CN109971112A - A kind of spray-free ABS composite material suitable for FDM and preparation method - Google Patents
A kind of spray-free ABS composite material suitable for FDM and preparation method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 89
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 51
- 239000000049 pigment Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 15
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 238000005507 spraying Methods 0.000 claims abstract description 9
- 239000002023 wood Substances 0.000 claims abstract description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims abstract 9
- 238000001125 extrusion Methods 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 25
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 14
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004595 color masterbatch Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 7
- 229910052618 mica group Inorganic materials 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000005469 granulation Methods 0.000 abstract description 9
- 230000003179 granulation Effects 0.000 abstract description 9
- 239000003086 colorant Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
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- 238000007639 printing Methods 0.000 description 8
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- 238000007254 oxidation reaction Methods 0.000 description 6
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004610 Internal Lubricant Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000430525 Aurinia saxatilis Species 0.000 description 1
- -1 acrylonitrile-butanediol Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 235000013312 flour Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007592 spray painting technique Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 238000012549 training Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0831—Gold
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
技术领域technical field
本发明属于FDM成形领域,更具体地,涉及一种适用于FDM的免喷涂ABS复合材料及制备方法一种适用于FDM的免喷涂ABS复合材料及制备方法。The invention belongs to the field of FDM forming, and more particularly relates to a spray-free ABS composite material suitable for FDM and a preparation method thereof, and a spray-free ABS composite material suitable for FDM and a preparation method.
背景技术Background technique
熔融沉积(Fused Deposition Modeling,FDM)是广为人知的一种增材制造方式,常见于3D打印培训机构等一些面向于大众的场合。由于其原理相对简单,设备较小,仅仅需要购买打印耗材就能长期使用,维护成本也较小,FDM式打印机在广大创客空间中均有出现。原理上只要想得到,均可以快速制作出实物,在办公室内就可以迅速让想法得到实现,因此受到了大量的追捧。Fused Deposition Modeling (FDM) is a well-known additive manufacturing method, which is commonly used in 3D printing training institutions and other public-oriented occasions. Because of its relatively simple principle and small equipment, it can be used for a long time only by purchasing printing consumables, and the maintenance cost is also small. FDM printers have appeared in the vast maker space. In principle, as long as you can think of it, you can quickly make a real object, and you can quickly realize the idea in the office, so it is highly sought after.
FDM成形方式中使用最多的材料为PLA,ABS,PC,TPU等,在这,些材料中,ABS材料价格便宜,经久耐用,稍有弹性,质量轻,容易挤出,综合性能良好,是3D打印材料中最稳定的一种材质等特点而受到较广泛应用。ABS塑料由丙烯腈20%-30%,丁二烯6%-30%,苯乙烯45%-70%,构成的三元共聚物,每一组分赋予ABS不同的性能,并表现出很好的协同作用。丙烯腈使其耐化学腐蚀、耐热,并有一定的表面硬度,丁二烯使其具有高弹性和韧性,苯乙烯使其具有表面高光泽性、易着色性和易加工性。The most used materials in FDM forming methods are PLA, ABS, PC, TPU, etc. Among these materials, ABS materials are cheap, durable, slightly elastic, light in weight, easy to extrude, and have good overall performance. It is widely used due to the characteristics of the most stable material in printing materials. ABS plastic is a terpolymer composed of acrylonitrile 20%-30%, butadiene 6%-30%, styrene 45%-70%, each component gives ABS different properties, and shows good performance synergy. Acrylonitrile makes it resistant to chemical corrosion and heat, and has a certain surface hardness, butadiene makes it have high elasticity and toughness, and styrene makes it have high surface gloss, easy coloring and easy processing.
