CN104893267A - 3D (Three-Dimensional) printing material with mosquito-repelling sensitization effect as well as preparation method and application thereof - Google Patents
3D (Three-Dimensional) printing material with mosquito-repelling sensitization effect as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a 3D (Three-Dimensional) printing material with a mosquito-repelling light-sensitive effect as well as a preparation method and application thereof. The 3D printing material is prepared from the following components in parts by weight: 110-145 parts of PLA (Poly Lactic Acid), 10-20 parts of mosquito repellent, 2-10 parts of sensitization color-variable toner, 2-8 parts of light diffusant, 10-20 parts of cross-linking agent, 2-5 parts of coupling agent, 10-30 parts of sodium lignin sulfonate, 2-8 parts of nanometer antimicrobial and 0.1-0.5 part of auxiliary. According to the preparation method, the network structure of the material is greatly enhanced, the tenacity of the 3D printing product is enhanced, the degradation rate is high, the antibacterial effect is good, and the 3D printing material is light-sensitive and light-variable and has a favorable mosquito-repelling efficacy. Most importantly, the mint flavonoid extract, rosemary extract and the like in the mosquito repellent have a mosquito-repelling effect, and have synergetic effects with other components, so that the oxidation resistance, sterilization and anti-bacteria performance and network structure of the 3D printing material are improved, and the 3D printing material are high in interestingness and practicability and remarkable in significance.
Description
Technical field
The invention belongs to 3D and print field, be specifically related to a kind of 3D printing material and preparation method thereof and application.
Background technology
Along with the development that 3D printing technique makes rapid progress, the concept that 3D prints is known by the public gradually.FDM technology utilizes ABS, polycarbonate (PC), polyphenylsulfone (PPSF), PLA and other thermoplastic material are subject to adding the filament be hot extruded into as semi-melting state, by the mode be deposited on storehouse basis layer by layer, from the direct construction prototype of 3D CAD data.This technology is applied to plastotype usually, assembling, functional test and conceptual design.In addition, FDM technology can be applied to and draw a design and quick manufacture.
Poly(lactic acid) (PLA) is a kind of novel biodegradable material, use reproducible plant resources (as corn) the starch material that proposes make.Mechanical property and physicals good.Poly(lactic acid) is applicable to the various working method such as blowing, thermoplastic, easy to process, applies very extensive.Consistency and degradability good.In field of medicaments application also widely, as produced disposable infusion apparatus, exempt to tear type operating sutures etc. open, low molecular weight pdlla does medicament slow release packaging agent etc. to poly(lactic acid).
Along with development in science and technology and social progress, 3D printed product starts to be not limited only to industrial design, building, engineering and construction (AEC), automobile, aerospace, dentistry and medical industries, education, geographical information system(GIS), civil engineering work, the fields such as gun, also start to come into daily life, in order to make some living utensils or ornament, but the purposes that the shape that the application at present in life is still embodied in printed product is brought, and the Artistic Design etc. of its color and shape formation, very large space is also existed to the application and development that 3D prints, simultaneously in degradable rate, toughness and intensity all need to be further improved.
Summary of the invention
Goal of the invention: for prior art Problems existing, first technical problem to be solved by this invention is to provide the 3D printed material with mosquito repellent photosensitive effect.Second technical problem to be solved by this invention is that this has the preparation method of the 3D printed material of mosquito repellent photosensitive effect.There is described in 3rd technical problem to be solved by this invention is to provide the application of the 3D printed material of mosquito repellent photosensitive effect.
Technical scheme: for solving the problems of the technologies described above, the invention provides a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component and make: PLA110 ~ 145 part according to parts by weight; Anophelifuge 10 ~ 20 parts; Sensitization discoloration toner 2 ~ 10 parts; Light diffusing agent 2 ~ 8 parts; Linking agent 10 ~ 20 parts; Coupling agent 2 ~ 5 parts; Sodium lignosulfonate 10 ~ 30 parts; Nano antibacterial agent 2 ~ 8 parts; Auxiliary agent 0.1 ~ 0.5 part.
Preferably, described anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 2 ~ 4 parts; Lemongrass cream 2 ~ 4 parts; Mint flavone extract 3 ~ 6 parts; Rosemary extract 3 ~ 6 parts.
Preferably, described light diffusing agent is organosilicon light diffusing agent.
