A water-washable SLA photosensitive resin material for 3D printing, its preparation method and usage method

Abstract

The present invention provides a water-washable SLA photosensitive resin material for 3D printing and a preparation and use method thereof. The preparation method of the water-washable resin comprises the following steps: adding a photocurable monomer, a resin, an initiator, and various additives to a container in sequence and stirring at a low speed to obtain a mixed liquid; filtering the stirred resin to remove impurities and then vacuuming and defoaming to obtain a water-washable resin liquid material; using an SLA printer to make a model sample, rinsing the cured resin sample with water and blowing it dry with an air gun, and then placing the sample in a UV lamp box for post-curing, and finally deciding whether to perform heat treatment based on the sample's usage conditions. The water-washable resin material of the present invention is suitable for mainstream SLA printers on the market. After light curing and heat curing, the resin sample has high surface detail accuracy, good dimensional stability, and excellent mechanical properties, which are mainly reflected in high strength and modulus, and high notched impact strength.

Description

Technical Field

[0001] The present invention relates to a light-curing resin material and a preparation and use method thereof, in particular to a water-washable SLA resin material and a preparation and use method thereof, belonging to the field of new 3D printing material development. Background Art

[0002] SLA printers, a type of 3D printer, have a high market share and are widely used. Currently, after curing, the accompanying photosensitive resin material requires cleaning with an organic solvent monomer to remove residual resin and produce a dry surface. Industrial alcohol, due to its low cost and ease of use, is widely used in SLA machine post-processing and cleaning workshops. However, this cleaning process is not only harmful to the human body and the surrounding environment, but is also flammable, explosive, and difficult to store. Therefore, there is an urgent need to develop a safe, environmentally friendly resin material with lower post-processing costs, while also exhibiting excellent mechanical properties, high build quality, and high printing efficiency.

[0003] CN110818852A discloses a photosensitive resin for DLP used in water-washable 3D printing, which is cured by a free radical initiator to obtain a photosensitive resin with excellent mechanical properties. In this formula, a simple acrylate system is used, which has a high shrinkage rate after curing. For models with large volume or large bottom area, it is very easy to cause large deformation and dimensional deviation, which brings great inconvenience to actual use. Therefore, this method is not suitable for use on large-format production machines; CN114573761A discloses a water-washable dual-curing photosensitive resin mixture, which is obtained by synthesizing a water-soluble curing agent to obtain a water-washable dual-curing 3D printing resin. Due to the presence of the curing agent, the local temperature rise caused by the heat released by resin polymerization during the printing and molding process is very likely to cause the resin in the non-molding area to solidify, thereby shortening the service life of the resin in the resin tank and even affecting the accuracy of the printed part, which brings great inconvenience to actual operation. Therefore, this method is not suitable for use on large-format production machines, especially SLA machines. Summary of the Invention

[0004] To address the aforementioned technical issues, the present invention aims to provide a water-washable photosensitive resin material suitable for large-format SLA machines, along with methods for its preparation and use. The water-washable photosensitive resin material exhibits low shrinkage and excellent mechanical properties, making it suitable for most mainstream SLA machines on the market.

[0005] To achieve the above-mentioned object, the present invention provides a water-washable SLA resin material for 3D printing. The raw material composition thereof includes, by weight percentage: 40%-70% acrylate monomer, 20%-50% acrylate resin, 1%-3% free radical initiator, 0.02%-0.08% defoaming agent, and 3%-10% filler, and the sum of the weight percentages of the raw materials is 100%.

[0006] In the above-mentioned water-washable SLA resin material, preferably, the acrylate monomer includes one or more of N-acryloylmorpholine (ACMO), diacetone acrylamide, and trimethylolpropane triacrylate (TMPTA).

[0007] In the above-mentioned water-washable SLA resin material, preferably, the acrylic resin includes one or a combination of E1220, E1228, E1231 of Guangdong Honeycomb Company, N3D-W1109, N3D-W2509 of ARKEMA Company.

[0008] In the above-mentioned water-washable SLA resin material, preferably, the free radical initiator includes one or a combination of acetophenone, α-hydroxyketone, α-aminoketone, and bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide.

[0009] In the above-mentioned water-washable SLA resin material, preferably, the defoaming agent is one or more of BYK 024, BYK 016, and BYK 028.

