CN107325246B - 一种改性聚氨酯低聚物、其制备方法及其在光固化数码喷墨印花中的应用 - Google Patents
一种改性聚氨酯低聚物、其制备方法及其在光固化数码喷墨印花中的应用 Download PDFInfo
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- CN107325246B CN107325246B CN201710622572.7A CN201710622572A CN107325246B CN 107325246 B CN107325246 B CN 107325246B CN 201710622572 A CN201710622572 A CN 201710622572A CN 107325246 B CN107325246 B CN 107325246B
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
- C08G18/3275—Hydroxyamines containing two hydroxy groups
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Abstract
本发明涉及一种改性聚氨酯低聚物、其制备方法及其在光固化数码喷墨印花中的应用，属于感光高分子材料领域。一种胺基改性聚氨酯丙烯酸酯低聚物，所述胺基改性聚氨酯丙烯酸酯低聚物的结构式如(I)所示：
Description
技术领域
本发明涉及一种改性聚氨酯低聚物、其制备方法及其在光固化数码喷墨印花中的应用，属于感光高分子材料领域。
背景技术
区别于传统技术，光固化是采用可见光、紫外光(UV)或激光等高效能源为引发手段，在常温下引发特殊配置的各种液体组分，使其全部迅速转化为固体的过程，具有节能，环保，经济，高效与操作简单的优良特点，发展迅猛。光固化涂料主要由光敏预聚物、光引发剂、活性稀释剂以及其他添加剂(如着色剂、平流剂、消泡剂等)组成。
数码喷墨加工技术的开发和应用对纺织、皮革及印刷等领域具有革命性的意义。然而，现有热固化数码喷墨技术仍然存在着耗能，耗水，耗时，污染等问题，因此已有一些专利，将光固化技术，尤其是紫外固化技术应用到数码喷墨中来，如哈尔滨大东方卷烟材料科技开发有限责任公司已授权的中国专利CN102286230B公开了一种紫外光固化油墨及其制备方法；东莞劲胜精密组件股份有限公司已授权的中国专利CN102558963B公开了一种能在紫外光固化涂层表面直接喷墨的可辐射固化油墨及其制备方法；江南大学已授权的中国专利CN104562780B中公开了一种纺织品UV光固化可发泡涂料；张家港威迪森化学有限公司申请的中国专利CN103102741B也公开了一种紫外光固化油墨。但是可以注意到，这些专利中大多是将原先应用于硬质基材表面的添加通用多官能团低聚物或单体配方经过简单复配得到，使得涂料与墨水黏度较高，容易堵塞碰头，无法满足数码喷印对墨水流变性能的需求，同时固化膜的硬度较高，断裂伸长率严重不足，摩擦牢度低，不适用于诸如纺织、皮革与印刷等对基材要求“柔、韧、强”的行业。
另外还有专门针对光固化数码喷墨的引发方式，着色体系等进行专门开发的相关专利被报道，如东华大学申请的中国专利CN1613925公开了一种数码印染用紫外光固化油墨及其制备方法；江南大学在已授权的中国专利CN103526570B中公开了一种紫外光固化喷墨印花用颜料墨水的制备方法；浙江理工大学则在已授权的中国专利CN103396698B中公开了一种蓝光固化(可见光固化)配方及纺织品数码功能整理方法，以及在已授权的中国专利CN103788771B中公开一种纺织品用蓝光固化墨水组合物及其数码喷印固化方法。以上专利中，为获得高引发效率及转化率，普遍添加小分子叔胺类促引发剂或活化剂。这类小分子叔胺存在易迁移，易黄变，使得无论紫外或者可见光固化涂料与墨水存在相容性差，储存困难，制备步骤繁多，工艺复杂，成本高，毒性大，产品有刺激性气味，易黄变，有潜在毒性与风险等问题，限制其在与人体直接接触的领域应用。
