CN111251603A - Method for photocuring 3D printing using solid-state cured photosensitive resin - Google Patents
Method for photocuring 3D printing using solid-state cured photosensitive resin Download PDFInfo
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- CN111251603A CN111251603A CN202010082196.9A CN202010082196A CN111251603A CN 111251603 A CN111251603 A CN 111251603A CN 202010082196 A CN202010082196 A CN 202010082196A CN 111251603 A CN111251603 A CN 111251603A
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- Prior art keywords
- acrylate
- photosensitive resin
- prepolymer
- room temperature
- acrylate monomer
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- 239000011347 resin Substances 0.000 title claims abstract description 146
- 229920005989 resin Polymers 0.000 title claims abstract description 146
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000010146 3D printing Methods 0.000 title claims abstract description 29
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 290
- 239000000178 monomer Substances 0.000 claims abstract description 139
- 239000007787 solid Substances 0.000 claims abstract description 87
- 238000007639 printing Methods 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 52
- 239000007788 liquid Substances 0.000 claims description 36
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 33
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 33
- 229920000728 polyester Polymers 0.000 claims description 29
- 238000001723 curing Methods 0.000 claims description 28
- 239000012752 auxiliary agent Substances 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 18
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 13
- 239000002356 single layer Substances 0.000 claims description 13
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 11
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 10
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 10
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 10
- ZOJPTQRKWVDKTP-UHFFFAOYSA-N decane methanol prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.CO.CO.CCCCCCCCCC ZOJPTQRKWVDKTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical group C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 6
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical group C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 6
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 6
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical group N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- OTRIMLCPYJAPPD-UHFFFAOYSA-N methanol prop-2-enoic acid Chemical compound OC.OC.OC(=O)C=C.OC(=O)C=C OTRIMLCPYJAPPD-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
Landscapes
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Optics & Photonics (AREA)
Abstract
The invention provides a solid-state cured ultralow-shrinkage photosensitive resin which comprises an acrylate prepolymer, an acrylate monomer and a photoinitiator, wherein the mass ratio of the acrylate prepolymer to the acrylate monomer is 2:8 to 8:2, the mass of the photoinitiator is 1 wt% -10 wt% of the total weight of acrylate prepolymerization and the acrylate monomer, and the photosensitive resin is solid at room temperature. The photosensitive resin which is solid at room temperature is used as printing slurry for photocuring 3D printing, the resin is melted and leveled by heating, and then the temperature is reduced until the resin is solid, and the printing slurry is exposed, cured and molded. The photosensitive resin reduces the shrinkage rate of the photosensitive resin material, achieves the shrinkage rate of less than 2%, and does not need to be supported in the printing process.
Description
Technical Field
The invention belongs to the field of photosensitive resin, and particularly relates to a method for carrying out photocuring 3D printing by using solid-state cured photosensitive resin.
Background
In the field of 3D printing, the photocuring 3D printing is long in development time, mature in process and wide in application. The light-cured material prepared by the technology has the advantages of high forming speed, high forming precision and good surface quality.
The raw material for photocuring molding is generally liquid photosensitive resin, is a mixture containing a photoinitiator, a monomer and a prepolymer, can immediately cause polymerization reaction under the irradiation of ultraviolet light with specific wavelength (250 nm-420 nm), and can finish curing, thereby producing a high-precision object.
The forming process of the photocuring printer comprises the following steps: in the initial state, the printing platform is lower than the liquid level of the photosensitive resin by one printing layer thickness, the light source selectively irradiates on the liquid level, the exposed part is polymerized and solidified into a solid, the first layer of printing is finished, the printing platform descends by one printing layer thickness, the layer of exposure is carried out after the photosensitive resin is leveled, and the operation is carried out in a circulating mode.
For guaranteeing the interlayer leveling, the viscosity of the resin in a printing state cannot be too high, but the thinner liquid cannot support the printing model, so that the suspended part of the formed object needs to be supported to guarantee the printing forming. However, the addition and removal of the supports require a great deal of post-processing work, and the shape, size and density of the supports can seriously affect the molding effect of the mold. In addition, the relatively dilute liquid starting material and the final solid polymer formed have a relatively large density difference, which results in a relatively large volume shrinkage and a relatively large stress deformation of the mold.
Therefore, there is a need in the art for a support-free, low-shrinkage photocuring 3D printing method.
Disclosure of Invention
In order to solve the problems, the invention applies the photosensitive resin which is solid at room temperature to the photocuring 3D printing, melts and levels the photosensitive resin by heating, cools the photosensitive resin until the photosensitive resin is solid, and exposes, cures and forms the photosensitive resin when the photosensitive resin is solid. The method of the invention not only reduces the volume shrinkage rate during curing, but also can realize unsupported printing.
