CN107353550B - 3D printing support material and preparation method thereof - Google Patents
3D printing support material and preparation method thereof Download PDFInfo
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- CN107353550B CN107353550B CN201710561988.2A CN201710561988A CN107353550B CN 107353550 B CN107353550 B CN 107353550B CN 201710561988 A CN201710561988 A CN 201710561988A CN 107353550 B CN107353550 B CN 107353550B
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- screw extruder
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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
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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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
- 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
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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
Abstract
The invention discloses a 3D printing support material and a preparation method thereof, wherein the material comprises the following components in percentage by weight: 75-90% of polyvinyl butyral resin, 5-15% of ethyl cellulose, 0-10% of carboxymethyl starch, 2-18% of plasticizer and 0.1-4% of processing aid. The wire prepared by the material ensures the stable and smooth establishment of the support part in the 3D printing process, and meanwhile, the support can be quickly removed by dissolving or swelling the product in nontoxic alcohol after the printing is finished. The preparation method of the 3D printing support material can be prepared by adopting the conventional double-screw extruder, is easy to prepare, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a 3D printing support material and a preparation method thereof.
Background
The 3D printing technology has attracted attention and rapidly developed over the years, and Fused Deposition Modeling (FDM) is an important branch of current 3D printing, and the basic principle thereof is to precisely send a polymer material monofilament or wire to a heating end through a gear for melt extrusion, and build a three-dimensional object in a layer-by-layer deposition manner under precise positioning.
In the 3D printing process, when printing and meeting a large suspension angle, the support is usually required to be printed below the suspension position, and the printed product can ensure high precision.
At present, polylactic acid (PLA) and acrylonitrile-butadiene-styrene copolymer (ABS) are mainly used as raw materials for 3D printing, and because PLA or ABS is used for printing and supporting and is difficult to remove, a polyvinyl alcohol (PVA) wire rod capable of being dissolved in water is developed in the market in recent years, and a product generated by printing can be placed in water and then the support can be removed.
But PVA wire rod has obvious shortcoming, on the one hand its hygroscopicity is too high, and the wire rod easily causes the wire rod to bond each other together at the laying time overlength, and the line footpath also changes because the moisture absorption is too much, and on the other hand PVA high temperature stability is relatively poor, easily takes place PVA cross-linking when printing the support again after meetting the waiting of longer time in the printing process, and then causes stifled shower nozzle phenomenon to the printing can't normally accomplish.
There is still an urgent need in the market for a stable printing support material, especially for printing a process model with high precision and difficult removal of the support.
The Chinese patent application with the application publication number of CN106189011A (application number of 201510233822.9) discloses a normal-temperature water-soluble 3D printing consumable, which is prepared by drying water-soluble thermoplastic polyvinyl alcohol resin prepared from raw materials including effective amounts of polyvinyl alcohol, plasticizer, soft water and processing aid at the temperature of 40-120 ℃, wherein the polymerization degree of the polyvinyl alcohol is 1000-2400 and the alcoholysis degree is 72-92 mol%, the plasticizer is one or a combination of more of glycerol, polyethylene glycol and triethanol diisocaprylate, and the processing aid is one or a combination of more of talcum powder, silicon dioxide and saturated aliphatic dicarboxylic acid ester. The prepared 3D printing consumable is used for dissolving in water at 20-40 ℃ after 3D printing, so that a three-dimensional product with hollow patterns is prepared.
The Chinese invention patent application with the application publication number of CN106700363A (application number of 201710036501.9) discloses a polyvinyl alcohol printing support material and a preparation method thereof, wherein the material comprises the following components in parts by weight: 100 parts of polyvinyl alcohol; 5-20 parts of glycerol; 0.3-3 parts of a lubricant; 1-15 parts of a sour removing agent; 1-5 parts of a stabilizer; 0.1-1 part of antioxidant; 5-20 parts of an interface compatibilizer. The technical scheme can be used for preparing the polyvinyl alcohol 3D printing soluble supporting material with good interface bonding fastness, and is used for printing polylactic acid and thermoplastic polyurethane parts with higher precision, complex shapes or nested structures.
The printing support materials are all water-soluble and are suitable for non-water-soluble printing products. At present, an alcohol-soluble printing support material is urgently needed to be suitable for non-alcohol-soluble printing products, so that different requirements of 3D printing are met.
