CN115386049A - SLA temperature-resistant photosensitive resin for 3D printing and preparation and use methods thereof - Google Patents
SLA temperature-resistant photosensitive resin for 3D printing and preparation and use methods thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 96
- 239000011347 resin Substances 0.000 title claims abstract description 96
- 238000010146 3D printing Methods 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 239000000523 sample Substances 0.000 claims description 33
- 239000002994 raw material Substances 0.000 claims description 13
- 125000005409 triarylsulfonium group Chemical group 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- -1 hexafluoroantimonate Chemical compound 0.000 claims description 7
- 150000003254 radicals Chemical class 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 6
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 claims description 6
- CGRJJOYCFCCGPX-UHFFFAOYSA-N 3-ethyloxetane Chemical compound CCC1COC1 CGRJJOYCFCCGPX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 238000013499 data model Methods 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 6
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 6
- 229920000647 polyepoxide Polymers 0.000 claims description 6
- 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 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- IDSLNGDJQFVDPQ-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-yl) hexanedioate Chemical compound C1CC2OC2CC1OC(=O)CCCCC(=O)OC1CC2OC2CC1 IDSLNGDJQFVDPQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000000016 photochemical curing Methods 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract 1
- 239000004840 adhesive resin Substances 0.000 abstract 1
- 229920006223 adhesive resin Polymers 0.000 abstract 1
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 239000003085 diluting agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000011344 liquid material Substances 0.000 abstract 1
- 238000001029 thermal curing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 3
- WKGDNXBDNLZSKC-UHFFFAOYSA-N oxido(phenyl)phosphanium Chemical compound O=[PH2]c1ccccc1 WKGDNXBDNLZSKC-UHFFFAOYSA-N 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- 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
-
- 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
- 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
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/08—Heat treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides SLA temperature-resistant photosensitive resin for 3D printing and preparation and use methods thereof, wherein the preparation method of the temperature-resistant resin comprises the following steps: sequentially adding a functional monomer, a diluent, resin, an initiator and various additives into a container, and stirring at a low speed to obtain a mixed liquid; filtering the stirred resin to remove impurities, and then vacuumizing and defoaming to obtain a temperature-resistant resin liquid material; and (3) manufacturing a model sample by using an SLA printer, cleaning the surface of the model sample with adhesive resin by using a special cleaning agent, drying the model sample by using an air gun, and finally placing the sample with a dry and comfortable surface in an oven for heat treatment. The temperature-resistant resin material is suitable for mainstream SLA printers in the market, the surface of a resin sample piece after photocuring and thermocuring is smooth and high in precision, and the mechanical property is excellent, and the temperature-resistant resin material is mainly reflected in higher thermal deformation temperature and notch impact strength.
Description
Technical Field
The invention relates to a photocuring resin material and preparation and use methods thereof, in particular to an SLA (SLA) temperature-resistant photosensitive resin for 3D printing and preparation and use methods thereof, and belongs to the field of development of new 3D printing materials.
Background
Due to the high precision, the high efficiency and the simple operation method of the photocuring 3D printer and the photocuring material, the occupancy rate of the photocuring 3D printer in the 3D printing market is very high, especially, an SLA printer is widely applied to the hand-board industry, and more design works are presented through the 3D printing technology. With the popularization of the application of the photocuring 3D printing market, the short adaptive material performance board is increasingly highlighted, for example, in different seasons, the material performance is excessively changed, the material is softened in summer to cause the deformation of a sample, and the material is poor in toughness in winter to cause the brittleness of the sample; the notch impact performance of the high-temperature resistant resin material on the market is poor, and the notch impact performance is difficult to realize in practical application. Therefore, a material which has good mechanical property stability at the temperature and humidity of four seasons, has certain temperature resistance and toughness and meets the actual production requirements of large-format machines, namely good material storage stability, high molding rate and printing efficiency and simple and convenient operation is urgently needed to be developed.
