CN105924571B - Continuous photocurable three-dimensional printing materials - Google Patents
Continuous photocurable three-dimensional printing materials Download PDFInfo
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- CN105924571B CN105924571B CN201610339660.1A CN201610339660A CN105924571B CN 105924571 B CN105924571 B CN 105924571B CN 201610339660 A CN201610339660 A CN 201610339660A CN 105924571 B CN105924571 B CN 105924571B
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- PCHOHILCCBEVPK-UHFFFAOYSA-N CCCOC(C(C)(C(CC1)C2=O)C1(C)C2=O)=O Chemical compound CCCOC(C(C)(C(CC1)C2=O)C1(C)C2=O)=O PCHOHILCCBEVPK-UHFFFAOYSA-N 0.000 description 1
- LEHPNZPXIKPYOO-TWGQIWQCSA-N CCCOC(C/C=C\C(C(c1ccccc11)=O)=C(C)C1=O)=O Chemical compound CCCOC(C/C=C\C(C(c1ccccc11)=O)=C(C)C1=O)=O LEHPNZPXIKPYOO-TWGQIWQCSA-N 0.000 description 1
- 0 CC[C@@](C)OC(C(CC1)(C(C)(C)C1C1=*)C1=O)=O Chemical compound CC[C@@](C)OC(C(CC1)(C(C)(C)C1C1=*)C1=O)=O 0.000 description 1
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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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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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
- C08F222/00—Copolymers 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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
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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
- C08F220/00—Copolymers 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
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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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
- C08F222/00—Copolymers 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
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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Abstract
A kind of continuous photocurable three-dimensional printing materials, including 50 100 parts by weight of activated monomers, 0.01 25 parts by weight photoinitiators, 0.01 25 parts by weight light inhibitors；The continuous photocurable three-dimensional printing materials have at least one minimum wavelength be, maximum wavelength beInitiation optical wavelength section, in the initiation optical wavelength section, the absorbance of the photoinitiator is the 2 times or more of the absorbance of the light inhibitor；The continuous photocurable three-dimensional printing materials have at least one minimum wavelength be, maximum wavelength beInhibition optical wavelength section, in the inhibition optical wavelength section, the absorbance of the light inhibitor is the 2 times or more of the absorbance of the photoinitiator.Material of the present invention makes three-dimensional Light Curing that can be carried out continuously at a high speed, and speed and precision are not limited to by light transmission base plate performance.
Description
Technical field
The invention belongs to rapid three dimensional printing forming field more particularly to a kind of continuous photocuring 3 D-printing materials of high speed
Material.
Background technology
Three-dimensional printing technology is the molding by automatic numerical control successively build-up materials realization threedimensional model.Relative to tradition
Processing technology for, three-dimensional printing technology need not separately make mold, directly process finished product, and can quickly be passed
System processing technology is difficult to the complex parts manufactured.Therefore, three-dimensional printing technology can shorten the research and development of products period, reduce enterprise
R＆D costs provide more effective technique solution, meet growing individual demand.
Stereo Lithography technology is that it is solid to being needed in two dimensional surface to control laser by computer using photosensitive resin as raw material
The region point by point scanning of change forms a two-dimensional silhouette.It is final required to obtain by successively accumulating such two-dimensional silhouette
Threedimensional model.With the development of digital projection technique, laser scanning system is replaced using digital projection system as excitation light source
More economical and efficient solution is provided for photocuring three-dimensional printing technology.
Digital projection photocurable three-dimensional printing technology can be divided into two major classes, i.e., top projection successively molding and bottom project successively
Molding.Successively in forming technique, digital projection is from top to bottom projected to liquid photosensitive resin surface for top projection, new cured photosensitive
Resin layer is located at the top of molded part.By constantly accumulating new cured layer from top, to realize threedimensional solid at
Type.After each illumination curing forms one layer of new solid-state thin layer, being loaded with the shaped platform of molded part can decline so that have become
Type is added to resin storage tank partially below the height of one setting of liquid level or new liquid photosensitive resin so that liquid level is higher than
The height of one setting of moulding section.Under both of these case, it is required for pause digital projection, waits for liquid photosensitive resin in gravity
Or it is covered in molded atop part again under the action of mechanical scraping device, it is ready for next layer of photocuring.This mistake
Journey can interrupt projection photocurable, and occupy the relatively long time, lead to the speed degradation of photocuring 3 D-printing.This
Outside, top projects in successively forming technique, and molded part is immersed in liquid resin always.When needing to be molded higher object
When, then it needs a height to be more than the resin storage tank of shaped object, and need to fill the resin storage tank with a large amount of photosensitive resin, beats
It also needs to recycle uncured resin after the completion of print, causes operating cost high and complicated for operation.
Successively in forming technique, the bottom of resin storage tank uses light transmission bottom plate, digital projection to pass through from the bottom to top saturating for bottom projection
Optical substrate is projected to the interface zone of liquid photosensitive resin and light transmission bottom plate so that the liquid between molded part and light transmission bottom plate
Photocuring occurs for state photosensitive resin thin layer.By constantly accumulating new cured layer from bottom, to realize the molding of threedimensional solid.
