CN108624061A - A kind of photo-curable silicone and its preparation method and application for 3D printing - Google Patents

Abstract

The invention discloses a photocurable silicone for 3D printing, a preparation method and application thereof. It is prepared from the following components in parts by mass: 100 parts of polysiloxane with vinyl groups in the side chain, 2 to 20 parts of small molecule crosslinking agents containing two or more mercapto groups, and 0.5 to 20 parts of photoinitiators 5 parts, surface-modified silica microspheres 0.08-0.17 parts, solvent 45-68 parts. The invention adopts the polysiloxane with vinyl group in the side chain and the mercapto group to quickly react and cure under the irradiation of ultraviolet light, and the curing time can reach within 3 s at normal temperature, there is no unpleasant smell after curing, the material performance is good, and the printing process does not need support The material has no solvent or a small amount of solvent in the preparation process, and the volume shrinkage rate is small; in addition, its preparation method is simple, and the product after photocuring has strong tear resistance and suitable hardness, which can meet the requirements of medical filling materials for 3D printing material with broad application prospects.

Description

A kind of photocurable silicone for 3D printing and its preparation method and application

technical field

The invention belongs to the technical field of 3D printing. More specifically, it relates to a photocurable silicone for 3D printing and its preparation method and application.

Background technique

3D printing technology, also known as additive manufacturing technology, is a technology that uses a computer to build a three-dimensional model of an object and uses it as a direct molding technology. Compared with the traditional forming technology, it does not require traditional tools, fixtures and multiple processing procedures, and can automatically and accurately manufacture parts of any complex shape through program control on one device, and greatly reduces the processing procedures. , Significantly shorten the development cycle of new products and reduce the cost of research and development. 3D printing technology has developed rapidly in recent years, and has developed more and more application directions in aviation, manufacturing, molds, education, medical care, food, etc. During the implementation of 3D printing, high temperature heating is not required, energy consumption is reduced, no special solvent is required, environmental pollution is reduced, UV curing is rapid, and production efficiency is greatly improved. The development of 3D printing materials is one of the three key technologies of 3D printing technology, and the material bottleneck has become the primary problem restricting the development of 3D printing. The main chain structure of silicone rubber is a polysiloxane structure, and its chemical properties are relatively stable. Its clinical use as a medical material has been widely recognized by the medical community. At present, many large companies have developed silicone rubber as a medical material. Use the scope as your own strategic goal. It has high temperature resistance, oxidation resistance, hydrophobicity, softness, permeability, aging resistance, high transparency, physiological inertia, non-adhesion with human tissue and blood, good biological adaptability, non-toxic, tasteless, and non-carcinogenic A series of excellent characteristics. Due to these characteristics of silicone rubber itself, polymethylsiloxane has become a typical silicone polymer material in medical polymer materials.

However, the curing time of silicone rubber is long, and its fluidity makes it impossible to maintain the accuracy of printing, so a support material is needed to complete the 3D printing of complex structures; in addition, the hydrophobicity and low surface free energy of silicone rubber, It limits its effective simultaneous printing with other materials; moreover, the existing silicone rubber will release an unpleasant smell during the printing process, so there are still big problems in the 3D printing of silicone rubber. Compared with the 3D printing of silicone rubber Difficult to achieve. At present, the technologies that can successfully realize silicone rubber 3D printing mainly include the following: (1) Hinton et al. invented a method for printing silicone rubber using a hydrophilic and hydrophobic carboxyvinyl polymer gel support material. After the two-component silicone rubber is mixed, it is printed by a 3D printer and cured at room temperature, and the 3D printing of silicone rubber is successfully realized. However, it needs support materials during the printing process, and the curing time is long, and after curing, it needs to be properly processed to remove the support materials, and the process is relatively cumbersome. (2) Chinese invention patent "A Preparation Method and Application of 3D Printed UV-cured Transparent Silicone Resin Composite Material" (Patent No. CN105331115A) discloses a 3D printed UV-cured transparent silicone resin composite material, the preparation of which The process is, firstly, use the organosilicon raw material with acryloyloxy group and alkoxysilane, under the action of a catalyst, prepare the organosilicon resin prepolymer with acryloyloxy group by gel sol method in a solvent; secondly, The organic silicon raw material with acryloyloxy group is added dropwise to white carbon black to obtain the reinforcing filler modified by acryloxy group; finally, the prepolymer, filler and photoinitiator are mixed and degassed to obtain a 3D Print UV-curable transparent silicone composites. The disadvantage of this method is that the raw material preparation process is complicated, the hardness is too high, and it is easy to break. (3) In addition, the Chinese invention patent "Preparation Method and Application of Silicon-Containing Nanogel Photocurable Resin for 3D Printing" (Patent No. CN106146754A) introduces a preparation method of silicon-containing nanogel photocurable resin for 3D printing and its application, the preparation process of this kind of material is to add modified silicone oil and acrylate monomer, chain transfer agent, free radical initiator and organic solvent into the reaction kettle, and purify the product after reaction to obtain silicon-containing nano-condensate Glue light curing resin. However, a large amount of organic solvent needs to be used in the raw material preparation process of this method, which does not meet the requirements of medical filling materials, and the product needs to be purified.

