CN105818382B - A kind of method based on digital light processing structure three-dimensional structure - Google Patents

A kind of method based on digital light processing structure three-dimensional structure Download PDF

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CN105818382B
CN105818382B CN201610239890.0A CN201610239890A CN105818382B CN 105818382 B CN105818382 B CN 105818382B CN 201610239890 A CN201610239890 A CN 201610239890A CN 105818382 B CN105818382 B CN 105818382B
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epoxy
photosensitive resin
dimensional structure
dimensional
acrylate
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CN105818382A (en
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谢涛
吴晶军
赵骞
黄丽媚
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Zhejiang University ZJU
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Zhejiang University ZJU
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)

Abstract

The invention discloses a kind of method based on digital light processing structure three-dimensional structure, comprise the following steps:Step (1):Photosensitive resin precursor liquid comprising monomer or performed polymer and light trigger is placed in plane die cavity;Step (2):Default two-dimensional pattern is pressed using DLP projector, and multiple partial projection, exposure curing are carried out to photosensitive resin precursor liquid;Obtain heterogeneous two dimensional surface;Step (3):The heterogeneous two dimensional surface that solidification obtains is soaked in solvent and is swelled, obtains 3-D solid structure.Method proposed by the present invention is simply, conveniently, low for equipment requirements, is highly suitable for preparing polymer accurate three-dimensional structure.

