WO2013016935A1 - Method for preparing micro-structure based on macromolecular material - Google Patents

Method for preparing micro-structure based on macromolecular material Download PDF

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WO2013016935A1
WO2013016935A1 PCT/CN2011/084557 CN2011084557W WO2013016935A1 WO 2013016935 A1 WO2013016935 A1 WO 2013016935A1 CN 2011084557 W CN2011084557 W CN 2011084557W WO 2013016935 A1 WO2013016935 A1 WO 2013016935A1
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Prior art keywords
microstructure
mixed solution
preparing
substrate
solution
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PCT/CN2011/084557
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French (fr)
Chinese (zh)
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刘若鹏
赵治亚
盖佐•法布里齐亚
何雪涵
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深圳光启高等理工研究院
深圳光启创新技术有限公司
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Publication of WO2013016935A1 publication Critical patent/WO2013016935A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C09D11/104—Polyesters

Definitions

  • the invention relates to a metamaterial neighborhood, and in particular to a method for preparing a microstructure based on a polymer material.
  • Metamaterial is a new type of material with special physicochemical properties that is not possessed by natural materials with artificial structure as the basic unit and spatial arrangement in a specific way. Its special property is not the chemical composition of its material itself. It is determined by the characteristics of its man-made structure.
  • metamaterials depend to a large extent on the key physical dimensions of the material. For example, crystals are ordered at the atomic scale. Because of this, crystalline materials possess physical properties that are not found in amorphous states. Such ratios, ordered at other levels, may yield a degree of physical properties not found in materials in nature. Typically the size of the man-made structure is one tenth of the desired response wavelength, otherwise the arrangement of these man-made structures cannot be considered continuous in space.
  • Metamaterials include man-made structures and materials attached to man-made structures that support the man-made structure and can therefore be any material that is different from the man-made structure. The superposition of these two materials creates an equivalent medium in space. Electrical constant and magnetic permeability, and these two physical parameters correspond to the electric field response and magnetic field response of the material, respectively.
  • the preparation of metamaterials is currently technically based on photolithography, electrochemical deposition, etc.
  • the material is plated with a copper layer with a specific repeating pattern.
  • the substrate material is typically a rigid FR4 board.
  • the flexible and flexible base material or packaging material is a hot spot that many research groups are working on at this stage.
  • the constituent materials of the microstructure unit are generally metals such as copper, gold, silver, etc., and the repeating pattern is mainly an open resonant ring.
  • the technical problem to be solved by the present invention is to provide a preparation method of a microstructure based on a polymer material, which uses a printing technique to directly print an organic solution onto a substrate, and a crosslinking reaction occurs to form a micro-material based micro-material on the substrate. Structure, achieving low-cost, high-efficiency industrial production of metamaterials.
  • the technical solution adopted by the present invention to solve the technical problem is: a method for preparing a microstructure based on a polymer material, characterized in that: the preparation method comprises the following steps:
  • the polyhydroxy compound solution and the polycarboxy compound solution are uniformly mixed, and formulated into a mixed solution to be cooled to room temperature;
  • the step further includes: d. drying the substrate.
  • the ratio of the number of hydroxyl groups to the number of carboxyl groups in the mixed solution is 3:10 to 4:5. Further, according to the functional groups of the polyhydroxy compound and the polycarboxy compound, a metamaterial having different properties such as electrical conductivity and biological properties is produced.
  • a diluent is added to the mixed solution to adjust the viscosity in the mixed solution so that the viscosity of the mixed solution is 2 to 30 CP.
  • a plasticizer is added to the mixed solution to adjust the viscosity in the mixed solution so that the viscosity of the mixed solution is 2 to 30 CP.
  • the mixed solution has a viscosity of 10 to 12 CP.
  • the shape of the microstructure is controlled by a computer system.
  • the diluent is benzene, toluene or n-butanol.
  • the plasticizer is dioctyl phthalate, dibutyl phthalate or polyethylene glycol.
  • the substrate is made of a hard or flexible sheet or film.
  • the substrate is a paper substrate.
