CN115286743A - Photocuring resin for high-precision matte 3D printing and preparation method thereof - Google Patents
Photocuring resin for high-precision matte 3D printing and preparation method thereof Download PDFInfo
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- CN115286743A CN115286743A CN202210988730.1A CN202210988730A CN115286743A CN 115286743 A CN115286743 A CN 115286743A CN 202210988730 A CN202210988730 A CN 202210988730A CN 115286743 A CN115286743 A CN 115286743A
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- 229920005989 resin Polymers 0.000 title claims abstract description 99
- 239000011347 resin Substances 0.000 title claims abstract description 99
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 35
- 238000010146 3D printing Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- -1 polydimethylsiloxane Polymers 0.000 claims description 31
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 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 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 11
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 claims description 11
- 239000006229 carbon black Substances 0.000 claims description 11
- 229920000058 polyacrylate Polymers 0.000 claims description 11
- 235000010215 titanium dioxide Nutrition 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 229920000728 polyester Polymers 0.000 claims description 9
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 8
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 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
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 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 5
- 238000001723 curing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 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 claims description 4
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 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
- 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 3
- 150000001412 amines Chemical class 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 125000005375 organosiloxane group Polymers 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Images
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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
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a photocuring resin for high-precision matte 3D printing and a preparation method thereof, and belongs to the technical field of photocuring resins. The light-cured resin for the high-precision matte 3D printing comprises the following raw materials in percentage by mass: 20 to 60 percent of oligomer resin, 30 to 75 percent of monomer diluent, 0.2 to 5 percent of photoinitiator, 3 to 8 percent of reaction auxiliary agent, 1 to 5 percent of filler and 0.1 to 2 percent of color paste. The light-cured resin provided by the invention can be rapidly cured, the volume shrinkage rate is small after the light-cured resin is completely cured, the molding precision is high, and meanwhile, the molded model has high matt degree and fine surface texture.
Description
Technical Field
The invention relates to the technical field of light-cured resin, in particular to light-cured resin for high-precision matte 3D printing and a preparation method thereof.
Background
The photosensitive resin is similar to the traditional engineering plastics (ABS, PBT and the like), has excellent performance, and is widely applied to the fields of manufacturing sample parts of medical appliances, automobiles, daily electronic products and the like. In recent years, 3D photosensitive resin is being used for 3D to print emerging trade, compares in traditional thermoplasticity 3D printing material, because of 3D photosensitive resin have print time short, product surface is smooth not have the wire drawing, the texture is full, product surface is exquisite, can be used to many advantages such as biomaterial and receive trade favor and attention.
The photosensitive resin is a liquid photocurable resin, also called UV resin, and under irradiation of ultraviolet light or visible light, the resin macromolecules are cross-linked and polymerized with the aid of a photoinitiator to form polymeric macromolecules, and the polymerization modes are classified into radical polymerization and cationic polymerization according to the difference of the photoinitiator. The photocuring process has the advantages of no pollution, no toxicity, no irritation, safe production and the like, and is an active research and development field at present.
Photosensitive resins for 3D printing may be classified into general hard resins, washable resins, flexible resins, elastic resins, red wax resins, transparent resins, ABS-like resins, high temperature resistant resins, and the like according to functional attributes. The red wax resin is widely applied to the industries of animation and jewelry due to excellent detail degree, and the surface of a model is smooth and fine without secondary processing and polishing. However, the domestic existing red wax resin is difficult to achieve higher detail degree due to higher resin shrinkage rate, and cannot simultaneously have high precision and high matte effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the photocuring resin for high-precision matte 3D printing, the photocuring resin can be quickly cured, the volume shrinkage rate is small after the photocuring resin is completely cured, the molding precision is high, and meanwhile, the molded model has high matte degree and fine surface texture.
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the high-precision matte photocuring resin for 3D printing comprises the following raw materials in percentage by mass: 20 to 60 percent of oligomer resin, 30 to 75 percent of monomer diluent, 0.2 to 5 percent of photoinitiator, 3 to 8 percent of reaction auxiliary agent, 1 to 5 percent of filler and 0.1 to 2 percent of color paste.
In a preferred embodiment of the present invention, the oligomer resin is at least one selected from the group consisting of aliphatic urethane acrylate, modified urethane acrylate, aromatic urethane acrylate, epoxy acrylate, and polyester acrylate.
In a preferred embodiment of the present invention, the monomer diluent is at least one selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 4-acryloylmorpholine, cyclotrimethylolpropane formal acrylate, isobornyl acrylate, trimethylolpropane triacrylate and dipentaerythritol hexaacrylate.
As a preferred embodiment of the present invention, the photoinitiator is selected from at least one of 1-hydroxy-cyclohexyl-benzophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphorus oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, or bis 2,6-difluoro-3-pyrrolylphenyltitanocene.
