阅读说明：本技术 3d打印感光聚合物组合物 (3D printing photopolymer composition ) 是由 张耀鹏 张雷 张长松 于 2019-10-15 设计创作，主要内容包括：本发明公开一种3D打印感光聚合物组合物,包括,丙烯酰基单体20-40份,丙烯酸酯10-40份,光引发剂0.4-8份,光稳定剂0.1-0.5份。本发明还公开了其制备方法,将丙烯酰基单体和光稳定剂放入反应釜,温度控制在30-50℃,通入氮气,预反应30-1h,再将丙烯酸酯和光引发剂投入S1反应釜中,搅拌1-3h。本发明可用于立体光刻(SLA)和数字光处理(DLP)的3D打印技术。本发明制备工艺简单,生成的产品强度高,稳定性好。(The invention discloses a 3D printing photosensitive polymer composition which comprises 20-40 parts of an acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of a photoinitiator and 0.1-0.5 part of a light stabilizer. The invention also discloses a preparation method thereof, which comprises the steps of placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, pre-reacting for 30-1h, then putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3 h. The invention can be used in the 3D printing technology of Stereolithography (SLA) and Digital Light Processing (DLP). The preparation method is simple in preparation process, and the prepared product is high in strength and good in stability.)

The 3D printing photopolymer composition is characterized by comprising the following raw materials in parts by weight:

20-40 parts of acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of photoinitiator and 0.1-0.5 part of light stabilizer.

2. The composition of claim 1, wherein the acryl monomer has a viscosity of 0.1 to 50 Pa-s.

3. The composition of claim 1 or 2, wherein the acryloyl monomer comprises: one or more of carboxyl acryloyl monomer, acid group acryloyl monomer, amine acryloyl monomer and hydroxyl acryloyl monomer.

4. The composition of claim 1, wherein the acrylate is one or more of tricyclodecane dimethanol diacrylate, 2-methyl-1, 3-propanediol diacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, propoxylated glycerol triacrylate, aliphatic acrylates, urethane acrylates, and epoxy acrylates.

5. The composition of claim 1, wherein the photoinitiator is one or more of 184D, 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the light stabilizer is benzotriazole.

6.3D printing photopolymer composition preparation method: the method is characterized by comprising the following steps:

s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;

s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.

7. The composition according to claim 1, characterized by 3D printing techniques useful for Stereolithography (SLA) and Digital Light Processing (DLP).

Technical Field

The invention belongs to the field of 3D printing consumable manufacturing, and particularly relates to a 3D printing photopolymer composition and a preparation method thereof.

Background

3D printing, one of the rapid prototyping technologies, is a technology for constructing an object by using an adhesive material such as powdered metal or plastic based on a digital model file and by printing layer by layer. 3D printing is typically achieved using digital technology material printers. The method is often used for manufacturing models in the fields of mold manufacturing, industrial design and the like, and is gradually used for directly manufacturing some products, and parts printed by the technology are already available. The technology has applications in jewelry, footwear, industrial design, construction, engineering and construction (AEC), automotive, aerospace, dental and medical industries, education, geographic information systems, civil engineering, firearms, and other fields.

The common printer used in daily life can print planar articles designed by a computer, the working principle of the 3D printer is basically the same as that of the common printer, only the printing materials are different, the printing materials of the common printer are ink and paper, the 3D printer is filled with different printing materials such as metal, ceramic, plastic, sand and the like, the printing materials are actual raw materials, after the printer is connected with the computer, the printing materials can be stacked layer by layer through computer control, and finally, a blueprint on the computer is changed into an actual object. Colloquially, a 3D printer is a device that can "print" out real 3D objects, such as printing a robot, printing a toy car, printing various models, even food, and so on. The generic name "printer" refers to the technical principle of a common printer, since the process of layered processing is very similar to inkjet printing. This printing technique is called a 3D stereoscopic printing technique.

There are many different techniques for 3D printing. They differ in the way the building components are built up in different layers, in the way the materials are available. Among these 3D printing techniques, photopolymerization techniques such as Stereolithography (SLA) and Digital Light Processing (DLP) generally use liquid to produce products through polymerization, and compared with other 3D printing techniques using solid materials such as powder and filament materials, the produced products have better intermolecular binding degree, higher precision and smoother surface.

In view of the need for photopolymerization technology and the deficiencies of existing 3D printing materials, there is a need to produce photopolymer compositions with better properties.

Disclosure of Invention

The invention aims to provide a photopolymer composition for 3D printing. The photosensitive resin has the advantages of high forming speed, simple preparation process, low viscosity and the like, and can be directly applied to 3D printing and manufacturing of products with complex structures.

The 3D printing photopolymer composition comprises the following raw materials in parts by weight:

20-40 parts of acryloyl monomer, 10-40 parts of acrylate, 0.4-8 parts of photoinitiator and 0.1-0.5 part of light stabilizer.

Preferably, the viscosity of the acryl monomer is 0.1 to 50 pas.

Preferably, the acryl monomer includes: one or more of carboxyl acryloyl monomer, acid group acryloyl monomer, amine acryloyl monomer and hydroxyl acryloyl monomer.

Preferably, the acrylate is one or more of tricyclodecane dimethanol diacrylate, 2-methyl-1, 3-propanediol diacrylate, 2-butyl-2-ethyl-1, 3-propanediol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, propoxylated glycerol triacrylate, aliphatic acrylates, urethane acrylates, and epoxy acrylates.

Preferably, the photoinitiator is one or more of 184D, 1-hydroxycyclohexyl phenyl ketone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and the light stabilizer is benzotriazole.

Preparation method of 3D printing photopolymer composition: the method comprises the following steps:

s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;

s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.

The 3D printing photopolymer composition prepared by the invention is used for 3D printing technologies of Stereolithography (SLA) and Digital Light Processing (DLP).

The invention has the beneficial effects that:

the polymer composition has excellent physical properties (high strength, high toughness, deformation resistance and stability), can greatly improve the performance characteristics of the existing 3D printing material, can replace and exceed similar imported products, and meanwhile, the preparation cost is greatly reduced, the reaction process is simple, safe and environment-friendly, and the polymer composition is very suitable for industrial mass production and has good economic benefit.

Detailed Description

The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.

Example 3D printing photopolymer composition preparation method below: the method is characterized by comprising the following steps:

s1, placing the acryloyl monomer and the light stabilizer into a reaction kettle, controlling the temperature at 30-50 ℃, introducing nitrogen, and pre-reacting for 30-1 h;

s2, putting the acrylate and the photoinitiator into an S1 reaction kettle, and stirring for 1-3h to prepare the 3D printing photopolymer composition.