Specifically, the present invention provides a method of photocuring 3D printing, the method comprising: the method comprises the steps of using photosensitive resin which is solid at room temperature as a raw material for photocuring 3D printing, heating to melt and level the photosensitive resin in the 3D printing process, cooling to the solid state of the photosensitive resin, and carrying out exposure curing molding when the photosensitive resin is solid.
In one or more embodiments, the volume shrinkage of the photosensitive resin after curing is less than 2%.
In one or more embodiments, the photosensitive resin includes an acrylate prepolymer, an acrylate monomer, a photoinitiator, and optionally an auxiliary.
In one or more embodiments, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 2:8 to 8: 2.
In one or more embodiments, the photosensitive resin has a mass of the photoinitiator of 1 wt% to 10 wt% of the total mass of the acrylate prepolymer and the acrylate monomer.
In one or more embodiments, in the photosensitive resin, the mass of the auxiliary agent is 0 wt% to 1 wt% of the total mass of the acrylate prepolymer and the acrylate monomer.
In one or more embodiments, the acrylate prepolymer is solid at room temperature.
In one or more embodiments, the acrylate prepolymer is selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, polyether urethane acrylates, and polyester urethane acrylates.
In one or more embodiments, the acrylate monomer is selected from one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, or a multifunctional acrylate monomer.
In one or more embodiments, the photoinitiator includes, but is not limited to, one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, methyl benzoylformate, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
In one or more embodiments, the adjuvant is selected from one or more of pigments, leveling agents, defoamers, light absorbers, and dispersants.
In one or more embodiments, the acrylate prepolymer is a urethane acrylate that is solid at room temperature, and the acrylate monomers consist of hydroxyethyl methacrylate and dipentaerythritol hexaacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 20:80 to 40:60, and the mass ratio of the hydroxyethyl methacrylate to the dipentaerythritol hexaacrylate in the acrylate monomer is 30:40 to 50: 20.
In one or more embodiments, the acrylate prepolymer is a polyester acrylate that is solid at room temperature, the acrylate monomer consisting of hydroxyethyl methacrylate and tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate; preferably, in the photosensitive resin, a mass ratio of the acrylate prepolymer to the acrylate monomer is 30:70 to 50:50, and a mass ratio of hydroxyethyl methacrylate to tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate in the acrylate monomer is 10:50 to 30: 30.
In one or more embodiments, the acrylate prepolymer is a polyether acrylate that is solid at room temperature, and the acrylate monomer is isobornyl methacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60: 40.
In one or more embodiments, the acrylate prepolymer is a polyether urethane acrylate that is solid at room temperature, and the acrylate monomer is dipropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70: 30.
In one or more embodiments, the acrylate prepolymer is comprised of an epoxy acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, the acrylate monomer being tripropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70:30, and the mass ratio of the epoxy acrylate that is solid at room temperature to the urethane acrylate that is liquid at room temperature in the acrylate prepolymer is 20:40 to 40: 20.
In one or more embodiments, the acrylate prepolymer is comprised of a polyester urethane acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, the acrylate monomers being comprised of hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60:40, the mass ratio of the polyester urethane acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 30:20 to 45:5, and the mass ratio of the hydroxyethyl methacrylate to the 1, 6-hexanediol diacrylate in the acrylate monomer is 10:40 to 30: 20.
In one or more embodiments, the light source used in printing has a wavelength of 280 to 480 nm.
In one or more embodiments, the light source used in printing has an intensity of 0.5 to 50mW/cm2。
In one or more embodiments, the material is printed with a single layer exposure time of 0.1 to 100 seconds.
In one or more embodiments, the single layer film thickness is 0.01 to 0.5mm when printed.
The present invention also provides a photocured 3D printed article prepared using the method described in any of the embodiments herein.
The invention also provides the use of a photosensitive resin that is solid at room temperature in photocured 3D printing.
In one or more embodiments of the use, the photosensitive resin has a volume shrinkage after curing of less than 2%.
In one or more embodiments of the use, the photosensitive resin includes an acrylate prepolymer, an acrylate monomer, a photoinitiator, and optionally an auxiliary.
In one or more embodiments of the use, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 2:8 to 8: 2.
In one or more embodiments of the use, the photosensitive resin has a mass of the photoinitiator of 1 wt% to 10 wt% of a total mass of the acrylate prepolymer and the acrylate monomer.
In one or more embodiments of the use, the photosensitive resin has a mass of the auxiliary agent of 0 wt% to 1 wt% of a total mass of the acrylate prepolymer and the acrylate monomer.
In one or more embodiments of the use, the acrylate prepolymer is solid at room temperature.
In one or more use embodiments, the acrylate prepolymer is selected from one or more of epoxy acrylates, urethane acrylates, polyester acrylates, polyether urethane acrylates and polyester urethane acrylates.