Chinese patent application No. CN107513247A discloses a high temperature resistant toughened photocurable resin for 3D printing, which achieves dual curing modes of curing and thermosetting for 3D printing by introducing a photocurable and thermosetting free radical initiator, and obtains a photosensitive resin with high curing efficiency, temperature resistance and good toughness. The thermosetting initiator is sensitive to heat, and the resin in a non-molding area is easily cured due to the local temperature rise of the resin polymerization heat release in the printing and forming process, so that the service life of the resin in a resin tank is shortened, the accuracy of a printed product is even influenced, and great inconvenience is brought to actual operation, so that the method is not suitable for a machine table for large-breadth SLA production; chinese patent application with publication number CN109517340A discloses a temperature-resistant transparent photosensitive resin for 3D printing, the impact strength of a notch of a formula after optimization is 32J/m at most, and the hardness at room temperature and 80 ℃ is 85D and 69D respectively; the hardness difference is small, the notch impact strength is 18-27J/m, the resin toughness is poor, and a sample piece is easily damaged manually in the process of shoveling and washing the piece, so that the waste of materials is caused, and the production efficiency is influenced. Although the above two patents have the effects of improving temperature resistance and toughening, the service life and practical operation cannot meet the market requirements, and thus, a photosensitive resin which has excellent temperature resistance and is suitable for production of large-sized machines is urgently needed.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide an SLA temperature-resistant photosensitive resin for 3D printing and preparation and use methods thereof. The temperature-resistant photosensitive resin material has low shrinkage and excellent toughness, and is suitable for most mainstream SLA machines in the market.
In order to achieve the purpose, the invention provides SLA temperature-resistant photosensitive resin for 3D printing, which comprises the following raw materials in percentage by weight: 5-15% of bismaleimide, 30-60% of epoxy monomer, 20-40% of acrylate monomer, 10-40% of epoxy resin, 10-30% of acrylate resin, 1-3% of free radical initiator, 3-6% of cationic initiator and 0.02-0.08% of defoaming agent, wherein the sum of the weight percentages of the raw materials is 100%.
In the above-mentioned photocurable temperature-resistant resin material, preferably, the bismaleimide is BMI-80 powder manufactured by KI corporation of japan.
In the above-mentioned photocurable temperature-resistant resin material, preferably, the epoxy monomer is one or a combination of 3-ethyl-3-oxetanemethanol and 3,3- [ oxybis-methylene ] -bis [ 3-ethyl ] oxetane.
In the light-curing temperature-resistant resin material, preferably, the acrylate monomer is one or a combination of trimethylolpropane triacrylate (TMPTA), N-Acryloylmorpholine (ACMO) and tris (2-hydroxyethyl) isocyanuric acid triacrylate (thecta).
In the light-cured temperature-resistant resin material, preferably, the defoaming agent is one or a combination of BYK 055 and BYK 067A.
In the above photocurable temperature-resistant resin material, preferably, the cationic initiator is one or a combination of triarylsulfonium hexafluoroantimonate and triarylsulfonium hexafluorophosphate.
In the above-mentioned photocurable temperature-resistant resin material, preferably, the radical initiator is one or a combination of acetophenone, a-hydroxy ketone, a-amino ketone, and bis- (2, 4, 6) -trimethylbenzoylphenylphosphine oxide.
In the light-cured temperature-resistant resin material, preferably, the epoxy resin is one or a combination of several of aliphatic epoxy resin UVACURE1534, UVR6110 and UVR 6128.
In the above light-cured temperature-resistant resin material, preferably, the acrylate resin is one or a combination of several of novolac epoxy acrylate and aromatic urethane acrylate.
The invention also provides a preparation method of the photocuring temperature-resistant resin material, which comprises the following steps:
(1) Sequentially weighing and adding an epoxy monomer, an acrylate monomer and bismaleimide into a beaker, inserting a temperature probe, starting a heating disc, and stirring at a low speed to obtain a mixed liquid;
(2) Sequentially weighing a defoaming agent, a free radical initiator, a cationic initiator, epoxy resin and acrylate resin, adding into the mixed liquid obtained in the step (1), and stirring to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring, vacuumizing and defoaming to obtain the finished product of the temperature-resistant resin liquid.
In the above production method, the low-speed stirring speed in the step (1) is preferably 300 to 800r/min.
In the above production method, it is preferable that the stirring speed in the step (2) is 400 to 1000r/min.
In the above production method, preferably, the number of mesh of the sieving screen in the step (3) is 40 to 100 mesh.
In the above production method, it is preferable that the vacuum temperature in the step (3) is 50 to 90 ℃ for 1 to 3 hours.
The invention also provides a using method of the photocuring temperature-resistant resin material, which comprises the following steps:
(1) Shoveling down the printed data model sample from the SLA machine platform printing platform and removing the support;
(2) Cleaning the sample piece in special cleaning solution, and then blowing the surface cleaning solution by using an air gun;
(3) Setting a temperature-raising program of the oven, and then placing the sample piece in the oven for heat treatment.
In the above production method, preferably, the temperature in the step (3) is 60 to 300 ℃.
In the above production method, the time in the step (3) is preferably 4 to 12 hours.
In the above preparation method, the amounts of the monomer, the resin, the initiator and the defoaming agent may be adjusted conventionally by those skilled in the art as long as the respective raw materials are completely mixed and proportioned.
