CN107312133A - A kind of visible light solidifying material and 3D printing device and product for 3D printing - Google Patents
A kind of visible light solidifying material and 3D printing device and product for 3D printing Download PDFInfo
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- CN107312133A CN107312133A CN201610266503.2A CN201610266503A CN107312133A CN 107312133 A CN107312133 A CN 107312133A CN 201610266503 A CN201610266503 A CN 201610266503A CN 107312133 A CN107312133 A CN 107312133A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
Abstract
3D printing device and product the invention discloses a kind of material for 3D printing and using the material and preparation method thereof, the material includes the component of following parts by weight：Polymerisable monomer, is oligomer and/or the dilution property parts by weight of monomer 100, the parts by weight of light trigger 0.01 5, the parts by weight of light trigger auxiliary agent 05, and other parts by weight of function additive 1 20；Wherein, the light trigger is the one or more in following active compounds under visible light wave range 415nm 780nm laser or monochromatic visible light light radiation：Quinones, titanocene complex, iodine salt compounds, sulphur salt compounds and compound in triazine class.The more common uv radiation source of light source used in the present invention has the advantages that safety, low cost.This method uses printed material to be liquid under normality, and viscosity can adjust, and has the advantages that printing precision is high, shaping speed is fast, printed product high mechanical strength.
Description
Technical field
The present invention relates to a kind of material for 3D printing and using the 3D printing device and product of the material,
The specifically related to a kind of visible light solidifying material for 3D printing and the 3D printing device and system using the material
Part.
Background technology
It is used as emerging rapid shaping (Rapid Prototyping Manufacturing) technology, 3D
Print (3D Printing) and rely on its unique manufacture advantage, receive the very big favor in each field, praised
For the mark of the third time industrial revolution.3D printing is based on material discrete/accumulation principle, is designed with Computerized three-dimensional
Model is source, using laser sintered, heating melting and the mode such as illumination curing by metal, ceramic powders or
The materials such as macromolecule resin, are controlled by computer digit software program, successively accumulate curing molding, so that
Produce entity products.This technology has the advantages that molding time is short, cost is low, product is ever-changing, right
Complicated in some, formed precision requires high product, and its advantage more shows.Current 3D printing technique
It has been widely studied and popularization and application, has been related to product design, industrial manufacture, space flight and aviation, science and grinds
Study carefully, build, automobile, the various fields such as medical treatment.
Based on Stereolithography principle, the printing technique using light-cured resin as raw material has stereolithography (SLA),
Digital light handles (DLP) and three dimensional ink jet printing (3DSP) three kinds of modes.With 3D printing in recent years
Technology is surged forward, and the demand of photosensitive resin is significantly increased, and 3D printing is used on current domestic and international market
Ripe photosensitive resin it is less, and wherein the overwhelming majority use Ultra-Violet Laser as curing light source, in security
And it is not fully up to expectations in cost of manufacture, limit its application.Therefore, it is photosensitive under exploitation new type light source
Resin, and being applied in 3D printing technique, at the same the mechanical performance for improving printed product be one urgently
The problem of solution.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of new material for 3D printing
Material, the material is solved the security existed in the prior art using ultraviolet light and asked by visible-light curing
Topic, while the quick solidifying of the material, excellent performance, are completely suitable for the requirement of 3D printing equipment.
It is another object of the present invention to provide a kind of 3D printing device of use above-mentioned material.
It is yet a further object of the present invention to provide a kind of product, it is made by the 3D printing device, institute
The various aspects of performance for stating product is very excellent.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of material for 3D printing, the material includes the component of following parts by weight：
Wherein, the light trigger is following laser in visible light wave range 415nm-780nm or monochromatic visible
One or more under light radiation in active compound：Quinones, titanocene complex, iodine
Salt compounds, sulphur salt compounds and compound in triazine class.
According to the present invention, the light trigger is preferably following laser in visible light wave range 415nm-780nm
Or the one or more under monochromatic visible light radiation in active compound：Quinones, luxuriant titanium class
Compound, iodine salt compounds or sulphur salt compounds.
According to the present invention, the quinones is, for example, camphorquinone (CQ).
According to the present invention, the titanocene complex be, for example, fluorinated diphenyl titanocenes (Irgacure 784),
Double (five fluorinated phenyls) titanocenes etc..