通用级ABS树脂外观为乳白色,无法满足实际应用中各种颜色的需求。采用传统的喷涂工艺:预处理,喷涂,固化,清理造成成本高,生产流程长,效率低,良品率低,非环保,污染环境,对操作者健康造成损害,安全风险大,而且难循环使用,和FDM成形方式的快速个性化定制不符,总之,现有技术中缺乏一种免喷涂的适用于FDM的的ABS复合材料。The appearance of general-purpose ABS resin is milky white, which cannot meet the needs of various colors in practical applications. Using traditional spraying process: pretreatment, spraying, curing, and cleaning cause high cost, long production process, low efficiency, low yield, non-environmental protection, environmental pollution, damage to operator's health, high safety risk, and difficult to recycle , which is inconsistent with the rapid customization of FDM forming methods. In short, there is a lack of a spray-free ABS composite material suitable for FDM in the prior art.
发明内容SUMMARY OF THE INVENTION
针对现有技术的以上缺陷或改进需求,本发明提供了一种适用于FDM的免喷涂ABS复合材料及制备方法,通过在在ABS中添加颜料形成复合材料,该复合材料的颜色可通过调节加入颜料的颜色进行改变,当该复合材料应用在FDM打印中时,即可打印出不同颜色的产品,免除后续的喷涂工艺,实现产品颜色的定制。In view of the above defects or improvement needs of the prior art, the present invention provides a spray-free ABS composite material suitable for FDM and a preparation method. The composite material is formed by adding pigments in ABS, and the color of the composite material can be added by adjusting The color of the pigment is changed. When the composite material is used in FDM printing, products of different colors can be printed, eliminating the subsequent spraying process and realizing the customization of product color.
为实现上述目的,按照本发明的一个方面,提供了一种适用于FDM的免喷涂ABS复合材料及制备方法,其特征在于,其原料按照质量份计包括:80~100份丙烯腈-丁二烯-苯乙烯原料,2~10份颜料,0.4~2份偶联剂,0~10份相容剂,0.4~1.5份加工助剂和0.1~0.5份抗氧剂,其中,所述颜料用于改变所述复合材料的颜色。In order to achieve the above object, according to one aspect of the present invention, a spray-free ABS composite material suitable for FDM and a preparation method are provided, wherein the raw materials include, in parts by mass: 80-100 parts of acrylonitrile-butanediol ene-styrene raw material, 2-10 parts of pigments, 0.4-2 parts of coupling agent, 0-10 parts of compatibilizer, 0.4-1.5 parts of processing aids and 0.1-0.5 parts of antioxidants, wherein the pigments are made of to change the color of the composite.
进一步优选地,所述颜料优选粒径为100目~400目的金,银,铜,铝,铁,硅,木粉,云母粉,色母粉末中的一种或几种,材料的加入会和ABS材料均匀混合,使得打印出的零件具有相应的金属颜色,100目到400目粒径粉末的选择有利于保证打印零件颜色的最佳表现效果,较大粒径的粉末会使得零件的表面看起来有颗粒感,而较小粒径的粉末很容易黏附在ABS材料的表面,很难做到让粉末在ABS材料中均匀混合。Further preferably, the pigment preferably has a particle size of 100 mesh to 400 mesh, one or more of gold, silver, copper, aluminum, iron, silicon, wood powder, mica powder, and color masterbatch powder. The ABS material is evenly mixed, so that the printed parts have the corresponding metal color. The selection of 100-mesh to 400-mesh particle size powder is conducive to ensuring the best performance of the color of the printed parts. The larger particle size powder will make the surface of the part look bad. It has a grainy feel, and the powder with smaller particle size is easy to adhere to the surface of the ABS material, and it is difficult to make the powder evenly mixed in the ABS material.
进一步优选地,所述丙烯腈-丁二烯-苯乙烯中各单体的质量百分比含量优选为20%~30%丙烯腈,6%~30%丁二烯和45%~70%苯乙烯,丙烯腈使得材料耐化学腐蚀,耐热,丁二烯使得材料具有高弹性和韧性,苯乙烯使得材料具有热塑性材料的加工塑性。Further preferably, the mass percentage content of each monomer in the acrylonitrile-butadiene-styrene is preferably 20%-30% acrylonitrile, 6%-30% butadiene and 45%-70% styrene, Acrylonitrile makes the material resistant to chemical corrosion and heat, butadiene makes the material highly elastic and tough, and styrene makes the material have the processing plasticity of thermoplastic materials.