In one or more embodiments of the use, the acrylate monomer is selected from one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, or a multifunctional acrylate monomer.
In one or more embodiments of the use, the photoinitiator includes, but is not limited to, one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, methyl benzoylformate, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide.
In one or more embodiments of the use, the adjuvant is selected from one or more of pigments, leveling agents, antifoaming agents, light absorbers, and dispersants.
In one or more embodiments of the use, the acrylate prepolymer is a urethane acrylate that is solid at room temperature, and the acrylate monomers consist of hydroxyethyl methacrylate and dipentaerythritol hexaacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 20:80 to 40:60, and the mass ratio of the hydroxyethyl methacrylate to the dipentaerythritol hexaacrylate in the acrylate monomer is 30:40 to 50: 20.
In one or more embodiments of the use, the acrylate prepolymer is a polyester acrylate that is solid at room temperature, the acrylate monomer consisting of hydroxyethyl methacrylate and tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate; preferably, in the photosensitive resin, a mass ratio of the acrylate prepolymer to the acrylate monomer is 30:70 to 50:50, and a mass ratio of hydroxyethyl methacrylate to tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate in the acrylate monomer is 10:50 to 30: 30.
In one or more embodiments of the use, the acrylate prepolymer is a polyether acrylate that is solid at room temperature, and the acrylate monomer is isobornyl methacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60: 40.
In one or more embodiments of the use, the acrylate prepolymer is a polyether urethane acrylate that is solid at room temperature, and the acrylate monomer is dipropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70: 30.
In one or more embodiments of the use, the acrylate prepolymer is composed of an epoxy acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, the acrylate monomer being tripropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70:30, and the mass ratio of the epoxy acrylate that is solid at room temperature to the urethane acrylate that is liquid at room temperature in the acrylate prepolymer is 20:40 to 40: 20.
In one or more embodiments of the use, the acrylate prepolymer is comprised of a polyester urethane acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, the acrylate monomers are comprised of hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60:40, the mass ratio of the polyester urethane acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 30:20 to 45:5, and the mass ratio of the hydroxyethyl methacrylate to the 1, 6-hexanediol diacrylate in the acrylate monomer is 10:40 to 30: 20.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, amounts and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
When the conventional liquid photosensitive resin is used for carrying out photocuring 3D printing, the suspended part of a formed object needs to be supported to ensure printing and forming. However, the addition and removal of the supports require a great deal of post-processing work, and the shape, size and density of the supports can seriously affect the molding effect of the mold. In addition, the density difference between the thinner liquid raw material and the finally formed solid polymer is large, which causes large volume shrinkage, and leads to large stress deformation of the model. In order to solve the above problems, the present invention provides a method for photocuring 3D printing, which can dispense with the operation of adding support, and perform cross-linking polymerization under the condition of high raw material density, so as to reduce final volume shrinkage.
Specifically, the method for photocuring 3D printing comprises the following steps: the method comprises the steps of using photosensitive resin which is solid at room temperature as a raw material for photocuring 3D printing, heating to melt and level the photosensitive resin in the 3D printing process, cooling to the solid state of the photosensitive resin, and carrying out exposure curing molding when the photosensitive resin is solid. Therefore, the photocuring 3D printing method of the present invention is solid-state curing 3D printing.
The photosensitive resin of the present invention is solid at room temperature. Preferably, the photosensitive resin of the present invention has a volume shrinkage of less than 2% after curing.
In the invention, the photosensitive resin comprises or consists of an acrylate prepolymer, an acrylate monomer, a photoinitiator and an optional auxiliary agent. In certain embodiments, the photosensitive resin of the present invention includes 20 to 80 parts by weight of an acrylate prepolymer, 20 to 80 parts by weight of an acrylate monomer, 1 to 10 parts by weight of a photoinitiator, and 0 to 1 part by weight (e.g., 0.1 to 1 part by weight) of an auxiliary.
The acrylate prepolymer suitable for use in the present invention may be one or more selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, polyether urethane acrylate and polyester urethane acrylate. The acrylate prepolymers suitable for use in the present invention are preferably solid at room temperature. Herein, when the acrylate prepolymer is a composition consisting of two or more selected from the group consisting of epoxy acrylate, urethane acrylate, polyester acrylate, polyether urethane acrylate and polyester urethane acrylate, the acrylate prepolymer is solid at room temperature means that the components of the composition are solid at room temperature after being mixed. Therefore, in the present invention, when the acrylate prepolymer is a composition, the state of each component at room temperature is not particularly limited and may be a solid or a liquid as long as each component is mixed and then is a solid at room temperature. Generally, in the present invention, when the acrylate prepolymer is a composition, at least one of the components is solid at room temperature.
