3D printing resin material for upper projection and application thereof

Abstract

The invention discloses a 3D printing resin material for upper projection and application thereof, and the 3D printing resin material for upper projection comprises the following raw material components by weight: 5-40 parts of a urethane acrylate cross-linking agent; 5 to 40 parts of a polyurethane acrylate oligomer; 25 to 40 parts of a monofunctional reactive diluent; 15-40 parts of a polyfunctional group reactive diluent; 1-5 parts of a photoinitiator; 0.1-3 parts of a leveling agent; 0.1 to 3 parts of a defoaming agent; 1-15 parts of a surface auxiliary agent; 0.5 to 3 parts of filler; 0.5 to 3 parts of scratch-resistant wax; 0.2 to 0.5 part of pigment; wherein the mass ratio of the polyurethane acrylate cross-linking agent to the polyurethane acrylate oligomer is (0.01 to 1): 1; the mass ratio of the monofunctional reactive diluent to the polyfunctional reactive diluent is (0.5-2): 1. The resin material is low in viscosity after being improved, is suitable for an upper projection 3D printing technology, is used for printing and manufacturing an implant tooth model, has high off-machine precision and high reverse scanning size stability, and is applied to the field of oral medicine.

Description

Technical Field

[0001] This invention belongs to the field of 3D printing materials, specifically relating to a 3D printing resin material for upward projection and its application. Background Technology

[0002] Dental implants have always been an important treatment method in dental restoration. Through dental implants, patients can achieve restorative results that are very similar to those of natural teeth in terms of function, structure, and aesthetics, and have become the preferred restoration method for an increasing number of patients with missing teeth.

[0003] Traditional implant treatment is a complex and cumbersome process, requiring high levels of skill from both doctors and technicians, and its success rate is influenced by many subjective and objective factors. In the era of digital dentistry, the entire implant process has undergone a qualitative transformation. The introduction of 3D scanning, CAD design, and 3D printing technologies has greatly simplified the implant treatment process, helping to improve efficiency and success rates. Digital implant technology uses a digital impression scanner to scan the implant's position and orientation, converting the implant site and depth into three-dimensional data using a dedicated intraoral scanning probe. The obtained data is then surface-matched with models in the implant database within the design software to obtain accurate implant information, thereby completing personalized restorations. Currently, the digital processing and production process of implant models is as follows: First, intraoral data is directly acquired using an intraoral scanner; then, the data is imported and personalized, such as adjusting the model's position and height, matching the implant type and position, and adjusting the occlusal relationship when necessary; next, the intraoral data (STL file) is imported into a 3D-DLP printer for processing and shaping, followed by alcohol cleaning and ultraviolet post-curing to obtain the implant model. This process not only improves the accuracy of personalized repairs, but also replaces the traditional silicone molding method with 3D printing technology, significantly improving the efficiency and quality of the repair process.

[0004] Most mainstream desktop DLP-3D printers on the market can process 2-4 planting models per batch, which is far below market demand. Improving production efficiency necessitates upgrading to higher-capacity equipment. Therefore, major equipment manufacturers are actively developing higher-efficiency (8 or more models per batch) top-projection printers to meet market demand. Currently, the resin materials used in bottom-projection DLP models are incompatible with top-projection printers because bottom-projection materials typically have a viscosity of 500-1000 cps (25℃), while top-projection printers require materials with lower viscosity (≤350 cps, 25℃). Furthermore, top-projection printers face oxygen inhibition issues; using conventional polyurethane acrylic resins results in rough model surfaces, unclear details, decreased mechanical properties, and poor dimensional stability during reverse scanning. Currently, commercially available top-projection model resins produce models with high viscosity, a glossy surface, a sticky feel, and significantly reduced dimensional stability after 30 days, failing to meet market demands. Therefore, there is an urgent need to develop a model resin suitable for top-projection 3D-DLP processing. Summary of the Invention

[0005] To address at least one of the aforementioned problems, this invention provides a 3D printing resin material for upward projection and its application. This resin material improves the scratch resistance and matte finish of the photocured model by introducing inorganic fillers and organic modified wax powder. The improved upward projection photosensitive resin is used to print dental implant molds using 3D printing technology, exhibiting high down-printing accuracy and high reverse scanning dimensional stability, and is applied in the field of oral medicine.