When using this method, molded part is not necessarily to be immersed in liquid resin, therefore even if if when needing to be molded higher object only
A shallower resin storage tank is needed, successively forming technique has a clear superiority relative to top projection.But then, every time
Illumination curing formed one layer of new solid-state thin layer after, be loaded with molded part shaped platform need rise one setting away from
From so that molded part is kept completely separate with light transmission bottom plate and keeps at a distance from a thickness again, therebetween by liquid photosensitive tree
Fat is filled, and is ready for next layer of photocuring.Since photosensitive resin cured after photocuring and light transmission bottom plate have bonded
Together, the two separation is needed into attention especially.This separation process can interrupt projection photocurable, and occupy relatively long
Time leads to the speed degradation of photocuring 3 D-printing, therefore successively there is no apparent for forming technique relative to top projection
It improves.
A kind of photocuring three-dimensional printer is disclosed in the patent document that publication No. is CN105122136A, uses and partly oozes
Permeability element is as light transmission bottom plate.When digital projection is projected across light transmission bottom plate to liquid photosensitive resin and light transmission bottom from the bottom to top
When the interface zone of plate, the polymerization inhibitor of light transmission bottom plate and liquid photosensitive resin interface area is entered by semipermeability element
The solidification of the region resin can be prevented, Inhibition of polymerization area is formed.Light initiating polymerizing reaction can only be in the area other than Inhibition of polymerization area
Domain occurs, and the photosensitive resin in Inhibition of polymerization area then remains liquid.When the shaped platform for being loaded with molded part rises,
Liquid photosensitive resin in Inhibition of polymerization area constitutes fluid channel so that the photosensitive resin on periphery is continuous under environmental pressure driving
Be flowed into molded part in the gap of light transmission bottom plate.During this, projection photocurable can be carried out continuously, to keep away
Exempt from the projection that traditional bottom projects in successively forming technique caused by separation process to interrupt, to significantly improve photocuring three-dimensional
The speed of printing.
Photocuring three-dimensional printer using semipermeability element as light transmission bottom plate, is continuously light-cured into although realizing
Type, but semipermeability element therein plays polymerization inhibitor channel, projecting light path, mechanical support structure, chemistry appearance simultaneously
The various rolls such as device, it is multinomial by molecular permeability, optical transmittance, mechanical strength, case hardness, chemical stability etc.
The comprehensive constraint of index causes final therefore, it is difficult to find the very excellent material of indices to be used as semipermeability element
The performance of machine is limited to.In order to meet infiltrative requirement, fluoropolymer is commonly used at present as semipermeability element, but
The elasticity modulus of the material is relatively low, is stressed and is easily bent in print procedure, causes Inhibition of polymerization area to deform, and influence light path
And image quality, this problem are particularly evident in the forming process of substantially surface member.In addition, in order to ensure polymerization inhibitor energy
Pass through semipermeability element, it is difficult in the fine and close functional coating of semipermeability element surface addition to be modified and increase
By force, it is also difficult to be controlled into trip temperature by thermal convection current or heat transfer semi-permeable element.
Invention content
It is an object of the invention to overcome the deficiencies of existing technologies, one kind is provided does not depend on semipermeability element and can be realized
The material of the continuous photocuring 3 D-printing of high speed.
To achieve the above object, the technical scheme is that：
A kind of continuous photocurable three-dimensional printing materials, which is characterized in that in terms of parts by weight, including following components：
50-100 parts of activated monomer；
0.01-25 parts of photoinitiator；
0.01-25 parts of light inhibitor；
The continuous photocurable three-dimensional printing materials have at least one minimum wavelength beMaximum wavelength isDraw
Emission wavelength section, in the initiation optical wavelength section, the absorbance of the photoinitiator is the extinction of the light inhibitor
The 2 times or more of degree；The continuous photocurable three-dimensional printing materials have at least one minimum wavelength beMaximum wavelength is
Inhibition optical wavelength section, in the inhibition optical wavelength section, the absorbance of the light inhibitor is the photoinitiator
The 2 times or more of absorbance.
Preferably, at least one wave-length coverage for causing optical wavelength sectionMore than 10 nanometers, and center
ValueBetween 150 nanometers to 1000 nanometers；The light caused in optical wavelength section can induce described in activation
Photoinitiator generates free radical, molecule or the ion for causing the continuous photocurable three-dimensional printing materials polymerization.
Preferably, at least one wave-length coverage for inhibiting optical wavelength sectionMore than 10 nanometers, and in
Center valueBetween 150 nanometers to 1000 nanometers；The light inhibited in optical wavelength section can induce activation
The light inhibitor generates and inhibits the active free radical of the photoinitiator, molecule or ion.
