核壳结构纳米喷墨CTP墨水开发研究
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摘要
本文用微乳液界面反应制备了含油溶性颜料、酚醛树脂的纳米核壳微球彩色微乳液，用TEM和激光散射粒度仪测定了微球形态粒径，为80～200nm球形。通过IR和DSC测定了壁材的结构，表明微球外壳为聚脲壳，芯为酚醛树脂。经SEM观察到微球喷涂到电解氧化的铝版基上成膜前后的形念，成膜前为球形；成膜后为团聚片状。成功解决了计算机直接喷墨制版技术的关键—成像液体配制，开发了一种在水基油墨中专用的能热分解的乳化剂，该乳化剂具有良好的乳化性能可以保证墨水的稳定性，在完成喷墨制版后能通过热处理方式失去再乳化作用。使印膜获得亲油拒水性，满足平版印刷的要求。这种系列的乳化剂结构为十二、十八烷基酸没食子脂酸钠，其中十二烷基酸没食子脂酸钠与十二烷基硫酸钠(K12)相比对苯乙烯、26~#白油的乳化能力远远高于K12，乳化苯乙烯能力是K12的2.17倍、乳化26~#白油能力是K12的2.89倍。用表面张力法测定了十二烷基酸没食子脂酸钠的CMC为0.267×10~(-3)mol／L，γ_(CMC)为48.0mN／m。最低表面张力在浓度0.810×10~(-3)mol／L时为29.0mN／m。用TG／DTG研究了乳化剂的热分解性能。在氮气流中。150.02℃开始分解。260℃分解速率最大。在200℃烘箱中10分钟涂膜即可热分解失去亲水基团而不再具有乳化作用，与水接触角达到最大。
以这种乳化剂制成的纳米核壳微球彩色微乳液经计算机直接喷墨成像在电解氧化形成砂目的铝版上制成喷墨CTP版，墨点清晰、无散点。并在胶印机上进行了印刷，耐印率达到了两万印。分辨率取决于喷墨打印机。
Core-shell colored nanoparticle latex which the core contains oil-soluble pigments and bakelite was prepared by interface microemulsion polymerization technology . Moreover, This paper investigated the effect of short chain alcohol used as co-emulsifier .The configuration was observed with TEM. Particle size and distribution was detected with laser scattering particle size distribution analyzer. This revealed particle size and distribution is 80～200nm. It was also proved the composition of shell material by IR and DSC. About thermal property of core-crust microsphere was studied with DSC. This proved that the microsphere was made up of Polyurea shell and bakelite core. The microsphere state was observed before and after it melted to form film on electrolyte-oxidation aluminium substrate. In the ink jet computer to printing plate system, the key work was image-form liquid .To prepare a water based ink , A special emulsifier was indespensible. Emulsificatio (n-dodecyl and n-octadecanoic acid carboxylate gallate) could be lost n by heat treatment after ink-jet plate making. Its capacity of emulsification to styrene and white oil (No,26~#) was superior than Sodium dodecyl sulfate. Critical micelle concentration was 0. 267 ×10~(-3) mol/L detected by surface tension method. Its γ cmc was 48.0mN/m,the lowest surface tension was 29.0mN/m at concentration 0. 810× 10~(-3)mol/L . Its thermal decompose property was studied with TG/DTG. This revealed when temperature reached 150.02℃ it began to lose hydrophile group and at 260℃ decomposed fastest at N_2 atmosphere. In oven it decompounded in ten minutes at 200℃ this leaded to become lipophilic (contact angle reached 120 ) when it was coated on certain substrates.
when the plate was made, its applicability for print was tested on a offset printing press. The version bears achieved twenty thousand copies. However, its resolution depended on the ink jet printer.
