Composition for 3D printing EVA-based composite material, 3D printing EVA-based composite material and preparation method of 3D printing EVA-based composite material
By preparing EVA-based composite materials and combining them with tackifiers and plasticizers, the shortcomings of ABS and PLA have been overcome, providing a low-temperature printing, pollution-free and recyclable 3D printing material that improves the mechanical properties and environmental friendliness of the material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-07
- Publication Date
- 2026-04-07
AI Technical Summary
Existing 3D printing materials such as ABS have problems such as easy deformation due to cooling shrinkage, harsh printing conditions, high equipment requirements, limited molding accuracy, and release of harmful gases that pollute the environment. PLA, on the other hand, has poor heat resistance, is brittle, and is prone to mold growth, making it unable to meet the requirements for long-term use.
Using ethylene-vinyl acetate copolymer as the matrix, combined with tackifiers, viscosity modifiers and plasticizers, EVA-based composite materials were prepared. 3D printing materials were then prepared by melt extrusion, optimizing their mechanical properties and environmental friendliness.
It has achieved a 3D printing material that is low-temperature printing, pollution-free, has excellent mechanical properties, and is recyclable, overcoming the shortcomings of ABS and PLA, and improving the stability and environmental friendliness of the material.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
Technical Field
[0001] This invention relates to a composition for EVA-based composite materials used in 3D printing, a 3D printed EVA-based composite material and its preparation method, belonging to the field of polymer 3D printing consumables technology. Background Technology
[0002] 3D printing is an emerging technology that integrates computer software, materials science, mechanical engineering and many other fields in a systematic and comprehensive manner. Compared with traditional manufacturing methods such as injection molding and casting, 3D printing has advantages such as high-precision manufacturing of complex structures, saving materials and time, high design freedom and personalized customization. It is constantly breaking through the limits of product design, manufacturing and usage, bringing new development opportunities to traditional manufacturing industries. Among them, fused deposition modeling (FDM) technology, which does not rely on lasers but heats and melts various thermoplastic materials to form shapes, has been widely used in the civilian field due to its ease of operation and high cost performance.
[0003] Printing materials are the foundation and guarantee of 3D printing technology. Currently, the most common 3D printing polymer materials on the market include acrylonitrile-butadiene-styrene copolymer (ABS), polylactic acid (PLA), and nylon (PA). While ABS, as a commonly used 3D printing material, has advantages such as excellent mechanical properties, good heat resistance, and strong processability, it also has many drawbacks, including easy deformation due to cooling shrinkage, printing odor and toxicity, and limited molding precision. PLA is also a common 3D printing material. Its advantage is that it has no unpleasant odor when melted, but its poor mechanical properties, susceptibility to brittle fracture, and tendency to mold greatly limit the performance and application of printed objects, resulting in high costs and failing to meet the long-term development needs of enterprises.
[0004] In view of the above, it is necessary to iteratively update the existing composite materials used for 3D printing and develop a new type of 3D printing material that can meet the requirements of current additive manufacturing. Summary of the Invention
[0005] In view of the problems existing in the prior art, one of the objectives of the present invention is to provide an EVA-based composite material composition for 3D printing. When using this composition to prepare 3D printing materials, it can overcome the shortcomings of ABS and PLA, and achieve pollution-free, zero-emission and recyclable production. It is a new type of 3D printing material that is both green and can improve new quality productivity.
[0006] The second objective of this invention is to provide a method for preparing 3D printed EVA-based composite materials, which is simple and easy to industrialize.
[0007] The third objective of this invention is to provide a 3D printing EVA-based composite material. The 3D printing composite material provided by this invention is not only recyclable, but also has the characteristics of low printing temperature and excellent mechanical properties.
[0008] To achieve the above objectives, a first aspect of the present invention is to provide a composition for 3D printing of EVA-based composite materials, the composition comprising the following components by mass:
[0009] 60-75 parts of ethylene-vinyl acetate copolymer;
[0010] 10-20 parts of thickener;
[0011] 10-15 parts viscosity modifier;
[0012] Plasticizer 5-10 parts;
[0013] The tackifier is a petroleum resin and / or a hydrogenated petroleum resin, and the plasticizer is a phthalate.
