CN103980410B - A kind of composition and method of making the same for 3D printing and goods - Google Patents
A kind of composition and method of making the same for 3D printing and goods Download PDFInfo
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Abstract
The composition and method of making the same printed for 3D and goods, described composition comprises following composition: photosensitive monomer 100 parts, light trigger 1-3 part, micro nano powder 1-30 part, linking agent 1-30 part, toughner 5-10 part, pigment 5-10 part.The present invention is at ambient temperature, by photosensitive monomer, and initiator, micro nano powder, linking agent, toughner and pigment Homogeneous phase mixing, use uv irradiating curing, implement 3D and print, without the need to heat in implementation process, reduce energy consumption, without the need to special solvent, reduce the harm to environment, ultra-violet curing is rapid, significantly enhance productivity, in 3D printed material, there is more wide application prospect.
Description
Technical field
The present invention relates to a kind of composition and method of making the same for 3D printing and goods.
Background technology
It is a kind of emerging rapid shaping technique that 3D prints, design a model as source with Computerized three-dimensional, utilize laser sintered, the modes such as heating and melting are by materials such as metal, ceramic powder or polymkeric substance, controlled by computer digit software program, successively pile up molding bonded, thus produce entity products.3D prints in simple terms, can be regarded as the superposition spatially of 2D printing technique.Use the material such as pressed powder or polymer melt as printing " ink ", designed by microcomputer modelling, the precision of precisely control product and size.This printing technique is compared to traditional forming technique, do not need complicated mould and technique, equipment is small and exquisite, program is by computer control, easy and simple to handle, and the concern be thus subject to gets more and more, wide application space has been opened up gradually in fields such as biology, medical science, building, aviations, especially short run is applicable to, personalized, baroque hollow part.
At present, fusion stacking forming technique is the 3D printing technique commonly used the most, usually uses nylon, the thermoplastic resins such as ABS, at high temperature after melting, prints, and layer by layer deposition solidifies, and forms the finished product.But this kind of thermoplastic material is under high-temperature fusion condition, easily there is the chemical reactions such as oxygenolysis, release unpleasant, toxic gas, cause the harm of environment and human body, limit its range of application to a certain extent.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of composition printed for 3D is provided, effectively prevent the defect producing unpleasant toxic gas in fusion stacking forming technique because of high-temperature fusion.
Another object of the present invention is the preparation method providing a kind of above-mentioned composition for 3D printing.
3rd object of the present invention is to provide a kind of by the above-mentioned goods obtained for the composition of 3D printing.
4th object of the present invention is the purposes providing a kind of above-mentioned composition for 3D printing, and it prints for 3D.
For achieving the above object, the present invention adopts following technical scheme:
For the composition that 3D prints, described composition comprises following component:
Described photosensitive monomer is the single functionality esters of acrylic acid that room temperature is in a liquid state.
According to the present invention, the single functionality esters of acrylic acid that described room temperature is in a liquid state is selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isopropyl methacrylate, benzyl methacrylate, one or more in lauryl methacrylate(LMA) and acrylate derivative.
According to the present invention, preferably, described light trigger is alkylbenzene ketone.Described alkylbenzene ketone is selected from α, one or more in α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones.
Micro nano powder of the present invention refers to the particulate matter of particle diameter between 1 nanometer and 100 microns.Preferably, described micro nano powder is selected from one or more in inorganic micro nano powder and organic inorganic hybridization micro nano powder.Described inorganic micro nano powder be selected from metal simple-substance particle, metal oxide particle, non-metal simple-substance particle, silver halide particle, carbonate particle and phosphate particle one or more.Preferably, described organic inorganic hybridization micro nano powder has shell structure or unsymmetrical structure.
Preferably, the particle diameter of described micro nano powder is between 50nm and 10 μm.
Preferably, described micro nano powder, is through the micro nano powder of surface modifying agent.
Preferably, described surface-modifying agent be selected from Dopamine HCL and silane coupling agent one or more, described silane coupling agent is such as KH550, KH560, KH570, KH792 or DL602.
