阅读说明：本技术 一种光固化3d打印低收缩陶瓷浆料的制备方法 (A kind of preparation method of photocuring 3D printing low shrinking ceramic slurry ) 是由 周彬彬 钱文 杜晖 于 2019-07-31 设计创作，主要内容包括：本发明公开了一种光固化3D打印低收缩陶瓷浆料的制备方法,包括以下步骤：1)将阳离子型单体、阳离子型低聚物、自由基型单体、自由基型低聚物、阳离子型引发剂、自由基型引发剂、分散剂搅拌混合得到光敏树脂；2)将陶瓷粉体、无水乙醇、分散剂、自由基引发剂经球磨混合、烘干得到表面改性氧化锆粉体；3)将光敏树脂与表面改性氧化锆粉体球磨混合得到陶瓷浆料。本发明光敏树脂由阳离子体系和自由基体系组成,光敏树脂的收缩性明显变小,本发明所制备的浆料体积收缩率达到2％～5％。(The invention discloses a kind of preparation methods of photocuring 3D printing low shrinking ceramic slurry, comprising the following steps: 1) is stirred cationic monomer, cationic oligomer, free radical type monomer, free radical type oligomer, cationic initiators, free radical type initiator, dispersing agent to obtain photosensitive resin；2) ceramic powder, dehydrated alcohol, dispersing agent, radical initiator are obtained into surface modified zirconia powder through ball milling mixing, drying；3) photosensitive resin and surface modified zirconia powder ball milling mixing are obtained into ceramic slurry.Photosensitive resin of the present invention is made of cationic system and free radical system, and the shrinkage of photosensitive resin obviously becomes smaller, and slurry volume shrinking percentage prepared by the present invention reaches 2%~5%.)

1. a kind of preparation method of photocuring 3D printing low shrinking ceramic slurry, which comprises the following steps:

1) cationic monomer, cationic oligomer, free radical type monomer, free radical type oligomer, cationic are caused Agent, free radical type initiator, dispersing agent are stirred to obtain photosensitive resin；

2) by ceramic powder, dehydrated alcohol, dispersing agent, radical initiator through ball milling mixing, to obtain surface modified oxidized for drying Zirconium powder body；

3) photosensitive resin and surface modified zirconia powder ball milling mixing are obtained into ceramic slurry.

2. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Step 1) cationic monomer is selected from least one of triethylene glycol divinyl ether, dodecyl vinyl；It is described sun from Subtype oligomer is selected from least one of aliphatic epoxy resin, cycloaliphatic epoxy resin, modified epoxy.

3. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Step 1) free radical type monomer is selected from dipropylene glycol diacrylate, tripropylene glycol diacrylate, two hexanediyls At least one of ester；The free radical type oligomer is selected from epoxy acrylic resin, aliphatic polyurethane acrylic resin, virtue At least one of fragrant adoption urethane acrylate resin.

4. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Cationic initiators are selected from one of aryl diazonium salts, diaryl iodonium salt, triaryl sulfonium salts, iron arene complexes.

5. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Free radical type initiator is selected from one of acetophenone derivs, acylphosphine oxide, anthraquinone derivative.

6. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Dispersing agent is selected from least one of BYK-163, BYK-2008, PM1590, oleic acid in step 1) and step 2).

7. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Ceramic powder is nano zirconium oxide powder, and partial size is 0.9~2 μm.

8. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Cationic monomer: cationic oligomer: cationic initiators: the weight percent of dispersing agent be 80:20:0.5%~ 5%:0.05%~0.2%；The free radical type monomer: free radical type oligomer: free radical type initiator: the weight of dispersing agent Percentage is 90%:10%:0.5%~5%:0.05%~0.2%.

9. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that described Step 1) mixing speed is 1500r/min~2000r/min, time 1h.

10. the preparation method of photocuring 3D printing low shrinking ceramic slurry according to claim 1, which is characterized in that institute State step 2) ceramic powder: dehydrated alcohol: radical initiator: the weight percent of dispersing agent is 100%:100%:0.5% ~0.2%:0.05%~0.2%；Step 2) the ball milling mixing specifically: 1h is dispersed with 2000r/min~2500r/min, Then 1000r/min~1500r/min disperses 12h；Step 3) the ball milling mixing specifically: 350r/min~650r/min points Dissipate 20h.

Technical field

The present invention relates to ceramic slurry technical fields, and in particular to be a kind of photocuring 3D printing low shrinking ceramic slurry Preparation method.

Background technique

Zirconium oxide porcelain material is inorganic non-metallic material.It has high-melting-point, high rigidity, high-wearing feature, resistance to oxidation etc. excellent Point can be used as structural material, cutter material etc.；Occupy very important status in current Material Field.But it is hard for ceramic material The advantages of spending high abrasion is but also ceramic material is difficult to form or process device with complex shape, traditional forming method The easy ceramic part of shape can only be prepared, is unable to satisfy the requirement of today's society, therefore increases material manufacturing technology already It comes into being.