According to the present invention, the iodine salt compounds be, for example, triaryl salt compounded of iodine, diaryl group iodized salt,
Alkyl salt compounded of iodine etc., preferably diaryl group iodized salt, more preferably 4,4'- dimethyl diphenyl salt compounded of iodine hexafluoro phosphorus
Hydrochlorate or diphenyl iodine hexafluorophosphate etc.；The sulphur salt compounds be, for example, triaryl sulfonium salts,
Diaryl sulfosalt, alkyl sulfosalt etc., preferably triaryl sulfonium salts.
According to the present invention, such as the light trigger be at least one quinones (as CQ), extremely
A kind of few titanocene complex (such as Irgacure 784), at least one quinones (such as CQ)
With at least one iodine salt compounds (such as diphenyl iodine hexafluorophosphate) or sulphur salt compounds
Arbitrary proportion mixture or at least one titanocene complex (such as Irgacure 784) and at least
A kind of iodine salt compounds (such as diphenyl iodine hexafluorophosphate) or sulphur salt compounds is any
The mixture of ratio.Preferably, at least one quinones (such as CQ) and at least one iodine
The arbitrary proportion of salt compounds (such as diphenyl iodine hexafluorophosphate) or sulphur salt compounds
The weight ratio of quinones and iodine salt compounds or sulphur salt compounds is 1 in mixture:(2~3).
Preferably, at least one titanocene complex (such as Irgacure 784) and at least one salt compounded of iodine class
In the mixture of the arbitrary proportion of compound (such as diphenyl iodine hexafluorophosphate) or sulphur salt compounds
The weight ratio of titanocene complex and iodine salt compounds or sulphur salt compounds is 1:(2~3).
According to the present invention, the content of the light trigger is preferably 0.05-2 parts by weight, more preferably
0.1-0.5 parts by weight.
According to the present invention, the material is mixed to get by the component.Preferably, the material is by institute
Component is stated to be mixed to get.
In the present invention, the material can be visible by visible light wave range 415nm-780nm laser or monochrome
Light carries out efficient photocuring, laser or monochromatic visible light of the material in visible light wave range 415nm-780nm
The irradiation following table solid time is preferably smaller than 5 seconds, is further preferably no larger than equal to 2 seconds；Secondly, the material
The high conversion rate of polymerisable monomer, more than 90%；Further, the viscosity of the material it is low (3~800cps, it is excellent
Select 40~700cps, normal temperature).Preferably, the light source of the laser or monochromatic visible light is, for example, thermoluminescence
Light source (such as incandescent lamp, Halogen lamp LED), glow discharge spot lamp (such as fluorescent lamp, metal halide) or
Solid light source (such as LD laser, LED laser) etc., its emission wavelength is 415nm-780nm.
It is preferred that, emission wavelength is 420nm-500nm, and further preferred emission wavelength is 430nm-480nm,
Preferred emission wavelength is 440nm-475nm.
According to the present invention, the oligomer be unsaturated polyester (UP), epoxy acrylate, urethane acrylate,
One in polyester acrylate, polyether acrylate, pure acrylate, epoxy resin, silicone oligomer
Plant or a variety of.It is highly preferred that the oligomer is unsaturated polyester (UP), epoxy acrylate, polyurethane propylene
One or more in acid esters or epoxy resin；It is further preferred that the unsaturated polyester (UP) is, for example, methyl
Glycidyl acrylate, the epoxy acrylate is, for example, bisphenol-a epoxy acrylate (such as E-51),
The epoxy resin is, for example, phenol aldehyde type epoxy resin (such as F-51).
According to the present invention, the dilution monomer be (methyl) acrylic ester compound (such as MMA,
BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA etc.), vinylic chemical compound
(such as St, VA, NVP), vinyl ethers compound, epoxy compounds (such as EPOX)
In one or more.It is highly preferred that it is described dilution property monomer be MMA, TMPTA, TMPTMA,
One or more in EPOX.
It is further preferred that when the polymerisable monomer only includes oligomer, the oligomer is unsaturation
Polyester, e.g. GMA；When simultaneously the polymerisable monomer includes oligomer and dilute
During the property released monomer, the oligomer is selected from epoxy acrylate (such as bisphenol-a epoxy acrylate), gathered
One or more in urethane acrylate and epoxy resin (such as phenol aldehyde type epoxy resin), the dilution
Monomer be selected from (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA,
TMPTMA, PETA etc.) and epoxy compounds (such as EPOX) in one or more；Work as institute
When stating polymerisable monomer only including dilution property monomer, the dilution monomer is at least one (methyl) propylene
Acid esters compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA
Deng) mixture with least one epoxy compounds (such as EPOX), for example, EPOX and TMPTA
Mixture.
