三维喷涂粘接用淀粉基材料体系及其制备方法所属技术领域本发明涉及快速成型技术，具体地说，本发明涉及一种供三维喷涂粘接快速成型技术使用的材料体系，包括基料以及与该基料配套的粘接剂，特别是基于淀粉的基料及与其配套的粘接剂材料体系。 Three-dimensional spray system and bonding TECHNICAL FIELD belongs starch-based materials of the present invention relates to a rapid prototyping technology, and more specifically, the present invention relates to a method for three-dimensional spray adhesive technology uses rapid prototyping material system, including binder and with The base material supporting the adhesive, especially starch-based materials and its supporting base adhesive material system. 背景技术由美国麻省理工学院Sachs等(US patent 5204055)首先提出的三维打印(Three Dimensional Printing, 3DP)快速成形技术是目前快速成形行业中最有生命力的技术，它具有传统制造业从未有过的高度加工灵活性，无须传统粉末加工成型的各种工具，不受任何几何形状的限制。 Background Rapid Prototyping by the Massachusetts Institute of Technology Sachs and other (US patent 5204055) first proposed the three-dimensional printing (Three Dimensional Printing, 3DP) Rapid Prototyping technology is the industry's most viable technology, it has never had traditional manufacturing industries flexibility over highly processed without conventional powder molding of a variety of tools, without any restriction geometry. 由于喷涂位置、喷涂次数、喷涂速度可以随意控制，不同的材料可以通过不同的喷头喷涂，喷涂物质可以是溶液、悬浮液、乳液及熔融物质等，因此，3DP成形技术可以很容易地控制局部材料组成、微观结构及表面特性。 Since the spray position, spray times, spraying speed can be controlled, different materials through different spray nozzles, spraying the substance can be solutions, suspensions, emulsions and melting substances, therefore, 3DP forming technique can be easily controlled local material composition, microstructure and surface properties. 由于3DP成形技术将众多传统加工过程统一为在一台机器上进行不断重复粘结的一个过程，易于设计研究，向工业生产转化过程中不存在规模化放大的工艺稳定性问题。 Due to the many traditional forming techniques 3DP process is carried out on a unified machine a bonding process is repeated, easy to design research, there is no large-scale amplification process stability issue to the industrial transformation process. 3DP成形技术最突出的优点是无需机械加工或任何模具，就能直接从计算机图形数据中生成任何形状的零件，从而极大地縮短产品的研制周期，提高生产率和降低生产成本，真正体现快速成形技术的优势。 3DP forming technology is the most prominent advantage is without any mold or machining can generate any shape parts directly from computer graphics data, which greatly shorten the product development cycle, improve productivity and reduce production costs, and really rapid prototyping technology advantage. 三维打印作为一种不依赖激光的成型技术，类似于喷墨打印机。 Three-dimensional printing without relying on laser forming technology, similar to an ink jet printer. 具体打印工艺过程是首先根据产品要求，通过计算机辅助设计建立CAD模型，用此CAD文件来表征物体的图像，经过数字处理模拟，将CAD文件转化为立体光刻格式(STL)，由计算机控制三维打印设备，依据"逐层打印，层层叠加" 的概念逐层制造实体，完成整个打印过程，随后再进行后处理，从而制备出具有特殊外型或复杂内部结构的物体。 Specific printing process is first based on product requirements, establish by computer-aided design CAD model, characterized by the CAD file image of an object, through digital processing simulation, CAD files into the format stereolithography (STL), computer-controlled three-dimensional printing apparatus, according to "print layer by layer, superimposed layers" concept layer by layer manufacturing entity, to complete the printing process, followed by post-processing, to prepare an object having a special shape or complicated internal structure. 