为解决在柔性基材领域对低黏高强高柔弹的光敏预聚体及配合有合适活性稀释剂的聚合体系的需求，同时解决小分子叔胺助引发剂的迁移性，气味，黄变与毒性问题，本发明采用化学方法，通过低聚物结构的设计，将一种活性胺基接入低聚物主链，并通过软硬段比例、结晶度与分子量等的调控合成了一种低黏、高柔弹并具有优良助引发性能和高单体转化率的一体化胺基改性聚氨酯丙烯酸酯低聚物。在此基础上，通过单体结构和比例的优选复配出高强高弹，反应活性高，最终转化率高，透明度高的数码喷印光固化聚合体系。最终和颜料及其它助剂复合制备符合主流数码喷印要求的高性能光固化数码喷印墨水。
发明内容
本发明提供了一种改性聚氨酯低聚物，该改性聚氨酯低聚物配合适当的活性稀释剂的聚合体系，具有优良的光反应活性，断裂强力与伸长率大，固含量与透明度高，黏度较低；同时，因其自身含有助引发结构，可避免小分子有机胺或醇导致的气味、泛黄与毒性问题，适用于纸张、皮革与纺织品等柔性基材的数码喷印加工。
本发明还提供了一种所述改性聚氨酯低聚物的制备方法。
本发明还提供了一种所述改性聚氨酯低聚物在配制光固化墨水进行光固化数码喷墨印花方面的应用。
本发明解决其技术问题所采用的技术方案是：
一种胺基改性聚氨酯丙烯酸酯低聚物，所述胺基改性聚氨酯丙烯酸酯低聚物的结构式如(I)所示：
其中R1代表分子量从400-2000的聚醚结构(CH2CHCH3O)n，(CH2CH2O)n，(CH2CH2CH2CH3O)n中的一种或多种，R2代表六亚甲基，4,4'-亚甲基双环己基，1,3,3-三甲基环己烷中的一种或多种；R3代表N-甲基二乙基，N-乙基二乙基，N-丙基二乙基，N-苯基二乙基中的一种或多种，R4代表烷烃链CH2CH2，CH2CH2CH2，CH2CH2CH2CH2中的一种或多种，R5代表OCH2CH2OC(O)，OCH2CH2CH2OC(O)，OCH2CH2CH2CH2OC(O)，OCH2CH2OC(O)CH3，OCH2CH2CH2OC(O)CH3中的一种或多种，n代表重复单元聚合度，从1到5。
作为优选，该胺基改性聚氨酯丙烯酸酯低聚物整体分子量为1500-8000。
作为优选，所述的胺基改性聚氨酯丙烯酸酯低聚物，其25℃条件下的黏度小于3.0Pa·s。
一种所述的胺基改性聚氨酯丙烯酸酯低聚物的制备方法，其特征在于该方法包括以下步骤：
①在惰性气体保护下，脂肪族双异氰酸酯与多元聚醚以3-3.5：1的摩尔比在75-85℃反应2-4h，脂肪族双异氰酸酯与多元聚醚预先经过脱水干燥处理；
②在惰性气体保护下，使反应体系降温至70-75℃，采用饥饿投料法，加入脂肪族双异氰酸酯摩尔数的5-50％的含有叔胺基的双官能度羟基扩链剂反应0.5-1h，确保式(I)中每个重复结构单元中含有1个R3结构，然后滴加含有R4组分的无胺扩链剂，反应2-4h扩链，扩链剂的总量为脂肪族双异氰酸酯摩尔数的33-67％。；
③在氮气保护中加入丙烯酸类活性封端剂，65-70℃反应1-1.5h，得到式(I)所述化合物，丙烯酸类活性封端剂的加入量为脂肪族双异氰酸酯摩尔数的10-100％。
异氰酸酯与活泼氢反应的动力学研究表明，聚氨酯形成氨基甲酸酯的反应为三级反应。在反应的起始阶段，按照异氰酸酯浓度为一级，活泼氢浓度为二级的速率反应。因此R值(nNCO/nOH)需要大于2:1，才能使反应顺利进行。由于胺基单体有自催化效应，无需外加催化剂，还应用饥饿投料法降低体系中的胺基单体比例，反应安全高效；应用饱和的脂肪类单体，同时控制胺基含量防止黄变；通过理论计算和在线监控NCO％，自主控制得到理想的分子量。
本发明所述的改性聚氨酯低聚物化合物的制备中，溶剂起到调节黏度与防止暴聚的作用，只要对试剂或反应无不良影响即可。合适的溶剂包括不含活泼氢的丙酮、四氢呋喃、N-甲基吡咯烷酮等。其中因合成反应体系温度大于丙酮等溶剂的沸点，应注意通风，对于沸点大于反应体系温度的溶剂，反应结束后应减压蒸馏除去溶剂。
作为优选，脂肪族双异氰酸酯选自异氟尔酮二异氰酸酯、1,6-己二异氰酸酯、二环已基甲烷-4,4'-二异氰酸脂中的一种或多种，多元聚醚选自聚乙二醇、聚丙二醇和聚四氢呋喃中的一种或多种，含有栓剂的双官能度羟基扩链剂选自N-甲基二乙醇胺、N-乙基二乙醇胺、N-二乙醇胺、N-苯基二乙醇胺中的一种或多种，无胺扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇中的一种或多种，封端剂选自丙烯酸乙酯、丙烯酸丙酯、丙烯酸丁酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯中的一种或多种。
