the dispersion and stability improved with hydrophilic groups content and neu- tralization degree rising;In light-cured properties,Darocur4265 is the best photoinitiator,and optimum dosage is 2%,the light-cured speed is the fastest when neutralization degree is 80%;The light-cured speed with NaOH as neutralizer is faster than triethylamine (TEA), But not emulsified completely.For the best ratio of reactants is that:n(TDI):n(PO3114):n(HEA): n(DMPA)=6:2:4:3.The cured film of synthetic resin has good water, solvent and acid resis- tance,but alkali resistant is bad.
In the determination of the polish oil formulation,when the solid content increased,the viscosity increased,the gloss of the cured film first increased,then decreased slightly,the light curing time increases firstly and then decreased,and solid content in the most appropriate is between 70 to 80 percent;The pH value is too high,viscosity reduced,gloss reduced,while pH value too low,alkaline weaken,viscosity higher,gloss reduced,The most appropriate pH value is 8-9.In the determination of ink formulations, the higher the solid content,the faster the cure; The pigment exist shield effect on light initiator;The base material that have smaller heat capacity will speed up the light-curing rate.
引文
[1]金养智.水性光固化涂料[J].涂料工业,2006,36(6):54~58
[2] G.E.Fonseca,T.F.McKenna,A.Dub Marc.Miniemulsion vs.conventional emulsion polym- erization for pressure-sensitive adhesives production[J].Chemical Engineering Science, 2010,65(9):2797~2810
[3] G.Kim,S.Lim,B.H.Lee,etal.Effect of homogeneity ofmethanol/water/monomer mixture on the mode of polymerization of MMA:Soap-free emulsion polymerization versus disersion polymerization[J].Polymer,2010,51(5):1197~1205
[4]居学成,哈鸿飞.辐射固化技术应用现状及发展趋势[J].精细与专用化学品,1999, (6):10~14
[5]魏燕彦,罗英武,李宝芳等.乳液型紫外光固化聚氨酯丙烯酸酯的涂膜性能及其影响因素[J].涂料工业,2007,37(5):30~33
[6] Masson F,Decker C,Jaworek T,eta.UV-radiation curing of waterbased urethane acrylate coatings[J].Prog Org Coatings,2000,39(24):115~126
[7] Allen N.S.Photoinitiators for UV and visible curing of coatings:mechanisms and properties [J].J Photo chem.Photobiology,A:Chemistry,1996,(100):101~103
[8]李和平,葛虹.精细化工工艺学[M],北京:科学出版社,1997,307
[9] Visconti M,Cataneo M.A highly efficient photoinitiator for water-borne UV-curable systems[J].Prog Org Coatings,2000,(40):243~25l
[10] P.G.Garratt,ICE Klimeseh.Radiation curable waterborne coatings[J].Polymers Paint Colour Joumal,1994,184(4343):30~32
[11]金林生.紫外光固化涂料的原料发展趋向[J].现代涂料与涂装,1999,(1):38
[12] J.C.Padge.Polymers for water-based coatings-A thematic overview[J].Journal of Coating Technology,1994.66(39):89~102
[13] P.Stenson.Radiation curable water-bome urethanes for the wood industry[J].Modem Paint and Coatings,1990,80(6):44~48
[14]王德海,江棂.紫外光固化材料-理论与应用[M],北京:科学出版社,2001,107
[15]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
[16]陈用烈,曾兆华等.光固化水性涂料的研究进展[C].第三届辐射固化年会论文集,张家界,1997,17~19
[17]卿宁,张晓镭等.皮革工业用聚氨酯材料研究的回顾与展望.中国皮革,1999, (7):50
[18]陈红等.自乳化型聚氨酯乳液研究进展.粘接,1998,19(3):19
[19]支剑,聂俊,何勇.双固化聚氨酯丙烯酸酯的性能研究[J].涂料工业,2008,38(9):1~4
[20]冯利邦,苏致兴,郭金山.紫外水性光固化聚氨酯-丙烯酸酯涂料研究[J].兰州大学学(自然科学版),2004,40(3):48~52
[21] Wei YY,Luo YW,Li BF,etal.Water-soluble UV curable urethane methyl acrylate coating: Preparation and properties [J].Journal of Zhejiang University:Science,2004,5(8):906~911
[22]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30~32.