Preferably, the degree of functionality of the activated monomer is 1, the activated monomer is selected from acrylic ester monomer, methyl
At least one of acrylic ester monomer, vinyl monomer, vinyl ethers monomer and epoxy monomer.
Preferably, the photoinitiator includes styrax photoinitiator, benzoin ether photoinitiator, liquid storax
Photoinitiator, benzil class photoinitiator, benzil ketals photoinitiator, α, α-dialkoxy benzene ketone-type photoinitiators,
Alpha-hydroxyalkyl benzophenone photoinitiator, α-amine alkyl phenones photoinitiator, α-sulfone alkyl phenones photoinitiator, benzoyl first
Acid esters photoinitiator, benzoyl ketoxime ester photoinitiator, thiobenzoate ester lightlike initiating agent, benzoyl hydroperoxide esters light
At least one of initiator, monoacylphosphine oxides photoinitiator and bis-acylphosphine oxides photoinitiator.
Preferably, the photoinitiator include Benzophenone-type light initiator, benzophenone diphenyl sulfide photoinitiator,
Thioxanthone photoinitiator, anthraquinone photoinitiator, camphorquinone photoinitiator, coumarin ketone photoinitiator, phenyl titanium
At least one of luxuriant photoinitiator and phenylalkyl boron salt photoinitiator.
Preferably, the photoinitiator includes
At least one of；R1For the alkyl containing 1-12 carbon ,-R2For one kind in following groups
Preferably, the photoinitiator includes aryl diazonium salts photoinitiator, diaryl iodonium salt photoinitiator, three
At least one of arylsulfonium salts photoinitiator and aryl cyclopentadienyl iron photoinitiator.
Preferably, the light inhibitor includes
At least one of；Wherein R1',R2',R3',R4' it is alkyl, aryl, alcohol radical, ethoxylated alkyl, propoxylation
One kind in alkyl.
Preferably, the light inhibitor includes carbamates light inhibitor, aryl formate ketoxime ester Xanthophyll cycle
Agent, triaryl methanol class light inhibitor, and
In one kind；Wherein R1" be straight chained alkyl containing 1-12 carbon, branched alkyl, multi-ring alkyl, with heteroatomic more
Naphthenic base or aryl ,-R2" be
In one kind, X-For tetrafluoroborate, tetraphenylborate, four (pentafluorophenyl group) borates, hexafluoro-phosphate radical, six
One kind in fluorine arsenate and hexafluoroantimonic anion.
Preferably, also including the aided initiating more than 0 and less than 25 parts by weight, the aided initiating includes alkyl amine
Aided initiating, alkyl alcohol radical amine aided initiating, alkyl ester group amine aided initiating, alkylarylamines aided initiating, N, N-
Dialkylaminobenzoic acid esters class aided initiating, N, N- dialkyl amido propionic acid ester aided initiatings and N, N- dialkyl amino propyl
At least one of dimethyl silicone polymer class aided initiating.
Preferably, also including the polyfunctional monomer that the degree of functionality more than 0 and less than 300 parts by weight is 2-6, more officials
Energy monomer includes esters of acrylic acid polyfunctional monomer, methyl acrylic ester polyfunctional monomer, vinyl-based polyfunctional monomer, second
At least one of alkenyl ethers polyfunctional monomer and epoxies polyfunctional monomer.
Preferably, also including the oligomer more than 0 and less than 300 parts by weight, the oligomer includes epoxy acrylic
Oligoesters, polyester acrylate oligomer, polyurethane acrylates oligomer, polyether acrylate oligomer and have
At least one of machine silica acrylic acid oligoesters.
Preferably, also including the initiation light absorber more than 0 and less than 20 parts by weight, the initiation light absorber is to extremely
Wavelength has the absorption photoextinction, the initiation light absorber to include some or all of in a few initiation optical wavelength section
Disperse yellow, disperse orange, disperse red, the green, disperse blue of dispersion, disperse violet, pigment yellow, pigment orange, paratonere, naphthol green, pigment blue,
Pigment violet, superfine titanic oxide, phenyl triazines ultraviolet absorber, benzotriazole ultraviolet absorber, salicylate type ultraviolet
At least one of absorbent and oxanilide class ultraviolet absorber.
Preferably, also including the inhibition light absorber more than 0 and less than 20 parts by weight, the inhibition light absorber is to extremely
Wavelength has the absorption photoextinction, the inhibition light absorber to include some or all of in a few inhibition optical wavelength section
Disperse yellow, disperse orange, disperse red, the green, disperse blue of dispersion, disperse violet, pigment yellow, pigment orange, paratonere, naphthol green, pigment blue,
Pigment violet, superfine titanic oxide, phenyl triazines ultraviolet absorber, benzotriazole ultraviolet absorber, salicylate type ultraviolet
At least one of absorbent and oxanilide class ultraviolet absorber.
