CN114181351A - Photocuring three-dimensional printing resin and preparation method thereof - Google Patents
Photocuring three-dimensional printing resin and preparation method thereof Download PDFInfo
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- QKQSRIKBWKJGHW-UHFFFAOYSA-N morpholine;prop-2-enoic acid Chemical compound OC(=O)C=C.C1COCCN1 QKQSRIKBWKJGHW-UHFFFAOYSA-N 0.000 claims description 4
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
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- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 3
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- BUFSQBVYLWPJRX-UHFFFAOYSA-N ethyl 2-phenylsulfanylprop-2-enoate Chemical compound CCOC(=O)C(=C)SC1=CC=CC=C1 BUFSQBVYLWPJRX-UHFFFAOYSA-N 0.000 description 3
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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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- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a photocuring three-dimensional printing resin and a preparation method thereof, wherein the photocuring three-dimensional printing resin comprises, by mass, 30-60 parts of acrylic resin, 15-65 parts of reactive diluent, 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator. According to the invention, the refractive index is improved by adding the nano zirconium dioxide, and the obtained photocuring three-dimensional printing resin has a high refractive index, so that a product printed by using the photocuring three-dimensional printing resin provided by the invention meets the requirements of optical devices.
Description
Technical Field
The invention belongs to the technical field of three-dimensional printing materials, and particularly relates to a photocuring three-dimensional printing resin and a preparation method thereof.
Background
With the progress of modern technologies, 3D printing technology has gradually occupied a certain position in current production technologies, and 3D printing technology can rapidly manufacture three-dimensional parts and perform design verification or be used as a tool for functional prototype and production, is an indispensable tool for shortening product design and development cycles, has subversive capability of free manufacturing and rapid manufacturing, is not limited by product shapes and structures in the production and manufacturing process of 3D printing technology, and can manufacture complex three-dimensional structures of arbitrary shapes and structures, and therefore, 3D printing technology is rapidly becoming a standard tool for product design and manufacturing, and has pushed the development of various industries due to its advantages.
Among all 3D printing technologies, the photocuring technology 3D printing technology is the printing method with the highest precision, the best detailed embodiment and the best surface precision, and the photocuring 3D printing is divided into three printing and forming technologies of Stereolithography (SLA), Digital Light Projection (DLP) and selective area photocuring (LCD), and due to the obvious advantages of the three technologies, the three technologies have been increasingly and widely applied at present. In order to meet different requirements, the requirements for the corresponding photosensitive resins are also increasing. At present, the photocuring 3D printing technology is widely applied to the fields of jewelry, shoes, industrial design, buildings, automobiles, aerospace, dentistry and medical industries, electronics and the like. Most researches on the aspects of improving the mechanical property, the wear resistance, the heat resistance and the like of the corresponding consumable 3D printing photosensitive resin are focused to widen the application range of the photosensitive resin. The photocuring 3D printing technology (including SLA, DLP and LCD) with high precision can be applied to preparation of optical devices with complex structures due to good surface quality and high precision, and photosensitive resin applied in the optical field does not attract attention of extensive researchers and enterprises all the time, so that the 3D printing photosensitive resin can be applied to few and few materials for manufacturing the optical devices, and the main reason is that the requirements on the materials are higher compared with the optical devices in other fields, and the refractive index requirements on the materials are particularly high except for the requirement on the good mechanical properties of the materials of general optical materials.
The 3D printing photosensitive resin supplied by the current market mostly pays attention to the mechanical property of the resin, the optical property of the resin is rarely paid attention to, and the refractive index of the current 3D printing transparent resin is lower, so that the processing requirement of an optical device cannot be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a photocuring three-dimensional printing resin and a preparation method thereof, which are used for solving the problems that the existing photocuring three-dimensional printing resin on the market has low refractive index and cannot enable a printed product to meet the requirements of optical devices.
The invention provides a photocuring three-dimensional printing resin which is applied to a 3D printer and comprises, by mass, 30-60 parts of acrylic resin, 15-65 parts of reactive diluent, 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator.
Further, the acrylic resin is high-refractive-index acrylic resin, and the refractive index of the high-refractive-index acrylic resin is not less than 1.60; wherein the high refractive index acrylic resin is at least one of HN-KG6500, HN-KG6700, HN-6024, Miramer SB, EM-2206-2 and EM-2209.
Further, the method also comprises the following steps of:
0.2-2 parts of dispersing agent, 0.3-1.5 parts of flatting agent, 0.2-1.2 parts of defoaming agent, 0.2-1.5 parts of photosensitizer and 0.1-1.2 parts of ultraviolet absorbent.