[23]张高文,褚衡,李纯清.水性紫外光固化涂料的研究进展[J].现代涂料与涂装, 2008, 11 (1):16~19
[24] M.E.Song,J.K.Kim,K.D.Suh.Preparation of UV-curable emulsions using PEG modified urethane acrylates and their coating properties[J].Joumal of Coatings Technology, 1996, 68(862):43~50
[25] S.Ramesh,G.Radhakrishnan.Polyurethane ionomersan overview[J].Journal of Polymer Materirals,1999,16(2):135~153
[26] Wang ZM,Gao DB,Yang JW,etal.Synthesis and Characterization of UV-Curable Water bome Polyurethane-Acrylate lonomers for Coatings[J].J Appl Polym Sci,1999,73: 2869~ 2876
[27] Daries WD,Hutchinson I.Development and application of waterbome radiation curable coatings[J].ACS Symp Ser,1997,663:81~94
[28] Ryu JH,Lee CY,Kim JW,etal.Water-Soluble Urethane Acrylate Ionomers and ultraviolet (UV) curing:prevention of moisture absorption[J].Pure Appl Chem,1999, 36(3):389~403
[29] Lee CHY,Kim JW,Suh KD.Synthesis of water-soluble urethane acrylate anionomers and their ultra-violet coating properties[J].J Mater Sci,1999,34(21):5343~5349
[30] Lee CHY,Kim JW,Sub KD.Water-soluble urethane acrylate ionomers:Effect of molecular structure on ultraviolet coating properties[J].J Appl Polym Sci,2000,78(1):1853~l860
[31] Ryu JH,Kim JW,Lee CHY,etal.Water-soluble urethane acrylate ionomers and their ultraviolet(UV) curing:Prevention of moisture absorption[J].J Macromol Sci Pure Appl Chem,1999,36(3):389~403
[32]周小群.水性光敏聚氨脂的合成[J],浙江化工,2001,32(2):16~18
[33]沈效峰,郁建华.交联型聚氨酯乳液的研究[J].聚氨酯工业,1998,13(2):9~11
[34]韩仕甸,金养智.紫外光固化水性聚酯型聚氨酯丙烯酸酯的合成及性能[J].北京化工大学学报,2001,28(4):19~22
[35]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30~32
[36]胡飞,唐黎明,李易等.紫外光固化水性聚氨酯涂料研究[J].化学世界,2002,(4):189~191
[37]白湘云,刘磊,金养智.紫外线固化水性聚氨酯丙烯酸树脂的研究[J].影像技术,2000, (3):33~36
[38]冯利邦,苏致兴,郭金山.紫外光固化水性聚氨酯-丙烯酸酯涂料研究[J].兰州大学学报(自然科学版),2004,40(3):48~52
[39] Kim BK,Paik SH.UV-curable polyethylene glycol-based polyurethane acrylatehydrogel [J].J Polym Sci,PartA:Polym Chem,1999,37(15):2703~2709
[40] Kim HD,Kim TW.Preparation and properties of UV-curable polyurethane acrylate ionomers[J].J Appl Polym Sci,1998,67(13):2153~2162
[41]陈云传,刘晓亚,胡红梅.UV固化涂料用水性聚氨酯及微凝胶的制备[J].涂料工业, 2004,34(5):8~11
[42]吕维忠.脂肪族水性聚氨酯胶膜的合成和性能研究[J].合成树脂及塑料,2003,20(2): 54~57
[43] Noh SH,Choi HS,Noh ST.Synthesis and Application of Water-based Urethane Acrylate Crosslinking Agent Containing Unsaturated Group[J].J Appl Polym Sci,2000,78: 1216~ 1223
[44] Asif Anila,Huang CY,Shi WF.Stucture-property study of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester for UV-curablecoatings [J].Colloid Polym Sci,2004,283:200~208