Preferably, described coupling agent is one or both the mixture in titanate coupling agent or silane coupling agent; Described linking agent is one or both the mixture in trimesic acid or methyl acetoacetate.
Preferably, described nano antibacterial agent is any one or the two or more mixture in nano titanium oxide, nano zine oxide or nanometer silver.
Preferably, described auxiliary agent comprises following component according to parts by weight and makes: 0.05 ~ 0.2 part, softening agent; Toughner 0.05 ~ 0.3 part.
Invention also provides for the above-mentioned preparation method with the 3D printed material of mosquito repellent photosensitive effect, comprise the steps:
1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting;
2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent;
3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even;
4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir;
5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.
Invention also provides the above-mentioned 3D printed material with mosquito repellent photosensitive effect and print the application had in the mosquito repellent ornament of microvoid structure.
Beneficial effect: the 3D printed material with mosquito repellent photosensitive effect provided by the invention, significantly enhances the network structure of material, and effectively improve the toughness of the 3D printed product made with this material, degradation rate is high, good anti-bacterial effect, what is more important, use the product that mosquito repellent type 3D printed material provided by the invention prints, on the basis with the basic function that moulding own and shape are brought, photosensitive on the one hand can variable color, namely under sunlight or ultraviolet irradiation change, produce the change of molecular structure and absorbing wavelength, thus colorific change or be reduced into original color, have excellent mosquito repellent function concurrently on the other hand, and while mosquito repellent, antibacterial, anti-inflammatory, the breeding of effective suppression worm's ovum, degree of cleaning are high, the most important thing is, Mint flavone extract in anophelifuge and rosemary extract etc. are while having mosquito-repelling function, also there is antioxygenation, the antioxidant property that further entirety significantly improves mosquito repellent type 3D printed material provided by the invention is worked in coordination with other components, bactericidal performance and network structure, add that overall composition works in coordination with diffusion effect good, make the present invention can be widely used in printing pendant driving mosquitos, Toy watch, footwear, ornament etc., be particularly useful for printing children, the accessories having mosquito repellent function concurrently of what old man carried with have microvoid structure, interesting practicality has concurrently, from 3D printed material aspect, the very big application development space expanded 3D and printed, meaning is remarkable.
Embodiment
Embodiment 1: a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component according to parts by weight and make: PLA110 part; Anophelifuge 10 parts; Sensitization discoloration toner 2 parts; Light diffusing agent 2 parts; Linking agent 10 parts; Coupling agent 2 parts; Sodium lignosulfonate 10 parts; Nano antibacterial agent 2 parts; Auxiliary agent 0.1 part.
Wherein anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 2 parts; Lemongrass cream 2 parts; Mint flavone extract 3 parts; Rosemary extract 3 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is titanate coupling agent.
Wherein linking agent is trimesic acid.
Wherein nano antibacterial agent is nano titanium oxide.
Wherein auxiliary agent comprises following component according to parts by weight and makes: 0.05 part, softening agent; Toughner 0.05 part.
Preparation method comprises the steps: 1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting; 2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent; 3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even; 4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir; 5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.After testing, the flexility of material reaches 81.5Mpa, notched Izod impact strength reaches 46.9MJ/m
2.
Embodiment 2: a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component according to parts by weight and make: PLA145 part; Anophelifuge 20 parts; Sensitization discoloration toner 10 parts; Light diffusing agent 8 parts; Linking agent 20 parts; Coupling agent 5 parts; Sodium lignosulfonate 30 parts; Nano antibacterial agent 8 parts; Auxiliary agent 0.5 part.
Wherein anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 4 parts; Lemongrass cream 4 parts; Mint flavone extract 6 parts; Rosemary extract 6 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is silane coupling agent.
Wherein linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is nano zine oxide.
Wherein auxiliary agent comprises following component according to parts by weight and makes: 0.2 part, softening agent; Toughner 0.3 part.
Preparation method comprises the steps: 1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting; 2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent; 3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even; 4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir; 5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.After testing, the flexility of material reaches 82Mpa, notched Izod impact strength reaches 47.7MJ/m
2.
Embodiment 3: a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component according to parts by weight and make: PLA130 part; Anophelifuge 15 parts; Sensitization discoloration toner 6 parts; Light diffusing agent 5 parts; Linking agent 15 parts; Coupling agent 3 parts; Sodium lignosulfonate 20 parts; Nano antibacterial agent 5 parts; Auxiliary agent 0.25 part.