Further, the reactive diluent is at least one of morpholine acrylate, 2-thiophenyl ethyl acrylate, ethoxylated (2) bisphenol S diacrylate, o-phenylphenoxyethyl acrylate, ethoxylated bisphenol fluorene diacrylate and bisphenol A dipropionate.
Further, the particle size of the nano zirconium dioxide is 10 nm-50 nm; and/or
The photoinitiator is a free radical type photoinitiator which can absorb under 250-440nm ultraviolet light, and the free radical type photoinitiator is at least one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl phosphonic acid ethyl ester, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, bis 2, 6-difluoro-3-pyrrolyl phenyl ferrocene, 2-isopropyl thioxanthone, 4-phenyl benzophenone and 2-phenyl benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
Further, the dispersant is at least one of BYK-2013, BYK-2012, Lencolo 1113, Lencolo 1110 and CM-3109.
Further, the leveling agent is at least one of BYK-3565, KYC-617, TEGO Rad 2600 and TEGO Rad 2700.
Further, the defoaming agent is at least one of BYK-1790, KSZ-108, KYC-733 and TEGOAirex 920; and/or
The ultraviolet absorbent is at least one of UV-327 and UV-P, UV-400; and/or the photosensitizer is at least one of UVS-1331, UVS-1101, UVS-581 and UVS-2171.
The second aspect of the present invention provides a method for preparing the photocurable three-dimensional printing resin, comprising:
mixing 15-65 parts of reactive diluent and 30-60 parts of acrylic resin, and heating the prepared mixture to 60-70 ℃ in a stirring state;
sequentially adding 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator into the mixture at the temperature of 60-70 ℃ for mixing, stirring at high speed in a stirrer, and obtaining the photocuring three-dimensional printing resin after uniform dispersion.
Further, the preparation method comprises the following steps of adding a dispersing agent, a photosensitizer, an ultraviolet absorbent, a leveling agent and a defoaming agent, wherein the preparation method comprises the following steps:
stirring 15-65 parts of reactive diluent at the rotating speed of 1200-1700 r/min for 50-80 min;
adding acrylic resin into the reactive diluent, stirring at the rotating speed of 1200-1700 r/min for 80-100 min, and heating to 60-70 ℃ to obtain a first mixture;
adding 0.2-2 parts of a dispersing agent into the first mixture, and stirring for 20-40 min at the temperature of 60-70 ℃ to obtain a second mixture;
heating the second mixture to 65-80 ℃, adding 2-10 parts of nano zirconium dioxide, increasing the rotating speed to 2200-2700 r/min, and continuing stirring for 100-140 min until the nano zirconium dioxide is completely dispersed to obtain a third mixture;
and (3) reducing the temperature of the third mixture to 50-70 ℃, adding 1-8 parts of photoinitiator, 0.2-1.5 parts of photosensitizer, 0.1-1.2 parts of ultraviolet absorbent, 0.3-1.5 parts of flatting agent and 0.2-1.2 parts of defoaming agent, and continuously stirring for 1.5-2.5 hours to obtain the target resin.
According to the photocuring three-dimensional printing resin and the preparation method thereof, the refractive index is improved by adding the nano zirconium dioxide, and the obtained photocuring three-dimensional printing resin has high refractive index and light transmittance, so that a product printed by using the photocuring three-dimensional printing resin provided by the invention meets the requirements of optical devices.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a molecular structural diagram of five high refractive index reactive diluents according to an exemplary embodiment of the present invention;
fig. 2 is a graph illustrating a change in light transmittance with time of a photocurable three-dimensional printing resin according to an exemplary embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Since only DSM Somos 1112 (for SLA of 355 nm) and Formlabs clear are common in the market at present, the refractive index, Abbe number, light transmittance, water absorption and mechanical properties of the transparent resin after processing and molding are different from those of the traditional thermoplastic and thermosetting optical resin materials. The refractive index is generally about 1.5, and the refractive index and the light transmittance are important parameters of the optical resin material, so that the high-refractive-index optical material is required to be found in order to make the optical device ultrathin, light, low in curvature and the like. The refractive index of the existing 3D printing transparent resin is low, the processing requirement of an optical device cannot be met, and the light transmittance of most of the transparent resin does not meet the requirement of manufacturing the optical device.
In view of the above, the photocuring three-dimensional printing resin provided by the invention is applied to a 3D printer and comprises, by mass, 30-60 parts of acrylic resin, 15-65 parts of reactive diluent, 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator.
