阅读说明：本技术 基于dlp打印的3d打印材料及3d打印产品以及打印方法 (3D printing material based on DLP printing, 3D printing product and printing method ) 是由 朱岳 宫涛 程立惠 席晓华 郝亚暾 张国才 白绍敏 孙跃翔 翟一丁 于 2021-01-30 设计创作，主要内容包括：本发明人涉及一种基于DLP打印的3D打印材料及3D打印产品以及该产品的打印方法,属于3D打印技术领域,具体包括该3D打印材料包括基础物料A和功能性物料B的质量比为10:1-1:2；基础物料A和功能性物料B单独配制,且在打印时根据需要进行混合,配制时,在室温条件下,分别将低聚物、稀释剂加入烧杯中,边加热边搅拌直到液体混合均匀,温度控制在20-80℃,然后再将其移入三口烧瓶中,在温度控制在20-80℃,真空度为-0.02MPa-0.1MPa的条件下,继续搅拌,同时加入阻聚剂,并加入引发剂、颜料、抗菌剂,搅拌1-5h,得到该3D打印材料,本发明能够满足人们对不同部位有不同颜色、抗菌性能等个性化产品要求的需要,提高了3D打印光敏树脂的应用范围。(The invention relates to a 3D printing material based on DLP printing, a 3D printing product and a printing method of the product, belongs to the technical field of 3D printing, and particularly comprises that the 3D printing material comprises a base material A and a functional material B in a mass ratio of 10:1-1: 2; the base material A and the functional material B are independently prepared and are mixed according to needs during printing, when the base material A and the functional material B are prepared, oligomer and diluent are respectively added into a beaker under the condition of room temperature, the mixture is stirred while being heated until the liquid is uniformly mixed, the temperature is controlled to be 20-80 ℃, then the mixture is moved into a three-neck flask, the mixture is continuously stirred under the conditions that the temperature is controlled to be 20-80 ℃ and the vacuum degree is-0.02 MPa-0.1MPa, meanwhile, polymerization inhibitor is added, initiator, pigment and antibacterial agent are added, and the mixture is stirred for 1-5 hours, so that the 3D printing material is obtained.)

1. The utility model provides a 3D printing material based on DLP prints which characterized in that: the 3D printing material comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, the base material A is used as a base raw material of a product, and the functional material B is quantitatively added into the base material A according to the product performance requirement;

the base material A is prepared from the following components in parts by weight: 30-60 parts of oligomer, 40-70 parts of reactive diluent, 0.5-6 parts of photoinitiator, 0.05-0.5 part of polymerization inhibitor and 0.1-5 parts of pigment;

the functional material B is prepared from the following components in parts by weight: 30-65 parts of oligomer, 30-70 parts of reactive diluent, 0.5-5 parts of photoinitiator, 0.05-0.5 part of polymerization inhibitor, 0.1-5 parts of pigment and 0.001-0.5 part of antibacterial agent;

and (2) independently preparing the base material A and the functional material B, mixing the base material A and the functional material B according to needs during printing, adding the oligomer and the diluent into a beaker respectively at room temperature, heating and stirring until the liquid is uniformly mixed, controlling the temperature to be 20-80 ℃, then transferring the mixture into a three-neck flask, continuously stirring while controlling the temperature to be 20-80 ℃ and the vacuum degree to be-0.02 MPa-0.1MPa, adding a polymerization inhibitor, adding an initiator, a pigment and an antibacterial agent, and stirring for 1-5 hours to obtain the 3D printing material.

2. The DLP printing-based 3D printing material according to claim 1, wherein: the oligomer is composed of one or more of epoxy acrylate, aliphatic polyurethane acrylate, aromatic polyurethane acrylate, polyether acrylate, polyester acrylate or organic silicon oligomer.

3. The DLP printing-based 3D printing material according to claim 1, wherein: the active diluent is one or more of isobornyl methacrylate, cyclic trimethylolpropane methylal acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, 3, 5-trimethylcyclohexyl acrylate, glycidyl methacrylate and ditrimethylolpropane tetraacrylate.

