CN111334022A - PC/ABS blending modified material for 3D printing high-adhesion base plate - Google Patents
PC/ABS blending modified material for 3D printing high-adhesion base plate Download PDFInfo
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- CN111334022A CN111334022A CN202010082480.6A CN202010082480A CN111334022A CN 111334022 A CN111334022 A CN 111334022A CN 202010082480 A CN202010082480 A CN 202010082480A CN 111334022 A CN111334022 A CN 111334022A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a PC/ABS blending modified material for a 3D printing high-adhesion base plate, which comprises bisphenol A polycarbonate resin (PC resin), ABS resin and a solubilizer, wherein the melt index of the bisphenol A polycarbonate resin under the condition of 300 ℃/1.2kg is 8g/10 min-20 g/10min, the weight average molecular weight of the ABS resin is 120000-160000, the acrylonitrile content in the ABS resin is 20-30%, the butadiene content is 25-30%, the styrene content is 40-70%, the melt index of the ABS resin under the condition of 200 ℃/1.2kg is 10 g/min-15 g/min, and the mixing ratio of the bisphenol A polycarbonate resin to the ABS resin is 70: 30-80: 20. The invention is applicable to most consumables, and the model is easy to take out without edge warping.
Description
Technical Field
The invention relates to a 3D printing technology, in particular to a PC/ABS blending modified material for a 3D printing high-adhesion base plate.
Background
Pure ABS material is used as a printing bottom plate in the market at present, however, the thermal deformation temperature of pure ABS is only about 87 ℃, the highest printing bottom plate temperature required by printing consumables of FDM technology needs to reach about 100 ℃ (PEEK consumables need to reach 120 ℃), the thermal deformation temperature range of ABS is exceeded, once the bottom plate is thermally deformed, model printing is influenced and cannot be reused, the deformed bottom plate has problems of leveling, and in addition, no discussion is provided for the printing bottom plate material and the surface roughness thereof in the field at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a PC/ABS blending modified material for a 3D printing high-adhesion soleplate, which can solve the problems provided by the background art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the modified material comprises bisphenol A polycarbonate resin (PC resin), ABS resin and a solubilizer, wherein the melt index of the bisphenol A polycarbonate resin under the condition of 300 ℃/1.2kg is 8g/10 min-20 g/10min, the weight average molecular weight of the ABS resin is 120000-160000, the acrylonitrile content in the ABS resin is 20-30%, the butadiene content is 25-30%, and the styrene content is 40-70%, the melt index of the ABS resin under the condition of 200 ℃/1.2kg is 10 g/min-15 g/min, and the mixing ratio of the bisphenol A polycarbonate resin to the ABS resin is 70: 30-80: 20.
Preferably, the mixing ratio of the Polycarbonate (PC) and the ABS resin is 70: 30.
Preferably, the solubilizer is selected from one or more of ethylene-n-butyl acrylate copolymer (E-BA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), maleic anhydride grafted EVA resin (EVA-G-MHA) and ethylene-ethyl acrylate-maleic anhydride triblock copolymer (E-MA-MAH).
Preferably, the modifying material further comprises an antioxidant and a lubricant.
Preferably, the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, phenyl tris (2, 4-di-tert-butyl) phosphite and dioctadecyl pentaerythritol diphosphite, and the lubricant is selected from one or more of silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleamide and ethylene bisstearamide.
The invention has the beneficial effects that: the invention tests the influence of different materials of a PC bottom plate mixture ratio on the printing performance of different consumables, and relates to the surface roughness of the bottom plate material and the temperature of the bottom plate. Various composite materials such as lattice glass, black diamond glass, flexible composite bottom plates and the like are also available in the market, and the materials are relatively complex in preparation mode and relatively high in cost, and are not well popularized in the current 3D printing market environment of price fighting; and all need be equipped with the heating bottom plate system, the adhesion effect is relatively weak under the condition that the bottom plate does not heat, and the more than 400mm jumbo size of actual measurement is printed and is also appeared comparatively serious limit condition of sticking up.