According to the present invention, the light trigger auxiliary agent is secondary-amine compound (such as diethylamine), tertiary amines
Compound (such as triethylamine, N, N- dimethyl ethyl aminobenzoates etc.), secondary alcohol compounds, tertiary alcohols
One kind in compound.Preferably, the light trigger auxiliary agent is tertiary amine compounds (such as triethylamine, N, N-
Dimethyl ethyl aminobenzoate etc.).Preferably, it is described when the light trigger includes quinones
The content of light trigger auxiliary agent is more than 0 parts by weight and is less than or equal to 5 parts by weight, preferably 0.05-1 parts by weight,
More preferably 0.1-0.5 parts by weight；But when the light trigger does not include quinones, the light trigger is helped
The content of agent is 0-5 parts by weight, preferably 0-1 parts by weight, more preferably 0-0.5 parts by weight.
According to the present invention, other described function additives include pigment (such as cadmium yellow, cadmium red, chrome green, barba hispanica).
Preferably, other described function additives also include filler (such as calcium carbonate, barium sulfate, montmorillonite, talcum powder
Deng).
According to the present invention, other described function additives still further comprise antioxidant, defoamer (such as ethanol,
N-butanol, organo-silicon ester, mineral oil etc.), wetting agent (such as lecithin, polyamino salt, polyvalent carboxylic acid's salt
Deng), the one or more in polymerization inhibitor (such as hydroxyanisol, hydroquinones).
According to the present invention, other described function additives are made up of pigment and filler.
According to the present invention, the viscosity of the material is 3~800cps, normal temperature；It is preferred that 40~700cps, normal temperature.
The present invention further provides following technical scheme：
A kind of 3D printing device of use photocuring technology, including light source, workbench and the use for accommodating the present invention
In the container of the material of 3D printing, the light source is provided by successively solidifying the container on the workbench
The material, to form product；Wherein, the light source is the laser that emission wavelength is 415nm-780nm
Or monochromatic visible light light source.
According to the present invention, the light source is that the thermoluminescence light source that emission wavelength is 415nm-780nm is (such as white
Vehement lamp, Halogen lamp LED etc.), glow discharge spot lamp (such as fluorescent lamp, metal halide) or solid state lighting light
Source (such as LD laser, LED laser).
According to the present invention, the emission wavelength of the light source is preferably 420nm-500nm, and further preferred is
430nm-480nm, more preferably 440nm-475nm.
According to the present invention, the light source is preferably 446nm or 470nm blue solids lighting source (such as LD
Laser, LED laser etc.).
The present invention further provides following technical scheme：
A kind of product, it is made by the material for 3D printing by above-mentioned 3D printing device.
The present invention further provides following technical scheme：
The preparation method of above-mentioned product, it is filled by the material for 3D printing by above-mentioned 3D printing
Preparation is put, is comprised the following steps：
1) by the polymerisable monomer of 100 parts by weight, the light trigger of 0.01-5 parts by weight, 0-5 parts by weight
Light trigger auxiliary agent, other function additives of 1-20 parts by weight are uniformly mixed in normal temperature environment, are obtained
Homogeneous state mixture；
2) step 1) in mixture product is successively cured to form on the workbench by the light source.
According to the present invention, the step 1) the preferred shading of mixture preserve；Further preferably hidden with masking foil
Light is preserved.
Beneficial effects of the present invention：
1st, the present invention creatively provide first it is a kind of can by 415nm-780nm laser or monochrome
The material for 3D printing of photocuring is seen, by selecting specific light trigger so that the material solidification
It hurry up, excellent performance is completely suitable for the requirement of 3D printing equipment, it is to avoid existing ultraviolet light solidification
The problems such as the security of 3D printing equipment.
2nd, the present invention creatively proposes the laser or monochromatic visible of use 415nm-780nm a kind of first
Light is as the 3D printing device of light source, and the device uses visible light source in print procedure, with use peace
Entirely, low cost of manufacture, the features such as efficiency of initiation is high.
3rd, the present invention further matches somebody with somebody by selecting the polymerisable monomer in the material, and with the light trigger
Close so that there is the material viscosity low (3~800cps, normal temperature), solidification rate height, solid product to receive
Many advantages, such as shrinkage is small.
4th, the polymerisable monomer and light trigger in material of the invention can be fine with various other function additives
Mixture, can be with the case where not influenceing the viscosity of the material, solidification rate, the precursor of solid product shrinkage factor
Prepare different color and lusters, the product of different performance.