作为优选，所述的多元聚醚以0.3-0.4d/s的速度滴加使其与脂肪族双异氰酸酯混合，控制搅拌速度在350±50r/min；双官能度羟基扩链剂的滴加速度为0.2-0.3d/s。
作为优选，该方法包括以下步骤：
①所有原料经过脱水干燥处理后，在四口烧瓶中加入3-3.5摩尔份数的脂肪族双异氰酸酯，再将1摩尔份数的多元聚醚置于恒压滴液漏斗中，以0.3d/s的速度滴加至烧瓶中，控制搅拌速度在350±50r/min，在N2气氛保护下80℃反应2-4h，进行第一步预聚反应；
②在N2气氛保护中降温至70℃，采用饥饿投料法，0.2d/s的速度滴加1摩尔份数经由丙酮稀释后的含有叔胺基的双官能度羟基扩链剂，反应0.5-1h；然后，滴加无胺扩链剂，反应2-4h扩链；
③在氮气保护中加入丙烯酸类活性封端剂，65℃反应1h，得到式(I)所述化合物。
一种含所述的胺基改性聚氨酯丙烯酸酯低聚物的光固化数码喷印组合物，该组合物包括：第一组分：胺基改性聚氨酯丙烯酸酯低聚物10-60wt％，活性稀释单体40-90wt％；第二组分：以第一组分为100％计，光引发剂0.5-5wt％，着色剂0.5-5wt％，分散稳定剂0.5-2wt％。光引发剂根据低聚物与活性稀释单体的种类进行选择。该光固化数码喷印组合物搅拌或超声波分散均匀后控制其黏度为0.01-0.08Pa·s。将配制好的光固化数码喷印组合物液体添加到数码喷印设备中，按需定点定位喷涂到纸张、皮革或纺织品等柔性基材表面获得所需图案后，选取适合引发剂引发波段的一定功率的辐射光源进行紫外或可见光辐照固化，固化时间仅需几至几十秒即可制得高柔、高强、颜色丰富多彩且节能环保、安全耐用的高性能产品。所述光固化数码喷印组合物在应用于光固化数码喷印时，无需添加4-二甲氨基苯甲酸乙酯或三乙胺等胺类小分子助引发剂，可充分利用大分子自身产生的自由基引发聚合反应。
作为优选，所述的活性稀释单体含有一个具有自由基聚合活性基团的丙烯酸酯类或乙烯基类单体中的一种或者多种，所述的丙烯酸酯类单体选自丙烯酸丁酯，丙烯酸异辛酯，丙烯酸羟乙酯，丙烯酸异冰片酯，甲基丙烯酸丁酯，甲基丙烯酸异辛酯，甲基丙烯酸羟乙酯，甲基丙烯酸异冰片酯，二环戊烯基丙烯酸酯，二缩三丙二醇二丙烯酸酯或三羟甲基丙烷三丙烯酸酯中的一种或多种；所述的乙烯基类单体是苯乙烯、N-乙烯基吡咯烷酮及乙酸乙烯酯中的一种或多种。
作为优选，所述的光引发剂包括二苯甲酮类、酰基氧化磷类、硫杂蒽酮类紫外光引发剂或樟脑醌类、双咪唑类可见光引发剂中的一种；所述的着色剂为能溶解于该体系或以粒径<800nm的颗粒状态稳定分散于该体系中的染料或者颜料；所述的分散稳定剂为带有锚固基团的高分子型超分散剂。着色剂和分散稳定剂可以根据本领域技术进行常规选择。
作为优选，该光固化数码喷印组合物的黏度为0.01-0.08Pa·s，固化后产物断裂伸长率为300-1000％，定长100％的模量为0.2-1.0MPa。
本发明采用化学方法将传统助引发剂小分子胺“嫁接”到光敏低聚物分子链中，具有多项优势：1)低聚物中引入带有正电荷的胺基，可显著提高聚合体系固化膜与带有负电荷基材(纸张、皮革和纺织品)的结合性能。同时，可有效降低粉尘粘附及pH敏感性；2)在聚合反应过程中，胺基作为自由基活性点参与到聚合交联反应中，不仅可提高固化体系的交联密度，改善断裂强度、断裂伸长率等力学性能，而且有效克服了小分子胺的迁移性。3)大分子主链上胺基的双基耦合终止概率低，自由基寿命长，使得光固化反应彻底，单体转化率高。此外，选用柔软聚醚链段和刚性脂环族二异氰酸酯作为原料，进一步改善了聚合固化膜的黄变和柔韧性。本发明所制备的胺基改性聚氨酯丙烯酸酯低聚物对引发剂具有良好的溶解性和光聚合反应性。
本发明所制备的胺基改性聚氨酯丙烯酸酯低聚物具有制备成本低、合成操作简便、安全环保、产率高、黏度低，及良好的光聚合反应活性和溶解性能与广泛的普适性，适用于现有的大多数光固化系统与设备，同时以其为低聚物的固化膜不易泛黄，低迁移，无毒无气味，在光固化与数码喷印领域具有广泛的应用前景。