  • the principle is: printing a mixed solution containing a polyhydroxy compound and a polycarboxy compound onto a substrate by using a printing technique, and during the printing and heating process, the high temperature causes the polyhydroxy compound and the polycarboxy compound to crosslink to form a polyester on the substrate. Forming a stable microstructure based on polymer materials.
  • the super-material micro-structural unit is made of a super material with electrical or biological properties according to different functional groups carried by the polymer material, and the functional application of the meta-material is expanded;
  • the shape of the microstructure can be controlled by the computer system, no need to make additional templates, simple and convenient.
  • Figure 1 is a reaction equation of the first embodiment.
  • a preparation method of a microstructure based on a polymer material comprising the following steps: a, uniformly mixing a polyhydroxy compound solution and a polycarboxy compound solution, preparing a mixed solution to be cooled to room temperature, and preparing the mixture
  • the ratio of the number of hydroxyl groups to the number of carboxyl groups in the mixed solution is 3: 10 ⁇ 4:5;
  • the prepared mixed solution is injected into the ink cartridge of the printer as the ink of the printer;
  • C In the heating process of printing, the polyhydroxy compound and the polycarboxy compound are cross-linked to form a polyester, thereby forming a stable polymer-based microstructure on the substrate, and the shape of the microstructure is determined by a computer system. Control programming, no additional production templates are required;
  • the principle is: printing a mixed solution containing a polyhydroxy compound and a polycarboxy compound onto a substrate by using a printing technique, and during the printing and heating process, the high temperature causes the polyhydroxy compound and the polycarboxy compound to crosslink to form a polyester on the substrate. Forming a stable microstructure based on polymer materials.
  • a diluent or a plasticizer to the mixed solution to adjust the viscosity in the mixed solution, so that the viscosity of the mixed solution is 2 ⁇ 30CP, preferably 10 ⁇ 12CP, and controlling the water content in the mixed solution to print out
  • the diluent is benzene, toluene or n-butanol
  • the plasticizer is dioctyl phthalate, dibutyl phthalate or polyethylene glycol
  • a microstructure unit using a polymer material as a metamaterial is formed according to the functional groups of the polyhydroxy compound and the polycarboxy compound. Metamaterials with different properties, such as electrical conductivity and biological properties, extend the functional application of metamaterials.
  • the material is a hard or flexible sheet or film, or it can be a paper substrate, which makes the selection range of the substrate wider, realizes the flexible substrate of the metamaterial, and reduces the metamaterial. the cost of.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Dissolve PVA powder in water fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 3:10.
  • the toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 10CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
  • the prepared organic polymer solution is injected into the printer ink cartridge as the ink of the printer.
  • the high temperature during the printing heating process causes the cross-linking reaction between PVA and SSA to form polyester, and the reaction equation is as shown in FIG. 1 to form a stable on the substrate.
  • the substrate is then dried in an oven at a temperature of 80 degrees Celsius; the shape of the microstructure is controlled by a computer system, and no additional template is required.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Dissolve PVA powder in water fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 3:5.
  • the toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 11CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Dissolve PVA powder in water fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 4:5.
  • the toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 12CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
  • the prepared organic polymer solution is injected into the printer ink cartridge as the ink of the printer.
  • the high temperature during the printing heating process causes the cross-linking reaction between the PVA and the SSA to form a polyester, thereby forming a stable polymer-based microstructure on the substrate.
  • the substrate is dried in an oven at a temperature of 85 degrees Celsius; the shape of the microstructure is controlled by a computer system, and no additional template is required.
  • the polyhydroxy compound and the polycarboxy compound are not only the PVA and SSA exemplified in the above examples, but any compound containing a plurality of hydroxyl groups and a plurality of carboxyl groups can be suitably used in the present invention; the amount of hydroxyl groups in the mixed solution The difference in the ratio of the number of carboxyl groups makes the hardness of the formed microstructure different.