According to the photocuring three-dimensional printing resin provided by the embodiment of the invention, the refractive index is improved by adding the nano zirconium dioxide, and the obtained photocuring three-dimensional printing resin has high refractive index and light transmittance, so that a product printed by using the photocuring three-dimensional printing resin provided by the invention meets the requirements of optical devices. And because the nano zirconium dioxide not only has high refractive index (refractive index is 2.17-2.21), the refractive index of a resin system can be improved, but also the mechanical properties of the resin in the aspects of wear resistance, hardness and the like can be improved by adding the nano zirconium dioxide, so that the photocuring three-dimensional printing resin provided by the invention has high refractive index and light transmittance, and is excellent in ageing resistance and mechanical properties, and further an ultrathin, light and low-curvature optical device can be prepared by using the photocuring three-dimensional printing resin in a 3D printing mode, the limitation of traditional processing can be broken through by preparing the optical device in a 3D printing mode, a designer can design and manufacture a device with a more complex shape structure, so that the requirements of the optical device in the aspects of ultrathin property, light weight and the like are met, and the efficiency of the designed and manufactured optical device is higher.
Since the acrylic resin determines the basic performance of the resin, in order to improve the refractive index and the light transmittance of the resin, in the embodiment of the invention, the acrylic resin is high-refractive-index acrylic resin, and the refractive index of the high-refractive-index acrylic resin is not less than 1.60; experiments prove that the refractive index is more than 1.60, the resin can be called high-refractive-index resin, and the resin can be directly used for printing optical devices with higher requirements on the refractive index by using a 3D printer, such as spectacle lenses; wherein, the selected acrylic resin structures all contain structural groups with larger polarizability and smaller molecular volume, namely, the high-refractive-index acrylic resin is at least one of HN-KG6500, HN-KG6700, HN-6024, Miramer SB, EM-2206-2 and EM-2209. In the embodiment of the present invention, the refractive index of the high refractive index acrylic resin includes but is not limited to 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70; the acrylic resin comprises HN-KG6700 and EM-2209, or comprises HN-6024 and EM-2209, or comprises HN-KG6500 and EM-2206-2, or comprises Miramer SB and HN-KG 6700. The amount of the high-refractive-index acrylic resin includes 30 to 60 parts by mass, for example, but not limited to 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts or 60 parts. It should be noted that: HN-KG6500 has a refractive index of 1.65 to 1.67, HN-KG6700 has a refractive index of 1.67 to 1.68, HN-6024 has a refractive index of 1.60 to 1.61, Miramer SB has a refractive index of 1.577, EM-2206-2 has a refractive index of 1.60, and EM-2209 has a refractive index of 1.61 to 1.62.
In the embodiment of the invention, the method further comprises the following steps of: 0.2-2 parts of dispersing agent, 0.3-1.5 parts of flatting agent, 0.2-1.2 parts of defoaming agent, 0.2-1.5 parts of photosensitizer and 0.1-1.2 parts of ultraviolet absorbent. Wherein, the dispersing agent can uniformly disperse the nano zirconium dioxide in the acrylic resin.
In the embodiment of the invention, the reactive diluent is at least one of acrylic morpholine, 2-thiophenyl ethyl acrylate, ethoxylated (2) bisphenol S diacrylate, o-phenylphenoxyethyl acrylate, ethoxylated bisphenol fluorene diacrylate and bisphenol A dipropionate. The amount of the reactive diluent is 15-65 parts by mass, and may be, but is not limited to, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts or 65 parts.
Since light itself is an electromagnetic wave, according to classical electromagnetic theory, the refractive index n is inversely proportional to the molecular volume, proportional to the molar refraction index, which is proportional to the dielectric polarizability, wherein the refractive index calculation formula is
RLL is the molar refractive index, V is the molar volume, and n is the refractive index; therefore, the refractive index of the resin is adjusted from the molecular structure, and it is necessary to have a large polarizability and a small molecular volume for the constituent groups of the molecule. According to a refractive index calculation formula as a guide, introducing molecular groups with higher polarizability and smaller molecular volume into the photocuring oligomer and the monomer, researching the influence of different groups on the refractive index, and simultaneously researching the influence of the introduction of different molecular groups on the heat resistance and mechanical properties of the resin so as to evaluate and design an optimal scheme and prepare the resin material with high refractive index, high light transmittance and high performance. The chemical structure and corresponding refractive index of the selected part of the reactive diluent are shown in figure 1.