In order to promote the development of 3D printing technology, it is necessary to develop a certain fluidity and low viscosity at room temperature, fast curing speed, no unpleasant smell, good 3D printing glue effect, and small volume shrinkage after the material is formed. The process does not require support materials, and the product after photocuring has strong tear resistance, suitable hardness, and 3D printing materials that can meet the requirements of medical filling materials.

Contents of the invention

The technical problem to be solved by the present invention is to overcome the deficiencies of the above-mentioned prior art, and provide a light-cured silicone material for 3D printing, which has low viscosity, fast curing speed, no unpleasant smell, and 3D printing glue-out effect. Good, the volume shrinkage rate of the material after molding is small, the printing process does not require support materials, and the product after photocuring has strong tear resistance and appropriate hardness, which can meet the requirements of medical filling materials. 3D printing materials.

The object of the present invention is to provide a photocurable silicone material for 3D printing.

Another object of the present invention is to provide a method for preparing the above photocurable silicone material.

Another object of the present invention is to provide the application of the above-mentioned photocurable silicone material as or in the preparation of medical products.

The above object of the present invention is achieved through the following technical solutions:

A light-curable silicone for 3D printing, prepared from the following components in parts by mass: 100 parts of polysiloxane with vinyl groups in the side chain, small molecule cross-linked molecules with two or more mercapto groups 2-20 parts of joint agent, 0.5-5 parts of photoinitiator, 0.08-0.17 parts of surface-modified silica microspheres, and 45-68 parts of solvent.

Based on the formula of the present invention, scientifically determine the compatibility of polysiloxanes containing vinyl groups in side chains, small molecule crosslinking agents containing two or more mercapto groups, photoinitiators, surface-modified silica microspheres and solvent raw materials ratio, which significantly improves the curing speed of silicone rubber materials, and the curing time at room temperature is less than 3s, which greatly improves the processing efficiency of 3D printing equipment, and after curing, there is no unpleasant smell, low toxicity, low pollution, and high fluidity , high toughness, low shrinkage, and controllable dimensional accuracy of printed materials.

Preferably, the photocurable silicone used for 3D printing is prepared from the following components in parts by mass: 100 parts of polysiloxanes containing vinyl groups in their side chains, 100 parts of polysiloxanes containing two or more mercapto groups 3-10 parts of small molecule cross-linking agent, 0.8-1.3 parts of photoinitiator, 0.1-0.15 parts of surface-modified silica microspheres, and 50-62.5 parts of solvent.

More preferably, the photocurable silicone used for 3D printing is prepared from the following components in parts by mass: 100 parts of polysiloxanes containing vinyl groups in their side chains, containing two or more mercapto groups 3 parts of small molecule cross-linking agent, 1 part of photoinitiator, 0.125 parts of surface-modified silica microspheres, and 62.5 parts of solvent.

Preferably, the viscosity of the polysiloxane containing vinyl groups in the side chain is 500-50000 cst; the vinyl content is 0.6-1.5 mmol/g.

More preferably, the viscosity of the polysiloxane containing vinyl groups in the side chain is 500-10000 cst; its vinyl content is 0.8-1.2 mmol/g.