5th, under material normality of the invention it is liquid, viscosity can adjust, with printing precision height, shaping speed
Hurry up, printed product high mechanical strength the advantages of.
Brief description of the drawings：
Different color and luster product comparison diagrams prepared by Fig. 1 the inventive method.Wherein, from left to right, the product
Color be followed successively by colourless, red, yellow and blueness.
A kind of structural representation of 3D printing device of Fig. 2 present invention.
The structural representation of another 3D printing device of Fig. 3 present invention.
The structural representation of the third 3D printing device of Fig. 4 present invention.
Embodiment
As it was previously stated, the present invention creatively proposes a kind of material for 3D printing, the material first
Include the component of following parts by weight：Polymerisable monomer, be oligomer and/or dilution property the parts by weight of monomer 100,
Light trigger 0.01-5 parts by weight, light trigger auxiliary agent 0-5 parts by weight, other function additives 1-20 weight
Part；Wherein, the light trigger is following laser in visible light wave range 415nm-780nm or monochromatic visible
One or more under light radiation in active compound：Quinones, titanocene complex, iodine
Salt compounds, sulphur salt compounds and compound in triazine class.
It is a discovery of the invention that during the above-mentioned light trigger of selection, without reusing photosensitive material, such as eosin,
The auxiliary agents such as flavine, you can realize the rapid curing under the visible light conditions of the present invention, the table solid time is several seconds
Clock, preferably smaller than 5 seconds, is further preferably no larger than equal to 2 seconds.
It is a discovery of the invention that when selecting following dilution monomers, the material for 3D printing of gained is (i.e.
Photosensitive resin) viscosity it is relatively low (3~800cps, normal temperature), surface tension is moderate, be suitable for the present invention
Using the 3D printing device of photocuring technology.Wherein, the dilution property monomer is (methyl) esters of acrylic acid
Compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA),
Vinylic chemical compound (such as St, VA, NVP), vinyl ethers compound, epoxy compounds
One or more in (such as EPOX).
As it was previously stated, the present invention creatively proposes a kind of 3D printing dress of use photocuring technology first
Put, include the container of the material for 3D printing of light source, workbench and the receiving present invention, the light source leads to
Cross and successively solidify the material that the container is provided on the workbench, to form product；Wherein, institute
It is the laser or monochromatic visible light light source that emission wavelength is 415nm-780nm to state light source.Preferably, the light
Source be emission wavelength be 415nm-780nm thermoluminescence light source (such as incandescent lamp, Halogen lamp LED), gas
(such as LD laser, LED swash for charging source (such as fluorescent lamp, metal halide) or solid light source
Light etc.).It is highly preferred that the emission wavelength of the light source is preferably 420nm-500nm, further preferred
For 430nm-480nm, more preferably 440nm-475nm.It is more preferred still that the light source is 446nm
Or 470nm blue solids lighting source (such as LD laser, LED laser).
In one embodiment, the 3D printing device includes light source, workbench, the use for accommodating the present invention
In the container, infusion device and shower nozzle of the material of 3D printing, wherein, the light source is that emission wavelength is
415nm-780nm laser or monochromatic visible light light source；The infusion device is beaten the present invention's for 3D
The material of print is sent into shower nozzle from the container, and shower nozzle is located at the top of the workbench, what the shower nozzle sprayed
The material solidifies under the laser or monochromatic visible light radiation of light source.Specifically, as shown in Fig. 2 institute
Stating 3D printing device includes light source (visible laser), workbench (lifting platform), the use for accommodating the present invention
In the container (print cartridge) of the material of 3D printing, infusion device (woven hose), shower nozzle and last item, the spray
Head controls to move by mechanical arm.During printing, the material in print cartridge is sent to shower nozzle by the woven hose,
The material is sprayed on the lifting platform while controlling the shower nozzle to move by mechanical arm, it is described visible
The laser that laser is sent is by the way that on the fiber-optic illuminated material sprayed to shower nozzle, the material is described visible sharp
The lower solidification of LASER Light Source radiation that light device is sent, after one layer of solidification, the reduction lifting platform carries out the second layer and consolidated
Change, so repeatedly until product is completed.In whole printing process, the effect of last item is to consolidate newest
Change lamination to put down, so that next layer of superposition solidifies.3D printing device shown in Fig. 2 with it is of the prior art
The principle and structure of 3DSP type 3D printers are identical, simply light source therein and the material for 3D printing
It is different.
