CN106696258A - Fast 3D printing method - Google Patents
Fast 3D printing method Download PDFInfo
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- CN106696258A CN106696258A CN201611040841.0A CN201611040841A CN106696258A CN 106696258 A CN106696258 A CN 106696258A CN 201611040841 A CN201611040841 A CN 201611040841A CN 106696258 A CN106696258 A CN 106696258A
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- epoxy
- monomer
- quick
- photosensitive resin
- acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
Abstract
The invention discloses a fast 3D printing method. The method includes: using a DLP projector to conduct repeated local projection and exposure curing on a photosensitive resin precursor solution according to a preset two-dimensional pattern so as to obtain a heterogeneous two-dimensional plane; soaking the heterogeneous two-dimensional plane obtained by curing in molten paraffin to undergo swelling, and then taking the product out for cooling; or taking the plane out of the photosensitive resin precursor solution, and performing illumination curing to obtain a three-dimensional structure. According to the invention, various structures in the swelling process can be fixed, and the obtained three-dimensional structure does not contain water and volatile solvent, and has strong practicability.
Description
Technical field
The present invention relates to Polymer Processing manufacture field, more particularly to a kind of method of quick 3D printing.
Background technology
Polymer product with 3-D solid structure is processed typically by the moulding method of mould.This tradition
Method can only often process some simple three-dimensional structures due to mould processing and the limitation of the later stage demoulding.And, mould is opened
The hair cycle is long, input is big, efficiency is low.
3D printing (increasing material manufacturing) is a kind of based on mathematical model file, come structure by way of successively printing
The forming technique of body, has been widely used for the direct manufacture of mould, the model manufacturing of industrial design and some products.3D printing
Technology is a kind of straight forming technology, it is not necessary to use mould.In addition, its most prominent advantage is can to build some not advise
Then, complicated three-dimensional structure.But, all 3D printing techniques (including fusion sediment FDM, selective Stereo Lithography SLA, number
Word light treatment DLP, selective laser sintering SLS etc.) it is required for cutting into slices target object, print layer by layer, so printing single thing
Time needed for body is relatively long., it is necessary to thickness is thinner during in particular for printing precision higher, the number of plies is more, its printing
Time is also just longer.Although the CLPS technologies of Carbon companies substantially increase the print speed of conventional DLP technologies, but its is absolute
Speed is still slower.
Chinese invention patent (A of CN 105818382) discloses a kind of side that three-dimensional structure is built based on digital light treatment
Method, the method is printed by digitized projection technology obtain a heterogeneous two dimensional surface for precise control first, then by this
Two dimensional surface is immersed in swelling in specific solvent, you can obtain a three-dimensional structure set in advance.The skill that the patent is disclosed
Art principle is the distribution density and gradient that material is there is inside heterogeneous two dimensional surface, and different zones are to the molten of homogeneous solvent
Expansibility is different, and a three-dimensional structure for stabilization will be formed when reaching swelling equilibrium.The patent greatly improves 3D printing
Speed, but there is also some limitation：Need just obtain a structure for stabilization, swelling process when complete swelling balance
In some intermediaries for coming in handy cannot be fixed up；The solvent for using is water or volatile organic solvent, limit
Make its application in specific occasion.
The content of the invention
The purpose of the present invention is to solve the shortcomings of the prior art, there is provided a kind of method of quick 3D printing, when swelling without
Need to wait until that complete swelling is balanced, the intermediary that can be remained with, and solvent used is aqueous or volatile organic solvent,
Make its three-dimensional structure for obtaining that there is bigger use scope and practical value.
Technical scheme provided by the present invention is：
A kind of method of quick 3D printing, comprises the following steps：
Step (1)：Photosensitive resin precursor liquid comprising monomer and light trigger is placed in plane die cavity；
Step (2)：Using DLP projector by default two-dimensional pattern photosensitive resin precursor liquid is carried out multiple partial projection,
Exposure curing, obtains heterogeneous two dimensional surface；
Step (3)：The heterogeneous two dimensional surface for obtaining will be solidified and be soaked in swelling, taking-up in the paraffin of thawing, cooled down, i.e.,
3-D solid structure can be obtained；
Or, heterogeneous two dimensional surface is soaked in swelling in photosensitive resin precursor liquid, take out, illumination curing, you can obtain
Obtain 3-D solid structure.
Innovative point of the invention is to use the paraffin or photosensitive resin precursor liquid that melt as the swelling solvent of two dimensional surface,
So as to produce mechanism and the effect entirely different with patent 201610239890.0.