[0006] To achieve the above objectives, the present invention employs the following technical means: A first aspect of the present invention provides a 3D printing resin material for upward projection, the resin material comprising the following raw material components in parts by weight: 5-40 parts of polyurethane acrylate crosslinking agent; 5-40 parts of polyurethane acrylate oligomer; 25-40 parts of monofunctional reactive diluent; 15-40 parts of polyfunctional reactive diluent; 1-5 parts of photoinitiator; 0.1-3 parts of leveling agent; 0.1-3 parts of defoamer; 1-15 parts of surface additives; 0.5-3 parts of filler; 0.5-3 parts of scratch-resistant wax; 0.2-0.5 parts of pigment; The mass ratio of the polyurethane acrylate crosslinking agent to the polyurethane acrylate oligomer is (0.01-1):1; the mass ratio of the monofunctional reactive diluent to the polyfunctional reactive diluent is (0.5-2):1.

[0007] In some embodiments of the present invention, the following components are included: 5-35 parts of polyurethane acrylate crosslinking agent; 10-35 parts of polyurethane acrylate oligomer; 30-40 parts of monofunctional reactive diluent; 20-40 parts of polyfunctional reactive diluent; 1-3 parts of photoinitiator; 0.5-2 parts of leveling agent; 0.5-2 parts of defoamer; 1-10 parts of surface additives; 0.5-2 parts of filler; 0.5-2 parts of scratch-resistant wax; and 0.3-0.5 parts of pigment.

[0008] In some embodiments of the present invention, the following components are included: 5-15 parts of polyurethane acrylate crosslinking agent; 10-35 parts of polyurethane acrylate oligomer; 30-40 parts of monofunctional reactive diluent; 20-40 parts of polyfunctional reactive diluent; 1-3 parts of photoinitiator; 0.5-2 parts of leveling agent; 0.5-2 parts of defoamer; 1-10 parts of surface additives; 0.5-2 parts of filler; 0.5-2 parts of scratch-resistant wax; and 0.3-0.5 parts of pigment.

[0009] The mass ratio of the polyurethane acrylate crosslinking agent to the polyurethane acrylate oligomer is (0.01-1):1; the mass ratio of the monofunctional reactive diluent to the polyfunctional reactive diluent is (0.5-2):1.

[0010] In some preferred embodiments of the present invention, the polyurethane acrylate crosslinking agent is a thiol-modified polyurethane acrylate with a molecular weight of 500-3000 and a viscosity of 1000-40000 cps (25℃) and 1000-30000 cps (60℃). In some embodiments of the present invention, the thiol-modified polyurethane acrylate is selected from BOMAR DYMAX BDT-1006, BOMAR DYMAX BDT-1015, and BOMAR DYMAX BDT-4330. The polyurethane acrylate crosslinking agent may also be selected from any one or more combinations of amine-modified polyurethane acrylate, aliphatic polyurethane acrylate, polyether polyurethane acrylate, and polyester polyurethane acrylate: the amine-modified polyurethane acrylate is selected from Baojun Chemical 6821, Haohui HU9271, Haohui CR92719, and Haohui CR93084. The aliphatic polyurethane acrylate is selected from Sartoma CU228NS and BOMAR DYMAX BR-970H. The polyether polyurethane acrylate is selected from BOMAR DYMAX BR-144B. The polyester polyurethane acrylate is selected from BOMAR DYMAX BR-941. A polyurethane acrylate crosslinking agent with low yellowing, good deep curing properties, suitability for LED curing, rapid curing, and low oxygen inhibition is preferred. Using this crosslinking agent instead of commonly used polyurethane acrylate crosslinking agents allows the obtained model resin viscosity to be less than 400 cPs at 25℃, improving the flowability of the photosensitive resin. More importantly, it also imparts excellent curing effect, machine accuracy, and dimensional stability to the photocurable material. From a structural principle perspective, resins with relatively low oxygen inhibition: thiol-modified polyurethane acrylate resin is superior to amine-modified polyurethane acrylate resin, which is superior to polyether polyurethane acrylate resin.

[0011] In some preferred embodiments of the present invention, the polyurethane acrylate oligomer is an amine-modified polyurethane acrylate with a molecular weight of 3000-6000 and a viscosity of 1000-10000 cps (25℃) and 1000-50000 cps (60℃). In some embodiments of the present invention, the amine-modified polyurethane acrylate is selected from Runao Chemical LuCure8524, Runao Chemical LuCure2921, Runao Chemical LuCure2923, Haohui CR92228, and RAHN 5271. Preferably, the amine-modified polyurethane acrylate is selected from Haohui CR92228 and / or Runao Chemical LuCure8524.