传统的零件设计都是二维三视图，现在的设计软件如UG、 Pro/ENGINEER等虽然能够设计立体视图，但是没有实现真正的模型设计， 只是概念设计。 The traditional two-dimensional part design are three views, the current design software such as UG, Pro / ENGINEER, etc. Although able to design three-dimensional view, but no real model design, but the design concept. 3DP成形技术将会使实体模型设计成为可能。 3DP forming technology will make it possible to design a solid model. 只需将通用软件设计的零件转换成STL格式，再利用三维立体打印机，不用多长时间，真实的三维立体模型就会出现在设计者的面前。 Just common software designed components converted into STL format, and then use three-dimensional printer, not how long, the real three-dimensional model will appear in front of the designer. 这样就可以大大节省开支，减少不必要的浪费，而且还可以加快产品的开发，迅速占领市场。 This can greatly save money, reduce unnecessary waste, but also accelerate the development of products to market quickly. 三维打印快速成形技术主要有以下三种主要方式：喷射微粒、喷墨打印成型、三维喷涂粘接。 Three-dimensional printing rapid prototyping technology mainly in the following three main ways: spraying particles, inkjet molding, three-dimensional spray adhesive. 其中，三维喷涂粘接的加工原理是依据计算机内的三维数据模型，将原型或零件进行分层切片，得到各层截面的轮廓数据。 Among them, three-dimensional spray adhesive processing principle is based on three-dimensional data within the computer model, or prototype parts for slicing, the outline of the data layers section. 计算机据此数据信息控制三维打印机上的打印喷头，按照原型或零件的分层截面轮廓，在每一层预先铺好的材料粉末层上有选择地喷涂一层液体粘接剂，喷过粘接剂的路径材料被粘接在一起，形成一个具有微小厚度的片状实体轮廓，而其他地方仍然是松散粉末。 According to the control computer data on a 3D printer print heads, according to the hierarchical profile prototype or part of the material in advance of each layer of powder layer is selectively laid a layer of liquid adhesive spray, sprayed adhesive agents path material are bonded together to form a sheet-like solid profile having a small thickness, while the rest remains loose powder. 一层粉末成形完成后，进行下一层粉末的粘接，如此循环，层层粘接后逐层堆积成一体，得到一个三维空间实体，去除粉末并进行后烧结就可以制造出所设计的新产品样件、模型或模具。 After forming a layer of powder is completed, the next layer of adhesive powder, and so on, layer by layer after layer piled into one bond to give a three-dimensional entity, after removal of the powder and sintered to create a new product can be designed prototypes, models or molds. 三维喷涂粘接快速成形技术的材料体系包括合适的粉末基料和与之相配套的粘接剂溶液。 Three-dimensional rapid prototyping technology Spray adhesive material system comprises a suitable powder base with the support of adhesive solution and. 其中对于粉末基料要求至少具有以下性能：1、 颗粒小、均匀，无明显团聚；2、 颗粒流动性好，能铺成薄层；3、 在溶液喷射冲击时，基料不会产生凹陷、溅散与孔洞；4、 与粘接剂溶液作用后能很快固化。 Wherein the powder base requires at least has the following properties: 1, the small particles, even without obvious reunion; 2, particle flow and good, paved thin; 3, when the solution is sprayed impact, the base material will not sag, sputtering and holes; 4, the role of adhesive solution and quickly cured. 对于粘接剂溶液也要求至少具备以下性能：1、 性能稳定，能长期储存；2、 对打印机喷头无腐蚀作用；3、 具有足够低的粘度和足够高的表面张力，以便可以按照预期的流量从打印机喷头中挤出；4、 不易干涸，能延长打印机喷头的抗堵塞时间。 For adhesive solution also requires that at least have the following properties: 1, stable, long-term storage; 2, the print head is non-corrosive; 3, with sufficiently low viscosity and surface tension is high enough so that it can flow as expected extruded from the nozzle of the printer; 4, easy to dry, can extend printer head of anti-clogging time. 