[0014] This invention innovatively uses EVA as a matrix to prepare 3D printing materials. Combined with the synergistic effect of the tackifier, viscosity modifier and plasticizer in this invention, it is possible to obtain a 3D printing EVA-based composite material with low printing temperature, excellent mechanical properties, no pollution, long storage time and recyclability. This composite material can overcome the problems of ABS being prone to deformation due to cooling shrinkage, harsh printing conditions, high equipment requirements, limited molding accuracy and environmental pollution caused by the release of harmful gases (such as VOCs), and it can also overcome the shortcomings of PLA such as poor heat resistance, high brittleness and easy mold growth.
[0015] As a preferred embodiment, the tackifier is selected from at least one of aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, C5 hydrogenated petroleum resins, C9 hydrogenated petroleum resins, and hydrogenated aliphatic-aromatic copolymer petroleum resins. In this preferred embodiment, the prepared 3D printing material exhibits superior holding strength and interfacial strength.
[0016] As a more preferred embodiment, the tackifier is selected from at least one of C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin, and hydrogenated aliphatic-aromatic copolymer petroleum resin. In this preferred embodiment, not only are the holding strength and interfacial strength of the prepared 3D printing material superior, but the stability is also further enhanced.
[0017] As a preferred embodiment, the composition comprises the following components by weight: 64-70 parts of ethylene-vinyl acetate copolymer, 10-17 parts of tackifier, 10-15 parts of viscosity modifier, and 5-10 parts of plasticizer. Under this preferred embodiment, the prepared 3D printing material exhibits superior mechanical properties.
[0018] As a preferred embodiment, the viscosity modifier is wax.
[0019] As a more preferred embodiment, the viscosity modifier is selected from at least one of microcrystalline wax, paraffin wax, and polyethylene wax.
[0020] As a preferred embodiment, the plasticizer is dioctyl phthalate and / or dibutyl phthalate. In this preferred embodiment, the melting rate can be accelerated, the melt viscosity of the 3D printing material can be reduced, and the toughness and low-temperature resistance (low-temperature brittleness) of the 3D printing material can be improved.
[0021] As a preferred embodiment, the composition further includes a gloss enhancer, and the gloss enhancer content is 1 to 3 parts. The addition of the gloss enhancer gives the 3D printed product a certain gloss, making the product more aesthetically pleasing. Generally, a gloss enhancer of around 400 mesh, or even smaller particle size, is added to prevent nozzle clogging during the printing process.
[0022] As a more preferred embodiment, the brightener is selected from at least one of talc, quartz powder, and glass powder.
[0023] A second aspect of the present invention provides a method for preparing 3D printed EVA-based composite materials, the method comprising using the components of the composition described in the first aspect above, including:
[0024] The raw materials, including ethylene-vinyl acetate copolymer, tackifier, viscosity modifier and plasticizer, are mixed and then melt-extruded to obtain the product.
[0025] As a preferred embodiment, the temperature of the melt extrusion is 120~150℃.
[0026] A third aspect of the present invention is to provide a 3D-printed EVA-based composite material prepared by the preparation method described in the second aspect above.
[0027] As a preferred embodiment, the printing temperature of the 3D printed EVA-based composite material is 110~130℃, and there is no need to set the base plate temperature.
[0028] As a preferred embodiment, the mixing speed is 50~100 r / min and the mixing time is 10~30 min.
[0029] As a preferred embodiment, the printing speed of the 3D printed EVA-based composite material is 50~200 PPV.
[0030] Compared with the prior art, the present invention has at least the following advantages:
[0031] The 3D printing EVA-based composite material provided by this invention can overcome the problems of ABS, such as easy deformation due to cooling shrinkage, harsh printing conditions, high equipment requirements, limited molding accuracy, and environmental pollution caused by the release of harmful gases (such as VOCs), and can also overcome the shortcomings of PLA, such as poor heat resistance, high brittleness, and easy mold growth.