The acrylate monomer suitable for the present invention is not particularly limited, and may be one or more of a monofunctional acrylate monomer, a bifunctional acrylate monomer, or a multifunctional acrylate monomer. Generally, the acrylate monomers suitable for use in the present invention are liquid at room temperature.
In the photosensitive resin of the present invention, the mass ratio of the acrylate prepolymer to the acrylate monomer is preferably 2:8 to 8:2, for example, 3:7 to 7:3, 3:7 to 6:4, etc.
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is urethane acrylate that is solid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and dipentaerythritol hexaacrylate; preferably, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 20:80 to 40:60, for example, 25:75 to 35:65, (30. + -.2): 70. + -.2; preferably, the mass ratio of hydroxyethyl methacrylate to dipentaerythritol hexaacrylate in the acrylate monomer is from 30:40 to 50:20, e.g., from 35:35 to 45:25, (40. + -.2): (30. + -.2).
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is a polyester acrylate that is solid at room temperature, and the acrylate monomer consists of hydroxyethyl methacrylate and tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate; preferably, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 30:70 to 50:50, for example 35:65 to 45:55, (40. + -.2): 60. + -.2; preferably, the mass ratio of hydroxyethyl methacrylate to tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate in the acrylate monomer is from 10:50 to 30:30, for example from 15:45 to 25:35, (20. + -.2): 40. + -.2.
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is a polyether acrylate that is solid at room temperature, and the acrylate monomer is isobornyl methacrylate; preferably, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 40:60 to 60:40, for example, 45:55 to 55:45, (50. + -.2): 50. + -.2.
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is a polyether urethane acrylate that is solid at room temperature, and the acrylate monomer is dipropylene glycol diacrylate; preferably, the photosensitive resin has a mass ratio of the acrylate prepolymer to the acrylate monomer of 50:50 to 70:30, for example 55:45 to 65:35, (60. + -.2): 40. + -.2.
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is composed of an epoxy acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, and the acrylate monomer is tripropylene glycol diacrylate; preferably, the photosensitive resin has a mass ratio of acrylate prepolymer to acrylate monomer of 50:50 to 70:30, such as 55:45 to 65:35, (60. + -.2): 40. + -.2; the mass ratio of the epoxy acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 20:40 to 40:20, for example, 25:35 to 35:25, (30. + -.2): 30. + -.2.
In certain embodiments, in the photosensitive resin of the present invention, the acrylate prepolymer is composed of a polyester urethane acrylate that is solid at room temperature and a urethane acrylate that is liquid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60:40, for example, 45:55 to 55:45, (50. + -.2): 50. + -.2; preferably, the mass ratio of the polyester urethane acrylate which is solid at room temperature and the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 30:20 to 45:5, for example, 35:15 to 45:5, (40 ± 2): 10 ± 2; preferably, the mass ratio of hydroxyethyl methacrylate to 1, 6-hexanediol diacrylate in the acrylate monomers is 10:40 to 30:20, for example 15:35 to 25:25, (20. + -.2): 30. + -.2.
The photoinitiator suitable for the present invention is not particularly limited, and may be a photoinitiator and a combination thereof commonly used in the art, including but not limited to one or more selected from the group consisting of 2-hydroxy-2-methyl-phenylacetone-1, 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrylbenzene, methyl benzoylformate, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, etc. when the photosensitive resin of the present invention contains a plurality of photoinitiators, the content ratio of each photoinitiator is not particularly limited.
The photoinitiator may be contained in the photosensitive resin of the present invention in an amount conventional in the art, and preferably, the total mass of the photoinitiator is 1 to 10 wt%, for example, 1 to 5 wt%, 2 to 5 wt%, 3 to 4 wt%, etc., based on the total weight of the acrylate prepolymer and the acrylate monomer.
The auxiliary agent suitable for the present invention may be one or more of various auxiliary agents commonly used in the art, including but not limited to pigments, leveling agents, antifoaming agents, light absorbers, dispersing agents, and the like. When the photosensitive resin of the present invention contains a plurality of auxiliaries, the content ratio of each auxiliary is not particularly limited.
In the photosensitive resin of the present invention, the content of various auxiliaries may be conventional in the art, for example, the total mass of the auxiliaries may be 0 wt% to 1 wt%, for example, 0.1 wt% to 1 wt%, etc., of the total weight of the acrylate prepolymer and the acrylate monomer, and the respective mass of the various auxiliaries may be 0 wt% to 1 wt%, for example, 0.05 wt% to 1 wt%, etc., of the total weight of the acrylate prepolymer and the acrylate monomer.