4. The DLP printing-based 3D printing material according to claim 1, wherein: the photoinitiator is one or more of 1-hydroxy-cyclohexyl basic ketone, 2-hydroxy-2 methyl-p-hydroxyethyl ether phenyl acetone-1, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

5. The DLP printing-based 3D printing material according to claim 1, wherein: the polymerization inhibitor is hydroquinone or p-hydroxyanisole.

6. The DLP printing-based 3D printing material according to claim 1, wherein: the pigment is one or more of titanium dioxide, zinc oxide, pigment red PR171, pigment red PR37, Hansa yellow PY10 and light blue slurry PB 61.

7. The DLP printing-based 3D printing material according to claim 1, wherein: the antibacterial agent is a quaternary ammonium salt antibacterial agent or a nano silver antibacterial agent.

8. A 3D printed product DLP printed from the 3D printed material of any of claims 1 to 7, the 3D printed product having different interlayer colors and antibacterial properties, and having different hardness.

9. A method of printing a 3D printed product according to claim 8, wherein: the operation is carried out according to the following steps,

a. adding a prepared base material A into a resin tank of a DLP printer, introducing a 3dp format printing file, setting printing process parameters as first layer exposure time of 20-60 seconds, base exposure time of 3-15 seconds, outline exposure time of 0.5-3 seconds, first layer lifting distance of 2-9mm, first layer breathing time of 1-3 seconds, first layer settling time of 1-3 seconds, printing layer lifting distance of 2-7mm, printing layer breathing time of 1-3 seconds and printing layer settling time of 1-3 seconds, and starting printing according to process requirements;

b. after a certain number of layers are printed, the printer is suspended, the working table surface can automatically rise, the functional material B is added into the resin tank according to the requirements of the product on different colors, antibacterial properties and hardness of different parts, the stirring and the mixing are continued, and the steps are repeated in this way, so that the products with different colors and antibacterial properties among the layers are printed;

c. and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight until a target product is obtained.

Technical Field

The invention relates to a 3D printing material based on DLP printing, a 3D printing product and a printing method, and belongs to the technical field of 3D printing.

Background

3D printing is also called additive manufacturing, and is a novel manufacturing technology for stacking materials layer by layer to manufacture a solid object on the basis of a digital model. The 3D printing equipment can be used for processing the product in a personalized and customized special structure.

3D prints photocuring forming technique, and it is higher to print the precision, and printing time is shorter, and printing temperature is lower, therefore 3D prints photocuring forming technique and develops rapidly. The principle of the DLP (Digital Light Processing) rapid prototyping technology is to slice a three-dimensional model of an object into slices by using slice software, convert the three-dimensional object into a two-dimensional layer, then irradiate the slices with a Digital Light source to cure photosensitive resin layer by layer, and finally obtain a solid material by layer.

The 3D printing photocuring molding technology can be applied to the aspects of automobiles, medical appliances, daily electronic products, storable conceptual models, air pipe tests, rapid casting models and the like.

The raw material used by the DLP surface molding 3D printer is liquid photosensitive resin which is cured under illumination with a wavelength of 405 nm. The composition of the liquid photosensitive resin and the printing process together affect the performance of DLP printed products.

At present, DLP printing can only print products with single color, which can not meet the requirements of people for individuation requirements of different parts such as different colors, performance and the like, and limits the application of DLP printers.

Summary of the invention

In order to solve the technical problems in the prior art, the inventor provides a 3D printing material based on DLP printing, a 3D printing product and a printing method, which can meet the requirements of people on individualized products with different colors, antibacterial performance and the like at different parts, and improve the application range of 3D printing photosensitive resin.