After a PC board with the roughness of Ra0.025-Ra0.05 is used as a printing bottom board material (the thermal deformation temperature of the PC board is about 137 ℃, the impact resistance toughness is good, and the characteristics meet the characteristic requirements of a 3D printing bottom board material), PLA is used as a printing consumable material to be tested, the adhesion performance of the bottom board is found to be excellent, but a detachable model behind a circle of printing base is required to be shoveled by a shoveling knife if the adhesion performance of the bottom board is excessive; in addition, the surface adhesion performance of the roughened PC base plate (surface roughness Ra100) is stronger, and the model is not easy to shovel by a shovel blade. Through the peeling strength detection, the peeling strength of the smooth PC and PLA consumables heated to 60 ℃ at the bottom plate temperature reaches 73.5N/25mm, and a large amount of consumables remained on the bottom plate are difficult to remove. And the wear resistance of the PC material is poor, and after the model is shoveled for a plurality of times, the surface is inevitably rough, the roughness is increased, and the adhesion is also increased. Therefore, the PC material is mixed with other materials to prepare a blended alloy material, so that the heat deformation temperature is reduced to a certain extent, but the wear resistance and toughness of the PC material are improved to meet the requirements of the printing bottom plate. The apparent viscosity of the PC is greatly influenced by the temperature, and other materials are added into the PC, so that the influence of the temperature on the viscosity of the PC is weakened, and the adhesion performance cannot fluctuate too much due to the temperature change in the printing cavity; on the other hand, the fluidity of the material is increased, the internal residual stress is easier to reduce, and the manufacturing process is easier to control.
The PC/ABS alloy is selected as a test material after a plurality of detection researches, and the performance of the PC/ABS alloy is specifically explained by attaching detection data. ABS materials are directly taken as printing bottom plates in the market, the thermal deformation temperature of ABS is about 87 ℃, the wear resistance is excellent, the non-wear resistance of PC is compensated to a certain extent, and the creep resistance is larger than that of PC. The ABS and the PC are blended to obtain the plastic alloy which has the advantages of the ABS and the PC and overcomes the defects of the ABS and the PC, and the alloy material has good mechanical property, rigidity and processing fluidity, higher heat resistance and dimensional stability and excellent high-low temperature impact property.
Detailed Description
The invention is further described below:
the modified material comprises bisphenol A polycarbonate resin (PC resin) with a melt index of 8G/10 min-20G/10 min at 300 ℃/1.2kg, ABS resin with a weight average molecular weight of 120000-160000, acrylonitrile content of 20-30%, butadiene content of 25-30% and styrene content of 40-70%, and ABS resin with a melt index of 10-15G/min at 200 ℃/1.2kg, wherein the mixing ratio of the bisphenol A polycarbonate resin to the ABS resin is 70: 30-80: 20, wherein the mixing ratio of the polycarbonate resin (PC) to the ABS resin is 70:30, the mixing ratio of the polycarbonate resin to the ABS resin is 70:30, the modified material is selected from ethylene-n-butyl acrylate copolymer (E-BA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), maleic anhydride grafted copolymer (EVA-G-MHA), ethylene-ethyl acrylate-maleic anhydride triblock copolymer (E-BA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (E-MAH-methyl methacrylate copolymer), maleic anhydride grafted maleic anhydride-ethylene-butyl acrylate-ethylene-methyl acrylate-methyl methacrylate copolymer (E-GMA), a modified material is selected from ethylene-butyl acrylate-ethylene-ethyl acrylate-methyl methacrylate copolymer (E-methyl methacrylate copolymer, pentaerythritol-butyl acrylate-ethyl acrylate-4-butyl acrylate-ethyl acrylate-pentaerythritol-4-pentaerythritol-4-butyl acrylate, pentaerythritol-3-4-butyl acrylate-pentaerythritol-3-pentaerythritol-butyl acrylate, and one or more antioxidant, and one or more selected from stearic acid amide, 3-5-butyl-4-butyl acrylate, 3.