In certain embodiments, the photosensitive resin of the present invention comprises or consists of 20 to 80 parts by weight, for example 30 to 70 parts by weight, 30 to 60 parts by weight of the acrylate prepolymer, 20 to 80 parts by weight, for example 30 to 70 parts by weight, 40 to 70 parts by weight of the acrylate monomer, 1 to 10 parts by weight, for example 1 to 5 parts by weight, of the photoinitiator and 0 to 1 part by weight, for example 0.1 to 1 part by weight, of the auxiliaries, based on 100 parts by weight of the total weight of the acrylate prepolymer and the acrylate monomer.
The photosensitive resin can be used as a raw material for photocuring 3D printing. In the 3D printing process, the photosensitive resin is melted and leveled by heating, then the temperature is reduced until the photosensitive resin is solid, and the photosensitive resin is exposed, cured and molded when the photosensitive resin is solid.
In some embodiments, the photosensitive resin of the present invention is placed in a drug cylinder of a printer, the temperature is raised to melt the photosensitive resin, the melted photosensitive resin is sent to a printing platform, after the photosensitive resin is leveled, the temperature is lowered to a solid state of the photosensitive resin, and then the layer is exposed and cured to realize layer-by-layer exposure curing molding.
In the present invention, the curing conditions may be conventional in the art. Preferably, the wavelength of the light source used in curing (printing) is 280-480 nm. Preferably, the intensity of the light source used in curing is 0.5-50 mW/cm2. Preferably, the exposure time of the single layer of the material during curing is 0.1-100 s. Preferably, the thickness of the single-layer film is 0.01-0.5 mm.
The invention also includes photocured 3D printed articles (prints) prepared using the method of any of the embodiments herein.
The invention also includes the application of the photosensitive resin which is solid at room temperature in the photocuring 3D printing; preferably, the photosensitive resin is a photosensitive resin as described in any of the embodiments herein.
Compared with the prior art, the invention has the following advantages:
1. the photosensitive resin obtained by mixing the components according to the formula is solid at room temperature, can become high-fluidity liquid after being heated, and can be restored to be solid after being cooled;
2. the 3D printing method provided by the invention has the advantages that the support is not needed in the printing process, the post-treatment process is simple, and the surface of the obtained printed piece is smooth;
3. by adopting the solid-state curing mode for molding, compared with the traditional photocuring printing, the printed product has low shrinkage, and the volume shrinkage rate is lower than 2%.
The technical scheme of the invention will be further described in detail with reference to examples, and common low-viscosity photosensitive resin materials are used as comparative examples. The scope of the present invention is not limited by the contents of the following examples. The scope of the present invention is defined only by the appended claims, and any omissions, substitutions, and changes in the form of the embodiments disclosed herein that may be made by those skilled in the art are intended to be included within the scope of the present invention.
The following examples and comparative examples use equipment conventional in the art. The experimental procedures of the following examples and comparative examples, in which specific conditions are not specified, are generally conducted under conventional conditions or under conditions recommended by the manufacturers. In the following examples and comparative examples, various starting materials were used, and unless otherwise specified, conventional commercially available products were used. In the description of the present invention and in the following examples and comparative examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Herein, the volume shrinkage after curing of the photosensitive resin is calculated as follows:
in the formula, VsVolume shrinkage after curing of the photosensitive resin, unit: percent; rhooDensity of the resin before curing, unit: g/cm3；ρcDensity of the product obtained after curing of the resin, unit: g/cm3。
The pigment used in the following examples and comparative examples was titanium dioxide, the dispersant was BYK-9010, the antifoaming agent was Tilo-2543, and the leveling agent was BYK-333.
Examples 1-6 solid-state photocuring 3D printing was performed using a photosensitive resin that was solid at room temperature, with specific printing operations including: uniformly mixing the acrylate prepolymer, the acrylate monomer, the photoinitiator and the auxiliary agent to obtain photosensitive resin, and pouring the photosensitive resin into a printer cylinder; the resin is changed into a solid state by cooling the medicine cylinder; the sample model does not need to be processed before printing; in the printing process, the resin is melted and leveled by heating, and then the temperature is reduced until the resin is solid, and the resin is exposed, cured and molded; after printing, the product only needs to be cleaned and post-cured, and a series of processes such as support removal, grinding and the like are not needed.
Example 1
Uniformly stirring an acrylate prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain the photosensitive resin, wherein the acrylate prepolymer is 30 parts by mass of polyurethane acrylate which is solid at room temperature, the acrylate monomer comprises 40 parts by mass of monofunctional hydroxyethyl methacrylate and 30 parts by mass of multifunctional dipentaerythritol hexaacrylate, the photoinitiator comprises 2 parts by mass of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and the auxiliary agent comprises 0.3 part by mass of pigment and 0.1 part by mass of dispersant. The wavelength of the light source used for printing was 405nm, and the intensity of the light source used for printing was 2mW/cm2The single-layer exposure time was 2s, and the film thickness was 0.05 mm. The volume shrinkage of the photosensitive resin of this example after curing was calculated by testing to be 1.82%.
