CN108422731A - A kind of the fire-retardant of the non-woven cloth containing engineering plastics mixes laminate - Google Patents
A kind of the fire-retardant of the non-woven cloth containing engineering plastics mixes laminate Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/20—All layers being fibrous or filamentary
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0261—Polyamide fibres
- B32B2262/0269—Aromatic polyamide fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/106—Carbon fibres, e.g. graphite fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/14—Mixture of at least two fibres made of different materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- Laminated Bodies (AREA)
Abstract
本发明提供了一种含工程塑料非织造布的阻燃混杂层合板，包括至少一层工程塑料非织造布，工程塑料非织造布与碳纤维织物、玻璃纤维织物、芳纶纤维织物中的一种或多种进行任意组合顺序的铺放，并通过树脂组分固化成型，得到含工程塑料非织造布的混杂层合板。工程塑料非织造布的制造原料为：聚醚砜、聚醚酰亚胺、聚苯硫醚、聚酰胺、聚四氟乙烯中的一种或多种的组合物。所述树脂组分按重量百分比含量包括：基础树脂60％‑80％、增韧剂5％‑30％、阻燃剂15％‑30％。本发明所用的工程塑料非织造布来源广泛，可利用回收产品，制得的混杂层合板具有成本低、比强度和比模量高、阻燃性好的优点，不仅具有可观的经济价值，还有重要的环保意义。
The invention provides a flame-retardant hybrid laminate containing engineering plastic non-woven fabrics, including at least one layer of engineering plastic non-woven fabrics, one of engineering plastic non-woven fabrics and carbon fiber fabrics, glass fiber fabrics, and aramid fiber fabrics or multiple layings in any combination order, and solidify and shape the resin components to obtain a hybrid laminate containing engineering plastic non-woven fabrics. The raw materials for the manufacture of engineering plastic nonwoven fabrics are: one or more combinations of polyethersulfone, polyetherimide, polyphenylene sulfide, polyamide, and polytetrafluoroethylene. The content of the resin component includes 60%-80% of base resin, 5%-30% of toughening agent and 15%-30% of flame retardant. The engineering plastic nonwoven fabric used in the present invention has a wide range of sources, and recycled products can be used. The hybrid laminated board has the advantages of low cost, high specific strength and specific modulus, and good flame retardancy. It not only has considerable economic value, but also It has important environmental significance.
Description
技术领域technical field
本发明涉及高分子材料技术领域，具体涉及一种含工程塑料非织造布的阻燃混杂层合板。The invention relates to the technical field of polymer materials, in particular to a flame-retardant hybrid laminate containing engineering plastic non-woven fabrics.
背景技术Background technique
工程塑料非织造布由于具有原料种类丰富、制备工艺灵活以及生产周期短的.优势，在环保工程、土木建筑、医疗卫生、农业技术等诸多领域被广泛应用。作为高分子材料，工程塑料非织造布具有较低的面密度，而且一些特种工程塑料非织造布还具有优良的力学性能、耐热性能、防腐性能和阻燃性能。Engineering plastic nonwovens are widely used in many fields such as environmental protection engineering, civil engineering, medical and health, and agricultural technology due to their advantages of rich types of raw materials, flexible preparation processes, and short production cycles. As a polymer material, engineering plastic nonwovens have a low surface density, and some special engineering plastics nonwovens also have excellent mechanical properties, heat resistance, corrosion resistance and flame retardancy.
近年来，航空、轨道交通、汽车、船舶等交通工具正朝着轻量化方向发展，对于轻质、阻燃材料的需求日益增长。目前普遍采用的高性能纤维(如碳纤维和芳纶纤维)增强聚合物复合材料，虽然具有优良的减重效果，但是其成本较高。工程塑料非织造布面积度低，性能良好，且价格相对便宜，作为增强体或填充物与聚合物基体复合，用于上述交通工具的内饰材料和次承力结构件具有一定的应用前景。In recent years, aviation, rail transit, automobiles, ships and other means of transportation are developing in the direction of lightweight, and the demand for lightweight and flame-retardant materials is increasing. High-performance fiber (such as carbon fiber and aramid fiber) reinforced polymer composite materials commonly used at present, although have excellent weight-reducing effect, but its cost is relatively high. Engineering plastic nonwovens have low area, good performance, and relatively cheap price. As reinforcements or fillers combined with polymer matrix, they have certain application prospects for interior materials and secondary load-bearing structural parts of the above-mentioned vehicles.
