CN103980410A - Composition for 3D printing and preparation method and product thereof - Google Patents
Composition for 3D printing and preparation method and product thereof Download PDFInfo
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Abstract
A composition for 3D printing and a preparation method and a product thereof. the composition contains the following components, by weight, 100 parts of a photosensitive monomer, 1-3 parts of a photoinitiator, 1-30 parts of a micro-nano powder, 1-30 parts of a cross-linking agent, 5-10 parts of a flexibilizer and 5-10 parts of a pigment. Under the condition of room temperature, the photosensitive monomer, the initiator, the micro-nano powder, the cross-linking agent, the flexibilizer and the pigment are uniformly mixed, and 3D printing is implemented by an ultraviolet radiation and curing method. During the implementation process, high-temperature heating is not required so as to reduce energy consumption; a special solvent is not required so as to reduce the harm to the environment; and ultraviolet curing is fast so as to greatly raise production efficiency. The composition provided by the invention has a wider application prospect in 3D printing materials.
Description
Technical field
The present invention relates to a kind of composition and method of making the same and goods of printing for 3D.
Background technology
It is a kind of emerging rapid shaping technique that 3D prints, the Computerized three-dimensional of take designs a model as source, utilize laser sintered, the modes such as heating and melting are by materials such as metal, ceramic powder or polymkeric substance, by computer digit software program, control, successively pile up molding bonded, thereby produce entity products.3D prints in simple terms, can be regarded as the stack spatially of 2D printing technique.Use the materials such as pressed powder or polymer melt as printing " ink ", by microcomputer modelling, design the precision of precisely control product and size.This printing technique is than 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, thereby the concern being subject to is more and more, in fields such as biology, medical science, building, aviations, opened up wide application space gradually, especially be applicable to short run, personalization, baroque hollow part.
At present, fusion stacking forming technique is the 3D printing technique of commonly using the most, conventionally uses the thermoplastic resins such as nylon, ABS, at high temperature, after melting, prints, and layer by layer deposition solidifies, and forms the finished product.Yet under high-temperature fusion condition, easily there is the chemical reactions such as oxygenolysis in this analog thermoplastic material, to emit unpleasantly, toxic gas, causes the harm of environment and human body, has limited to a certain extent its range of application.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of composition of printing for 3D is provided, effectively avoided because of high-temperature fusion, producing in fusion stacking forming technique the defect of unpleasant toxic gas.
Another object of the present invention is to provide a kind of preparation method of the above-mentioned composition of printing for 3D.
The 3rd object of the present invention is to provide a kind of goods that made by the above-mentioned composition of printing for 3D.
The 4th object of the present invention is to provide a kind of purposes of the above-mentioned composition of printing for 3D, and it is printed for 3D.
For achieving the above object, the present invention adopts following technical scheme:
A composition of printing 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.
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, methacrylic acid benzyl ester, one or more in lauryl methacrylate(LMA) and acrylate derivative.
According to the present invention, preferred, 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 that particle diameter is between the particulate matter 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 is selected from one or more in metal simple-substance particle, metal oxide particle, non-metal simple-substance particle, silver halide particle, carbonate particle and phosphate particle.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 μ m.
Preferably, described micro nano powder, is the micro nano powder through surface-modifying agent modification.
Preferably, described surface-modifying agent is selected from one or more in Dopamine HCL and silane coupling agent, and described silane coupling agent is for example KH550, KH560, KH570, KH792 or DL602.
According to the present invention, preferred, 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, preferred, described toughner is liquid polysulphide rubber.
According to the present invention, preferred, described pigment is inorganic color(ed)pigment.Described inorganic color(ed)pigment is selected from one or more in 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.).
The present invention also provides following technical scheme:
A preparation method for the above-mentioned composition of printing for 3D, it comprises the mixing step of each component.
According to the present invention, described method specifically comprises the following steps:
1) pigment of the linking agent of the micro nano powder of the photosensitive monomer of 100 weight parts, 1-30 weight part, 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 ℃) condition.
According to the present invention, step 1) mixing in is by mechanical stirring, under rotating speed 1000-4000rpm condition, fully to mix 1-2 hour.
According to the present invention, step 2) be in lucifuge, under rotating speed 1000-4000rpm condition, fully mix 1-2 hour.
The present invention also provides following technical scheme:
Goods, it is printed and is made by 3D by the above-mentioned composition of printing for 3D.
A purposes for the above-mentioned composition of printing for 3D, it is printed for 3D.
Beneficial effect of the present invention is:
1, the present invention uses and under room temperature, has the photosensitive monomer of superior fluidity as the raw material of 3D printing, mixes, without special main equipment and heating unit by simple method with micro nano powder.
2, photosensitive monomer of the present invention curing molding rapidly under uv irradiating, has significantly improved production efficiency.
3,3D printed material of the present invention in use can not give off poisonous gas, and has reduced 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 adds by change micro nano powder and pigment, can obtain different colours, the product of different performance.
Embodiment
As mentioned above, the invention discloses a kind of composition of printing 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.
Under the photosensitive monomer room temperature that the present invention uses, be low-viscosity (mobile) liquid, convenient operation mixes, and has added micro nano powder in matrix simultaneously, has given mechanical property and the multifunctionality of mixture excellence.
