UV固化环氧丙烯酸酯胶粘剂的制备及改性研究
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摘要
紫外光(UV)固化技术是二十世纪60年代以来开发的一种新型环境友好、绿色环保技术,它具有高效、节能、少污染、固化产物性能优异等优点,在涂料、胶粘剂和油墨工业进行了广泛的、大量的应用。本文对光化学、光聚合、光敏树脂、光引发剂、活性单体、UV固化等的研究进展进行了综述。
环氧丙烯酸酯是辐射固化领域中一类重要的感光树脂,它具有极高的光活性,固化产物性能优异等特点。但其自身具有较高的粘度(正常情况下,室温可高达数百甚至上千帕·秒),实际应用中需要大量活性稀释剂来调节其粘度。本文通过改变配方,着重研究了一种低粘度树脂的合成工艺,讨论了催化剂、反应温度、阻聚剂、原料配比等因素对合成树脂的影响,确定了合成反应的最佳反应条件,并通过红外对合成预聚物进行了表征。
在紫外光固化胶部分,研究了光敏胶粘剂的固化机理、光敏剂与光引发剂的协同作用、光源与引发剂的匹配性等问题,深入分析了影响胶粘剂光固化的各种因素。实验合成了性能良好的环氧丙烯酸酯预聚物,选择并复配了与紫外光源匹配的光引发剂,得到了符合快速固化工艺要求的光敏体系。
鉴于自由基固化型紫外光敏体系存在固化体积收缩率较大的问题,一般在8%-12%左右。实验中,我们合成了螺环膨胀单体3,9-二羟甲基-3′,9′-二乙基-1,5,7,11-四氧杂螺环[5,5]十一烷,并对产物进行了红外、核磁表征,符合预期合成产物。
实验中,我们利用螺环膨胀单体固化时产生体积膨胀效应对固化体系进行了改性,固化体系以自由基-阳离子混杂固化方式进行,分析了膨胀单体的加入对体系的各种影响。实验结果表明,混杂固化方式表现出良好的协同效应,添加20%的3,9-二羟甲基-3′,9′-二乙基-1,5,7,11-四氧杂螺环[5,5]十一烷可以使固化体系体积收缩率从11.77%降至3.22%,且固化产物具有优异的综合性能。
The UV curing technology is a kind of new environmental friendly、green environmental protection technology, it is developed since the 1960s because of its advantages in high efficiency、energy saving、less environmental pollution and excellent properties of UV cured products. It is applied widely in coating、adhesives and printing inks. In this paper, research progresses of UV curing materials are reviewed, it includes photochemistry, photo polymerization, photo sensitive resin, photo initiator, reactive monomers and UV curing and so on.
Epoxy acrylate resin is an important photosensitive resin, it has excellent light activity, the UV cured products hold excellent properties. But the viscosity of epoxy acrylate resin is very high, we need the massive reactive diluents to adjust the viscosity. In this paper, we try to change formula, the synthesis of low viscosity resin is studied. Influences of the catalyst、reaction temperature、inhibitor、ratio of reacting material on the synthesis of resin are discussed, the synthetic prepolymers are characterized by IR.
In the field of UV curing adhesive, the mechanism of curing、the synergistic effect between sensitizer and initiator、the matching degree of illuminant-initiator and the factors affecting the UV curing of adhesive are studied in detail. The epoxy acrylate with excellent properties is synthesized, and the fit UV curing system is brought out by using the prepared prepolymer as well as the synergistic initiators which are sensitive to UV light.
In view of the high rate of volumetric shrinkage for the free radical UV cured, generally about 8%-12%. The expansion monomer: 3,9-dihydroxymethyl-3',9'-diethyl -1,5,7,11-tetraoxaspiro[5,5] undecane is synthesis. The synthetic prepolymers are characterized by IR、~1H-NMR spectroscopy.
In experiment, UV photosensitive system is modified by adding 3,9-dihydroxymethyl-3',9'-diethyl-1, 5,7,11-tetraoxaspiro[5,5] undecane which is expandable, the hybrid light-curable is the main curing method. Meanwhile, influence of adding expansion monomer is discussed. The results show that the hybrid light-curable holds superior synergistic effect and the rate of volumetric shrinkage of the system decreases by 11.77% to 3.22% with adding 20% spiro orthocabonate and the comprehensive properties of the cured products are still good.