According to the present invention, preferably, described linking agent is polyfunctional acrylic ester class.Described polyfunctional acrylic ester class is selected from difunctionality linking agent (as glycol ether double methyl methacrylate, triethylene glycolbismethyl-acrylate, three contracting four Diethylene Glycol double methyl methacrylates etc.), one or more in three-functionality-degree linking agent (as trimethylolpropane trimethacrylate, Viscoat 295 etc.).
According to the present invention, preferably, described toughner is liquid polysulphide rubber.
According to the present invention, preferably, described pigment is inorganic color(ed)pigment.Described inorganic color(ed)pigment be selected from chromate pigments (as lead-chrome yellow, molybdate orange etc.), cadmium pigment (as cadmium yellow, cadmium red etc.), iron pigment (as iron oxide yellow, iron oxide red etc.), veridian (as chrome green, chromoxide green etc.) and blue pigments (as barba hispanica, ultramarine etc.) one or more.
The present invention also provides following technical scheme:
A preparation method for the above-mentioned composition for 3D printing, it comprises the mixing step of each component.
According to the present invention, described method specifically comprises the following steps:
1) pigment of the micro nano powder of the photosensitive monomer of 100 weight parts, 1-30 weight part, the linking agent of 1-30 weight part and 5-10 weight part is mixed;
2) by step 1) in the compound that obtains mix with the toughner of 5-10 weight part, the light trigger of 1-3 weight part.
According to the present invention, above-mentioned married operation all carries out under room temperature (20-40 DEG C) condition.
According to the present invention, step 1) in mixing be with mechanical stirring abundant mixing 1-2 hour under rotating speed 1000-4000rpm condition.
According to the present invention, step 2) be in lucifuge, fully mix 1-2 hour under rotating speed 1000-4000rpm condition.
The present invention also provides following technical scheme:
A kind of goods, it prints obtained by the above-mentioned composition for 3D printing by 3D.
A purposes for the above-mentioned composition for 3D printing, it prints for 3D.
Beneficial effect of the present invention is:
1, the raw material that the photosensitive monomer that the present invention has superior fluidity under using room temperature prints as 3D, is mixed with micro nano powder by simple method, without the need to special main equipment and heating unit.
2, photosensitive monomer of the present invention under uv irradiating can rapid solidification shaping, significantly improve production efficiency.
3,3D printed material of the present invention in use can not give off poisonous gas, and reduces the harm to environment.
4, production cost of the present invention is low, and production process is simple, is easy to suitability for industrialized production.
5, the present invention is by changing the micro nano powder and pigment that add, can obtain different colours, the product of different performance.
Embodiment
As mentioned above, the invention discloses a kind of composition printed for 3D, described composition comprises following component:
Described photosensitive monomer is the single functionality esters of acrylic acid that room temperature is in a liquid state.
Be low-viscosity (mobile) liquid under the photosensitive monomer room temperature that the present invention uses, convenient operation mixes, and adds micro nano powder in the base simultaneously, imparts mechanical property and the multifunctionality of mixture excellence.
Optical soliton interaction method (SLA---StereoLithographyApparatus) is the one of 3D printing technique, is the rapid prototyping technique occurred the earliest, has higher ripening degree.The unsaturated polymer monomer of usual use liquid state or performed polymer, add a small amount of light trigger, and crosslinking curing under the UV-irradiation of specific wavelength and intensity, successively piles up, form final 3D solid.The raw material that this method uses is generally liquid, and have good mobility, without the need to applying high temperature, room temperature can operate, and environmental pollution is little, and shaping speed is fast, with short production cycle, without the need to cutting tool and mould, is applicable to making complex structure and is difficult to shaping material.In aerospace, automobile making, mould development, there is important application in the fields such as electrical equipment.Acrylate and homologue thereof, owing to there is highly active terminal olefinic link, get final product polymerized at room temperature under UV-irradiation.Polymerisate has excellent oil-proofness and high-temperature oxidation, is thus widely used in sizing agent, synthetic resins, specialty elastomer and plastic applications.The goods that the 3D above-mentioned performance of acrylate and homologue thereof organically combined with the advantage of optical soliton interaction method in the present invention, provide that a kind of production cost is low, production process is simple, being easy to suitability for industrialized production prints.