Wherein anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 3 parts; Lemongrass cream 3 parts; Mint flavone extract 5 parts; Rosemary extract 4 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is the mixture of titanate coupling agent and silane coupling agent, and ratio is 2:3.
Wherein linking agent is mixture in trimesic acid and methyl acetoacetate, and ratio is 3:1.
Wherein nano antibacterial agent is nanometer silver.
Wherein auxiliary agent comprises following component according to parts by weight and makes: 0.1 part, softening agent; Toughner 0.15 part.
Preparation method comprises the steps: 1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting; 2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent; 3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even; 4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir; 5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.After testing, the flexility of material reaches 82.5Mpa, notched Izod impact strength reaches 48.3MJ/m
2.
Embodiment 4: a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component according to parts by weight and make: PLA125 part; Anophelifuge 14 parts; Sensitization discoloration toner 5 parts; Light diffusing agent 5 parts; Linking agent 12 parts; Coupling agent 3 parts; Sodium lignosulfonate 15 parts; Nano antibacterial agent 4 parts; Auxiliary agent 0.2 part.
Wherein anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 3 parts; Lemongrass cream 3 parts; Mint flavone extract 4 parts; Rosemary extract 4 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein coupling agent is titanate coupling agent.
Wherein linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is the mixture of nano titanium oxide, nano zine oxide and nanometer silver.
Wherein auxiliary agent comprises following component according to parts by weight and makes: 0.1 part, softening agent; Toughner 0.1 part.
Preparation method comprises the steps: 1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting; 2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent; 3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even; 4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir; 5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.After testing, the flexility of material reaches 79.8Mpa, notched Izod impact strength reaches 47.5MJ/m
2.
Embodiment 5: a kind of 3D printed material with mosquito repellent photosensitive effect, comprises following component according to parts by weight and make: PLA135 part; Anophelifuge 18 parts; Sensitization discoloration toner 8 parts; Light diffusing agent 6 parts; Linking agent 18 parts; Coupling agent 4 parts; Sodium lignosulfonate 18 parts; Nano antibacterial agent 6 parts; Auxiliary agent 0.3 part.
Wherein anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 4 parts; Lemongrass cream 4 parts; Mint flavone extract 5 parts; Rosemary extract 5 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is the mixture of titanate coupling agent and silane coupling agent.
Wherein linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is the mixture of nano titanium oxide and nanometer silver.
Wherein auxiliary agent comprises following component according to parts by weight and makes: 0.15 part, softening agent; Toughner 0.15 part.
Preparation method comprises the steps: 1) by the melting of PLA particle high-temperature, add linking agent and mix, grafting; 2) be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent; 3) by step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even; 4) then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir; 5) be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.After testing, the flexility of material reaches 81.6Mpa, notched Izod impact strength reaches 48.1MJ/m
2.
The 3D printed material of what above-described embodiment provided have mosquito repellent and sensitization discoloration effect is applied in and prints in mosquito repellent ornament, especially be applied in the ornament or apparatus printing and there is microvoid structure, as in apparatus of camping, gardens decoration or the mosquito repellent accessories carried with etc., have a wide range of applications market and significant Practical significance, can widely promote.
Above implementation column does not form restriction to the present invention, and relevant staff is in the scope not departing from the technology of the present invention thought, and the various change carried out and amendment, all drop in protection scope of the present invention.
Claims (8)
1. there is a 3D printed material for mosquito repellent photosensitive effect, it is characterized in that, comprise following component according to parts by weight and make: PLA110 ~ 145 part; Anophelifuge 10 ~ 20 parts; Sensitization discoloration toner 2 ~ 10 parts; Light diffusing agent 2 ~ 8 parts; Linking agent 10 ~ 20 parts; Coupling agent 2 ~ 5 parts; Sodium lignosulfonate 10 ~ 30 parts; Nano antibacterial agent 2 ~ 8 parts; Auxiliary agent 0.1 ~ 0.5 part.
2. the 3D printed material with mosquito repellent photosensitive effect according to claim 1, is characterized in that, described anophelifuge comprises following component according to parts by weight and makes: Root of Lindley Butterflybush extract 2 ~ 4 parts; Lemongrass cream 2 ~ 4 parts; Mint flavone extract 3 ~ 6 parts; Rosemary extract 3 ~ 6 parts.