Example 2
Uniformly stirring an acrylate prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain the photosensitive resin, wherein the acrylate prepolymer is 40 parts by mass of polyester acrylate which is solid at room temperature, and the acrylate monomer is 20 parts by mass of monofunctional hydroxyethyl methacrylate and 40 parts by mass of bifunctional tricyclo [5.2.1.0(2,6) ]]Decane diMethanol diacrylate, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator, 0.15 part by mass of pigment as an auxiliary agent, 0.1 part by mass of a dispersant and 0.5 part by mass of an antifoaming agent. The wavelength of the light source used in printing was 365nm, and the intensity of the light source used in printing was 20mW/cm2The single-layer exposure time was 10s, and the film thickness was 0.05 mm. The volume shrinkage of the photosensitive resin of this example after photocuring was calculated to be 1.67% by test.
Example 3
Uniformly stirring an acrylate prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain the photosensitive resin, wherein the acrylate prepolymer is 50 parts by mass of polyether acrylate which is solid at room temperature, the acrylate monomer is 50 parts by mass of monofunctional isobornyl methacrylate, the photoinitiator is 3 parts by mass of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, and the auxiliary agent is 0.1 part by mass of pigment, 0.1 part by mass of a dispersant and 0.1 part by mass of an antifoaming agent. The wavelength of the light source used for printing was 405nm, and the intensity of the light source used for printing was 5mW/cm2The exposure time for the single layer was 4s, and the film thickness was 0.08mm, as calculated by the test, the volume shrinkage of the photosensitive resin of this example after photocuring was 1.63%.
Example 4
Uniformly stirring an acrylate prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain the photosensitive resin, wherein the acrylate prepolymer is 60 parts by mass of polyether urethane acrylate which is solid at room temperature, the acrylate monomer is 40 parts by mass of bifunctional dipropylene glycol diacrylate, the photoinitiator is 2 parts by mass of 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and the auxiliary agent is 0.2 part by mass of pigment, 0.1 part by mass of a dispersing agent, 0.2 part by mass of an antifoaming agent and 0.1 part by mass of a leveling agent. The wavelength of the light source used for printing was 405nm, and the intensity of the light source used for printing was 45mW/cm2The single-layer exposure time was 20 seconds, and the film thickness was 0.06 mm. The volume shrinkage of the photosensitive resin of this example after curing was calculated by testing to be 1.48%.
Example 5
Mixing acrylic esterUniformly stirring a prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain a photosensitive resin, wherein the acrylate prepolymer is 30 parts by mass of epoxy acrylate which is solid at room temperature and 30 parts by mass of urethane acrylate which is liquid at room temperature, the acrylate monomer is 40 parts by mass of bifunctional tripropylene glycol diacrylate, the photoinitiator is 0.5 part by mass of α -hydroxyisobutyrophenone, 1 part by mass of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone, the auxiliary agent is 0.3 part by mass of a pigment, 0.3 part by mass of a dispersant and 0.1 part by mass of an antifoaming agent, the wavelength of a light source used in printing is 385nm, and the intensity of the light source used in printing is 15mW/cm2The single-layer exposure time was 5s, and the film thickness was 0.06 mm. The volume shrinkage of the photosensitive resin of this example after curing was calculated by the test to be 1.64%.
Example 6
Uniformly stirring an acrylate prepolymer, an acrylate monomer, a photoinitiator and an auxiliary agent to obtain the photosensitive resin, wherein the acrylate prepolymer is 40 parts by mass of polyester polyurethane acrylate which is solid at room temperature and 10 parts by mass of polyurethane acrylate which is liquid at room temperature, the acrylate monomer is 20 parts by mass of monofunctional hydroxyethyl methacrylate and 30 parts by mass of difunctional 1, 6-hexanediol diacrylate, the photoinitiator is 2 parts by mass of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide and 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone, and the auxiliary agent is 0.4 part by mass of pigment, 0.2 part by mass of dispersant, 0.1 part by mass of defoamer and 0.1 part by mass of leveling agent. The wavelength of the light source used for printing was 405nm, and the intensity of the light source used for printing was 10.2mW/cm2The single-layer exposure time was 12s, and the film thickness was 0.18 mm. The volume shrinkage of the photosensitive resin of this example after curing was calculated by testing to be 1.58%.
