CN108822494A - A kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity - Google Patents
A kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity Download PDFInfo
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- CN108822494A CN108822494A CN201810607917.6A CN201810607917A CN108822494A CN 108822494 A CN108822494 A CN 108822494A CN 201810607917 A CN201810607917 A CN 201810607917A CN 108822494 A CN108822494 A CN 108822494A
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- graphene
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- dimensional printing
- printing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Manufacturing & Machinery (AREA)
- Combustion & Propulsion (AREA)
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- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The present invention discloses a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity, which includes following raw material：Resin material, photoinitiator, auxiliary agent, modifying agent or pigments or dyes, wherein, the resin material or modification sections are fully modified using graphene, make the graphene of photocurable three-dimensional printing materials 0.1%-5% containing weight percent, and graphene uniform is scattered in photocurable three-dimensional printing materials.The present invention makes full use of the high-termal conductivity, high intensity and high tenacity of graphene, realizes that 3 D-printing entity has high conductive high strength high tenacity, wherein thermal conductivity>10w/m.k, bending strength>66mpa, extensibility>7%, to realize application of the printing entity in terms of the molds such as hot flow path or injection moulding, enable the present invention that there is the extremely strong market competitiveness.
Description
Technical field：
The present invention relates to 3D printing technique fields, refer in particular to a kind of photocuring 3 D-printing material of high conductive high strength high tenacity
Material.
Background technique：
SLA technology is that the photopolymerization principle based on liquid photosensitive resin works.This liquid material in certain wavelength and
Photopolymerization reaction can occur under the ultraviolet light of intensity rapidly, molecular weight increased dramatically, and material is also just transformed into from liquid solid
State.
SLA working principle：Liquid photosensitive resin is filled in liquid bath, laser beam, can be in liquid photosensitive under deflecting mirror effect
It is scanned on resin surface, the presence or absence of the track of scanning and light are controlled by computer, the ground that laser beam spots or hot spot are got to
Side, liquid photosensitive resin will solidify.When molding starts, depth of the workbench in the next determination of liquid level, swashing after focusing
Beam spots or hot spot press the instruction point by point scanning of computer, i.e., point-by-point solidification on liquid level.When one layer scanning after the completion of not by
The place of irradiation is still liquid photosensitive resin.Then lifting platform band moving platform declines a layer height, cloth again in molded level
Full one layer of liquid photosensitive resin, scraper plate strike off the biggish photosensitive resin liquid level of viscosity, then carry out next layer of scanning again, newly
Cured one layer is firmly sticked in preceding layer, so repeats to finish until entire 3D model manufacturing, obtains a 3D solid
Model.
SLA 3 D-printing entity has precision high, high-efficient, inexpensive etc. excellent in terms of prototype and evaluated for appearance
SLA light-cured component is commercialized in gesture, but the entity for requiring (such as heatproof, conduction, thermally conductive, high tenacity) with certain function
Including photosensitive resin, photoinitiator, auxiliary agent, modifying agent, pigments or dyes, it is usually using the 3D solid that above-mentioned component prints
The non-conductor of heat, thermal conductivity<0.2w/m.k can not achieve the function of heat transfer or heat exchange, other special business
Change SLA entity and uses larger amount of ceramic powder, the thermal conductivity with class ceramics, about 1.0-2.0w/m.k of thermal conductivity, but extensibility
<1.0%, poor toughness, easy fracture under a certain pressure, it is impossible to be used in the entity for having high heat resistance high-intensity and high-tenacity requirement, such as
Hot flow path or injection moulding etc..Therefore the photocurable three-dimensional printing materials in need for developing a kind of high conductive high strength high tenacity.
In view of this, the present inventor proposes following technical scheme.
Summary of the invention：
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of photocurings of high conductive high strength high tenacity
3 D-printing material.
In order to solve the above-mentioned technical problem, present invention employs following technical proposals：The high conductive high strength high tenacity
Photocurable three-dimensional printing materials include following raw material：Resin material, photoinitiator, auxiliary agent, modifying agent, pigments or dyes；Institute
Resin material or modification sections or fully modified using graphene are stated, make photocurable three-dimensional printing materials containing weight percent
For the graphene of 0.1%-5%, and graphene uniform is scattered in photocurable three-dimensional printing materials.
Furthermore, in above-mentioned technical proposal, the resin material includes being obtained using graphene modified epoxy
Then the pre-mixed resin of 10% graphene content forms photocuring 3 D-printing material by weight percentage for 20% additive amount
Material.
Furthermore, in above-mentioned technical proposal, the resin material includes using graphene oxide modified TPU, is made
Then the modified resin of 10% graphene content forms photocurable three-dimensional printing materials by weight percentage for 5% additive amount.
Furthermore, in above-mentioned technical proposal, the resin material include using the modified graphene dispersion in surface in
The pre-mixed resin of 10% graphene content is made in oxetanes, then forms light by weight percentage for 15% additive amount
Solidify 3 D-printing material.