Description

A kind of method based on digital light processing structure three-dimensional structure
Technical field
The present invention relates to Polymer Processing manufacturing field, more particularly to one kind to use digitized projection technology rapid build three The method for tieing up structure.
Background technology
It is process with 3-D solid structure polymer product typically by the moulding method of mould.This tradition side Method can only often process some simple three-dimensional structures due to the limitation that mould is processed and the later stage is stripped.Moreover, the exploitation of mould 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, have 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 uses 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 processing 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 which thickness is thinner during in particular for higher printing precision, the number of plies is more, and it is printed 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.
It is a kind of special material preparation technology that heterogeneous two dimensional surface is converted into three-dimensional structure under certain condition.Its General principle is that the distribution density and gradient of material are introduced in two dimensional surface preparation, is stored in the heterogeneous two dimensional surface of formation Internal stress, under certain condition internal stresses release, the two dimensional surface in mechanics unstable state is specific three with regard to spontaneous nuclear transformation Tie up structure.Because the preparation speed of two dimensional surface is very fast, the process that two dimensional surface is converted into three-dimensional structure is also very fast, so Such a technology is expected to turn into a kind of fast construction method of three-dimensional structure.But above-mentioned heterogeneous two dimensional surface is mainly at present The distribution of one of network is realized to realize in dual network structure by the use of photomask, design freedom is not It is high.Because final three-dimensional structure is determined by the inhomogeneous distribution in two dimensional surface, so the technological means obtains at present Also be some relatively simple three-dimensional structures.
The content of the invention
To solve the defects of prior art, the invention provides a kind of method of rapid build polymer three-dimensional structure:It is logical Cross digitized projection technology and obtain a heterogeneous two dimensional surface accurately controlled, the two dimensional surface is converted under certain condition Three-dimensional structure set in advance.
A kind of method based on digital light processing structure three-dimensional structure, 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 press default two-dimensional pattern photosensitive resin precursor liquid is carried out multiple partial projection, Exposure curing;Obtain heterogeneous two dimensional surface;
Step (3):The heterogeneous two dimensional surface that solidification obtains is soaked in solvent and is swelled, obtains 3-D solid structure.
The present invention obtains a heterogeneous two dimensional surface accurately controlled by digitized projection technology, and two dimensional surface is different The swelling character in region is different, and the two dimensional surface can be converted into three-dimensional structure set in advance in swelling process.Present invention side The committed step of method is that multiple selective area projection, exposure are carried out to photosensitive resin using DLP projector, has different zones There is different degree of swelling;When determining that required projection is fully cured in resin by the kinetics of polymerization reaction of photosensitive resin Between, it is distributed according to counter its swellbility required in two dimensional surface that push away of final required three-dimensional structure, so that it is determined that projection every time Time and projection figure.
In the present invention, DLP projector is connected by G code with computer, launches out specific X-Y scheme to photosensitive tree Fat forerunner's liquid level.Polymerisation occurs for photosensitive resin at projection and crosslinking curing.Control the single projection time so that single is thrown Photosensitive resin polymerisation is incomplete under shadow, and crosslinking curing is insufficient, i.e. the conversion ratio of 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 increase with crosslink density.Projection, photocuring operation repeat repeatedly, until poly- It is complete to close reaction.The process of multiple projections comprises at least two kinds of different graphics (view field of different graphic can be overlapped), So that the two dimensional surface finally given comprises at least the region of two kinds of differentiated yields and crosslink density.This two dimensional surface is placed in Fully it is swelled in solvent, the degree of swelling of different zones is different, and so as to produce local stress in two dimensional surface, flexing occurs Deformation, form three-dimensional structure.
In the present invention, step (1) the photosensitive resin precursor liquid includes monomer and light trigger.
Monomer contains active function groups, can be 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, described monomer is acrylate monomer or epoxy monomer;
In the acrylate monomer, at least containing two acrylate-based functional groups;
In the epoxy monomer, at least containing 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 triggers monomer to carry out free radical Polymerisation.The active function groups of described epoxy monomer are 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;
Epoxy monomer is the 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, itself can occur 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.
For the mechanical property of resin after regulation photosensitive resin precursor liquid viscosity and crosslinking curing, aforesaid propylene acid ester monomer In, in acrylate monomer, 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, R1For methyl or hydrogen, R2For the alkyl of 1-20 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 more 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 The 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 comprising mono-epoxy-functional is (epoxy functionalized comprising one Group).Described epoxy active diluent is the low molecular compound of a kind of one epoxy radicals of band.Preferably, described epoxy Reactive diluent is the 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 acrylate monomer uses is free radical photo-initiation;The light trigger that epoxy monomer monomer uses For cation light initiator;Light trigger mass fraction shared in photosensitive resin precursor liquid is 0.1-5%.
Free radical photo-initiation is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, two The 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, mass fraction of the described initiator shared by photosensitive resin precursor liquid is 0.2-1%.