Below by way of embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from aforesaid method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.
Embodiment 1
A kind of 3D prints goods A
1) by the methyl methacrylate of 100 weight parts, the Nano-meter CaCO3 of 10 parts
3powder, the glycol ether double methyl methacrylate of 10 parts, 5 parts of barba hispanicas under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the compound that obtains and the liquid polysulphide rubber of 1 part, the α of 1 part, α-diethoxy acetophenone under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods A.
Described goods A is in blue.Nano-meter CaCO3
3adding of powder makes goods have excellent dimensional stability, and intensity and toughness also significantly improve.
Embodiment 2
A kind of 3D prints goods B
1) by the β-dimethyl-aminoethylmethacrylate of 100 weight parts, the Nano-Ag Powders of 15 parts, the glycol ether double methyl methacrylate of 10 parts, 5 parts of barba hispanicas under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the liquid polysulphide rubber of the compound that obtains and 5 parts, the alpha-hydroxyalkyl benzophenone of 2 parts under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods B.
Described goods B is in blue.Nano-Ag Powders add the dimensional stability making goods, intensity and toughness are improved, and have excellent conductivity simultaneously.The high connductivity goods of special shape can be printed according to demand.
Embodiment 3
A kind of 3D prints goods C
1) by the methyl methacrylate of 100 weight parts, the nanometer Fe of 20 parts
3o
4powder, the glycol ether double methyl methacrylate of 10 parts, 10 parts of chrome green under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the liquid polysulphide rubber of the compound that obtains and 10 parts, the alpha-hydroxyalkyl benzophenone of 3 parts under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods C.
Described goods C is in green.Nanometer Fe
3o
4powder add the dimensional stability making goods, intensity and toughness are improved, and have responsiveness to magnetic field simultaneously.
Embodiment 4
A kind of 3D prints room temperature ultraviolet-curable materials
1) by the methyl methacrylate of 100 weight parts, the micron Al of 30 parts
2o
3powder, the triethylene glycolbismethyl-acrylate of 20 parts, 10 parts of iron oxide yellows, under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the liquid polysulphide rubber of the compound that obtains and 1 part, the alpha-hydroxyalkyl benzophenone of 2 parts under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods D.
Described goods D is in yellow.Micron Al
2o
3adding of powder makes product size stability, and intensity and toughness are improved, and has good heat conductivility simultaneously, can be applicable to thermal conduction and Electronic Packaging field.
Embodiment 5
A kind of 3D prints goods E
1) by the propyl methacrylate of 100 weight parts, the micron polynite powder of 10 parts, the trimethylolpropane trimethacrylate of 20 parts, 5 parts of iron oxide yellows under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the liquid polysulphide rubber of the compound that obtains and 5 parts, the α-amine alkyl phenones of 1 part under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods E.
Described goods E is in yellow.Adding of micron polynite powder makes goods shock resistance, and resistance to fatigue and gas barrier property significantly improve.
Embodiment 6
A kind of 3D prints goods F
1) by the benzyl methacrylate of 100 weight parts, the micron ZrO of 15 parts
2powder, the Viscoat 295 of 30 parts, 10 parts of cadmium reds under 2000rpm rotating speed, mixed at room temperature 1h;
2) by step 1) in the compound that obtains and the liquid polysulphide rubber of 10 parts, the α of 2 parts, α-diethoxy acetophenone under 2000rpm rotating speed, room temperature lucifuge mixing 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, printed by CAD time variable control, under room temperature, ultra-violet curing is shaping, obtains goods F.