Preferably, the small molecule crosslinking agent containing two or more mercapto groups is selected from trimethylolpropane tris (2-mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate) , 1,4-butanediol bis(mercaptoacetate), 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol alcohol, 1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 2,2′-(1,2-ethylenedioxy)diethanethiol or ethyl dimercaptoacetate One or more mixtures of glycol esters; when used in combination, the mixing ratio is not strictly limited.

Preferably, the photoinitiator is a free radical photoinitiator.

More preferably, the photoinitiator is selected from benzoin dimethyl ether, benzoin ethyl ether, benzoin, isopropyl ether, benzoin butyl ether, diphenyl ethyl ketone, α, α-diethoxyacetophenone, α- One or more mixtures of hydroxyalkyl phenones or α-aminoalkyl phenones; when used in combination, the mixing ratio is not strictly limited.

In order to further increase the curing speed and remove the unpleasant gas, it is further preferred that the photoinitiator is benzoin dimethyl ether or diphenyl ethyl ketone.

Preferably, the surface-modified silica microspheres are prepared by the following method: adding silica nano-microspheres and a surface modifier into toluene, reacting at 60-110°C for 4-10 hours, cooling, and centrifuging , washing, and vacuum drying to obtain surface-modified silica microspheres; wherein, the mass-volume ratio of silica nano-microspheres to the surface modifier is 1:3-10.

Preferably, the particle size of the silica microspheres is 15-100 nm.

Preferably, the surface modifier is (3-mercaptopropyl)triethoxysilane and/or (3-mercaptopropyl)methyldiethoxysilane.

Preferably, the silicon dioxide nano-microspheres are ultrasonically dispersed in toluene for 30 minutes.

Preferably, the reaction condition is: react at 80° C. for 8 hours.

Preferably, the washing conditions are: washing with ethanol and water for 3-5 times.

The present invention also provides the preparation method of the photocurable silicone for 3D printing, comprising the following steps:

S1. Prepare surface-modified silica microspheres according to the above-mentioned method;

S2. Add a photoinitiator to the polysiloxane containing vinyl groups in the side chain, stir to dissolve it, and then add the surface-modified silica microspheres of step S1 and the polysiloxane containing two or more mercapto groups in proportion. The small molecule cross-linking agent and solvent are uniformly mixed, and the air bubbles are removed by vacuuming to obtain the photocurable silicone for 3D printing.

In the present invention, the solvent used is not particularly limited, preferably tetrahydrofuran, ethyl acetate and the like.

In addition, the application of the photocurable silicone used for 3D printing as a raw material for 3D printing, especially as or in the preparation of medical products, is also within the scope of protection.

The medical products refer to medical filling materials, including but not limited to heart stents, artificial blood vessels, etc.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention utilizes the polysiloxane containing vinyl groups in the side chain and the small molecule cross-linking agent containing two or more mercapto groups to quickly react and cure under ultraviolet light irradiation. Smell, good material performance, can be used as a 3D printing material; and this light-cured silicone rubber is used in 3D printing technology, the printing process does not require support materials, the material preparation process has no solvent or a small amount of solvent, and the volume shrinkage rate of the material after molding is small ; In addition, the preparation method is simple, and the product after photocuring has strong tear resistance and appropriate hardness, and can meet the requirements of medical filling materials for 3D printing materials. This 3D printing material with excellent comprehensive properties has broad application prospects.

Detailed ways

The present invention will be further described below in conjunction with specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.

Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

Example 1

1. A light-cured silicone for 3D printing, prepared by the following method:

(1) Preparation of surface-modified silica nanospheres

Take 2 g of silica nanospheres with a particle size of 15 nm prepared by the gas phase method, ultrasonically disperse them in a three-necked flask containing 150 mL of toluene, and ultrasonically disperse for 30 min; In an oil bath, heat to 80°C; measure 6mL of surface modifier (3-mercaptopropyl)triethoxysilane (MPES), put it into a constant pressure funnel, and add it dropwise to the reaction system, and the dropping time is about After the addition is completed, the reaction is continued for 4 hours. After the reaction is completed, it is cooled, centrifuged, washed with ethanol and water for 3 to 5 times, and vacuum-dried at 50° C. to obtain surface-modified silica nanospheres.