Disclosure of Invention
Aiming at the problems of the existing supporting material, the invention provides a 3D printing supporting material and a preparation method thereof, wherein a wire prepared from the material ensures the stable and smooth establishment of a supporting part in the 3D printing process, and the supporting part can be quickly removed by dissolving or swelling a product in nontoxic alcohol after printing is finished.
The 3D printing support material comprises the following components in percentage by weight:
according to the invention, polyvinyl butyral resin is used as a main material, ethyl cellulose, a plasticizer, a processing aid and selectively added carboxymethyl starch are added, so that the components can interact with each other, a good supporting structure can be formed, the stable and smooth establishment of a supporting part in the 3D printing process is ensured, and the support can be rapidly removed by dissolving or swelling the product in nontoxic alcohol after printing is completed.
The following are preferred technical schemes of the invention:
the weight average molecular weight of the polyvinyl butyral resin is 10000-100000.
The plasticizer is one or more (including two) of triethylene glycol diisocaprylate, triethylene glycol dioctyl/caprate and glycerol.
The processing aid comprises 0.05-2 wt% of lubricant and 0.05-2 wt% of antioxidant, and more preferably, 0.1-1 wt% of lubricant and 0.1-0.5 wt% of antioxidant.
The lubricant is one or more than two (including two) of N, N-ethylene bis stearamide, calcium stearate, polyethylene wax, paraffin and monoglyceride.
The antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant and phosphate antioxidant.
The 3D printing support material can be dissolved or partially dissolved in alcohol liquid, and the alcohol liquid in which the support material can be dissolved or partially dissolved is one or more than two (including two) of ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol and glycerol.
Further preferably, the 3D printing support material comprises the following components in percentage by weight:
still further preferably, the 3D printing support material is composed of the following components in percentage by weight:
the plasticizer is triethylene glycol diisocaprylate.
A preparation method of a 3D printing support material comprises the following steps:
1) uniformly mixing polyvinyl butyral resin, ethyl cellulose, a plasticizer, a processing aid and selectively added carboxymethyl starch to obtain a uniformly mixed material;
2) extruding the uniformly mixed materials through a double-screw extruder, cooling and dicing to obtain a blending modified material;
3) and drying the blended modified material, and extruding a monofilament through a single-screw extruder to obtain the 3D printing support material.
In the step 2), the extrusion temperature of the double-screw extruder is 120-145 ℃, more preferably 125-137 ℃, and the screw rotation speed is 230-290 r/min, more preferably 250-270 r/min.
Compared with the prior art, the invention has the following advantages:
according to the invention, polyvinyl butyral resin is used as a main material, ethyl cellulose, a plasticizer, a processing aid and selectively added carboxymethyl starch are added, so that the components can interact with each other, a good supporting structure can be formed, the stable and smooth establishment of a supporting part in the 3D printing process is ensured, and the support can be rapidly removed by dissolving or swelling the product in nontoxic alcohol after printing is completed.
The preparation method of the 3D printing support material can be prepared by adopting the conventional double-screw extruder, is easy to prepare, and is suitable for industrial production.
Compared with the common water-soluble support material, the invention is more convenient to produce, the generated wire rod is more convenient to store for a long time, the stability of the printing strip is obviously improved, and the invention is suitable for industrial production and has wide application prospect.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims. In the following examples, unless otherwise specified, the parts are all parts by mass.
Example 1
85 parts of polyvinyl butyral resin (with the weight-average molecular weight of 35000 and 55000, mixed according to the mol ratio of 1: 1) powder, 8 parts of ethyl cellulose, 6 parts of triethylene glycol dioctyl/decanoate, 0.7 part of N, N-ethylene bis stearamide, 0.3 part of composite antioxidant [1010 and 168 and triphenyl phosphate (in the mass ratio of 1:2:3) are uniformly mixed in a high-speed mixer, the uniformly mixed material is extruded by a co-rotating double-screw extruder (the extrusion temperature is 132 ℃, the screw rotating speed is 260r/min), and the support material blending particles are obtained by air-cooling, drawing and chain-dragging.