具体实施方式
下面通过具体实施例，对本发明的技术方案作进一步的具体说明。应当理解，本发明的实施并不局限于下面的实施例，对本发明所做的任何形式上的变通和/或改变都将落入本发明保护范围。
在本发明中，若非特指，所有的份、百分比均为重量单位，所采用的设备和原料等均可从市场购得或是本领域常用的。下述实施例中的方法，如无特别说明，均为本领域的常规方法。
实施例1：
所有原料经过脱水干燥处理后，在四口烧瓶中加入35.30mmol的异氟尔酮二异氰酸酯，再将10mmol的分子量为800的聚丙二醇置于恒压滴液漏斗中，0.3滴/秒(以下简写为d/s)的速度滴加至烧瓶中，控制搅拌速度在350r/min左右，N2气氛保护下80℃反应4h。继续在N2气氛保护中降温至70℃，采用饥饿投料法，0.2d/s的速度滴加10.50mmol经由3ml丙酮稀释后的N-甲基乙二醇胺反应0.5h后，再滴加入7.55mmol的1,4-丁二醇反应3h扩链，注意体系黏度与转速的变化，至NCO值降到理论值2.90％。随后加入14.63mmol甲基丙烯酸羟乙酯作为活性封端剂，65℃反应1h，得到平均分子量为3200的式(I)所述化合物(Ⅱ)。
产品经红外与1H-NMR进行结构鉴定，1HNMR(THF-D8,600mHz)：δ(ppm):1.34(CH3)；2.74,3.73(CH2)；5.93 6.27 6.50(RCH＝CH2,NH)；7.25(CH)。
实施例2：
所有原料经过脱水干燥处理后，在四口烧瓶中加入34.55mmol的六亚甲基二异氰酸酯，再将10mmol的分子量为2000的聚乙二醇置于恒压滴液漏斗中，0.3d/s的速度滴加至烧瓶中，控制搅拌速度在350r/min左右，N2气氛保护下80℃反应4h。继续在N2气氛保护中降温至65℃，采用饥饿投料法，0.2d/s的速度滴加10.50mmol经由3ml丙酮稀释后的N-甲基乙二醇胺反应0.5h后再，滴加入11.60mmol的1,4-丁二醇反应4h扩链，注意体系黏度与转速的变化，至NCO值降到理论值1.25％。随后加入6.42mmol丙烯酸羟乙酯作为活性封端剂，65℃反应1h，得到平均分子量为7900的式(I)所述化合物(Ⅲ)。
产品经红外与1H-NMR进行结构鉴定，1H-NMR(THF-D8,600mHz)：δ(ppm):2.29(N-CH3)；2.74,3.73(CH2)；5.93，6.27，6.50(RCH＝CH2,NH)。
实施例3：
所有原料经过脱水干燥处理后，在四口烧瓶中加入31.56mmol的4,4-二异氰酸酯二环己基甲烷，再将10mmol的分子量为1200的聚四氢呋喃置于恒压滴液漏斗中，0.3d/s的速度滴加至烧瓶中，控制搅拌速度在350r/min左右，N2气氛保护下80℃反应2h。继续在N2气氛保护中降温至65℃，采用饥饿投料法，0.2d/s的速度滴加10.50mmol经由3ml丙酮稀释后的N-苯基乙二醇胺反应0.5h后，再滴加入4.44mmol的1,4-丁二醇反应2h扩链，注意体系黏度与转速的变化，至NCO值降到理论值4.30％。随后加入20.05mmol甲基丙烯酸羟乙酯作为活性封端剂，65℃反应1h，得到平均分子量为2800的式(I)所述化合物(Ⅳ)。
产品经红外与1H-NMR进行结构鉴定，1HNMR(THF-D8,600mHz)：δ(ppm):1.34(CH3)；2.74,3.73(CH2)；5.93，6.27，6.50(RCH＝CH2,NH)；7.24,7.48,7.59,7.80,7.87(CH,Ar)。
实施例1-3中红外与核磁1HNMR使用如下设备及测试标准测得：
红外光谱由采用Nexus-670型红外光谱分析仪(FTIR-ATR)，样品在溶剂为浓度0.1g/L的四氢呋喃，在分辨率为4cm-1背景样品各扫描32次下测得。
核磁共振氢谱由Agilent 600 DD2 Onenmr型600mHz核磁共振仪测得。
实施例4：