In order to achieve the above object, the technical solution adopted by the present inventors is a 3D printing material based on DLP printing, which is characterized in that: the 3D printing material comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, the base material A is used as a base raw material of a product, the functional material B is quantitatively added into the base material A according to the product performance requirement, and the product performance is changed by changing the components and the dosage of the functional material B;

the base material A is prepared from the following components in parts by weight: 30-60 parts of oligomer, 40-70 parts of reactive diluent, 0.5-6 parts of photoinitiator, 0.05-0.5 part of polymerization inhibitor and 0.1-5 parts of pigment;

the functional material B is prepared from the following components in parts by weight: 30-65 parts of oligomer, 30-70 parts of reactive diluent, 0.5-5 parts of photoinitiator, 0.05-0.5 part of polymerization inhibitor, 0.1-5 parts of pigment and 0.001-0.5 part of antibacterial agent;

and (2) independently preparing the base material A and the functional material B, mixing the base material A and the functional material B according to needs during printing, adding the oligomer and the diluent into a beaker respectively at room temperature, heating and stirring until the liquid is uniformly mixed, controlling the temperature to be 20-80 ℃, then transferring the mixture into a three-neck flask, continuously stirring while controlling the temperature to be 20-80 ℃ and the vacuum degree to be-0.02 MPa-0.1MPa, adding a polymerization inhibitor, adding an initiator, a pigment and an antibacterial agent, and stirring for 1-5 hours to obtain the 3D printing material.

Preferably, the oligomer is one or more of epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyether acrylate, polyester acrylate or organic silicon oligomer.

Preferably, the reactive diluent is one or more of isobornyl methacrylate, cyclic trimethylolpropane formal acrylate, tripropylene glycol diacrylate, dipropylene glycol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, 3, 5-trimethylcyclohexyl acrylate, glycidyl methacrylate and trimethylolpropane diacrylate.

Preferably, the photoinitiator is one or more of 1-hydroxy-cyclohexbasically ketone, 2-hydroxy-2 methyl-p-hydroxyethyl ether phenyl acetone-1, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and bis (2,4, 6-trimethylbenzoyl) phosphine oxide.

Preferably, the polymerization inhibitor is hydroquinone or p-hydroxyanisole.

Preferably, the pigment is one or more of titanium dioxide, zinc oxide, pigment red PR171, pigment red PR37, Hansa yellow PY10 and pigment blue slurry PB 61.

Preferably, the antibacterial agent is a quaternary ammonium salt antibacterial agent or a nano silver antibacterial agent.

A 3D printed product having different interlayer colors and antibacterial properties, and having different hardness.

A printing method of 3D printing products is operated according to the following steps,

a. adding a prepared base material A into a resin tank of a DLP printer, introducing a 3dp format printing file, setting printing process parameters as first layer exposure time of 20-60 seconds, base exposure time of 3-15 seconds, outline exposure time of 0.5-3 seconds, first layer lifting distance of 2-9mm, first layer breathing time of 1-3 seconds, first layer settling time of 1-3 seconds, printing layer lifting distance of 2-7mm, printing layer breathing time of 1-3 seconds and printing layer settling time of 1-3 seconds, and starting printing according to process requirements;

b. after a certain number of layers are printed, the printer is suspended, the working table surface can automatically rise, the functional material B is added into the resin tank according to the requirements of the product on different colors, antibacterial properties and hardness of different parts, the stirring and the mixing are continued, and the steps are repeated in this way, so that the products with different colors and antibacterial properties among the layers are printed;

c. and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight until a target product is obtained.

Compared with the prior art, the invention has the following technical effects: the DLP printing product with different interlayer colors and antibacterial properties has the advantages of simple preparation method, easy operation and high yield. The DLP prints products with different interlayer colors and antibacterial properties, target products with different interlayer colors are printed, and the product is changed into multiple colors from a single color, so that the aesthetic value of the product is improved; meanwhile, the printed products also have different performances, such as different antibacterial properties or different hardness. The invention aims to explain the problems simply and clearly, and the main printing products are divided into two products with different colors and antibacterial properties, and are changed more, and new functional materials B are prepared and the printing process is adjusted. According to the invention, the problem that the consumable of the DLP equipment for 3D printing at present mainly depends on the high-price imported foreign 3D printing photosensitive resin is solved, the requirements of people on individuation requirements of different parts such as different colors, antibacterial performance and the like are met, and the application range of DLP printing is enlarged.

Drawings

FIG. 1 is a schematic representation of a prior art single color printed product.

Fig. 2 is a schematic diagram of a printed product according to a first embodiment of the invention.