  • the present invention has been described by way of example only, and the present invention may be modified in various ways without departing from the spirit and scope of the invention.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

The present invention relates to a method for preparing a micro-structure based on a macromolecular material. The preparing method comprises the following steps: uniformly mixing a polyhydroxy compound solution and a polycarboxylic compound solution, to formulate a mixed solution, and cooling the mixed solution to room temperature; injecting the formulated solution into an ink box of a printer; and in a printing heating process, enabling a cross-linking reaction between the polyhydroxy compound and the polycarboxylic compound to generate polyester, so as to form a stable micro-structure based on a macromolecular material on a substrate. The printing technology is used to print the mixed solution on the substrate directly, thereby implementing low-cost and high-efficient industrial production of a meta-material. Because the photoetching technology is not used, requirements for thickness and hardness on the substrate are not strict, and a wider range of the substrate materials can be selected. Various kinds of hard or flexible plate films, and even paper materials can be selected, thereby implementing a flexible substrate of the meta-material and reducing the cost of the meta-material.

Description

说 明 书 一种基于高分子材料的微结构的制备方法 Description of a method for preparing a microstructure based on a polymer material
【技术邻域】 [Technology Neighborhood]
本发明涉及超材料邻域，尤其涉及一种基于高分子材料的微结构的制备 方法。  The invention relates to a metamaterial neighborhood, and in particular to a method for preparing a microstructure based on a polymer material.
【背景技术】  【Background technique】
超材料是一种以人造结构为基本单元、并以特定方式进行空间排布的具 有自然界材料所不具有的、特殊物理化学性质的新型材料， 它的特殊性质不 是由其材料本身的化学组成， 而是由其人造结构的特征所决定的。  Metamaterial is a new type of material with special physicochemical properties that is not possessed by natural materials with artificial structure as the basic unit and spatial arrangement in a specific way. Its special property is not the chemical composition of its material itself. It is determined by the characteristics of its man-made structure.
超材料的特殊性质在很大程度上取决于材料的关键物理尺度，例如晶体 在原子尺度上是排列有序的， 正因为如此， 晶体材料拥有一些无定型态所不 具有的物理特征， 由此类比， 在其它层次上的有序排列则可能获得一定程度 的自然界中的材料所不具有的物理性质。通常人造结构的尺寸为所需响应波 长的十分之一， 否则这些人造结构所组成的排列在空间中不能被视为连续。  The special properties of metamaterials depend to a large extent on the key physical dimensions of the material. For example, crystals are ordered at the atomic scale. Because of this, crystalline materials possess physical properties that are not found in amorphous states. Such ratios, ordered at other levels, may yield a degree of physical properties not found in materials in nature. Typically the size of the man-made structure is one tenth of the desired response wavelength, otherwise the arrangement of these man-made structures cannot be considered continuous in space.
超材料包括人造结构以及人造结构所附着的材料，该附着材料对人造结 构起到支撑作用， 因此可以是任何与人造结构不同的材料， 这两种材料的叠 加会在空间中产生一个等效介电常数与磁导率，而这两个物理参数分别对应 了材料的电场响应与磁场响应。  Metamaterials include man-made structures and materials attached to man-made structures that support the man-made structure and can therefore be any material that is different from the man-made structure. The superposition of these two materials creates an equivalent medium in space. Electrical constant and magnetic permeability, and these two physical parameters correspond to the electric field response and magnetic field response of the material, respectively.
超材料的制备在技术上目前主要通过光蚀刻、电化学沉积等技术在基底 材料上镀上有特定重复图案的铜层来实现。 由于光蚀刻等技术本身的限制， 基底材料一般为硬质的 FR4板。柔性可弯曲伸缩的基底材料或封装材料是现 阶段许多研究小组正在致力研究的热点。 目前所报道的超材料中， 微结构单 元的组成材料一般都是金属， 如铜、 金、 银等， 重复图案主要为开口谐振环The preparation of metamaterials is currently technically based on photolithography, electrochemical deposition, etc. The material is plated with a copper layer with a specific repeating pattern. Due to limitations in techniques such as photolithography, the substrate material is typically a rigid FR4 board. The flexible and flexible base material or packaging material is a hot spot that many research groups are working on at this stage. Among the supermaterials reported so far, the constituent materials of the microstructure unit are generally metals such as copper, gold, silver, etc., and the repeating pattern is mainly an open resonant ring.