(2) Preparation of light-cured silicone rubber

Take 100 parts by mass of silicone oil containing vinyl in the side chain (viscosity is 500cst, vinyl content is 0.8mmol/g), add 1 part by mass of photoinitiator diphenyl ethyl ketone, stir to dissolve the photoinitiator, add the above-mentioned surface modification 0.125 parts by mass of silica nanospheres, and then add 3 parts by mass of small molecule cross-linking agent 2,2'-(1,2-ethylenediyldioxo)diethanethiol and 62.5 parts by mass of tetrahydrofuran, and mix well , and evacuated to remove air bubbles to obtain photocurable silicone for 3D printing.

2. The viscosity of the photocurable silicone prepared in this embodiment is about 150 cps. When used for 3D printing, it can be cured in 1.5s at room temperature, and there is no unpleasant smell during printing and after curing.

Example 2

1. A light-cured silicone for 3D printing, prepared by the following method:

(1) Preparation of surface-modified silica nanospheres

Take 2 g of silica nanospheres with a particle size of 15 nm prepared by the gas phase method, ultrasonically disperse them in a three-necked flask containing 150 mL of toluene, and ultrasonically disperse for 30 min; In an oil bath, heat to 80°C; measure 8mL of surface modifier (3-mercaptopropyl)triethoxysilane (MPES), put it into a constant pressure funnel, and drop it into the reaction system for about After the dropwise addition is completed, continue to react for 6 hours. After the reaction is completed, cool, centrifuge, wash with ethanol and water for 3 to 5 times, and dry in vacuum at 50°C to obtain surface-modified silica nanospheres.

(2) Preparation of light-cured silicone rubber

Take 100 parts by mass of silicone oil containing vinyl groups in the side chain (viscosity is 1000cst, vinyl content is 1.2mmol/g), add 0.8 parts by mass of photoinitiator benzoin dimethyl ether, stir to dissolve the photoinitiator, add the above surface modification 0.1 parts by mass of silica nanospheres, then add 3 parts by mass of small molecule cross-linking agent 2,2'-(1,2-ethylenedioxy) diethanethiol and 50 parts by mass of tetrahydrofuran, mix uniformly, And vacuumize to remove air bubbles to obtain photocurable silicone for 3D printing.

2. The viscosity of the photocurable silicone prepared in this embodiment is about 300 cps. When used for 3D printing, it can be cured in 2 seconds at room temperature, and there is no unpleasant smell during printing and after curing.

Example 3

1. A light-cured silicone for 3D printing, prepared by the following method:

(1) Preparation of surface-modified silica nanospheres

Take 3g of silica nanospheres with a particle size of 30nm prepared by the gas phase method, ultrasonically disperse them in a three-necked flask filled with 200 mL of toluene, and ultrasonically disperse for 30min; In an oil bath, heat to 80°C; Measure 10mL of surface modifier (3-mercaptopropyl) methyldiethoxysilane (MPES), put it into a constant pressure funnel, add it dropwise to the reaction system, add dropwise The time is about 30 minutes; after the dropwise addition is completed, the reaction is continued for 6 hours. After the reaction is completed, it is cooled, centrifuged, washed with ethanol and water for 3 to 5 times, and vacuum-dried at 50°C to obtain surface-modified silica nanospheres.

(2) Preparation of light-cured silicone rubber

Take 100 parts by mass of silicone oil containing vinyl groups in the side chain (viscosity is 5000cst, vinyl content is 0.6mmol/g), add 1.3 parts by mass of photoinitiator benzoin dimethyl ether, stir to dissolve the photoinitiator, add the above surface modification 0.15 parts by mass of silica nanospheres, then add 10 parts by mass of small molecule crosslinking agent 1,11-undecanedithiol and 50 parts by mass of tetrahydrofuran, mix uniformly, and vacuumize to remove air bubbles to obtain 3D printing light-curing silicone.

2. The viscosity of the photocurable silicone prepared in this embodiment is about 2000 cps. When used for 3D printing, it can be cured in 2 seconds at room temperature, and there is no unpleasant smell during printing and after curing.

Example 4

1. A light-cured silicone for 3D printing, prepared by the following method:

(1) Preparation of surface-modified silica nanospheres

Take 3 g of silica nanospheres with a particle size of 70 nm prepared by the gas phase method, ultrasonically disperse them in a three-necked flask containing 200 mL of toluene, and ultrasonically disperse for 30 min; In an oil bath, heat to 80°C; measure 18mL of surface modifier (3-mercaptopropyl) methyldiethoxysilane (MPES), put it into a constant pressure funnel, add dropwise to the reaction system, add dropwise The time is about 30 minutes; after the dropwise addition is completed, the reaction is continued for 6 hours. After the reaction is completed, it is cooled, centrifuged, washed with ethanol and water for 3 to 5 times, and vacuum-dried at 50°C to obtain surface-modified silica nanospheres.