[0012] In other embodiments of the present invention, the polyurethane acrylate oligomer may be selected from any one or more combinations of thiol-modified polyurethane acrylate, aliphatic polyurethane acrylate, and polyether polyurethane acrylate: the thiol-modified polyurethane acrylate is selected from Haohui CR93034, Haohui HU9310, Haohui CR92509, Haohui CR93456, and Runao Chemical LuCure7814. The aliphatic polyurethane acrylate is selected from RAHN 4425, BOMAR DYMAX BR-970BT, and BOMAR DYMAX BR-990. The polyether polyurethane acrylate is selected from BOMAR DYMAX BR-541S, BOMAR DYMAX BR-571, BOMAR DYMAX BR-582E8, and BOMAR DYMAX BR-582I10. The preferred polyurethane acrylate oligomers are those with low heat release, low yellowing, good deep curing properties, suitability for LED curing, rapid curing, and low oxygen inhibition. Using these oligomers instead of commonly used polyurethane acrylate oligomers can result in a resin viscosity of less than 400 cPs at 25°C, improving the fluidity of the photosensitive resin. More importantly, it also imparts higher curing effect, toughness, and dimensional stability to the photocurable material.

[0013] In some embodiments of the present invention, the monofunctional reactive diluent is acrylamide morpholine, which has low odor, low irritation, fast curing speed, good flexibility, and is easy to clean with alcohol and isopropanol. The polyfunctional reactive diluent is any one or a combination of two of dipropylene glycol diacrylate and tri(2-hydroxyethyl) isocyanurate triacrylate. Dipropylene glycol diacrylate is a difunctional reactive diluent containing a propylene glycol structure, possessing low viscosity, strong dilution ability, easy cleaning with alcohol or isopropanol, and affordable price. Tri(2-hydroxyethyl) isocyanurate triacrylate is a trifunctional reactive diluent with a cyclic molecular structure, which can effectively reduce the volume shrinkage rate of the material. It has high rigidity, high glass transition temperature, temperature and water resistance, and a certain crosslinking density, which can maintain high reverse sweep dimensional stability. The combination of dipropylene glycol diacrylate and tri(2-hydroxyethyl) isocyanurate triacrylate can improve the material's unloading accuracy.

[0014] In some embodiments of the present invention, the photoinitiator is any one or a combination of trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide.

[0015] In some embodiments of the present invention, the leveling agent is a combination of a polyether-modified dimethyl polysiloxane leveling agent and an acrylic leveling agent. The combined use of leveling agents can achieve both long-wave and short-wave leveling, significantly reducing surface tension, enabling rapid material leveling, and improving processing performance. Two key indicators in the processing of projection materials are viscosity and leveling performance. Materials with poor leveling performance will exhibit obvious textures in the planting model, affecting practical use.

[0016] In some embodiments of the present invention, the surface additive is an amine-modified surface additive, selected from any one or more combinations of RAHN 5695, Baojun Chemical 8600, Runao Chemical LuCure 5186, Sartoma CN551NS, Sartoma CN371NS, and Baojun Chemical 8000. Amine-modified surface additives can effectively improve oxygen inhibition polymerization, resulting in good surface detail in the processed model, excellent surface curing, and a non-sticky finish. Materials without surface additives exhibit rough and fuzzy surfaces, unclear details, and poor surface drying during processing with projection equipment. Therefore, surface additives must be added to improve the surface curing effect.

[0017] In some embodiments of the present invention, the defoamer is selected from any one or more combinations of BYK-A515, BYK-1796, BYK-1790 or BYK-1797.

[0018] In some embodiments of the present invention, the leveling agent is selected from any one or more combinations of BYK-333, BYK-355, BYK-378 or BYK-397.

[0019] In some embodiments of the present invention, the filler is selected from any one or more combinations of AEROSIL R972, AEROSIL R106, and AEROSIL R970.

[0020] In some embodiments of the present invention, the scratch-resistant wax is a polyethylene-modified scratch-resistant wax selected from any one or a combination of at least two of BYK 950, BYK991, and BYK 929.

[0021] In some embodiments of the present invention, the pigment is selected from any one or more combinations of Cashestar Chemical LA9W008 (white) and Cashestar Chemical LA9B001 (black).

[0022] In some embodiments of the present invention, the combined use of silica filler and polyethylene-modified scratch-resistant wax can effectively reduce surface gloss, resulting in a matte and smooth surface, and can be used to replace the function of matting powder. Adding too much organic or inorganic filler can easily lead to poor dispersion and noticeable particles in the liquid resin.