Since the reactive diluent in the resin is mainly used to reduce the viscosity of the resin, and meanwhile, the reactive diluents with different structures can be based on different mechanical, thermal and optical properties of the resin, it is preferable to use the high refractive index reactive diluents in the embodiment of the present invention, such as the five high refractive index reactive diluents shown in fig. 1, that is: the refractive index R of 2-phenylthioethyl acrylate is 1.557, the refractive index R of ethoxylated (2) bisphenol S diacrylate is 1.564, the refractive index R of o-phenylphenoxyethyl acrylate is 1.577, the refractive index R of ethoxylated bisphenol fluorene diacrylate is 1.550, and the refractive index R of bisphenol a dipropionic acid is 1.610, and in order to further adjust the mechanical properties and viscosity of the resin, reactive diluents such as morpholine Acrylate (ACMO), morpholine acrylate, 2-phenylthioethyl acrylate, ethoxylated (2) bisphenol S diacrylate, o-phenylphenoxyethyl acrylate, ethoxylated bisphenol fluorene diacrylate, and bisphenol a dipropionic acid may be added. In embodiments of the invention, the reactive diluent comprises acrylic morpholine, 2-thiophenyl ethyl acrylate and o-phenylphenoxyethyl acrylate; or acrylic morpholine and o-phenylphenoxyethyl acrylate; or 2-thiophenylethyl acrylate, ethoxylated (2) bisphenol S diacrylate and o-phenylphenoxyethyl acrylate; or comprises acrylic morpholine, ethoxylated bisphenol fluorene diacrylate and bisphenol A dipropionic acid, or comprises 2-phenylthioethyl acrylate and bisphenol A dipropionic acid.
In the embodiment of the invention, the particle size of the nano zirconium dioxide is 10 nm-50 nm. In addition, the amount of the nano zirconium dioxide includes 2 to 10 parts by mass, and may be, but is not limited to, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.
The nanometer zirconium dioxide with the particle size of 10 nm-50 nm is added in the acrylic resin, so that the resin has excellent light transmittance while the refractive index of the resin is improved, the particle size of the added nanometer zirconium dioxide is selected to be 10 nm-50 nm, the nanometer zirconium dioxide can be uniformly dispersed in the high-refractive-index acrylic resin, the refractive index and the light transmittance of the resin can be effectively improved, and the mechanical properties of the resin in the aspects of wear resistance, hardness and the like can be improved.
In an embodiment of the present invention, the photoinitiator is a radical photoinitiator that absorbs ultraviolet light of 250-440nm, and the radical photoinitiator is at least one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphosphonate, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, bis 2, 6-difluoro-3-pyrrolylphenyl ferrocene, 2-isopropyl thioxanthone, 4-phenylbenzophenone, and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl-phenyl) butanone. The photoinitiator is a key material for initiating the resin to be cured, the photoinitiator is decomposed to generate free radicals under the irradiation of light to initiate the polymerization and curing of the acrylic resin, and the amount of the photoinitiator is 1-8 parts by mass, and can be, for example but not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts. In embodiments of the invention, the photoinitiator comprises phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide; or include phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 4-phenylbenzophenone.
In order to uniformly disperse the nano zirconium dioxide in the resin and prevent agglomeration, precipitation and the like after long-term storage, in the embodiment of the invention, the dispersing agent is at least one of BYK-2013, BYK-2012, Lencolo 1113, Lencolo 1110 and CM-3109. The amount of the dispersant includes 0.2 to 2 parts by mass, and may be, for example, but not limited to, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part, 1.4 part, 1.6 part, 1.8 part, or 1 part.
In order to reduce the surface tension of a resin system and increase the interface fluidity of the resin, in the embodiment of the invention, the leveling agent is at least one of BYK-3565, KYC-617, TEGO Rad 2600 and TEGO Rad 2700. The amount of the leveling agent is 0.3-1.5 parts by mass, and may be, but is not limited to, 0.3 part, 0.6 part, 0.9 part, 1.2 parts or 1.5 parts.
In order to eliminate air bubbles in the resin system and suppress the generation of air bubbles to prevent the generation of air bubbles in the model during printing, in the embodiment of the present invention, the defoaming agent is at least one of BYK-1790, KSZ-108, KYC-733 and TEGOAirex 920. The amount of the defoaming agent includes 0.2 to 1.2 parts by mass, and may be, for example, but not limited to, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part or 1.2 parts.
In an embodiment of the invention, the photosensitizer is at least one of UVS-1331, UVS-1101, UVS-581 and UVS-2171. The photosensitizer is a substance capable of absorbing light energy and transferring energy to the initiator to promote the reaction efficiency of the photoinitiator, and the amount of the photosensitizer includes 0.2 to 1.5 parts by mass, for example, but not limited to, 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part, 1.2 part or 1.5 parts.