以这种乳化剂制成的纳米核壳微球彩色微乳液经计算机直接喷墨成像在电解氧化形成砂目的铝版上制成喷墨CTP版，墨点清晰、无散点。并在胶印机上进行了印刷，耐印率达到了两万印。分辨率取决于喷墨打印机。
Core-shell colored nanoparticle latex which the core contains oil-soluble pigments and bakelite was prepared by interface microemulsion polymerization technology . Moreover, This paper investigated the effect of short chain alcohol used as co-emulsifier .The configuration was observed with TEM. Particle size and distribution was detected with laser scattering particle size distribution analyzer. This revealed particle size and distribution is 80～200nm. It was also proved the composition of shell material by IR and DSC. About thermal property of core-crust microsphere was studied with DSC. This proved that the microsphere was made up of Polyurea shell and bakelite core. The microsphere state was observed before and after it melted to form film on electrolyte-oxidation aluminium substrate. In the ink jet computer to printing plate system, the key work was image-form liquid .To prepare a water based ink , A special emulsifier was indespensible. Emulsificatio (n-dodecyl and n-octadecanoic acid carboxylate gallate) could be lost n by heat treatment after ink-jet plate making. Its capacity of emulsification to styrene and white oil (No,26~#) was superior than Sodium dodecyl sulfate. Critical micelle concentration was 0. 267 ×10~(-3) mol/L detected by surface tension method. Its γ cmc was 48.0mN/m,the lowest surface tension was 29.0mN/m at concentration 0. 810× 10~(-3)mol/L . Its thermal decompose property was studied with TG/DTG. This revealed when temperature reached 150.02℃ it began to lose hydrophile group and at 260℃ decomposed fastest at N_2 atmosphere. In oven it decompounded in ten minutes at 200℃ this leaded to become lipophilic (contact angle reached 120 ) when it was coated on certain substrates.
when the plate was made, its applicability for print was tested on a offset printing press. The version bears achieved twenty thousand copies. However, its resolution depended on the ink jet printer.
引文
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[2] 蒋文燕，嵇俊。CTP技术的新秀-喷墨CTP[J]．今日印刷，2005，(9)：24
[3] K. HONG, S. PARK; Morphologies and release behavior of polyurea microcapsules from different polyisocyanates[J], journal of materials science, 1999, (34):3161～3164
[4] E. N. BROWN; Microcapsule induced toughening in a self-healing polymer composite[J], journal of materials science, 2004, (39):1703～1710
[5] M. Takasu, H. Kawaguchi. Preparation of colored latex with polyurea shell by miniemulsion polymerization[J], Colloid Poly Sci, 2005, (283): 805～811
[6] Mayuko Takasu, et al., Preparation of colored latex containing oil-soluble dyes with high dye content by mini-emulsion polymerization[J], Colloid Polym Sci. 2003, (282): 119～126
[7] Mayuko Takasu, et al., Improvement of the storage stabilityand photostability of colored latex prepared by miniemulsion polymerization[J], Colloid Polym Sci 2004, (282): 740～746
[8] J. Mendel, D. Bugner and A. D. Bermel, et al. Particle generation and ink particle size effects in pigmented inkjet inks-PartⅡ[J], Journal of Nanoparticle Research, 1999, (1): 421～424
[9] Etoh, et al. Microcapsule-containing oil-based coating liquid, ink, coated sheet, and method of preparing the same[P]. United States Patent, 5, 798, 315. 2001-02-11
