WO2020228054A1

WO2020228054A1 - Photosensitive resin ceramic and stereolithography preparation method therefor

Info

Publication number: WO2020228054A1
Application number: PCT/CN2019/088295
Authority: WO
Inventors: 程艳玲; 张海南; 魏世宏; 黎可旭; 杨盛凯; 林华泰
Original assignee: 广东工业大学
Priority date: 2019-05-16
Filing date: 2019-05-24
Publication date: 2020-11-19
Also published as: CN110092873A

Abstract

The present invention relates to the technical field of 3D printing, and in particular, to a photosensitive resin ceramic and a stereolithography preparation method therefor. The present invention provides a stereolithography preparation method for a photosensitive resin ceramic. The method comprises the following steps: step 1: mixing vinyl polysilazane with a reactive diluent to obtain a mixed solution; step 2: adding a photoinitiator and a free radical scavenger to the mixed solution to obtain a ceramic precursor mixed solution; and step 3: performing stereolithography on the ceramic precursor mixed solution to obtain a photosensitive resin ceramic. The present invention also provides a photosensitive resin ceramic prepared by the preparation method. The present invention provides a photosensitive resin ceramic and a stereolithography preparation method therefor, which solves the technical problem of the low yield of ceramic in the existing preparation method.

Description

Photosensitive resin ceramic and preparation method of stereo light curing To

Technical field

The invention relates to the technical field of 3D printing, in particular to a photosensitive resin ceramic and a preparation method of stereo light curing thereof.

Background technique

Three-dimensional light curing molding technology is a method of additive manufacturing technology. It is an indirect additive manufacturing technology. The traditional light curing molding technology uses a dot-line-surface molding method, which uses laser to emit ultraviolet rays. Then, the lens is used to reflect the laser, and the molding can be achieved by changing the deflection angle of the lens. The molding efficiency is relatively low in this way. In order to improve the efficiency of the printer, the digital light processing printer came into being, which changed the traditional molding method and adopted directly. Surface molding, each layer is exposed by a single layer, so faster construction speed can be achieved. At present, there are two main ceramic light-curing three-dimensional molding methods, which are ceramic powder and resin mixed system and ceramic precursor solution mixed system. Compared with the former, the latter has the following advantages. The ceramic precursor solution mixing system has relatively low refractive index and reflectivity because there are no ceramic particles, which is relatively better for the molding effect. In addition, the ceramic precursor system can produce three Yuan or multiple mixtures.

Nowadays, most ceramic precursor solution systems mainly adopt polysiloxane system, but the yield of polysiloxane ceramics is low. Therefore, the low ceramic yield of existing preparation methods has become an urgent problem for those skilled in the art. technical problem. To

Summary of the invention

The invention provides a photosensitive resin ceramic and a three-dimensional light curing preparation method thereof, which solves the technical problem of low ceramic yield in the existing preparation method.

The invention provides a three-dimensional light curing molding preparation method of photosensitive resin ceramics, which comprises the following steps:

Step 1: Mix vinyl polysilazane and reactive diluent to obtain a mixed solution;

Step 2: Add a photoinitiator and a free radical scavenger to the mixed solution to obtain a ceramic precursor mixed solution;

Step 3: Light-curing and molding the ceramic precursor mixture solution to obtain photosensitive resin ceramics.

Preferably, the mass ratio of the vinyl polysilazane, reactive diluent, free radical scavenger and photoinitiator is (10-60): (10-50): (0.1-5): (0.2-10) .

Preferably, the vinyl polysilazane includes 1,3-divinyl-1,1,3,3-tetramethyldisilazane and/or mercapto-vinylsilazane.

Preferably, the reactive diluent is acrylate.

Preferably, the acrylate includes one or more of polyethylene glycol diacrylate, hexanediol diacrylate, and trimethylolpropane triacrylate.

Preferably, the mixing in step 1 specifically includes stirring and mixing; the stirring time is 15-40 min.

Preferably, the rotation speed of the stirring is 800-1000 rpm.

Preferably, the photoinitiator includes photoinitiator 184D, 1-hydroxycyclohexyl phenone, phenyl bis (2,4 ,6-trimethylbenzoyl)phosphine oxide, one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.

Preferably, the free radical scavenger is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene and/or tris[2.4 -Di-tert-butylphenyl] phosphite.

The invention also provides a photosensitive resin ceramic, which is prepared by the above-mentioned preparation method.

The present invention has the following beneficial effects:

(1) The present invention provides a new ceramic precursor light-curing molding solution system, which has a higher ceramic yield than the polysiloxane system.

(2) The present invention is different from the previous ceramic powder and resin mixing system. The ceramic precursor solution mixing system has no ceramic particles, which avoids the adverse effect of the powder on the slurry, saves it for a longer time in the dark, and improves the slurry The stability of the ceramic is relatively better for the molding effect. In addition, the ceramic precursor system can produce a ternary or multiple mixture after sintering.

Description of the drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art.