( SRR ) 或者传输线结构。 (SRR) or transmission line structure.
【发明内容】  [Summary of the Invention]
本发明所要解决的技术问题是提供一种基于高分子材料的微结构的制 备方法， 利用打印技术将有机溶液直接打印到基板上， 发生交联反应， 从而 在基板上形成基于高分子材料的微结构， 实现超材料的低成本、高效率的工 业化生产。  The technical problem to be solved by the present invention is to provide a preparation method of a microstructure based on a polymer material, which uses a printing technique to directly print an organic solution onto a substrate, and a crosslinking reaction occurs to form a micro-material based micro-material on the substrate. Structure, achieving low-cost, high-efficiency industrial production of metamaterials.
本发明解决技术问题所采用的技术方案为：一种基于高分子材料的微结 构的制备方法， 其特征在于： 所述的制备方法包括以下步骤：  The technical solution adopted by the present invention to solve the technical problem is: a method for preparing a microstructure based on a polymer material, characterized in that: the preparation method comprises the following steps:
a、 将多羟基化合物溶液和多羧基化合物溶液均匀混合， 配制成混合溶液冷 却至室温； a, the polyhydroxy compound solution and the polycarboxy compound solution are uniformly mixed, and formulated into a mixed solution to be cooled to room temperature;
b、 将配制好的混合溶液注入到打印机的墨盒内， 作为打印机的墨水； c、 在打印的加热过程中， 促使多羟基化合物与多羧基化合物发生交联反应 生成聚酯， 从而在基板上形成稳定的基于高分子材料的微结构。 b. injecting the prepared mixed solution into the ink cartridge of the printer as the ink of the printer; c. during the heating process of printing, causing the polyhydroxy compound to cross-link with the polycarboxy compound to form a polyester, thereby forming on the substrate. Stable polymer-based microstructure.
所述的步骤还包括： d、 将所述的基板烘干。  The step further includes: d. drying the substrate.
所述的混合溶液中羟基数量与羧基数量比为 3: 10~4:5。 进一步改进，根据所述的多羟基化合物和所述的多羧基化合物所带的官 能团不同， 制成具有不同性能的超材料， 如导电性、 生物性能。 The ratio of the number of hydroxyl groups to the number of carboxyl groups in the mixed solution is 3:10 to 4:5. Further, according to the functional groups of the polyhydroxy compound and the polycarboxy compound, a metamaterial having different properties such as electrical conductivity and biological properties is produced.
所述的混合溶液中加入稀释剂来调节混合溶液中的粘度，使混合溶液的 粘度为 2~30CP。  A diluent is added to the mixed solution to adjust the viscosity in the mixed solution so that the viscosity of the mixed solution is 2 to 30 CP.
所述的混合溶液中加入增塑剂来调节混合溶液中的粘度，使混合溶液的 粘度为 2~30CP。  A plasticizer is added to the mixed solution to adjust the viscosity in the mixed solution so that the viscosity of the mixed solution is 2 to 30 CP.
所述的混合溶液的粘度为 10~12CP。  The mixed solution has a viscosity of 10 to 12 CP.
进一步改进，控制所述混合溶液中的含水量来控制被打印出的微结构的 效果。  Further improved, controlling the water content in the mixed solution to control the effect of the printed microstructure.
所述的微结构的形状由电脑系统控制编排。  The shape of the microstructure is controlled by a computer system.
所述的稀释剂为苯、 甲苯或正丁醇。  The diluent is benzene, toluene or n-butanol.
所述的增塑剂为邻苯二甲酸二辛酯、 邻苯二甲酸二丁酯或聚乙二醇。 所述的基板材质为硬质的或柔性的板材或薄膜。  The plasticizer is dioctyl phthalate, dibutyl phthalate or polyethylene glycol. The substrate is made of a hard or flexible sheet or film.