进一步优选地,所述偶联剂优选为硅烷偶联剂,钛酸酯偶联剂中的一种或几种,所述的偶联剂和ABS材料进行反应而结合,同时水解而与无机粉末结合,将无机粉末和ABS材料结合起来。Further preferably, the coupling agent is preferably one or more of a silane coupling agent and a titanate coupling agent. The coupling agent reacts with the ABS material to combine, and is hydrolyzed to combine with the inorganic powder. Combine, combine inorganic powder and ABS material.
进一步优选地,所述相容剂优选为ST-4,ST-8,ST-9中的一种或几种,相容剂可以和ABS树脂及无机粉末之间发生物理和化学的作用而形成分子间的键合力,使得粉末更好的分散并和ABS材料结合。Further preferably, the compatibilizer is preferably one or more of ST-4, ST-8, ST-9, and the compatibilizer can be formed by physical and chemical action with ABS resin and inorganic powder. The bonding force between molecules makes the powder better dispersed and combined with ABS material.
进一步优选地,所述加工助剂优选为EBS,添加量为0.5%-1.5%,EBS与ABS树脂有一定的相容性,能降低ABS分子间的相互作用力,起到内润滑剂的作用,同时可从熔体内部迁移到表面,减少ABS材料之间,材料与加工设备之间的摩擦,提高材料的成形尺寸,改善制品的外观。Further preferably, the processing aid is preferably EBS, the addition amount is 0.5%-1.5%, EBS has a certain compatibility with ABS resin, can reduce the interaction force between ABS molecules, and play the role of internal lubricant At the same time, it can migrate from the inside of the melt to the surface, reduce the friction between ABS materials, between materials and processing equipment, increase the forming size of materials, and improve the appearance of products.
进一步优选地,所述抗氧剂优选为抗氧剂168或抗氧剂618中的一种或几种,抗氧剂的使用能与ABS树脂氧化产生的自由基反应,生成稳定物质,阻止ABS氧化反应的循环进行。Further preferably, the antioxidant is preferably one or more of the antioxidant 168 or the antioxidant 618. The use of the antioxidant can react with the free radicals generated by the oxidation of the ABS resin to generate stable substances and prevent ABS. The cycle of oxidation reaction proceeds.
按照本发明的另一方面,提供了一种如上述所述的免喷涂ABS复合材料的制备方法,其特征在于,该方法包括下列步骤:按照上述比例选取各个原料后,将所有原料混合后经双螺杆改性造粒形成复合材料颗粒,然后将复合材料颗粒采用单螺杆挤出成形,获得所需的免喷涂ABS复合材料丝材。According to another aspect of the present invention, there is provided a method for preparing a spray-free ABS composite material as described above, characterized in that the method comprises the following steps: after selecting each raw material according to the above ratio, mixing all the raw materials, The twin-screw modified granulation forms composite material particles, and then the composite material particles are extruded with a single screw to obtain the desired spray-free ABS composite material wire.