[0023] The second aspect of the present invention provides a method for preparing the 3D printing resin material for top projection as described in the first aspect. The preparation method is as follows: Take each raw material according to the weight parts in the formula, add polyurethane acrylate oligomer, polyurethane acrylate crosslinking agent, monofunctional reactive diluent, polyfunctional reactive diluent, photoinitiator, defoamer, leveling agent, filler, scratch-resistant wax, pigment and surface additive to the mixing tank and mix. Maintain the temperature at 35-40℃ and stir at 1200-1500 rpm / min for 1.5-2 hours. After mixing evenly, the 3D printing resin material for top projection is obtained.

[0024] A third aspect of the present invention provides a method of using the 3D printing resin material for upward projection described in the first aspect, the method of use being as follows: (1) Pour the obtained resin material into the photocurable DLP-3D printing equipment and print it at 23±2℃ and 50±20% humidity. The printed model is cured for the first time by ultraviolet light. (2) Place the model under a curing light source at 23±2℃ and 50±20% humidity for 10-15 minutes for a second UV curing to obtain the planting model.

[0025] The fourth aspect of the present invention provides the application of the 3D printing resin for upward projection described in the first aspect in the preparation of planting models.

[0026] Beneficial effects of the present invention Compared with the prior art, the present invention has the following beneficial effects: The 3D printing resin material for projection provided in this disclosure incorporates a polyurethane acrylic resin system suitable for LED curing, with excellent deep curing properties, low oxygen inhibition, low yellowing, and fast surface drying, along with a reactive diluent system to improve the printing accuracy and dimensional stability of the photocured model material. Inorganic fillers and organic modified wax powder are introduced to enhance the scratch resistance and matte finish of the photocured model. It also has a low viscosity (less than 350 cps at 25°C) and good leveling properties. The resulting model resin has excellent surface details, a matte finish, is scratch-resistant, has a dry surface, and is easy to clean.

[0027] Using the 3D printing resin material for upward projection provided in this disclosure, and with the synergistic effect of materials such as polyurethane acrylate crosslinking agent, polyurethane acrylate oligomer, monofunctional reactive diluent, and multifunctional reactive diluent, the prepared photocured model has excellent printing accuracy: the printing accuracy can reach up to 86.33% (compared with the original model at a comparison accuracy of 0.05); and it can have high dimensional stability after long-term storage (storage conditions: 23℃*50RH%): the dimensional stability remains above 80% after 30 days, which can meet the storage requirements when applied to dental implant restoration treatment. Attached Figure Description

[0028] Figure 1 The image shows a dental model obtained by printing with a 3D printer using 3D printing resin material for upper projection in Embodiment 1 of the present invention. Detailed Implementation

[0029] The following examples are used to illustrate preferred embodiments of the invention. Those skilled in the art will understand that the techniques disclosed in the examples represent techniques discovered by the inventors that can be used to implement the invention, and therefore can be considered preferred embodiments for implementing the invention. However, those skilled in the art should understand from this specification that many modifications can be made to the specific embodiments disclosed herein, still yielding the same or similar results, without departing from the spirit or scope of the invention.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, and all materials disclosed herein and cited therein are incorporated herein by reference. Many equivalent techniques of specific embodiments of the invention described herein will be recognized or can be understood by ordinary experimentation by those skilled in the art. These equivalents will be included in the claims.

[0031] A 3D printing resin material for projection, comprising the following raw material components in parts by weight: 5-40 parts of polyurethane acrylate crosslinking agent; 5-40 parts of polyurethane acrylate oligomer; 25-40 parts of monofunctional reactive diluent; 15-40 parts of polyfunctional reactive diluent; 1-5 parts of photoinitiator; 0.1-3 parts of leveling agent; 0.1-3 parts of defoamer; 1-15 parts of surface additives; 0.5-3 parts of filler; 0.5-3 parts of scratch-resistant wax; 0.2-0.5 parts of pigment; The mass ratio of polyurethane acrylate crosslinking agent to polyurethane acrylate oligomer is (0.01-1):1; the mass ratio of monofunctional reactive diluent to polyfunctional reactive diluent is (0.5-2):1.