此外，随着社会经济的不断进步和发展，每年工业界产生大量废旧的工程塑料非织造布，这些废旧的工程塑料非织造布目前主要采取焚烧和陆地填埋的方式进行处理，对生态环境造成破坏。回收和再利用这些废旧的工程塑料非织造布，不仅具有可观的经济价值，还有重要的环保意义。In addition, with the continuous progress and development of the social economy, a large number of waste engineering plastic nonwovens are produced in the industry every year. These waste engineering plastic nonwovens are currently mainly disposed of by incineration and landfill, which has a negative impact on the ecological environment. destroy. Recycling and reusing these waste engineering plastic nonwovens not only has considerable economic value, but also has important environmental protection significance.
综上所述，利用工程塑料非织造布包括其回收物，开发轻质、阻燃的复合材料值得研究。In summary, the development of lightweight, flame-retardant composites using engineering plastic nonwovens, including their recycled content, is worth researching.
发明内容Contents of the invention
本发明要解决的技术问题是如何利用工程塑料非织造布，开发轻质、阻燃的复合材料。The technical problem to be solved by the invention is how to use engineering plastic non-woven fabrics to develop light-weight, flame-retardant composite materials.
为了解决上述技术问题，本发明的技术方案是提供一种含工程塑料非织造布的阻燃混杂层合板，其特征在于：包括至少一层工程塑料非织造布，工程塑料非织造布与碳纤维织物、玻璃纤维织物、芳纶纤维织物中的一种或多种进行任意组合顺序的铺放，并通过树脂组分固化成型，得到含工程塑料非织造布的阻燃混杂层合板。In order to solve the above technical problems, the technical solution of the present invention is to provide a flame-retardant hybrid laminate containing engineering plastic nonwovens, which is characterized in that it includes at least one layer of engineering plastics nonwovens, engineering plastics nonwovens and carbon fiber fabrics One or more of glass fiber fabrics, aramid fiber fabrics are laid in any combination order, and are cured and formed by resin components to obtain a flame-retardant hybrid laminate containing engineering plastic non-woven fabrics.
优选地，所述工程塑料非织造布的面密度为400-1000gsm。Preferably, the engineering plastic nonwoven fabric has an areal density of 400-1000 gsm.
优选地，所述工程塑料非织造布为毡状、布状、网状、纸状或其任意组合。Preferably, the engineering plastic nonwoven fabric is in the shape of felt, cloth, mesh, paper or any combination thereof.
优选地，所述工程塑料非织造布的制造原料为：聚醚砜、聚醚酰亚胺、聚苯硫醚、聚酰胺、聚四氟乙烯中的一种或多种的组合物。Preferably, the engineering plastic nonwoven fabric is made of one or more combinations of polyethersulfone, polyetherimide, polyphenylene sulfide, polyamide, and polytetrafluoroethylene.
优选地，所述树脂组分按重量百分比含量包括：基础树脂60％-80％、增韧剂5％-30％、阻燃剂15％-30％。Preferably, the resin component includes by weight percentage: 60%-80% of base resin, 5%-30% of toughening agent, and 15%-30% of flame retardant.
更优选地，所述基础树脂为环氧树脂、不饱和聚酯树脂或酚醛树脂中的一种。More preferably, the base resin is one of epoxy resin, unsaturated polyester resin or phenolic resin.
更优选地，所述增韧剂为纳米二氧化硅、核壳结构橡胶粒子、丁腈橡胶、氢化丁腈橡胶、端胺基丁腈橡胶、端羧基丁腈橡胶中的一种或多种的组合。More preferably, the toughening agent is one or more of nano-silica, core-shell rubber particles, nitrile rubber, hydrogenated nitrile rubber, amino-terminated nitrile rubber, carboxyl-terminated nitrile rubber combination.
更优选地，所述阻燃剂为磷酸酯类、含磷环氧类、三聚氰胺磷酸盐、聚磷酸铵、三聚氰胺、微胶囊化红磷、氢氧化铝、氢氧化镁中的一种或多种的组合物。More preferably, the flame retardant is one or more of phosphoric acid esters, phosphorus-containing epoxy, melamine phosphate, ammonium polyphosphate, melamine, microencapsulated red phosphorus, aluminum hydroxide, and magnesium hydroxide Compositions.
优选地，所述工程塑料非织造布与碳纤维织物、玻璃纤维织物、芳纶纤维织物中的一种或多种进行任意组合顺序的铺放后，与树脂组分通过真空辅助树脂注射或手糊工艺成型，经加热和/或加压固化，得到含工程塑料非织造布的阻燃混杂层合板。Preferably, the engineering plastic nonwoven fabric and one or more of carbon fiber fabrics, glass fiber fabrics, and aramid fiber fabrics are placed in any combination sequence, and then mixed with the resin components by vacuum-assisted resin injection or hand lay-up. Process molding, heating and/or pressure curing, to obtain a flame-retardant hybrid laminate containing engineering plastic non-woven fabrics.