总体而言,通过本发明所构思的以上技术方案与现有技术相比,能够取得下列有益效果:In general, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:
1、本发明提供的适用于FDM成形方式的免喷涂ABS复合材料可以一次性成形具有制造出具有金属色、仿木、仿石等特定颜色的三维实体零件,扩大现有ABS材料的颜色范围,免去了喷涂流程,提高了生产效率,缩短了获得成品的时间,进一步提高了FDM打印方式相对于传统加工方式的竞争力,而且更环保,有利于工作人员的健康安全;1. The spray-free ABS composite material suitable for the FDM forming method provided by the present invention can produce three-dimensional solid parts with specific colors such as metallic color, imitation wood, imitation stone, etc. at one time, and expand the color range of the existing ABS material, It eliminates the spraying process, improves production efficiency, shortens the time to obtain finished products, further improves the competitiveness of FDM printing method compared to traditional processing methods, and is more environmentally friendly, which is beneficial to the health and safety of workers;
2、本发明中通过选取金,银,铜,铝,铁,硅,木粉,云母粉,色母粉末中的一种或几种作为颜料,其目的在于获得一种适用于FDM的免喷涂ABS材料,所用的颜料覆盖现有喷涂材料的全部颜色,按照本发明专利的步骤可以得到目前所需要的各种颜色的ABS丝材,免去了传统的喷涂工艺,所获得的丝材具有一定的抗氧化性能,同时颜料很均匀地分散在ABS材料的各部分,没有色差,没有颗粒感,具有良好的外观,所述的材料具有很好的遮盖力,能有效的遮盖住ABS材料氧化而导致的泛黄颜色,避免传统喷漆工艺带来的气泡,针孔,鱼眼,流挂,橘皮,波浪纹,掉漆,水印,色差等问题。2. In the present invention, one or more of gold, silver, copper, aluminum, iron, silicon, wood powder, mica powder, and color masterbatch powder are selected as pigments, and the purpose is to obtain a spray-free suitable for FDM. ABS material, the used pigments cover all the colors of the existing spraying materials, according to the steps of the patent of the present invention, the ABS wires of various colors required at present can be obtained, the traditional spraying process is omitted, and the obtained wires have certain characteristics. At the same time, the pigments are evenly dispersed in each part of the ABS material, there is no color difference, no graininess, and a good appearance. The material has good covering power and can effectively cover the ABS material. The resulting yellowing color avoids the problems of air bubbles, pinholes, fish eyes, sagging, orange peel, wavy lines, paint peeling, watermarks, chromatic aberration, etc. caused by the traditional spray painting process.
附图说明Description of drawings
图1是按照本发明的优选实施例所构建的适用于FDM的免喷涂ABS复合材料及制备方法流程图。FIG. 1 is a flow chart of a spray-free ABS composite material suitable for FDM and a preparation method constructed according to a preferred embodiment of the present invention.
具体实施方式Detailed ways
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。此外,下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
本发明提供的一种适用于FDM的免喷涂ABS复合材料的制备方法,结合ABS材料染色特性及螺杆挤出机的特点进行筛粉和烘干处理,接着进行高速混合搅拌,随后经双螺杆改性造粒,最后由单螺杆挤出成形,得到适用于FDM成形方式的免喷涂ABS复合材料。The invention provides a preparation method of a spray-free ABS composite material suitable for FDM, which combines the dyeing characteristics of ABS materials and the characteristics of a screw extruder to carry out sieving and drying treatment, followed by high-speed mixing and stirring, followed by twin-screw modification. Finally, it is extruded by a single screw to obtain a spray-free ABS composite material suitable for FDM molding.
具体包括以下步骤:Specifically include the following steps:
(1)使用100目和400目的网筛筛选出具有合适粒径的特殊颜料,并进行烘干处理,烘干温度为45℃~55℃,以金,银,铜,铝,铁,硅,木粉,云母粉,色母粉末中的一种或几种为特殊颜料。色母为以ABS为载体的专用色母,色母比例为1:20用于ABS材料,使用前ABS色母需要进行烘干处理。(1) Use 100-mesh and 400-mesh mesh sieves to screen out special pigments with suitable particle sizes, and dry them at a drying temperature of 45°C to 55°C, using gold, silver, copper, aluminum, iron, silicon, One or more of wood powder, mica powder and color master powder are special pigments. The color masterbatch is a special color masterbatch with ABS as the carrier. The color masterbatch ratio is 1:20 for ABS materials. The ABS color masterbatch needs to be dried before use.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈20%~30%,丁二烯6%~30%,苯乙烯45%~70%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The monomer content of acrylonitrile-butadiene-styrene is 20% to 30% of acrylonitrile, 6% to 30% of butadiene, and 45% to 70% of styrene. The obtained ABS material is subjected to Drying treatment, drying temperature is 45 ℃ ~ 55 ℃.