所述的基板为纸质基板。  The substrate is a paper substrate.
其原理为：利用打印技术将含有多羟基化合物和多羧基化合物的混合溶 液打印到基板上， 在打印加热过程中， 高温使得多羟基化合物和多羧基化合 物发生交联反应生成聚酯， 在基板上形成稳定的基于高分子材料的微结构。  The principle is: printing a mixed solution containing a polyhydroxy compound and a polycarboxy compound onto a substrate by using a printing technique, and during the printing and heating process, the high temperature causes the polyhydroxy compound and the polycarboxy compound to crosslink to form a polyester on the substrate. Forming a stable microstructure based on polymer materials.
本发明的有益效果为：  The beneficial effects of the invention are:
1、 没有采用传统的金属材料如金、 银、 铜等， 而是采用高分子材料作 为超材料的微结构单元，根据高分子材料所带的官能团不同制成具有电学或 生物性能的超材料， 拓展了超材料的功能应用； 1. Instead of using traditional metal materials such as gold, silver, copper, etc., The super-material micro-structural unit is made of a super material with electrical or biological properties according to different functional groups carried by the polymer material, and the functional application of the meta-material is expanded;
2、 相对于传统的光蚀刻技术对材料的局限性和多步骤操作的复杂性， 采用灵活简单且低成本、 高效率的打印技术， 实现超材料的低成本、 高效率 的工业化生产； 同时也使得基板的选材范围变宽了， 可以选择各类硬质或柔 性的板材薄膜， 也可以甚至是纸质的， 实现了超材料的柔性基板， 降低了超 材料的成本；  2. Compared with the traditional photolithography technology, the limitations of materials and the complexity of multi-step operation, using flexible, simple, low-cost, high-efficiency printing technology to achieve low-cost, high-efficiency industrial production of metamaterials; The substrate selection range is widened, and various hard or flexible sheet films can be selected, or even paper, which realizes a flexible substrate of metamaterial, which reduces the cost of the metamaterial;
3、 微结构的形状可以由电脑系统控制编排， 不需要额外的制作模板， 简单、 方便。  3, the shape of the microstructure can be controlled by the computer system, no need to make additional templates, simple and convenient.
【附图说明】  [Description of the Drawings]
图 1为本实施例一的反应方程式。  Figure 1 is a reaction equation of the first embodiment.
【具体实施方式】  【detailed description】
为了使本发明的目的、技术方案及优点更加清楚明白， 以下结合附图及 实施例， 对本发明进行进一步详细说明。 应当理解， 此处所描述的具体实施 例仅仅用以解释本发明， 并不用于限定本发明。  The present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
一种基于高分子材料的微结构的制备方法，所述的制备方法包括以下步 骤： a、 将多羟基化合物溶液和多羧基化合物溶液均匀混合， 配制成混合溶液冷 却至室温， 所述的配制好的混合溶液中羟基数量与羧基数量比为 3: 10~4:5； b、 将配制好的混合溶液注入到打印机的墨盒内， 作为打印机的墨水； C、 在打印的加热过程中， 促使多羟基化合物与多羧基化合物发生交联反应 生成聚酯， 从而在基板上形成稳定的基于高分子材料的微结构， 所述的微结 构的形状由电脑系统控制编排， 不需要额外的制作模板； A preparation method of a microstructure based on a polymer material, the preparation method comprising the following steps: a, uniformly mixing a polyhydroxy compound solution and a polycarboxy compound solution, preparing a mixed solution to be cooled to room temperature, and preparing the mixture The ratio of the number of hydroxyl groups to the number of carboxyl groups in the mixed solution is 3: 10~4:5; b, the prepared mixed solution is injected into the ink cartridge of the printer as the ink of the printer; C. In the heating process of printing, the polyhydroxy compound and the polycarboxy compound are cross-linked to form a polyester, thereby forming a stable polymer-based microstructure on the substrate, and the shape of the microstructure is determined by a computer system. Control programming, no additional production templates are required;
d、 将所述的基板烘干。 d. drying the substrate.