此外，还应保证所使用的基料和粘接剂均无毒、无污染。 Furthermore, it should ensure the base material and the adhesive used are non-toxic, non-polluting. 发明内容本发明的目的是提供一种适合于三维喷涂粘接快速成型技术的材料体系，以及该材料体系的制备方法。 Object of the present invention is to provide an adhesive suitable for coating three-dimensional rapid prototyping material system technology, as well as a method for preparing the material system. 本发明的材料体系包括一种复合基料和与之配套的粘接剂，其中，所述的复合基料是由下述重量份数的： 、淀粉75〜85 粘结剂10〜15 速凝剂CMC 1〜2 分散剂白碳黑0.5〜3 增强剂1〜3 硼砂1〜5 混合制成；所述的粘接剂是由下述重量份数的：氧化剂次氯酸钠或高锰酸钾0.5〜3NaOH 0.5〜3水基聚氨酯胶粘剂0.5〜3酚类树脂0.5〜2非离子表面活性剂0.5〜3醇类助溶剂1〜3去离子水90〜95 混合制成。 Material system of the present invention comprises a composite binder and accompanying adhesive, wherein the composite matrix material by the following parts by weight: starch 75~85 10 to 15 quick-setting adhesive Agent CMC 1~2 white carbon black dispersant borax 1 ~ 5 ~ 3 0.5~3 enhancer blend; said adhesive by the following weight parts: sodium hypochlorite or potassium permanganate oxidant 0.5~ 3NaOH 0.5~3 water-based polyurethane adhesive 0.5~3 phenolic resin 0.5~2 nonionic surfactant 0.5~3 alcohol cosolvents 1~3 90~95 prepared by mixing deionized water. 其中，淀粉基复合基料组成中的骨架成分是淀粉，所述的淀粉最好是玉米淀粉或薯类淀粉。 Among them, the starch-based composite material consisting of a skeleton base ingredient is starch, the starch is preferably corn starch or potato starch. 其它组份中，使用的粘结剂为聚乙烯醇或丙烯酸树脂乳液。 Other components of the binder used is polyvinyl alcohol or an acrylic resin emulsion. 聚乙烯醇是一种水溶性的多羟基高分子聚合物，其水溶液有一定的粘性，对纤维材料具有很好的亲和性和比较好的湿润性及粘结性。 Polyvinyl alcohol is a water-soluble polyhydroxy polymer, the water has a certain viscosity, the fiber material has a good affinity and good wettability and adhesion. 丙烯酸树脂乳液是丙烯酸酯类单体以水为分散介质，在乳化剂和机械搅拌作用下，经乳液聚合而成的高分子化合物水乳液，它无毒、无污染、原料易得、粘着力强。 Acrylic resin emulsion is an acrylic monomer to water as the dispersion medium, at emulsifier and mechanical stirring, the emulsion polymers derived aqueous emulsion, it non-toxic, non-polluting, raw materials, adhesion strength . 在淀粉基复合基料中还添加有速凝剂羧甲基纤维素钠（CMC)和分散剂白碳黑，并添加玻璃纤维、锂硅粉或无水硫酸钙晶须作为增强剂。 The starch-based binder composite accelerator further added sodium carboxymethylcellulose (CMC) and a dispersing agent white carbon, and glass fiber, silica fume or lithium anhydrous calcium sulfate whisker as a reinforcing agent. 最后，本发明还在淀粉基复合基料中添加有硼砂作为无机填料。 Finally, the present invention is also based starch borax complex binder added as an inorganic filler. 硼砂的分子式为]^2(1120)8(8405(0印4)，易溶于水，通常具有交联增强粘接的作用， 有利于提高初粘力和增加快速干燥的速度。淀粉基复合基料中加入硼砂，可以使短链的氧化淀粉以其羟基或羟基与硼原子形成络合物，通过这些不规则的交联，形成网状结构，具有交联增粘作用，有利于提高初粘力和加快干燥速度，另外还起到防腐、防渗及终止反应作用。但硼砂的用量并不是越多越好，过多的用量会使基料的流动性变差。相应地，与上述淀粉基复合基料配套的粘接剂由氧化剂、糊化剂、胶粘剂、增流剂、润湿剂和助溶剂混合组成。常用的氧化剂为次氯酸钠和高锰酸钾。为了使淀粉基复合基料具有较好的成型性能，氧化适当，淀粉溶解性能提高，成膜能力好，粘接力强，应该向粘接剂中加入次氯酸钠或高锰酸钾氧化剂。在粘接剂中还添加有NaOH作为糊化剂。糊化剂的作用是使其分子与淀粉中的醇基化合，破坏部分氢键，使淀粉大分子间的作用力减弱，分子变得较为舒缓，有利于氧化反应的发生；其次，糊化剂溶于淀粉后会放出大量的热，使得淀粉分子膨胀、糊化，从而使淀粉具有很强的粘结力；另外，糊化剂还使粘接剂具有较好的流动性。在粘接剂中添加水基聚氨酯胶粘剂作为胶粘剂，添加酚类树脂作为增流剂，增流剂的作用是降低粘接剂的表面张力，不致使其堵塞喷头。