(3)将下列重量比原料加入高速混合器中进行混合2~3个小时。其中偶联剂为硅烷偶联剂,钛酸酯偶联剂中的一种或几种,相容剂为ST-4,ST-8,ST-9中的一种或几种,加工助剂为EBS,抗氧剂为抗氧剂168或抗氧剂618中的一种或几种。(3) The following weight ratio raw materials are added to a high-speed mixer and mixed for 2 to 3 hours. Wherein the coupling agent is one or more of silane coupling agent, titanate coupling agent, compatibilizer is one or more of ST-4, ST-8, ST-9, processing aid For EBS, the antioxidant is one or more of Antioxidant 168 or Antioxidant 618.
丙烯腈-丁二烯-苯乙烯原料:80~100份Acrylonitrile-butadiene-styrene raw material: 80~100 parts
特殊颜料:2~10份,在不影响ABS材料机械性能的前提下,能得到很好的颜色效果,遮盖原有ABS材料氧化导致的泛黄颜色。Special pigment: 2-10 parts, under the premise of not affecting the mechanical properties of the ABS material, it can get a good color effect and cover the yellow color caused by the oxidation of the original ABS material.
偶联剂:0.4~2份,根据所加颜料的不同选择不同含量的偶联剂,通过偶联剂和ABS材料及颜料粉末的化学反应即可将颜料和ABS材料很好的结合。Coupling agent: 0.4 to 2 parts, choose different content of coupling agent according to the different pigments added, through the chemical reaction of coupling agent and ABS material and pigment powder, the pigment and ABS material can be well combined.
相容剂:0~10份,相容剂可以和ABS材料及颜料粉末之间发生物理化学的作用而形成分子间的键合力,使得颜料粉末更好的分散并和ABS材料结合,根据相应的颜料选择不同的份数。Compatibilizer: 0-10 parts, the compatibilizer can interact with the ABS material and the pigment powder to form intermolecular bonding force, so that the pigment powder can be better dispersed and combined with the ABS material. Choose from different servings of paint.
加工助剂:0.4~1.5份,加工助剂与ABS树脂有一定的相容性,能降低ABS分子间的相互作用力,起到内润滑剂的作用,同时可从熔体内部迁移到表面,减少ABS材料之间,材料与加工设备之间的摩擦,提高材料的成形尺寸,改善制品的外观,根据加入的颜料选择不同的分数。Processing aid: 0.4~1.5 parts, the processing aid has a certain compatibility with ABS resin, can reduce the interaction force between ABS molecules, play the role of internal lubricant, and can migrate from the inside of the melt to the surface, Reduce friction between ABS materials and between materials and processing equipment, increase the forming size of materials, and improve the appearance of products. Different fractions are selected according to the added pigments.
抗氧剂:0.1~0.5份,抗氧剂的使用能与ABS树脂氧化产生的自由基反应,生成稳定物质,阻止ABS氧化反应的循环进行,避免了ABS材料氧化导致的泛黄颜色,根据所选颜料的遮盖力程度选择不同份数的抗氧剂。Antioxidant: 0.1-0.5 parts, the use of antioxidant can react with the free radicals generated by the oxidation of ABS resin to generate stable substances, prevent the cycle of ABS oxidation reaction, and avoid the yellowing color caused by the oxidation of ABS material. Choose the degree of hiding power of the pigment to choose different parts of antioxidants.
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到复合材料(5) Putting the modified particles into a single screw and extruding to obtain a composite material
综上所述,本发明的总体思路主要包括以下三个方面,一是按照要求准备特定要求的材料;二是将准备的材料放入高速混合器中进行混合;三是将混合的材料经双螺杆改性造粒,然后由单螺杆挤出成形获得适用于FDM成形方式的免喷涂ABS复合材料。To sum up, the general idea of the present invention mainly includes the following three aspects: one is to prepare materials with specific requirements according to the requirements; the other is to put the prepared materials into a high-speed mixer for mixing; Screw modified granulation, and then extruded by a single screw to obtain a spray-free ABS composite material suitable for FDM molding.