Comparative example
Comparative examples 1 to 6 are conventional photo-curing 3D printing using a common photosensitive resin (liquid at room temperature), and specific printing operations include: uniformly mixing an acrylate prepolymer, an acrylate monomer, a photoinitiator, a pigment and a dispersant according to the proportion shown in Table 1 to obtain photosensitive resin, and pouring the photosensitive resin into a printer cylinder; adding support to the sample model before printing, loading the sample model into a printing system, enabling the printer to be lower than the liquid level by one printing layer thickness through a printing platform in an initial state, selectively irradiating the liquid level by a light source, polymerizing and curing an exposure part into a solid, finishing the first layer printing, descending the printing platform by one printing layer thickness, carrying out the layer exposure after the leveling is finished, and circularly working according to the layer; and after printing, carrying out post-treatment on the product, wherein the post-treatment comprises a series of processes such as cleaning, support removing, post-curing, polishing and the like.
In comparative examples 1 to 6, the acrylate prepolymer was an epoxy acrylate that was liquid at room temperature, the acrylate monomer was isobornyl acrylate (IBOA), and the photoinitiator was (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide (TPO); the wavelength of the light source used in printing was 365nm, and the intensity of the light source used in printing was 20mW/cm2The single-layer exposure time was 10s, and the film thickness was 0.05 mm.
The volume shrinkage after curing of the photosensitive resins of comparative examples 1 to 6 was measured and calculated, and the results are shown in table 1.
Table 1: components (unit: parts by mass) and volume shrinkage after curing of the photosensitive resins of comparative examples 1 to 6
Claims (10)
1. A method of photocuring 3D printing, the method comprising: the method comprises the steps of using photosensitive resin which is solid at room temperature as a raw material for photocuring 3D printing, heating to melt and level the photosensitive resin in the 3D printing process, cooling to the solid state of the photosensitive resin, and carrying out exposure curing molding when the photosensitive resin is solid.
2. The method of claim 1, wherein the photosensitive resin has a volume shrinkage of less than 2% after curing.
3. The method of claim 1, wherein the photosensitive resin comprises an acrylate prepolymer, an acrylate monomer, a photoinitiator, and optionally an auxiliary agent.
4. The method of claim 3, wherein the method has one or more of the following features:
in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 2:8 to 8: 2;
in the photosensitive resin, the mass of the photoinitiator is 1-10 wt% of the total mass of the acrylate prepolymer and the acrylate monomer; and
in the photosensitive resin, the mass of the auxiliary agent is 0 wt% -1 wt% of the total mass of the acrylate prepolymer and the acrylate monomer.
5. The method of claim 3, wherein the acrylate prepolymer is solid at room temperature.
6. The method of claim 3, wherein the method has one or more of the following features:
the acrylate prepolymer is selected from one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether polyurethane acrylate and polyester polyurethane acrylate;
the acrylate monomer is selected from one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer or a multifunctional acrylate monomer;
the photoinitiator includes, but is not limited to, one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, methyl benzoylformate, (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and
the auxiliary agent is selected from one or more of pigments, flatting agents, defoaming agents, light absorbing agents and dispersing agents.
7. The photosensitive resin material according to claim 3,
the acrylate prepolymer is polyurethane acrylate which is solid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and dipentaerythritol hexaacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 20:80 to 40:60, and in the acrylate monomer, the mass ratio of the hydroxyethyl methacrylate to the dipentaerythritol hexaacrylate is 30:40 to 50: 20; or
The acrylate prepolymer is polyester acrylate which is solid at room temperature, and the acrylate monomer consists of hydroxyethyl methacrylate and tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 30:70 to 50:50, and in the acrylate monomer, the mass ratio of the hydroxyethyl methacrylate to the tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate is 10:50 to 30: 30; or
The acrylate prepolymer is polyether acrylate which is solid at room temperature, and the acrylate monomer is isobornyl methacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60: 40; or
The acrylate prepolymer is polyether urethane acrylate which is solid at room temperature, and the acrylate monomer is dipropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70: 30; or
The acrylate prepolymer is composed of epoxy acrylate which is solid at room temperature and urethane acrylate which is liquid at room temperature, and the acrylate monomer is tripropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70:30, and in the acrylate prepolymer, the mass ratio of the epoxy acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature is 20:40 to 40: 20; or
The acrylate prepolymer is composed of polyester urethane acrylate which is solid at room temperature and urethane acrylate which is liquid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60:40, the mass ratio of the polyester urethane acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 30:20 to 45:5, and the mass ratio of the hydroxyethyl methacrylate to the 1, 6-hexanediol diacrylate in the acrylate monomer is 10:40 to 30: 20.
8. The method of claim 1, wherein the method has one or more of the following features:
the wavelength of a light source adopted during printing is 280-480 nm;
the intensity of the light source adopted during printing is 0.5-50 mW/cm2(ii) a And
the single-layer exposure time of the material during printing is 0.1-100 s, and the thickness of the single-layer film is 0.01-0.5 mm.