The solvent that photosensitive resin precursor liquid described in step (1) also selectively uses comprising step (3), before photosensitive resin The content for driving the solvent in liquid is the 0-80% of solvent gross mass needed for photosensitive resin complete swelling.It is also contemplated that described is molten Agent can add a part during step (1) and (but be no more than solvent gross mass needed for photosensitive resin complete swelling 80%), the swelling process of step (3) adds remaining part.The solvent and step included in step (1) in photosensitive resin precursor liquid (3) make the solvent needed for the swelling of the photosensitive resin after solidification consistent in, photocuring effect can be so improved, in addition, can also accelerate The swelling efficiency of resin after solidification.
Solvent can be calculated by retrodicting needed for photosensitive resin complete swelling.
The selection of solvent is adapted to the hydrophilicity of photosensitive resin made from solidification, and step (3) described solvent is to be swelled Inorganic, the organic solvent of photosensitive resin after solidification.
Photosensitive resin is hydrophilic compounds, and solvent is selected from water and/or ethanol;
Or photosensitive resin is hydrophobic compound, solvent be selected from ethyl acetate, butyl acetate, dichloromethane, chloroform, benzene, One or more in toluene, tetrahydrofuran, dimethylformamide and the paraffin of thawing.
The thickness of plane mould can influence projection, curing efficiency.Preferably, described plane die cavity is by parallel two panels Glass forms 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 in step (1) photosensitive resin precursor liquid carry out partial projection, exposure, Solidification, the pattern of projection are transmitted to DLP projector by the CAD model of CAD;Step (2) circulation carries out at least two Secondary, the pattern projected every time is different.
The method of digitized projection technique construction three-dimensional structure proposed by the present invention, final three-dimensional structure are flat by two dimension Different zones different conversion ratio in face determines with crosslink density.By its conversion ratio of region that multiple projections expose repeatedly and crosslinking Density is higher, on the contrary then low.So the key of the present invention is that photosensitive resin is fully cured into the required time to 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.
The wave band that DLP projector light source is sent is 400-700nm, and in step (2), the single projection time is 0.5-5s. The power and described photosensitive resin precursor liquid coordinated, polymerisation efficiency is improved, shorten the 3D structures structure time.
DLP projector can also be used the light source of the ultraviolet band less than 400nm to replace the light source in DLP projector.
Compared with prior art, beneficial effects of the present invention are embodied in:
(1) conversion ratio in two dimensional surface is distributed by computer and projecting apparatus co- controlling with crosslink density, and precision is high, reason By the two dimensional surface that can above build Arbitrary distribution, the three-dimensional structure of arbitrary structures also can be finally built.
(2) structure speed is fast, and the structure of two dimensional surface is no more than 30s.
Brief description of the drawings
Fig. 1 is digitized projection equipment and schematic device;
Fig. 2 is gained three-dimensional structure pictorial diagram after the two dimensional surface of embodiment 1 and swelling;
Fig. 3 is gained three-dimensional structure pictorial diagram after the two dimensional surface of embodiment 2 and swelling;
Fig. 4 is gained three-dimensional structure pictorial diagram after the two dimensional surface of embodiment 3 and swelling.
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, digitized projection equipment and device that the present invention uses 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, put down Face mould intracavitary is filled with photosensitive resin precursor liquid 5.
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, more Secondary solidification.After the completion of solidification, the photosensitive resin (heterogeneous two dimensional surface) that solidification obtains is swelled in a solvent, obtains three-dimensional knot Structure.
Embodiment 1 (hydrophilic acrylate's photosensitive resin)
Photosensitive resin precursor liquid raw material:
A) hydroxy-ethyl acrylate (HEA):Sigma-Aldrich companies;
B) 3- propyl sulfonic acids metering system acid potassium salt (PSPMA):Sigma-Aldrich companies;
C) ethylene glycol diacrylate methyl esters (EGDMA), Sigma-Aldrich company;
D) double (2,4,6- trimethylbenzoyls) phosphine oxides (Irgacure 819) of phenyl:Sigma-Aldrich companies;
By monomer (mass fraction HEA by a certain percentage:PSPMA:EGDMA=1:0.1:0.01, Irgacure 819 in light Shared mass fraction is 0.5% in quick resin precursor liquid.) well mixed, precursor liquid is being introduced into two sheet glass with syringe Among the plane mould (thickness 1mm) of composition, then the sample of preparation is placed in below projector lens at 15cm.
Circulation projection, exposure and solidification are carried out using digitized projection equipment illustrated in Figure 1 and installation drawing:DLP is projected The wave band that instrument light source is sent is 400-700nm, and the single projection time is 2s, and each projecting figure is accumulated as following two dimensional surface and shown It is intended to (see Fig. 2 (a) part), color is deeper, and the more i.e. light application times of representative projection number are longer.
Swelling:The two dimensional surface film transfer after solidifying will be projected into deionized water, it is fully swelled, be converted into three-dimensional Structure chart (see Fig. 2 (b) part).
Embodiment 2 (epoxy photosensitive resin)
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 phenenyl -4- aminomethyl phenyl iodine hexafluorophosphates (Irgacure 250):You Yang Science and Technology Ltd.s;
By monomer (mass fraction DER732 by a certain percentage:EA:Irgacure 250=1:0.2:0.005) mixing is equal It is even, among precursor liquid is introduced into the plane mould (thickness 1mm) that two sheet glass are formed with syringe, then by the sample of preparation It is placed in below projector lens at 15cm.
The two dimensional surface schematic diagram (see Fig. 3 (c) part) of projection exposure, the solvent of swelling is ethyl acetate, and conversion obtains The tomograph obtained (see Fig. 3 (d) part).
Embodiment 3 (hydrophobic acrylic acid's ester photosensitive resin)
Photosensitive resin precursor liquid raw material:
Butyl acrylate (BA):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 BA by a certain percentage:EGDMA:Irgacure 819=1:0.01:0.005) mixing is equal It is even, among precursor liquid is introduced into the plane mould (thickness 1mm) that two sheet glass are formed with syringe, then by the sample of preparation It is placed in below projector lens at 15cm.
The two dimensional surface schematic diagram of projection exposure (see Fig. 4 (e) part).
Swelling:
The two dimensional surface film transfer after solidifying will be projected into butyl acetate, it is fully swelled, be converted into three-dimensional structure Figure is (see Fig. 4 (f) part).

