CN115232514A - Structural color material capable of developing color in presence of water and preparation method thereof - Google Patents
Structural color material capable of developing color in presence of water and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000004005 microsphere Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 239000005909 Kieselgur Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 229920005553 polystyrene-acrylate Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000013065 commercial product Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
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- 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
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Abstract
本发明提供了一种遇水显色结构色材料及其制备方法，所述制备方法是先将亚微米级胶体微球和黑色吸光物质混匀，然后加入白色微米级散射体，充分分散即得到所述遇水显色结构色材料。本发明的材料制备工艺简单，成本低廉，环境友好；所述材料可实现难以复制的公众光学防伪，可产业化成为防伪图案编辑，具备特殊加密要求的工商业产品包装的防伪手段。在高分子涂料行业、特种光学防伪油墨行业等领域具有重要的应用价值和广阔的应用前景，同时可赋予新一代纸币防彩色复印的防伪特性，从而促进高附加值产业链的良性发展。The invention provides a water-contacting color-developing structural color material and a preparation method thereof. The preparation method is as follows: firstly mixing submicron colloidal microspheres and black light-absorbing substances, then adding white micron scatterers, and fully dispersing to obtain The water color developing structural color material. The material of the invention has the advantages of simple preparation process, low cost and environmental friendliness; the material can realize optical anti-counterfeiting which is difficult to copy, and can be industrialized into anti-counterfeiting pattern editing and anti-counterfeiting means for industrial and commercial product packaging with special encryption requirements. It has important application value and broad application prospects in the polymer coating industry, special optical anti-counterfeiting ink industry and other fields. At the same time, it can endow the new generation of banknotes with anti-counterfeiting properties of anti-color copying, thereby promoting the healthy development of high value-added industrial chains.
Description
技术领域technical field
本发明涉及特种光学防伪油墨技术领域，特别涉及一种遇水显色结构色材料及其制备方法。The invention relates to the technical field of special optical anti-counterfeiting inks, in particular to a water-contacting color-developing structural color material and a preparation method thereof.
背景技术Background technique
光学防伪是商品辨识、现代纸币等经济交易的关键支撑技术，对于高附加值商品的保护和经济信息化的建设起到极其重要的作用。传统光学防伪技术所采用的热敏、荧光油墨等都存在防伪标识易仿，技术手段辨识度和门槛低等问题，因此迫切需要创新防伪技术。虽然国内外光学防伪的理论研究成果丰硕，但实际应用的技术和成本问题至今仍未能解决。防伪领域的特殊性也决定了技术门槛低且具有大量公开文献的相关技术不能被广泛应用。Optical anti-counterfeiting is a key supporting technology for commodity identification, modern banknotes and other economic transactions, and plays an extremely important role in the protection of high value-added commodities and the construction of economic informatization. The thermal and fluorescent inks used in traditional optical anti-counterfeiting technology have problems such as easy imitation of anti-counterfeiting labels, low recognition of technical means and low threshold, so there is an urgent need for innovative anti-counterfeiting technology. Although the theoretical research results of optical anti-counterfeiting at home and abroad are fruitful, the technical and cost problems of practical application have not yet been solved. The particularity of the anti-counterfeiting field also determines that related technologies with low technical thresholds and a large number of published documents cannot be widely used.
专利CN110484078A公开了一种遇水变透明涂料及其制备方法，制备得到的涂料具有较好的遇水变透明特性，但是其涂料本身不具有可调的颜色，需要作为涂层覆盖在化学颜料物质上层，遇水变透明才得以显现出下面物质的颜色，因而在涂料、颜料、油墨等领域应用受限。Patent CN110484078A discloses a water-transparent paint and a preparation method thereof. The prepared paint has good water-transparency properties, but the paint itself does not have an adjustable color, and needs to be covered as a coating on chemical pigment substances. The upper layer becomes transparent in contact with water to reveal the color of the underlying material, so its application in coatings, pigments, inks and other fields is limited.