Photocuring technology have can straight forming go out the advantages of complicated shape ceramics, current photocuring technology is developed existing Shape, mainly photocuring slurry, the slurry system for influencing ceramic member comprehensive performance are made of photosensitive resin and ceramic powder, and The main reason for bright quick tree can shrink in solidification, this is influence 3D printing precision, while ceramic powder and resin are mixed After conjunction be easy sedimentation, slurry system it is unstable, equally will affect printing effect.

Therefore, how reducing the shrinking percentage of 3D printing ceramics and improving the stability of ceramic slurry is one urgently to be solved Problem.

Summary of the invention

In view of the above shortcomings, the purpose of the present invention is to provide a kind of photocuring 3D printing low shrinking ceramic slurries Preparation method, the advantage with lower shrinkage.

Technical solution of the present invention is summarized as follows:

A kind of preparation method of photocuring 3D printing low shrinking ceramic slurry, wherein the following steps are included:

1) by cationic monomer, cationic oligomer, free radical type monomer, free radical type oligomer, cationic Initiator, free radical type initiator, dispersing agent are stirred to obtain photosensitive resin；

2) ceramic powder, dehydrated alcohol, dispersing agent, radical initiator surface is obtained through ball milling mixing, drying to be modified Zirconium powder；

3) photosensitive resin and surface modified zirconia powder ball milling mixing are obtained into ceramic slurry.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the step 1) sun Ionic comonomer is selected from least one of triethylene glycol divinyl ether, dodecyl vinyl；The cationic is oligomeric Object is selected from least one of aliphatic epoxy resin, cycloaliphatic epoxy resin, modified epoxy.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the step 1) is certainly By fundamental mode monomer in dipropylene glycol diacrylate, tripropylene glycol diacrylate, two hexanediyl esters extremely Few one kind；The free radical type oligomer is selected from epoxy acrylic resin, aliphatic polyurethane acrylic resin, fragrant adoption ammonia At least one of ester acrylic resin.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the cationic Initiator is selected from one of aryl diazonium salts, diaryl iodonium salt, triaryl sulfonium salts, iron arene complexes.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the free radical type Initiator is selected from one of acetophenone derivs, acylphosphine oxide, anthraquinone derivative.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the step 1) and Dispersing agent is selected from least one of BYK-163, BYK-2008, PM1590, oleic acid in step 2).

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the ceramic powder For nano zirconium oxide powder, partial size is 0.9~2 μm.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the cationic Monomer: cationic oligomer: cationic initiators: the weight percent of dispersing agent is 80:20:0.5%~5%: 0.05%~0.2%；The free radical type monomer: free radical type oligomer: free radical type initiator: the weight percent of dispersing agent Than for 90%:10%:0.5%~5%:0.05 %~0.2%.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the step 1) is stirred Mixing speed is 1500r/min~2000r/min, time 1h.

Preferably, the preparation method of the photocuring 3D printing low shrinking ceramic slurry, wherein the step 2) pottery Porcelain powder: dehydrated alcohol: radical initiator: the weight percent of dispersing agent is 100%:100%:0.5%~0.2%: 0.05%~0.2%；Step 2) the ball milling mixing specifically: 1h is dispersed with 2000r/min~2500r/min, then 1000r/min~1500r/min disperses 12h；Step 3) the ball milling mixing specifically: 350r/min~650r/min dispersion 20h.Since nano zircite particle surface has great amount of hydroxy group (- OH), lead to the poor compatibility with photosensitive resin, it is heavy to be easy Drop, so to be modified processing to nano zircite.The slurry of processed nano zirconium oxide powder is added, 20 can be stored It, does not occur delamination.

The beneficial effects of the present invention are:

(1) photosensitive resin of the present invention is made of cationic system and free radical system, the common photosensitive tree of free radical system Rouge advantage is that curing reaction speed is fast, the disadvantage is that shrinking greatly, is influenced obviously by oxygen inhibition, cationic system photosensitive resin advantage is It shrinks small, is not influenced vulnerable to oxygen inhibition, the disadvantage is that curing reaction speed is slow, after two kinds of systems combine, the shrinkage of photosensitive resin Obviously become smaller, slurry volume shrinking percentage prepared by the present invention reaches 2%~5%.

(2) nano zircite is mixed with free radical type initiator, dispersing agent, dehydrated alcohol, by nano oxidized modified zirconia, The stability of slurry can be not only greatly improved, but also the ability that curing reaction occurs under ultraviolet light can be improved, Compensate for the slow defect of cationic system photosensitive resin curing rate.

(3) processed nano zircite is added by carrying out surface modification treatment to nano zircite particle in the present invention The slurry of powder is stored >=20 days, delamination does not occur.

Detailed description of the invention

Fig. 1 is the schematic diagram of the preparation method of photocuring 3D printing low shrinking ceramic slurry in the present invention.

Specific embodiment

The present invention will be further described in detail below with reference to the embodiments, to enable those skilled in the art referring to specification Text can be implemented accordingly.