下面将结合具体的实施例对本发明的方案进行进一步的说明。The solution of the present invention will be further described below with reference to specific embodiments.
实施例1Example 1
(1)使用100目和400目的网筛筛选金粉并进行烘干处理,烘干温度为60℃~70℃。(1) Use 100-mesh and 400-mesh mesh sieves to screen the gold powder and dry it at a drying temperature of 60°C to 70°C.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈25%,丁二烯10%,苯乙烯65%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The content of each monomer of acrylonitrile-butadiene-styrene is 25% of acrylonitrile, 10% of butadiene, and 65% of styrene, and the obtained ABS material is subjected to drying treatment, and the drying temperature is 45% ℃~55℃.
(3)将下列重量比原料加入高速混合器中进行混合2个小时。(3) The following weight ratio raw materials were added to a high-speed mixer and mixed for 2 hours.
丙烯腈-丁二烯-苯乙烯原料:80份Acrylonitrile-butadiene-styrene raw material: 80 parts
金粉:3份Gold Dust: 3 servings
硅烷偶联剂:1份Silane coupling agent: 1 part
ST-4:2份ST-4: 2 servings
EBS:1份EBS: 1 serving
抗氧剂168:0.2份Antioxidant 168: 0.2 servings
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到带有金色的ABS复合材料。经FDM成形方式加工打印,得到带有金色的ABS零件。(5) Putting the modified particles into a single screw and extruding to obtain a gold-colored ABS composite material. Processed and printed by FDM forming method to obtain ABS parts with gold color.
实施例2Example 2
(1)使用100目和400目的网筛筛选银粉,并进行烘干处理,烘干温度为60℃~70℃。(1) Use 100-mesh and 400-mesh mesh sieves to screen the silver powder, and carry out drying treatment, and the drying temperature is 60 ℃ ~ 70 ℃.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈22%,丁二烯15%,苯乙烯63%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The monomer contents of acrylonitrile-butadiene-styrene are: 22% of acrylonitrile, 15% of butadiene, 63% of styrene, and the obtained ABS material is subjected to drying treatment, and the drying temperature is 45% ℃~55℃.
(3)将下列重量比原料加入高速混合器中进行混合2.5个小时。(3) The following weight ratio raw materials were added to a high-speed mixer and mixed for 2.5 hours.
丙烯腈-丁二烯-苯乙烯原料:85份Acrylonitrile-butadiene-styrene raw material: 85 parts
银粉:10份Silver powder: 10 servings
硅烷偶联剂:0.4份Silane coupling agent: 0.4 part
ST-8:3份ST-8: 3 servings
EBS:0.8份EBS: 0.8 servings
抗氧剂618:0.5份Antioxidant 618: 0.5 parts
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到带有银色的ABS复合材料。经FDM成形方式加工打印,得到带有银色的ABS零件。(5) Putting the modified particles into a single screw and extruding to obtain a silver-colored ABS composite material. After processing and printing by FDM forming method, ABS parts with silver color are obtained.
实施例3Example 3
(1)使用100目和400目的网筛筛选木粉,并进行烘干处理,烘干温度为45℃~55℃。(1) Use 100-mesh and 400-mesh mesh sieves to screen the wood powder, and dry it at a drying temperature of 45°C to 55°C.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈20%,丁二烯20%,苯乙烯60%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The monomer content of acrylonitrile-butadiene-styrene is 20% of acrylonitrile, 20% of butadiene, and 60% of styrene, and the obtained ABS material is subjected to drying treatment, and the drying temperature is 45% ℃~55℃.
(3)将下列重量比原料加入高速混合器中进行混合3个小时。(3) The following weight ratio raw materials were added to a high-speed mixer and mixed for 3 hours.