[0032] The novel recyclable 3D printing composite material provided by this invention has the advantages of low printing temperature, excellent mechanical properties, no pollution, long storage time and recyclability. Detailed Implementation
[0033] The endpoints and any values of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of the various ranges, the endpoint values of the various ranges and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.
[0034] In this invention, room temperature refers to 25±2℃.
[0035] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following specific embodiments. Obviously, the embodiments described below are only a part of the embodiments, and all other embodiments obtained by those skilled in the art without creative effort are still within the scope of protection of the present invention.
[0036] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this invention can be purchased from the market or prepared by existing methods.
[0037] Ethylene-vinyl acetate copolymer, model number 7470M, was purchased from Taiwan Plastics Industries Co., Ltd.
[0038] Brightener: Quartz powder, particle size less than 400 mesh.
[0039] Hydrogenated aliphatic-aromatic copolymer petroleum resin: model D0313, purchased from Shenzhen Yoshida Chemical Co., Ltd.
[0040] Aliphatic-aromatic copolymer petroleum resin: model D0204, purchased from Shenzhen Yoshida Chemical Co., Ltd.
[0041] C5 hydrogenated petroleum resin: model D309, purchased from Shenzhen Yoshida Chemical Co., Ltd.
[0042] C9 hydrogenated petroleum resin: model D0312, purchased from Shenzhen Yoshida Chemical Co., Ltd.
[0043] In the following examples, 1 part by mass means 1g.
[0044] Example 1
[0045] (1) At room temperature, the ethylene-vinyl acetate copolymer, tackifier, viscosity modifier, plasticizer and brightener are mixed at high speed and uniformly (rotation speed of 80 r / min, time of 20 min) to ensure that each component is completely dispersed;
[0046] (2) The mixed material is extruded into filament by a single screw extruder at 120°C and then wound up to obtain composite 3D printing filament.
[0047] For details on the types and amounts of each raw material used in this embodiment, please refer to Table 1.
[0048] Unless otherwise specified, the remaining examples follow the method of Example 1, except that the types and amounts of the substances used are different in each example, as detailed in Table 1.
[0049]
[0050] Example 7
[0051] This embodiment is carried out using a method similar to that of Example 1, except that an equal mass of aliphatic-aromatic copolymer petroleum resin is used instead of the hydrogenated aliphatic-aromatic copolymer petroleum resin in Example 1.
[0052] Example 8
[0053] This embodiment is carried out using a method similar to that of Example 1, except that the amount of ethylene-vinyl acetate copolymer is adjusted to 75 parts by mass.
[0054] The results showed that the material could be processed into usable rods and could also be printed, but the material's toughness was lower than that of Example 1, and the printed products were relatively soft.
[0055] Comparative Example 1
[0056] This comparative example was conducted using a method similar to that of Example 1, except that the amount of ethylene-vinyl acetate copolymer was adjusted to 55 parts by mass.
[0057] The results showed that the material could be processed into usable rods, but it was prone to crumbling during the printing process.
[0058] Comparative Example 2
[0059] This comparative example was conducted using a method similar to that of Example 1, except that the type of tackifier remained the same, and the amount of tackifier was adjusted to 22 parts by weight.
[0060] Comparative Example 3
[0061] This comparative example was conducted using a method similar to that of Example 1, except that the plasticizer was adjusted to be an equal mass of diisodecyl adipate.
[0062] The results showed that the material's processing properties were inadequate and it could not be extruded into shiny rods.
[0063] Test Example 1
[0064] The printing performance and mechanical properties of the composite 3D printing materials prepared in the above examples were tested. The mechanical properties were all tested using an XLW-PC universal testing machine at room temperature. The specific test results are shown in Table 2.
[0065] The mechanical property testing method is as follows: after melting the composite 3D printing material sample at 140℃, a sample with a length, thickness and width of 750mm×40mm×2mm is prepared. The mechanical properties are measured at room temperature (25℃) using an intelligent tensile testing machine according to standard GB / T 1040-1992.