Preferably, also including the antifoaming agent more than 0 and less than 10 parts by weight, the antifoaming agent is defoamed selected from mineral oils
At least one of agent, organic silicon antifoaming agent, polyethers antifoaming agent, polyesters antifoaming agent and lower aliphatic alcohols antifoaming agent.
Preferably, also including the levelling agent more than 0 and less than 10 parts by weight, the levelling agent is selected from acroleic acid resin class
At least one of levelling agent, organic siliconresin class levelling agent and fluorocarbon resin class levelling agent.
Preferably, also including 0-500 parts of solid powders, the solid powder is selected from silica, alundum (Al2O3), two
At least one of zirconium oxide, silicon nitride and silicon carbide powder.
Compared with the existing technology, the invention has the advantages that or advantage：
1. add light inhibitor in photosensitive resin, by after the light selective excitation of specific wavelength light transmission bottom plate with
The interface of liquid photosensitive resin inhibits the generation of polymerization, Inhibition of polymerization area is formed, to not depend on semipermeability element
Realize continuous photocuring 3 D-printing.
2. light inhibitor activity is controlled by illumination completely, activity disappears under the conditions of non-lighting activation, not will produce by half
Phenomenon is inhibited caused by the General polymeric inhibitor that osmotic component imports.
3. inhibitor is not necessarily to be added by light-transparent substrate, therefore without any requirement to its permeability.Light-transparent substrate only needs full
The requirement of sufficient optical transmittance, mechanical strength, case hardness, chemical stability, selection range is wide, and performance indicator is compared with semipermeability
Element can be substantially improved.
4. light-transparent substrate surface can also carry out various coating treatments to further enhance performance according to special requirement so that this
The continuous photocurable three-dimensional printing materials of patented invention have more advantage in terms of stamp with the size, print speed and printing precision.
Description of the drawings
Fig. 1 is the mechanism schematic diagram for causing light and acting solely on material of the present invention；
Fig. 2 is the mechanism schematic diagram for inhibiting light to act solely on material of the present invention；
Fig. 3 is to cause light and inhibit light while acting on the mechanism schematic diagram of material of the present invention；
Fig. 4 is the structural schematic diagram using the continuous photocuring 3D printing equipment of material of the present invention；
Fig. 5 is the light-source system structural schematic diagram using the continuous photocuring 3D printing equipment of material of the present invention；
Fig. 6 is the light-source system emission spectrum schematic diagram using the continuous photocuring 3D printing equipment of material of the present invention；
Fig. 7 is the molding pattern principle schematic using the continuous photocuring 3D printing equipment of material of the present invention.
Specific implementation mode
Below in conjunction with the accompanying drawings and embodiment, present invention is further described in detail.
Embodiment 1
Referring to Fig. 1, wherein have liquid photosensitive resin thin layer 104 between light transmission bottom plate 102 and shaped platform 105, it is photosensitive
Resin includes following ingredient：100 parts by weight of acrylic acid lauryls, 100 parts by weight tripropylene glycol diacrylates, 3 parts by weight camphor trees
Brain quinone, 2 parts by weight N, N- dimethyl amino benzoates, 6 parts by weight tetraethylthiuram disulfides.Wavelength is received for 470 ± 5
The initiation light 101 of rice is irradiated to across light transmission bottom plate 102 on photosensitive resin thin layer 104.Due to light absorption effect, causes light and setting
Light intensity in fat is curve 103.Cause in optical wavelength range, the absorbance of photoinitiator camphorquinone is far above two sulphur of light inhibitor
The absorbance for changing Thiuram, after illumination, camphorquinone is generated by aided initiating N, N- dimethyl amino benzoates
Living radical, and tetraethylthiuram disulfide can not then be activated, to free radical polymerization that can not be in suppression system
Journey.Light source is closed after irradiation 10s, it is found that the photosensitive resin thin layer 106 between light transmission bottom plate 102 and shaped platform 105 is completely solid
Change.
Embodiment 2
Referring to Fig. 2, wherein have liquid photosensitive resin thin layer 204 between light transmission bottom plate 202 and shaped platform 205, it is photosensitive
Resin component is same as Example 1.Wavelength is that 365 ± 5 nanometers of inhibition light 201 is irradiated to photosensitive tree across light transmission bottom plate 202
On fat thin layer 204.Due to light absorption effect, it is curve 203 to inhibit light intensity of the light in resin.Inhibit in optical wavelength range, light
The absorbance of inhibitor tetraethylthiuram disulfide is far above the absorbance of photoinitiator camphorquinone, after illumination, curing four
Ethyl thiuram generates the dithiocarbamates carboxyphenyl free radical of low activity, and the rate for itself causing free radical polymerization is very low, and
Camphorquinone can not then be activated, to radical polymerization process that can not be in initiation system.Light source is closed after irradiation 10s, is found
Photosensitive resin thin layer 206 between light transmission bottom plate 202 and shaped platform 205 is still liquid.