Drying the support material blending particles at 60 ℃ for 4 hours, then extruding the support material blending particles in a single-screw extruder at 185 ℃, cooling the extruded melt in a water tank, air-drying and drawing to obtain a monofilament wire with the diameter of 1.75 mm, rolling the monofilament, and then drying the coiled monofilament in an oven at 50 ℃ for 3 hours to obtain the 3D printing support material (wire).
The prepared 3D printing support material (wire) and the PLA wire are printed on a double-nozzle printer, the printing temperature of the PLA is 200 ℃, the printing temperature of the support wire is 195 ℃, the printing layer thickness is 0.2mm, the printed product is high in precision, and the support material can better support the suspended solid part. The support portion completely disappeared after the product was put in ethanol for 12 hours, and there was no visible mark where the support contacted the solid.
Example 2
80 parts of polyvinyl butyral resin (with the weight-average molecular weight of 35000 and 55000, mixed according to the mol ratio of 1: 1) powder, 15 parts of ethyl cellulose, 4 parts of triethylene glycol diisocaprylate, 0.7 part of N, N-ethylene bis stearamide, 0.3 part of composite antioxidant [1010 and 168 ] and triphenyl phosphate (in the mass ratio of 1:2:3) are uniformly mixed in a high-speed mixer, the uniformly mixed material is extruded by a co-rotating double-screw extruder (the extrusion temperature is 132 ℃, the screw rotating speed is 260r/min), and the support material blending particles are obtained by air-cooling, drawing and chain-drag granulating.
Drying the support material blended particles at 60 ℃ for 5 hours, then extruding the support material blended particles in a single-screw extruder at 185 ℃, cooling the extruded melt in a water tank, air-drying and drawing to obtain a monofilament wire with the diameter of 1.75 mm, rolling the monofilament, and then drying the coiled monofilament in an oven at 50 ℃ for 3 hours to obtain the 3D printing support material (wire).
The prepared 3D printing support material (wire) and the PLA wire are printed on a double-nozzle printer, the printing temperature of the PLA is 200 ℃, the printing temperature of the support wire is 195 ℃, the printing layer thickness is 0.2mm, the printed product is high in precision, and the support material can better support the suspended solid part. The support portion completely disappeared after the product was put in ethanol for 12 hours, and there was almost no trace of the place where the support was in contact with the solid.
Example 3
80 parts of polyvinyl butyral resin (weight average molecular weight of 35000 and 55000, mixed according to a mol ratio of 1: 1) powder, 10 parts of ethyl cellulose, 5 parts of carboxymethyl starch (reputed chemical source manufacturers), 4 parts of triethylene glycol diisocaprylate, 0.7 part of N, N-ethylene bis-stearamide and 0.3 part of composite antioxidant [1010 and 168 and triphenyl phosphate (mass ratio of 1:2:3) are uniformly mixed in a high-speed mixer, the uniformly mixed material is extruded by a co-rotating double-screw extruder (the extrusion temperature is 132 ℃, the screw rotating speed is 260r/min), and the support material blending particles are obtained by air-cooling, drawing and chain-dragging grain-sized dicing.
Drying the support material blending particles at 60 ℃ for 6 hours, then extruding the support material blending particles in a single-screw extruder at 185 ℃, cooling the extruded melt in a water tank, air-drying and drawing to obtain a monofilament wire with the diameter of 1.75 mm, rolling the monofilament, and then drying the coiled monofilament in an oven at 50 ℃ for 3 hours to obtain the 3D printing support material (wire).
The prepared 3D printing support material (wire) and the PLA wire are printed on a double-nozzle printer, the printing temperature of the PLA is 200 ℃, the printing temperature of the support wire is 195 ℃, the printing layer thickness is 0.2mm, the printed product is high in precision, and the support material can better support the suspended solid part. The support portion completely disappeared after the product was placed in ethanol for 12 hours, and no trace was visible to the naked eye where the support was in contact with the solid.
TABLE 1
The 3D printing support materials prepared in the embodiments 1, 2 and 3 have high precision of printed products, which shows that the 3D printing support material can form a good support structure, so that the stable and smooth establishment of a support part in the 3D printing process is ensured, and the support can be quickly removed by dissolving or swelling the product in nontoxic alcohol after the printing is finished. Compared with the embodiments 1 and 2, the embodiment 3 has the advantages that more carboxymethyl starch is added, a supporting part can be better constructed in the 3D printing process, the supporting structure is more stable, and the 3D product obtained by printing has higher precision.