In a preferred embodiment of the present invention, the reaction auxiliary agent is at least one selected from the group consisting of acrylate copolymers, polydimethylsiloxanes, polymethylphenylsiloxanes, polyether polyester-modified organosiloxanes, modified acrylate polymers, higher alcohol fatty acid ester complexes, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxanes.
As a preferred embodiment of the present invention, the filler is selected from at least one of silica, zirconia, or alumina.
As a preferable embodiment of the invention, the color paste is one of fast red, iron oxide yellow, titanium white and carbon black.
In a preferred embodiment of the present invention, the wavelength of the ultraviolet light used for curing the photocurable resin is 405nm.
As a preferred embodiment of the present invention, the photocurable resin is suitable for use in an LCD-3D printer or a DLP-3D printer.
The invention also provides a preparation method of the photocuring resin for high-precision matte 3D printing, which comprises the following steps: and (2) blending the oligomer resin, the monomer diluent, the photoinitiator, the reaction auxiliary agent, the filler and the color paste according to the formula ratio at the temperature of 40-60 ℃, and uniformly stirring to form a uniform and stable system, thus obtaining the photocuring resin. The oligomer resin selected by the invention has higher viscosity, and the blending efficiency of the raw materials can be improved by blending at the temperature.
Compared with the prior art, the invention has the beneficial effects that:
1. the low-polymer resin with small shrinkage rate is selected and the content of the low-polymer resin is controlled to further reduce the shrinkage rate, meanwhile, as the volume of the resin is increased in the curing process, the content of the resin in unit volume is reduced by adding the inert material filler to further effectively reduce the shrinkage rate, and in addition, the absorption and transmittance of light in the light curing process can be regulated and controlled by adding the color paste and the filler, so that the purpose of reducing the shrinkage rate by controlling the curing speed is achieved. By reducing the shrinkage rate (generally less than 3%) from the above aspects, the forming precision is greatly improved.
2. According to the invention, the filler and the reaction auxiliary agent are added into the photocuring resin, so that the printed model has high matte degree and fine surface texture.
3. According to the invention, the amount of each component is scientifically mixed, so that the amount of the photoinitiator is matched with the number of C = C double bonds in the photosensitive resin, and the photocurable resin can be rapidly cured.
In conclusion, the model printed by the photocuring resin for 3D printing has the effects of high precision and high matte, the surface texture is fine, and the problem that the red wax resin in China is difficult to have high precision and high matte brightness at the same time at present is effectively solved.
The preparation method of the photocureable resin for 3D printing provided by the invention is simple, easy to operate and high in yield.
Drawings
FIG. 1 is a diagram showing the effects of a plurality of models printed by the photocurable resin prepared in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the effects of a photo-curable resin printed model obtained in example 1 of the present invention;
FIG. 3 is a graph showing the comparison of the effects of a photo-curable resin printed on a mold according to comparative example 1 of the present invention;
FIG. 4 is a graph showing the comparison of the effects of a photo-curable resin printed on a mold according to comparative example 2 of the present invention;
FIG. 5 is a graph showing the comparison of the effects of the photo-curable resin prepared in comparative example 3 according to the present invention on the printed model.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
The invention provides a high-precision matte photocuring resin for 3D printing, which comprises the following raw materials in percentage by mass: 20 to 60 percent of oligomer resin, 30 to 75 percent of monomer diluent, 0.2 to 5 percent of photoinitiator, 3 to 8 percent of reaction auxiliary agent, 1 to 5 percent of filler and 0.1 to 2 percent of color paste.
Wherein the oligomer resin is at least one selected from aliphatic urethane acrylate, modified urethane acrylate, aromatic urethane acrylate, epoxy acrylate and polyester acrylate. The monomer diluent is at least one selected from the group consisting of tripropylene glycol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 4-acryloylmorpholine, cyclotrimethylolpropane formal acrylate, isobornyl acrylate, trimethylolpropane triacrylate and dipentaerythritol hexaacrylate. The photoinitiator is at least one selected from 1-hydroxy-cyclohexyl-benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphorus oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide or bis 2,6-difluoro-3-pyrrol-ylphenyltitanocene. The reaction auxiliary agent is at least one selected from acrylate copolymer, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organic siloxane, modified acrylate polymer, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane. The filler is selected from at least one of silica, zirconia, or alumina. The color paste is one of fast red, yellow iron oxide, titanium white and carbon black.
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps: and (2) blending the oligomer resin, the monomer diluent, the photoinitiator, the reaction auxiliary agent, the filler and the color paste according to the formula ratio at the temperature of 40-60 ℃, and uniformly stirring to form a uniform and stable system, thus obtaining the photocuring resin.