The PC and the ABS have certain compatibility, but the compatibility of the PC and the ABS is greatly influenced by factors such as the types, the proportion, the processing technology and the like of the two components. In order to effectively improve the interfacial compatibility, the most effective method is to add a compatibilizer to the blend system. Typical compatibilizers are: maleic anhydride MAH grafted POE, ABS graft, PE graft, polystyrene maleic anhydride grafted copolymer (SMA), acrylic acid or methacrylate copolymer, amino, SAN, two-component compatibilization and the like, wherein the compatibilizer adopted by the invention is one or more of E-BA, EMA-GMA, EVA-g-MHA and E-MA-MAH.
The blending alloy material inevitably uses a compatibilizer or an elastomer, but the proportion is relatively small, and the printing substrate materials described in the patent are all stable blending alloys, so the specific usage amount of the compatibilizer, the antioxidant and the lubricant is not discussed herein.
According to the related paper, the heat distortion temperature of PC/ABS decreases with the increase of ABS content, and the heat distortion temperature of PC/ABS is about 122 ℃ when the blending ratio reaches 70/30. Considering that the final application scenario of the printing backplane is to print all materials that can be printed by FDM technology nowadays, and the printing backplane temperature requirement of FDM consumable materials nowadays is 120 ℃ at most, 70/30 blending ratio backward is not detected here.
The invention selects PLA, ABS, TPU, PC as consumables to test, compared with the roughness of the alloy plate of the invention, the roughness of the alloy plate is Ra0.025-Ra0.05.
Since this patent only discusses the adhesion effect of the printing substrate material and the printing consumables, the data outside this patent scope does not discuss, such as printing speed, withdrawal length, support line width, wall thickness layer degree, etc.; and listing corresponding data influencing the material, such as printing temperature, the temperature of the forming cabin body, the temperature of the bottom plate and printing speed.
The data of this patent test are surveyed by Himalayan brand HIM-6080 constant temperature industrial printer, and the short range feeding possesses the cabin body constant temperature function in shaping storehouse.
In the performance test tables of the above respective examples and comparative examples, the test items of higher soleplate temperatures are not listed when the strong adhesion has occurred when the soleplate temperature reaches a certain temperature.
The bonding strength of the printing consumables and the PC/ABS alloy can be represented by a 180 ℃ peeling strength value, and is detected according to GB/T2790-1995; when the value is in the range of 18.6 to 36.5, the mold is easily taken out, and a value higher than this range means that the higher the adhesion, the more difficult the mold is to be taken out; values below this range mean that the adhesion is weak, meaning that the mold is easily detached from the base plate.
The warping property is expressed by warping deformation, the larger the area of the bottom surface of a test model is, the more easily the edge is warped, in order to pursue the accuracy and the stability of data, the measured data of the patent is based on printing a cube model of 40cm × 40cm × 40cm, the four corners of the cube contacting the bottom plate surface are warped away from the average height value of the bottom plate plane, the warping deformation is represented by delta H, the smaller the delta H is, the smaller the warping property is, the better the adhesion between the model and the bottom plate is in printing, when the bonding strength is higher, 0 < delta H is less than or equal to 1.0mm, the model and the bottom plate can be considered not to be separated, the model is represented as micro warping and is close to the degree of no warping, 1 < delta H < 10, the model and the bottom plate are considered to be partially separated, the model and the bottom plate are represented as low warping, the printing model and the model can be completely separated from the bottom plate when the delta H is more than or equal to 10.0mm, so that the printing can not be carried out, according to the forming requirement of 3D printing, the model can be normally printed, the appearance.
Wherein the test protocols and results are shown in tables 1 to 4.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
The experimental data are integrated to obtain that when the PC/ABS mixing ratio reaches 70/30, the surface roughness of the material is Ra0.025-Ra0.05, the temperature of the bottom plate is adjusted according to different consumables, the method is suitable for most consumables, the adhesion condition of the printing model and the bottom plate is in an un-separated state, the model is easy to take out and does not warp edges, the 180 ℃ stripping strength value (N/25mm) reaches 18.6-36.5, and the requirement of the 3D printing bottom plate material is met.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not limiting (e.g., changing the formulation ratio, adding small amounts of flame retardant, glass fiber, etc., changing the surface texture of the substrate, etc.).