In the embodiment of the invention, the ultraviolet absorbent is at least one of UV-327 and UV-P, UV-400. The ultraviolet absorbent is a substance capable of absorbing ultraviolet light, the ultraviolet absorbent is added into the resin system mainly for improving the printing precision of the resin, and the amount of the ultraviolet absorbent is 0.1-1.2 parts by mass, such as but not limited to 0.2 part, 0.4 part, 0.6 part, 0.8 part, 1 part or 1.2 parts.
The invention provides a preparation method of a photocuring three-dimensional printing resin, which comprises the following steps:
1. mixing 15-65 parts of reactive diluent and 30-60 parts of acrylic resin, and heating the prepared mixture to 60-70 ℃ in a stirring state;
2. sequentially adding 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator into the mixture at the temperature of 60-70 ℃ for mixing, stirring at high speed in a stirrer, and obtaining the photocuring three-dimensional printing resin after uniform dispersion.
The preparation method of the photocuring three-dimensional printing resin provided by the embodiment of the invention further comprises the step of adding a dispersing agent, a photosensitizer, an ultraviolet absorbent, a leveling agent and a defoaming agent, and the preparation method comprises the following steps:
1. stirring 15-65 parts of reactive diluent at the rotating speed of 1200-1700 r/min for 50-80 min;
2. adding acrylic resin into the reactive diluent, stirring at the rotating speed of 1200-1700 r/min for 80-100 min, and heating to 60-70 ℃ to obtain a first mixture;
3. adding 0.2-2 parts of a dispersing agent into the first mixture, and stirring for 20-40 min at the temperature of 60-70 ℃ to obtain a second mixture;
4. heating the second mixture to 65-80 ℃, adding 2-10 parts of nano zirconium dioxide, increasing the rotating speed to 2200-2700 r/min, and continuing stirring for 100-140 min until the nano zirconium dioxide is completely dispersed to obtain a third mixture;
5. reducing the temperature of the third mixture to 50-70 ℃, adding 1-8 parts of photoinitiator, 0.2-1.5 parts of photosensitizer, 0.1-1.2 parts of ultraviolet absorbent, 0.3-1.5 parts of flatting agent and 0.2-1.2 parts of defoaming agent, and continuously stirring for 1.5-2.5 h to obtain target resin;
and filtering the target resin to obtain the photocuring three-dimensional printing resin.
The photocuring three-dimensional printing resin prepared by the preparation method of the photocuring three-dimensional printing resin provided by the invention has the following advantages:
1. by adding nano zirconium dioxide, high-refractive-index acrylic resin and high-refractive-index reactive diluent, the obtained photocuring three-dimensional printing photosensitive resin has high refractive index and light transmittance, when the refractive index of the resin is high, the light transmittance of the resin is also high due to the high refractive index, the refractive index of most of the prior three-dimensional printing resin is about 1.5, and the refractive index of the photocuring three-dimensional printing photosensitive resin prepared by the invention is more than 1.60;
2. the light-cured three-dimensional printing resin prepared by the invention has high light transmittance and weather resistance through the matching of the nano zirconium dioxide, the high-refractive-index acrylic resin and the high-refractive-index active diluent, the light transmittance of the prepared resin printing optical device can reach more than 98 percent (1mm thick sample), and meanwhile, the resin has weather resistance, is not yellowed after being placed for a long time and is not reduced in light transmittance, as shown in figure 2.
3. By adding the nano zirconium dioxide, the photocuring three-dimensional printing resin prepared by the invention also has good mechanical properties, heat resistance and other properties, and the specific properties are shown in table 1.
4. By adding the ultraviolet absorbent into the resin, the printing precision of the resin prepared by the invention can be adjusted in a wide range, the printing precision of 2-100 micrometers in the Z direction can be met, the printing precision of pixels with the maximum of 1 micrometer can be realized in the XY direction, and the resin can be suitable for printing on SLA, DLP and LCD equipment with various precisions in the current market.
TABLE 1 optical and mechanical Properties of photo-cured three-dimensional printing resins
| Performance parameter | Performance data | Unit of | Test standard |
| Viscosity of the oil | 200-500 | cps@25℃ | GB/T 5561-1994 |
| Tensile strength | 60-70 | MPa | ASTM D638 |
| Modulus of elasticity | 3.0-3.6 | GPa | ASTM D638 |
| Elongation at break | 6.0-10 | ％ | ASTM D638 |
| Bending strength | 70-90 | MPa | ASTM D790 |
| Flexural modulus | 2.5-3.0 | GPa | ASTM D790 |
| Impact strength | 35-40 | J/m | ASTM D 256-10 |
| Heat distortion temperature | 60-80 | ℃ | ASTM D648@0.45MPa |
| Hardness of | 80-85 | Shore D | ASTM D2240 |
| Dp | 30-100 | μm | —— |
| Light transmittance | ≥98 | —— | —— |
| Refractive index | 1.62-1.68 | —— | —— |
The technical solutions and advantages of the present invention are described below with reference to the embodiments of the present invention.