[0010] In the above water-washable SLA resin material, preferably, the filler includes hollow glass microspheres HM 15 .

[0011] The present invention also provides a method for preparing a water-washable SLA resin material, comprising the following steps:

[0012] (1) Weigh acrylate monomer and acrylate resin in sequence and add them to a beaker. Insert a temperature probe, turn on the heating plate, and stir at a low speed to obtain a mixed liquid.

[0013] (2) weighing a defoamer, a free radical initiator, and a filler in sequence and adding them to the mixed liquid of step (1), stirring to obtain a water-washed resin mixed liquid;

[0014] (3) The stirred mixed resin liquid is sieved, vacuumed and defoamed to obtain the finished water-washed resin liquid.

[0015] In the above preparation method, preferably, the low-speed stirring speed in step (1) is 300-800 r / min.

[0016] In the above preparation method, preferably, the stirring speed in step (2) is 400-1000 r / min.

[0017] In the above preparation method, preferably, the mesh size of the sieving filter in step (3) is 40-100 meshes.

[0018] In the above preparation method, preferably, the vacuum temperature in step (3) is 50-90° C. and the time is 1-3 hours.

[0019] The present invention also provides a method for using a water-washable SLA resin material, comprising the following steps:

[0020] (1) Scrape off the printed data model sample from the SLA machine printing platform and remove the support;

[0021] (2) Rinse the sample in water and then use an air gun to blow away any residual liquid on the surface;

[0022] (3) The sample is placed in a UV light box for curing;

[0023] (4) After setting the oven heating program, place the sample in the oven for heat treatment.

[0024] In the above preparation method, preferably, the heating temperature in step (4) is 100-150°C.

[0025] In the above preparation method, preferably, the curing time in step (3) is 4-12 hours.

[0026] In the above preparation method, the amounts of monomers, resins, initiators and defoamers can be adjusted routinely by those skilled in the art, as long as all the raw materials can be completely mixed and in the right proportions.

[0027] Models printed with the light-curable, water-washable resin material of the present invention have a flexural strength of 45-60 MPa, a flexural modulus of 900-1500 MPa, a notched impact strength of 25-45 J / m, a high molding rate, and a smooth and delicate surface. The samples produced with the resin of the present invention have stable mechanical properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 These are photos of the sample printed from the water-washable resin material of Example 1 before and after heat treatment.

[0029] Figure 2 This is a photo of a sample printed out of the water-washable resin material of Example 2.

[0030] Figure 3 This is a photo of a sample printed out of the water-washable resin material of Example 3. DETAILED DESCRIPTION

[0031] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present invention, the technical solution of the present invention is now described in detail below, but it should not be understood as limiting the scope of implementation of the present invention.

[0032] It should be noted that in the following examples, all raw materials used are commercially available; and all percentages mentioned are by weight. Specific embodiment 1

[0034] The present invention provides a water-washable SLA photosensitive resin material for 3D printing. The raw material composition of the material comprises, by weight percentage, 60% by weight of N-acryloylmorpholine (ACMO), 27% by weight of E 1220, 0.05% by weight of BYK 016, 2.95% by weight of bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and 10% by weight of HM 15.

[0035] The above-mentioned water-washable SLA photosensitive resin material for 3D printing is prepared by the following method:

[0036] (1) ACMO and E1220 were weighed and added to a beaker in sequence. After inserting a temperature probe, the heating temperature was set to 70°C and the mixture was stirred at a speed of 450 r / min for 60 minutes to obtain a mixed liquid.

[0037] (2) BYK 016, bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and HM 15 were weighed in sequence and added to the mixed liquid of step (1), and stirred at a speed of 700 r / min for 60 minutes to obtain a water-washed resin mixed liquid;

[0038] (3) The water-washed resin mixed liquid obtained by stirring is sieved through a 50-mesh sieve, and vacuumed at 75° C. for 100 minutes to defoam, thereby obtaining the water-washed resin liquid product.

[0039] The above-mentioned method for using water-washable SLA photosensitive resin for 3D printing includes the following steps:

[0040] (1) Scrape the printed data model sample off the SLA machine printing platform and remove the support.

[0041] (2) Rinse the sample in water and use an air gun to blow away any residual liquid on the surface.

[0042] (3) Place the sample in a UV light box for curing.

[0043] (4) Set the oven temperature program to 150℃ and keep it warm for 6 hours, then place the sample in the oven for heat treatment.

