Method for 3D printing single and composite light-responsive plastic parts and applications

Abstract

The application belongs to the technical field of 3D printing, and particularly relates to a method for 3D printing single and composite light-responsive plastic parts and application. The method for 3D printing single light-responsive plastic parts comprises the following steps: step S1, obtaining a 3D printing single light-responsive plastic part or a plastic part; in step S1, after obtaining the plastic part, the following sub-steps are further included: step A1, weighing plastic powder and fluorescent material, stirring and blending to obtain mixed powder; step A2, stirring the plastic part and the mixed powder; step A3, performing color fixing treatment on the plastic part; step A4, drying the plastic part to obtain a 3D printing single light-responsive plastic part. The application further provides a method for 3D printing composite light-responsive plastic parts. The 3D printing single and composite light-responsive plastic parts obtained by the application can be applied to various fields after printing, and meet the individual needs of people.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of 3D printing, and particularly relates to a method for 3D printing single and composite light response type plastic parts and application. BACKGROUND

[0002] In recent years, 3D printing technology has been paid more and more attention by relevant researchers at home and abroad, and breakthroughs and leap-forward development have been achieved in the core manufacturing technology in the fields of aerospace, energy, national defense, automobiles, biological medicine and the like. The element of 3D printing technology is to add or connect materials layer by layer in sequence in the whole product, and the design process of 3D printing is generally to model through a computer modeling software first, then to divide the three-dimensional model built into cross sections layer by layer, i.e. to slice, so as to guide the printer to print layer by layer. The advantage of 3D printing lies in that it can manufacture high-complexity geometric parts, the raw materials can be selected widely, the processing is convenient and fast, and the technology develops rapidly. Among them, selective laser sintering (SLS) is a kind of powder-based additive manufacturing, which adopts powder materials to form, and obtains printed parts through layer-by-layer sintering of the powder by a high-intensity laser. The SLS printed parts include hard plastic PA12, PP and flexible plastic TPU, TPA and the like, the flexible 3D printed plastic parts are suitable for the fields of shoe sole cushioning, automobile or bicycle seats, protective lining and the like, and the hard 3D printed plastic parts are suitable for the fields of automobile parts, medical devices and the like.

[0003] The building process of SLS printing divides the three-dimensional model of the part along the Z direction by slicing, sets the process parameters such as preheating temperature, scanning rate, scanning power, single layer thickness and the like, then spreads a layer of powder material on the workbench by a powder spreading roller, and the laser beam emitted by the laser is controlled by the computer according to the data of each cross section of the geometric body, and selectively scans the powder layer. In the area scanned by the laser, the powder at the junction is melted, and the powders are bonded to each other, and the part not irradiated by the laser still presents a loose state, which serves as the support for the work and the next layer of powder; after one layer of sintering is completed, the workbench is lowered by the height of one cross section layer, and the next layer of powder spreading and sintering is carried out, and the cycle is repeated to obtain the designed three-dimensional solid part.

[0004] Fluorescent materials can produce different fluorescent responses under the action of ultraviolet or visible light, can be applied to various fields, and can be combined with various products to meet people's demand for diversity and individualization of products. Related research progress shows that 3D printing technology can prepare products with fluorescent response. However, the products with fluorescent effect obtained by SLS printing technology are mostly applied to scientific and high-tech fields such as biological medicine, and lack of application in other fields, such as the field of civilian consumer goods, which cannot meet people's demand for diversity and individualization. SUMMARY

[0005] In order to overcome the defects of the prior art, the present application provides a method for 3D printing single and composite light-responsive plastic parts and application, which aims to make the printed light-responsive plastic parts applicable to various fields and meet the individual needs of people.