Photocuring shaping method (SLA---Stereo Lithography Apparatus) is a kind of of 3D printing technique, is the rapid prototyping technique occurring the earliest, has higher ripening degree.Conventionally use liquid unsaturated polymer monomer or performed polymer, add a small amount of light trigger, crosslinking curing under the UV-irradiation of specific wavelength and intensity, successively piles up, and forms final 3D solid.The raw material that this method is used is generally liquid, has good mobility, and without applying high temperature, room temperature can operate, and environmental pollution is little, and shaping speed is fast, with short production cycle, without cutting tool and mould, is applicable to making the material that complex structure is difficult to moulding.In aerospace, automobile making, mould development, there is important application in the fields such as electrical equipment.Acrylate and homologue thereof, owing to there being highly active terminal olefinic link, get final product polymerized at room temperature under UV-irradiation.Polymerisate has excellent oil-proofness and high-temperature oxidation, thereby is widely used in sizing agent, synthetic resins, specialty elastomer and plastics field.In the present invention, the advantage of the above-mentioned performance of acrylate and homologue thereof and photocuring shaping method is organically combined to the goods that the 3D that provide that a kind of production cost is low, production process is simple, is easy to suitability for industrialized production prints.
Below by embodiment, the present invention is described in further detail, but this should be interpreted as to scope of the present invention only limits to following example.In the situation that not departing from aforesaid method thought of the present invention, various replacements or the change according to ordinary skill knowledge and customary means, made, 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 nanometer CaCO 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 is under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods A.
It is blue that described goods A is.Nanometer CaCO
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, the alpha-hydroxyalkyl benzophenone of 2 parts of the compound that obtains and 5 parts under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods B.
It is blue that described goods B is.Nano-Ag Powders add the dimensional stability that makes goods, intensity and toughness are improved, and have excellent conductivity simultaneously.Can print according to demand the high conductive articles of special shape.
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, the alpha-hydroxyalkyl benzophenone of 3 parts of the compound that obtains and 10 parts under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods C.
It is green that described goods C is.Nanometer Fe
3o
4powder add the dimensional stability that makes goods, intensity and toughness are improved, and magnetic field are had to responsiveness simultaneously.
Embodiment 4
A kind of 3D prints room temperature ultraviolet-curable materials
1) by the methyl methacrylate of 100 weight parts, 30 parts micron Al
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, the alpha-hydroxyalkyl benzophenone of 2 parts of the compound that obtains and 1 part under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods D.
It is yellow that described goods D is.Micron Al
2o
3adding of powder makes product size stability, and intensity and toughness are improved, and have 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, α-amine alkyl phenones of 1 part of the compound that obtains and 5 parts under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods E.
It is yellow that described goods E is.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 methacrylic acid benzyl ester of 100 weight parts, 15 parts micron ZrO
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 is under 2000rpm rotating speed, room temperature lucifuge is mixed 1h;
3) by step 2) in the compound of gained use PROJET1200 type SLA3D printer, by CAD time variable control, print, ultra-violet curing moulding under room temperature, obtains goods F.
Described goods F takes on a red color.Micron ZrO
2adding of powder significantly improves the resistivity against fire of product, can be for printing special refractory.
Claims (8)
1. a composition of printing 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.
2. composition 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, methacrylic acid benzyl ester, one or more in lauryl methacrylate(LMA) and acrylate derivative.
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.
Described micro nano powder refers to that particle diameter is between the particulate matter 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.Preferably, described inorganic micro nano powder is selected from one or more in metal simple-substance particle, metal oxide particle, non-metal simple-substance particle, silver halide particle, carbonate particle and phosphate particle.Preferably, described organic inorganic hybridization micro nano powder has shell structure or unsymmetrical structure.
3. composition according to claim 1 and 2, is characterized in that, the particle diameter of described micro nano powder is between 50nm and 10 μ m.
Preferably, described micro nano powder, is the micro nano powder through surface-modifying agent modification.
Preferably, described surface-modifying agent is selected from one or more in Dopamine HCL and silane coupling agent, and described silane coupling agent is for example KH550, KH560, KH570, KH792 or DL602.
4. according to the composition described in any one in claims 1 to 3, it is characterized in that, described linking agent is polyfunctional acrylic ester class; Preferably, 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.).
Preferably, described toughner is liquid polysulphide rubber.
Preferably, described pigment is inorganic color(ed)pigment; More preferably, described inorganic color(ed)pigment is selected from one or more in 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.).
5. a preparation method for the composition of printing for 3D described in any one in claim 1 to 4, it comprises the mixing step of each component.
Preferably, described method specifically comprises the following steps:
1) pigment of the linking agent of the micro nano powder of the photosensitive monomer of 100 weight parts, 1-30 weight part, 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.
6. preparation method according to claim 5, is characterized in that, described married operation all carries out under room temperature (20-40 ℃) condition.
Preferably, the mixing step 1) is by mechanical stirring, under rotating speed 1000-4000rpm condition, fully to mix 1-2 hour.
Preferably, step 2) be in lucifuge, under rotating speed 1000-4000rpm condition, fully mix 1-2 hour.
7. goods, it is printed and is made by 3D by the composition of printing for 3D described in any one in claim 1 to 4.
8. a purposes for the composition of printing for 3D described in any one in claim 1 to 4, it is printed 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 |
| PCT/CN2015/077360 WO2015165363A1 (en) | 2014-04-30 | 2015-04-24 | Material for 3d printing and preparation method therefor and product thereof |
| US15/507,670 US11299569B2 (en) | 2014-04-30 | 2015-04-24 | Material for 3D printing, process for preparing the same and article 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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| CN103980410B CN103980410B (en) | 2016-02-24 |
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| 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 |
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| CN111484699A (en) * | 2020-04-17 | 2020-08-04 | 阜阳师范大学 | Epoxy acrylate 3D printing photosensitive resin and preparation method 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 |
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