Furthermore, in above-mentioned technical proposal, the resin material includes epoxy resin, epoxy active diluent, third
Olefin(e) acid resin, graphene modified resin, each raw-material weight percentage are：Epoxy resin 60-80%, epoxy active diluent 5-
25%, acrylic resin 5-15%, graphene modified resin 1-20%, photoinitiator 1-14%, auxiliary agent 1-10%, filler and change
Property agent 0-5% or pigments or dyes 0-1%.
After adopting the above technical scheme, the present invention has the advantages that compared with prior art：The present invention is abundant
Using the high-termal conductivity, high intensity and high tenacity of graphene, realize that 3 D-printing entity has high conductive high strength high tenacity,
In, thermal conductivity>10w/m.k, bending strength>66mpa, extensibility>7%, to realize printing entity in hot flow path or injection
Application in terms of the molds such as molding enables the present invention have the extremely strong market competitiveness.
Specific embodiment：
The present invention is further described combined with specific embodiments below.
The present invention is a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity comprising following raw material：
Resin material, photoinitiator, auxiliary agent, modifying agent, pigments or dyes, wherein the resin material or modification sections or whole
Ground is modified using graphene, makes the graphene of photocurable three-dimensional printing materials 0.1%-5% containing weight percent, and graphite
Alkene is dispersed in photocurable three-dimensional printing materials.The present invention makes full use of the high-termal conductivity, high intensity and high-ductility of graphene
Property, realize that 3 D-printing entity has high conductive high strength high tenacity, wherein thermal conductivity>10w/m.k, bending strength>66mpa,
Extensibility>7%, to realize application of the printing entity in terms of the molds such as hot flow path or injection moulding, the present invention is enabled to have
The extremely strong market competitiveness.
The resin material includes epoxy resin, epoxy active diluent, acrylic resin, graphene modified resin, respectively
Raw-material weight percentage is：Epoxy resin 60-80%, epoxy active diluent 5-25%, acrylic resin 5-15%, graphite
Alkene modified resin 1-20%, photoinitiator 1-14%, auxiliary agent 1-10%, filler and modifying agent 0-5% or pigments or dyes 0-
1%.
The photoinitiator includes cationic photopolymerization transmitting-receiving agent 1-8% and radical initiator 0.5-6%.
The auxiliary agent includes chain-transferring agent.
The epoxy resin includes but is not limited to cycloaliphatic epoxy resin, bisphenol A epoxide resin, novolac epoxy resin etc.
One of.
The epoxy active diluent, as trihydroxymethylpropanyltri diglycidyl ether, methacrylic acid oxetane,
Cyclohexanedimethanol glycidol ether, the third oxidation base glycerol triglycidyl ether, vinyl ethers, oxetanes etc..
The acrylic resin, including epoxy acrylate, simple function (methyl) acrylic monomers, difunctionality (methyl) third
One of acrylic monomer, polyfunctional acrylic monomer and polyurethane allyl resin etc..
The graphene modified resin, such as graphene modified epoxy, graphene modified acroleic acid oxetanes tree
Rouge, graphene modified polyurethane resin, etc..
The chain-transferring agent, such as tetrahydrofuran polyether PTHF1000/2000, polycarbonate glycol, ethoxylated bisphenol A,
Deng.
The cationic photopolymerization receives and dispatches agent, such as phosphate cation light initiator, triaryl sulfonium salts hexafluoro antimonate UVI-
6976/CPI100, triaryl sulfonium salts hexafluorophosphate UVI-6992/CPI200K, etc..
The radical initiator, such as 819 1173 (the long day chemistry in Tianjin) of TPO.
The filler and modifying agent, such as silica, aluminum oxide, rubber elastomer, etc..
The pigments or dyes, such as titanium dioxide, barium sulfate, colorless crystal violet, lemon yellow.
Embodiment one：
The resin material includes obtaining the pre-mixed resin of 10% graphene content using graphene modified epoxy
EP5001 is graphene modified epoxy, then forms photocuring 3 D-printing by weight percentage for 20% additive amount
Material EX1.
Embodiment two：
The resin material includes using graphene oxide modified TPU, and the modified resin of 10% graphene content is made
GT98 is graphene modified polyurethane resin, then forms photocuring 3 D-printing material by weight percentage for 5% additive amount
Expect EX2.
Embodiment three：
The resin material includes that 10% graphene is made in oxetanes using the modified graphene dispersion in surface
The pre-mixed resin GOX101 of content is graphene modified acroleic acid oxetane resin, is then by weight percentage 15%
Additive amount form photocurable three-dimensional printing materials EX3.
Light-cured component FP-15 is commercialized in comparative example 1, is denoted as C1.
Light-cured component PerForm is commercialized in comparative example 2, is denoted as C2.
Light-cured component FP-19 is commercialized in comparative example 3, is denoted as C3.