[0006] In order to achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A method for 3D printing single and composite light-responsive plastic parts, comprising the following steps:

[0008] Step S1, the printing material is weighed as the printing raw material, the printer is adjusted to the appropriate parameters for printing, and the excess powder on the surface of the printed material is cleaned to obtain a plastic part; when the printing material is plastic powder and fluorescent material, it needs to be weighed according to the mass ratio, stirred and blended in a mechanical stirrer, the mixed powder is used as the printing raw material, and after printing, a color fixing treatment is performed to obtain a 3D printed single light-responsive plastic part; when the printing material is plastic powder, a plastic part is obtained;

[0009] In step S1, after obtaining the plastic part, the following sub-steps are further included:

[0010] Step A1, the printed plastic part is weighed, plastic powder and fluorescent material are weighed according to the mass ratio according to the weight of the plastic part, and the mixed powder of plastic powder and fluorescent material is obtained by stirring and blending in a mechanical stirrer;

[0011] Step A2, the plastic part and the mixed powder of plastic powder and fluorescent material are stirred by a stirrer to obtain a preliminary 3D printed single light-responsive plastic part;

[0012] Step A3, the preliminary 3D printed single light-responsive plastic part is post-treated, an organic good solvent of plastic is selected, the organic good solvent is placed on the surface of the preliminary 3D printed single light-responsive plastic part by spraying or dipping, and a color fixing treatment is performed;

[0013] Step A4, the preliminary single light-responsive plastic part with the organic solvent is taken out and placed in a blast drying machine for sufficient drying to remove the organic solvent, and naturally cooled to room temperature to obtain a 3D printed single light-responsive plastic part.

[0014] Further, in step S1, the printer is a selective laser sintering 3D printer; the way to clean the excess powder on the surface of the printed material is to use a sandblasting machine to sandblast for 2-5 minutes; the mass ratio is plastic powder: fluorescent material = 100: (5-20); the stirring and blending time in the mechanical stirrer is 30-60 minutes;

[0015] In step A1, the mass ratio of the plastic part: plastic powder: fluorescent material is 50:(500-1000):(20-40); the blending time of the mechanical stirrer is 15-45 minutes;

[0016] In step A2, the stirring time of the stirrer is 30-60 minutes;

[0017] In step A3, the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide;

[0018] In step A4, the sufficient drying condition is a drying temperature of 50℃ and a drying time of 12-48 hours.

[0019] The application also provides a method for 3D printing a composite light response type plastic part, which is realized based on the above method for 3D printing a single light response type plastic part and comprises the following steps:

[0020] In step B1, the above 3D printed single light response type plastic part is treated with inorganic or organic fluorescent material, so that the treated plastic part has two or more fluorescent responses; and the plastic part with two or more fluorescent responses is subjected to a color fixing treatment.

[0021] In step B2, the plastic part with two or more fluorescent responses and organic solvent is taken out and placed in an air drying machine for sufficient drying, and then naturally cooled to room temperature to obtain a 3D printed composite light response type plastic part.

[0022] Further, in step B1, the treatment method of the inorganic fluorescent material is as follows: the 3D printed single light response type plastic part is weighed, plastic powder and fluorescent material are weighed according to the mass ratio, the plastic powder and the fluorescent material are blended and stirred in a mechanical stirrer to obtain a mixed powder of the plastic powder and the fluorescent material; the 3D printed single light response type plastic part and the mixed powder are stirred by a stirrer, so that the plastic part has two or more fluorescent responses; an organic good solvent of plastic is selected, and the organic good solvent is placed on the surface of the plastic part with two or more fluorescent responses by spraying or dipping, and subjected to a color fixing treatment.

[0023] Further, the inorganic fluorescent material is one of yellow-green luminescent powder, blue-green luminescent powder, sky blue luminescent powder, RYA029, RYA039, RYPO28, and RYB035-8.

[0024] Further, the mass ratio of the 3D printed single photoresponsive plastic part, plastic powder, and fluorescent material is 50:(500-1000):(20-40); the blending time of the mechanical stirrer is 15-45 minutes; the stirring time of the stirrer is 30-60 minutes; the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide.

[0025] Further, in step B1, the processing method of the organic fluorescent material is to select an organic good solvent of the plastic, uniformly mix the organic fluorescent material and the organic good solvent according to a proportion, to obtain a fluorescent solvent mixture; the fluorescent solvent mixture is placed on the surface of the 3D printed single photoresponsive plastic part by spraying or dipping, the organic fluorescent material in the fluorescent solvent mixture penetrates into the 3D printed single photoresponsive plastic part, so that the plastic part has two or more fluorescent responses; and the organic good solvent in the fluorescent solvent mixture realizes the color fixing treatment of the plastic part with two or more fluorescent responses.