The present invention obtains a heterogeneous two dimensional surface for precise control by digitized projection technology, due to flat in two dimension
The swelling rate of the different zones in face is different, and three-dimensional structure set in advance can be converted into two dimensional surface during swelling equilibrium,
And any one intermediary in swelling process can be fixed.When solvent is made using the paraffin for melting,
As long as any stage of swelling process takes out sample, paraffin cooling, solidification, can just fix down three-dimensional structure at room temperature
Come；When solvent is made using photosensitive resin precursor liquid, after sample is taken out at any time, specific absorption wavelength is placed on
Fully also can be fixed up for three-dimensional structure by solidification under light source.
The committed step of the inventive method be using DLP projector photosensitive resin is carried out multiple selective area projection,
Exposure, makes different zones have different material distribution gradients；Determine that resin is complete by the kinetics of polymerization reaction of photosensitive resin
Projection time required for all solidstate, counter its swellbility required in two dimensional surface that push away of three-dimensional structure according to needed for final is divided
Cloth, so that it is determined that the figure of the time of projection and projection every time.
In the present invention, DLP projector is connected by G code with computer, delivers out specific X-Y scheme to photosensitive tree
Fat forerunner's liquid level.There is polymerisation and crosslinking curing in photosensitive resin at projection.The control single projection time so that single is thrown
Not exclusively, crosslinking curing is insufficient for photosensitive resin polymerisation under shadow, i.e. the conversion ratio of the photosensitive resin under this projection and crosslinking
Density is relatively low.DLP projector carries out reprojection, and the photosensitive resin of (repeat region of multiple projections pattern) is further at projection
Generation polymerisation, monomer conversion gradually increases with crosslink density.Projection, photocuring operation repeat repeatedly, until poly-
Close reaction complete.The process of multiple projections at least includes two kinds of different graphics (view field of different graphic can be overlapped),
So that the two dimensional surface for finally giving comprises at least the region of two kinds of differentiated yields and crosslink density.
In the present invention, the photosensitive resin precursor liquid described in step (1) and step (3) includes monomer and light trigger.
Monomer contains active function groups, can under light illumination by light trigger initiated polymerization.At least one in monomer
Individual component includes two or more active function groups, so that polymeric acceptor forms cross-linked structure.
Preferably, the monomer of photosensitive resin precursor liquid described in step (1) and step (3) for acrylate monomer or
Epoxy monomer；
In the acrylate monomer, at least contain two acrylate-based functional groups；
In the epoxy monomer, at least contain two epoxy-functionals.
In the acrylate monomer, including at least a kind of compound acrylate-based containing two and the above；It is described
Epoxy monomer in, including at least a kind of compound containing two and above epoxy-functional.
The active function groups of described acrylate monomer are acrylate-based, and light trigger initiation monomer carries out free radical
Polymerisation.The active function groups of described epoxy monomer be epoxy-functional, light trigger trigger epoxy monomer carry out sun from
Sub- polymerisation.
Preferably, the acrylate monomer be selected from polyethyleneglycol diacrylate, ethyleneglycol dimethyacrylate,
One or more in epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin and amino acrylic resin；
The epoxy monomer is one or more in bisphenol-A epoxy, Bisphenol F epoxy, alicyclic epoxy.
Cited acrylate monomer and epoxy monomer contain two and above active function groups, but itself occurs
Crosslinking.Wherein, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin and amino acrylic resin are pre-
Polymers.
Further preferably, the acrylate monomer is selected from polyethyleneglycol diacrylate and/or methacrylate second
Diol ester.
It is the mechanical property of resin after regulation photosensitive resin precursor liquid viscosity and crosslinking curing, aforesaid propylene acid ester monomer
In, also (methyl) acrylate comprising mono acrylic ester base functional group.
An acrylate-based functional group is included in described (methyl) acrylate, preferably, described (methyl)
The structural formula of acrylate is as shown in Equation 1：
Wherein, R1It is methyl or hydrogen, R2It is the 1-20 alkyl of carbon atom.
Further preferably, (methyl) acrylate is preferably methyl methacrylate, methyl acrylate, methacrylic acid second
Ester, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-Propenoic acid, 2-methyl-, octyl ester, 2-ethyl hexyl acrylate, methacrylic acid
Certain herbaceous plants with big flowers ester, acrylic acid certain herbaceous plants with big flowers ester, cyclohexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, isobomyl acrylate
One kind or many in ester, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate and hydroxypropyl acrylate
Kind.
(methyl) acrylate of described acrylate-based functional group accounts for the 60-95% of acrylate monomer weight.Can
Think that the acrylate of single active function groups accounts for the 60-95% of the heavy amount of acrylate monomer.