3. the 3D printed material with mosquito repellent photosensitive effect according to claim 1, is characterized in that, described light diffusing agent is organosilicon light diffusing agent.
4. the 3D printed material with mosquito repellent photosensitive effect according to claim 1, is characterized in that, described coupling agent is one or both the mixture in titanate coupling agent or silane coupling agent; Described linking agent is one or both the mixture in trimesic acid or methyl acetoacetate.
5. the 3D printed material with mosquito repellent photosensitive effect according to claim 1, is characterized in that, described nano antibacterial agent is any one or two or more mixtures in nano titanium oxide, nano zine oxide or nanometer silver.
6. the 3D printed material with mosquito repellent photosensitive effect according to claim 1, is characterized in that, described auxiliary agent comprises following component according to parts by weight and makes: 0.05 ~ 0.2 part, softening agent; Toughner 0.05 ~ 0.3 part.
7. the preparation method with the 3D printed material of mosquito repellent photosensitive effect described in claim 1 ~ 6, is characterized in that comprising the steps:
By the melting of PLA particle high-temperature, add linking agent and mix, grafting;
Be cooled to 20 DEG C ~ 30 DEG C after stirring, put into forcing machine, heating, extrudes, and pulverizes and obtains the PLA powder preparing graft crosslinking agent;
By step 2) obtain by the PLA powder of corresponding parts by weight, sodium lignosulfonate, nano antibacterial agent, coupling agent and auxiliary agent, heating mixing and high-speed stirring even;
Then add the anophelifuge of corresponding parts by weight, continue mix and stir; Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue mix and stir;
Be cooled to 50 DEG C ~ 55 DEG C, put into forcing machine, add hot-extrudable, vacuum-drying, prepare target product.
8. the 3D printed material with mosquito repellent photosensitive effect described in claim 1 ~ 6 is printing the application had in the mosquito repellent ornament of microvoid structure.
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| CN201510287240.9A CN104893267B (en) | 2015-05-29 | 2015-05-29 | 3D printed material with anophelifuge photosensitive effect and preparation method and application |
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| CN201610196600.9A Division CN105733217A (en) | 2015-05-29 | 2015-05-29 | Preparation method of 3D printing material with photosensitive mosquito repelling effect |
| CN201610196882.2A Division CN105778448A (en) | 2015-05-29 | 2015-05-29 | Application of 3D printing material with light-sensitive mosquito-repellent effect |
| CN201610197367.6A Division CN105733218A (en) | 2015-05-29 | 2015-05-29 | 3D printing material with photosensitive mosquito repelling effect |
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| CN105778398A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with function of multiply trapping and killing insects and preparation method thereof |
| CN105778397A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | Multiple insect trapping and killing type 3D printing material easy in molding and preparation method thereof |
| CN105778395A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with function of trapping and killing insects and preparation method thereof |
| CN105778396A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with bacteriostatic function and preparation method thereof |
| CN105778399A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | Bacteriostatic 3D printing material easy in molding and preparation method thereof |
| CN105994391A (en) * | 2016-05-25 | 2016-10-12 | 江苏浩宇电子科技有限公司 | Insect trapping and killing 3D printed product with micropore structure and preparation method thereof |
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| CN107987495A (en) * | 2017-12-12 | 2018-05-04 | 成都育芽科技有限公司 | A kind of microcellular structure 3D printing lures insecticidal materials and preparation method thereof |
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| CN105778398A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with function of multiply trapping and killing insects and preparation method thereof |
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| CN105778395A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with function of trapping and killing insects and preparation method thereof |
| CN105778396A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | 3D printing material with bacteriostatic function and preparation method thereof |
| CN105778399A (en) * | 2016-05-20 | 2016-07-20 | 江苏浩宇电子科技有限公司 | Bacteriostatic 3D printing material easy in molding and preparation method thereof |
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| CN108546395A (en) * | 2018-04-04 | 2018-09-18 | 合肥永泰新型建材有限公司 | A kind of preparation process of nano zinc oxide modified Wood-plastic floor |
| CN112980211A (en) * | 2021-03-26 | 2021-06-18 | 衢州佛卡勒科技有限公司 | 3D printing material with antibacterial effect and preparation method thereof |
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