[10] 安博萍译 施劳莫·马格戴西等著。微珠乳液型喷墨墨水的特性与性能[J]，办公设备技术与信息，2004，(1)：12～15
[11] 徐谷仓。我国数码喷墨印花技术的发展[J]，新纺织，2005，(23)：22-26
[12] H. M. NVR, J. H. SONG; J. R. G. EVANS. ink-jet printing of gold conductive tracks[J], joural of material science:material electronics, 2002, (13):213～219
[13] Kazuhiro Murata Junichi Matsumoto Akira Tezuka, etal. Super-fine ink-jet printing: toward the minimal manufacturing system[J], Microsyst Technol, 2005, (9):005～0023
[14] B. Y. TAY, M. J. EDIRISINGHE. Dispersion and stability of silver inks[J], Joural of material science, 2002, (37):4653～4661
[15] 王利军，梁兴国，刘志华等。喷墨打印技术及喷墨打印用墨水[J]，电子计算 机与外部设备 1997，21(4)：7～10
[16] NEW PRODUCTS[R]. China chemical reporter 2004, (11):26
[17] BIERI N. R., CHUG J, POULIKAKOS D. etal. An experimental investigation of microresistor aser printing with gold nanoparticle-laden inks[J], Applied Physics A, 2005, (80):1485～1495
[18] Haq, Iain Fraser, gonMatijeViC. Preparation and characterization of finely ispersed pigment particles [J], Colloid Polym Sci 2003, (281): 542～549
[19] B. Y. TAY, M. J. EDIRISINGHE. Dispersion and stability of silver inks[J], JOURNAL OF MATERIALS SCIENCE. 2002, (37):653～4661
[20] S. OBATA, H. YOKOYAMA, T. OISHI, M. USUI, Preparation of aqueous pigment slurry for decorating whiteware by ink jet printing[J], JOURNAL OF MATERIALS SCIENCE. 2004, (39)2581～2584
[21] Chung; Chao-Jen (North Wales, PA); Finley; Maureen Joanne (Churchville, PA); Fu; Zhenwen (Lansdale, PA); Sheasley; William David (New Britain, PA). Non-pigmented ink jet inks [P]. United States Patent. 6, 930, 135. 2003-01-05
[22] Kanga, Rustom Sam; (Marietta, GA); Rosen, Daniel; (Acworth, GA). Processless digitally imaged printing plate using microspheres[P]. U S. 20030180636. 2003-09-15
[23] B. Y. TAY, M. J. EDIRISINGHE. On substrate selection for direct ink-jet printing[J], journal of materials science letters. 2002, (21):279～281
[24] 许锦枫。中国印刷及设备器材工业现状与发展前景[J]，印刷工业，2006，(1)：9～10
[25] 刘万瑞。2005年我国印刷工业产值及印刷设备器材生产、进出口统计[J]，印刷工业，2006，(1)：44～45
[26] 余尚先。从Drupa2000看我国CTP版才发展策略[J]，今日印刷杂志社，2004，118～120
[27] 徐克勋。精细有机化工原料及中间体手册．[M]：北京：化学工业出版社，1998．2～44
[28] De Wettink K, Huyghebaet A. Fluidized bed coating food technology[J], Trends in Food Science&Technology, 1999, (10): 163～168
[29] Raze Arshady, Waters Even, Ticky Andelie, etal. Suspension. dispersion, and interracial polycondensation: a methodological survey[J], Polym England Sci. 1993, 33(14): 865～876
[30] 吴克刚，佘纲哲。油脂喷雾干燥微胶囊化的研究[J]，食品科学，1998，19(1)：34～36
[31] Green B K, Rale Madene, Mikeny Simon, etal. Manifold record material[P]. US'2730456.1956-06-10
[32] Green B. K. Oil-containing microsopic and mehod of making them[P]. US 2800458. 1957-07-23
[33] 宋健，陈磊，李效军。微胶囊化技术及应用．[M]：北京：化学工业出版 社精细化工出版中心，2001。156～170
[34] 张可达，徐冬梅，王平。微胶囊化方法[J]，功能高分子学报，2001；14(4)：474～480
[35] 梁治齐．微胶囊技术及其应用．[M]：北京：中国轻工业出版社，2001，80～143
[36] 陆彬．药物新剂型与新技术．[M]：北京：人民卫生出版社，1998，15～38
[37] 马小军．微胶囊与人工器官．[M]：北京：化学工业出版社，2002，55～77
[38] Amory J K, Anawalt B D, Blaskovich P D, etal. Testosterone release from a subcutaneous, biodegradable microcapsule formulation(Viatrel) in hypogonadal men[J], Journal of Andrology, 2002; 23(1): 84～91
[39] Yoon Yeo, Alvin U. Chen, Osman A. Basaran, etal. Solvent Exchange Method:A Novel Microencapsulation Technique Using Dual Microdispensers[J], Pharmaceutical Research. 2004, (21)8:1419～1426
[40] 刘永霞，于才渊。微胶囊技术的应用及其发展[J]，中国粉体技术．2003，(9)，3：37～40