The specific title material and formula of above three embodiments and three comparative examples：
Stock chart is used in table (one) experiment
Table (two) experimental example and comparative example composition composition
Using 3 D-printing entity test block respectively to the reality of 3 D-printing made of above embodiments 1-3 and comparative example 1-3
Body tests thermal conductivity, bending strength, extensibility.Thermal conductivity testing standard ASTM E1530, the resistance to hot instrument HFM436 that speeds of Germany, bending
Intensity, elongation at break press D638M, specific performance parameter such as following table：
It will be evident that the thermal conductivity and extensibility of the photocurable three-dimensional printing materials of high conductive high strength high tenacity are higher,
With high conductive high strength high tenacity.
Certainly, the above is only a specific embodiment of the present invention, be not to limit the scope of the present invention, it is all according to
The equivalent change or modification that structure, feature and principle described in scope of the present invention patent is done should be included in Shen of the present invention
It please be in the scope of the patents.
Claims (5)
1. a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity comprising following raw material：Resin material, light
Initiator, auxiliary agent, modifying agent, pigments or dyes；
It is characterized in that：The resin material or modification sections are fully modified using graphene, beat photocuring three-dimensional
The graphene that material is 0.1%-5% containing weight percent is printed, and graphene uniform is scattered in photocurable three-dimensional printing materials
In.
2. a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity according to claim 1, feature exist
In：The resin material includes obtaining the pre-mixed resin of 10% graphene content using graphene modified epoxy, is then pressed
The additive amount that weight percent is 20% forms photocurable three-dimensional printing materials.
3. a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity according to claim 1, feature exist
In：The resin material includes using graphene oxide modified TPU, and the modified resin of 10% graphene content is made, then presses
The additive amount that weight percent is 5% forms photocurable three-dimensional printing materials.
4. a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity according to claim 1, feature exist
In：The resin material includes that 10% graphene content is made in oxetanes using the modified graphene dispersion in surface
Then pre-mixed resin forms photocurable three-dimensional printing materials by weight percentage for 15% additive amount.
5. a kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity according to claim 1, feature exist
In：The resin material includes epoxy resin, epoxy active diluent, acrylic resin, graphene modified resin, each raw material
Weight percent is：Epoxy resin 60-80%, epoxy active diluent 5-25%, acrylic resin 5-15%, graphene are modified
Resin 1-20%, photoinitiator 1-14%, auxiliary agent 1-10%, filler and modifying agent 0-5% or pigments or dyes 0-1%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810607917.6A CN108822494A (en) | 2018-06-13 | 2018-06-13 | A kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810607917.6A CN108822494A (en) | 2018-06-13 | 2018-06-13 | A kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity |
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| CN201810607917.6A Pending CN108822494A (en) | 2018-06-13 | 2018-06-13 | A kind of photocurable three-dimensional printing materials of high conductive high strength high tenacity |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110083013A (en) * | 2019-04-19 | 2019-08-02 | 西安交通大学 | A kind of photocurable graphene oxide and preparation method thereof |
| CN111117103A (en) * | 2019-12-22 | 2020-05-08 | 同济大学 | Reinforced wire rod for fused deposition molding and preparation method thereof |
| CN114103125A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of high-thermal-conductivity micro device |
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| CN106167537A (en) * | 2016-07-29 | 2016-11-30 | 佛山市高明区诚睿基科技有限公司 | The photocurable resin material that a kind of 3D with self-cleaning antibacterial prints |
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| CN107187027A (en) * | 2017-06-29 | 2017-09-22 | 张辉开 | A kind of graphene photocuring 3D printing method and its application |
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2018
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Patent Citations (4)
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| CN104830159A (en) * | 2014-12-17 | 2015-08-12 | 青岛科技大学 | Preparation method and application of photo-curing color paste containing graphene |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110083013A (en) * | 2019-04-19 | 2019-08-02 | 西安交通大学 | A kind of photocurable graphene oxide and preparation method thereof |
| WO2020211183A1 (en) * | 2019-04-19 | 2020-10-22 | 西安交通大学 | Photocurable graphene oxide and preparation method therefor |
| CN111117103A (en) * | 2019-12-22 | 2020-05-08 | 同济大学 | Reinforced wire rod for fused deposition molding and preparation method thereof |
| CN114103125A (en) * | 2021-09-30 | 2022-03-01 | 哈尔滨工业大学（威海） | Preparation method of high-thermal-conductivity micro device |
| CN114103125B (en) * | 2021-09-30 | 2022-06-28 | 哈尔滨工业大学（威海） | Preparation method of high-thermal-conductivity micro device |
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| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20201223 Address after: 523000 Ou Deng Li Chi Di, Gaopo Town, Dongguan City, Guangdong Province Applicant after: DONGGUAN ZHANSHENG MOLD Co.,Ltd. Address before: 523000 building e, Lianshang Zhizao Industrial Park, Chuangxing Road, Xiaoyong village, Gaopo Town, Dongguan City, Guangdong Province Applicant before: DONGGUAN YUANLI WUXIAN PRINTING TECHNOLOGY Co.,Ltd. |
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Application publication date: 20181116 |