[0032] The polyurethane acrylate crosslinking agent is any one or a combination of thiol-modified polyurethane acrylate, amine-modified polyurethane acrylate, aliphatic polyurethane acrylate, polyether polyurethane acrylate, and polyester polyurethane acrylate, with a molecular weight of 500-3000 and a viscosity of 1000-40000 cps (25℃) and 1000-30000 cps (60℃); the polyurethane acrylate oligomer is any one or a combination of amine-modified polyurethane acrylate, thiol-modified polyurethane acrylate, aliphatic polyurethane acrylate, polyether polyurethane acrylate, and polyester polyurethane acrylate, with a molecular weight of 3000-6000 and a viscosity of 1000-10000 cps (25℃) and 1000-50000 cps (60℃); the monofunctional reactive diluent is acrylamide morpholine, and the polyfunctional reactive diluent is any one or a combination of two of dipropylene glycol diacrylate and tris(2-hydroxyethyl)isocyanurate triacrylate.

[0033] The photoinitiator is any one or a combination of trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide. The leveling agent is a combination of polyether-modified dimethylpolysiloxane leveling agent and acrylic leveling agent. The surface additives are amine-modified surface additives; the defoamer is selected from any one or more combinations of BYK-A515, BYK-1796, BYK-1790 or BYK-1797; the leveling agent is selected from any one or more combinations of BYK-333, BYK-355, BYK-378 or BYK-397; the filler is selected from any one or more combinations of AEROSIL R972, AEROSIL R106, AEROSIL R970; the scratch-resistant wax is selected from any one or at least two combinations of BYK 950, BYK 991, BYK 929; the pigment is selected from any one or more combinations of Kaistar Chemical LA9W008 (white) and Kaistar Chemical LA9B001 (black).

[0034] The technical solution of this application will be further described in detail below with reference to specific embodiments.

[0035] Example 1 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 30 parts acrylamide, 20 parts tri(2-hydroxyethyl) isocyanurate triacrylate, 20 parts dipropylene glycol diacrylate, 10 parts BOMAR DYMAX BDT-1006, 20 parts Runao Chemical LuCure8524, 1 part trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK991, 0.39 parts white LA9W008, 0.01 parts black LA9B001.

[0036] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0037] Example 2 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 20 parts Haohui New Materials CR92228, 15 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 10 parts Tris(2-Hydroxyethyl) Isocyanurate Triacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0038] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0039] Example 3 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 5 parts BOMAR DYMAX BDT-1006, 10 parts Haohui New Materials CR92228, 20 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 10 parts Tris(2-Hydroxyethyl) Isocyanurate Triacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0040] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0041] Example 4 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 10 parts BOMAR DYMAX BDT-1006, 25 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 10 parts Tris(2-Hydroxyethyl) Isocyanurate Triacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0042] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0043] Example 5 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 10 parts BOMAR DYMAX BDT-1006, 25 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 15 parts Dipropylene Glycol Diacrylate, 15 parts Tris(2-Hydroxyethyl) Isocyanurate Triacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0044] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0045] Example 6 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 10 parts BOMAR DYMAX BDT-1006, 25 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 10 parts Dipropylene Glycol Diacrylate, 20 parts Tris(2-Hydroxyethyl) Isocyanurate Triacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0046] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0047] Example 7 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 20 parts Haohui New Materials CR92228, 15 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 10 parts BOMAR DYMAX BDT-1006, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0048] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0049] Example 8 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 20 parts Haohui New Materials CR92228, 20 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 5 parts BOMAR DYMAX BDT-1006, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0050] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0051] Example 9 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 5 parts BOMAR DYMAX BDT-1006, 25 parts Haohui New Materials CR92228, 35 parts Acrylamidomorpholine, 35 parts Dipropylene glycol diacrylate, 1 part Trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0052] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0053] Example 10 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 5 parts BOMAR DYMAX BDT-1006, 25 parts BOMAR DYMAX BR-541S, 35 parts Acrylamidomorpholine, 35 parts Dipropylene glycol diacrylate, 1 part Trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0054] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0055] Example 11 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 35 parts LuCure8524 from Runao Chemical, 35 parts acrylamide morpholine, 20 parts dipropylene glycol diacrylate, 10 parts tris(2-hydroxyethyl) isocyanurate triacrylate, 1 part trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts white LA9W008, 0.01 parts black LA9B001.

[0056] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0057] Example 12 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 25 parts tri(2-hydroxyethyl) isocyanurate triacrylate, 30 parts acrylmorpholine, 15 parts dipropylene glycol diacrylate, 15 parts RAHN 4425, 15 parts BOMAR DYMAX BR-970BT, 1 part trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts white LA9W008, 0.01 parts black LA9B001.