9. A photocured 3D printed article prepared using the method of any one of claims 1-8.
10. Use of a photosensitive resin that is solid at room temperature in photocuring 3D printing;
preferably, the volume shrinkage of the photosensitive resin after curing is less than 2%;
preferably, the photosensitive resin comprises an acrylate prepolymer, an acrylate monomer, a photoinitiator and an optional auxiliary agent;
preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 2:8 to 8: 2;
preferably, in the photosensitive resin, the mass of the photoinitiator is 1 wt% to 10 wt% of the total mass of the acrylate prepolymer and the acrylate monomer;
preferably, in the photosensitive resin, the mass of the auxiliary agent is 0 wt% -1 wt% of the total mass of the acrylate prepolymer and the acrylate monomer;
preferably, the acrylate prepolymer is solid at room temperature;
preferably, the acrylate prepolymer is selected from one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether polyurethane acrylate and polyester polyurethane acrylate;
preferably, the acrylate monomer is selected from one or more of a monofunctional acrylate monomer, a difunctional acrylate monomer, or a multifunctional acrylate monomer;
preferably, the photoinitiator includes, but is not limited to, one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, α -hydroxyisobutyrophenone, methyl benzoylformate, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide, and phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide;
preferably, the auxiliary agent is selected from one or more of pigments, leveling agents, defoaming agents, light absorbing agents and dispersing agents;
preferably, the acrylate prepolymer is polyurethane acrylate which is solid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and dipentaerythritol hexaacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 20:80 to 40:60, and in the acrylate monomer, the mass ratio of the hydroxyethyl methacrylate to the dipentaerythritol hexaacrylate is 30:40 to 50: 20;
preferably, the acrylate prepolymer is a polyester acrylate that is solid at room temperature, and the acrylate monomer consists of hydroxyethyl methacrylate and tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 30:70 to 50:50, and in the acrylate monomer, the mass ratio of the hydroxyethyl methacrylate to the tricyclo [5.2.1.0(2,6) ] decane dimethanol diacrylate is 10:50 to 30: 30;
preferably, the acrylate prepolymer is polyether acrylate which is solid at room temperature, and the acrylate monomer is isobornyl methacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60: 40;
preferably, the acrylate prepolymer is polyether urethane acrylate which is solid at room temperature, and the acrylate monomer is dipropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70: 30;
preferably, the acrylate prepolymer is composed of epoxy acrylate which is solid at room temperature and urethane acrylate which is liquid at room temperature, and the acrylate monomer is tripropylene glycol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 50:50 to 70:30, and in the acrylate prepolymer, the mass ratio of the epoxy acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature is 20:40 to 40: 20;
preferably, the acrylate prepolymer is composed of polyester urethane acrylate which is solid at room temperature and urethane acrylate which is liquid at room temperature, and the acrylate monomer is composed of hydroxyethyl methacrylate and 1, 6-hexanediol diacrylate; preferably, in the photosensitive resin, the mass ratio of the acrylate prepolymer to the acrylate monomer is 40:60 to 60:40, the mass ratio of the polyester urethane acrylate which is solid at room temperature to the urethane acrylate which is liquid at room temperature in the acrylate prepolymer is 30:20 to 45:5, and the mass ratio of the hydroxyethyl methacrylate to the 1, 6-hexanediol diacrylate in the acrylate monomer is 10:40 to 30: 20.
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|---|---|---|---|---|
| CN111793175A (en) * | 2020-06-19 | 2020-10-20 | 湖南电气职业技术学院 | Enhanced multi-thorn laser curing 3D printing shape memory material and preparation method thereof |
| CN113174015A (en) * | 2020-09-07 | 2021-07-27 | 珠海市三绿实业有限公司 | Rigid photosensitive resin composition based on polyurethane acrylate and production method thereof |
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| CN109438632A (en) * | 2018-10-23 | 2019-03-08 | 西华大学 | 3D printing photosensitive resin of ultralow cubical contraction and preparation method thereof |
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| CN108673882A (en) * | 2018-06-28 | 2018-10-19 | 博纳云智（天津）科技有限公司 | It is a kind of without support 3D printing system and Method of printing |
| CN109438632A (en) * | 2018-10-23 | 2019-03-08 | 西华大学 | 3D printing photosensitive resin of ultralow cubical contraction and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111793175A (en) * | 2020-06-19 | 2020-10-20 | 湖南电气职业技术学院 | Enhanced multi-thorn laser curing 3D printing shape memory material and preparation method thereof |
| CN113174015A (en) * | 2020-09-07 | 2021-07-27 | 珠海市三绿实业有限公司 | Rigid photosensitive resin composition based on polyurethane acrylate and production method thereof |
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