环氧丙烯酸酯是辐射固化领域中一类重要的感光树脂,它具有极高的光活性,固化产物性能优异等特点。但其自身具有较高的粘度(正常情况下,室温可高达数百甚至上千帕·秒),实际应用中需要大量活性稀释剂来调节其粘度。本文通过改变配方,着重研究了一种低粘度树脂的合成工艺,讨论了催化剂、反应温度、阻聚剂、原料配比等因素对合成树脂的影响,确定了合成反应的最佳反应条件,并通过红外对合成预聚物进行了表征。
在紫外光固化胶部分,研究了光敏胶粘剂的固化机理、光敏剂与光引发剂的协同作用、光源与引发剂的匹配性等问题,深入分析了影响胶粘剂光固化的各种因素。实验合成了性能良好的环氧丙烯酸酯预聚物,选择并复配了与紫外光源匹配的光引发剂,得到了符合快速固化工艺要求的光敏体系。
鉴于自由基固化型紫外光敏体系存在固化体积收缩率较大的问题,一般在8%-12%左右。实验中,我们合成了螺环膨胀单体3,9-二羟甲基-3′,9′-二乙基-1,5,7,11-四氧杂螺环[5,5]十一烷,并对产物进行了红外、核磁表征,符合预期合成产物。
实验中,我们利用螺环膨胀单体固化时产生体积膨胀效应对固化体系进行了改性,固化体系以自由基-阳离子混杂固化方式进行,分析了膨胀单体的加入对体系的各种影响。实验结果表明,混杂固化方式表现出良好的协同效应,添加20%的3,9-二羟甲基-3′,9′-二乙基-1,5,7,11-四氧杂螺环[5,5]十一烷可以使固化体系体积收缩率从11.77%降至3.22%,且固化产物具有优异的综合性能。
The UV curing technology is a kind of new environmental friendly、green environmental protection technology, it is developed since the 1960s because of its advantages in high efficiency、energy saving、less environmental pollution and excellent properties of UV cured products. It is applied widely in coating、adhesives and printing inks. In this paper, research progresses of UV curing materials are reviewed, it includes photochemistry, photo polymerization, photo sensitive resin, photo initiator, reactive monomers and UV curing and so on.
Epoxy acrylate resin is an important photosensitive resin, it has excellent light activity, the UV cured products hold excellent properties. But the viscosity of epoxy acrylate resin is very high, we need the massive reactive diluents to adjust the viscosity. In this paper, we try to change formula, the synthesis of low viscosity resin is studied. Influences of the catalyst、reaction temperature、inhibitor、ratio of reacting material on the synthesis of resin are discussed, the synthetic prepolymers are characterized by IR.
In the field of UV curing adhesive, the mechanism of curing、the synergistic effect between sensitizer and initiator、the matching degree of illuminant-initiator and the factors affecting the UV curing of adhesive are studied in detail. The epoxy acrylate with excellent properties is synthesized, and the fit UV curing system is brought out by using the prepared prepolymer as well as the synergistic initiators which are sensitive to UV light.
In view of the high rate of volumetric shrinkage for the free radical UV cured, generally about 8%-12%. The expansion monomer: 3,9-dihydroxymethyl-3',9'-diethyl -1,5,7,11-tetraoxaspiro[5,5] undecane is synthesis. The synthetic prepolymers are characterized by IR、~1H-NMR spectroscopy.
In experiment, UV photosensitive system is modified by adding 3,9-dihydroxymethyl-3',9'-diethyl-1, 5,7,11-tetraoxaspiro[5,5] undecane which is expandable, the hybrid light-curable is the main curing method. Meanwhile, influence of adding expansion monomer is discussed. The results show that the hybrid light-curable holds superior synergistic effect and the rate of volumetric shrinkage of the system decreases by 11.77% to 3.22% with adding 20% spiro orthocabonate and the comprehensive properties of the cured products are still good.