Further preferably, (methyl) acrylate of described acrylate-based functional group accounts for acrylate monomer weight
80-90%.
Further preferably, described epoxy monomer is selected from novolac epoxy resin, diglycidyl ethers of bisphenol-A, the ring of Bisphenol F two
It is oxygen glycerin ether, the Synthesis of Oligo Ethylene Glycol of pentaerythrite four, tetrabromobisphenol A diglycidyl ether, 1,6- hexylene glycols diglycidyl ether, double
One or more of phenol A polyethylene glycol diglycidyl ether, epoxidation polyunsaturated fatty acid and epoxidized vegetable oil.
In above-mentioned epoxy monomer, the epoxy active diluent also including mono-epoxy-functional is (epoxy functionalized comprising one
Group).Described epoxy active diluent is a class with a low molecular compound for epoxy radicals.Preferably, described epoxy
Reactive diluent is one or more in butyl glycidyl ether, phenyl glycidyl ether, acrylic glycidol ether.
Described epoxy active diluent accounts for the 60-95% of epoxy monomer weight.It is believed that the epoxy of single active function groups
Compound accounts for the 60-95% of the heavy amount of epoxy monomer.
Further preferably, epoxy active diluent accounts for the 80-90% of epoxy monomer weight.
In step (1), selected according to the difference of polymerisation type (Raolical polymerizable, cationic polymerization)
Adaptable light trigger.
The light trigger that the acrylate monomer is used is free radical photo-initiation；What the epoxy monomer monomer was used
Light trigger is cation light initiator；The shared mass fraction in photosensitive resin precursor liquid of the light trigger is 0.1-
5%.
Free radical photo-initiation is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, two
One or more of Benzophenone class and thioxanthones；Cation light initiator be selected from diaryl group iodized salt, triaryl salt compounded of iodine,
One or more in alkyl salt compounded of iodine, isopropylbenzene cyclopentadienyl iron hexafluorophosphate.
Further preferably, free radical photo-initiation is selected from styrax, benzoin dimethylether, diphenylethan, dimethoxy
Phenyl acetophenone, hydroxyalkyl phenones, aroyl phosphorous oxides, benzophenone, 2,4-DihydroxyBenzophenone and thio propoxyl group
One or more in thioxanthone.
Preferably, the shared mass fraction in photosensitive resin precursor liquid of described initiator is 0.2-1%.
In the present invention, be used for swelling heterogeneous two dimensional surface described in step (3) is the paraffin or photosensitive tree for melting
Fat precursor liquid.
Preferably, the temperature of the paraffin melted described in step (3) is 45-65 DEG C.
Melting point of paraffin wax is different each variant according to the trade mark, in 45-65 DEG C of scope, fusing point need to be only heated to when using
Melt above and can be used.
Photosensitive resin precursor liquid can directly be selected from the formula in step (1), it is also possible to separately prepare.
Preferably, described plane die cavity is formed by two parallel sheet glass by the way that pad is closely sealed, between two sheet glass
Spacing be 0.5-5mm.
The thickness of plane mould can influence projection, curing efficiency.Preferably, described plane die cavity is by parallel two panels
Glass is formed by the way that pad is closely sealed, and the spacing between two sheet glass is 0.5-5mm.
Spacing between glass it is also contemplated that photosensitive resin precursor liquid plane mould filling thickness.
In step (2), using DLP projector the photosensitive resin precursor liquid in step (1) is carried out partial projection, exposure,
Solidification, the pattern of projection is transmitted to DLP projector by the CAD model of CAD；Step (2) circulation carries out at least two
Secondary, the pattern of projection every time is different.
The method of digitized projection technique construction three-dimensional structure proposed by the present invention, final three-dimensional structure is flat by two dimension
Different zones different conversion ratio in face is determined with crosslink density.Its conversion ratio of the region exposed repeatedly by multiple projections and crosslinking
Density is higher, otherwise then low.So key of the invention be by photosensitive resin be fully cured needed for time be divided into some sections,
The different region of projection in every time.
The DLP projector of DLP projector commodity in use in the present invention.
Preferably, the optical source wavelength of DLP projector described in step (2) is 200-700nm.
Preferably, the DLP projector single projection time described in step (2) is 0.5-5s.
In the power and described photosensitive resin precursor liquid coordinated, polymerisation efficiency is improved, shorten 3D structure structures
Build the time.
DLP projector also can be used the light source in the light source displacement DLP projector of the ultraviolet band less than 400nm.