[45] Garratt PG,Klimesch KF.Radiation curable water-bome coatings[J].Polym Paint Colour Journal,1994,184(43):30~32
[46] Kim JW,Suh KD.Viscosity properties for aqueous solution of urethane acrylate cationomer[J].JMacromol Sci Chem,1998,A35(9):1587~1601
[47] Ryu JH,Kim JW,Suh KD.Synthsis of Water-soluble Urethane Acrylate Cationomers and Their Ultraviolet Coating Properties[J].JMacromol Sci-Pure Appl chem.1999,A36(4): 571~586
[48] Meixner J,Kremer W.Unsaturated prepolymers as binders for water-thinnable fumiture coating,15thinternational conference on organic coatings and technology,Athens,Greece, 1989,7:489~506
[49] Song ME,Kim JY,Suh KD.Preparation of UV-Curable Emulsions Using PEG-Modified Urethane Acrylaters:The Effect of Nonionic and Anionic Groups[J].J Appl Polym Sci,1996,62:1775~1782
[50] Park NH,Suh KD,Kim JY,etal.Preparation of UV-curable emulsions using PEG modified urethane acrylates:the effect of chain length of polyoxyethylene[J].J Appl Polym Sci, 1997,64:2657~2664
[51] Suh KD,Chon YS,Kim JY,etal.Preparation of UV-curable emulsions using PEG modified urethane acrylates:the effect of epoxy acrylate[J].Polym Bull,1997,38:287~294
[52] Suh KD,Kim JY.Synthesis of PEG-modified urethane acrylates and their soap-free emulsification[J].J Macromol Chem Phys,1996,197:2429~2438
[53]韩飞雁,杨小毛,杨建文等.紫外光固化水性涂料[J].胶体与聚合物,2001,19(2):23~26
[54]金其良,陈来,魏平等.水性丙烯酸树脂的合成和UV固化研究[J].核技术,2000,23(12): 873~878
[55] Stenson PH,Coogan RG.Rad Tech Rep,1993,2(1):18~23
[56] Hegedus CR,Kloiber KA.Aqueous Acrylic-Polyurethane Hybrid Dispersions and their use in Industrial Coatings[J].J Coat Technol,l996,68(860):39~48
[57]杨建文,曾兆华,王志明等.聚甲基丙烯酸酯改性聚氨酯光固化水性体系研究[J].应用化学,2001,18(8):631~635
[58] Yu Hao,Yuan QL,Wang DN,etal.Preparation of an Ultraviolet-CurableWater-BornePoly (urethane acrylate)/Silica Dispesion and Properties of its Hybrid Film[J].J Appl Polym Sci,2004,94:1347~1352
[59] Christian D,Frederic M,Reinhold S.Duble-Curing of WaterborneUrethane-Acrylate Coatings by UV and Thermal Processing[J].Macromol Mater Eng,2003,288(I):17~28
[60]陈乐培,王海杰,武志明.光敏树脂及其紫外光固化涂料发展新动向[J].热固性树脂, 2003, 18(5):33~36
[61]杨建文,曾兆华,王志明等.紫外光固化水性涂料的发展概况,信息记录材料[J].2001, 2(1):32~35
[62]杨建文等.光固化水性涂料,辐射固化通讯,1999,(2):21
[63]白新德,查萍,尹应武.紫外光固化涂料的研究现状[J].清华大学学报(自然科学版), 2001,41(10):30~32
[64]王德海,江棂.紫外光固化材料-理论与应用[M].北京:科学出版社,2001
[65]金振华,秦明南.纸印刷品UV上光油的应用[J].印刷工程,2003,2:40
[66]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):52
[67]陈希荣.试论UV上光油的技术及应用[J].中国包装-包装印刷,2007,2
[68]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):53