[0026] Further, the organic fluorescent material is one of hydroxymethyl coumarin, Brilliant Ultra Violet 395, Brilliant Ultra Violet 661, and Brilliant Ultra Violet 563; the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; and the proportion is (1-10):100.

[0027] Further, in step B2, the sufficient drying condition is a drying temperature of 50°C and a drying time of 12-48 hours.

[0028] The application further provides a 3D printed single and composite photoresponsive plastic part, which is prepared by the above-mentioned method for 3D printing a single photoresponsive plastic part and the method for 3D printing a composite photoresponsive plastic part; and the 3D printed single and composite photoresponsive plastic part is applied to one or more of the fields of biomedicine, building construction, aerospace, road transportation, anti-counterfeiting identification, special textiles, and consumer products.

[0029] Advantages

[0030] 1. The method for 3D printing a single and composite photoresponsive plastic part according to the application can be applied to various fields after printing, and meets the individual needs of people.

[0031] 2. The 3D printed single light response type plastic product of the present application can exhibit good fluorescent response, and the fluorescent performance is more stable and durable, and the processing is convenient, and is widely applicable to the fields of life medicine, aerospace, civil consumer goods and the like;

[0032] 3. The 3D printed composite light response type plastic product of the present application can realize two or more fluorescent responses, and provides more personalized selection, and is applicable to more complex conditions. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 It is a method block diagram of a 3D printed single light response type plastic product;

[0034] Figure 2 It is a method block diagram of a 3D printed composite light response type plastic product;

[0035] Figure 3 It is a picture of hydroxymethyl coumarin under an optical microscope;

[0036] Figure 4 It is a picture of a thermoplastic polyurethane elastomer (TPU) product under irradiation of a 365nm ultraviolet lamp;

[0037] Figure 5 It is a picture of a 3D printed single light response type thermoplastic polyurethane elastomer (TPU) product under irradiation of a 365nm ultraviolet lamp;

[0038] Figure 6 It is a picture of blue-green night light powder under an optical microscope;

[0039] Figure 7 It is a picture of a 3D printed single light response type polyamide (PA) product in a dark environment;

[0040] Figure 8 It is a picture of fluorescent material Brilliant Ultra Violet 395 in a dimethyl sulfoxide and ethanol mixed solution in a dark environment;

[0041] Figure 9 It is a picture of a 3D printed composite light response type polyamide product in a dark environment;

[0042] Figure 10 It is a picture of a 3D printed composite light response type polyamide product under irradiation of an ultraviolet lamp;

[0043] Figure 11 It is a picture of a 3D printed composite light response type thermoplastic polyurethane elastomer product in a dark environment;

[0044] Figure 12A picture of a 3D printed composite photoresponsive thermoplastic polyurethane elastomer part under the irradiation of a 365 nm ultraviolet lamp. DETAILED DESCRIPTION

[0045] The present application is further illustrated by the following specific examples, which are intended to be illustrative only and are not intended to be limiting.

[0046] Example 1

[0047] A method for 3D printing a single photoresponsive plastic part, comprising the following steps:

[0048] Step S1, the plastic powder and the fluorescent material are weighed according to the mass ratio, and are blended in a mechanical stirrer to obtain a mixed powder of the plastic powder and the fluorescent material;

[0049] Step S2, the obtained mixed powder is used as a printing raw material, the printer is adjusted to appropriate parameters for printing, and after printing, the surface of the printed material is cleaned of excess powder and is subjected to a color fixing treatment to obtain a 3D printed single photoresponsive plastic part.

[0050] The 3D printed single photoresponsive plastic part obtained by the present example has a fluorescent response in the overall structure of the inside and outside. When the fluorescent material is an organic fluorescent material, the organic fluorescent material and the plastic polymer will react to form a covalent bond under the high temperature environment in the printing process, making the fluorescent performance more stable and persistent. The obtained 3D printed single photoresponsive plastic part is suitable for fields with higher service life requirements, such as biomedical, building construction, aerospace, road transportation, anti-counterfeiting identification, and special textile fields. When the fluorescent material is an inorganic fluorescent material, there is no chemical reaction between the inorganic fluorescent material and the plastic polymer during the blending and printing process. The inorganic fluorescent material exists in the form of filling in the voids inside the printed part. The obtained 3D printed single photoresponsive plastic part shows good fluorescent response in a dark environment, and has better universality and cost performance in the field of consumer goods.