[0058] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0059] Example 13 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 35 parts acrylamide morpholine, 20 parts dipropylene glycol diacrylate, 5 parts BOMAR DYMAX BDT-1006, 40 parts Sartoma CU228NS, 1 part trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts white LA9W008, 0.01 parts black LA9B001.

[0060] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0061] Example 14 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 25 parts Bahe New Materials BWL427, 20 parts Runao Chemical LuCure8524, 35 parts Acrylamide Morpholine, 20 parts Dipropylene Glycol Diacrylate, 1 part Trimethylbenzoyl-Diphenylphosphine Oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts White LA9W008, 0.01 parts Black LA9B001.

[0062] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0063] Example 15 This embodiment provides a 3D printing resin material for upward projection, which, by weight, consists of the following components: 35 parts acrylamide, 35 parts dipropylene glycol diacrylate, 5 parts BOMAR DYMAX BDT-1006, 20 parts Runao Chemical LuCure8524, 5 parts Haohui New Materials CR92228, 1 part trimethylbenzoyl-diphenylphosphine oxide, 0.5 parts BYKA515, 1 part BYK333, 1 part BYK355, 5 parts RAHN 5695, 1.5 parts AEROSIL R972, 2 parts BYK 991, 0.39 parts white LA9W008, 0.01 parts black LA9B001.

[0064] The preparation method is as follows: add the above components into a mixing tank and mix. Stir at 1500 rpm / min for 2 hours at 40°C to obtain the resin material for 3D printing of planting models.

[0065] Comparative Example 1 This comparative example provides a 3D printing resin material for upward projection, namely the RP-405-TA01 photosensitive resin material developed by Shanghai Pulisheng Electromechanical Technology Co., Ltd.

[0066] Comparative Example 2 This comparative example provides a 3D printing resin material for upward projection, namely Syn 405U, manufactured by Shanghai UnionTech Technology Co., Ltd.

[0067] Example 16 A method of using a 3D printing resin material for upward projection, the method being as follows: (1) Pour the obtained resin material into the photocurable DLP-3D printing equipment and print it at 23±2℃ and 50±20% humidity. The printed model is cured for the first time by ultraviolet light. (2) Place the model under a curing light source at 23±2℃ and 50±20% humidity for 10-15 minutes for a second UV curing to obtain the planting model.

[0068] Dental implant models were printed using the resin materials corresponding to Examples 1-15 and Comparative Examples 1-2. The method included the following steps: (1) The resin materials in Examples 1-15 and Comparative Examples 1-2 were poured into a 3D printer for printing. The printing was carried out at 23±2℃ and 50±20% humidity. The printing was carried out in a photopolymer DLP-3D printing equipment. The model was a D-type dental model. The ultraviolet light with a wavelength of 405nm was used. Two models were processed each time. (2) The model was then placed under a secondary curing light source at 23±2℃ and 50±20% humidity for 10 minutes for secondary UV curing.

[0069] Among them, the dental model obtained by printing with a 3D printer using the 3D printing resin material for upper projection in Example 1 is as follows: Figure 1 As shown.

[0070] The dental implant models printed with the resin materials provided in Examples 1-15 and Comparative Examples 1-2 were subjected to performance tests according to the following methods: The photocured models printed from the resin materials provided in Examples 1-15 and Comparative Examples 1-2 were placed in a constant temperature and humidity chamber at 23±2℃ and 50±20% relative humidity for 14 days and 30 days, respectively. The data of the stored models were collected using a scanner, and the dimensional stability was tested in Geomagic Qulify software under a comparison accuracy of 0.05 and compared with the original model files.

[0071] The test model printed that day was scanned to collect model data, and the accuracy of the model was tested in Geomagic Qulify software under a comparison accuracy of 0.05, and compared with the original model file.

[0072] For each sample, two sets of tests were conducted to assess the accuracy after machine removal, dimensional stability after 14 days, and dimensional stability after 30 days, and the average value was taken.

[0073] The machine-on accuracy, 14-day dimensional stability, and 30-day dimensional stability are tested using internal company standards, which are based on industry and customer needs: at a comparison accuracy of 0.05, the machine-on accuracy is above 83% compared to the original model, and the dimensional stability remains above 80% after 30 days.

[0074] (1) Tensile strength and elongation at break were tested according to ASTM-D790 standard; (2) Perform bending strength and bending modulus tests according to ISO-178; (3) Perform Shore hardness test according to ISO-868; (4) Perform viscosity testing according to ISO-3219; The samples were observed to determine if they were matte; tested for dryness and stickiness by touch; and tested for scratch resistance by scratch testing.