[0066]
[0067] Test Example 2
[0068] The composite 3D printing material prepared in the above example was crushed, and the crushed waste was extruded into rods at 130°C using a single screw extruder to obtain recycled composite 3D printing rods. The mechanical properties of the obtained recycled composite 3D printing rods were tested using an XLW-PC universal testing machine at room temperature. The specific test results are shown in Table 3.
[0069] The mechanical property testing method is as follows: after melting the composite 3D printing material sample at 140℃, a sample with a length, thickness and width of 750mm×40mm×2mm is prepared. The mechanical properties are measured at room temperature (25℃) using an intelligent tensile testing machine according to standard GB / T 1040-1992.
[0070]
[0071] Test Example 3
[0072] The stability of the composite 3D printing materials prepared in Examples 1-6 and Example 7, as well as ABS and pLA, was tested using a weather resistance test. The materials were placed directly in a real environment, and changes in appearance, mechanical properties, and chemical properties were observed. The test results are as follows:
[0073] Examples 1-6: The prepared composite 3D printing materials showed no change after being left for 30 days.
[0074] Example 7: After 30 days, a light yellow color will appear on the surface, and the color change will be more obvious under ultraviolet light.
[0075] ABS: After about 30 days of storage, the luster will fade and the color will lighten. It is prone to photodegradation under ultraviolet light. After six months of outdoor exposure, the impact strength may decrease by 50%.
[0076] PLA: It may develop some mold after about 15 days of storage and is easily hydrolyzed.
[0077] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.
Claims
1. A composition for use in 3D printing of EVA-based composite materials, characterized in that: The composition comprises the following components by weight: 60-75 parts of ethylene-vinyl acetate copolymer; 10-20 parts of thickener; 10-15 parts viscosity modifier; Plasticizer 5-10 parts; The tackifier is a petroleum resin and / or a hydrogenated petroleum resin, and the plasticizer is a phthalate.
2. The composition for EVA-based composite materials used in 3D printing according to claim 1, characterized in that: The tackifier is selected from at least one of aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, C5 hydrogenated petroleum resins, C9 hydrogenated petroleum resins, and hydrogenated aliphatic-aromatic copolymer petroleum resins.
3. The composition for EVA-based composite materials used in 3D printing according to claim 2, characterized in that: The tackifier is selected from at least one of C5 hydrogenated petroleum resin, C9 hydrogenated petroleum resin, and hydrogenated aliphatic-aromatic copolymer petroleum resin.
4. A composition for 3D printing of EVA-based composite materials according to any one of claims 1 to 3, characterized in that: The viscosity modifier is a wax; And / or, the plasticizer is dioctyl phthalate and / or dibutyl phthalate.
5. The composition for EVA-based composite materials used in 3D printing according to claim 4, characterized in that: The viscosity modifier is selected from at least one of microcrystalline wax, paraffin wax, and polyethylene wax.
6. A composition for 3D printing of EVA-based composite materials according to any one of claims 1 to 3, characterized in that: The composition further includes a brightener, and the content of the brightener is 1 to 3 parts; Preferably, the brightener is selected from at least one of talc, quartz powder, and glass powder.
7. A method for preparing 3D printed EVA-based composite materials, characterized in that: This method is performed using any of the components in the composition according to any one of claims 1 to 6, comprising: The raw materials, including ethylene-vinyl acetate copolymer, tackifier, viscosity modifier and plasticizer, are mixed and then melt-extruded to obtain the product.
8. The method for preparing a 3D printed EVA-based composite material according to claim 7, characterized in that: The temperature of the melt extrusion is 120~150℃.
9. The 3D printed EVA-based composite material prepared by the preparation method according to any one of claims 7 to 8.
10. The 3D printed EVA-based composite material according to claim 9, characterized in that: The printing temperature of the 3D printed EVA-based composite material is 110~130℃, and there is no need to set the base plate temperature.