In another embodiment, the 3D printing device includes light source, workbench and accommodates the present invention's
Container for the material of 3D printing；The light source is located at the lower section of the container, the bottom tool of the container
Have a lens, the light source by the lens projects material for 3D printing in the above-described container simultaneously
The material selectivity is solidified, the workbench is located at the top of the container and can be from the container
Bottom up is vertically moved.Specifically, as shown in figure 3, the 3D printing device is (visible to swash including light source
Light device), workbench (lifting platform) and accommodate the present invention the material for 3D printing container, it is described can
See that laser is located at the lower section of the container, the bottom of the container is just set to the position of the visible laser
Put a lens, the light source that the visible laser is sent being used in the above-described container by the lens projects
Solidify on the material of 3D printing and by the material selectivity, the lifting platform is in the control of lifting platform control arm
Under vertically move.During printing, the lifting platform is located at the bottom of the container, between lifting platform and bottom
Material solidify to form one layer under the visible laser light sources project, and the lifting platform is controlled by control arm
Move up, successively print and product is made.3D printing device and DLP types 3D of the prior art shown in Fig. 3
The principle and structure of printer are identical, and simply light source therein is different with the material for 3D printing.
In another embodiment, the 3D printing device includes light source, workbench and accommodates the present invention's
Container for the material of 3D printing；The workbench is located in the container；The light source is located at described hold
The top of device.Specifically, as shown in figure 4, the 3D printing device include light source (visible laser and by
Its launch visible laser beam), workbench (lifting platform), accommodate the present invention the material for 3D printing
Container and scraper；The lifting platform is located in the container, and the lifting is controlled by lifting platform control arm
Vertically moved above and below platform；The light source is located at the top of the container；Container institute receiving material liquid level
Top sets a scraper, for striking off newest cured layer, so that next layer of superposition solidifies.Printing starts
When, the lifting platform is located on the downside of the upper surface of the material in the container, i.e., have one layer of institute on lifting platform
Material is stated, the visible laser beam sent by visible laser irradiates, the material solidification, mobile scraper,
Obtain one layer of curing materials with flat surface；Lifting platform is controlled to send behind by control arm, in repetition
State step；By that analogy, successively print and product is made.3D printing device shown in Fig. 4 with the prior art
SLA type 3D printers principle and structure it is identical, simply light source therein and the material for 3D printing
Material is different.
As described above, the present invention provides a kind of product and preparation method thereof, with the 3D printing device shown in Fig. 2
Exemplified by, the preparation method of the product comprises the following steps：
1) by the polymerisable monomer of 100 parts by weight, the light trigger of 0.01-5 parts by weight, 0-5 parts by weight
Light trigger auxiliary agent, other function additives of 1-20 parts by weight are uniformly mixed in normal temperature environment, are obtained
Homogeneous state mixture；
2) by step 1) in obtained mixture by the infusion device of above-mentioned 3D printing device from described
Container is sent into shower nozzle, and the mixture that the shower nozzle sprays is in the laser or monochromatic visible light radiation of light source
Lower solidification.
Wherein, the step 2) be specially：By step 1) in obtained mixture beaten by above-mentioned 3D
The infusion device that printing equipment is put is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, sprays simultaneously
Spray the mixture on the table, the mixture is in the laser or monochromatic visible the continuous constant of head
Radiant radiation is lower to be solidified, and successively accumulates, the product is made.
Wherein, the step 1) the preferred shading of mixture preserve；Further preferably preserved with masking foil shading.
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this
Content disclosed by specification understands other advantages and effect of the present invention easily.The present invention can also pass through
Different embodiments are embodied or practiced, and the various details in this specification can also be based on difference
The application of aspect, without departing from the spirit of the present invention carries out various modifications or alterations.
Embodiment 1
1) by the bisphenol-a epoxy acrylate (E-51) of 30 parts by weight, the methacrylic acid of 70 parts by weight
Methyl esters (MMA), the camphorquinone (CQ) of 0.1 parts by weight, the triethylamine of 0.1 parts by weight, 5 parts by weight
Micro-calcium carbonate powder, the lead chromate yellow of 1 parts by weight is uniformly mixed in normal temperature environment, obtains homogeneous state
Mixture；
2) by step 1) in obtained mixture pass through the transfusion of the 3D printing device shown in Fig. 2 of the present invention
Device is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, while the continuous constant of shower nozzle
Spray the mixture, 446nm blue laser light source of the mixture in the 3D printing device of the present invention
Radiation is lower to be solidified, and is successively accumulated, is shaped, the product of the present invention is made.
The viscosity of the material (i.e. described homogeneous state mixture) for 3D printing in the embodiment is low (about
220cps, normal temperature), curing rate fast (the table solid time is about 2 seconds), monomer conversion it is high (being more than 90%).
