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One-component epoxy resin modified photosensitive resin composition for 3D printing and preparation method thereof

An epoxy resin, 3D printing technology, applied in the direction of additive processing, etc., can solve the problems of high product brittleness, interlayer separation of 3D printed products, high shrinkage rate, and achieve good interlayer bonding force and heat resistance. Interfacial compatibility, the effect of improving the bonding force between layers

Active Publication Date: 2021-02-19
SOUTH CHINA INST OF COLLABORATIVE INNOVATION
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] However, the photosensitive resin materials currently on the market are mainly acrylates. By combining high molecular weight acrylate oligomers with low molecular weight acrylate diluents to form photocurable resins with low viscosity and good molding properties, but There are often problems of high brittleness and high shrinkage after molding, which greatly affects the printing accuracy and comprehensive performance of 3D printing devices
In order to improve the toughness of the photosensitive resin and reduce the shrinkage of the material, it is an effective way to effectively reduce the proportion of low molecular weight acrylate diluent in the photosensitive resin formulation, but it often leads to a higher viscosity of the photosensitive resin, which is not conducive to uncured The liquid photosensitive resin covers the cured resin layer. The photosensitive resin has poor 3D printing performance, which is not conducive to the improvement of the bonding force between layers during the printing process of 3D printing products.
[0004] The post-curing methods used after 3D printing are ultraviolet light and thermal radiation. Due to the limited penetration depth of ultraviolet light, post-curing with ultraviolet light is easy to cause uneven curing. Therefore, post-heat curing is a more common method. This is a post-processing method, but the low interlayer bonding force will lead to interlayer separation in the subsequent heating and curing process of the 3D printed molded product, which will directly lead to the scrapping of the product
In short, it is difficult to obtain a 3D printing photosensitive resin composition with ideal material toughness, interlayer bonding force and heat resistance by simply using acrylate and its reactive diluent

Method used

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  • One-component epoxy resin modified photosensitive resin composition for 3D printing and preparation method thereof
  • One-component epoxy resin modified photosensitive resin composition for 3D printing and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0038] (1) Preparation of copolymer BCP:

[0039] According to the total molar preferred ratio of 1,2-epoxy-4-vinylcyclohexane (UVR, Aladdin's reagent, the same below), glycidyl methacrylate (GMA, Aladdin's reagent, the same below) is 1: 3 Measure the two monomers. Put all the UVR into the reaction kettle, divide the GMA monomer into the G1 part that is added to the reaction kettle first and the G2 part that dissolves the initiator in a molar ratio of 1:1, and add 9% of the total mass of the two monomers to the initiator. Dissolve the dibenzoyl oxide initiator in G2 to obtain the mixed solution M, pass nitrogen gas, stir, and add the mixed solution M into the reaction kettle dropwise at a temperature of 45°C, and drop it in 30 to 60 minutes. The temperature was raised to 80° C. for 2 hours at a speed of 1 minute, and the copolymer BCP1 was obtained.

[0040] (2) Preparation of one-component epoxy resin:

[0041] At room temperature, 40 parts by mass of latent epoxy curing a...

Embodiment 2

[0049] (1) Preparation of copolymer BCP:

[0050] The two monomers should be measured according to the preferred total molar ratio of 1,2-epoxy-4-vinylcyclohexane (UVR molecular weight: 124.18) and glycidyl methacrylate (GMA molecular weight: 142.15). Put all the UVR into the reaction kettle, divide the GMA monomer into the G1 part that is added to the reaction kettle first and the G2 part that dissolves the initiator in a molar ratio of 3:2, and mix the total mass of the two monomers with 6% of the initiator. Dissolve the dibenzoyl oxide initiator in G2 to obtain the mixed solution M, pass in nitrogen gas, stir, and add the mixed solution M into the reaction kettle dropwise at 60°C, finish the dropwise addition in 30-60 minutes, then raise the temperature to 70°C for reaction 4h to obtain the copolymer BCP2.

[0051] (2) Preparation of one-component epoxy resin:

[0052] At room temperature, 70 parts by mass of 594 curing agent (Guangzhou Huayue Viscose Chemical Co., Ltd.) ...

Embodiment 3

[0060] (1) Preparation of copolymer BCP:

[0061] The preferred total molar ratio of 1,2-epoxy-4-vinylcyclohexane (UVR molecular weight: 124.18) and glycidyl methacrylate (GMA molecular weight: 142.15) is 6:5 to measure the two monomers. Put all the UVR into the reaction kettle, divide the GMA monomer into the G1 part that is added to the reaction kettle first and the G2 part that dissolves the initiator at a molar ratio of 6:5, and add 9% of the total mass of the two monomers to the initiator. Dissolve the dibenzoyl oxide initiator in G2 to obtain the mixed solution M, pass in nitrogen gas, and add the mixed solution M dropwise into the reaction kettle under stirring at 65°C. After 30-60 minutes, the dropwise addition is completed, and the temperature is raised to 85°C for 2 hours. The copolymer BCP3 is obtained.

[0062] (2) Preparation of one-component epoxy resin:

[0063] At room temperature, 70 parts by mass of 594 curing agent (Guangzhou Huayue Viscose Chemical Co., L...

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Abstract

The invention belongs to the technical field of photocuring 3D printing materials, and discloses a one-component epoxy resin modified photosensitive resin composition for 3D printing and a preparation method thereof. The resin composition of the present invention comprises the following components in mass percentage: 10-30% of one-component epoxy resin; 24-50% of bifunctional acrylate prepolymer; 10-30% of multifunctional acrylate monomer; reactive diluent 11-30%; photoinitiator 1.5-4%; the single-component epoxy resin is composed of liquid epoxy resin compound, copolymer whose side chain is epoxy group and latent epoxy curing agent. The present invention also provides a preparation method of the above resin composition. The resin composition of the present invention can be applied to the SLA and DLP technologies of 3D printing. After curing and molding, a light-cured molding product with good toughness, interlayer bonding force and heat resistance can be obtained. A defect where splitting occurs between printed layers.

Description

technical field [0001] The invention belongs to the technical field of photocurable 3D printing materials, in particular to a one-component epoxy resin modified photosensitive resin composition for 3D printing and a preparation method thereof. Background technique [0002] Photocuring molding is the earliest 3D printing molding technology, and it is also a relatively mature 3D printing technology. The working process is under computer control, and the ultraviolet laser beam scans the photosensitive resin in the raw material pool sequentially based on the profile data of each layered cross-section. In the area where the ultraviolet light passes, the photosensitive resin absorbs the light energy and undergoes photopolymerization and curing to form a thin cross-sectional layer. When one layer is cured, control the workbench to move a layer thickness height, the liquid resin is evenly spread on the previous layer of cured resin layer, repeat the above UV curing process, and so ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C08L63/00C08L33/14C08F220/32C08F222/16C08F220/18B33Y70/10
CPCB33Y70/00C08F220/32C08L63/00C08L2201/08C08L33/14C08F220/1812C08F220/18C08F222/104
Inventor 郑华德王永珍张明
Owner SOUTH CHINA INST OF COLLABORATIVE INNOVATION
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