The model printed by the photocuring temperature-resistant resin material has the advantages of thermal deformation temperature of 80-150 ℃, notch impact strength of 40-70J/m, high molding rate and smooth and fine surface. The sample piece prepared from the resin has stable mechanical property and can be used as a terminal piece.
Drawings
FIG. 1 is SEM photographs of a sample printed with the temperature-resistant resin material of example 1 before and after heat treatment.
FIG. 2 is SEM photographs of a sample printed with the temperature-resistant resin material of example 2 before and after heat treatment.
FIG. 3 is SEM photographs of a sample printed with the temperature-resistant resin material of example 3 before and after heat treatment.
FIG. 4 is SEM photographs of a sample printed with the temperature-resistant resin material of example 4 before and after heat treatment.
FIG. 5 is a photograph showing a tapping operation performed on a heat-treated sample of the temperature-resistant resin material of example 3.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
In the following examples, all the raw materials were commercially available; the percentages mentioned are percentages by weight.
Detailed description of the preferred embodiment 1
The invention provides SLA temperature-resistant photosensitive resin for 3D printing, which comprises the following raw materials in percentage by weight: BMI-80%, 3-ethyl-3-oxetanemethanol 33%, N-Acryloylmorpholine (ACMO) 15%, tris (2-hydroxyethyl) isocyanurate Triacrylate (THEICA) 10%, BYK 055 0.05%, triarylsulfonium hexafluoroantimonate 4%, bis- (2, 4, 6) -trimethylbenzoylphenylphosphine oxide 2.95%, UVR 6112%, epoxy novolac acrylate 13%. BMI-80 powder was produced by KI of Japan.
The SLA temperature-resistant resin for 3D printing is prepared by the following method:
(1) Sequentially weighing 3-ethyl-3-oxetanylcarbinol, ACMO, THEICA and BMI-80, adding into a beaker, inserting a temperature probe, setting the heating temperature at 70 ℃, and stirring at the rotating speed of 450r/min for 60 minutes to obtain a mixed liquid;
(2) Sequentially weighing BYK 055, triaryl sulfonium hexafluoroantimonate, bis- (2, 4, 6) -trimethylbenzoyl phenyl phosphine oxide, UVR6110 and novolac epoxy acrylate, adding into the mixed liquid in the step (1), and stirring at 600r/min for 70 minutes to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring through a 60-mesh screen, vacuumizing at 70 ℃ for 120 minutes, and defoaming to obtain the finished product of the temperature-resistant resin liquid.
The use method of the SLA temperature-resistant resin for 3D printing comprises the following steps:
(1) Shoveling the printed data model sample from the SLA machine platform printing platform and removing the support;
(2) Cleaning the sample piece in special cleaning liquid and then blowing the surface cleaning liquid by using an air gun;
(3) Setting the temperature raising program of the oven to be 180 ℃ and preserving the temperature for 5 hours, and then placing the sample piece into the oven for heat treatment.
A antithetical SLA printer is used for printing temperature-resistant photosensitive resin, SEM pictures of the front surface and the rear surface of a cured resin model before heat treatment are shown in figure 1, after heat treatment, the bending strength of the resin with the formula is 96MPa, the bending modulus is 2809MPa, the heat deformation temperature is 97 ℃, and the notch impact strength is 61J/m.
Specific example 2
The invention provides SLA temperature-resistant photosensitive resin for 3D printing, which comprises the following raw materials in percentage by weight: the raw materials comprise:
BMI-80%, 3- [ oxybis-methylene ] -bis [ 3-ethyl ] oxetane 30%, TMPTA15%, THEIPTA 8%, BYK 055 0.05%, triaryl sulfonium hexafluoroantimonate 5%, a-hydroxy ketone 1.95%, UVR 6110%, and aromatic urethane acrylate 18%.
The SLA temperature-resistant resin for 3D printing is prepared by the following method:
(1) Sequentially weighing 3- [ oxybis-methylene ] -bis [ 3-ethyl ] oxetane, TMPTA, THEICTA and BMI-80, adding into a beaker, inserting a temperature probe, setting the heating temperature to 75 ℃, and stirring at the rotating speed of 500 r/min for 50 minutes to obtain a mixed liquid;
(2) Sequentially weighing BYK 055, triaryl sulfonium hexafluoroantimonate, a-hydroxy ketone, UVR6110 and aromatic urethane acrylate, adding into the mixed liquid obtained in the step (1), and stirring at 700r/min for 60 minutes to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring through a 70-mesh screen, vacuumizing at 80 ℃ for 110 minutes, and defoaming to obtain the finished product of the temperature-resistant resin liquid.