本发明所用的工程塑料非织造布来源广泛，可利用回收产品，制得的混杂阻燃层合板具有成本低、比强度和比模量高、阻燃性好的优点，不仅具有可观的经济价值，还有重要的环保意义。The engineering plastic non-woven fabric used in the present invention has a wide range of sources, and recycled products can be used. The hybrid flame-retardant laminated board produced has the advantages of low cost, high specific strength and specific modulus, and good flame retardancy, and not only has considerable economic value , as well as important environmental significance.
附图说明Description of drawings
图1为实施例1中两层碳纤维平纹织物-两层聚苯硫醚针刺毡-两层碳纤维平纹织物的铺层示意图。Fig. 1 is the layup schematic diagram of two layers of carbon fiber plain weave fabric - two layers of polyphenylene sulfide needle felt - two layers of carbon fiber plain weave fabric in Example 1.
具体实施方式Detailed ways
下面结合具体实施例，进一步阐述本发明。Below in conjunction with specific embodiment, further illustrate the present invention.
实施例1Example 1
在一涂有脱模剂的平板钢化玻璃上，将聚苯硫醚针刺毡(面密度：400gsm，安徽元琛环保科技有限公司)和碳纤维平纹织物HF20-12K(江苏恒神股份有限公司)按下面铺层方法铺层：两层碳纤维平纹织物1-两层聚苯硫醚针刺毡2-两层碳纤维平纹织物1，如图1所示，形成预制体。On a flat tempered glass coated with a release agent, polyphenylene sulfide needle felt (area density: 400gsm, Anhui Yuanchen Environmental Protection Technology Co., Ltd.) and carbon fiber plain fabric HF20-12K (Jiangsu Hengshen Co., Ltd.) Lay layers according to the following laying method: two layers of carbon fiber plain weave fabric 1-two layers of polyphenylene sulfide needle felt 2-two layers of carbon fiber plain weave fabric 1, as shown in Figure 1, to form a prefabricated body.
在预制体上铺放脱模布和导流网，其中脱模布应完全覆盖住预制体，导流网的边缘距离预制体边缘约3cm。随后打真空袋密封，并铺设一个树脂入口和一个树脂出口，用阀门控制其开关。连接真空泵，检查真空袋的气密性，确认气密性完好后，配制树脂组分。Lay release cloth and deflector net on the prefabricated body, wherein the release cloth should completely cover the prefabricated body, and the edge of the deflected net is about 3cm away from the edge of the prefabricated body. Then make a vacuum bag to seal it, and lay a resin inlet and a resin outlet, and use a valve to control its switch. Connect the vacuum pump, check the airtightness of the vacuum bag, and prepare the resin components after confirming that the airtightness is intact.
在一搅拌釜内按重量百分含量分别加入42％环氧树脂4324A(广东博汇新材)、18％环氧树脂固化剂4324B(广东博汇新材)、10％硅橡胶核壳粒子增韧剂ALBIDUR@EP-2240A(德国赢创工业)和30％环状磷酸酯阻燃剂FR-CU(江苏立思德化工)，搅拌均匀后，在真空下脱气30min，倒入塑料容器内，插入导胶管。Add 42% epoxy resin 4324A (Guangdong Bohui New Materials), 18% epoxy resin curing agent 4324B (Guangdong Bohui New Materials), 10% silicone rubber core-shell particle additives in a stirred tank according to weight percentage. Toughener ALBIDUR@EP-2240A (Germany Evonik Industry) and 30% cyclic phosphate flame retardant FR-CU (Jiangsu Liside Chemical Industry), after stirring evenly, degas under vacuum for 30min, pour it into a plastic container , insert the guide tube.
打开真空袋两侧的树脂进、出口阀门及真空泵，在真空辅助下开始注胶，将预制体充分浸润后，多余的树脂从出口抽出。Open the resin inlet and outlet valves and vacuum pumps on both sides of the vacuum bag, and start to inject glue with the assistance of vacuum. After the preform is fully infiltrated, the excess resin is drawn out from the outlet.