[0044] Use Liantai SLA printer to print water-washable photosensitive resin. Photos of the resin model before and after heat treatment after curing are attached. Figure 1 As shown, the flexural strength of the resin before and after heat treatment is 40 MPa and 79 MPa respectively, the flexural modulus is 1500 MPa and 2750 MPa respectively, and the notched impact strength is 30 J / m and 35 J / m respectively. Specific embodiment 2

[0046] The present invention provides a water-washable SLA photosensitive resin material for 3D printing. The raw material composition of the material comprises, by weight percentage, 50% by weight of N-acryloylmorpholine (ACMO), 7% by weight of diacetone acrylamide, 30% by weight of E 1220, 0.05% by weight of BYK016, 2.95% by weight of bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and 10% by weight of HM 15.

[0047] The above-mentioned water-washable SLA photosensitive resin material for 3D printing is prepared by the following method:

[0048] (1) N-acryloylmorpholine (ACMO), diacetone acrylamide, and E 1220 were weighed and added to a beaker in sequence. After inserting a temperature probe, the heating temperature was set to 75°C and the mixture was stirred at a speed of 500 r / min for 50 minutes to obtain a mixed liquid;

[0049] (2) BYK 024, bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and HM 15 were weighed in sequence and added to the mixed liquid of step (1), and stirred at a speed of 600 r / min for 60 minutes to obtain a water-washed resin mixed liquid;

[0050] (3) The water-washed resin mixed liquid obtained by stirring is sieved through a 70-mesh sieve, and vacuumed at 80° C. for 100 minutes to defoam, thereby obtaining the water-washed resin liquid product.

[0051] The above-mentioned method for using the water-washable SLA photosensitive resin material for 3D printing includes the following steps:

[0052] (1) Scrape the printed data model sample off the SLA machine printing platform and remove the support.

[0053] (2) Rinse the sample in water and use an air gun to blow away any residual liquid on the surface.

[0054] (3) Place the sample in a UV light box for curing.

[0055] (4) After setting the oven temperature program to 100°C for 10 hours, the sample is placed in the oven for heat treatment.

[0056] Use Liantai SLA printer to print water-washable photosensitive resin. The photo of the resin model after curing is as shown in the attached picture. Figure 2 As shown, the flexural strength of the resin formula is 42 MPa, the flexural modulus is 1449 MPa, and the notched impact strength is 41 J / m. Specific embodiment 3

[0058] The present invention provides a water-washable SLA photosensitive resin material for 3D printing. The raw material composition of the material comprises, by weight percentage, 60% by weight of N-acryloylmorpholine (ACMO), 30% by weight of E1220, 8% by weight of E1231, 0.05% by weight of BYK028, 1.95% by weight of bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, 1% by weight of α-hydroxy ketone, and 5% by weight of HM15.

[0059] The above-mentioned water-washable SLA photosensitive resin material for 3D printing is prepared by the following method:

[0060] (1) N-acryloylmorpholine (ACMO), E 1220, and E1231 were weighed and added to a beaker in sequence. After inserting a temperature probe, the heating temperature was set to 80°C and the mixture was stirred at a speed of 350 r / min for 60 minutes to obtain a mixed liquid.

[0061] (2) BYK 028, bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, α-hydroxyketone, and HM15 were weighed in sequence and added to the mixed liquid of step (1), and stirred at a speed of 600 r / min for 70 minutes to obtain a water-washed resin mixed liquid;

[0062] (3) The water-washed resin mixed liquid obtained by stirring is sieved through a 50-mesh sieve, and vacuumed at 75° C. for 100 minutes to defoam, thereby obtaining the water-washed resin liquid product.

[0063] The above-mentioned method for using the water-washable SLA photosensitive resin material for 3D printing includes the following steps:

[0064] (1) Scrape the printed data model sample off the SLA machine printing platform and remove the support.

[0065] (2) Rinse the sample in water and use an air gun to blow away any residual liquid on the surface.

[0066] (3) Place the sample in a UV light box for curing.

[0067] (4) Set the oven temperature program to 110℃ and keep it warm for 11 hours, then place the sample in the oven for heat treatment.