Fig. 3 is a schematic diagram of the antibacterial performance of the printed product according to the first embodiment of the present invention.

Fig. 4 is a schematic diagram of a prior art single color printed product.

Fig. 5 is a schematic diagram of a printed product according to a third embodiment of the present invention.

Fig. 6 is a schematic diagram of the antibacterial performance of the bacteriostatic ring of the printed product in the third embodiment of the invention.

Detailed Description

In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the inventors and do not limit the inventors.

Example one

A3D printing material based on DLP printing comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, and the color, antibacterial property and hardness index of a 3D printing product are adjusted by adjusting the mixing ratio of the base material A to the functional material B.

Wherein, when preparing the base material A, respectively putting 100g of oligomer consisting of aliphatic urethane acrylate, 50g of aromatic urethane acrylate and 30g of epoxy acrylate and 20g of tripropylene glycol diacrylate, 20g of dipropylene glycol diacrylate, 25g of trimethylolpropane triacrylate, 100g of cyclotrimethylolpropane formal acrylate and 15g of 3 and 3, 5-trimethylcyclohexyl acrylate into a 500ml beaker, heating and stirring at 40 ℃ until the liquid is uniformly mixed, transferring the mixture into a three-necked flask, continuously stirring at 40 ℃ and certain vacuum condition of-0.06 MPa, adding 0.66g of polymerization inhibitor, and sequentially adding 5.6g of 1-hydroxy-cyclohexyl basic ketone, 1.85g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.65g of 2, 2.8g of yellow pigment and 0.2g of blue pigment, and stirring for 3.5h to obtain a base material A for DLP printing.

When preparing the functional material B, 60g of aliphatic urethane acrylate, 50g of aromatic urethane acrylate, 30g of oligomer consisting of epoxy acrylate and silicone oligomer, 10g of tripropylene glycol diacrylate, 10g of dipropylene glycol diacrylate, 20g of trimethylolpropane triacrylate, 80g of cyclotrimethylolpropane formal acrylate, 10g of 3,3, 5-trimethylcyclohexyl acrylate and 10g of pentaerythritol triacrylate are respectively put into a 500ml beaker and stirred while heating at 40 ℃ until the liquids are uniformly mixed, the beaker is transferred into a three-neck flask, the mixture is continuously stirred at 35 ℃ and-0.06 MPa, 0.36g of polymerization inhibitor is added, and 2.1g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.6g of 2 are sequentially added, and adding 0.6g of blue pigment and 0.5g of quaternary ammonium salt antibacterial agent into an initiator consisting of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and stirring for 3 hours to obtain a functional material B for DLP printing.

Adding a base material A250g into a resin tank of a DLP printer, introducing a 3dp format print file, setting printing process parameters as first layer exposure time of 45 seconds, base exposure time of 13 seconds, outline exposure time of 0.1 second, first layer lifting distance of 5mm, first layer breathing time of 2 seconds, first layer deposition time of 2 seconds, printing layer lifting distance of 4mm, printing layer breathing time of 1 second and printing layer deposition time of 1 second, and starting printing according to process requirements; after 125 layers are printed, the printer is paused, the working table surface can automatically rise, according to the requirements of the product on different colors of different parts, functional materials B50g are added into the resin tank, the mixture is stirred and mixed evenly, the printing is resumed by clicking, and the printing is carried out to 324 layers (the printing is finished); according to the designed printing scheme, products with different interlayer colors and antibacterial properties are printed by pausing and adjusting the colors; and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight to obtain the target product.

According to the process method, the tooth models with different interlayer colors are printed by pausing printing and changing material proportion, and the printed products are shown in figures 2 and 3. Compared with the prior art, such as the product shown in fig. 1, the test result of the first embodiment is as follows:

1) the density of the base A was 1.05g/cm³Viscosity 280.3 mPa.s.

2) The density of the functional material B is 1.06g/cm³Viscosity 289.2 mPa.s.

3) The bottom of the tooth model is green, the top of the tooth model is blue-green, the hardness of the bottom of the tooth model is 76D, and the hardness of the top of the tooth model is 85D.