其原理为：利用打印技术将含有多羟基化合物和多羧基化合物的混合溶 液打印到基板上， 在打印加热过程中， 高温使得多羟基化合物和多羧基化合 物发生交联反应生成聚酯， 在基板上形成稳定的基于高分子材料的微结构。  The principle is: printing a mixed solution containing a polyhydroxy compound and a polycarboxy compound onto a substrate by using a printing technique, and during the printing and heating process, the high temperature causes the polyhydroxy compound and the polycarboxy compound to crosslink to form a polyester on the substrate. Forming a stable microstructure based on polymer materials.
所述的混合溶液中加入稀释剂或增塑剂来调节混合溶液中的粘度，使混 合溶液的粘度为 2~30CP， 优选为 10~12CP， 控制所述混合溶液中的含水量， 使打印出的微结构的效果更佳； 所述的稀释剂为苯、 甲苯或正丁醇， 所述的 增塑剂为邻苯二甲酸二辛酯、 邻苯二甲酸二丁酯或聚乙二醇；  Adding a diluent or a plasticizer to the mixed solution to adjust the viscosity in the mixed solution, so that the viscosity of the mixed solution is 2~30CP, preferably 10~12CP, and controlling the water content in the mixed solution to print out The effect of the microstructure is better; the diluent is benzene, toluene or n-butanol, and the plasticizer is dioctyl phthalate, dibutyl phthalate or polyethylene glycol;
没有采用传统的金属材料如金、 银、 铜等， 而是采用高分子材料作为超 材料的微结构单元，根据所述的多羟基化合物和所述的多羧基化合物所带的 官能团不同， 制成具有不同性能的超材料， 如导电性、 生物性能， 拓展了超 材料的功能应用。  Instead of using a conventional metal material such as gold, silver, copper, or the like, a microstructure unit using a polymer material as a metamaterial is formed according to the functional groups of the polyhydroxy compound and the polycarboxy compound. Metamaterials with different properties, such as electrical conductivity and biological properties, extend the functional application of metamaterials.
相对于传统的光蚀刻技术对材料的局限性和多步骤操作的复杂性，采用 灵活简单且低成本、 高效率的打印技术， 实现超材料的低成本、 高效率的工 业化生产； 所述的基板材质为硬质的或柔性的板材或薄膜， 也可以是纸质基 板， 使得基板的选材范围变宽了， 实现了超材料的柔性基板， 降低了超材料 的成本。 Compared with the traditional photolithography technology, the limitations of materials and the complexity of multi-step operation, flexible, simple, low-cost, high-efficiency printing technology is used to realize low-cost, high-efficiency industrial production of metamaterials; The material is a hard or flexible sheet or film, or it can be a paper substrate, which makes the selection range of the substrate wider, realizes the flexible substrate of the metamaterial, and reduces the metamaterial. the cost of.
实施例一：  Embodiment 1:
将 PVA粉末溶于水中， 充分溶解形成均匀的 PVA水溶液， 将适量的 SSA 溶液加入到 PVA水溶液中搅拌均匀冷却至室温，配制成羟基数量与羧基数量 比为 3: 10的有机高分子溶液， 加入甲苯稀释剂调节有机高分子溶液的粘度， 使有机高分子溶液的粘度为 10CP, 并且控制所述有机高分子溶液中的含水 量， 使打印出的微结构的效果更佳；  Dissolve PVA powder in water, fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 3:10. The toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 10CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
将制备好的有机高分子溶液注入到打印机墨盒内， 作为打印机的墨水， 打印加热过程中高温促使 PVA与 SSA发生交联反应生成聚酯， 反应方程式 如图 1所示， 从而在基板上形成稳定的基于高分子材料的微结构， 然后将所 述的基板在温度为 80摄氏度的烘箱中烘干； 所述的微结构的形状由电脑系 统控制编排， 不需要额外的制作模板。  The prepared organic polymer solution is injected into the printer ink cartridge as the ink of the printer. The high temperature during the printing heating process causes the cross-linking reaction between PVA and SSA to form polyester, and the reaction equation is as shown in FIG. 1 to form a stable on the substrate. Based on the microstructure of the polymer material, the substrate is then dried in an oven at a temperature of 80 degrees Celsius; the shape of the microstructure is controlled by a computer system, and no additional template is required.