[0068] Use Liantai SLA printer to print water-washable photosensitive resin. The photo of the resin model after curing is as shown in the attached picture. Figure 3 As shown, the flexural strength of the resin formulation is 37 MPa, the flexural modulus is 1150 MPa, and the notched impact strength is 47 J / m. Specific embodiment 4

[0070] The present invention provides a water-washable SLA photosensitive resin material for 3D printing. The raw material composition of the material comprises, by weight percentage, 70% by weight of N-acryloylmorpholine (ACMO), 12% by weight of E1220, 5% by weight of N3D-W1109, 2% by weight of TMPTA, 0.05% by weight of BYK 028, 2.95% by weight of bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and 8% by weight of HM15.

[0071] The above-mentioned water-washable SLA photosensitive resin material for 3D printing is prepared by the following method:

[0072] (1) N-acryloylmorpholine (ACMO), E1220, N3D-W1109, and TMPTA were weighed in sequence and added to a beaker. After inserting a temperature probe, the heating temperature was set to 60°C and the mixture was stirred at a speed of 550 r / min for 65 minutes to obtain a mixed liquid.

[0073] (2) 0.05% BYK 028, 2.95% bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide, and HM15 were weighed in sequence and added to the mixed liquid in step (1), and stirred at a speed of 550 r / min for 90 minutes to obtain a water-washed resin mixed liquid;

[0074] (3) The water-washed resin mixed liquid is sieved through an 80-mesh sieve and vacuumed at 70° C. for 100 minutes to defoam, thereby obtaining the water-washed resin liquid product.

[0075] The above-mentioned method for using the water-washable SLA photosensitive resin material for 3D printing includes the following steps:

[0076] (1) Scrape the printed data model sample off the SLA machine printing platform and remove the support.

[0077] (2) Rinse the sample in water and use an air gun to blow away any residual liquid on the surface.

[0078] (3) Place the sample in a UV light box for curing.

[0079] (4) Set the oven temperature program to 130℃ and keep it warm for 9 hours, then place the sample in the oven for heat treatment.

[0080] The water-washable photosensitive resin was printed using a Liantai SLA printer. The resin formula has a flexural strength of 45MPa, a flexural modulus of 1390MPa, and a notched impact strength of 28J / m.

Claims

1. A water-washable SLA photosensitive resin material for 3D printing, characterized in that: The raw materials include, by weight percentage, 40%-70% of acrylate monomer, 20%-50% of acrylate resin, 1%-3% of free radical initiator, 0.02%-0.08% of defoamer, and 3%-10% of filler, and the sum of the weight percentages of the raw materials is 100%. The acrylate monomer includes a mixture of N-acryloylmorpholine (ACMO) and diacetone acrylamide; The acrylic resin includes one or a combination of E1220, E1228, E1231 of Guangdong Honeycomb Company, N3D-W1109 and N3D-W2509 of ARKEMA Company; The free radical initiator includes one or a combination of acetophenone, α-hydroxyketone, α-aminoketone, bis-(2,4,6)-trimethylbenzoylphenylphosphine oxide; The defoaming agent is one or more of BYK 024, BYK 016, and BYK 028; The filler includes hollow glass microspheres HM 15.

2. A method for preparing the water-washable SLA photosensitive resin material according to claim 1, characterized in that: The following steps are involved: (1) Weigh acrylate monomer and acrylate resin in sequence and add them to a beaker. Insert a temperature probe, turn on the heating plate, and stir at a low speed to obtain a mixed liquid. (2) weighing a defoamer, a free radical initiator, and a filler in sequence and adding them to the mixed liquid of step (1), stirring to obtain a water-washed resin mixed liquid; (3) The stirred water-washed resin mixed liquid is sieved and vacuumed to defoam to obtain the water-washed resin liquid finished product.

3. The preparation method according to claim 2, characterized in that The low-speed stirring speed in step (1) is 300-800 r / min, and the stirring speed in step (2) is 400-1000 r / min.

4. The preparation method according to claim 2, characterized in that The mesh size of the sieving filter in step (3) is 40-100 meshes, the vacuum temperature is 50-90° C., and the time is 1-3 hours.

5. A method for using the water-washable SLA photosensitive resin material according to claim 1, characterized in that: The following steps are involved: (1) Scrape off the printed data model sample from the SLA machine printing platform and remove the support; (2) Rinse the sample in water and then use an air gun to blow away any residual liquid on the surface; (3) The sample is placed in a UV light box for curing; (4) After setting the oven heating program, place the sample in the oven for heat treatment.

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