还添加有非离子表面活性剂作为润湿剂，所述的非离子表面活性剂为失水山梨醇单月桂酸酯类或烷基聚氧乙烯酯类表面活性剂。此外，还添加有醇类助溶剂，助溶剂的作用是使淀粉基料在粘接剂中的溶解度达到最大，从而使最终成型件的结构均匀，连接强度高。所述的醇类助溶剂为乙醇、甘油、丙二醇、聚乙二醇中的一种或几种。上述淀粉基复合基料的制备方法是以淀粉为主料，辅以其它助剂进行改性处理，最后筛分得到复合基料，具体的制备方法是：a) 、将淀粉冷却到一60'C〜一15(TC，粉碎、筛分制得淀粉细粉；b) 、将粘结剂、速凝剂CMC、分散剂白碳黑、增强剂和硼砂依次添加到a)的细粉中，用高速混合机混合均匀；c) 、混合好的b)粉料经震动筛筛分后得到所需细度的复合基料。 Borax formula] ^ 2 (1120) 8 (8405 (0 India 4), soluble in water, typically having a crosslinked enhanced bonding effect, help to improve tack and increasing the speed of fast drying. Starch matrix composites First base compound by adding borax, you can make a short chain of oxidized starch in its hydroxy or hydroxy boron atom form a complex, cross-linked by the irregular form a network structure, having a crosslinked thickening effect, it will help improve tack and speed drying, also play a preservative, impermeable and action to terminate the reaction, but the amount of borax is not possible, the amount of excess liquidity will base deteriorates. Accordingly, the above Starch-based composite matrix material supporting the adhesive from the oxidant, pasting agents, adhesives, increasing flow agents, wetting agents and a mixture of solvents commonly used oxidizing agent is sodium hypochlorite and potassium permanganate. In order to make starch-based composite base has good formability, oxidation appropriate starch to improve solubility, good film-forming ability, strong bonding, the adhesive should be added to the oxidizing agent sodium hypochlorite or potassium permanganate in adhesive also added as NaOH . gelatinization gelatinization agent agent role is to make the starch molecule alcohol compounds, partial destruction of hydrogen bonds, so that the force of weakening the starch macromolecules, molecules become more soothing, favor the oxidation reaction; secondly pasting agents will release a lot of heat when dissolved starch, making the starch molecules swell, pasting, so that the starch has a strong cohesive force; in addition, pasting the adhesive agent also has good mobility. Add water-based polyurethane adhesive in an adhesive as an adhesive, a phenolic resin added as a thickening flow agents, flow agent serves to reduce the surface tension of the adhesive, so that it will not clog the nozzle. also added a non-ionic surfactant as a wetting agent, the nonionic surfactant is sorbitan monolaurate polyoxyethylene alkyl esters or ester surfactant. In addition, co-solvent alcohols are also added, the role of the co-solvent is The solubility of the starch binder in the adhesive reaches the maximum, so that the structure of the final molded article uniform, high connection strength of the alcohol co-solvent is ethanol, glycerol, propylene glycol, polyethylene glycol or a . Several preparation method of the starch-based composite matrix material is starch-based material, modified with other additives, and finally sieved to obtain a composite base material, the specific methods of preparation are: a), the starch was cooled to a 60'C~ a 15 (TC, pulverized and sieved to obtain starch powder; b), the adhesive, accelerator CMC, dispersants white carbon black, a reinforcing agent and borax sequentially added to a) a fine powder, mixed with a high speed mixer; c), mixing a good b) after the powder by shaking sieve to obtain the desired fineness of the composite binder. 