丙烯腈-丁二烯-苯乙烯原料:90份Acrylonitrile-butadiene-styrene raw material: 90 parts
木粉:2份Wood flour: 2 servings
钛酸酯偶联剂:1份Titanate coupling agent: 1 part
ST-9:10份ST-9: 10 servings
EBS:1份EBS: 1 serving
抗氧剂618:0.3份Antioxidant 618: 0.3 parts
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到带有木色的ABS复合材料。经FDM成形方式加工打印,得到带有木色的ABS零件。(5) Putting the modified particles into a single screw and extruding to obtain a wood-colored ABS composite material. After processing and printing by FDM forming method, ABS parts with wood color are obtained.
实施例4Example 4
(1)使用100目和400目的网筛筛选云母粉,并进行烘干处理,烘干温度为50℃~60℃。(1) Use 100-mesh and 400-mesh mesh sieves to screen the mica powder, and dry it at a drying temperature of 50°C to 60°C.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈25%,丁二烯15%,苯乙烯60%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The content of each monomer of acrylonitrile-butadiene-styrene is 25% of acrylonitrile, 15% of butadiene, and 60% of styrene, and the obtained ABS material is subjected to drying treatment, and the drying temperature is 45% ℃~55℃.
(3)将下列重量比原料加入高速混合器中进行混合3个小时。(3) The following weight ratio raw materials were added to a high-speed mixer and mixed for 3 hours.
丙烯腈-丁二烯-苯乙烯原料:85份Acrylonitrile-butadiene-styrene raw material: 85 parts
云母粉:4份Mica Powder: 4 servings
硅烷偶联剂:0.5份Silane coupling agent: 0.5 part
ST-4:3份ST-4: 3 servings
EBS:0.4份EBS: 0.4 servings
抗氧剂168:0.1份Antioxidant 168: 0.1 serving
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到带有云母色的ABS复合材料。经FDM成形方式加工打印,得到带有云母色的ABS零件。(5) Putting the modified particles into a single screw and extruding to obtain an ABS composite material with mica color. After processing and printing by FDM forming method, ABS parts with mica color are obtained.
实施例5Example 5
(1)将以ABS为载体的专用ABS色母进行烘干处理,烘干温度为45℃~55℃。(1) Dry the special ABS color masterbatch with ABS as the carrier, and the drying temperature is 45℃~55℃.
(2)丙烯腈-丁二烯-苯乙烯的各单体含量为,丙烯腈30%,丁二烯20%,苯乙烯50%,将获得的ABS材料进行烘干处理,烘干温度为45℃~55℃。(2) The monomer content of acrylonitrile-butadiene-styrene is 30% of acrylonitrile, 20% of butadiene, and 50% of styrene, and the obtained ABS material is subjected to drying treatment, and the drying temperature is 45% ℃~55℃.
(3)将下列重量比原料加入高速混合器中进行混合3个小时。(3) The following weight ratio raw materials were added to a high-speed mixer and mixed for 3 hours.
丙烯腈-丁二烯-苯乙烯原料:100份Acrylonitrile-butadiene-styrene raw material: 100 parts
色母:4.5份Masterbatch: 4.5 copies
钛酸酯偶联剂:2份Titanate coupling agent: 2 parts
ST-8:1.5份ST-8: 1.5 servings
EBS:0.5份EBS: 0.5 servings
抗氧剂168:0.1份Antioxidant 168: 0.1 serving
(4)将混合好的材料放入双螺杆中进行改性造粒。(4) Put the mixed material into the twin screw for modified granulation.
(5)将改性颗粒放入单螺杆中挤出成形得到带有色母颜色的ABS复合材料。经FDM成形方式加工打印,得到带有色母颜色的ABS零件。(5) Putting the modified particles into a single screw and extruding to obtain an ABS composite material with a masterbatch color. After processing and printing by FDM forming method, ABS parts with masterbatch color are obtained.
本领域的技术人员容易理解,以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。Those skilled in the art can easily understand that the above are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, etc., All should be included within the protection scope of the present invention.
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