实施例二：  Embodiment 2:
将 PVA粉末溶于水中， 充分溶解形成均匀的 PVA水溶液， 将适量的 SSA 溶液加入到 PVA水溶液中搅拌均匀冷却至室温，配制成羟基数量与羧基数量 比为 3:5的有机高分子溶液， 加入甲苯稀释剂调节有机高分子溶液的粘度， 使有机高分子溶液的粘度为 11CP, 并且控制所述有机高分子溶液中的含水 量， 使打印出的微结构的效果更佳；  Dissolve PVA powder in water, fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 3:5. The toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 11CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
将制备好的有机高分子溶液注入到打印机墨盒内， 作为打印机的墨水， 打印加热过程中高温促使 PVA与 SSA发生交联反应生成聚酯， 从而在基板 上形成稳定的基于高分子材料的微结构， 然后将所述的基板在温度为 70摄 氏度的烘箱中烘干； 所述的微结构的形状由电脑系统控制编排， 不需要额外 的制作模板。 Injecting the prepared organic polymer solution into the printer cartridge as the ink of the printer. The high temperature during the printing heating process causes the PVA to cross-link with the SSA to form a polyester, thereby forming a stable polymer-based microstructure on the substrate, and then drying the substrate in an oven at a temperature of 70 degrees Celsius; The shape of the microstructure described is controlled by a computer system and does not require additional template creation.
实施例三：  Embodiment 3:
将 PVA粉末溶于水中， 充分溶解形成均匀的 PVA水溶液， 将适量的 SSA 溶液加入到 PVA水溶液中搅拌均匀冷却至室温，配制成羟基数量与羧基数量 比为 4:5的有机高分子溶液， 加入甲苯稀释剂调节有机高分子溶液的粘度， 使有机高分子溶液的粘度为 12CP, 并且控制所述有机高分子溶液中的含水 量， 使打印出的微结构的效果更佳；  Dissolve PVA powder in water, fully dissolve to form a uniform aqueous solution of PVA, add appropriate amount of SSA solution to PVA aqueous solution, stir and cool to room temperature, and prepare an organic polymer solution with a ratio of hydroxyl group to carboxyl group of 4:5. The toluene diluent adjusts the viscosity of the organic polymer solution to make the viscosity of the organic polymer solution 12CP, and controls the water content in the organic polymer solution to make the printed microstructure more effective;
将制备好的有机高分子溶液注入到打印机墨盒内， 作为打印机的墨水， 打印加热过程中高温促使 PVA与 SSA发生交联反应生成聚酯， 从而在基板 上形成稳定的基于高分子材料的微结构， 然后将所述的基板在温度为 85摄 氏度的烘箱中烘干； 所述的微结构的形状由电脑系统控制编排， 不需要额外 的制作模板。  The prepared organic polymer solution is injected into the printer ink cartridge as the ink of the printer. The high temperature during the printing heating process causes the cross-linking reaction between the PVA and the SSA to form a polyester, thereby forming a stable polymer-based microstructure on the substrate. Then, the substrate is dried in an oven at a temperature of 85 degrees Celsius; the shape of the microstructure is controlled by a computer system, and no additional template is required.
应当理解，多羟基化合物和多羧基化合物不仅仅是上述实施例所列举的 PVA 和 SSA, 只要是含有多个羟基的化合物和多个羧基的化合物都可以适 用于本发明；混合溶液中羟基的数量与羧基的数量的比不同使所形成的微结 构的硬度也不相同。 在上述实施例中， 仅对本发明进行了示范性描述， 但是本邻域技术人员 在阅读本专利申请后可以在不脱离本发明的精神和范围的情况下对本发明 进行各种修改。 It should be understood that the polyhydroxy compound and the polycarboxy compound are not only the PVA and SSA exemplified in the above examples, but any compound containing a plurality of hydroxyl groups and a plurality of carboxyl groups can be suitably used in the present invention; the amount of hydroxyl groups in the mixed solution The difference in the ratio of the number of carboxyl groups makes the hardness of the formed microstructure different. In the above-described embodiments, the present invention has been described by way of example only, and the present invention may be modified in various ways without departing from the spirit and scope of the invention.