因此，构筑一种具有浸润性、遇水能够显现本征结构色的有色环保型油墨对于特种光学防伪油墨以及基于此类应用的行业具有重要的应用价值。Therefore, it is of great application value for special optical anti-counterfeiting inks and industries based on such applications to construct a colored and environmentally friendly ink that has wettability and can exhibit intrinsic structural color in contact with water.
发明内容SUMMARY OF THE INVENTION
本发明旨在提供一种遇水显色结构色材料及其制备方法。基于亚微米级胶体微球的形貌、折射率、尺寸可控的制备技术，在系统探索胶体微球制备工艺和光学特性的基础上，利用形貌尺寸可控微球的光学散射现象，完善微球功能化运用及油墨复配工艺，研究微球结构、复配比例、聚合物组织结构等参数对光学防伪体系特性的影响，最终调控得到拥有不同颜色的遇水显色结构色材料。提供一种易于重复制备的物理结构色连续可调，适用范围广，低生产成本实现特种光学防伪的油墨。The present invention aims to provide a water color-developing structural color material and a preparation method thereof. Based on the preparation technology of submicron colloidal microspheres with controllable morphology, refractive index and size, on the basis of systematically exploring the preparation process and optical properties of colloidal microspheres, the optical scattering phenomenon of microspheres with controllable morphology and size is used to improve the The functional application of microspheres and the ink compounding process are used to study the influence of parameters such as microsphere structure, compounding ratio, and polymer structure on the characteristics of the optical anti-counterfeiting system. Provided is a continuously adjustable physical structure color that is easy to be repeatedly prepared, has a wide application range, and realizes special optical anti-counterfeiting ink with low production cost.
本发明的目的是提供一种遇水显色结构色材料及其制备方法。The purpose of the present invention is to provide a water color-developing structural color material and a preparation method thereof.
本发明的另一目的是提供所述制备方法制备得到的遇水显色结构色油墨。Another object of the present invention is to provide the water-influencing structural color ink prepared by the preparation method.
本发明上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
本发明提供了一种遇水显色结构色材料的制备方法，所述制备方法是先将亚微米级胶体微球和黑色吸光物质混匀，然后加入白色微米级散射体，充分分散即得到所述遇水显色结构色材料。The invention provides a preparation method of a color-developing structural color material in contact with water. The preparation method is to first mix submicron colloidal microspheres and a black light-absorbing substance, then add white micron scatterers, and fully disperse to obtain the obtained Describe the structural color material that develops color in contact with water.
本发明通过设计低成本的聚合物乳液体系，将亚微米级胶体微球与白色微米级散射体混合，从而破坏其堆积的有序度产生无角度依赖性的物理结构色，通过黑色吸光物质增强结构色饱和度和乳液复配，构筑一种低成本、颜色可调(以连续可调的物理结构色替代重金属颜料物质，包括各种彩色以及纯白、半透明)、遇水显色的环保油墨。By designing a low-cost polymer emulsion system, the invention mixes submicron-scale colloidal microspheres with white micron-scale scatterers, thereby destroying the orderly degree of their stacking to produce an angle-independent physical structural color, which is enhanced by black light-absorbing substances Structural color saturation and emulsion are compounded to build a low-cost, color-adjustable (replace heavy metal pigment substances with continuously adjustable physical structural colors, including various colors, pure white and translucent), and water-colored environmental protection. ink.
优选地，所述亚微米级微球的平均直径为100～300nm。Preferably, the average diameter of the submicron microspheres is 100-300 nm.
优选地，所述亚微米级微球为二氧化硅、二氧化钛、聚苯乙烯、聚甲基丙烯酸甲酯中的任一种。Preferably, the submicron microspheres are any one of silicon dioxide, titanium dioxide, polystyrene, and polymethyl methacrylate.
优选地，所述白色微米级散射体为介孔二氧化硅、二氧化钛、硅藻土中的任一种。Preferably, the white micro-scale scatterer is any one of mesoporous silica, titania, and diatomaceous earth.