The product obtained in the present embodiment is in yellow, with excellent heat resistance, chemical-resistant stability and machinery
Intensity.
Embodiment 2
1) by the urethane acrylate of 70 parts by weight, the trimethylol propane trimethyl acrylic acid of 30 parts by weight
Ester (TMPTMA), the fluorinated diphenyl titanium cyclopentadienyl of 0.1 parts by weight, the nano-sized carbon powder of 5 parts by weight, 1 weight
The chrome red of amount part is uniformly mixed in normal temperature environment, obtains homogeneous state mixture；
2) by step 1) in obtained mixture pass through the transfusion of the 3D printing device shown in Fig. 2 of the present invention
Device is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, while the continuous constant of shower nozzle
Spray the mixture, 470nm LED blue laser of the mixture in the 3D printing device of the present invention
Solidify under radiation of light source, successively accumulate, shape, the product of the present invention is made.
The viscosity of the material (i.e. described homogeneous state mixture) for 3D printing in the embodiment is low (about
500cps, normal temperature), curing rate fast (the table solid time is about 1.5 seconds), monomer conversion height (be more than
90%).
The product obtained in the present embodiment takes on a red color, with excellent heat resistance, and chemical stability and machinery are strong
Degree.In addition, the addition of nano-sized carbon so that the product also has excellent electric conductivity.
Embodiment 3
1) by the GMA (GMA) of 100 parts by weight, the fluorination hexichol of 0.1 parts by weight
Ji Taimao, the diphenyl iodine hexafluorophosphate of 0.25 parts by weight, the Fe of 5 parts by weight3O4Powder, 3 weight
The iron oxide yellow of part is uniformly mixed in normal temperature environment, obtains homogeneous state mixture；
2) by step 1) in obtained mixture pass through the transfusion of the 3D printing device shown in Fig. 2 of the present invention
Device is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, while the continuous constant of shower nozzle
Spray the mixture, 470nm LED blue laser of the mixture in the 3D printing device of the present invention
Solidify under radiation of light source, successively accumulate, shape.
The viscosity of the material (i.e. described homogeneous state mixture) for 3D printing in the embodiment is low (about
50cps, normal temperature), curing rate fast (the table solid time is about 2 seconds), monomer conversion it is high (being more than 90%).
The product obtained in the present embodiment is in yellow, and with excellent heat resistance, chemical stability and machinery are strong
Degree.In addition, nanometer Fe3O4Addition so that the product also have magnetic field responsiveness.
Embodiment 4
1) by the phenol aldehyde type epoxy resin (F-51) of 50 parts by weight, the 3,4- epoxycyclohexyl first of 50 parts by weight
Base 3,4- epoxycyclohexyls formic acid esters (EPOX), the camphorquinone (CQ) of 0.1 parts by weight, 0.1 parts by weight
N, N- dimethyl ethyl aminobenzoates, the diphenyl iodine hexafluorophosphate of 0.25 parts by weight, 5 parts by weight
Micron Al2O3Powder, the chrome green of 4 parts by weight is uniformly mixed in normal temperature environment, is obtained homogeneous state and is mixed
Compound.
2) by step 1) in obtained mixture pass through the transfusion of the 3D printing device shown in Fig. 2 of the present invention
Device is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, while the continuous constant of shower nozzle
Spray the mixture, 446nm blue laser light source of the mixture in the 3D printing device of the present invention
Radiation is lower to be solidified, and is successively accumulated, is shaped.
The viscosity of the material (i.e. described homogeneous state mixture) for 3D printing in the embodiment is low (about
650cps, normal temperature), curing rate fast (the table solid time is about 2 seconds), monomer conversion it is high (being more than 90%).
The product obtained in the present embodiment is in green, and with excellent heat resistance, chemical stability and machinery are strong
Degree.In addition, micron Al2O3The addition of powder so that the product also has excellent thermal conductivity.
Embodiment 5
1) by the trimethylolpropane trimethacrylate (TMPTA) of 50 parts by weight, the 3,4- of 50 parts by weight
Epoxycyclohexyl-methyl 3,4- epoxycyclohexyls formic acid esters (EPOX), the camphorquinone (CQ) of 0.2 parts by weight,
The N of 0.2 parts by weight, N- dimethyl ethyl aminobenzoate, the diphenyl iodine hexafluorophosphate of 0.5 parts by weight,
The micron montmorillonite powder of 10 parts by weight, the chrome blue of 5 parts by weight is uniformly mixed in normal temperature environment, obtained
To homogeneous state mixture；
2) by step 1) in obtained mixture pass through the transfusion of the 3D printing device shown in Fig. 2 of the present invention
Device is sent into shower nozzle, and shower nozzle is moved according to desired guiding trajectory under the control of the computer, while the continuous constant of shower nozzle
Spray the mixture, 446nm blue laser light source of the mixture in the 3D printing device of the present invention
Radiation is lower to be solidified, and is successively accumulated, is shaped.