引文
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[3]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.
[4]魏杰,金养智.光固化涂料[M].北京:化学工业出版社.2005,4
[5]Paul Mills.Robotic UV Curing Saves Time and Money[J].UV-curable coatings,2004,4:40-44
[6]杜官本.光辐射固化胶粘剂的机理[J].粘接.1994,15(2):18
[7]焦书科,黄次沛,蔡夫柳等.高分子化学[M].纺织工业出版社.1994,118-215
[8]Max Hunziker,Richard Leyden.Rapid Prototyping and Manufacturing.Fundamentals of Stereolithography,SME.Dearborn,MI,1992.25-56
[9]唐薰,陈洪,汤建新等.UV阳离子固化及研究进展[J].化学通报.2003.
[10]陆企亭.快速成型胶粘剂.科学出版社,1992:162-195
[11]William C.Perkins.New developments in photo-induced cationic polymerizations.Journal of Radiation Curing.1981(1):16-23
[12]唐薰,潘山存,陈洪等.UV辐射固化胶粘剂综述[J].化学与粘合.2003(6):296-298
[13]C.Decker et al.New photoinitiator for ultrafast light-induced polymerization[J].J.Polymer.Science,1989,27:347
[14]N.S.Allen et al.A comparative kinetic study of commercial photoinitiators for UV/visible curable acrylate clear coatings[J].Surface Coatings international,1999,2:67-76.
[15]V.Desobry et al.A novel photoinitiators for modern technology[J].Polymer.Mat.Science.Eng,1989,60:26
[16]J.V.Crivello et al.Photoinitiated cationic polymerization by dialkyl-4-hydrox-yphenylsulfonium salts[J].J.Polymer.Chemistry.Ed,1980,18(3):1021-1034
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[18]张秋禹,牛云青.Z941系列UV-固化胶粘剂的研制[J].粘接,1995,16(2):5-10
[19]张秋禹,李长国,沈卫新.Z97光敏胶粘剂的研制[J].中国胶粘剂,1998,7(4):4-6
[20]李桂芝,周重光.光固化聚氨酯甲基丙烯酸酯胶/环氧丙烯酸酯胶共混体系的结构与性能[J].化学与粘合.2001(3):97-99
[21]Tanaka,Akifumi,Yoshikawa.UV-curable pressure-sensitive adhesive compositions for peelable pressure-sensitive sheets[P].JP200111395.2001-01-16
[22]Haraguchi Kazutoshi.Active energy ray-curable polymer compositions for cured products with good transparency,high water angle,and low surface free energy[P].JP09-309905.1997
[23]H.Mazured Mieczyslaw et al.Radiation-curable acrylate/silicone permanently removable pressure-sensitive adhesives[P].WO 94-205831994
[24]Watanaba Takeo et al.Adhesives for bonding optical disk bases and manufacture of optical disks thereform[P].JP10102007.1998
[25]Iyoshi Shuzo.UV curable adhesive compositions[P].JP200111424.2001-01-16.
[26]Amano Hirofumi.Epoxy resin-based photocurable adhesive compositions[P]JP10-17843.1998
[27]Ishii Kazuhiko.Acrylic epoxy resin adhesive compositions for bonding light-nonpermeable substrates at low temperatures and bonding of the substrates using the adhesive[P].JP 1143660.1999
[28]Maruno Tohru.J.Adhesive.Sciencei.Technology.1995,9(10):1343-1355
[29]Ito,Daisuke.UV-curable epoxy adhesive compositions for manufacture of optical disks[P].JP2001131518.2001-03-15
[30]Fukui Koji.Photocurable and pressure-sensitive adhesive hooks and their conventional method of sticking to walls with high strength[P].JP1100255.1999
[31]KH.Schumacher UV-curable acrylate adhesives[J].Coating.1999,32(1):18-21
[32]杨治中,郑牧等.紫外光固化改性环氧-茨烯衍生物基活性大分子单体及其共聚合反应[J],粘接,1996,17(4):1-6,11
[33]Onusseit Herman.Photosensitive adhesive systems for one-or multistep adhesive binding of printed matter[P].WO9840225.1998
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