[69]邬克宁,UV上光-印刷材料加工的新工艺[J],印刷质量与标准化,1999,2(32)
[70]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):52
[71]金振华.环保型水性上光油的研制与应用[J].包装工程,2003,24(1):16~17
[72] Bruen,Davidson K,Sydes Daniel FE,etal.Benefits of UV-curable Coatings[J].European Coatings Journal,2004,(4):42~48
[73] Ackermann C,Putz HJ.Deinkability of waterborne flexo inks byflotation[J].Pulp and Paper Canada,1994,95(8):28
[74]赵晨飞,兀旦晖,吴民祥等.柔性版水性油墨的性能与印品质量的关系,包装工程[J]. 2007,7,(28):7
[2] G.E.Fonseca,T.F.McKenna,A.Dub Marc.Miniemulsion vs.conventional emulsion polym- erization for pressure-sensitive adhesives production[J].Chemical Engineering Science, 2010,65(9):2797~2810
[3] G.Kim,S.Lim,B.H.Lee,etal.Effect of homogeneity ofmethanol/water/monomer mixture on the mode of polymerization of MMA:Soap-free emulsion polymerization versus disersion polymerization[J].Polymer,2010,51(5):1197~1205
[4]居学成,哈鸿飞.辐射固化技术应用现状及发展趋势[J].精细与专用化学品,1999, (6):10~14
[5]魏燕彦,罗英武,李宝芳等.乳液型紫外光固化聚氨酯丙烯酸酯的涂膜性能及其影响因素[J].涂料工业,2007,37(5):30~33
[6] Masson F,Decker C,Jaworek T,eta.UV-radiation curing of waterbased urethane acrylate coatings[J].Prog Org Coatings,2000,39(24):115~126
[7] Allen N.S.Photoinitiators for UV and visible curing of coatings:mechanisms and properties [J].J Photo chem.Photobiology,A:Chemistry,1996,(100):101~103
[8]李和平,葛虹.精细化工工艺学[M],北京:科学出版社,1997,307
[9] Visconti M,Cataneo M.A highly efficient photoinitiator for water-borne UV-curable systems[J].Prog Org Coatings,2000,(40):243~25l
[10] P.G.Garratt,ICE Klimeseh.Radiation curable waterborne coatings[J].Polymers Paint Colour Joumal,1994,184(4343):30~32
[11]金林生.紫外光固化涂料的原料发展趋向[J].现代涂料与涂装,1999,(1):38
[12] J.C.Padge.Polymers for water-based coatings-A thematic overview[J].Journal of Coating Technology,1994.66(39):89~102
[13] P.Stenson.Radiation curable water-bome urethanes for the wood industry[J].Modem Paint and Coatings,1990,80(6):44~48
[14]王德海,江棂.紫外光固化材料-理论与应用[M],北京:科学出版社,2001,107
[15]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
[16]陈用烈,曾兆华等.光固化水性涂料的研究进展[C].第三届辐射固化年会论文集,张家界,1997,17~19
[17]卿宁,张晓镭等.皮革工业用聚氨酯材料研究的回顾与展望.中国皮革,1999, (7):50
[18]陈红等.自乳化型聚氨酯乳液研究进展.粘接,1998,19(3):19
[19]支剑,聂俊,何勇.双固化聚氨酯丙烯酸酯的性能研究[J].涂料工业,2008,38(9):1~4
[20]冯利邦,苏致兴,郭金山.紫外水性光固化聚氨酯-丙烯酸酯涂料研究[J].兰州大学学(自然科学版),2004,40(3):48~52
[21] Wei YY,Luo YW,Li BF,etal.Water-soluble UV curable urethane methyl acrylate coating: Preparation and properties [J].Journal of Zhejiang University:Science,2004,5(8):906~911
[22]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30~32.