4) The bottom of the tooth model has no antibacterial property and no antibacterial ring.

5) The top of the tooth model has antibacterial property, the diameter of the antibacterial ring is 9.6mm, and the national standard that the diameter of the antibacterial ring is more than 7mm is the antibacterial property is met.

Example two

A3D printing material based on DLP printing comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, and the color, antibacterial property and hardness index of a 3D printing product are adjusted by adjusting the mixing ratio of the base material A to the functional material B.

Wherein, when preparing the base material A, respectively putting 100g of polyether acrylate, 50g of oligomer consisting of aromatic urethane acrylate and 30g of polyester acrylate, 20g of isobornyl methacrylate, 20g of dipropylene glycol diacrylate, 25g of pentaerythritol triacrylate, 100g of cyclotrimethylolpropane formal acrylate and 15g of 3,3, 5-trimethylcyclohexyl acrylate as reactive diluents into a 500ml beaker, heating and stirring at 40 ℃ until the liquid is uniformly mixed, transferring the mixture into a three-neck flask, continuously stirring at 40 ℃ and a certain vacuum condition of-0.06 MPa, adding 0.66g of polymerization inhibitor, and sequentially adding 5.6g of 1-hydroxy-cyclohexyl ketone, 1.85g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide, 0.65g of initiator consisting of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide and 2.8g of yellow pigment under the condition of room temperature And 0.2g of blue pigment, and stirring for 3.5 hours to obtain a base material A for DLP printing.

When preparing the functional material B, 60g of aliphatic urethane acrylate, 50g of aromatic urethane acrylate, 30g of polyether acrylate and 10g of silicone oligomer, 10g of glycidyl methacrylate, 10g of dipropylene glycol diacrylate, 20g of trimethylolpropane triacrylate, 80g of trimethylolpropane diacrylate, 10g of 3,3, 5-trimethylcyclohexyl acrylate and 10g of pentaerythritol triacrylate are added into a 500ml beaker and stirred at 40 ℃ until the liquids are uniformly mixed, the beaker is transferred into a three-necked flask, the flask is continuously stirred at 35 ℃ and-0.06 MPa, 0.36g of polymerization inhibitor is added, and 2.1g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.6g of 2 are added in sequence, and adding 0.6g of blue pigment and 0.5g of quaternary ammonium salt antibacterial agent into an initiator consisting of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and stirring for 3 hours to obtain a functional material B for DLP printing.

Adding a base material A250g into a resin tank of a DLP printer, introducing a 3dp format print file, setting printing process parameters as first layer exposure time of 45 seconds, base exposure time of 13 seconds, outline exposure time of 0.1 second, first layer lifting distance of 5mm, first layer breathing time of 2 seconds, first layer deposition time of 2 seconds, printing layer lifting distance of 4mm, printing layer breathing time of 1 second and printing layer deposition time of 1 second, and starting printing according to process requirements; after 125 layers are printed, the printer is paused, the working table surface can automatically rise, according to the requirements of the product on different colors of different parts, functional materials B50g are added into the resin tank, the mixture is stirred and mixed evenly, the printing is resumed by clicking, and the printing is carried out to 324 layers (the printing is finished); according to the designed printing scheme, products with different interlayer colors and antibacterial properties are printed by pausing and adjusting the colors; and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight to obtain the target product.

According to the process method, the tooth models with different interlayer colors are printed by pausing printing and changing material proportion, and the test results are as follows:

1) the density of the base A was 1.03g/cm³Viscosity 281.1 mPa.s.

2) The density of the functional material B is 1.04g/cm³Viscosity 285.2 mPa.s.

3) The bottom of the tooth model is green, the top of the tooth model is blue-green, the hardness of the bottom of the tooth model is 73D, and the hardness of the top of the tooth model is 82D.

4) The bottom of the tooth model has no antibacterial property and no antibacterial ring.

5) The top of the tooth model has antibacterial property, the diameter of the antibacterial ring is 9.2mm, and the national standard that the diameter of the antibacterial ring is more than 7mm is the antibacterial property is met.