所有原料经过脱水干燥处理后，在四口烧瓶中加入35.08mmol的4,4-二异氰酸酯二环己基甲烷，再将10mmol的分子量为400的聚乙二醇置于恒压滴液漏斗中，0.3d/s的速度滴加至烧瓶中，控制搅拌速度在350r/min左右，N2气氛保护下80℃反应2h。继续在N2气氛保护中降温至65℃，采用饥饿投料法，0.2d/s的速度滴加10.50mmol经由3ml丙酮稀释后的N-乙基乙二醇胺反应0.5h后，再滴加入3.10mmol的乙二醇反应2h扩链，注意体系黏度与转速的变化，至NCO值降到理论值4.73％。随后加入23.17mmol丙烯酸羟丁酯作为活性封端剂，65℃反应1h，得到平均分子量为1600的式(I)所述化合物(Ⅴ)。
产品经红外与1H-NMR进行结构鉴定，1HNMR(THF-D8,600mHz)：δ(ppm):1.31(CH3)；1.51(CH2)；2.34(N-CH2-C),3.85(O-CH2)；5.93，6.27，6.50(RCH＝CH2,NH)。
应用实施例1：
一种纸张用紫外固化数码喷印油墨组合物，其各组分如下：
第一组分，低聚物：自制聚氨酯丙烯酸酯(化合物Ⅱ)60wt％，
单体：丙烯酸丁酯(江苏三木)30wt％，
单体：丙烯酸异冰片酯(阿拉丁试剂)10wt％；
第二组分，以第一组分为100％计，
紫外引发剂：Darocur 1173(巴斯夫)2wt％，
着色剂：色素碳黑(巴斯夫)5wt％，
超分散剂Tech-5401(泰格聚合物)0.4wt％。
其中，紫外引发剂Darocur 1173为2-羟基-2-甲基苯基丙酮；
用紫外固化数码喷印油墨的制备方法包含如下：a.将低聚物、活性稀释单体、分散稳定剂和着色剂经高速剪切机在2000rpm转速下剪切15分钟进行预分散；b.预分散液加入球磨机使用0.1mm玛瑙珠进行进一步研磨分散，直至着色剂颗粒粒径小于800nm，得研磨分散液。c.将紫外引发剂按照配比与上述研磨分散液混合后在避光条件下超声分散30min，制得紫外固化数码喷印油墨，其黏度为0.05Pa·s。
应用上述紫外固化数码喷印油墨喷印及固化方法，包括如下步骤：将配置好的紫外固化数码喷印油墨添加到经过改装HP 1112喷墨打印机中，通过数码控制按需定位喷印到打印纸张表面获得所需文字图案，选取250W365nm主波长高压汞灯进行紫外光辐照60s固化。产物无任何刺激性气味，无明显黄变。
应用实施例2：
一种人造革用紫外固化数码喷印涂料，其各组分如下：
第一组分，低聚物：自制聚氨酯丙烯酸酯(化合物Ⅲ)50wt％，
单体：二缩三丙二醇二丙烯酸酯(江苏三木)30wt％，
单体：SR285(沙多玛)10wt％，
单体：丙烯酸异冰片酯(阿拉丁)10wt％；
第二组分，以第一组分为100％计，
紫外引发剂：ITX(Sigma Aldrich)1wt％，
着色剂：颜料棕25(宁波海曙唐彩化工)2wt％，
超分散剂Tech-5401(泰格聚合物)0.6wt％。
其中，紫外引发剂ITX为4-异丙基硫杂蒽酮；单体SR285为四氢呋喃丙烯酸酯。
用人造革用紫外固化数码喷印涂料的制备方法包含如下：a.将低聚物、活性稀释单体、分散稳定剂和着色剂经高速剪切机在2000rpm转速下剪切30分钟进行预分散；b.预分散液加入球磨机使用0.1mm玛瑙珠进行进一步研磨分散，直至着色剂颗粒粒径小于800nm，得研磨分散液。c.将紫外引发剂按照配比与上述研磨分散液混合后在避光条件下超声分散30min，制得人造革用紫外固化数码喷印涂料，其黏度为0.30Pa·s。
应用人造革用紫外固化数码喷印涂料及固化方法，包括如下步骤：将配置好的紫外固化数码喷印油墨添加到皮革数码喷涂机中，通过数码控制按需定位喷印到人造革基布表面获得所需图案，覆上PET塑料膜后100℃热压30s后，选取2000W365nm主波长高压汞灯进行紫外光辐照30s固化后取下塑料膜。产物无任何刺激性气味，无明显黄变。
应用实施例3：
一种棉用蓝光固化数码喷墨印花墨水组合物，其各组分如下：
第一组分，低聚物：自制聚氨酯丙烯酸酯(化合物Ⅳ)30wt％，
单体：丙烯酸羟乙酯(阿拉丁试剂)70wt％；
第二组分，以第一组分为100％计，
蓝光引发剂：樟脑醌(Sigma Aldrich)0.5wt％，
着色剂：颜料蓝60(克莱恩)1wt％，
超分散剂Tech-5401(泰格聚合物)0.4wt％。
其中，蓝光引发剂樟脑醌为1,7,7-三甲基-二环[2.2.1]庚烷-2,3-二酮。
