Light-curable 3D printing material, light-curable 3D printing gel product and preparation method of light-curable 3D printing gel product

Abstract

The invention provides a photocurable 3D printing material, a photocurable 3D printing gel product and a preparation method thereof, the photocurable 3D printing material comprises a polymerizable monomer, an ultraviolet light initiator and an imidazole ionic liquid without carbon-carbon double bonds, and a polymerization inhibitor or an ultraviolet light absorber is not added. The invention finds that the ionic liquid has a polymerization inhibition function for the first time, a polymerization inhibitor or an ultraviolet light absorber is not added into the photocurable 3D printing material, and the ionic liquid replaces the polymerization inhibitor and can also prevent implosion. In addition, the photocuring 3D printing gel product is good in transparency, can be applied to various occasions and has excellent conductivity, and a research thought is provided for manufacturing a high-precision conductive sensor.

Description

Technical Field

[0001] The present invention relates to the technical field of intelligent polymer materials, and more specifically to materials capable of photocuring 3D printing, photocuring 3D printing gel products and preparation methods thereof. Background Art

[0002] In 3D printing technology, the most important light-curing 3D printing technology is SLA (Stereo Lithography Apparatus), DLP (Digital Light Processing), and the CLIP (Continuous Liquid Interface Production) technology developed from it. Light-curing 3D printing is suitable for models or products with high printing precision, good surface quality, and fine details. Light-curing 3D printing is the most widely used 3D printing technology in the current industrial field. At present, the materials used in light-curing 3D printing are photosensitive resins, including epoxy resins, phenolic resins, acrylic resins, amino resins, polyethersulfone resins, fluorocarbon resins, bio-based resins and other types of photosensitive resins.

[0003] In the prior art, in order to prevent the sudden polymerization during the photocuring 3D process from affecting the printing accuracy, a certain amount of polymerization inhibitor is often added to the system to prevent the sudden polymerization during the printing process and improve the printing accuracy. However, the polymerization inhibitor is generally a dye containing color, and the printed sample will have different colors (for example, at present, oresin is a relatively effective polymerization inhibitor, which makes the sample appear yellow), which limits its application in some occasions where the sample needs to have good transparency.

[0004] In view of the problems and defects of the existing technology, the preparation of gradient materials with adjustable tribological properties needs further improvement and development. Summary of the invention

[0005] The present invention provides a material capable of photocuring 3D printing, a photocuring 3D printing gel product and a preparation method thereof. The specific technical scheme is as follows:

[0006] A material capable of photocuring 3D printing, comprising a polymerizable monomer, an ultraviolet light initiator and an imidazole ionic liquid without a carbon-carbon double bond, wherein no polymerization inhibitor or ultraviolet light absorber is added, and the imidazole ionic liquid serves as a polymerization inhibitor;

[0007] Further, the imidazole ionic liquid without carbon-carbon double bonds is 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate or 1-ethyl-3-methylimidazolium ethyl sulfate;

[0008] Further, the polymerizable monomer is acrylamide and / or acrylic acid;

[0009] Further, the polymerizable monomers are acrylamide and acrylic acid;

[0010] Further, polyethylene glycol diacrylate is also included;

[0011] Further, the polymerizable monomer is 50-80 parts, the ultraviolet light initiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts;

[0012] In addition, the present invention also provides a photocurable 3D printed gel product, which is obtained by printing the above-mentioned photocurable 3D printable material through a photocurable 3D printing method.

[0013] The present invention also provides a method for preparing a photocurable 3D printed gel product, comprising the following steps: mixing and dissolving various raw materials in water according to a proportion to obtain a mixed solution, introducing the mixed solution into a resin tank of a 3D printing device, performing 3D modeling using the software part of a photocurable 3D printer, and performing 3D printing after modeling to obtain a gel product.

[0014] Furthermore, the UV light exposure time is 6-10s for each layer of product printed.

[0015] Furthermore, the power of the ultraviolet light is 100-200 mW.

[0016] Due to the adoption of the above technical solution, the beneficial technical effects of the present invention are:

[0017] 1. The present invention first discovered that ionic liquids have an anti-polymerization function. The photocurable 3D printing material does not need to add an inhibitor or an ultraviolet light absorber. Ionic liquids can replace inhibitors and also prevent violent polymerization.