[23]张高文,褚衡,李纯清.水性紫外光固化涂料的研究进展[J].现代涂料与涂装, 2008, 11 (1):16~19
[24] M.E.Song,J.K.Kim,K.D.Suh.Preparation of UV-curable emulsions using PEG modified urethane acrylates and their coating properties[J].Joumal of Coatings Technology, 1996, 68(862):43~50
[25] S.Ramesh,G.Radhakrishnan.Polyurethane ionomersan overview[J].Journal of Polymer Materirals,1999,16(2):135~153
[26] Wang ZM,Gao DB,Yang JW,etal.Synthesis and Characterization of UV-Curable Water bome Polyurethane-Acrylate lonomers for Coatings[J].J Appl Polym Sci,1999,73: 2869~ 2876
[27] Daries WD,Hutchinson I.Development and application of waterbome radiation curable coatings[J].ACS Symp Ser,1997,663:81~94
[28] Ryu JH,Lee CY,Kim JW,etal.Water-Soluble Urethane Acrylate Ionomers and ultraviolet (UV) curing:prevention of moisture absorption[J].Pure Appl Chem,1999, 36(3):389~403
[29] Lee CHY,Kim JW,Suh KD.Synthesis of water-soluble urethane acrylate anionomers and their ultra-violet coating properties[J].J Mater Sci,1999,34(21):5343~5349
[30] Lee CHY,Kim JW,Sub KD.Water-soluble urethane acrylate ionomers:Effect of molecular structure on ultraviolet coating properties[J].J Appl Polym Sci,2000,78(1):1853~l860
[31] Ryu JH,Kim JW,Lee CHY,etal.Water-soluble urethane acrylate ionomers and their ultraviolet(UV) curing:Prevention of moisture absorption[J].J Macromol Sci Pure Appl Chem,1999,36(3):389~403
[32]周小群.水性光敏聚氨脂的合成[J],浙江化工,2001,32(2):16~18
[33]沈效峰,郁建华.交联型聚氨酯乳液的研究[J].聚氨酯工业,1998,13(2):9~11
[34]韩仕甸,金养智.紫外光固化水性聚酯型聚氨酯丙烯酸酯的合成及性能[J].北京化工大学学报,2001,28(4):19~22
[35]韩仕甸,金养智,王菲.水性紫外光固化体系中光固化速度的影响因素[J].北京化工大学学报,2002,29(1):30~32
[36]胡飞,唐黎明,李易等.紫外光固化水性聚氨酯涂料研究[J].化学世界,2002,(4):189~191
[37]白湘云,刘磊,金养智.紫外线固化水性聚氨酯丙烯酸树脂的研究[J].影像技术,2000, (3):33~36
[38]冯利邦,苏致兴,郭金山.紫外光固化水性聚氨酯-丙烯酸酯涂料研究[J].兰州大学学报(自然科学版),2004,40(3):48~52
[39] Kim BK,Paik SH.UV-curable polyethylene glycol-based polyurethane acrylatehydrogel [J].J Polym Sci,PartA:Polym Chem,1999,37(15):2703~2709
[40] Kim HD,Kim TW.Preparation and properties of UV-curable polyurethane acrylate ionomers[J].J Appl Polym Sci,1998,67(13):2153~2162
[41]陈云传,刘晓亚,胡红梅.UV固化涂料用水性聚氨酯及微凝胶的制备[J].涂料工业, 2004,34(5):8~11
[42]吕维忠.脂肪族水性聚氨酯胶膜的合成和性能研究[J].合成树脂及塑料,2003,20(2): 54~57
[43] Noh SH,Choi HS,Noh ST.Synthesis and Application of Water-based Urethane Acrylate Crosslinking Agent Containing Unsaturated Group[J].J Appl Polym Sci,2000,78: 1216~ 1223
[44] Asif Anila,Huang CY,Shi WF.Stucture-property study of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester for UV-curablecoatings [J].Colloid Polym Sci,2004,283:200~208
[45] Garratt PG,Klimesch KF.Radiation curable water-bome coatings[J].Polym Paint Colour Journal,1994,184(43):30~32
[46] Kim JW,Suh KD.Viscosity properties for aqueous solution of urethane acrylate cationomer[J].JMacromol Sci Chem,1998,A35(9):1587~1601