蓝光固化数码喷墨印花墨水的制备方法包含如下：a.将低聚物、活性稀释单体经高速剪切机在5000rpm转速下剪切30分钟进行预分散；b.在预分散液中加入分散稳定剂和着色剂，再在球磨机中使用0.1mm玛瑙珠进行进一步研磨分散，直至着色剂颗粒粒径小于800nm，得研磨分散液。c.将蓝光引发剂、活化剂按照配比与上述研磨分散液混合后在避光条件下超声分散10min，制得蓝光固化墨水，其黏度为0.02Pa·s。
应用上述蓝光固化墨水的数码喷印及固化方法，包括如下步骤：将蓝光固化墨水添加至数码印花设备中，通过数码控制按需定位喷印到棉布或麻布表面获得所需图案；待完成图案喷印后将织物引入氮气气氛，并选用50W蓝光LED灯辐照2min后使墨水完成固化。产物无任何刺激性气味，无明显黄变。
应用实施例4：
一种涤纶用蓝光固化数码喷墨印花墨水组合物，其各组分如下：
第一组分，低聚物：自制聚氨酯丙烯酸酯(化合物Ⅳ)10wt％，
单体：丙烯酸羟乙酯(阿拉丁试剂)90wt％，
第二组分，以第一组分为100％计，
蓝光引发剂：樟脑醌(Sigma Aldrich)0.5wt％，
着色剂：分散红3B(浙江振光化工)2wt％，
超分散剂Tech-5401(泰格聚合物)0.4wt％。
其中，蓝光引发剂樟脑醌为1,7,7-三甲基-二环[2.2.1]庚烷-2,3-二酮。
蓝光固化数码喷墨印花墨水的制备、喷印及固化方法与应用实施例3相同，喷印基材为涤纶，其黏度为0.01Pa·s。产物无任何刺激性气味，无明显黄变。
对应用实施例1-4中光固化液黏度，引发效率和光固化膜应力应变性能以及使用如下设备及测试标准测得：
光固化液黏度由Anton Paar(MCR 52)旋转流变仪使用cc27同轴圆筒附件测试所得；
光固化液的光引发效率采用TA Q2000型光差示扫描量热仪
光固化薄膜的拉伸应力应变性能使用万能材料试验机Instron3367根据标准ISO1184—1983《塑料薄膜拉伸性能的测定》测试所得；
对于应用实施例2-4中印花织物与人造革的摩擦色牢度和手感使用如下设备及测试标准测得：
织物与人造革摩擦色牢度使用织物耐摩擦色牢度试验仪根据标准GB/T 3920-2008《纺织品色牢度试验耐摩擦色牢度》测试所得；
织物与人造革手感指标(硬挺、平滑、柔软等)使用智能风格仪NucybertekPhabromet测试所得。
上述应用实施例1-4的光固化液配方的黏度、引发效率以及光固化膜应力应变性能和列于表1中，上述应用实施例2-4的光固化印花织物与人造革的色牢度和手感指标见表2。
表1应用于纸张、织物与皮革的光固化配方的相关性能参数
注：对比1为市售光固化聚氨酯丙烯酸酯6202(江苏三木)参照实施例3进行，与常规方法相比未加入小分子叔胺助引发剂，未固化；对比2为市售光固化聚氨酯丙烯酸酯6202参照实施例3进行，加入常用小分子助引发剂4-二甲氨基苯甲酸乙酯(EDB,阿拉丁,1wt％)
表2蓝光固化数码喷墨印花织物摩擦色牢度及手感指标
注：原样1为标准棉贴衬布，应用实施例2为人造革用底衬布，应用实施例3为标准贴衬棉布，应用实施例4为标准贴衬涤纶，对比2为标准棉贴衬布，为市售光固化聚氨酯丙烯酸酯6202参照实施例3进行，加入常用小分子助引发剂4-二甲氨基苯甲酸乙酯(EDB,阿拉丁,1wt％)
根据表1和表2的数据可知，应用实施例1-4中光固化数码喷墨液均具有相当低的黏度，符合主流数码喷墨设备对墨水黏度的要求。光固化数码喷印墨水在无助引发剂胺时，仍具有优异的引发效率和最终转化率。且胺烷基自由基也参与到了大分子网络中，固化后的产物交联密度高，可以通过优选柔顺长链聚醚，在保证相对优秀的断裂强力的情况下有着优异的断裂伸长率，使得光固化薄膜柔弹强，符合各产业对柔性的要求。胺基的加入还增加了负电性颜料染料对负电性基底的亲和力和黏着性，因此最终产品的色牢度与手感相对于已有传统工艺产品，性能优秀，令人满意。整个加工过程属于绿色加工，无有毒有害添加剂，产品无任何刺激性气味，无明显黄变；采取高效能源加工，节能环保生产效率高，低聚物工艺简单，产率高，整个固化体系固化率高，引发效率高，成膜率高，无水节电，具有较大的经济价值。
以上所述的实施例只是本发明的一种较佳的方案，并非对本发明作任何形式上的限制，在不超出权利要求所记载的技术方案的前提下还有其它的变体及改型。