(2) Preparation of light-cured silicone rubber

Take 100 parts by mass of silicone oil containing vinyl in the side chain (viscosity is 10000cst, vinyl content is 1.0mmol/g), add 0.5 parts by mass of photoinitiator benzoin dimethyl ether, stir to dissolve the photoinitiator, add the above surface modification 0.08 parts by mass of silica nanospheres, then add 2 parts by mass of small molecule cross-linking agent 1,11-undecanedithiol and 45 parts by mass of tetrahydrofuran, mix well, and vacuumize to remove air bubbles to obtain 3D printing light-curing silicone.

2. The viscosity of the photocurable silicone prepared in this embodiment is about 4000 cps. When used for 3D printing, it can be cured in 2 seconds at room temperature, and there is no unpleasant smell during printing and after curing.

Example 5

1. A light-cured silicone for 3D printing, prepared by the following method:

(1) Preparation of surface-modified silica nanospheres

Take 3 g of silica nanospheres with a particle size of 100 nm prepared by the gas phase method, ultrasonically disperse them in a three-necked flask containing 200 mL of toluene, and ultrasonically disperse for 30 min; In an oil bath, heat to 80°C; measure 30mL of surface modifier (3-mercaptopropyl) methyldiethoxysilane (MPES), put it into a constant pressure funnel, add dropwise to the reaction system, add dropwise The time is about 30 minutes; after the dropwise addition is completed, the reaction is continued for 6 hours. After the reaction is completed, it is cooled, centrifuged, washed with ethanol and water for 3 to 5 times, and vacuum-dried at 50°C to obtain surface-modified silica nanospheres.

(2) Preparation of light-cured silicone rubber

Take 100 parts by mass of silicone oil containing vinyl in the side chain (viscosity is 50000cst, vinyl content is 1.0mmol/g), add 5 parts by mass of photoinitiator benzoin dimethyl ether, stir to dissolve the photoinitiator, add the above surface modification 0.17 parts by mass of silica nanospheres, then add 20 parts by mass of small molecule crosslinking agent 1,11-undecanedithiol and 68 parts by mass of tetrahydrofuran, mix evenly, and vacuumize to remove air bubbles to obtain 3D printing light-curing silicone.

2. The viscosity of the photocurable silicone prepared in this embodiment is about 10000 cps. When used for 3D printing, it can be cured in 1.5s at room temperature, and there is no unpleasant smell during printing and after curing.

Comparative example 1 does not add surface modified silica microspheres

The method used in this comparative example is the same as that used in Example 1, except that the surface-modified silica microspheres in step (1) are not prepared, and the surface-modified silica microspheres are not added in step (2).

Compared with the photocurable silicone 3D printing material prepared in Example 1, the tear strength of the object printed with the photocurable silicone 3D printing material prepared in this comparative example is significantly reduced, which cannot meet the needs of use.

Comparative example 2 adds unmodified silica microspheres

This comparative example is the same as the method used in Example 1, the only difference being that the surface-modified silica microspheres of the preparation step (1) are not carried out, and the unmodified silica microspheres (particles) are directly added in the step (2). 15 nm in diameter).

Compared with the photocurable silicone 3D printing material prepared in Example 1, the object printed with the photocurable silicone 3D printing material prepared in this comparative example has a lower tear strength than that without adding surface-modified silica The object of microsphere has been improved to some extent, but the degree of improvement is small, and it still cannot meet the needs of use.

Comparative Example 3 Change the ratio of materials

This comparative example provides a method for preparing photocurable silicone for 3D printing. The photocurable silicone for 3D printing is prepared from the following components in parts by mass: silicone oil with vinyl groups in the side chain 100 parts by mass, 40 parts by mass of small molecule cross-linking agent 2,2'-(1,2-ethylenedioxy) diethanethiol, 1 part by mass of photoinitiator, surface-modified silica microspheres 0.125 parts by mass, solvent 99.5 parts by mass; all the other steps and operations are consistent with Example 1.