The use method of the SLA temperature-resistant resin for 3D printing comprises the following steps:
(1) And shoveling the printed data model sample piece from the SLA machine platform printing platform and removing the support.
(2) And cleaning the sample piece in special cleaning solution and then blowing the surface cleaning solution by using an air gun.
(3) Setting the temperature raising program of the oven as 220 ℃ and preserving the heat for 4.5 hours, and then placing the sample piece into the oven for heat treatment.
A temperature-resistant photosensitive resin is printed by a antitai SLA printer, SEM pictures of the front surface and the rear surface of a cured resin model before heat treatment are shown in figure 2, the bending strength of the resin in the formula after heat treatment is 116MPa, the bending modulus is 3142MPa, the heat deformation temperature is 105 ℃, and the notch impact strength is 59J/m.
Specific example 3
The invention provides SLA temperature-resistant photosensitive resin for 3D printing, which comprises the following raw materials in percentage by weight: the raw materials comprise: BMI-80%, 3- [ oxybis-methylene ] -bis [ 3-ethyl ] oxetane 25%, THEIPTA 22%, BYK 055 0.05%, triarylsulfonium hexafluoroantimonate 4%, bis- (2, 4, 6) -trimethylbenzoylphenylphosphine oxide 3.95%, UVR 6110%, epoxy novolac acrylate 15%.
The SLA temperature-resistant resin for 3D printing is prepared by the following method:
(1) Sequentially weighing 3- [ oxybis-methylene ] -bis [ 3-ethyl ] oxetane, THEICA and BMI-80, adding into a beaker, inserting a temperature probe, setting the heating temperature at 85 ℃, and stirring at the rotating speed of 400r/min for 50 minutes to obtain a mixed liquid;
(2) Sequentially weighing BYK 055, triaryl sulfonium hexafluoroantimonate, bis- (2, 4, 6) -trimethylbenzoyl phenyl phosphine oxide, UVR6110 and novolac epoxy acrylate, adding into the mixed liquid in the step (1), and stirring at 550r/min for 80 minutes to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring through a 50-mesh screen, vacuumizing at 80 ℃ for 120 minutes, and defoaming to obtain the finished product of the temperature-resistant resin liquid.
The use method of the SLA temperature-resistant resin for 3D printing comprises the following steps:
(1) And shoveling the printed data model sample piece from the SLA machine platform printing platform and removing the support.
(2) And cleaning the sample piece in special cleaning solution and then blowing the surface cleaning solution by using an air gun.
(3) Setting the temperature raising program of the oven to be 260 ℃ and preserving heat for 6 hours, and then placing the sample piece into the oven for heat treatment.
A antithetical SLA printer is used for printing temperature-resistant photosensitive resin, SEM pictures of the front surface and the rear surface of a cured resin model before heat treatment are shown in figure 3, after heat treatment, the bending strength of the resin with the formula is 143MPa, the bending modulus is 3789MPa, the heat deformation temperature is 147 ℃, and the notch impact strength is 43J/m.
Specific example 4
The invention provides SLA temperature-resistant photosensitive resin for 3D printing, which comprises the following raw materials in percentage by weight: the raw material composition comprises: BMI-80%, 3-ethyl-3-oxetanemethanol 30%, THEIPTA 10%, TMPTA 12%, BYK 055 0.05%, triarylsulfonium hexafluoroantimonate 3%, bis- (2, 4, 6) -trimethylbenzoylphenylphosphine oxide 2.95%, UVR 6128%, aromatic urethane acrylate 20%.
The SLA temperature-resistant resin for 3D printing is prepared by the following method:
(1) Sequentially weighing 3-ethyl-3-oxetanylcarbinol, THEICA and BMI-80, adding into a beaker, inserting a temperature probe, setting the heating temperature to 65 ℃, and stirring for 50 minutes at the rotating speed of 400r/min to obtain a mixed liquid;
(2) Sequentially weighing BYK 055, triaryl sulfonium hexafluoroantimonate, bis- (2, 4, 6) -trimethylbenzoyl phenyl phosphine oxide, UVR6110 and aromatic polyurethane acrylate, adding into the mixed liquid obtained in the step (1), and stirring at 600r/min for 70 minutes to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring through a 60-mesh screen, and vacuumizing at 65 ℃ for 120 minutes for defoaming to obtain the finished product of the temperature-resistant resin liquid.
The use method of the SLA temperature-resistant resin for 3D printing comprises the following steps:
(1) And shoveling the printed data model sample piece from the SLA machine platform printing platform and removing the support.
(2) And cleaning the sample piece in special cleaning solution and then blowing the surface cleaning solution by using an air gun.