[0018] 2. The light-cured 3D printing gel product of the present invention has good transparency and can be used in various occasions;

[0019] 3. The photocurable 3D printed gel product of the present invention has excellent electrical conductivity, which provides a research idea for manufacturing high-precision conductive sensors. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a picture of the gel product prepared in Example 1;

[0021] Figure 2 This is a picture of the gel product prepared in Comparative Example 1.

[0022] Figure 3 This is a picture of the gel product prepared in Comparative Example 2. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] A material capable of photocuring 3D printing comprises a polymerizable monomer, an ultraviolet light initiator and an imidazole ionic liquid free of carbon-carbon double bonds, wherein no polymerization inhibitor or ultraviolet light absorber is added, and the imidazole ionic liquid serves as a polymerization inhibitor. The present invention does not add a polymerization inhibitor or an ultraviolet light absorber, and the ionic liquid replaces the polymerization inhibitor, which can also prevent violent polymerization, and the prepared product has good transparency. In addition, due to the addition of the ionic liquid, the prepared product has an intentional conductive property. The present invention solves the problem in the prior art that the addition of the polymerization inhibitor causes the product to have different colors.

[0025] The imidazole ionic liquids without carbon-carbon double bonds are 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate or 1-ethyl-3-methylimidazolium ethyl sulfate. If the imidazole ionic liquids contain carbon-carbon double bonds, the carbon-carbon double bonds will react with the double bonds of the polymerizable monomers, participate in the polymerization and affect the performance of the product.

[0026] The polymerizable monomers are acrylamide and / or acrylic acid. More preferably, the polymerizable monomers are acrylamide and acrylic acid.

[0027] In addition, materials that can be photocured for 3D printing also include polyethylene glycol diacrylate, which is a chain extender used for chain growth in 3D printing.

[0028] Calculated by weight, the polymerizable monomer is 50-80 parts, the ultraviolet light initiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts.

[0029] The preparation method of a photocurable 3D printed gel product comprises the following steps: mixing a polymerizable monomer, an ultraviolet light initiator and an imidazole ionic liquid without a carbon-carbon double bond in water according to a proportion to obtain a mixed solution, introducing the mixed solution into a resin tank of a 3D printing device, performing 3D modeling using the software part of a photocurable 3D printer, and performing 3D printing after modeling to obtain a gel product.

[0030] Furthermore, the UV light exposure time is 6-10s for each layer of product printed.

[0031] Furthermore, the power of the ultraviolet light is 100-200mW. Compared with the light-curing 3D printing in the prior art, the present invention adjusts the ultraviolet light irradiation time and the power of the ultraviolet light according to the actual preparation method of the light-curing 3D printing gel product, and the ultraviolet light irradiation time and the power of the ultraviolet light match the paper cup method, so that the curing effect of the gel product is optimal.

[0032] Example 1

[0033] Preparation method of light-cured 3D printed gel product

[0034] According to the proportion, 35 parts of acrylamide, 30 parts of acrylic acid, 0.2 parts of ultraviolet light initiator, 1 part of 1-butyl-3-methylimidazolium tetrafluoroborate and 4 parts of polyethylene glycol diacrylate are mixed and dissolved in 100 parts of water to obtain a mixed solution, and the mixed solution is introduced into a resin tank of a 3D printing device, and 3D modeling is performed using the software part of a light-curing 3D printer. After modeling, 3D printing is performed, and the ultraviolet light irradiation time for each printed layer of the product is controlled to be 8 seconds, and the power of the ultraviolet light is 150 mW to obtain a gel product.

[0035] Example 2

[0036] Preparation method of light-cured 3D printed gel product

[0037] According to the proportion, 50 parts of acrylamide, 0.1 parts of ultraviolet light initiator, 0.5 parts of 1,3-dimethylimidazole nitrate and 3 parts of polyethylene glycol diacrylate are mixed and dissolved in 100 parts of water to obtain a mixed solution, and the mixed solution is introduced into the resin tank of the 3D printing equipment, and 3D modeling is performed using the software part of the light-curing 3D printer. After modeling, 3D printing is performed, and the ultraviolet light irradiation time for each printed layer of the product is controlled to be 6 seconds, and the power of the ultraviolet light is 200 mW to obtain a gel product.

[0038] Example 3

[0039] Preparation method of light-cured 3D printed gel product

[0040] According to the proportion, 80 parts of acrylic acid, 0.3 parts of ultraviolet initiator, 2 parts of 1,3-dimethylimidazole nitrate and 6 parts of polyethylene glycol diacrylate are mixed and dissolved in 100 parts of water to obtain a mixed solution, and the mixed solution is introduced into the resin tank of the 3D printing equipment, and 3D modeling is performed using the software part of the light-curing 3D printer. After modeling, 3D printing is performed, and the ultraviolet light irradiation time for each printed layer of the product is controlled to be 10 seconds, and the power of the ultraviolet light is 100 mW to obtain a gel product.