EXAMPLE III

A3D printing material based on DLP printing comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, and the color, antibacterial property and hardness index of a 3D printing product are adjusted by adjusting the mixing ratio of the base material A to the functional material B.

Wherein, when preparing the base material A, respectively putting 100g of oligomer consisting of aliphatic urethane acrylate, 50g of aromatic urethane acrylate and 30g of epoxy acrylate and 20g of tripropylene glycol diacrylate, 20g of dipropylene glycol diacrylate, 25g of trimethylolpropane triacrylate, 100g of cyclotrimethylolpropane formal acrylate and 15g of 3 and 3, 5-trimethylcyclohexyl acrylate into a 500ml beaker, heating and stirring at 40 ℃ until the liquid is uniformly mixed, transferring the mixture into a three-necked flask, continuously stirring at 40 ℃ and certain vacuum condition of-0.06 MPa, adding 0.66g of polymerization inhibitor, and sequentially adding 5.6g of 1-hydroxy-cyclohexyl basic ketone, 1.85g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.65g of 2, 2.8g of red pigment and 1.2g of yellow pigment by using an initiator consisting of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and stirring for 3.5 hours to obtain a base material A for DLP printing.

When preparing the functional material B, respectively putting 50g of aliphatic urethane acrylate, 50g of aromatic urethane acrylate, 30g of oligomer consisting of epoxy acrylate and 10g of organosilicon oligomer, 10g of tripropylene glycol diacrylate, 10g of dipropylene glycol diacrylate, 20g of trimethylolpropane triacrylate, 80g of cyclotrimethylolpropane formal acrylate, 10g of 3,3, 5-trimethylcyclohexyl acrylate and 10g of pentaerythritol triacrylate into a 500ml beaker, heating and stirring at 40 ℃ until the liquids are uniformly mixed, transferring the beaker into a three-neck flask, continuously stirring at 35 ℃ and-0.06 MPa, adding 0.36g of polymerization inhibitor, and sequentially adding 2.1g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.6g of 2, and adding 0.8g of blue pigment and 0.6g of quaternary ammonium salt antibacterial agent into an initiator consisting of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and stirring for 3 hours to obtain a functional material B for DLP printing.

Adding a base material A150g into a resin tank of a DLP printer, introducing a 3dp format print file, setting printing process parameters as first layer exposure time of 45 seconds, base exposure time of 13 seconds, outline exposure time of 0.1 second, first layer lifting distance of 5mm, first layer breathing time of 2 seconds, first layer settling time of 2 seconds, printing layer lifting distance of 4mm, printing layer breathing time of 1 second and printing layer settling time of 1 second, and starting printing according to process requirements; after printing 40 layers, pausing the printer, automatically lifting the working table top, adding a functional material B50g into the resin tank according to the requirements of the product on different colors of different parts, uniformly stirring and mixing, clicking to resume printing, and printing to 80 layers (printing is finished); according to the designed printing scheme, products with different interlayer colors and antibacterial properties are printed by pausing and adjusting the colors; and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight to obtain the target product.

According to the process method, the spline models with different interlayer colors are printed by pausing printing and changing material proportion, and the printed products are shown in fig. 5 and 6. Compared with the prior art such as the product shown in fig. 4, the test result of the second embodiment is as follows:

1) the density of the base A was 1.04g/cm³Viscosity of 278.5 mPa.s.

2) The density of the functional material B is 1.06g/cm³Viscosity 286.3 mPa.s.

3) The bottom of the spline model is red, the top is reddish brown, the hardness of the bottom of the model is 75D, and the hardness of the top of the tooth model is 85D.

4) The bottom of the sample band model has no antibacterial property and no antibacterial ring.

5) The top of the spline model has antibacterial property, the diameter of the antibacterial ring is 10.1mm, and the national standard with antibacterial property is obtained when the diameter of the antibacterial ring is more than 7 mm.

Example four

A3D printing material based on DLP printing comprises a base material A and a functional material B which are independently stored before use, wherein the mass ratio of the base material A to the functional material B is 10:1-1:2, and the color, antibacterial property and hardness index of a 3D printing product are adjusted by adjusting the mixing ratio of the base material A to the functional material B.

