Penetrable light-cured photosensitive resin material and preparation method thereof

Abstract

The invention discloses a penetrable light-cured photosensitive resin material and a preparation method thereof, and belongs to the technical field of additive manufacturing. The penetrable light-cured photosensitive resin material disclosed by the invention is prepared from the following components in percentage by mass: 79 to 99 percent of photosensitive resin, 5 to 10 percent of Cs2ZrCl6 and 0 to 1 percent of a photoinitiator 784. According to the penetrable light-cured photosensitive resin material, the synergistic effect of Cs2ZrCl6 and the photoinitiator 784 is utilized, X-ray photons are absorbed, the photo-crosslinking reaction of the photosensitive resin is induced, the problem that an existing light curing technology does not have penetrability is solved, the penetrable light-cured photosensitive resin material can be applied to internal curing of objects, and the penetrable light-cured photosensitive resin material has important value in the field of additive manufacturing.

Description

Technical Field

[0001] The present invention relates to a penetrable photocurable photosensitive resin material and a preparation method thereof, belonging to the technical field of additive manufacturing. Background Art

[0002] Photocrosslinking has become a powerful technology with wide applications in various fields. Traditional photocuring 3D printing technology refers to the polymerization of computer-controlled liquid photosensitive resin at specific positions on the printing platform under the irradiation of visible / ultraviolet light sources, forming a three-dimensional structure layer by layer, while the areas not exposed to light remain liquid.

[0003] The photosensitive materials used in photocuring 3D printing mainly consist of monomers and photoinitiators. Most photoinitiators absorb photons with wavelengths below 450 nm, generating free radicals or cations to initiate the polymerization reaction of monomers. Therefore, traditional methods mainly rely on ultraviolet / visible light (UV / Vis) for activation. However, this has great limitations. UV / Vis light exhibits limited penetration ability, usually only a few millimeters, seriously hindering its wider applications.

[0004] In recent years, although near-infrared light (NIR) has been explored as an excitation light source to alleviate these limitations, its penetration depth is still insufficient. In addition, the luminescence efficiency of the light conversion materials used in NIR-based 3D printing technology is low, slowing down the curing speed. Therefore, there is an urgent need for a photocuring method with deep penetration. The penetration depth of X-rays is more superior compared to UV, VIS, and NIR, and can be used as an excitation light source to achieve deeper and faster penetrable photocuring. Summary of the Invention

[0005] In order to overcome the problems in the background art, the purpose of the present invention is to provide a penetrable photocurable photosensitive resin material and a preparation method thereof.

[0006] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0007] A penetrable photocurable photosensitive resin material, comprising components in the following mass percentage: 79%-99% photosensitive resin, 5-10% Cs 2 ZrCl 6 , 0-1% photoinitiator 784.

[0008] More preferably, the penetrable photocurable photosensitive resin material comprises components in the following mass percentage: 89% photosensitive resin, 10% Cs 2 ZrCl 6 , 1% photoinitiator 784. At this time, the penetrable photocurable photosensitive resin material has the best photocuring effect.

[0009] More preferably, the preparation method of the penetrable photocurable photosensitive resin material includes:

[0010] (1) Dissolve CsCl and Zr(CO 3 ) 2 in hydrochloric acid, and then perform a hydrothermal reaction to obtain Cs 2 ZrCl 6 ;

[0011] (2) Uniformly mix the photosensitive resin, Cs 2 ZrCl 6 and photoinitiator 784 in the dark, and store in the dark to obtain the penetrable photocurable photosensitive resin material.

[0012] More preferably, the molar ratio of CsCl and Zr(CO 3 ) 2 is 2:1. The amount of hydrochloric acid added in the present invention is such that CsCl and Zr(CO 3 ) 2 can be dissolved.

[0013] More preferably, the photosensitive resin includes methyl methacrylate.

[0014] More preferably, the temperature of the hydrothermal reaction is 180 °C and the time is 12 h.

[0015] Advantages of the present invention: The penetrable photocurable photosensitive resin material of the present invention utilizes the synergistic effect of Cs 2 ZrCl 6 and photoinitiator 784 to absorb X-ray photons, improve the photo-crosslinking reaction of the induced photosensitive resin, solve the problem that the existing photocuring technology does not have penetrability, and can be applied to internal curing of objects. The present invention has important value in the field of additive manufacturing. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 Schematic diagrams of the X-ray curing systems of Examples 1-3 and Comparative Examples 1-4.