[0051] Example 2

[0052] A method for 3D printing a single photoresponsive thermoplastic polyurethane elastomer part, comprising the following steps:

[0053] Step S1, the thermoplastic polyurethane elastomer (TPU) powder and the hydroxymethyl coumarin powder are placed in a mechanical stirrer and blended for 30 min at a mass ratio of 100:5 to obtain a mixed powder of hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU);

[0054] Step S2, take hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU) mixed powder as the raw material for selective laser sintering printing, adjust the selective laser sintering printer to the appropriate parameters for printing, in the sintering process, hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU) chemical reaction, make thermoplastic polyurethane elastomer (TPU) on the introduction of the fluorescent effect of chromophore group, clean the surface of the printed material after printing the excess powder, get a kind of 3D printing single light response type thermoplastic polyurethane elastomer product.

[0055] 3D printing single light response type thermoplastic polyurethane elastomer product fluorescence response analysis

[0056] Figure 3 The picture of hydroxymethyl coumarin under optical microscope; Figure 4 The picture of thermoplastic polyurethane elastomer (TPU) product under 365nm ultraviolet lamp irradiation; Figure 5 The picture of 3D printing single light response type thermoplastic polyurethane elastomer (TPU) product under 365nm ultraviolet lamp irradiation.

[0057] Through the method of the embodiment, hydroxymethyl coumarin is introduced into the thermoplastic polyurethane elastomer (TPU) product, and the obtained 3D printing single light response type thermoplastic polyurethane elastomer (TPU) product has single light response and presents blue-violet fluorescence under 365nm ultraviolet lamp irradiation.

[0058] Example 3

[0059] A method for 3D printing single light response type plastic product, comprising the following steps:

[0060] Step S1, taking plastic powder as the printing raw material, adjusting the printer to the appropriate parameters for printing, cleaning the surface of the printed material after printing the excess powder, obtaining a plastic product;

[0061] Step S2, weighing the printed plastic product, according to the weight of the plastic product, taking plastic powder and fluorescent material according to the mass ratio, blending in the mechanical stirrer, obtaining the mixed powder of plastic powder and fluorescent material;

[0062] Step S3, stirring the plastic product and the mixed powder through the stirrer, obtaining the preliminary 3D printing single light response type plastic product;

[0063] Step S4, post-processing the obtained preliminary 3D printing single light response type plastic product, selecting the organic good solvent of plastic, and placing the organic good solvent on the surface of the preliminary 3D printing single light response type plastic product by spraying or dipping, and performing color fixing treatment;

[0064] Step S5, the primary single light-responsive plastic product with organic solvent is taken out and placed in a forced air dryer to dry the organic solvent and cool naturally to room temperature to obtain a 3D printed single light-responsive plastic product.

[0065] The mixed powder of plastic powder and fluorescent material used in the embodiment can be recycled, the printing method saves materials, reduces costs, is environmentally friendly, efficient and convenient to process. The 3D printed single light-responsive plastic product obtained by the embodiment is suitable for consumer goods such as protective products such as helmets and gloves. For example, the current popular cycling movement, some cycling enthusiasts like to ride at night in groups. A unique 3D printed product with fluorescent response can be customized on the outside of the cycling helmet and the back of the glove according to the characteristics of the team. When riding at night, the distance between the cycling enthusiasts can be controlled to prevent accidents. In most outdoor activities, monitoring of ultraviolet light is also very important. Fluorescent wearable products with ultraviolet response can provide real-time feedback on the intensity of ultraviolet light during exercise.