Compared with prior art, beneficial effects of the present invention are embodied in：
(1) method of quick 3D printing provided by the present invention, is carried out using the paraffin or photosensitive resin precursor liquid that melt
When swelling, the arbitrary structures in swelling process can be all fixed up.
(2) method of quick 3D printing provided by the present invention, not aqueous and volatile solvent in the three-dimensional structure for obtaining,
It is practical.
Brief description of the drawings
Fig. 1 is digitized projection equipment and schematic device；
Fig. 2 is the two dimensional surface of embodiment 1 and swelling rear gained three-dimensional structure pictorial diagram；
Fig. 3 is the two dimensional surface of embodiment 2 and swelling rear gained three-dimensional structure pictorial diagram；
Fig. 4 is the two dimensional surface of embodiment 3 and swelling rear gained three-dimensional structure pictorial diagram.
Specific embodiment
The present invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the scope of example expression.
As shown in figure 1, the digitized projection equipment and device of present invention use include computer 1, the peace of DLP projector 2
Face mould has；Plane mould includes two sheet glass 3 and pad 4, and two sheet glass 3 enclose (closely sealed) into plane die cavity by pad 4, puts down
Photosensitive resin precursor liquid 5 is filled with face mould chamber.
DLP projector 2 is connected by G code with computer 1, the pattern of projection by the Computer Aided Design of computer 1 CAD model
Transmit to DLP projector 2；The surface of photosensitive resin precursor liquid 5 is repeatedly projected to by the way that DLP projector 2 is local, is carried out local, many
Secondary solidification.After the completion of solidification, the photosensitive resin (heterogeneous two dimensional surface) for obtaining will be solidified in the paraffin or photosensitive tree for melting
It is swelling in fat precursor liquid, obtain three-dimensional structure.
Embodiment 1
Photosensitive resin precursor liquid raw material：
Lauryl acid esters (HLA)：Sigma-Aldrich companies；
Ethylene glycol diacrylate methyl esters (EGDMA), Sigma-Aldrich companies；
Double (2,4,6- trimethylbenzoyls) phosphine oxides (Irgacure 819) of phenyl：Sigma-Aldrich companies；
By monomer (mass fraction HLA by a certain percentage:EGDMA=1:0.01, Irgacure 819 in photosensitive resin forerunner
Shared mass fraction is 0.5% in liquid.) well mixed, precursor liquid is being introduced into the plane that two sheet glass are constituted with syringe
Among mould (thickness 1mm), then the sample of preparation is placed at the 15cm of projector lens lower section.
Projection, exposure are circulated using digitized projection equipment illustrated in Figure 1 and installation drawing and are solidified：DLP is projected
The wave band that instrument light source sends is 400-700nm, and the single projection time is 2s, and each projecting figure is accumulated as following two dimensional surface and shows
It is intended to (see Fig. 2 (a)), color is deeper, and the more i.e. light application times of representative projection number of times are more long.
It is swelling：The two dimensional surface film after solidification (shown in such as Fig. 2 (b)) will be projected to be transferred in the paraffin of thawing, temperature 70
DEG C, make its swelling, taken out in swelling process, cooling, shown in the three-dimensional structure stablized such as Fig. 2 (c)；Thawing is placed on again
Paraffin in continue swelling, shown in three-dimensional structure such as Fig. 2 (d) of final stabilization.
Embodiment 2
Photosensitive resin precursor liquid raw material：
Hydroxy-ethyl acrylate (HEA)：Sigma-Aldrich companies；
Ethylene glycol diacrylate methyl esters (EGDMA)：Sigma-Aldrich companies；
Double (2,4,6- trimethylbenzoyls) phosphine oxides (Irgacure 819) of phenyl：Sigma-Aldrich companies；
By monomer (mass fraction HEA by a certain percentage:EGDMA:Irgacure 819=1:0.2:0.005) mix equal
It is even, among precursor liquid to be introduced the plane mould (thickness 1mm) that two sheet glass are constituted with syringe, the sample that then will be prepared
It is placed at the 15cm of projector lens lower section.
Shown in two dimensional surface schematic diagram such as Fig. 3 (a) of projection exposure, shown in the two dimensional surface for obtaining such as Fig. 3 (b), by it
It is swelling in the precursor liquid being placed in this example, be deformed into shown in three-dimensional structure such as Fig. 3 (c), take out, be placed in ultra-violet curing case make it is molten
The swollen precursor liquid entered is fully cured, three-dimensional structure stabilization.