Wherein, when preparing the base material A, 100g of aliphatic urethane acrylate, 50g of aromatic urethane acrylate, 20g of polyester acrylate and 10g of epoxy acrylate are respectively put into a 500ml beaker together with 20g of tripropylene glycol diacrylate, 20g of dipropylene glycol diacrylate, 25g of trimethylolpropane triacrylate, 60g of isobornyl methacrylate, 20g of glycidyl methacrylate, 20g of cyclotrimethylolpropane formal acrylate and 15g of 3,3, 5-trimethylcyclohexyl acrylate to be stirred at 40 ℃ until the liquid is uniformly mixed, the liquid is transferred into a three-necked flask, the stirring is continued at 40 ℃ and under certain vacuum condition of-0.06 MPa, 0.66g of polymerization inhibitor is added, and 5.6g of 1-hydroxy-cyclohexyl ketone is sequentially added, 1.85g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.65g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide were used as an initiator, and 2.8g of red pigment and 1.2g of yellow pigment were stirred for 3.5 hours to obtain a DLP printing base material A.

When preparing the functional material B, respectively putting 50g of aliphatic urethane acrylate, 50g of aromatic urethane acrylate, 30g of oligomer consisting of epoxy acrylate and 10g of organosilicon oligomer, 10g of tripropylene glycol diacrylate, 10g of dipropylene glycol diacrylate, 20g of trimethylolpropane triacrylate, 80g of cyclotrimethylolpropane formal acrylate, 10g of 3,3, 5-trimethylcyclohexyl acrylate and 10g of pentaerythritol triacrylate into a 500ml beaker, heating and stirring at 40 ℃ until the liquids are uniformly mixed, transferring the beaker into a three-neck flask, continuously stirring at 35 ℃ and-0.06 MPa, adding 0.36g of polymerization inhibitor, and sequentially adding 2.1g of bis (2,4, 6-trimethylbenzoyl) phosphine oxide and 0.6g of 2, and adding 0.8g of blue pigment and 0.6g of quaternary ammonium salt antibacterial agent into an initiator consisting of 4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and stirring for 3 hours to obtain a functional material B for DLP printing.

Adding a base material A150g into a resin tank of a DLP printer, introducing a 3dp format print file, setting printing process parameters as first layer exposure time of 45 seconds, base exposure time of 13 seconds, outline exposure time of 0.1 second, first layer lifting distance of 5mm, first layer breathing time of 2 seconds, first layer settling time of 2 seconds, printing layer lifting distance of 4mm, printing layer breathing time of 1 second and printing layer settling time of 1 second, and starting printing according to process requirements; after printing 40 layers, pausing the printer, automatically lifting the working table top, adding a functional material B50g into the resin tank according to the requirements of the product on different colors of different parts, uniformly stirring and mixing, clicking to resume printing, and printing to 80 layers (printing is finished); according to the designed printing scheme, products with different interlayer colors and antibacterial properties are printed by pausing and adjusting the colors; and finally, carrying out post-treatment on the printed and formed product, soaking the product in absolute ethyl alcohol for 1 minute, cleaning the product for 2 times, and then curing the product for 1 day under sunlight to obtain the target product.

According to the process method, the spline models with different interlayer colors are printed by pausing printing and changing the material ratio, and the test results are as follows:

1) the density of the base A was 1.03g/cm³Viscosity 276.5 mPa.s.

2) The density of the functional material B is 1.06g/cm³Viscosity 287.3 mPa.s.

3) The bottom of the spline model is red, the top is reddish brown, the hardness of the bottom of the model is 74D, and the hardness of the top of the tooth model is 84D.

4) The bottom of the sample band model has no antibacterial property and no antibacterial ring.

5) The top of the spline model has antibacterial property, the diameter of the antibacterial ring is 9.8mm, and the national standard that the diameter of the antibacterial ring is more than 7mm is the antibacterial property is met.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, but rather as the description is intended to cover all modifications, equivalents, and improvements falling within the spirit and scope of the present invention.