Embodiment 3
Referring to Fig. 3, wherein have liquid photosensitive resin thin layer 307 between light transmission bottom plate 303 and shaped platform 308, it is photosensitive
Resin component is same as Example 1.The inhibition light that the initiation light 301 that wavelength is 470 ± 5 nanometers is 365 ± 5 nanometers with wavelength
302 are irradiated to also cross light transmission bottom plate 303 on photosensitive resin thin layer 307.Due to light absorption effect, cause light in resin
Light intensity is curve 304, and it is curve 305 to inhibit light intensity of the light in resin, and it is curve to cause light and inhibit the difference of the intensity of light
306.In the present embodiment, photoinitiator camphorquinone is activated simultaneously with light inhibitor tetraethylthiuram disulfide.Close to molding
The region of platform 308, due to causing light intensity in inhibiting light, the dithiocarbamates carboxyphenyl number of free radical of low activity is less than camphor
The high mars free radical concentration that quinone is generated by aided initiating N, N- dimethyl amino benzoates, low activity free radical can not
All high mars free radicals are captured completely, therefore free radical polymerization can be normally carried out.The region of close light transmission bottom plate 303, by
In inhibiting light intensity, the dithiocarbamates carboxyphenyl number of free radical of low activity is more than camphorquinone by aided initiating N in causing light,
The high mars free radical concentration that N- dimethyl amino benzoates generate, low activity free radical can capture rapidly most height
Living radical, to inhibit free radical polymerization.Light source is closed after irradiation 10s, is found close to the region of shaped platform 308,
Photosensitive resin is cured；Close to the region of light transmission bottom plate 303, photosensitive resin is still liquid, therefore can be easily by light transmission bottom
Plate 303 is detached with shaped platform 308.
Embodiment 1-3 is application case of the material of the present invention based on free radical polymerization.
Embodiment 4
Referring to Fig. 1, wherein there is liquid photosensitive resin thin layer 104 between light transmission bottom plate 102 and shaped platform 105,
Photosensitive resin includes following ingredient：100 parts by weight phenyl glycidyl ethers, bis- (3, the 4- epoxycyclohexyls of 100 parts by weight adipic acids
Methyl esters), 10 parts by weight camphorquinones, 20 parts by weight (4- decyloxies phenyl) phenyl-iodide hexafluorophosphate, 20 parts by weight naphthalene formyls
Methylene quinuclidine tetraphenyl borate salts.It is photosensitive that wavelength is that 470 ± 5 nanometers of initiation light 101 is irradiated to across light transmission bottom plate 102
In thin resin layer 104.Due to light absorption effect, it is curve 103 to cause light intensity of the light in resin.Cause in optical wavelength range,
The absorbance of photoinitiator camphorquinone is far above the absorbance of light inhibitor naphthalene formyl methylene quinuclidine tetraphenyl borate salts, light
According to rear, camphorquinone generates acid cation by photoinitiator (4- decyloxies phenyl) phenyl-iodide hexafluorophosphate, and naphthalene first
Acyl methylene quinuclidine tetraphenyl borate salts can not then be activated, to cationic polymerization processes that can not be in suppression system.According to
Light source is closed after penetrating 50s, it is found that the photosensitive resin thin layer 106 between light transmission bottom plate 102 and shaped platform 105 is fully cured.
Embodiment 5
Referring to Fig. 2, wherein there is liquid photosensitive resin thin layer 204 between light transmission bottom plate 202 and shaped platform 205,
Photosensitive resin ingredient is same as Example 4.Wavelength is that 365 ± 5 nanometers of inhibition light 201 is irradiated to light across light transmission bottom plate 202
In quick thin resin layer 204.Due to light absorption effect, it is curve 203 to inhibit light intensity of the light in resin.Inhibit optical wavelength range
Interior, the absorbance of light inhibitor naphthalene formyl methylene quinuclidine tetraphenyl borate salts is far above the extinction of photoinitiator camphorquinone
Degree, after illumination, naphthalene formyl methylene quinuclidine tetraphenyl borate salts generate alkaline quinoline ring, itself cause epoxy group polymerization
Rate is very low, and camphorquinone can not then be activated, to cationic polymerization processes that can not be in initiation system.It is closed after irradiation 50s
Black out source, it is liquid to find the photosensitive resin thin layer 206 between light transmission bottom plate 202 and shaped platform 205 still.