[0017] Figure 2 Photoluminescence spectrum of Cs 2 ZrCl 6 prepared in Example 2 and absorption spectrum of IRGACURE 784.

[0018] Figure 3 Pattern A cured by the method of Example 2.

[0019] Figure 4 Pattern B cured by the method of Example 2. DETAILED DESCRIPTION

[0020] The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0021] In the present invention, the photosensitive resin is a commercially available product, purchased from the photosensitive resin of the standard rigid resin + photocuring consumables product of Creality 3D.

[0022] Example 1

[0023] A penetrable photocuring photosensitive resin material includes that the mass fraction of the photosensitive resin (the main component is methyl methacrylate) is 94%; the mass fraction of IRGACURE 784 is 1.0% and Cs 2 ZrCl 6 has a mass fraction of 5%.

[0024] The preparation method of the penetrable photocuring photosensitive resin material includes:

[0025] (1) Put 1.3536 g of CsCl and 0.8492 g of Zr(CO 3 ) 2 into the inner liner of a 25 ml reaction kettle, add 15 ml of hydrochloric acid to dissolve, place the reaction kettle in an oven, heat to 180 °C, keep warm for 12 h, cool to room temperature and take out, suck the product solution into a centrifuge tube with a dropper, centrifuge once, then add absolute ethanol and centrifuge 3 times, the rotation speed is 10000 r / min, 10 minutes each time, pour out the absolute ethanol solution, put the centrifuge tube in an oven at 80 °C and dry for 4 h to obtain dry Cs 2 ZrCl 6 pure substance, and grind the prepared Cs 2 ZrCl 6 for 10 min.

[0026] (2) Mix the photosensitive resin, IRGACURE 784 and Cs 2 ZrCl 6 uniformly in the dark according to the formula ratio, the mixing time is 10 minutes, and store in the dark to obtain the penetrable photocuring photosensitive resin material.

[0027] Adopt the Figure 1 shown system for the curing process: Wrap the mixed penetrable photocuring photosensitive resin material with a plastic film, place it under the X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0028] Example 2

[0029] A penetrable photocuring photosensitive resin material includes that the mass fraction of the photosensitive resin (the main component is methyl methacrylate) is 89%; the mass fraction of IRGACURE 784 is 1.0% and Cs2 ZrCl 6 The mass fraction of

[0030] The preparation method of the penetrable photocurable photosensitive resin material includes

[0031] (1) Put 1.3536 g of CsCl and 0.8492 g of Zr(CO 3 ) 2 into the inner liner of a 25 ml reactor, add 15 ml of hydrochloric acid to dissolve, place the reactor in an oven, heat to 180 °C, keep warm for 12 h, cool to room temperature and take out. Use a dropper to suck the product solution into a centrifuge tube, centrifuge once, then add absolute ethanol and centrifuge 3 times at a speed of 10000 r / min for 10 minutes each time. Pour out the absolute ethanol solution, put the centrifuge tube in an oven and dry at 80 °C for 4 h to obtain dry Cs 2 ZrCl 6 pure substance. Grind the prepared Cs 2 ZrCl 6 for 10 min.

[0032] (2) Mix the photosensitive resin, IRGACURE 784 and Cs 2 ZrCl 6 uniformly in the dark according to the formula ratio. The mixing time is 10 minutes, and store in the dark to obtain the penetrable photocurable photosensitive resin material.

[0033] Curing process: Wrap the mixed penetrable photocurable photosensitive resin material with a plastic film, place it under an X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0034] Example 3

[0035] A penetrable photocurable photosensitive resin material includes that the mass fraction of the photosensitive resin (the main component is methyl methacrylate) is 90%; Cs 2 ZrCl 6 The mass fraction of

[0036] The preparation method of the penetrable photocurable photosensitive resin material includes

[0037] (1) Put 1.3536 g of CsCl and 0.8492 g of Zr(CO 3 ) 2Put it into the inner liner of a 25 ml reaction kettle, add 15 ml of hydrochloric acid for dissolution, place the reaction kettle in an oven, heat it to 180 °C, keep it warm for 12 h, cool it to room temperature and take it out. Use a dropper to suck the product solution into a centrifuge tube, centrifuge it once, then add absolute ethanol and centrifuge 3 times at a speed of 10000 r / min for 10 minutes each time. Pour out the absolute ethanol solution, put the centrifuge tube into the oven and dry it at 80 °C for 4 h to obtain dry Cs 2 ZrCl 6 pure substance. The prepared Cs 2 ZrCl 6 Grind for 10 min.