Experimental group 1
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. adding 200g of low-viscosity reactive diluent acryloyl morpholine, 300g of 2-thiophenyl ethyl acrylate and 400g of o-phenylphenoxyethyl acrylate into a 3000ml three-neck flask, and then stirring at the rotating speed of 1200r/min for 50min to uniformly mix.
2. Adding high refractive index functional resin HN-KG 6700250 g and EM-2209630 g into the flask, heating to 65 ℃, and continuing to stir for 80min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuing to stir for 20min, continuing to heat to 65 ℃, then adding 100g of nano zirconium dioxide with the particle size of 20nm, increasing the rotating speed to 2200r/min, and continuing to stir for 100min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 50 ℃, adding 60g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 60g of photosensitizer UVS-58120 g, 8g of ultraviolet absorbent UV-P, 260012 g of flatting agent TEGO Rad, and 3 g of defoaming agent BYK-179010 g, and continuously stirring for 2 hours.
5. And (4) filtering the stirred resin in the step (4) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. adding 200g of low-viscosity reactive diluent acryloyl morpholine, 300g of 2-thiophenyl ethyl acrylate and 400g of o-phenylphenoxyethyl acrylate into a 3000ml three-neck flask, and then stirring at the rotating speed of 1700r/min for 80min to uniformly mix.
2. Adding HN-6024480 g and EM-2209500 g of high-refractive-index functional resin into the flask, heating to 65 ℃, and continuing to stir for 100min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuing to stir for 40min, continuing to heat to 80 ℃, adding 80g of nano zirconium dioxide with the particle size of 30nm, increasing the rotating speed to 2700r/min, and continuing to stir for 140min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 70 ℃, adding 50g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 30g of 4-phenylbenzophenone, 30g of photosensitizer UVS-58120 g, UV-32710 g of ultraviolet absorber, BYK-356512 g of flatting agent and BYK-17908 g of defoaming agent, and continuing stirring for 2 hours.
5. And (4) filtering the stirred resin in the step (4) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
Experimental group 3
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. adding 300g of low-viscosity reactive diluent acryloyl morpholine, 150g of 2-thiophenyl ethyl acrylate and 350g of o-phenylphenoxyethyl acrylate into a 3000ml three-neck flask, and then stirring at the rotating speed of 1500r/min for 60min to uniformly mix.
2. Adding high refractive index functional resin HN-KG 6500550 g and EM-2206-2430 g into the flask, heating to 65 ℃, and continuing to stir for 90min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuously stirring for 30min, continuously heating to 75 ℃, adding 100g of nano zirconium dioxide with the particle size of 20nm, increasing the rotating speed to 2500r/min, and continuously stirring for 120min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 60 ℃, adding 60g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 60g of photosensitizer UVS-58120 g, 8g of ultraviolet absorbent UV-P, 8g of flatting agent BYK-356512 g and 179010 g of defoaming agent, and continuously stirring for 2 hours.
5. And (4) filtering the stirred resin in the step (4) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. 300g of low-viscosity reactive diluent ethoxylated bisphenol fluorene diacrylate, 400g of ethoxylated (2) bisphenol S diacrylate and 300g of o-phenylphenoxyethyl acrylate are added into a 3000ml three-neck flask and then stirred at the rotating speed of 1500r/min for 60min to be uniformly mixed.
2. Adding high refractive index functional resin Miramer SB 350g and HN-KG 6700410 g into the flask, heating to 65 ℃, and continuing to stir for 90min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuously stirring for 20min, continuously heating to 75 ℃, adding 120g of nano zirconium dioxide with the particle size of 20nm, increasing the rotating speed to 2500r/min, and continuously stirring for 120min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 60 ℃, adding 50g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 50g of photosensitizer UVS-110130 g, 8g of ultraviolet absorbent UV-P, 8g of flatting agent BYK-356512 g and 10g of defoaming agent KSZ-10810 g, and continuously stirring for 2 hours.
5. And (4) filtering the stirred resin in the step (4) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
Experimental group 5
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. adding 400g of low-viscosity reactive diluent acryloyl morpholine, 200g of ethoxylated bisphenol fluorene diacrylate and 350g of bisphenol A dipropionate into a 3000ml three-neck flask, and then stirring at the rotating speed of 1500r/min for 60min to mix uniformly.