Claims (10)

  1. A kind of 1. method based on digital light processing structure three-dimensional structure, it is characterised in that comprise the following steps:
    Step (1):Photosensitive resin precursor liquid comprising monomer or performed polymer and light trigger is placed in plane die cavity;
    Step (2):Default two-dimensional pattern is pressed using DLP projector, and multiple partial projection, exposure are carried out to photosensitive resin precursor liquid Solidification;Obtain heterogeneous two dimensional surface;
    Step (3):The heterogeneous two dimensional surface that solidification obtains is soaked in solvent and is swelled, obtains 3-D solid structure.
  2. 2. the method according to claim 1 based on digital light processing structure three-dimensional structure, it is characterised in that described list Body is epoxy monomer;Described prepolymer is acrylate prepolymer body;
    In the acrylate prepolymer body, at least containing two acrylate-based functional groups;
    In the epoxy monomer, at least containing two epoxy-functionals.
  3. 3. the method according to claim 2 based on digital light processing structure three-dimensional structure, it is characterised in that the propylene Acid esters performed polymer is selected from polyethyleneglycol diacrylate, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylic tree One or more in fat and amino acrylic resin;
    Epoxy monomer is the one or more in bisphenol-A epoxy, Bisphenol F epoxy, alicyclic epoxy.
  4. 4. the method according to claim 3 based on digital light processing structure three-dimensional structure, it is characterised in that acrylate In performed polymer, also (methyl) acrylate comprising mono acrylic ester base functional group;
    In epoxy monomer, the also epoxy active diluent comprising mono-epoxy-functional.
  5. 5. the method according to claim 2 based on digital light processing structure three-dimensional structure, it is characterised in that acrylate The light trigger that performed polymer uses is free radical photo-initiation;The light trigger that epoxy monomer uses is cation light initiator; Light trigger mass fraction shared in photosensitive resin precursor liquid is 0.1-5%.
  6. 6. the method according to claim 5 based on digital light processing structure three-dimensional structure, it is characterised in that free radical light Initiator is selected from benzoin and derivative, benzil class, alkylbenzene ketone, acyl group neighbour oxide, benzophenone and thioxanthene The one or more of ketone;Cation light initiator is selected from diaryl group iodized salt, triaryl salt compounded of iodine, alkyl salt compounded of iodine, isopropyl One or more in benzene cyclopentadienyl iron hexafluorophosphate.
  7. 7. the method according to claim 1 based on digital light processing structure three-dimensional structure, it is characterised in that step (1) Described in the solvent that is also selectively used comprising step (3) of photosensitive resin precursor liquid, solvent in photosensitive resin precursor liquid Content is the 0-80% of solvent gross mass needed for photosensitive resin complete swelling.
  8. 8. the method according to claim 1 based on digital light processing structure three-dimensional structure, it is characterised in that described is flat Face mould chamber is formed by two parallel sheet glass by the way that pad is closely sealed, and the spacing between two sheet glass is 0.5-5mm.
  9. 9. the method according to claim 1 based on digital light processing structure three-dimensional structure, it is characterised in that step (2) In, the single projection time is 0.5-5s.
  10. 10. the method according to claim 1 based on digital light processing structure three-dimensional structure, it is characterised in that photosensitive tree Fat is hydrophilic compounds, and solvent is selected from water and/or ethanol;
    Or photosensitive resin is hydrophobic compound, solvent be selected from ethyl acetate, butyl acetate, dichloromethane, chloroform, benzene, toluene, One or more in tetrahydrofuran, dimethylformamide and the paraffin of thawing.
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CN106696258B (en) * 2016-11-21 2019-09-03 浙江大学 A kind of method of quick 3D printing
CN110341097B (en) * 2019-08-05 2020-06-23 浙江大学 Thermoplastic polymer based on DLP photocuring 3D printing and application

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JP2010094938A (en) * 2008-10-20 2010-04-30 Hitachi Ltd Stereolithography apparatus
CN104890245A (en) * 2015-04-28 2015-09-09 北京金达雷科技有限公司 Photosensitive resin pool, photocuring 3D (three-dimensional) printer using photosensitive resin pool and printing method

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Publication number Priority date Publication date Assignee Title
JP2008066193A (en) * 2006-09-08 2008-03-21 Nitto Denko Corp Crosslinked fine porous membrane
JP2010094938A (en) * 2008-10-20 2010-04-30 Hitachi Ltd Stereolithography apparatus
CN104890245A (en) * 2015-04-28 2015-09-09 北京金达雷科技有限公司 Photosensitive resin pool, photocuring 3D (three-dimensional) printer using photosensitive resin pool and printing method

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