The viscosity of the material (i.e. described homogeneous state mixture) for 3D printing in the embodiment is low (about
200cps, normal temperature), curing rate fast (the table solid time is about 2 seconds), monomer conversion it is high (being more than 90%).
The product obtained in the present embodiment is in blueness, and with excellent heat resistance, chemical stability and machinery are strong
Degree.
Claims (10)
1. a kind of material for 3D printing, the material includes the component of following parts by weight：
Wherein, the light trigger is following laser in visible light wave range 415nm-780nm or monochromatic visible
One or more under light radiation in active compound：Quinones, titanocene complex, iodine
Salt compounds, sulphur salt compounds and compound in triazine class.
2. material according to claim 1, it is characterised in that the light trigger be preferably it is following
Under visible light wave range 415nm-780nm laser or monochromatic visible light radiation in active compound
It is one or more：Quinones, titanocene complex, iodine salt compounds or sulphur salt compounds.
Preferably, the quinones is, for example, camphorquinone (CQ).Preferably, the titanocene complex example
Such as it is fluorinated diphenyl titanocenes (Irgacure 784), double (five fluorinated phenyls) titanocenes.Preferably,
The iodine salt compounds are, for example, triaryl salt compounded of iodine, diaryl group iodized salt, alkyl salt compounded of iodine etc., excellent
Select diaryl group iodized salt, more preferably 4,4'- dimethyl diphenyl salt compounded of iodine hexafluorophosphates or diphenyl iodine
Hexafluorophosphate etc.；The sulphur salt compounds are, for example, triaryl sulfonium salts, diaryl sulfosalt, alkane
Base sulfosalt etc., preferably triaryl sulfonium salts.Preferably, for example described light trigger is at least one quinones
Compound (such as CQ), at least one titanocene complex (such as Irgacure 784), at least one
Plant quinones (such as CQ) and at least one iodine salt compounds (such as diphenyl iodine hexafluoro phosphorus
Hydrochlorate etc.) or sulphur salt compounds arbitrary proportion mixture or at least one titanocene complex (such as
Irgacure 784 etc.) and at least one iodine salt compounds (such as diphenyl iodine hexafluorophosphate) or
The mixture of the arbitrary proportion of sulphur salt compounds.Preferably, at least one quinones is (such as
CQ etc.) and at least one iodine salt compounds (such as diphenyl iodine hexafluorophosphate) or sulfosalt class
Quinones and iodine salt compounds or sulphur salt compounds in the mixture of the arbitrary proportion of compound
Weight ratio be 1:(2~3).Preferably, at least one titanocene complex (such as Irgacure 784) and
At least one iodine salt compounds (such as diphenyl iodine hexafluorophosphate etc.) or sulphur salt compounds
The weight of titanocene complex and iodine salt compounds or sulphur salt compounds in the mixture of arbitrary proportion
Than for 1:(2~3).
Preferably, the content of the light trigger is preferably 0.05-2 parts by weight, more preferably 0.1-0.5
Parts by weight.
Preferably, the material being mixed to get by the component.Preferably, the material is by described group
Divide and be mixed to get.
3. material according to claim 1 or 2, it is characterised in that the oligomer is unsaturated poly-
Ester, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, pure propylene
One or more in acid esters, epoxy resin, silicone oligomer.It is highly preferred that the oligomer is not
One or more in saturated polyester, epoxy acrylate, urethane acrylate or epoxy resin；Enter one
Preferably, the unsaturated polyester (UP) is, for example, GMA to step, the epoxy acrylate
E.g. bisphenol-a epoxy acrylate (such as E-51), the epoxy resin is, for example, phenolic epoxy tree
Fat (such as F-51).
Preferably, it is described dilution property monomer be (methyl) acrylic ester compound (such as MMA, BA,
IDA, LA, EHA, TMPTA, TMPTMA, PETA etc.), vinylic chemical compound (such as St,
VA, NVP etc.), vinyl ethers compound, one kind in epoxy compounds (such as EPOX)
Or it is a variety of.It is highly preferred that the dilution property monomer is MMA, TMPTA, TMPTMA, EPOX
In one or more.