优选地，所述黑色吸光物质为炭黑、碳纳米管、石墨烯、聚多巴胺中的任一种。Preferably, the black light-absorbing substance is any one of carbon black, carbon nanotubes, graphene, and polydopamine.
优选地，所述亚微米级胶体微球、黑色吸光物质和白色微米级散射体的质量比为1:0.001～0.01:0.5～2。Preferably, the mass ratio of the submicron colloidal microspheres, the black light absorbing substance and the white micron scatterer is 1:0.001-0.01:0.5-2.
本发明还提供上述制备方法得到的遇水显色结构色材料。The present invention also provides the water-influencing structural color material obtained by the above preparation method.
本发明制备的遇水显色结构色材料的结构色主要受微球粒径控制，显色机制主要受白色微米级散射体控制。通过选择不同粒径的微球，控制其表面形貌，可获得具有不同结构色的微球体系，与具有遇水折射率变化的白色微米级散射体形成复合油墨，在特种光学防伪油墨行业具有很大的应用前景。The structural color of the water color-developing structural color material prepared by the invention is mainly controlled by the particle size of the microspheres, and the color developing mechanism is mainly controlled by the white micron scatterers. By selecting microspheres with different particle sizes and controlling their surface morphology, microsphere systems with different structural colors can be obtained, and composite inks can be formed with white micro-scale scatterers with changes in the refractive index of water. Great application prospects.
本发明还提供上述方法制备得到的遇水显色结构色材料制备涂层的方法，所述方法为：将基底擦拭干净并干燥，然后将材料进行喷涂或涂敷到基底表面，干燥后即可制得涂层。The present invention also provides a method for preparing a coating from the water-reactive structural color material prepared by the above method. The method includes: wiping the substrate clean and drying, then spraying or coating the material on the surface of the substrate, and drying A coating is produced.
发明人通过大量的研究探索，得到遇水显色结构色材料的微球表面形貌的完整性，和白色微米级散射体混合后的均匀性都会影响材料的显色效果，而保证该复合材料微球表面形貌完整性和材料整体均匀性的制备关键有以下几个方面：胶体微球粒径的控制、胶体微球与黑色吸光物质、白色微米级散射体混合比例的控制。胶体微球与黑色吸光物质、白色微米级散射体混合比例失调，会影响材料的显色效果，导致材料干燥状态下呈现颜色或遇水无法显色。Through a lot of research and exploration, the inventors have found that the integrity of the surface morphology of the microspheres of the color-forming structural color material in contact with water, and the uniformity of mixing with the white micron-scale scatterers will affect the color rendering effect of the material, and ensure the composite material. The key to the preparation of the integrity of the surface morphology of the microspheres and the overall uniformity of the material are the following aspects: the control of the particle size of the colloidal microspheres, the control of the mixing ratio of the colloidal microspheres with the black light-absorbing substances and the white micro-scale scatterers. The mixing ratio of colloidal microspheres with black light-absorbing substances and white micro-scale scatterers is out of balance, which will affect the color rendering effect of the material, resulting in the color of the material in the dry state or the inability to develop color in contact with water.
本发明具有以下有益效果：The present invention has the following beneficial effects:
1、本发明制备遇水显色结构色材料的方法操作简单方便，所用原材料廉价易得，无须贵重仪器，成本低廉，适合工业化制备，适合于多种用途，具有很好的实际推广应用价值。1. The method of the present invention for preparing the color-developing structural color material in water is simple and convenient to operate, the raw materials used are cheap and easy to obtain, no expensive instruments are required, the cost is low, it is suitable for industrial preparation, and is suitable for various purposes, and has good practical application value.
2、通过选择粒径不同的胶体微球，得到不同的结构色特征，进而根据实际需求，连续调控复合材料的结构色。2. By selecting colloidal microspheres with different particle sizes, different structural color characteristics can be obtained, and then the structural color of the composite material can be continuously adjusted according to actual needs.