[0066] Embodiment 4

[0067] A method for 3D printing a single light-responsive polyamide product, comprising the following steps:

[0068] Step S1, using polyamide (PA) powder as a printing raw material, adjusting a selective laser sintering printer to suitable parameters for printing, and cleaning the surface of the printed material after printing to remove excess powder, to obtain a polyamide (PA) product;

[0069] Step S2, weighing the mass of the obtained polyamide (PA) product to determine that the mass is 50 g, taking 1000 g of polyamide (PA) powder and 20 g of blue-green night light powder, and stirring and blending the polyamide (PA) powder and the blue-green night light powder in a mechanical stirrer for 30 min to obtain a mixed powder of polyamide (PA) powder and blue-green night light powder;

[0070] Step S3, stirring the mixed powder of polyamide (PA) powder and blue-green night light powder with the polyamide (PA) product by a stirrer for 60 min to make the mixed powder wrap and enter the pores of the polyamide (PA) product by mechanical action, and to make the polyamide (PA) have fluorescent response by physical adsorption and weak chemical bonding between the powders. The polyamide (PA) product is taken out and the surface floating powder is shaken off for use;

[0071] Step S4, select the organic good solvent dimethyl sulfoxide (DMSO) and ethanol of polyamide (PA), mix dimethyl sulfoxide (DMSO) and ethanol uniformly at room temperature according to the proportion of 5:1, obtain the organic solvent mixed solution for solidification, put the polyamide (PA) part into the mixed solution of dimethyl sulfoxide (DMSO) and ethanol and soak for 1 min, so that the micropores on the surface of the polyamide (PA) part are closed and smoothed, and the blue-green night light powder in the micropores is further fixed;

[0072] Step S5, take out the polyamide (PA) part treated by the organic solvent, drain and then put it into the air drying machine, adjust the temperature to 50℃, and dry for 24 h, so that the residual solvent is removed, take out and cool to room temperature naturally, and obtain a 3D printing single light response type polyamide (PA) part.

[0073] Fluorescence response analysis of 3D printing single light response type polyamide part

[0074] Figure 6 The picture of the blue-green night light powder under the optical microscope is shown in Figure 1. Figure 7 The picture of the 3D printing single light response type polyamide (PA) part in the dark environment is shown in Figure 2.

[0075] Through the method of the embodiment, the blue-green night light powder is introduced into the polyamide (PA) part, and the obtained 3D printing single light response type polyamide (PA) part has single light response and presents blue-green fluorescence in the dark environment.

[0076] Surface roughness analysis of polyamide part and 3D printing single light response type polyamide part

[0077] The surface roughness of the polyamide (PA) part and the 3D printing single light response type polyamide (PA) part is measured, and the surface roughness data is summarized in Table 1. It is found that the surface roughness of the 3D printing single light response type polyamide (PA) part is small. This is because the polyamide (PA) part is treated by color fixing, and the organic solvent mixed solution for color fixing makes the surface micropores of the 3D printing single light response type polyamide (PA) part closed and smoothed, so that the surface roughness of the 3D printing single light response type polyamide (PA) part is smaller.

[0078] Table 1 Surface roughness of PA part and 3D printing single light response type PA part

[0079]

[0080] Example 5

[0081] A method for 3D printing a composite light response type plastic part, comprising the following steps:

[0082] Step S1, the plastic powder and the fluorescent material are weighed according to the mass ratio, and are blended in a mechanical stirrer to obtain a mixed powder of the plastic powder and the fluorescent material;

[0083] Step S2, the obtained mixed powder is used as a printing raw material, a printer is adjusted to appropriate parameters for printing, and after printing, the surface of the printed material is cleaned of excess powder, and a color fixing treatment is performed to obtain a 3D printed single light response type plastic product;

[0084] Step S3, the 3D printed single light response type plastic product is treated with inorganic or organic fluorescent materials, so that the treated plastic product has two or more fluorescent responses, and the plastic product with two or more fluorescent responses is subjected to a color fixing treatment;

[0085] Step S4, the two or more fluorescent response plastic product with organic solvent is taken out and placed in a forced air drying machine for sufficient drying, and naturally cooled to room temperature to obtain a 3D printed composite light response type plastic product.