Described goods F takes on a red color.Micron ZrO
2adding of powder makes the resistivity against fire of product significantly improve, and may be used for printing special refractory.
Claims (19)
1. goods, it prints obtained by the composition for 3D printing comprising following component by 3D:
Described photosensitive monomer is the single functionality esters of acrylic acid that room temperature is in a liquid state.
2. goods according to claim 1, it is characterized in that, the single functionality esters of acrylic acid that described room temperature is in a liquid state is selected from methyl methacrylate, β-dimethyl-aminoethylmethacrylate, propyl methacrylate, isopropyl methacrylate, benzyl methacrylate, one or more in lauryl methacrylate(LMA).
3. goods according to claim 1 and 2, is characterized in that, described light trigger is alkylbenzene ketone, and described alkylbenzene ketone is selected from α, one or more in α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones.
4. goods according to claim 1 and 2, it is characterized in that, described micro nano powder refers to the particulate matter of particle diameter between 1 nanometer and 100 microns, described micro nano powder be selected from inorganic micro nano powder and organic inorganic hybridization micro nano powder one or more.
5. goods according to claim 4, is characterized in that, described inorganic micro nano powder be selected from metal simple-substance particle, metal oxide particle, non-metal simple-substance particle, silver halide particle, carbonate particle and phosphate particle one or more; Described organic inorganic hybridization micro nano powder has shell structure or unsymmetrical structure.
6. goods according to claim 4, is characterized in that, the particle diameter of described micro nano powder is between 50nm and 10 μm.
7. goods according to claim 1 and 2, is characterized in that, described micro nano powder, are through the micro nano powder of surface modifying agent.
8. goods according to claim 7, is characterized in that, described surface-modifying agent be selected from Dopamine HCL and silane coupling agent one or more, described silane coupling agent is selected from KH550, KH560, KH570, KH792 or DL602.
9. goods according to claim 1 and 2, is characterized in that, described linking agent is polyfunctional acrylic ester class.
10. goods according to claim 9, is characterized in that, described polyfunctional acrylic ester class is selected from difunctionality linking agent, one or more in three-functionality-degree linking agent.
11. goods according to claim 10, is characterized in that, described difunctionality linking agent is selected from glycol ether double methyl methacrylate, one or more in triethylene glycolbismethyl-acrylate; Three-functionality-degree linking agent is selected from trimethylolpropane trimethacrylate, one or more in Viscoat 295.
12. goods according to claim 1 and 2, is characterized in that, described toughner is liquid polysulphide rubber.
13. goods according to claim 1 and 2, is characterized in that, described pigment is inorganic color(ed)pigment.
14. goods according to claim 13, is characterized in that, described inorganic color(ed)pigment be selected from chromate pigments, cadmium pigment, iron pigment, veridian and blue pigments one or more.
15. goods according to claim 14, it is characterized in that, described chromate pigments is selected from lead-chrome yellow or molybdate orange, described cadmium pigment is selected from cadmium yellow or cadmium red, described iron pigment is selected from iron oxide yellow or iron oxide red, described veridian is selected from chrome green or chromoxide green, and described blue pigments is selected from barba hispanica or ultramarine.
The preparation method of the goods described in 16. 1 kinds of any one of claim 1 to 15, is characterized in that, described composition adopts the method preparation comprised the following steps:
1) pigment of the micro nano powder of the photosensitive monomer of 100 weight parts, 1-30 weight part, the linking agent of 1-30 weight part and 5-10 weight part is mixed;
2) by step 1) in the compound that obtains mix with the toughner of 5-10 weight part, the light trigger of 1-3 weight part.
17. preparation methods according to claim 16, is characterized in that, described married operation, all in room temperature, namely carries out under 20-40 DEG C of condition.
18. preparation methods according to claim 16 or 17, is characterized in that, step 1) in mixing be with mechanical stirring abundant mixing 1-2 hour under rotating speed 1000-4000rpm condition;
Step 2) be in lucifuge, fully mix 1-2 hour under rotating speed 1000-4000rpm condition.