[47] Ryu JH,Kim JW,Suh KD.Synthsis of Water-soluble Urethane Acrylate Cationomers and Their Ultraviolet Coating Properties[J].JMacromol Sci-Pure Appl chem.1999,A36(4): 571~586
[48] Meixner J,Kremer W.Unsaturated prepolymers as binders for water-thinnable fumiture coating,15thinternational conference on organic coatings and technology,Athens,Greece, 1989,7:489~506
[49] Song ME,Kim JY,Suh KD.Preparation of UV-Curable Emulsions Using PEG-Modified Urethane Acrylaters:The Effect of Nonionic and Anionic Groups[J].J Appl Polym Sci,1996,62:1775~1782
[50] Park NH,Suh KD,Kim JY,etal.Preparation of UV-curable emulsions using PEG modified urethane acrylates:the effect of chain length of polyoxyethylene[J].J Appl Polym Sci, 1997,64:2657~2664
[51] Suh KD,Chon YS,Kim JY,etal.Preparation of UV-curable emulsions using PEG modified urethane acrylates:the effect of epoxy acrylate[J].Polym Bull,1997,38:287~294
[52] Suh KD,Kim JY.Synthesis of PEG-modified urethane acrylates and their soap-free emulsification[J].J Macromol Chem Phys,1996,197:2429~2438
[53]韩飞雁,杨小毛,杨建文等.紫外光固化水性涂料[J].胶体与聚合物,2001,19(2):23~26
[54]金其良,陈来,魏平等.水性丙烯酸树脂的合成和UV固化研究[J].核技术,2000,23(12): 873~878
[55] Stenson PH,Coogan RG.Rad Tech Rep,1993,2(1):18~23
[56] Hegedus CR,Kloiber KA.Aqueous Acrylic-Polyurethane Hybrid Dispersions and their use in Industrial Coatings[J].J Coat Technol,l996,68(860):39~48
[57]杨建文,曾兆华,王志明等.聚甲基丙烯酸酯改性聚氨酯光固化水性体系研究[J].应用化学,2001,18(8):631~635
[58] Yu Hao,Yuan QL,Wang DN,etal.Preparation of an Ultraviolet-CurableWater-BornePoly (urethane acrylate)/Silica Dispesion and Properties of its Hybrid Film[J].J Appl Polym Sci,2004,94:1347~1352
[59] Christian D,Frederic M,Reinhold S.Duble-Curing of WaterborneUrethane-Acrylate Coatings by UV and Thermal Processing[J].Macromol Mater Eng,2003,288(I):17~28
[60]陈乐培,王海杰,武志明.光敏树脂及其紫外光固化涂料发展新动向[J].热固性树脂, 2003, 18(5):33~36
[61]杨建文,曾兆华,王志明等.紫外光固化水性涂料的发展概况,信息记录材料[J].2001, 2(1):32~35
[62]杨建文等.光固化水性涂料,辐射固化通讯,1999,(2):21
[63]白新德,查萍,尹应武.紫外光固化涂料的研究现状[J].清华大学学报(自然科学版), 2001,41(10):30~32
[64]王德海,江棂.紫外光固化材料-理论与应用[M].北京:科学出版社,2001
[65]金振华,秦明南.纸印刷品UV上光油的应用[J].印刷工程,2003,2:40
[66]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):52
[67]陈希荣.试论UV上光油的技术及应用[J].中国包装-包装印刷,2007,2
[68]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):53
[69]邬克宁,UV上光-印刷材料加工的新工艺[J],印刷质量与标准化,1999,2(32)
[70]修澄.UV上光-材料及工艺指标[J].包装工业,2003,11(113):52
[71]金振华.环保型水性上光油的研制与应用[J].包装工程,2003,24(1):16~17
[72] Bruen,Davidson K,Sydes Daniel FE,etal.Benefits of UV-curable Coatings[J].European Coatings Journal,2004,(4):42~48
[73] Ackermann C,Putz HJ.Deinkability of waterborne flexo inks byflotation[J].Pulp and Paper Canada,1994,95(8):28
[74]赵晨飞,兀旦晖,吴民祥等.柔性版水性油墨的性能与印品质量的关系,包装工程[J]. 2007,7,(28):7