[0086] The 3D printed composite light response type plastic product obtained by the embodiment can realize two or more fluorescent responses, provide more personalized choices, and be suitable for more complex situations. By designing the material and processing method to realize multiple complex responses, such as special clothing, anti-counterfeit identification, etc. The 3D printed plastic product with fluorescent response can be combined with clothes as accessories, accessories or brand logos to realize anti-counterfeiting, color changing and other personalized needs. It can also be used as a warning and rescue sign to provide different light signal feedback for rescue during the day or at night. When going outdoors or in the wild, custom-made plastic and luminescent materials with good durability can be used as guide signs and road signs for long-term use. It can also be used in anti-counterfeiting products, such as high-end luxury products and other valuable products or other products that are easy to imitate, etc. The printed composite light response type product or part can prevent imitation, allowing consumers to more intuitively distinguish the authenticity of the product.

[0087] Example 6

[0088] A method for 3D printing of a composite light response type polyamide product, comprising the following steps:

[0089] Step S1, the polyamide (PA) powder and the yellow-green night light powder are placed in a mechanical stirrer at a mass ratio of 100:5 for 30 minutes to obtain a mixed powder of the yellow-green night light powder and the polyamide (PA);

[0090] Step S2, the yellow-green night light powder is mixed with the polyamide (PA) powder as the raw material for selective laser sintering printing, and the selective laser sintering printer is adjusted to the appropriate parameters for printing. During the sintering process, the yellow-green night light powder exists in the form of filling in the voids inside the polyamide (PA) part. After printing, the surface of the printed material is cleaned of excess powder, and a polyamide (PA) part with fluorescent response is obtained.

[0091] Step S3, select the organic good solvent dimethyl sulfoxide (DMSO) and ethanol of polyamide (PA), mix dimethyl sulfoxide (DMSO) and ethanol uniformly at room temperature according to the mass ratio of 5:1, obtain the organic solvent mixture for fixing, mix the polymer fluorescent material Brilliant Ultra Violet 395 with the organic solvent mixture according to the mass ratio of 3:100, fully stir to obtain the fluorescent organic mixture solution;

[0092] Step S4, put the polyamide (PA) part into the fluorescent organic mixture solution and soak for 60 seconds. The fluorescent material Brilliant Ultra Violet 395 is directly introduced into the surface and microporous structure of the polyamide (PA) part by immersion, and the fluorescent material Brilliant Ultra Violet 395 enters and coats the printed polyamide (PA) part through physical adsorption, so that it has fluorescent response. Through the dissolution effect of the organic solvent, the surface of the polyamide (PA) part is slightly dissolved to close the surface pores of the polyamide (PA) part, and the fixing process is completed;

[0093] Step S5, take out the polyamide (PA) part treated with organic solvent, drain, and put it into a forced air drying machine. Adjust the temperature to 50℃ and the time to 24h. Fully dry, remove residual solvent, take out and cool to room temperature naturally. A 3D printed composite light response type polyamide (PA) part is obtained.

[0094] Fluorescent response analysis of 3D printed composite light response type polyamide part

[0095] Figure 8 Picture of fluorescent material Brilliant Ultra Violet 395 in dimethyl sulfoxide and ethanol mixed solution in dark environment; Figure 9 Picture of 3D printed composite light response type polyamide part in dark environment; Figure 10 Picture of 3D printed composite light response type polyamide part under ultraviolet lamp irradiation.

[0096] By the method of the embodiment, the yellow-green luminescent powder and the polymer fluorescent material Brilliant UltraViolet 395 are introduced into a polyamide (PA) part, and a 3D printed composite light-responsive polyamide (PA) part with two light responses is obtained, which emits yellow-green fluorescence in a dark environment and emits purple fluorescence under ultraviolet light irradiation.