Claims

权 利 要 求 书 Claim
1、 一种基于高分子材料的微结构的制备方法， 其特征在于： 所述的制备方 法包括以下步骤：  A method for preparing a microstructure based on a polymer material, characterized in that: the preparation method comprises the following steps:
a、 将多羟基化合物溶液和多羧基化合物溶液均匀混合， 配制成混合溶液冷 却至室温； a, the polyhydroxy compound solution and the polycarboxy compound solution are uniformly mixed, and formulated into a mixed solution to be cooled to room temperature;
b、 将配制好的混合溶液注入到打印机的墨盒内， 作为打印机的墨水； c、 在打印的加热过程中， 促使多羟基化合物与多羧基化合物发生交联反应 生成聚酯， 从而在基板上形成稳定的基于高分子材料的微结构。 b. injecting the prepared mixed solution into the ink cartridge of the printer as the ink of the printer; c. during the heating process of printing, causing the polyhydroxy compound to cross-link with the polycarboxy compound to form a polyester, thereby forming on the substrate. Stable polymer-based microstructure.
2、 根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的步骤还包括： d、 将所述的基板烘干。  2. The method for preparing a microstructure based microstructure according to claim 1, wherein: the step further comprises: d. drying the substrate.
3、 根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的混合溶液中羟基数量与羧基数量比为 3: 10~4:5。  3. The method for preparing a microstructure based on a microstructure according to claim 1, wherein: the ratio of the number of hydroxyl groups to the number of carboxyl groups in the mixed solution is 3:10 to 4:5.
4、 根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的混合溶液中加入稀释剂来调节混合溶液中的粘度， 使混合溶液的 粘度为 2~30CP。  The method for preparing a microstructure based on a microstructure according to claim 1, wherein: the diluent is added to the mixed solution to adjust the viscosity in the mixed solution, so that the viscosity of the mixed solution is 2~30CP. .
5、 根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的混合溶液中加入增塑剂来调节混合溶液中的粘度， 使混合溶液的 粘度为 2~30CP。  The method for preparing a microstructure based on a microstructure according to claim 1, wherein: the plasticizer is added to the mixed solution to adjust the viscosity in the mixed solution, so that the viscosity of the mixed solution is 2~ 30CP.
6、 根据权利要求 4或 5所述的基于高分子材料的微结构的制备方法， 其特 征在于： 所述的混合溶液的粘度为 10~12CP。 6. The method for preparing a microstructure based on a polymer material according to claim 4 or 5, The viscosity of the mixed solution is 10~12CP.
7、 根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的微结构的形状由电脑系统控制编排。  7. The method for preparing a microstructure based microstructure according to claim 1, wherein: the shape of the microstructure is controlled by a computer system.
8、 根据权利要求 4所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的稀释剂为苯、 甲苯或正丁醇。  The method for preparing a microstructure based microstructure according to claim 4, wherein the diluent is benzene, toluene or n-butanol.
9、 根据权利要求 5所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的增塑剂为邻苯二甲酸二辛酯、 邻苯二甲酸二丁酯或聚乙二醇。 The method for preparing a microstructure based on a polymer material according to claim 5, wherein: the plasticizer is dioctyl phthalate, dibutyl phthalate or polyethylene. alcohol.
10、根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的基板材质为硬质的或柔性的板材或薄膜。 The method for preparing a microstructure based microstructure according to claim 1, wherein the substrate is made of a hard or flexible sheet or film.
11、根据权利要求 1所述的基于高分子材料的微结构的制备方法， 其特征在 于： 所述的基板为纸质基板。  The method for preparing a microstructure based on a polymer material according to claim 1, wherein the substrate is a paper substrate.
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