(3) Setting the temperature raising program of the oven to be 170 ℃ and preserving the temperature for 8 hours, and then placing the sample piece into the oven for heat treatment.
A antitarnish SLA printer is used for printing temperature-resistant photosensitive resin, SEM pictures of the front surface and the rear surface of a cured resin model before heat treatment are shown in the attached figure 4, the bending strength of the resin with the formula after heat treatment is 87MPa, the bending modulus is 2247MPa, the heat deformation temperature is 82 ℃, and the notch impact strength is 70J/m.
The above description is only a preferred embodiment of the present invention, and all equivalent changes or modifications of the structure, characteristics and principles described in the present invention are included in the scope of the present invention.
Claims (11)
1. The SLA temperature-resistant photosensitive resin for 3D printing is characterized by comprising the following raw materials in percentage by weight: 5-15% of bismaleimide, 30-60% of epoxy monomer, 20-40% of acrylate monomer, 10-40% of epoxy resin, 10-30% of acrylate resin, 1-3% of free radical initiator, 3-6% of cationic initiator and 0.02-0.08% of defoaming agent, wherein the sum of the weight percentages of the raw materials is 100%.
2. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the bismaleimide is BMI-80 powder manufactured by KI corporation of japan.
3. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the epoxy monomer is one or a combination of 3-ethyl-3-oxa-cyclomethanol and 3,3- [ oxy-bis-methylene ] -bis [ 3-ethyl ] oxetane.
4. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the acrylate monomer is one or a combination of trimethylolpropane triacrylate (TMPTA), N-acryloyl morpholine (ACMO), tris (2-hydroxyethyl) isocyanurate triacrylate (THEIPTA).
5. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the defoaming agent is one or a combination of BYK 055 and BYK 067A.
6. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the cationic initiator is one or a combination of triarylsulfonium hexafluoroantimonate and triarylsulfonium hexafluorophosphate.
7. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the free radical initiator is one or a combination of acetophenone, a-hydroxy ketone, a-amino ketone, bis- (2, 4, 6) -trimethylbenzoylphenylphosphine oxide.
8. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the epoxy resin is one or a combination of aliphatic epoxy resin UVACURE1534, UVR6110 and UVR 6128.
9. The SLA temperature-resistant photosensitive resin for 3D printing according to claim 1, wherein the acrylate resin is one or a combination of phenolic epoxy acrylate and aromatic urethane acrylate.
10. A method for preparing the temperature-resistant photosensitive resin of any one of claims 1 to 9, comprising the steps of:
(1) Sequentially weighing and adding an epoxy monomer, an acrylate monomer and bismaleimide into a beaker, inserting a temperature probe, starting a heating disc, and stirring at a low speed to obtain a mixed liquid;
(2) Sequentially weighing a defoaming agent, a free radical initiator, a cationic initiator, epoxy resin and acrylate resin, adding into the mixed liquid obtained in the step (1), and stirring to obtain a temperature-resistant resin mixed liquid;
(3) And sieving the mixed resin liquid obtained by stirring, vacuumizing and defoaming to obtain the finished product of the temperature-resistant resin liquid.
11. A method of using the temperature-resistant photosensitive resin according to any one of claims 1 to 9, comprising the steps of:
(1) Shoveling the printed data model sample from the SLA machine platform printing platform and removing the support;
(2) Cleaning the sample piece in special cleaning liquid and then blowing the surface cleaning liquid by using an air gun;
(3) Setting a temperature-raising program of the oven, and then placing the sample piece in the oven for heat treatment.
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| CN106749987A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | It is a kind of for the SLA photosensitive resin compositions of 3D printing and its application |
| US20170173872A1 (en) * | 2015-12-22 | 2017-06-22 | Carbon, Inc. | Wash liquids for use in additive manufacturing with dual cure resins |
| CN106947205A (en) * | 2017-04-19 | 2017-07-14 | 塑成科技（北京）有限责任公司 | A kind of epoxy phenolic resin of Stereo Lithography Apparatus Rapid Prototyping and preparation method thereof |
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2022
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170173872A1 (en) * | 2015-12-22 | 2017-06-22 | Carbon, Inc. | Wash liquids for use in additive manufacturing with dual cure resins |
| CN106749987A (en) * | 2016-12-12 | 2017-05-31 | 中山大简高分子材料有限公司 | It is a kind of for the SLA photosensitive resin compositions of 3D printing and its application |
| CN106947205A (en) * | 2017-04-19 | 2017-07-14 | 塑成科技（北京）有限责任公司 | A kind of epoxy phenolic resin of Stereo Lithography Apparatus Rapid Prototyping and preparation method thereof |
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