[0097] Example 7

[0098] A method for preparing a 3D printed composite light-responsive thermoplastic polyurethane elastomer part, comprising the following steps:

[0099] Step S1, thermoplastic polyurethane elastomer (TPU) powder and hydroxymethyl coumarin powder are placed in a mechanical stirrer at a mass ratio of 100:3 and stirred and blended for 30 min to obtain a hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU) mixed powder;

[0100] Step S2, the hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU) mixed powder is used as the raw material for selective laser sintering printing, and the selective laser sintering printer is adjusted to the appropriate parameters for printing. During the sintering process, the hydroxymethyl coumarin and thermoplastic polyurethane elastomer (TPU) undergo a chemical reaction, introducing a chromophore group with a fluorescent effect onto the thermoplastic polyurethane elastomer (TPU). After printing, the surface of the printed material is cleaned of excess powder to obtain a thermoplastic polyurethane elastomer (TPU) part with fluorescent response;

[0101] Step S3, the thermoplastic polyurethane elastomer (TPU) part with fluorescent response, thermoplastic polyurethane elastomer (TPU) powder, and blue-green luminescent powder are mixed at a mass ratio of 1:200:3. The mixed thermoplastic polyurethane elastomer (TPU) powder and blue-green luminescent powder are stirred and blended in a mechanical stirrer for 30 min to obtain a mixed powder of thermoplastic polyurethane elastomer (TPU) powder and blue-green luminescent powder;

[0102] Step S4, the mixed powder of thermoplastic polyurethane elastomer (TPU) powder and blue-green luminescent powder is stirred with the thermoplastic polyurethane elastomer (TPU) part by a stirrer for 60 min of tumbling, so that the mixed powder enters the pores of the thermoplastic polyurethane elastomer (TPU) part through mechanical action, and has fluorescent response through physical adsorption and weak chemical bonding. The thermoplastic polyurethane elastomer (TPU) part is removed and the surface loose powder is shaken off for use.

[0103] Step S5, select the organic good solvent dimethylacetamide (DMA) of thermoplastic polyurethane elastomer (TPU) and ethanol, mix dimethylacetamide (DMA) and ethanol uniformly at room temperature according to the proportion of 5:1, obtain the organic solvent mixed solution for solidification, put the thermoplastic polyurethane elastomer (TPU) into the mixed solution of dimethylacetamide (DMA) and ethanol and soak for 1 min, so that the micropores on the surface of the thermoplastic polyurethane elastomer (TPU) are closed and smoothed, and the blue-green night light powder in the micropores is further fixed;

[0104] Step S6, take out the thermoplastic polyurethane elastomer (TPU) treated by organic solvent, drain and then put it into the air drying machine, adjust the temperature to 50℃, and dry for 24h, so as to remove the residual solvent, take out and cool to room temperature, and obtain a 3D printing composite light response type thermoplastic polyurethane elastomer (TPU) part.

[0105] 3D printing composite light response type thermoplastic polyurethane elastomer part fluorescence response analysis

[0106] Figure 11 It is the picture of 3D printing composite light response type thermoplastic polyurethane elastomer part in dark environment. Figure 12 It is the picture of 3D printing composite light response type thermoplastic polyurethane elastomer part under 365nm ultraviolet lamp irradiation.

[0107] Through the method of the embodiment, hydroxymethyl coumarin and blue-green night light powder are introduced into the thermoplastic polyurethane elastomer (TPU) part, and the obtained 3D printing composite light response type thermoplastic polyurethane elastomer (TPU) part has two kinds of light response, presents blue-green fluorescence in dark environment, and presents blue-purple fluorescence under 365nm ultraviolet lamp irradiation.