[0075] The test results of each sample in Examples 1-15 and Comparative Examples 1-2 are recorded in Table 1 below.

[0076] Table 1. Test results of each sample in Examples 1-15 and Comparative Examples 1-2.

[0077] Table 1 shows that, as can be seen from Examples 1-7, 5-10 parts of polyurethane acrylate crosslinking agent and 20-35 parts of polyurethane acrylate oligomer, combined with monofunctional reactive diluent, polyfunctional reactive diluent and other components, can all obtain a viscosity of less than 350°C within the range of the formulation disclosed herein. This material is suitable for printing on projection equipment and has excellent printing accuracy and long-term dimensional stability.

[0078] As can be seen from Examples 2 and 7, the addition of thiol polyurethane acrylate to replace the trifunctional monomer significantly reduced the accuracy of the machine. This shows that tri(2-hydroxyethyl) isocyanurate triacrylate combined with dipropylene glycol diacrylate can maintain good accuracy of the machine.

[0079] Example 8 reduced the amount of thiol polyurethane acrylate and added amine polyurethane acrylate based on Example 7, which improved the precision of the product. However, the comparison showed that the curing effect was significantly worse. The dimensional stability of Example 8 at 14 days and 30 days was significantly worse than that of Example 7, indicating that the antioxidant and polymerization inhibition ability of thiol polyurethane acrylate is significantly better than that of amine polyurethane acrylate.

[0080] A comparison of Examples 9 and 10 shows that, in the absence of the trifunctional monomer tri(2-hydroxyethyl) isocyanurate triacrylate, neither of them achieved the required curing precision. This indicates that the combination of tri(2-hydroxyethyl) isocyanurate triacrylate and dipropylene glycol diacrylate is crucial for improving the curing precision of the material. Furthermore, the dimensional stability of both materials indicates that the curing effect of amine polyurethane acrylate is significantly better than that of polyether polyurethane acrylate.

[0081] A comparison of Examples 11 and 4 shows that without the addition of thiol polyurethane acrylate, the dimensional stability data from 14 to 30 days clearly indicates a worse curing effect. This also indirectly confirms that thiol polyurethane acrylate has better antioxidant and polymerization-inhibiting capabilities than amine polyurethane acrylate. Furthermore, the viscosity of this example increased significantly because BOMAR DYMAX BDT-1006 has a much lower viscosity than Runao Chemical's LuCure8524. For these reasons, the printing speed of Example 11 decreased significantly due to the increased viscosity and longer printing wait time, affecting actual production efficiency. Moreover, with increased addition of Runao Chemical's LuCure8524, the surface becomes sticky and difficult to clean; therefore, the addition amount of Runao Chemical's LuCure8524 should not exceed 25 parts.

[0082] Example 12 illustrates that without adding thiols and amine acrylates, only adding highly crosslinked monomers and highly functional fast-curing polyurethane acrylates, the deep curing effect of the 4-functional oligomer rahn 4425 is not good. Although the crosslinking density is theoretically very high, it cannot achieve excellent deep curing effect in the upper projection, resulting in poor dimensional stability.

[0083] Example 13 illustrates that even without adding a trifunctional monomer, only adding a portion of thiol acrylate, combined with the fast-curing polyurethane acrylate resin CU228NS, resulted in poor curing performance. To meet enterprise standards and surpass competitors, it is necessary to increase the depth of curing and the crosslinking density.

[0084] Comparing Example 15 and Example 9, the dimensional stability of the two is not much different. Runao Chemical's LuCure8524 has a better elongation at break, indicating better toughness and making it more suitable for practical use. Furthermore, the addition of Runao Chemical's LuCure8524 results in higher precision in the machine.

[0085] Compared to Comparative Example 1, the models printed using the resin material prepared by the method of this application exhibit superior printing accuracy, 14-day dimensional stability, and 30-day dimensional stability. Comparative Example 2, also a commonly used 3D printing resin material, produces products suitable only for short-term storage (around 7 days). Therefore, its cross-linking density is low, and while its elongation at break is relatively good, the lack of cross-linking results in poor 14-day and 30-day dimensional stability, making long-term storage impossible. In contrast, the method of this application, compared to Comparative Example 2, has a viscosity more suitable for upward projection printing, meets application requirements in terms of printing accuracy, and exhibits good 14-day and 30-day stability. Furthermore, compared to Comparative Examples 1 and 2, the products prepared using the method of this application have a smooth, matte, scratch-resistant surface that is easy to clean and leaves the hands dry and non-sticky.