Embodiment 6
Referring to Fig. 3, wherein there is liquid photosensitive resin thin layer 307 between light transmission bottom plate 303 and shaped platform 308,
Photosensitive resin ingredient is same as Example 4.The inhibition that the initiation light 301 that wavelength is 470 ± 5 nanometers is 365 ± 5 nanometers with wavelength
Light 302 is irradiated to also cross light transmission bottom plate 303 on photosensitive resin thin layer 307.Due to light absorption effect, cause light in resin
Light intensity be curve 304, it is curve 305 to inhibit light intensity of the light in resin, and the difference for causing light and the intensity for inhibiting light is curve
306.In the present embodiment, photoinitiator camphorquinone is swashed simultaneously with light inhibitor naphthalene formyl methylene quinuclidine tetraphenyl borate salts
It is living.Close to the region of shaped platform 308, due to causing light intensity in inhibition light, alkaline quinoline ring concentration passes through light less than camphorquinone
The acid cation concentration that initiator (4- decyloxies phenyl) phenyl-iodide hexafluorophosphate generates, alkaline quinoline ring can not be complete
All acid cations are captured, therefore cationic polymerization can be normally carried out.Close to the region of light transmission bottom plate 303, due to inhibiting
Light intensity passes through photoinitiator (4- decyloxies phenyl) phenyl-iodide hexafluoro phosphorus in initiation light, alkaline quinoline ring concentration more than camphorquinone
The acid cation concentration that hydrochlorate generates, alkaline quinoline ring can capture rapidly most acid cations, to inhibit sun
Ionic polymerization.Light source is closed after irradiation 50s, it is found that close to the region of shaped platform 308, photosensitive resin is cured；Close to thoroughly
The region of optical substrate 303, photosensitive resin is still liquid, therefore can easily be detached light transmission bottom plate 303 with shaped platform 308.
Embodiment 4-6 is application case of the material of the present invention based on cationic polymerization.
Fig. 4, which is illustrated, a kind of to be set using photocurable three-dimensional printing materials of the invention continuous as the continuous Stereolithography of raw material
It is standby, by shaped platform 401, resin storage tank 403, light transmission bottom plate 405, feeding system 407, control system 406 and at least one projection
System 408 is constituted.Light transmission bottom plate 405 is located at 403 bottom of resin storage tank, and liquid photosensitive resin 404, resin are housed in resin storage tank 403
Liquid level maintained by feeding system 407.Shaped platform 401 is fixed on holder 410, and can be along the method for light transmission bottom plate 405
Line direction moves up and down.Control system 406 controls optical projection system 408 and generates digital projection, and controls shaped platform 401 and synchronize
It rises.Digital projection is placed through the light transmission bottom plate 405 of 403 bottom of resin storage tank so that light transmission bottom after the reflection of reflecting element 409
Photosensitive resin thin layer near plate 405 is solidified into the pattern consistent with digital projection.Three-dimensional structure 402 after curing molding adheres to
On shaped platform 401, and as shaped platform 401 moves.
Fig. 5 illustrates the light-source system of continuous Stereolithography equipment shown in Fig. 4, by two independent luminescence units
5010,5020, collimating element 5011,5021, beam splitter 511, even optical element 521 and control system 522 are constituted.Luminescence unit
5010,5020 light that send out are distinguished after collimated elements 5011,5021 collimate, and light beam is synthesized by light splitting piece 511, and by
Even optical element 521 is converted into a branch of uniform illuminating ray, is used as the light source of digital projection system.Luminescence unit 5010,5020
Transmission power it is mutual indepedent, controlled respectively by control system 522.The minimum wavelength of 5010 emission spectrum of luminescence unit is
Peak wavelength isMaximum wavelength isThe minimum wavelength of 5020 emission spectrum of luminescence unit isPeak wavelength isMost
Big wavelength isAs shown in fig. 6, the emission spectrum 5012 of luminescence unit 5010 and the emission spectrum 5022 of transmitter unit 5020 are complete
It is not overlapped entirely, i.e., wave-length coverage meets mathematical relationshipOrIn the emission spectrum of one of luminescence unit
Wavelength can induce activation photoinitiator, generate free radical, molecule or the ion for causing continuous photocurable three-dimensional printing materials polymerization；
Wavelength in the emission spectrum of one of luminescence unit can induce activation light inhibitor, generates and inhibits photoinitiator active certainly
By base, molecule or ion.
The light-source system of continuous photocuring 3D printing equipment can include more mutual indepedent and power adjustable luminous
Unit is synthesized light beam by the way of Fig. 5, and is converted into a branch of uniform illuminating ray by even optical element, and arbitrary
The emission spectrum of two luminescence units is not overlapped, and alternative excites different light inhibitor or photoinitiator.Light source system
The peak wavelength λ of any one luminescence unit of systemi pBetween 150 nanometers to 1000 nanometers, spectral widthIt is less than
100 nanometers；Preferably, the peak wavelength λ of each luminescence uniti pBetween 250 nanometers to 800 nanometers, spectral width
Less than 50 nanometers；It is furthermore preferred that the peak wavelength λ of each luminescence uniti pBetween 300 nanometers to 600 nanometers, spectral widthLess than 20 nanometers；It is further preferred that the peak wavelength λ of each luminescence uniti p350 nanometers to 500 nanometers it
Between, spectral widthLess than 10 nanometers.