[0038] (2) Mix the photosensitive resin and Cs 2 ZrCl 6 uniformly in the dark according to the formula ratio. The mixing time is 10 minutes, and store it in the dark to obtain the penetrable photocurable photosensitive resin material.

[0039] Curing process: Wrap the mixed penetrable photocurable photosensitive resin material with a plastic film, place it under an X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0040] Comparative Example 1

[0041] A photocurable photosensitive resin material includes 99% by mass of a photosensitive resin (the main component is methyl methacrylate); 1.0% by mass of IRGACURE 784.

[0042] The preparation method of the photocurable photosensitive resin material includes mixing the photosensitive resin and the photoinitiator uniformly in the dark according to the formula ratio. The mixing time is 10 minutes, and store it in the dark to obtain the photocurable photosensitive resin material.

[0043] Curing process: Wrap the mixed photocurable photosensitive resin material with a plastic film, place it under an X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0044] Comparative Example 2

[0045] A penetrable photocurable photosensitive resin material includes 84% by mass of a photosensitive resin (the main component is methyl methacrylate); 1.0% by mass of IRGACURE 784 and Cs 2 ZrCl 6 with a mass fraction of 15%.

[0046] The preparation method of the penetrable photocurable photosensitive resin material includes,

[0047] (1) Mix 1.3536 g of CsCl and 0.8492 g of Zr(CO3 ) 2 Put it into the inner liner of a 25 ml reaction kettle, add 15 ml of hydrochloric acid for dissolution, place the reaction kettle in an oven, heat it to 180 °C, keep it warm for 12 h, cool it to room temperature and take it out. Use a dropper to suck the product solution into a centrifuge tube, centrifuge once, then add absolute ethanol and centrifuge 3 times at a speed of 10,000 r / min for 10 minutes each time. Pour out the absolute ethanol solution, put the centrifuge tube in the oven and dry it at 80 °C for 4 h to obtain dry Cs 2 ZrCl 6 pure substance. The prepared Cs 2 ZrCl 6 Grind for 10 min.

[0048] (2) Mix the photosensitive resin, IRGACURE 784 and Cs 2 ZrCl 6 uniformly in the dark according to the formula ratio. The mixing time is 10 minutes, and store it in the dark to obtain the penetrable photocurable photosensitive resin material.

[0049] Curing process: Wrap the mixed penetrable photocurable photosensitive resin material with a plastic film, place it under an X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0050] Comparative Example 3

[0051] A penetrable photocurable photosensitive resin material includes: the mass fraction of the photosensitive resin (the main component is methyl methacrylate) is 79%; the mass fraction of IRGACURE 784 is 1.0% and Cs 2 ZrCl 6 is 20% by mass fraction.

[0052] The preparation method of the penetrable photocurable photosensitive resin material includes

[0053] (1) Put 1.3536 g of CsCl and 0.8492 g of Zr(CO 3 ) 2 into the inner liner of a 25 ml reaction kettle, add 15 ml of hydrochloric acid for dissolution, place the reaction kettle in an oven, heat it to 180 °C, keep it warm for 12 h, cool it to room temperature and take it out. Use a dropper to suck the product solution into a centrifuge tube, centrifuge once, then add absolute ethanol and centrifuge 3 times at a speed of 10,000 r / min for 10 minutes each time. Pour out the absolute ethanol solution, put the centrifuge tube in the oven and dry it at 80 °C for 4 h to obtain dry Cs 2 ZrCl 6 pure substance. The prepared Cs 2 ZrCl 6 Grind for 10 min.

[0054] (2) Mix the photosensitive resin, IRGACURE 784 and Cs 2 ZrCl 6 uniformly in the dark according to the formulation ratio. The mixing time is 10 minutes, and store it in the dark. This is the penetrable photocurable photosensitive resin material.

[0055] Curing process: Wrap the mixed penetrable photocurable photosensitive resin material with plastic film, place it under the X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0056] Comparative Example 4

[0057] A penetrable photocurable photosensitive resin material includes: the mass fraction of the photosensitive resin (the main component is methyl methacrylate) is 94%; the mass fraction of the photoinitiator 819 is 1.0% and Cs 2 ZrCl 6 is 5%.