Claims (5)
1. The PC/ABS blending modified material for the 3D printing high-adhesion base plate is characterized by comprising bisphenol A polycarbonate resin (PC resin), ABS resin and a solubilizer, wherein the melt index of the bisphenol A polycarbonate resin under the condition of 300 ℃/1.2kg is 8g/10 min-20 g/10min, the weight average molecular weight of the ABS resin is 120000-160000, the acrylonitrile content in the ABS resin is 20-30%, the butadiene content is 25-30%, and the styrene content is 40-70%, the melt index of the ABS resin under the condition of 200 ℃/1.2kg is 10 g/min-15 g/min, and the mixing ratio of the bisphenol A polycarbonate resin to the ABS resin is 70: 30-80: 20.
2. The PC/ABS blended modified material for the 3D printing high-adhesion base plate according to claim 1, wherein the mixing ratio of the Polycarbonate (PC) and the ABS resin is 70: 30.
3. The PC/ABS blended modified material for the 3D printing high-adhesion base plate according to claim 1, wherein the solubilizer is selected from one or more of ethylene-n-butyl acrylate copolymer (E-BA), ethylene-methyl acrylate-glycidyl methacrylate copolymer (EMA-GMA), maleic anhydride grafted EVA resin (EVA-G-MHA), and ethylene-ethyl acrylate-maleic anhydride triblock copolymer (E-MA-MAH).
4. The 3D printing high adhesion base plate PC/ABS blended modified material as claimed in claim 1, wherein the modified material further comprises an antioxidant and a lubricant.
5. The 3D printing high adhesion base plate PC/ABS blending modification material as claimed in claim 1, wherein the antioxidant is selected from one or more of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, phenyl tris (2, 4-di-tert-butyl) phosphite and dioctadecyl pentaerythritol diphosphite, and the lubricant is selected from one or more of silicone oil, silicone powder, paraffin, stearic acid, butyl stearate, oleamide and ethylene bis stearamide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010082480.6A CN111334022A (en) | 2020-02-07 | 2020-02-07 | PC/ABS blending modified material for 3D printing high-adhesion base plate |
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| CN202010082480.6A CN111334022A (en) | 2020-02-07 | 2020-02-07 | PC/ABS blending modified material for 3D printing high-adhesion base plate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479339A (en) * | 2022-01-19 | 2022-05-13 | 金发科技股份有限公司 | ABS alloy material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191150A1 (en) * | 2016-05-04 | 2017-11-09 | Covestro Deutschland Ag | Copolycarbonate as a supporting material in 3-d printing |
| CN110157175A (en) * | 2019-06-05 | 2019-08-23 | 金旸（厦门）新材料科技有限公司 | A kind of 3D printing height adherency micro- warpage of bottom plate is without cracking PC modified material |
| CN110437598A (en) * | 2019-08-15 | 2019-11-12 | 上海远铸智能技术有限公司 | A kind of preparation method of 3D printing special engineering plastics backing material and its wire rod |
-
2020
- 2020-02-07 CN CN202010082480.6A patent/CN111334022A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017191150A1 (en) * | 2016-05-04 | 2017-11-09 | Covestro Deutschland Ag | Copolycarbonate as a supporting material in 3-d printing |
| CN110157175A (en) * | 2019-06-05 | 2019-08-23 | 金旸（厦门）新材料科技有限公司 | A kind of 3D printing height adherency micro- warpage of bottom plate is without cracking PC modified material |
| CN110437598A (en) * | 2019-08-15 | 2019-11-12 | 上海远铸智能技术有限公司 | A kind of preparation method of 3D printing special engineering plastics backing material and its wire rod |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479339A (en) * | 2022-01-19 | 2022-05-13 | 金发科技股份有限公司 | ABS alloy material and preparation method and application thereof |
| CN114479339B (en) * | 2022-01-19 | 2023-11-03 | 金发科技股份有限公司 | ABS alloy material and preparation method and application thereof |
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