其中，淀粉经粉碎后，筛分选用其40〜60pm的细粉。 Among them, the starch after grinding, screening choose their 40~60pm fines. 与上述复合基料配套的粘接剂的制备方法是：a) 、用去离子水溶解氧化剂次氯酸钠或高锰酸钾；b) 、加入NaOH使完全溶解；c) 、依次加入水基聚氨酯胶粘剂、酚类树脂、非离子表面活性剂；d)、加入醇类助溶剂，混合搅拌均匀，得到所需粘接剂。 And the composite base material supporting the preparation of the adhesive is: a), was dissolved in deionized water, an oxidizing agent sodium hypochlorite or potassium permanganate; b), NaOH was added to effect complete solution; c), followed by the addition of water-based polyurethane adhesive, phenolic resins, non-ionic surfactant; d), alcohol cosolvents added, uniformly mixed and stirred to obtain a desired adhesive. 本发明提供的三维喷涂粘接用淀粉基材料体系由淀粉基复合基料和与之配套的粘接剂组成，其中，淀粉基复合基料具有以下特点：1、 粉末外观白色，平均粒径5(Vm;2、 粉末颗粒级配好，铺粉密度高，无明显团聚；3、 颗粒流动性好，能铺成薄层；4、 在溶液喷射冲击时，基料不会产生凹陷、溅散与孔洞；5、 与粘接剂溶液作用后能很快固化，凝结时间《4min;6、 制成的成型件精度高、尺寸变形小，成型件尺寸误差《0.02mm;7、 成型件后处理简单方便，可使成型件美观大方。相应地，与上述复合基料配套的粘接剂具有良好的流动性能，可以在6(Him以下孔径喷嘴中受控高密度喷出，不堵塞喷头；同时由具有一定的表面张力，流量可控；而且无毒无污染，对喷头无腐蚀作用。目前，相对于其它快速成型技术，3DP技术发展迅速，需要进一步研究开发出更具良好综合性能的成形材料。本发明针对三维喷涂粘接快速成形技术的特点，选用成本相对低廉的原料，经过简单的工艺制备过程，得到了完全可满足使用要求的成型复合基料和与之配套的粘接剂。 具体实施方式实施例1取75g玉米淀粉，在冷冻设备中冷却到一120。C，粉碎加工、筛分后制得平均粒径为40〜60Mm范围的玉米淀粉。在处理后的玉米淀粉中依次加入15g丙烯酸树脂乳液、2gCMC、 2g白碳黑、2g玻璃纤维、4g硼砂，在高速混合机中混合均匀。将上述已改性的粉料在震动筛中筛分，得到平均粒径为40〜6(Him的复合玉米淀粉基料。将lg次氯酸钠加入到95g去离子水中均匀搅拌，再加入0.8gNaOH，使其完全溶解。依次加入lg水基聚氨酯胶粘剂、0.5g酚类树脂、0.7g烷基聚氧乙烯醚类湿润剂和lg乙醇，搅拌均匀，得到与之配套的粘接剂溶液。实施例2取80g玉米淀粉，在冷冻设备中冷却到一7(TC，粉碎加工、筛分后制得平均粒径为40〜60Mm范围的玉米淀粉。在处理后的玉米淀粉中依次加入12g聚乙烯醇、2g CMC、 1.5g白碳黑、2.5g锂硅粉、2g硼砂，在高速混合机中混合均匀。将上述已改性的粉料在震动筛中筛分，得到平均粒径为40〜6(^m 的复合玉米淀粉基料。将lg高锰酸钾加入到92g去离子水中均匀搅拌。再加入0.5gNaOH，使其完全溶解。依次加入1.5g水基聚氨酯胶粘剂、0.5g酚类树脂、0.5g失水山梨醇单月桂酸酯类湿润剂和lg丙二醇，搅拌均匀，得到与之配套的粘接剂溶液。实施例3取85g土豆淀粉，在冷冻设备中冷却到一9(TC，粉碎加工、筛分后制得平均粒径为40〜60pm范围的土豆淀粉。 The present invention provides a three-dimensional spray adhesive with a starch-based material system consisting of starch-based composite material and accompanying base adhesive composition, wherein the starch-based composite base material has the following characteristics: 1, the appearance of white powder, the average particle diameter of 5 (Vm; 2, powder particle size distribution, high powder spreading density, no significant agglomeration; 3, particle flow and good, paved thin; 4, when the solution is sprayed impact, the base material will not sag, sputter Holes; 5, and after the adhesive solution can quickly curing effect, setting time "4min; 6, high precision molded parts made of the size of small deformation, moldings size error" 0.02mm; 7, after forming parts processing simple, elegant moldings can Accordingly, the above compound base material supporting the adhesive has good flow properties, in 6 (Him less pore controlled high density spray nozzle, do not plug the nozzle; at the same time having a certain degree of surface tension, flow-controllable; Also toxic pollution, no corrosion on the nozzle at present, compared to other rapid prototyping techniques, 3DP technology is developing rapidly, the