Fig. 1 is a side view of a first molded part of photosensitive resin ceramic prepared in Example 1 of the present invention;

2 is a side view of the second molded part of photosensitive resin ceramic prepared in Example 1 of the present invention;

3 is a cross-sectional view of the first molded part of the photosensitive resin ceramic prepared in Example 1 of the present invention;

4 is a cross-sectional view of the second molded piece of photosensitive resin ceramic prepared in Example 1 of the present invention.

Detailed ways

The embodiment of the present invention provides a photosensitive resin ceramic and a preparation method for stereo light curing thereof, which solves the technical problem of low ceramic yield in the existing preparation method.

The following will give a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some representative embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by ordinary technicians without creative work belong to the protection scope of the present invention.

Example 1

(1) Weigh 15 g of vinyl polysilazane, add 14.7 g of reactive diluent polyethylene glycol diacrylate, stir with a magnetic stirrer for 30 minutes at a predetermined speed of 800 rpm, and stir to obtain a light yellow mixed solution.

(2) Select 0.09g of antioxidant 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and select 0.147g of light Initiator phenyl bis (2 ,4 ,6-Trimethylbenzoyl)phosphine oxide, and 0.063g of photoinitiator 184D was selected. Add all of them to the mixed solution prepared in step (1), stir for 30 minutes at a predetermined 800 rpm with a magnetic stirrer, and obtain a ceramic precursor light-cured molding solution after uniform magnetic stirring. ;

(3) The ceramic precursor photocuring molding solution prepared above is used for UV light curing molding, and the morphology of the molded part is shown in Figure 1 and Figure 2. Figure 1 and Figure 2 are the side views of the molded part. It can be seen that the delamination is not obvious, the layers are tightly combined, and the molding effect is good; Figure 3 and Figure 4 are the cross-sectional views of the molded part, and the internal layering is not obvious. There is more obvious delamination at the edge, and the mechanical properties are better.

Example 2

(1) Weigh 18 g of vinyl polysilazane and 15.21 g of polyoxalic acid diacrylate and mix, stir with a magnetic stirrer for 30 minutes at a predetermined speed of 1000 rpm, and obtain a light yellow solution after uniform mixing.

(2) 0.24g phenyl bis(2,4 , 6-trimethylbenzoyl) phosphine oxide, and add 0.06g of photosensitizer 184D at the same time, and add all of it to the mixed solution prepared in step (1). The magnetic stirrer is scheduled to be 1000 rpm and stirred for 30 minutes. Obtain the ceramic precursor light curing molding solution.

(3) Finally, the precursor light-curing molding solution prepared in the above embodiment is provided to the light-curing printing device, and after printing to obtain a green embryo, the green embryo is degreased and sintered to obtain the desired ceramic structure. The precursor light-cured molding solution obtained by this embodiment has a long storage time, good molding effect, and high ceramic molding accuracy. The ceramic obtained after sintering has the same linear shrinkage rate in the three-dimensional direction, and the unsintered vinyl polysilazane The alkane accounts for 50% of the mass ratio, and about 49% of the mass remains after the firing is relatively unfired, indicating that the photosensitive resin ceramic prepared in the embodiment of the present invention has a higher yield.

In summary, the precursor light-curing molding solution given by the foregoing method has good stability, good fluidity, a long storage time, and good molding ability. It is used for light-curing molding technology. Good molding accuracy.

Those skilled in the art can make various modifications to the above content without departing from the spirit and scope of the present invention as determined by the claims. Therefore, the scope of the present invention is not limited to the above description, but is determined by the scope of the claims.

Claims

A method for preparing photosensitive resin ceramics by three-dimensional light curing, which is characterized in that it comprises the following steps:

Step 1: Mix vinyl polysilazane and reactive diluent to obtain a mixed solution;

Step 2: Add a photoinitiator and a free radical scavenger to the mixed solution to obtain a ceramic precursor mixed solution;

Step 3: Light-curing and molding the ceramic precursor mixture solution to obtain photosensitive resin ceramics.
The preparation method according to claim 1, wherein the mass ratio of the vinyl polysilazane, reactive diluent, free radical scavenger and photoinitiator is (10-60):(10-50): (0.1～5): (0.2～10). To
The preparation method according to claim 1, wherein the vinyl polysilazane comprises 1,3-divinyl-1,1,3,3-tetramethyldisilazane and/or Base-vinylsilazane. To
The preparation method according to claim 1, wherein the reactive diluent is acrylate.
The preparation method according to claim 4, wherein the acrylate comprises one or more of polyethylene glycol diacrylate, hexanediol diacrylate, and trimethylolpropane triacrylate. To
The preparation method according to claim 1, wherein the mixing in step 1 specifically includes stirring and mixing; the stirring time is 15-40 min. To
The preparation method according to claim 6, wherein the rotation speed of the stirring is 800-1000 rpm.
The preparation method according to claim 1, wherein the photoinitiator comprises photoinitiator 184D, 1-hydroxycyclohexyl phenone, phenyl bis (2,4 ,6-trimethylbenzoyl)phosphine oxide, one or more of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide.
The preparation method of claim 1, wherein the free radical scavenger is 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4- Hydroxybenzyl)benzene and/or tris[2.4-di-tert-butylphenyl]phosphite. To
A photosensitive resin ceramic characterized by being prepared by the preparation method according to any one of claims 1-9.