[0086] In summary, the resin disclosed herein has superior finishing precision and dimensional stability compared to currently commercially available products, enabling the product to be stored for a long time and better meet application requirements.

[0087] All documents mentioned in this invention are incorporated herein by reference as if each document were individually incorporated by reference. Furthermore, it should be understood that after reading the foregoing teachings of this invention, those skilled in the art can make various alterations or modifications to this invention, and these equivalent forms also fall within the scope defined by this application.

Claims

1. A 3D printing resin material for upward projection, characterized in that, The resin material comprises the following raw material components in parts by weight: 5-40 parts of polyurethane acrylate crosslinking agent; 5-40 parts of polyurethane acrylate oligomer; 25-40 parts of monofunctional reactive diluent; 15-40 parts of polyfunctional reactive diluent; 1-5 parts of photoinitiator; 0.1-3 parts of leveling agent; 0.1-3 parts of defoamer; 1-15 parts of surface additives; 0.5-3 parts of filler; 0.5-3 parts of scratch-resistant wax; 0.2-0.5 parts of pigment; The mass ratio of the polyurethane acrylate crosslinking agent to the polyurethane acrylate oligomer is (0.01-1):1; the mass ratio of the monofunctional reactive diluent to the polyfunctional reactive diluent is (0.5-2):

1.

2. The 3D printing resin material for upward projection according to claim 1, characterized in that, The polyurethane acrylate crosslinking agent is a thiol-modified polyurethane acrylate with a molecular weight of 500-3000; the polyurethane acrylate oligomer is an amine-modified polyurethane acrylate with a molecular weight of 3000-6000.

3. The 3D printing resin material for upward projection according to claim 1, characterized in that, The monofunctional reactive diluent is acrylamide morpholine, and the polyfunctional reactive diluent is any one or a combination of two of dipropylene glycol diacrylate and tri(2-hydroxyethyl) isocyanurate triacrylate.

4. The 3D printing resin material for upward projection according to claim 1, characterized in that, The photoinitiator is any one or a combination of trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphine acid, and 2,4,6-trimethylbenzoyl-di(p-tolyl)phosphine oxide.

5. The 3D printing resin material for upward projection according to claim 1, characterized in that, The leveling agent is a combination of polyether-modified dimethyl polysiloxane leveling agent and acrylic leveling agent.

6. The 3D printing resin material for upward projection according to claim 1, characterized in that, The surface additive is an amine-modified surface additive, selected from any one or more combinations of RAHN 5695, Baojun Chemical 8600, Runao 5186, Sartoma CN551, Sartoma CN371 and Baojun Chemical 8000.

7. The 3D printing resin material for upward projection according to claim 1, characterized in that, The defoamer is selected from any one or more combinations of BYK-A515, BYK-1796, BYK-1790, or BYK-1797; the leveling agent is selected from any one or more combinations of BYK-333, BYK-355, BYK-378, or BYK-397; the filler is selected from any one or more combinations of AEROSIL R972, AEROSIL R106, or AEROSIL R970; the scratch-resistant wax is selected from any one or at least two combinations of BYK 950, BYK991, or BYK 929; and the pigment is selected from any one or more combinations of LA9W008 and LA9B001.

8. A method for preparing a 3D printing resin material for upward projection as described in any one of claims 1-7, characterized in that, The preparation method is as follows: Take each raw material according to the weight parts in the formula, add polyurethane acrylate oligomer, polyurethane acrylate crosslinking agent, monofunctional reactive diluent, polyfunctional reactive diluent, photoinitiator, defoamer, leveling agent, filler, scratch-resistant wax, pigment and surface additive to the mixing tank and mix. Maintain the temperature at 35-40℃ and stir at 1200-1500 rpm / min for 1.5-2 hours. The mixture is uniform to obtain the 3D printing resin material for upper projection.

9. A method of using the 3D printing resin material for upward projection according to any one of claims 1-7, characterized in that, The usage method is as follows: (1) Pour the obtained resin material into the photocurable DLP-3D printing equipment and print it at 23±2℃ and 50±20% humidity. The printed model is cured for the first time by ultraviolet light. (2) Place the model under a curing light source at 23±2℃ and 50±20% humidity for 10-15 minutes for a second UV curing to obtain the planting model.

10. The use of the 3D printing resin for upward projection as described in any one of claims 1-7 in the preparation of planting models.

Images