[0058] The preparation method of the penetrable photocurable photosensitive resin material includes,

[0059] (1) Put 1.3536 g of CsCl and 0.8492 g of Zr(CO 3 ) 2 into the inner liner of a 25 ml reaction kettle, add 15 ml of hydrochloric acid to dissolve it, place the reaction kettle in an oven, heat it to 180 °C, keep it warm for 12 h, cool it to room temperature and take it out. Use a dropper to suck the product solution into a centrifuge tube, centrifuge once, then add absolute ethanol and centrifuge 3 times, the rotation speed is 10000 r / min, 10 minutes each time. Pour out the absolute ethanol solution, put the centrifuge tube in an oven and dry it at 80 °C for 4 h to obtain the dry Cs 2 ZrCl 6 pure substance. Grind the prepared Cs 2 ZrCl 6 for 10 min.

[0060] (2) Mix the photosensitive resin, photoinitiator 819 and Cs 2 ZrCl 6 uniformly in the dark according to the formulation ratio. The mixing time is 10 minutes, and store it in the dark. This is the penetrable photocurable photosensitive resin material.

[0061] Curing process: Wrap the mixed penetrable photocurable photosensitive resin material with plastic film, place it under the X-ray source, the X-ray irradiation time is 1 min, and the X-ray irradiation is 40 KV and 30 mA.

[0062] Table 1 shows the curing quality of the samples prepared in Examples 1-3 and Comparative Examples 1-4 in 1 min

[0063]

[0064] As can be seen from Table 1, within the same curing time, the materials of Examples 1-3 all have a curing effect, and the curing efficiency is improved. Among them, the material prepared in Example 2 has the best curing effect.

[0065] It is known from Figure 2 that there is a large area overlap between the broadband blue light with an emission peak at 448 nm and the absorption band of IRGACURE 784. Therefore, the luminescence of Cs 2 ZrCl 6 can excite IRGACURE 784 to decompose into active free radicals, enabling the photosensitive resin to undergo a photocrosslinking reaction. 2 ZrCl 6

[0066] According to Figures 3 - 4 it can be known that using the method of Example 2 can successfully cure Pattern A and Pattern B.

[0067] According to Examples 1-3 and Comparative Examples 3-4, it can be seen that the amount of Cs 2 ZrCl 6 is crucial for the curing effect. When the amount of Cs 2 ZrCl 6 exceeds 10%, the penetrable photocurable photosensitive resin material has no curing effect within 1 minute.

[0068] Finally, it should be noted that the above preferred embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit. Although the present invention has been described in detail through the above preferred embodiments, those skilled in the art should understand that various changes can be made in terms of form and details without departing from the scope defined by the claims of the present invention.​

Claims

1. A transmissive light-curable photosensitive resin material, characterized in that: The invention comprises the following components in percentage by weight: 79%-99% of photosensitive resin, 5%-10% of Cs2ZrCl6 and 0%-1% of photoinitiator 784.

2. The transmissive light-curable photosensitive resin material according to claim 1, characterized in that: The transmissive light-curable photosensitive resin material comprises the following components in percentage by weight: 89% photosensitive resin, 10% Cs2ZrCl6 and 1% photoinitiator 784.

3. The transmissive light-curable photosensitive resin material according to claim 1, characterized in that: The photosensitive resin includes methyl methacrylate.

4. The method for preparing a transmissive light-curable photosensitive resin material according to any one of claims 1 to 3, characterized in that: include: (1) CsCl and Zr(CO3)2 are dissolved in hydrochloric acid, and then subjected to a hydrothermal reaction to obtain Cs2ZrCl6; (2) Mix the photosensitive resin, Cs2ZrCl6 and photoinitiator 784 evenly in the dark, and store in the dark to obtain a transmissive light-curable photosensitive resin material.

5. The method for preparing the transmissive light-curable photosensitive resin material according to claim 4, characterized in that: The molar ratio of CsCl and Zr(CO3)2 is 2:

1.

6. The method for preparing a transmissive light-curable photosensitive resin material according to claim 4, characterized in that: The temperature of the hydrothermal reaction is 180° C. and the time is 12 h.

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