Claims

1. A method of 3D printing a composite photoresponsive plastic article, the method comprising: It comprises the following steps: ​ Step S1, the printing material is weighed as a printing raw material, the printer is adjusted to the appropriate parameters for printing, and the surface of the printed material is cleaned after printing to remove excess powder, thereby obtaining a plastic part; when the printing material is plastic powder and fluorescent material, it needs to be weighed according to the mass ratio, stirred and blended in a mechanical stirrer, the mixed powder is used as the printing raw material, and after printing, the color fixing treatment is performed to obtain a 3D printed single light response type plastic part; when the printing material is plastic powder, a plastic part is obtained; In step S1, after obtaining the plastic part, the following substeps are further included: Step A1, the printed plastic part is weighed, plastic powder and fluorescent material are weighed according to the mass ratio based on the weight of the plastic part, and stirred and blended in a mechanical stirrer to obtain a mixed powder of plastic powder and fluorescent material; Step A2, the plastic part and the mixed powder of plastic powder and fluorescent material are stirred by a stirrer to obtain a preliminary 3D printed single light response type plastic part; Step A3, the preliminary 3D printed single light response type plastic part is post-processed, an organic good solvent for plastic is selected, the organic good solvent is placed on the surface of the preliminary 3D printed single light response type plastic part by spraying or dipping, and color fixing treatment is performed; Step A4, the preliminary single light response type plastic part with the organic solvent is taken out and dried in a forced air drying machine to remove the organic solvent, and then naturally cooled to room temperature to obtain a 3D printed single light response type plastic part; It further comprises the following steps: Step B1, the 3D printed single light response type plastic part is treated with inorganic or organic fluorescent material, so that the treated plastic part has two or more fluorescent responses, and the plastic part with two or more fluorescent responses is subjected to color fixing treatment; Step B2, the plastic part with two or more fluorescent responses and the organic solvent is taken out and dried in a forced air drying machine, and then naturally cooled to room temperature to obtain a 3D printed composite light response type plastic part; In step S1, the printer is a selective laser sintering 3D printer; the method for cleaning the surface of the printed material to remove excess powder is to use a sandblaster to sandblast for 2-5 minutes; the mass ratio is plastic powder: fluorescent material = 100: (5-20); the stirring and blending time in the mechanical stirrer is 30-60 minutes; In step A1, the mass ratio is plastic part: plastic powder: fluorescent material = 50: (500-1000): (20-40); the stirring and blending time in the mechanical stirrer is 15-45 minutes; In step A2, the stirring time of the stirrer is 30-60 minutes; In step A3, the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; In step A4, the sufficient drying conditions are a drying temperature of 50°C and a drying time of 12-48 hours; In step B1, the treatment method of the inorganic fluorescent material is weighing the 3D printed single light-responsive plastic part, taking the plastic powder and the fluorescent material according to the mass ratio, blending the plastic powder and the fluorescent material in a mechanical stirrer to obtain a mixed powder of the plastic powder and the fluorescent material; stirring the 3D printed single light-responsive plastic part and the mixed powder in a stirrer to make the plastic part have two or more fluorescent responses; selecting an organic good solvent of plastic, and placing the organic good solvent on the surface of the plastic part with two or more fluorescent responses by spraying or dipping to perform color fixing treatment; The inorganic fluorescent material is one of yellow-green luminescent powder, blue-green luminescent powder, sky blue luminescent powder, RYA029, RYA039, RYPO28, and RYB035-8. The mass ratio is 3D printed single light-responsive plastic part: plastic powder: fluorescent material = 50: (500-1000): (20-40); the blending time of the mechanical stirrer is 15-45 minutes; the stirring time of the stirrer is 30-60 minutes; the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; In step B1, the treatment method of the organic fluorescent material is selecting an organic good solvent of plastic, uniformly mixing the organic fluorescent material and the organic good solvent according to a proportion to obtain a fluorescent solvent mixture; placing the fluorescent solvent mixture on the surface of the 3D printed single light-responsive plastic part by spraying or dipping, so that the organic fluorescent material in the fluorescent solvent mixture penetrates into the 3D printed single light-responsive plastic part, making the plastic part have two or more fluorescent responses; and the organic good solvent in the fluorescent solvent mixture realizes color fixing treatment of the plastic part with two or more fluorescent responses. The organic fluorescent material is one of hydroxymethyl coumarin, Brilliant Ultra Violet 395, Brilliant Ultra Violet 661, and Brilliant Ultra Violet 563; the organic good solvent is two or more of ethanol, acetone, chloroform, dichloromethane, hexafluoroisopropanol, dimethylacetamide, N,N-dimethylformamide, and dimethyl sulfoxide; and the proportion is organic fluorescent material: organic good solvent = (1-10):

100.

2. The method of claim 1, wherein: In step B2, the sufficient drying condition is a drying temperature of 50℃ and a drying time of 12-48 hours.

3. Use of a 3D light-responsive plastic article, characterized in that: The light-responsive plastic part is prepared by the method of any one of claims 1-2; and the light-responsive plastic part is applied to one or more of the fields of biomedicine, building construction, aerospace, road transportation, anti-counterfeiting identification, special textiles, and consumer products.

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