Claims (5)
1. The 3D printing support material is characterized by comprising the following components in percentage by weight:
the plasticizer is one or more than two of triethylene glycol diisocaprylate, triethylene glycol dioctyl/caprate and glycerol;
the processing aid comprises a lubricant and an antioxidant, wherein the lubricant accounts for 0.05-2% and the antioxidant accounts for 0.05-2% in percentage by weight;
the lubricant is one or more than two of N, N-ethylene bis stearamide, calcium stearate, polyethylene wax, paraffin and monoglyceride;
the antioxidant is one or more of hindered phenol antioxidant, phosphite antioxidant and phosphate antioxidant.
2. The 3D printing support material according to claim 1, wherein the polyvinyl butyral resin has a weight average molecular weight of 10000 to 100000.
3. The method for preparing a 3D printing support material according to claim 1 or 2, characterized by comprising the following steps:
1) uniformly mixing polyvinyl butyral resin, ethyl cellulose, a plasticizer, a processing aid and selectively added carboxymethyl starch to obtain a uniformly mixed material;
2) extruding the uniformly mixed materials through a double-screw extruder, cooling and dicing to obtain a blending modified material;
3) and drying the blended modified material, and extruding a monofilament through a single-screw extruder to obtain the 3D printing support material.
4. The preparation method of claim 3, wherein in the step 2), the extrusion temperature of the twin-screw extruder is 120-145 ℃, and the screw rotating speed is 230-290 r/min.
5. The preparation method of claim 4, wherein in the step 2), the extrusion temperature of the twin-screw extruder is 125-137 ℃, and the screw rotation speed is 250-270 r/min.
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| CN201710561988.2A CN107353550B (en) | 2017-07-11 | 2017-07-11 | 3D printing support material and preparation method thereof |
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| CN107353550B true CN107353550B (en) | 2020-08-28 |
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| CN107868433B (en) * | 2017-11-30 | 2020-04-21 | 惠州市优恒科三维材料有限公司 | Water-soluble 3D printing support wax and preparation method thereof |
| CN108215158A (en) * | 2018-03-01 | 2018-06-29 | 辽宁聚高智造科技有限公司 | A kind of silica gel physical model 3D printing processing method |
| CN108561504B (en) * | 2018-06-04 | 2023-06-30 | 青岛科技大学 | Synchronous belt material formed by 3D printing and preparation method thereof |
| CN111471261A (en) * | 2020-04-28 | 2020-07-31 | 深圳市智能派科技有限公司 | Bio-based ultraviolet curing 3D printing resin and preparation method thereof |
| CN113185793B (en) * | 2021-06-01 | 2022-12-27 | 浙江柏明胜医疗科技有限公司 | Modified polyvinyl alcohol used as supporting material, preparation method and removal method |
| CN114163693B (en) * | 2021-12-07 | 2022-10-18 | 南京大学 | Natural plant fiber for 3D printing and printing method thereof |
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| KR101148770B1 (en) * | 2003-05-21 | 2012-05-24 | 3디 시스템즈 인코오퍼레이티드 | Thermoplastic Powder Material System for Appearance Models from 3D Printing Systems |
| CN105462130A (en) * | 2015-12-24 | 2016-04-06 | 福建省蓝天阳信息科技有限公司 | Special alcohol-soluble supporting wire for 3D printers and manufacturing technique thereof |
| CN106832709A (en) * | 2017-02-20 | 2017-06-13 | 苏州聚冠复合材料有限公司 | A kind of PVB bases 3D printing wire rod and preparation method thereof |
| CN106832710A (en) * | 2017-02-20 | 2017-06-13 | 苏州聚冠复合材料有限公司 | A kind of water-soluble support type PVB bases 3D printing wire rod and preparation method thereof |
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Denomination of invention: A 3D printing support material and its preparation method Effective date of registration: 20210602 Granted publication date: 20200828 Pledgee: Zhejiang Tailong Commercial Bank Co.,Ltd. Hangzhou Lin'an sub branch Pledgor: HANGZHOU ZHUOPU NEW MATERIALS TECHNOLOGY Co.,Ltd. Registration number: Y2021330000503 |
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