need for further research to develop more good overall performance of the molding material The present invention is directed to a three-dimensional spray adhesive characteristics of rapid prototyping technology, the choice of a relatively low cost of raw materials, through simple preparation process has been fully meet the requirements of molded composite base and accompanying adhesive. Specific the implementation of the first embodiment take 75g corn starch cases, cooling to a 120.C in refrigeration equipment, the crushing process, after screening to obtain an average particle size range 40~60Mm corn starch in corn starch treated sequentially added 15g of acrylic resin emulsion, 2gCMC, 2g white carbon, 2g of glass fiber, 4g borax, mixed in a high speed mixer. The above has been modified in shock sieve sieved powder having an average particle size of 40~6 (Him composite corn starch-based material would lg Stir 95g sodium hypochlorite is added to deionized water, then add 0.8gNaOH, it is completely dissolved. successively added lg water-based polyurethane adhesive, 0.5g phenolic resin, 0.7g alkyl poly polyoxyethylene ethers, wetting agents and lg ethanol, stir to obtain a complete set of adhesive solution. 2 Example 80g of corn starch, cooled to a 7 (TC, smashing processing in refrigeration equipment, obtained after screening 40~60Mm average particle size range of corn starch in corn starch treated sequentially added 12g polyvinyl alcohol, 2g CMC, 1.5g of white carbon black, 2.5g of lithium silicon powder, 2g borax, mixed in a high-speed mixer uniform. The above has been modified in vibration sieve sieve powder having an average particle size of 40~6 (^ m composite corn starch-based material would lg Stir 92g potassium permanganate is added to the deionized water. then add 0.5gNaOH, it is completely dissolved. successively added 1.5g of water-based polyurethane adhesive, 0.5g phenolic resin, 0.5g sorbitan monolaurate wetting agents and lg propylene glycol esters, stir to obtain a complete set of adhesive solution. Example 3 85g Potato starch taken, cooled to a 9 (TC in refrigeration equipment, grinding processing, after screening to obtain an average particle size range 40~60pm potato starch. 在处理后的土豆淀粉中依次加入10g 聚乙烯醇、1.5g CMC、 lg白碳黑、1.5g无水硫酸钙晶须、lg湖砂，在高速混合机中混合均匀。 In potato starch treated sequentially added 10g polyvinyl alcohol, 1.5g CMC, lg white carbon black, 1.5g of anhydrous calcium sulfate whisker, lg lake sand, mixed in a high speed mixer. 将上述已改性的粉料在震动筛中筛分，得到平均粒径为40〜60^m的复合土豆淀粉基料。 The above has been modified in vibration sieve sieve powder having an average particle size of 40~60 ^ m composite potato starch-based material. 将2g次氯酸钠加入到90g去离子水中均匀搅拌。 2g of sodium hypochlorite was added to 90g of deionized water was stirred uniformly. 再加入1.5gNaOH,使其完全溶解。 Added 1.5gNaOH, and completely dissolved. 依次加入2.5g水基聚氨酯胶粘剂、lg酚类树脂、lg烷基聚氧乙烯醚类湿润剂和2g聚乙二醇，搅拌均匀，得到与之配套的粘接剂溶液。 Followed by adding 2.5g of water-based polyurethane adhesive, lg phenolic resin, lg alkyl polyoxyethylene ethers wetting agents and 2g of polyethylene glycol, stir to obtain a complete set of adhesive solution.