Embodiment 7
Referring to Fig. 7, wherein cause light 701 is irradiated to cured molding with light 702 is inhibited also cross light transmission bottom plate 703
Three-dimensional structure 707 and light transmission bottom plate 703 between liquid photosensitive resin layer.It is similar with embodiment 3, close to light transmission bottom plate
703 region, due to inhibiting light intensity in initiation light, photosensitive resin keeps liquid, forms the Inhibition of polymerization that thickness is 0.001-1mm
Layer 704；Close to the region of cured molding three-dimensional structure 707, due to causing light intensity in inhibiting light, photosensitive resin generation is admittedly
Change, forms the polymerization initiating layer 705 that thickness is 0.001-1mm.Cured molding three-dimensional structure 707 is attached to shaped platform
On 708, and as shaped platform 708 rises.Liquid photosensitive resin 706 will be along liquid polymerization inhibition layer under pressure difference driving
704 flow into and fill up the gap left in 707 uphill process of three-dimensional structure.It is three-dimensionally shaped in entire photocuring in the present embodiment
In stage, optical projection system continuously projects digitized video, and photopolymerization reaction recurs in polymerization initiating layer 705, liquid photosensitive
Resin 706 continuously flows into polymerization initiating layer 705 to provide new reaction raw materials, and no any additional act interrupts entire photocuring mistake
Journey, therefore shaping speed is obviously improved compared with traditional handicraft.
Although the present invention has been disclosed in the preferred embodiments as above, present invention is not limited to this.Any art technology
Personnel can make various changes or modifications, therefore protection scope of the present invention is answered without departing from the spirit and scope of the present invention
When being subject to claim limited range.
Claims (16)
1. a kind of continuous photocurable three-dimensional printing materials, which is characterized in that in terms of parts by weight, including following components：
50-100 parts of activated monomer；
0.01-25 parts of photoinitiator；
0.01-25 parts of light inhibitor；
The continuous photocurable three-dimensional printing materials have at least one minimum wavelength beMaximum wavelength isInitiation light
Range of wavelengths, in the initiation optical wavelength section, the absorbance of the photoinitiator is the 2 of the absorbance of the light inhibitor
Times or more；The continuous photocurable three-dimensional printing materials have at least one minimum wavelength beMaximum wavelength isSuppression
Optical wavelength section processed, in the inhibition optical wavelength section, the absorbance of the light inhibitor is the extinction of the photoinitiator
The 2 times or more of degree；At least one wave-length coverage for causing optical wavelength sectionMore than 10 nanometers, and central valueBetween 150 nanometers to 1000 nanometers；The light caused in optical wavelength section can induce the activation light
Initiator generates free radical, molecule or the ion for causing the continuous photocurable three-dimensional printing materials polymerization；
At least one wave-length coverage for inhibiting optical wavelength sectionMore than 10 nanometers, and central valueBetween 150 nanometers to 1000 nanometers；The light inhibited in optical wavelength section can induce described in activation
Light inhibitor generates and inhibits the active free radical of the photoinitiator, molecule or ion.
2. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the function of the activated monomer
Degree is 1, and the activated monomer is selected from acrylic ester monomer, methacrylate-based monomer, vinyl monomer, vinyl ethers
At least one of class monomer and epoxy monomer.
3. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the photoinitiator includes peace
The fragrant photoinitiator of breath, benzoin ether photoinitiator, liquid storax photoinitiator, benzil class photoinitiator, benzil
Ketal photoinitiator, α, α-dialkoxy benzene ketone-type photoinitiators, alpha-hydroxyalkyl benzophenone photoinitiator, α-amine alkyl phenones
Photoinitiator, α-sulfone alkyl phenones photoinitiator, benzoyl formic acid ester lightlike initiating agent, benzoyl ketoxime ester are light-initiated
Agent, thiobenzoate ester lightlike initiating agent, benzoyl hydroperoxide ester lightlike initiating agent, monoacylphosphine oxides photoinitiator and two acyls
At least one of base phosphinoxides photoinitiator.
4. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the photoinitiator includes two
Benzophenone photoinitiator, benzophenone diphenyl sulfide photoinitiator, thioxanthone photoinitiator, anthraquinone photoinitiator,
Camphorquinone photoinitiator, coumarin ketone photoinitiator, phenyl titanium cyclopentadienyl photoinitiator and phenylalkyl boron salt class are light-initiated
At least one of agent.
5. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the photoinitiator includes
At least one of；R1For the alkyl containing 1-12 carbon ,-R2For one kind in following groups
6. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the photoinitiator includes virtue
Aryldiazonium salt photoinitiator, diaryl iodonium salt photoinitiator, triaryl sulfonium salts photoinitiator and aryl cyclopentadienyl iron class light
At least one of initiator.
7. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the light inhibitor includes
At least one of；Wherein R1',R2',R3',R4' it is alkyl, aryl, alcohol radical, ethoxylated alkyl, propoxylated alkyl
In one kind.
8. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that the light inhibitor includes ammonia
Carbamate class light inhibitor, aryl formate ketoxime ester light inhibitor, triaryl methanol class light inhibitor, and
In one kind；Wherein R1" be straight chained alkyl containing 1-12 carbon, branched alkyl, multi-ring alkyl, with heteroatomic polynaphthene
Base or aryl ,-R2" be
In one kind, X-For tetrafluoroborate, tetraphenylborate, four (pentafluorophenyl group) borates, hexafluoro-phosphate radical, hexafluoro arsenic
One kind in acid group and hexafluoroantimonic anion.
9. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The aided initiating of 25 parts by weight, the aided initiating include alkyl amine aided initiating, alkyl alcohol radical amine aided initiating, alkyl
Ester group amine aided initiating, alkylarylamines aided initiating, N, N- dialkylaminobenzoic acid esters classes aided initiating, N, N- bis-
Alkyl aminopropionic acid esters aided initiating and N, at least one in N- dialkyl amino propyl dimethyl silicone polymer class aided initiatings
Kind.
10. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The degree of functionality of 300 parts by weight is the polyfunctional monomer of 2-6, and the polyfunctional monomer includes esters of acrylic acid polyfunctional monomer, first
Base esters of acrylic acid polyfunctional monomer, vinyl-based polyfunctional monomer, vinyl ethers polyfunctional monomer and epoxies are multifunctional
At least one of monomer.
11. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The oligomer of 300 parts by weight, the oligomer include Epoxy Acrylates oligomer, polyester acrylate oligomer, gather
At least one of urethane acrylate quasi-oligomer, polyether acrylate oligomer and organic silicon acrylic ester quasi-oligomer.
12. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The initiation light absorber of 20 parts by weight, it is described cause light absorber at least one part caused in optical wavelength section or
Whole wavelength have absorption photoextinction, and the initiation light absorber includes disperse yellow, disperse orange, disperse red, dispersion is green, is disperseed
Indigo plant, disperse violet, pigment yellow, pigment orange, paratonere, naphthol green, pigment blue, pigment violet, superfine titanic oxide, phenyl triazines are purple
In outer absorbent, benzotriazole ultraviolet absorber, salicylate type ultraviolet absorbent and oxanilide class ultraviolet absorber
It is at least one.
13. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The inhibition light absorber of 20 parts by weight, it is described inhibit light absorber at least one part inhibited in optical wavelength section or
Whole wavelength have absorption photoextinction, and the inhibition light absorber includes disperse yellow, disperse orange, disperse red, dispersion is green, is disperseed
Indigo plant, disperse violet, pigment yellow, pigment orange, paratonere, naphthol green, pigment blue, pigment violet, superfine titanic oxide, phenyl triazines are purple
In outer absorbent, benzotriazole ultraviolet absorber, salicylate type ultraviolet absorbent and oxanilide class ultraviolet absorber
It is at least one.
14. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The antifoaming agent of 10 parts by weight, the antifoaming agent are selected from mineral oil defoaming agent, organic silicon antifoaming agent, polyethers antifoaming agent, gather
At least one of esters antifoaming agent and lower aliphatic alcohols antifoaming agent.
15. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include more than 0 and to be less than
The levelling agent of 10 parts by weight, the levelling agent are selected from crylic acid resin levelling agent, organic siliconresin class levelling agent and fluorine carbon tree
At least one of lipid levelling agent.
16. continuous photocurable three-dimensional printing materials according to claim 1, which is characterized in that also include 0-500 parts of solids
Powder, the solid powder in silica, alundum (Al2O3), zirconium dioxide, silicon nitride and silicon carbide powder at least
It is a kind of.
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| CN106735241B (en) * | 2016-12-29 | 2018-09-25 | 西安铂力特增材技术股份有限公司 | A kind of reinforced resin optical soliton interaction method |
| CN107225248B (en) * | 2017-06-13 | 2019-06-14 | 北京科技大学 | A kind of pair solidifies the method that 3D gel printing prepares magnetic material product |
| EP3638485A4 (en) * | 2017-06-16 | 2021-06-16 | Holo, Inc. | Methods and systems for stereolithography three-dimensional printing |
| EP3732021A1 (en) * | 2017-12-29 | 2020-11-04 | DSM IP Assets B.V. | Compositions and articles for additive fabrication and methods of using the same |
| CN110275393A (en) * | 2019-05-17 | 2019-09-24 | 华中科技大学 | A kind of photoresist applied to double light beam laser |
| CN110341097B (en) * | 2019-08-05 | 2020-06-23 | 浙江大学 | Thermoplastic polymer based on DLP photocuring 3D printing and application |
| CN110804276A (en) * | 2019-10-18 | 2020-02-18 | 南京大学 | High-resolution photocuring three-dimensional printing compound |
| WO2021261497A1 (en) * | 2020-06-26 | 2021-12-30 | 株式会社Adeka | Compound, initiator, composition, cured product and method for producing cured product |
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| CN114228147A (en) * | 2021-12-13 | 2022-03-25 | 瑞迪光电(深圳)有限公司 | Multispectral synthesis ultraviolet light source module and DLP surface projection system |
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