2. Adding high refractive index functional resin HN-KG 6700250 g and EM-2209530 g into the flask, heating to 65 ℃, and continuing to stir for 90min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuously stirring for 20min, continuously heating to 75 ℃, adding 150g of nano zirconium dioxide with the particle size of 30nm, increasing the rotating speed to 2500r/min, and continuously stirring for 120min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 60 ℃, adding 60g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 60g of photosensitizer UVS-58120 g, 8g of ultraviolet absorbent UV-P, 270012 g of flatting agent TEGO Rad, and 3526 g of defoaming agent BYK-179010 g, and continuously stirring for 2 hours.
5. And filtering the stirred resin in the step 4 by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
A preparation method of a photocuring three-dimensional printing resin comprises the following steps:
1. 100g of low-viscosity reactive diluent acryloyl morpholine, 300g of 2-thiophenyl ethyl acrylate and 200g of bisphenol A dipropionate are added into a 3000ml three-neck flask, and then the mixture is stirred at the rotating speed of 1500r/min for 60min and uniformly mixed.
2. Adding high refractive index functional resin HN-KG 6700470 g and EM-2209630 g into the flask, heating to 65 ℃, and continuing to stir for 90min at the rotating speed.
3. And (3) adding 10g of dispersant BYK-2012 into the flask obtained in the step (2), then continuously stirring for 20min, continuously heating to 75 ℃, adding 100g of nano zirconium dioxide with the particle size of 20nm, and increasing the rotating speed to 2500r/min to continuously stir for 120min until the nano zirconium dioxide is completely dispersed.
4. And (3) reducing the temperature of the flask in the step (3) to 60 ℃, adding 100g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 100g of photosensitizer UVS-110120 g, UV-4008 g of ultraviolet absorbent, BYK-356512 g of flatting agent and BYK-179010 g of defoaming agent, and continuing stirring for 2 hours.
5. And (4) filtering the stirred resin in the step (4) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
Comparative example 1
2. The preparation method of the photo-curing three-dimensional printing resin provided by the comparative example comprises the following steps:
1. 100g of low-viscosity reactive diluent acryloyl morpholine, 300g of 2-thiophenyl ethyl acrylate and 200g of bisphenol A dipropionate are added into a 3000ml three-neck flask, and then the mixture is stirred at the rotating speed of 1500r/min for 60min and uniformly mixed.
2. 470g of polyester acrylate and 630g of polyurethane acrylate are added into the flask, then the temperature is raised to 65 ℃, and the stirring is continued for 90min under the rotating speed.
3. And (3) reducing the temperature of the flask in the step (2) to 60 ℃, adding 100g of initiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide, 100g of photosensitizer UVS-110120 g, UV-4008 g of ultraviolet absorbent, BYK-356512 g of flatting agent and BYK-179010 g of defoaming agent, and continuing stirring for 2 hours.
4. And (4) filtering the stirred resin in the step (3) by using a 500-mesh filter screen to obtain the photocuring three-dimensional printing resin.
The refractive index of the photo-curing three-dimensional printing photosensitive resin prepared by the comparative example 1 is about 1.5, the light transmittance and the weather resistance of the photo-curing three-dimensional printing resin prepared by the comparative example are low, and the light transmittance of the prepared resin printing optical device can not meet the requirement of manufacturing the optical device.
And placing the photocuring three-dimensional printing resin obtained by the experimental groups 1 to 6 and the photocuring three-dimensional printing resin obtained by the comparative example 1 into a material box of a 3D printer, printing, taking down the model after printing, and testing the refractive index and the light transmittance of the model, wherein the test results are shown in a table 2.
TABLE 2
Therefore, the light-cured three-dimensional printing resin prepared by the experimental groups 1 to 6 has the following advantages:
1. the prepared light-cured three-dimensional printing photosensitive resin has high refractive index which is more than 1.60;
2. meanwhile, the prepared light-cured three-dimensional printing resin has high light transmittance and weather resistance, the light transmittance of the prepared resin printing optical device can reach more than 98 percent (1mm thick sample), and meanwhile, the resin has weather resistance, is not yellowed after being placed for a long time and has no reduction of light transmittance.
3. Besides the optical properties, the prepared photocuring three-dimensional printing resin also has good mechanical properties, heat resistance and other properties.
4. The adjustable range of the precision of resin printing is wide, the requirement of 2-100 micron precision printing in the Z direction can be met, the highest 1 micron pixel precision printing in the XY direction can be realized, and the resin can be suitable for printing on SLA, DLP and LCD equipment with various precisions in the current market.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The photocuring three-dimensional printing resin is applied to a 3D printer and is characterized by comprising 30-60 parts of acrylic resin, 15-65 parts of reactive diluent, 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator by mass.