3、本发明提供了一种遇水显色结构色材料的制备方法，通过该方法制备得到的材料，克服了传统光学防伪技术所采用的热敏、荧光油墨等都存在防伪标识易仿，技术手段辨识度和门槛低等问题，适用范围广。3. The present invention provides a method for preparing a color-forming structural color material in contact with water. The material prepared by this method overcomes the existence of anti-counterfeiting marks, which are easy to imitate, such as heat-sensitive and fluorescent inks used in traditional optical anti-counterfeiting technology. Problems such as means recognition and low threshold are widely applicable.
4、利用所述材料制备的涂层遇水能够显现出本征结构色，在高分子涂料、玩具行业具有重要的应用价值和广阔的应用前景。4. The coating prepared by using the material can show intrinsic structural color in contact with water, and has important application value and broad application prospect in the polymer coating and toy industries.
附图说明Description of drawings
图1是遇水显色结构色材料干燥状态下的照片(从左往右，红、绿、蓝)；Figure 1 is a photo of the water-based structural color material in a dry state (from left to right, red, green, and blue);
图2是遇水显色结构色材料湿润状态下的照片(从左往右，红、绿、蓝)；Figure 2 is a photo of the water-based structural color material in a wet state (from left to right, red, green, and blue);
图3是蓝色遇水显色结构色材料湿润前后的反射光谱图；Fig. 3 is the reflection spectrum of the blue structural color material before and after wetting;
图4是绿色遇水显色结构色材料湿润前后的反射光谱图；Fig. 4 is the reflection spectrum diagram of the green structural color material before and after wetting;
图5是红色遇水显色结构色材料湿润前后的反射光谱图。Figure 5 is the reflection spectrum of the red structural color material before and after wetting.
具体实施方式Detailed ways
以下结合说明书附图和具体实施例来进一步说明本发明，但实施例并不对本发明做任何形式的限定。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The present invention is further described below with reference to the accompanying drawings and specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
除非特别说明，以下实施例所用试剂和材料均为市购。Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
实施例1Example 1
本实施例的遇水显色结构色材料的制备方法包括以下步骤：将平均直径为150nm的聚苯乙烯微球粉末与炭黑按质量比为1:0.002混合研磨均匀，加入平均孔体积为1.1cm3/g的介孔二氧化硅(介孔二氧化硅与微球的质量比为0.5:1)，充分分散即得到所述遇水显色结构色材料。The preparation method of the structural color material in the present embodiment includes the following steps: mixing and grinding polystyrene microsphere powder with an average diameter of 150 nm and carbon black at a mass ratio of 1:0.002, adding an average pore volume of 1.1 cm 3 /g of mesoporous silica (the mass ratio of mesoporous silica to microspheres is 0.5:1), and fully dispersed to obtain the water color-developing structural color material.
将本实施例的遇水显色结构色材料进行性能测试，材料在干燥状态下呈现白色，被水浸润后显现蓝色，如图1(右)和图2(右)所示，反射光谱图证实了这点，如图3所示。The performance test of the water color structural color material of this embodiment is carried out. The material appears white in the dry state, and appears blue after being soaked in water, as shown in Figure 1 (right) and Figure 2 (right), the reflection spectrum diagram This is confirmed, as shown in Figure 3.
实施例2Example 2
本实施例的遇水显色结构色材料的制备方法包括以下步骤：将平均直径为200nm的聚苯乙烯微球粉末与炭黑按质量比为1:0.002混合研磨均匀，加入平均孔体积为1.1cm3/g的介孔二氧化硅(介孔二氧化硅与微球的质量比为0.5:1)，充分分散即得到所述遇水显色结构色材料。The preparation method of the structural color material in the present embodiment includes the following steps: mixing and grinding polystyrene microsphere powder with an average diameter of 200 nm and carbon black in a mass ratio of 1:0.002, adding an average pore volume of 1.1 cm 3 /g of mesoporous silica (the mass ratio of mesoporous silica to microspheres is 0.5:1), and fully dispersed to obtain the water color-developing structural color material.