Embodiment 3
Photosensitive resin precursor liquid raw material：
Polyglycols 2-glycidyl ether resin (DER732)：Sigma-Aldrich companies；
Ethyl acetate (EA)：Chemical Reagent Co., Ltd., Sinopharm Group；
4- isobutyl phenenyls -4- aminomethyl phenyl iodine hexafluorophosphate (Irgacure 250)：You Yang Science and Technology Ltd.s；
By monomer (mass fraction DER732 by a certain percentage:EGDMA:Irgacure 819=1:0.01:0.005) mix
Uniformly, among precursor liquid to be introduced the plane mould (thickness 1mm) that two sheet glass are constituted with syringe, the sample that then will be prepared
Product are placed at the 15cm of projector lens lower section.
Shown in two dimensional surface schematic diagram such as Fig. 4 (a) of projection exposure, the two dimensional surface for obtaining is placed on photosensitive resin
(HEA in precursor liquid:EGDMA:Irgacure 819=1:0.1:0.01), it is deformed into shown in three-dimensional structure such as Fig. 4 (b), takes out,
Being placed in ultra-violet curing case is fully cured the swelling precursor liquid entered, three-dimensional structure stabilization.
Claims (9)
1. a kind of method of quick 3D printing, it is characterised in that comprise the following steps：
Step (1)：Photosensitive resin precursor liquid comprising monomer and light trigger is placed in plane die cavity；
Step (2)：Multiple partial projection, exposure are carried out to photosensitive resin precursor liquid by default two-dimensional pattern using DLP projector
Solidification, obtains heterogeneous two dimensional surface；
Step (3)：The heterogeneous two dimensional surface for obtaining will be solidified and be soaked in swelling, taking-up, cooling, you can obtain in the paraffin of thawing
Obtain 3-D solid structure；
Or, heterogeneous two dimensional surface is soaked in swelling in photosensitive resin precursor liquid, take out, illumination curing, you can obtain three
Dimension stereochemical structure.
2. the method for quick 3D printing according to claim 1, it is characterised in that described in step (1) and step (3)
The monomer of photosensitive resin precursor liquid is acrylate monomer or epoxy monomer；
In the acrylate monomer, at least contain two acrylate-based functional groups；
In the epoxy monomer, at least contain two epoxy-functionals.
3. the method for quick 3D printing according to claim 2, it is characterised in that the acrylate monomer is selected from poly- second
Omega-diol diacrylate, ethyleneglycol dimethyacrylate, epoxy acrylic resin, polyurethane acrylic resin, polyester
One or more in acid resin and amino acrylic resin；
The epoxy monomer is one or more in bisphenol-A epoxy, Bisphenol F epoxy and alicyclic epoxy.
4. the method for quick 3D printing according to claim 2, it is characterised in that in the acrylate monomer, also wrap
(methyl) acrylate of the functional group of base containing mono acrylic ester；
In the epoxy monomer, the also epoxy active diluent comprising mono-epoxy-functional.
5. the method for quick 3D printing according to claim 2, it is characterised in that the light that the acrylate monomer is used
Initiator is free radical photo-initiation；The light trigger that the epoxy monomer monomer is used is cation light initiator；The light
The shared mass fraction in photosensitive resin precursor liquid of initiator is 0.1-5%.
6. the method for quick 3D printing according to claim 1, it is characterised in that DLP projector described in step (2)
Optical source wavelength is 200-700nm.
7. the method for quick 3D printing according to claim 1, it is characterised in that the paraffin melted described in step (3)
Temperature be 45-65 DEG C.
8. the method for quick 3D printing according to claim 1, it is characterised in that described plane die cavity is by parallel two
Sheet glass is formed by the way that pad is closely sealed, and the spacing between two sheet glass is 0.5-5mm.
9. the method for quick 3D printing according to claim 1, it is characterised in that DLP projector list described in step (2)
Secondary projection time is 0.5-5s.
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| CN201611040841.0A CN106696258B (en) | 2016-11-21 | 2016-11-21 | A kind of method of quick 3D printing |
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| CN106696258B CN106696258B (en) | 2019-09-03 |
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| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN108786482A (en) * | 2018-06-05 | 2018-11-13 | 福州大学 | A kind of quaternary anion-exchange membrane based on photocuring 3D printing technique |
| CN110341097A (en) * | 2019-08-05 | 2019-10-18 | 浙江大学 | A kind of thermoplastic polymer and application based on DLP photocuring 3D printing |
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| CN104085106A (en) * | 2014-01-21 | 2014-10-08 | 上海坤融实业有限公司 | DLP principle based 3D printer |
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| Publication number | Publication date |
|---|---|
| CN106696258B (en) | 2019-09-03 |
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