It is further preferred that when the polymerisable monomer only includes oligomer, the oligomer is unsaturation
Polyester, e.g. GMA；When simultaneously the polymerisable monomer includes oligomer and dilute
During the property released monomer, the oligomer is selected from epoxy acrylate (such as bisphenol-a epoxy acrylate), gathered
One or more in urethane acrylate and epoxy resin (such as phenol aldehyde type epoxy resin), the dilution
Monomer be selected from (methyl) acrylic ester compound (such as MMA, BA, IDA, LA, EHA, TMPTA,
TMPTMA, PETA etc.) and epoxy compounds (such as EPOX) in one or more；Work as institute
When stating polymerisable monomer only including dilution property monomer, the dilution monomer is at least one (methyl) propylene
Acid esters compound (such as MMA, BA, IDA, LA, EHA, TMPTA, TMPTMA, PETA
Deng) mixture with least one epoxy compounds (such as EPOX), for example, EPOX and TMPTA
Mixture.
4. the material according to claim any one of 1-3, it is characterised in that the light trigger auxiliary agent
For secondary-amine compound (such as diethylamine), tertiary amine compounds (such as triethylamine, N, N- Dimethylaminobenzenes
Ethyl formate etc.), secondary alcohol compounds, one kind in tertiary alcohols compound.Preferably, it is described light-initiated
Agent aid is tertiary amine compounds (such as triethylamine, N, N- dimethyl ethyl aminobenzoates etc.).Preferably,
When the light trigger includes quinones, the content of the light trigger auxiliary agent is more than 0 parts by weight
Less than or equal to 5 parts by weight, preferably 0.05-1 parts by weight, more preferably 0.1-0.5 parts by weight；But it is described light-initiated
When agent does not include quinones, the content of the light trigger auxiliary agent is 0-5 parts by weight, preferably 0-1 weight
Part, more preferably 0-0.5 parts by weight.
5. the material according to claim any one of 1-4, it is characterised in that other described function additives
Including pigment (such as cadmium yellow, cadmium red, chrome green, barba hispanica).Preferably, other described function additives are also wrapped
Include filler (such as calcium carbonate, barium sulfate, montmorillonite, talcum powder).
Preferably, other described function additives still further comprise antioxidant, defoamer (such as ethanol, just
Butanol, organo-silicon ester, mineral oil etc.), wetting agent (such as lecithin, polyamino salt, polyvalent carboxylic acid's salt),
One or more in polymerization inhibitor (such as hydroxyanisol, hydroquinones).
Preferably, other described function additives are made up of pigment and filler.
Preferably, the viscosity of the material is 3~800cps, normal temperature；It is preferred that 40~700cps, normal temperature.
6. a kind of 3D printing device of use photocuring technology, it is characterised in that described device include light source,
Workbench and the container for accommodating the material for being used for 3D printing described in claim any one of 1-5, the light source lead to
Cross and successively solidify the material that the container is provided on the workbench, to form product；Wherein, institute
It is the laser or monochromatic visible light light source that emission wavelength is 415nm-780nm to state light source.
7. 3D printing device according to claim 6, it is characterised in that the light source is luminous ripple
A length of 415nm-780nm thermoluminescence light source (such as incandescent lamp, Halogen lamp LED), glow discharge spot lamp are (such as
Fluorescent lamp, metal halide etc.) or solid light source (such as LD laser, LED laser).
Preferably, the emission wavelength of the light source is 420nm-500nm, and further preferred is
430nm-480nm, more preferably 440nm-475nm.
Preferably, the light source is preferably that (such as LD swashs 446nm or 470nm blue solids lighting source
Light, LED laser etc.).
8. a kind of product, it is characterised in that the product described in claim any one of 1-5 as being used for 3D
The material of printing is made by the 3D printing device described in claim 6 or 7.
9. the preparation method of the product described in claim 8, it is characterised in that the preparation method is included such as
Lower step：
1) by the polymerisable monomer of 100 parts by weight, the light trigger of 0.01-5 parts by weight, 0-5 parts by weight
Light trigger auxiliary agent, other function additives of 1-20 parts by weight are uniformly mixed in normal temperature environment, are obtained
Homogeneous state mixture；
2) step 1) in mixture product is successively cured to form on the workbench by the light source.
10. preparation method according to claim 9, it is characterised in that the step 1) mixture
It is preferred that shading is preserved；Further preferably preserved with masking foil shading.
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