Example 1
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps:
30g of trifunctional aliphatic urethane acrylate, 10g of trifunctional modified urethane acrylate, 30g of 4-acryloyl morpholine, 30g of tricyclodecane dimethanol diacrylate, 3g of diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, 1.5g of acrylate copolymer, 1.5g of polymethylphenylsiloxane, 0.5g of modified acrylate polymer, 3g of silicon dioxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath, heated and stirred for 2 hours at the speed of 200r/min to obtain the photocuring resin, and the photocuring resin is stored in a dark place.
Example 2
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps:
20g of trifunctional aliphatic urethane acrylate, 20g of difunctional aromatic urethane acrylate, 40g of 4-acryloyl morpholine, 20g of tripropylene glycol diacrylate, 3g of 1-hydroxy-cyclohexyl-benzophenone, 1.5g of acrylate copolymer, 1.5g of polydimethylsiloxane, 0.5g of modified acrylate polymer, 3g of silicon dioxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath, heated and stirred at the speed of 200r/min for 2 hours, and the photocuring resin is obtained and stored in a dark place.
Example 3
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps:
30g of trifunctional modified polyurethane acrylate, 10g of bifunctional aromatic polyurethane acrylate, 30g of dipropylene glycol diacrylate, 30g of tricyclodecane dimethanol diacrylate, 3g of diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, 1.5g of polymethylphenylsiloxane, 1.5g of polyether polyester modified organosiloxane, 0.5g of modified acrylate polymer, 3g of zirconium oxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath pot, heated and stirred for 2 hours at the speed of 200r/min, and the light-cured resin is obtained and stored in a dark place.
Example 4
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps:
20g of trifunctional aliphatic urethane acrylate, 20g of trifunctional epoxy acrylate, 30g of isobornyl acrylate, 30g of dipentaerythritol hexaacrylate, 3g of bis 2,6-difluoro-3-pyrrol phenyl titanocene, 1.5g of polyether polyester modified organosiloxane, 1.5g of high-carbon alcohol fatty acid ester compound, 0.5g of modified acrylate polymer, 3g of aluminum oxide, 0.3g of titanium white, 0.05g of fast red, 0.3g of iron oxide yellow and 0.001g of carbon black are mixed, placed in a 50 ℃ water bath kettle, heated and stirred at the speed of 200r/min for 2 hours to obtain the photocuring resin, and the photocuring resin is stored in a dark place.
Example 5
The preparation method of the photocuring resin for high-precision matte 3D printing comprises the following steps:
30g of trifunctional aromatic urethane acrylate, 10g of trifunctional polyester acrylate, 30g of dipentaerythritol hexaacrylate, 30g of trimethylolpropane triacrylate, 3g of bis-2,6-difluoro-3-pyrrol-phenyl titanocene, 1.5g of polyoxypropylene polyoxyethylene glycerol ether, 1.5g of polydimethylsiloxane, 0.5g of modified acrylate polymer, 2g of alumina, 0.3g of titanium white, 0.05g of fast red, 0.3g of iron oxide yellow and 0.001g of carbon black are mixed, placed in a 50 ℃ water bath pot, heated and stirred at the speed of 200r/min for 2 hours to obtain the photocuring resin, and the photocuring resin is stored in a dark place.
Comparative example 1
The preparation method of the light-cured resin for 3D printing comprises the following steps:
40g of trifunctional aliphatic urethane acrylate, 20g of trifunctional modified urethane acrylate, 20g of 4-acryloyl morpholine, 20g of tricyclodecane dimethanol diacrylate, 3g of diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, 1.5g of acrylate copolymer, 1.5g of polymethylphenylsiloxane, 0.5g of modified acrylate polymer, 3g of silicon dioxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath, heated and stirred for 2 hours at the speed of 200r/min to obtain the light-cured resin, and the light-cured resin is stored in a dark place.
Comparative example 2
The preparation method of the photocuring resin for 3D printing comprises the following steps:
30g of trifunctional aromatic urethane acrylate, 10g of trifunctional polyester acrylate, 30g of 4-acryloyl morpholine, 30g of tricyclodecane dimethanol diacrylate, 3g of diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, 1.5g of acrylate copolymer, 1.5g of polymethylphenyl siloxane, 0.5g of modified acrylate polymer, 3g of silicon dioxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath pot, heated and stirred at the speed of 200r/min for 2 hours to obtain the photocuring resin, and stored in a dark place.
Comparative example 3
The preparation method of the light-cured resin for 3D printing comprises the following steps:
30g of trifunctional aliphatic urethane acrylate, 10g of trifunctional modified urethane acrylate, 30g of 4-acryloyl morpholine, 30g of tricyclodecane dimethanol diacrylate, 3g of diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide, 1.5g of acrylate copolymer, 1.5g of polymethylphenyl siloxane, 0.5g of modified acrylate polymer, 3g of zirconium oxide, 0.4g of titanium white, 0.03g of fast red, 0.5g of iron oxide yellow and 0.002g of carbon black are mixed, placed in a 50 ℃ water bath pot, heated and stirred at the speed of 200r/min for 2 hours to obtain the photocuring resin, and the photocuring resin is stored in a dark place.