注胶结束后，关闭阀门，在室温下固化6小时，最后在80℃下后固化4小时，脱模后得到含工程塑料非织造布的混杂层合板。所得混杂层合板的性能如下：树脂含量43％，弯曲强度(ASTM-D790)215MPa，弯曲模量(ASTM-D790)9265MPa，玻璃化转变温度(动态力学分析仪)85℃，极限氧指数(GB/T2406)34。After the glue injection, the valve was closed, cured at room temperature for 6 hours, and finally post-cured at 80°C for 4 hours, and a hybrid laminate containing engineering plastic nonwovens was obtained after demoulding. The performance of gained hybrid laminate is as follows: resin content 43%, flexural strength (ASTM-D790) 215MPa, flexural modulus (ASTM-D790) 9265MPa, glass transition temperature (dynamic mechanical analyzer) 85 ℃, limiting oxygen index (GB /T2406) 34.
实施例2Example 2
在一涂有脱模剂的平板钢化玻璃上，将回收清理后的旧聚四氟乙烯增强聚苯硫醚针刺毡(面密度：1000gsm)和玻纤平纹织物(苏州久恒玻纤织造有限公司)按下面铺层方法铺层：两层玻纤平纹织物-两层聚四氟乙烯增强聚苯硫醚针刺毡-两层玻纤平纹织物，形成预制体。On a flat tempered glass coated with a release agent, the recycled and cleaned old PTFE reinforced polyphenylene sulfide needle felt (area density: 1000gsm) and glass fiber plain fabric (Suzhou Jiuheng Glass Fiber Weaving Co., Ltd. ) Lay layers according to the following laying method: two layers of glass fiber plain weave fabric - two layers of polytetrafluoroethylene reinforced polyphenylene sulfide needle felt - two layers of glass fiber plain weave fabric to form a prefabricated body.
在一搅拌釜内按重量百分含量分别加入78％不饱和聚酯HR-802J(常州市华润复合材料有限公司)、2％引发剂V388(北京科瑞迪特化工有限公司)、5％氢化丁腈橡胶Therban 3446(上海品氟实业有限公司)和15％聚磷酸铵(济宁佰一化工有限公司)，搅拌均匀后，在真空下脱气30min，倒入塑料容器内，待用。Add 78% unsaturated polyester HR-802J (Changzhou China Resources Composite Material Co., Ltd.), 2% initiator V388 (Beijing Keruidite Chemical Co., Ltd.), 5% hydrogenation Nitrile rubber Therban 3446 (Shanghai Pinfu Industrial Co., Ltd.) and 15% ammonium polyphosphate (Jining Baiyi Chemical Co., Ltd.), after being stirred evenly, were degassed under vacuum for 30 minutes, poured into a plastic container, and set aside.
在一涂有脱模剂的平板钢化玻璃上，将预制体与上述树脂组分通过手糊工艺成型，在室温下放置24h后，转移至热压机中，在压力为0.3MPa下，经温度80℃固化4h，制得混杂层合板。所得混杂层合板的性能如下：树脂含量44％，弯曲强度(ASTM-D790)192MPa，弯曲模量(ASTM-D790)7825MPa，玻璃化转变温度(动态力学分析仪)84℃，极限氧指数(GB/T2406)37。On a flat tempered glass coated with a release agent, the preform and the above resin components are hand-laid into shape. After standing at room temperature for 24 hours, they are transferred to a hot press. Under a pressure of 0.3MPa, the temperature Cured at 80°C for 4 hours to obtain a hybrid laminate. The performance of gained hybrid laminate is as follows: resin content 44%, flexural strength (ASTM-D790) 192MPa, flexural modulus (ASTM-D790) 7825MPa, glass transition temperature (dynamic mechanical analyzer) 84 ℃, limiting oxygen index (GB /T2406) 37.
以上所述，仅为本发明的较佳实施例，并非对本发明任何形式上和实质上的限制，应当指出，对于本技术领域的普通技术人员，在不脱离本发明方法的前提下，还将可以做出若干改进和补充，这些改进和补充也应视为本发明的保护范围。凡熟悉本专业的技术人员，在不脱离本发明的精神和范围的情况下，当可利用以上所揭示的技术内容而做出的些许更动、修饰与演变的等同变化，均为本发明的等效实施例；同时，凡依据本发明的实质技术对上述实施例所作的任何等同变化的更动、修饰与演变，均仍属于本发明的技术方案的范围内。The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any form and in essence. Several improvements and supplements can be made, and these improvements and supplements should also be regarded as the protection scope of the present invention. Those who are familiar with this profession, without departing from the spirit and scope of the present invention, when they can use the technical content disclosed above to make some changes, modifications and equivalent changes of evolution, are all included in the present invention. Equivalent embodiments; at the same time, all changes, modifications and evolutions of any equivalent changes made to the above-mentioned embodiments according to the substantive technology of the present invention still belong to the scope of the technical solution of the present invention.
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