2. The photocurable three-dimensional printing resin according to claim 1, wherein the acrylic resin is a high refractive index acrylic resin having a refractive index of not less than 1.60; wherein the high refractive index acrylic resin is at least one of HN-KG6500, HN-KG6700, HN-6024, Miramer SB, EM-2206-2 and EM-2209.
3. The photocurable three-dimensional printing resin according to claim 2, further comprising, in parts by mass:
0.2-2 parts of dispersing agent, 0.3-1.5 parts of flatting agent, 0.2-1.2 parts of defoaming agent, 0.2-1.5 parts of photosensitizer and 0.1-1.2 parts of ultraviolet absorbent.
4. The photocurable three-dimensional printing resin according to any of claims 1-3, wherein the reactive diluent is at least one of morpholine acrylate, 2-thiophenylethyl acrylate, ethoxylated (2) bisphenol S diacrylate, o-phenylphenoxyethyl acrylate, ethoxylated bisphenol fluorene diacrylate, bisphenol A dipropionate.
5. The photocurable three-dimensional printing resin according to any one of claims 1 to 3, wherein the nano zirconium dioxide has a particle size of 10nm to 50 nm; and/or
The photoinitiator is a free radical type photoinitiator which can absorb under 250-440nm ultraviolet light, and the free radical type photoinitiator is at least one of phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 2,4, 6-trimethylbenzoyl phosphonic acid ethyl ester, diphenyl (2,4, 6-trimethylbenzoyl) phosphine oxide, bis 2, 6-difluoro-3-pyrrolyl phenyl ferrocene, 2-isopropyl thioxanthone, 4-phenyl benzophenone and 2-phenyl benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone.
6. The photocurable three-dimensional printing resin according to claim 3, wherein the dispersant is at least one of BYK-2013, BYK-2012, Lencolo 1113, Lencolo 1110 and CM-3109.
7. The photocurable three-dimensional printing resin of claim 3, wherein the leveling agent is at least one of BYK-3565, KYC-617, TEGO Rad 2600, TEGO Rad 2700.
8. The photocurable three-dimensional printing resin according to claim 3, wherein the defoamer is at least one of BYK-1790, KSZ-108, KYC-733, TEGOAirex 920; and/or
The ultraviolet absorbent is at least one of UV-327 and UV-P, UV-400; and/or
The photosensitizer is at least one of UVS-1331, UVS-1101, UVS-581 and UVS-2171.
9. The method for preparing the photocurable three-dimensional printing resin according to any one of claims 1 to 8, comprising:
mixing 15-65 parts of reactive diluent and 30-60 parts of acrylic resin, and heating the prepared mixture to a preset temperature in a stirring state;
sequentially adding 2-10 parts of nano zirconium dioxide and 1-8 parts of photoinitiator into the mixture at a preset temperature, mixing, stirring at a high speed in a stirrer, and obtaining the photocuring three-dimensional printing resin after uniform dispersion.
10. The method for preparing the photocurable three-dimensional printing resin according to claim 9, further comprising adding a dispersant, a photosensitizer, an ultraviolet absorber, a leveling agent, and a defoaming agent, the method comprising: the preset temperature is 60-70 ℃;
stirring 15-65 parts of reactive diluent at the rotating speed of 1200-1700 r/min for 50-80 min;
adding acrylic resin into the reactive diluent, stirring at the rotating speed of 1200-1700 r/min for 80-100 min, and heating to 60-70 ℃ to obtain a first mixture;
adding 0.2-2 parts of a dispersing agent into the first mixture, and stirring for 20-40 min at the temperature of 60-70 ℃ to obtain a second mixture;
heating the second mixture to 65-80 ℃, adding 2-10 parts of nano zirconium dioxide, increasing the rotating speed to 2200-2700 r/min, and continuing stirring for 100-140 min until the nano zirconium dioxide is completely dispersed to obtain a third mixture;
and (3) reducing the temperature of the third mixture to 50-70 ℃, adding 1-8 parts of photoinitiator, 0.2-1.5 parts of photosensitizer, 0.1-1.2 parts of ultraviolet absorbent, 0.3-1.5 parts of flatting agent and 0.2-1.2 parts of defoaming agent, and continuously stirring for 1.5-2.5 hours to obtain the target resin.
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| WO2024127031A1 (en) * | 2022-12-16 | 2024-06-20 | Ucl Business Ltd | Photodynamic antimicrobial compositions and objects, and methods of making them |
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