Performance comparison experiment:
the photo-curing resins obtained in examples 1 to 5 and comparative examples 1 to 3 were photo-cured, printed and molded by an LCD type 3D printer under the same printing parameters, and the shrinkage and gloss were measured, and the test data are shown in table 1:
TABLE 1 comparison of Performance index results for examples 1-5 and comparative examples 1-3
As shown in table 1 and fig. 1 to 5, the examples and comparative examples, in which trifunctional aliphatic urethane acrylate was used as one of the oligomers, were compared to each other to have lower shrinkage, the examples and comparative examples, in which trifunctional specially modified urethane acrylate was used as one of the oligomers, had lower gloss, and the shrinkage measured in example 1 was the lowest and the gloss was the lowest, it was seen that example 1 had high precision and high matte effect.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (9)
1. The utility model provides a high accuracy is mute light cured resin for 3D prints which characterized in that: the composite material comprises the following raw materials in percentage by mass: 20 to 60 percent of oligomer resin, 30 to 75 percent of monomer diluent, 0.2 to 5 percent of photoinitiator, 3 to 8 percent of reaction auxiliary agent, 1 to 5 percent of filler and 0.1 to 2 percent of color paste.
2. The light-curable resin for high-precision matte 3D printing according to claim 1, wherein: the oligomer resin is at least one selected from aliphatic urethane acrylate, modified urethane acrylate, aromatic urethane acrylate, epoxy acrylate and polyester acrylate.
3. The light-cured resin for high-precision matte 3D printing according to claim 1, wherein the light-cured resin comprises: the monomer diluent is at least one selected from tripropylene glycol diacrylate, dipropylene glycol diacrylate, tricyclodecane dimethanol diacrylate, 4-acryloyl morpholine, cyclotrimethylolpropane formal acrylate, isobornyl acrylate, trimethylolpropane triacrylate or dipentaerythritol hexaacrylate.
4. The light-curable resin for high-precision matte 3D printing according to claim 1, wherein: the photoinitiator is selected from at least one of 1-hydroxy-cyclohexyl-benzophenone, phenyl bis (2,4,6-trimethylbenzoyl) phosphorus oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphorus oxide or bis 2,6-difluoro-3-pyrrol-lphenyl titanocene.
5. The light-curable resin for high-precision matte 3D printing according to claim 1, wherein: the reaction auxiliary agent is at least one selected from acrylate copolymer, polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organic siloxane, modified acrylate polymer, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether and polydimethylsiloxane.
6. The light-cured resin for high-precision matte 3D printing according to claim 1, wherein the light-cured resin comprises: the filler is selected from at least one of silica, zirconia or alumina.
7. The light-curable resin for high-precision matte 3D printing according to claim 1, wherein: the color paste is one of fast red, yellow iron oxide, titanium white and carbon black.
8. The light-cured resin for high-precision matte 3D printing according to claim 1, wherein the light-cured resin comprises: the wavelength of ultraviolet light used for curing the light-cured resin is 405nm.
9. The method for preparing the photocuring resin for high-precision matte 3D printing according to any one of claims 1 to 8, wherein the method comprises the following steps: the oligomer resin, the monomer diluent, the photoinitiator, the reaction auxiliary agent, the filler and the color paste with the formula amount are mixed and stirred evenly at the temperature of 40-60 ℃ to form a uniform and stable system, thus obtaining the photocuring resin.
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| CN114375248A (en) * | 2019-03-29 | 2022-04-19 | 阿科玛法国公司 | Acrylic compositions for 3D printing |
| CN114573763A (en) * | 2022-03-22 | 2022-06-03 | 广州黑格智造信息科技有限公司 | 3D printing photocuring material for dental model and preparation method thereof |
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| CN114375248A (en) * | 2019-03-29 | 2022-04-19 | 阿科玛法国公司 | Acrylic compositions for 3D printing |
| CN111500042A (en) * | 2020-03-25 | 2020-08-07 | 上海金发科技发展有限公司 | Matte PC/ABS alloy material and preparation method thereof |
| CN112812241A (en) * | 2021-01-22 | 2021-05-18 | 中科三维成型技术（深圳）有限公司 | Controlled-activity photocuring 3D printing resin and preparation method and application thereof |
| CN114573763A (en) * | 2022-03-22 | 2022-06-03 | 广州黑格智造信息科技有限公司 | 3D printing photocuring material for dental model and preparation method thereof |
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