The purposes of the composition for 3D printing described in the goods described in 19. 1 kinds of any one of claim 1 to 15, it prints for 3D.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410183540.8A CN103980410B (en) | 2014-04-30 | 2014-04-30 | A kind of composition and method of making the same for 3D printing and goods |
| US15/507,670 US11299569B2 (en) | 2014-04-30 | 2015-04-24 | Material for 3D printing, process for preparing the same and article thereof |
| PCT/CN2015/077360 WO2015165363A1 (en) | 2014-04-30 | 2015-04-24 | Material for 3d printing and preparation method therefor and product thereof |
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| CN201410183540.8A CN103980410B (en) | 2014-04-30 | 2014-04-30 | A kind of composition and method of making the same for 3D printing and goods |
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| CN103980410A CN103980410A (en) | 2014-08-13 |
| CN103980410B true CN103980410B (en) | 2016-02-24 |
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| WO2015165363A1 (en) * | 2014-04-30 | 2015-11-05 | 中国科学院化学研究所 | Material for 3d printing and preparation method therefor and product thereof |
| CN104505151B (en) * | 2014-12-16 | 2017-04-19 | 安徽凤阳德诚科技有限公司 | Chromium-containing high-dispersity conductive silver paste |
| CN106032425A (en) * | 2015-03-09 | 2016-10-19 | 优克材料科技股份有限公司 | Ceramic resin printing raw material for light cured three dimensional printing |
| CN105294936B (en) * | 2015-10-19 | 2017-07-18 | 杭州龙勤新材料科技有限公司 | Two degree of functionality acrylic ester cross-linking agents and its application in 3D printing |
| JP6706327B2 (en) | 2015-10-23 | 2020-06-03 | ヒューレット−パッカード デベロップメント カンパニー エル．ピー．Ｈｅｗｌｅｔｔ‐Ｐａｃｋａｒｄ Ｄｅｖｅｌｏｐｍｅｎｔ Ｃｏｍｐａｎｙ， Ｌ．Ｐ． | Three-dimensional (3D) printing |
| CN107501477B (en) * | 2016-06-14 | 2019-11-05 | 珠海赛纳打印科技股份有限公司 | It is a kind of for the photo-curing material of 3D inkjet printing and preparation and Method of printing |
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| CN107245314A (en) * | 2017-05-26 | 2017-10-13 | 苏州汉力新材料有限公司 | A kind of 3D printing powder ultraviolet light curing adhesive and preparation method thereof |
| CN107603201B (en) * | 2017-09-07 | 2021-02-26 | 金华造物新材料有限公司 | 3D printing photosensitive resin for precision casting of ornaments and dentistry |
| CN108285330B (en) * | 2017-12-28 | 2021-06-22 | 哈尔滨工业大学 | Ceramic liquid for laser deposition molding 3D printing and preparation and use methods thereof |
| CN108727709B (en) * | 2018-04-11 | 2021-02-19 | 杭州科技职业技术学院 | Preparation method of 3D printing soft material |
| CN109777023B (en) * | 2018-12-20 | 2021-09-17 | 宁波浙创科技有限公司 | SLA flexible photosensitive resin for 3D printing and preparation method thereof |
| CN109777024B (en) * | 2019-01-08 | 2021-06-01 | 宁波浙创科技有限公司 | SLA elastic photosensitive resin for 3D printing and preparation method thereof |
| US12037424B2 (en) | 2019-09-12 | 2024-07-16 | Institute Of Chemistry, Chinese Academy Of Sciences | Enhanced, self-healable or recoverable and recyclable 3D printed article and preparation method and use thereof |
| CN111484699B (en) * | 2020-04-17 | 2023-10-13 | 阜阳师范大学 | Epoxy acrylate 3D printing photosensitive resin and preparation method thereof |
| CN111702166A (en) * | 2020-06-23 | 2020-09-25 | 西安汇创贵金属新材料研究院有限公司 | Metal composite material and preparation method thereof |
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