值得注意的是，与本发明思路类似的，即：将小分子胺引入聚氨酯丙烯酸酯低聚物和采用胺基改性的低黏度高柔性聚氨酯丙烯酸酯与活性稀释单体及相关助剂作为光固化数码喷墨液，均在本发明的保护范围之内。
Claims (8)
1.一种含有胺基改性聚氨酯丙烯酸酯低聚物的光固化数码喷印组合物，其特征在于该组合物包括：
第一组分：
胺基改性聚氨酯丙烯酸酯低聚物10-60wt％，
活性稀释单体40-90wt％；
所述胺基改性聚氨酯丙烯酸酯低聚物的结构式如(I)所示：
其中R1代表分子量从400-2000的聚醚结构(CH2CHCH3O)n，(CH2CH2O)n，(CH2CH2CH2CH3O)n中的一种或多种，R2代表六亚甲基，4,4'-亚甲基双环己基，1,3,3-三甲基环己烷中的一种或多种；R3代表N-甲基二乙基，N-乙基二乙基，N-丙基二乙基，N-苯基二乙基中的一种或多种，R4代表烷烃链CH2CH2，CH2CH2CH2，CH2CH2CH2CH2中的一种或多种，R5代表OCH2CH2OC(O)，OCH2CH2CH2OC(O)，OCH2CH2CH2CH2OC(O)，OCH2CH2OC(O)CH3，OCH2CH2CH2OC(O)CH3中的一种或多种，n代表重复单元聚合度，从1到5；
第二组分：以第一组分为100％计，
光引发剂0.5-5wt％，
着色剂0.5-5wt％，
分散稳定剂0.5-2wt％。
2.根据权利要求1所述的光固化数码喷印组合物，其特征在于：所述的活性稀释单体含有一个具有自由基聚合活性基团的丙烯酸酯类或乙烯基类单体中的一种或者多种，所述的丙烯酸酯类单体选自丙烯酸丁酯，丙烯酸异辛酯，丙烯酸羟乙酯，丙烯酸异冰片酯，甲基丙烯酸丁酯，甲基丙烯酸异辛酯，甲基丙烯酸羟乙酯，甲基丙烯酸异冰片酯，二环戊烯基丙烯酸酯，二缩三丙二醇二丙烯酸酯或三羟甲基丙烷三丙烯酸酯中的一种或多种；所述的乙烯基类单体是苯乙烯、N-乙烯基吡咯烷酮及乙酸乙烯酯中的一种或多种；所述的光引发剂包括二苯甲酮类、酰基氧化磷类、硫杂蒽酮类紫外光引发剂或樟脑醌类、双咪唑类可见光引发剂中的一种；所述的着色剂为能溶解于该体系或以粒径<800nm的颗粒状态稳定分散于该体系中的染料或者颜料；所述的分散稳定剂为带有锚固基团的高分子型超分散剂。
3.根据权利要求1所述的光固化数码喷印组合物，其特征在于：该光固化数码喷印组合物的黏度为0.01-0.08Pa·s，固化后产物断裂伸长率为300-1000％，定长100％的模量为0.2-1.0MPa。
4.根据权利要求1所述的光固化数码喷印组合物，其特征在于：该胺基改性聚氨酯丙烯酸酯低聚物整体分子量为1500-8000。
5.根据权利要求1所述的光固化数码喷印组合物，其特征在于：所述的胺基改性聚氨酯丙烯酸酯低聚物，其25℃条件下的黏度小于3.0Pa·s。
6.根据权利要求1所述的光固化数码喷印组合物，其特征在于：所述的胺基改性聚氨酯丙烯酸酯低聚物的制备方法包括以下步骤：
①所有原料经过脱水干燥处理后，在四口烧瓶中加入3-3.5摩尔份数的脂肪族双异氰酸酯，再将1摩尔份数的多元聚醚置于恒压滴液漏斗中，以0.3d/s的速度滴加至烧瓶中，控制搅拌速度在350±50r/min，在N2气氛保护下80℃反应2-4h，进行第一步预聚反应；
②在N2气氛保护中降温至70℃，采用饥饿投料法，0.2d/s的速度滴加1摩尔份数经由丙酮稀释后的含有叔胺基的双官能度羟基扩链剂，反应0.5-1h；然后，滴加无胺扩链剂，反应2-4h扩链；
③在氮气保护中加入丙烯酸类活性封端剂，65℃反应1h，得到式(I)所述化合物。
7.根据权利要求6所述的光固化数码喷印组合物，其特征在于：脂肪族双异氰酸酯选自异氟尔酮二异氰酸酯、1,6-己二异氰酸酯、二环已基甲烷-4,4'-二异氰酸脂中的一种或多种，多元聚醚选自聚乙二醇、聚丙二醇和聚四氢呋喃中的一种或多种，含有叔胺基的双官能度羟基扩链剂选自N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、N-苯基二乙醇胺中的一种或多种，无胺扩链剂选自乙二醇、1,3-丙二醇、1,4-丁二醇中的一种或多种，封端剂选自丙烯酸羟乙酯、丙烯酸羟丙酯、丙烯酸羟丁酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯中的一种或多种。