将本实施例的遇水显色结构色材料进行性能测试，同实施例1的测试方法，材料在干燥状态下呈现白色，被水浸润后显现绿色，如图1(中)和图2(中)所示，反射光谱图证实了这点，如图4所示。The performance test of the water color-developing structural color material of this embodiment is carried out with the test method of Example 1. The material is white in the dry state, and green after being soaked in water, as shown in Figure 1 (middle) and Figure 2 (middle). ), which is confirmed by the reflectance spectrum, as shown in Figure 4.
实施例3Example 3
本实施例的遇水显色结构色材料的制备方法包括以下步骤：将平均直径为110nm的二氧化硅微球粉末与炭黑按质量比为1:0.002混合研磨均匀，加入平均孔体积为1.1cm3/g的介孔二氧化硅(介孔二氧化硅与微球的质量比为0.5:1)，充分分散即得到所述遇水显色结构色材料。The preparation method of the water color-developing structural color material of this embodiment includes the following steps: mixing and grinding silica microsphere powder with an average diameter of 110 nm and carbon black at a mass ratio of 1:0.002, adding an average pore volume of 1.1 cm 3 /g of mesoporous silica (the mass ratio of mesoporous silica to microspheres is 0.5:1), and fully dispersed to obtain the water color-developing structural color material.
将本实施例的遇水显色结构色材料进行性能测试，同实施例1的测试方法，材料在干燥状态下呈现白色，被水浸润后显现蓝色。The performance test of the water color-developing structural color material in this example is the same as the test method in Example 1. The material appears white in a dry state, and appears blue after being soaked in water.
实施例4Example 4
本实施例的遇水显色结构色材料的制备方法包括以下步骤：将平均直径为150nm的聚甲基丙烯酸甲酯微球粉末与炭黑按质量比为1:0.002混合研磨均匀，加入平均孔体积为1.1cm3/g的介孔二氧化硅(介孔二氧化硅与微球的质量比为0.5:1)，充分分散即得到所述遇水显色结构色材料。The preparation method of the structural color material with water color in this embodiment includes the following steps: mixing and grinding polymethyl methacrylate microsphere powder with an average diameter of 150 nm and carbon black in a mass ratio of 1:0.002, adding an average pore The mesoporous silica with a volume of 1.1 cm 3 /g (the mass ratio of mesoporous silica to microspheres is 0.5:1) is fully dispersed to obtain the water-influencing structural color material.
将本实施例的遇水显色结构色材料进行性能测试，同实施例1的测试方法，材料在干燥状态下呈现白色，被水浸润后显现蓝色。The performance test of the water color-developing structural color material in this example is the same as the test method in Example 1. The material appears white in a dry state, and appears blue after being soaked in water.
实施例5Example 5
本实施例的遇水显色结构色材料的制备方法包括以下步骤：将平均直径为300nm的二氧化钛微球粉末与炭黑按质量比为1:0.002混合研磨均匀，加入平均孔体积为1.1cm3/g的介孔二氧化硅(介孔二氧化硅与微球的质量比为0.5:1)，充分分散即得到所述遇水显色结构色材料。The preparation method of the water color-developing structural color material of this embodiment includes the following steps: mixing and grinding titanium dioxide microsphere powder with an average diameter of 300 nm and carbon black at a mass ratio of 1:0.002, adding an average pore volume of 1.1 cm 3 /g of mesoporous silica (the mass ratio of mesoporous silica to microspheres is 0.5:1), and fully dispersed to obtain the water color-developing structural color material.
将本实施例的遇水显色结构色材料进行性能测试，同实施例1的测试方法，材料在干燥状态下呈现白色，被水浸润后显现红色，如图1(左)和图2(左)所示，反射光谱图证实了这点，如图5所示。The performance test of the water color-developing structural color material of the present embodiment is carried out with the test method of Example 1. The material appears white in the dry state, and appears red after being soaked in water, as shown in Figure 1 (left) and Figure 2 (left). ), the reflectance spectra confirm this, as shown in Figure 5.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that, The technical solutions of the present invention may be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention.
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