[0041] Comparative Example 1

[0042] Compared with Example 1, 1-butyl-3-methylimidazolium tetrafluoroborate was not added, and the other steps were the same as those in Example 1.

[0043] Comparative Example 2

[0044] Compared with Example 1, 1-butyl-3-methylimidazolium tetrafluoroborate was not added, 0.1 parts of orisin inhibitor was added, and the other steps were the same as those in Example 1.

[0045] The products obtained in Example 1 and Comparative Examples 1-2 were observed for their appearance. The results are as follows: Figure 1-3 shown. Figure 1 The product has no other colors. Figure 2 The product implodes and Figure 2 The color of part A is yellow, and Figure 3 The color of the product B is yellow, which is due to the addition of the polymerization inhibitor, which makes the product appear yellow. In Comparative Example 1, the reaction was imploded, and the prepared product could not be used normally.

[0046] The products obtained in Examples 1-3 and Comparative Examples 1-2 were tested for electrical conductivity, and the test results are shown in Table 1 below.

[0047] Table 1 Conductivity test results of the products obtained in Examples 1-3 and Comparative Examples 1-2

[0048] resistance Example 1 180kΩ Example 2 212kΩ Example 3 120kΩ Comparative Example 1 5MΩ Comparative Example 2 3MΩ

[0049] It can be clearly seen from Table 1 above that the resistance values ​​of the products obtained in Examples 1-3 and Comparative Examples 1-2 are not of the same order of magnitude, and the resistance values ​​of the products obtained in Examples 1-3 are much smaller than those obtained in Comparative Examples 1-2, that is, the conductivity of the products in Examples 1-3 is better than that of the products obtained in Comparative Examples 1-2, which provides a research idea for manufacturing high-precision conductive sensors. In addition, the conductivity of the product is also related to the amount of the example liquid added, and the more the example liquid is added, the better the conductivity of the product.

[0050] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A material capable of photocuring 3D printing, characterized in that: The invention comprises a polymerizable monomer, an ultraviolet light initiator and an imidazole ionic liquid without a carbon-carbon double bond, wherein no polymerization inhibitor or ultraviolet light absorber is added.

2. A photocurable 3D printing material according to claim 1, characterized in that: The material that can be photocured for 3D printing consists of a polymerizable monomer, a UV photoinitiator and an imidazole ionic liquid that does not contain a carbon-carbon double bond.

3. The photocurable 3D printing material according to claim 1, characterized in that: The imidazolium ionic liquid without carbon-carbon double bonds is 1-butyl-3-methylimidazolium tetrafluoroborate, 1,3-dimethylimidazolium nitrate or 1-ethyl-3-methylimidazolium ethyl sulfate.

4. The photocurable 3D printing material according to claim 1, characterized in that: The polymerizable monomers are acrylamide and / or acrylic acid.

5. The photocurable 3D printing material according to claim 1, characterized in that: Also included are polyethylene glycol diacrylates.

6. The photocurable 3D printing material according to claim 5, characterized in that: Calculated by weight, the polymerizable monomer is 50-80 parts, the ultraviolet light initiator is 0.1-0.3 parts, the imidazole ionic liquid without carbon-carbon double bonds is 0.5-2 parts, and the polyethylene glycol diacrylate is 3-6 parts.

7. A light-cured 3D printed gel product, characterized in that: The photocurable 3D printable material according to any one of claims 1 to 6 is obtained by printing through a photocurable 3D printing method.

8. A method for preparing the light-cured 3D printed gel product according to claim 7, characterized in that: The following steps are involved: The raw materials are mixed and dissolved in water according to a certain proportion to obtain a mixed solution, which is then introduced into a resin tank of a 3D printing device. 3D modeling is performed using the software part of a light-curing 3D printer, and 3D printing is performed after modeling to obtain a gel product.

9. The method for preparing a light-cured 3D printed gel product according to claim 8, characterized in that: During 3D printing, the UV light exposure time is 6-10s for each layer of product printed.

10. The method for preparing a light-cured 3D printed gel product according to claim 8, characterized in that: During 3D printing, the power of UV light is 100-200mW.

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