[41] Frederiksen L, Anton K, Hoogevest P, etal. Preparation of liposomes encapsulating water-soluble compounds using supercritical carbon dioxide[J], Pharm Sci, 1997; 86(8): 921～928
[42] 朱红军。可分解表面活性剂的研究进展[J]，精细化工．2002，19(8)：7～10
[43] 夏青天，脱羧反应的历程及其应用[J]，黔南民族师范学院学报．2004，(6)：15～18
[44] 邢晓坤，路华。印刷制版版材现状及未来发展趋势[J]，影像技术，2004，(2)：9～12
[45] 李鸣虎，喷墨印刷业的发展趋势[J]，丝网印刷，2004，(7)：33～35
[46] Kricheldorf H R, Kreiser-saunders Polylactones Anionic Polymerization of L-Lactide in Solution[J], Macromol. Chem. Phys., 1990, 191(5): 1057～1066
[47] 蔡超，高作宁。阳离子表面活性剂溶液的临界胶束浓度及扩散系数[J]，化学研究与应用。2004，(16)，5：663～666
[48] 孙国春，尹宝霖，魏西莲。表面活性剂胶束溶液的增溶及相转移自由能[J]，聊城大学学报．2005，(18)，6：36～39
[49] 苑世领，冯大诚，徐桂英。用定量结构性质关系预测表面活性剂的Krafft点[J]，结构化学．2003，(26)，6：739～743
[50] 蒲嘉陵，喷墨技术及应用[J]，今日印刷2005(2)：2-8
[51] 张心亚，瞿金清。核壳聚合与核壳结构聚合物乳液[J]，现代化工．2002，22(9)：58～61
[52] O'Toole J T[J], polym scl Part C. 1982, (21): 172
[53] undberg D C and Eliassen J D Polymer colids Plenum press[M]: New York. 1990, 153
[54] 冀林仙，石敏先，隆泉。脲醛树脂微胶囊的制备[J]，材料导报，2005，19(5)：109～110
[55] 江红涛，王秀峰，牟善勇等；反相微乳液法制备陶瓷装饰用彩喷墨水[J]，陶瓷，2004，(4)：13～18
[56] 岳德茂，2005年我国胶印板材发展状况解析[J]，印刷工业，2006，(1)：38～41
[2] 蒋文燕，嵇俊。CTP技术的新秀-喷墨CTP[J]．今日印刷，2005，(9)：24
[3] K. HONG, S. PARK; Morphologies and release behavior of polyurea microcapsules from different polyisocyanates[J], journal of materials science, 1999, (34):3161～3164
[4] E. N. BROWN; Microcapsule induced toughening in a self-healing polymer composite[J], journal of materials science, 2004, (39):1703～1710
[5] M. Takasu, H. Kawaguchi. Preparation of colored latex with polyurea shell by miniemulsion polymerization[J], Colloid Poly Sci, 2005, (283): 805～811
[6] Mayuko Takasu, et al., Preparation of colored latex containing oil-soluble dyes with high dye content by mini-emulsion polymerization[J], Colloid Polym Sci. 2003, (282): 119～126
[7] Mayuko Takasu, et al., Improvement of the storage stabilityand photostability of colored latex prepared by miniemulsion polymerization[J], Colloid Polym Sci 2004, (282): 740～746
[8] J. Mendel, D. Bugner and A. D. Bermel, et al. Particle generation and ink particle size effects in pigmented inkjet inks-PartⅡ[J], Journal of Nanoparticle Research, 1999, (1): 421～424
[9] Etoh, et al. Microcapsule-containing oil-based coating liquid, ink, coated sheet, and method of preparing the same[P]. United States Patent, 5, 798, 315. 2001-02-11
[10] 安博萍译 施劳莫·马格戴西等著。微珠乳液型喷墨墨水的特性与性能[J]，办公设备技术与信息，2004，(1)：12～15
[11] 徐谷仓。我国数码喷墨印花技术的发展[J]，新纺织，2005，(23)：22-26
[12] H. M. NVR, J. H. SONG; J. R. G. EVANS. ink-jet printing of gold conductive tracks[J], joural of material science:material electronics, 2002, (13):213～219
[13] Kazuhiro Murata Junichi Matsumoto Akira Tezuka, etal. Super-fine ink-jet printing: toward the minimal manufacturing system[J], Microsyst Technol, 2005, (9):005～0023
[14] B. Y. TAY, M. J. EDIRISINGHE. Dispersion and stability of silver inks[J], Joural of material science, 2002, (37):4653～4661
[15] 王利军，梁兴国，刘志华等。喷墨打印技术及喷墨打印用墨水[J]，电子计算 机与外部设备 1997，21(4)：7～10
[16] NEW PRODUCTS[R]. China chemical reporter 2004, (11):26
[17] BIERI N. R., CHUG J, POULIKAKOS D. etal. An experimental investigation of microresistor aser printing with gold nanoparticle-laden inks[J], Applied Physics A, 2005, (80):1485～1495
[18] Haq, Iain Fraser, gonMatijeViC. Preparation and characterization of finely ispersed pigment particles [J], Colloid Polym Sci 2003, (281): 542～549