The experimental results show that there is a small amount of sticky substance on the surface of the cured sample, which affects the use.

Comparative Example 4 Change the ratio of materials

This comparative example provides a method for preparing photocurable silicone for 3D printing. The photocurable silicone for 3D printing is prepared from the following components in parts by mass: silicone oil with vinyl groups in the side chain 100 parts by mass, 1 part by mass of small molecule cross-linking agent 2,2'-(1,2-ethylenedioxy) diethanethiol, 1 part by mass of photoinitiator, surface-modified silica microspheres 0.125 parts by mass, 64.5 parts by mass of solvent; all the other steps and operations are consistent with Example 1.

The experimental results showed that the sample was not fully cured, a large amount of vinyl polysiloxane did not participate in the reaction, and the size of the sample did not meet the requirements.

Experimental example 3D printing material product performance test results

Table 1 Performance data of photocurable silicone of the present invention

Note: The degree of curing of the sample obtained in Comparative Example 4 is too small to be tested for mechanical properties.

Claims (10)

1. a kind of photo-curable silicone for 3D printing, which is characterized in that by the component preparation including following mass fraction At：Side chain contains 100 parts of the polysiloxanes of vinyl, 2~20 parts of the small molecule crosslinking agent containing two or more sulfydryls, 0.5~5 part of photoinitiator, 0.08~0.17 part of surface modified silicon dioxide microballoon, 45~68 parts of solvent.

2. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that by including following mass parts Several components are prepared：Side chain contains 100 parts of the polysiloxanes of vinyl, the small molecule containing two or more sulfydryls 3~10 parts of crosslinking agent, 0.8~1.3 part of photoinitiator, 0.1~0.15 part of surface modified silicon dioxide microballoon, solvent 50~62.5 Part.

3. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the side chain contains second The viscosity of the polysiloxanes of alkenyl is 500~50000 cst；Its contents of ethylene is 0.6~1.5 mmol/g.

4. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that it is described containing there are two or two The small molecule crosslinking agent of a above sulfydryl is selected from trimethylolpropane tris（2- mercaptoacetates）, trimethylolpropane tris（3- mercaptos Base propionic ester）, 1,4- butanediols it is double（Mercaptoacetate）, 1,6- ethanthiols, pungent two mercaptan of 1,8-, two mercaptan of 1,9- nonyls, 1, Two mercaptan of the 10- last of the ten Heavenly stems, two mercaptan of 1,11- hendecanes, four（3- mercaptopropionic acids）Pentaerythritol ester, 2,2 '-（1,2- second diyl dioxygens Generation）One or more of double ethyl mercaptans or glycol dimercaptosuccinate mixture.

5. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the photoinitiator is certainly By fundamental mode photoinitiator.

6. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the surface is modified two Silicon oxide microsphere is prepared by the following method：Silicon dioxide nanosphere and surface modifier are added in toluene, in 60~ 110 DEG C of 4~10 h of reaction, cooling, centrifugation, washing, vacuum drying obtain surface modified silicon dioxide microballoon；Wherein, two The mass volume ratio of silica nanoparticle and surface modifier is 1:3~10.

7. the photo-curable silicone according to claim 6 for 3D printing, which is characterized in that the silica is micro- The grain size of ball is 15~100 nm；The surface modifier is（3- mercaptopropyis）Triethoxysilane and/or（3- sulfenyls third Base）Methyldiethoxysilane.

8. according to any photo-curable silicone for being used for 3D printing of claim 1~7, which is characterized in that by including following The method of step is prepared：

S1. surface modified silicon dioxide microballoon is prepared according to the method described in claim 6；

S2. contain to side chain in the polysiloxanes of vinyl and photoinitiator is added, stir to dissolve, then add successively in proportion Enter the surface modified silicon dioxide microballoon of step S1, small molecule crosslinking agent and solvent containing two or more sulfydryls, mixes It closes uniformly, vacuumizes removing bubble, obtain the photo-curable silicone for being used for 3D printing.

9. any photo-curable silicone for 3D printing of claim 1~7 is in terms of the raw material as 3D printing Using.

10. any photo-curable silicone for 3D printing of claim 1~7 as or in terms of preparing curable product Using.