8.根据权利要求6所述的光固化数码喷印组合物，其特征在于：所述的多元聚醚以0.3-0.4d/s的速度滴加使其与脂肪族双异氰酸酯混合，控制搅拌速度在350±50r/min；双官能度羟基扩链剂的滴加速度为0.2-0.3d/s。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090272A (ja) * | 1983-10-24 | 1985-05-21 | Toyo Tire & Rubber Co Ltd | 磁性塗料組成物 |
| US5364741A (en) * | 1992-08-28 | 1994-11-15 | W. R. Grace & Co.-Conn. | Aqueous developable photosensitive polyurethane-(meth)acrylate |
| CN102304341A (zh) * | 2011-06-23 | 2012-01-04 | 太原理工大学 | 一种紫外光固化胶粘剂的制备方法 |
| CN103012722A (zh) * | 2012-12-26 | 2013-04-03 | 河北智生环保科技有限公司 | 用于皮革或合成革涂饰的光固化聚氨酯树脂及其制备方法 |
| CN103788771A (zh) * | 2014-01-28 | 2014-05-14 | 浙江理工大学 | 一种纺织品用蓝光固化墨水组合物及其数码喷印固化方法 |
-
2017
- 2017-07-27 CN CN201710622572.7A patent/CN107325246B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090272A (ja) * | 1983-10-24 | 1985-05-21 | Toyo Tire & Rubber Co Ltd | 磁性塗料組成物 |
| US5364741A (en) * | 1992-08-28 | 1994-11-15 | W. R. Grace & Co.-Conn. | Aqueous developable photosensitive polyurethane-(meth)acrylate |
| CN102304341A (zh) * | 2011-06-23 | 2012-01-04 | 太原理工大学 | 一种紫外光固化胶粘剂的制备方法 |
| CN103012722A (zh) * | 2012-12-26 | 2013-04-03 | 河北智生环保科技有限公司 | 用于皮革或合成革涂饰的光固化聚氨酯树脂及其制备方法 |
| CN103788771A (zh) * | 2014-01-28 | 2014-05-14 | 浙江理工大学 | 一种纺织品用蓝光固化墨水组合物及其数码喷印固化方法 |
Non-Patent Citations (2)
| Title |
|---|
| "Conjugated dyes carrying N, N-dialkylamino and ketone groups: One-component visible light Norrish type II photoinitiators";Ge Ding，等;《Dyes and Pigments》;20161026;第137卷;第456-467页 * |
| "Novel PU-type polymeric photoinitiator comprising side-chain benzophenone and coinitiator amine for photopolymerization of PU acrylate";Jun Wei，等;《POLYMERS FOR ADVANCED TECHNOLOGIES》;20080715;第19卷(第12期);第1763-1770页 * |
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