[19] B. Y. TAY, M. J. EDIRISINGHE. Dispersion and stability of silver inks[J], JOURNAL OF MATERIALS SCIENCE. 2002, (37):653～4661
[20] S. OBATA, H. YOKOYAMA, T. OISHI, M. USUI, Preparation of aqueous pigment slurry for decorating whiteware by ink jet printing[J], JOURNAL OF MATERIALS SCIENCE. 2004, (39)2581～2584
[21] Chung; Chao-Jen (North Wales, PA); Finley; Maureen Joanne (Churchville, PA); Fu; Zhenwen (Lansdale, PA); Sheasley; William David (New Britain, PA). Non-pigmented ink jet inks [P]. United States Patent. 6, 930, 135. 2003-01-05
[22] Kanga, Rustom Sam; (Marietta, GA); Rosen, Daniel; (Acworth, GA). Processless digitally imaged printing plate using microspheres[P]. U S. 20030180636. 2003-09-15
[23] B. Y. TAY, M. J. EDIRISINGHE. On substrate selection for direct ink-jet printing[J], journal of materials science letters. 2002, (21):279～281
[24] 许锦枫。中国印刷及设备器材工业现状与发展前景[J]，印刷工业，2006，(1)：9～10
[25] 刘万瑞。2005年我国印刷工业产值及印刷设备器材生产、进出口统计[J]，印刷工业，2006，(1)：44～45
[26] 余尚先。从Drupa2000看我国CTP版才发展策略[J]，今日印刷杂志社，2004，118～120
[27] 徐克勋。精细有机化工原料及中间体手册．[M]：北京：化学工业出版社，1998．2～44
[28] De Wettink K, Huyghebaet A. Fluidized bed coating food technology[J], Trends in Food Science&Technology, 1999, (10): 163～168
[29] Raze Arshady, Waters Even, Ticky Andelie, etal. Suspension. dispersion, and interracial polycondensation: a methodological survey[J], Polym England Sci. 1993, 33(14): 865～876
[30] 吴克刚，佘纲哲。油脂喷雾干燥微胶囊化的研究[J]，食品科学，1998，19(1)：34～36
[31] Green B K, Rale Madene, Mikeny Simon, etal. Manifold record material[P]. US'2730456.1956-06-10
[32] Green B. K. Oil-containing microsopic and mehod of making them[P]. US 2800458. 1957-07-23
[33] 宋健，陈磊，李效军。微胶囊化技术及应用．[M]：北京：化学工业出版 社精细化工出版中心，2001。156～170
[34] 张可达，徐冬梅，王平。微胶囊化方法[J]，功能高分子学报，2001；14(4)：474～480
[35] 梁治齐．微胶囊技术及其应用．[M]：北京：中国轻工业出版社，2001，80～143
[36] 陆彬．药物新剂型与新技术．[M]：北京：人民卫生出版社，1998，15～38
[37] 马小军．微胶囊与人工器官．[M]：北京：化学工业出版社，2002，55～77
[38] Amory J K, Anawalt B D, Blaskovich P D, etal. Testosterone release from a subcutaneous, biodegradable microcapsule formulation(Viatrel) in hypogonadal men[J], Journal of Andrology, 2002; 23(1): 84～91
[39] Yoon Yeo, Alvin U. Chen, Osman A. Basaran, etal. Solvent Exchange Method:A Novel Microencapsulation Technique Using Dual Microdispensers[J], Pharmaceutical Research. 2004, (21)8:1419～1426
[40] 刘永霞，于才渊。微胶囊技术的应用及其发展[J]，中国粉体技术．2003，(9)，3：37～40
[41] Frederiksen L, Anton K, Hoogevest P, etal. Preparation of liposomes encapsulating water-soluble compounds using supercritical carbon dioxide[J], Pharm Sci, 1997; 86(8): 921～928
[42] 朱红军。可分解表面活性剂的研究进展[J]，精细化工．2002，19(8)：7～10
[43] 夏青天，脱羧反应的历程及其应用[J]，黔南民族师范学院学报．2004，(6)：15～18
[44] 邢晓坤，路华。印刷制版版材现状及未来发展趋势[J]，影像技术，2004，(2)：9～12
[45] 李鸣虎，喷墨印刷业的发展趋势[J]，丝网印刷，2004，(7)：33～35
[46] Kricheldorf H R, Kreiser-saunders Polylactones Anionic Polymerization of L-Lactide in Solution[J], Macromol. Chem. Phys., 1990, 191(5): 1057～1066
[47] 蔡超，高作宁。阳离子表面活性剂溶液的临界胶束浓度及扩散系数[J]，化学研究与应用。2004，(16)，5：663～666
[48] 孙国春，尹宝霖，魏西莲。表面活性剂胶束溶液的增溶及相转移自由能[J]，聊城大学学报．2005，(18)，6：36～39
[49] 苑世领，冯大诚，徐桂英。用定量结构性质关系预测表面活性剂的Krafft点[J]，结构化学．2003，(26)，6：739～743
[50] 蒲嘉陵，喷墨技术及应用[J]，今日印刷2005(2)：2-8
[51] 张心亚，瞿金清。核壳聚合与核壳结构聚合物乳液[J]，现代化工．2002，22(9)：58～61
[52] O'Toole J T[J], polym scl Part C. 1982, (21): 172
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