CN104893267B - 3D printed material with anophelifuge photosensitive effect and preparation method and application - Google Patents
3D printed material with anophelifuge photosensitive effect and preparation method and application Download PDFInfo
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Abstract
The invention discloses 3D printed material with anophelifuge photosensitive effect and preparation method and application, according to parts by weight, this 3D printed material includes that following components is made: PLA110～145 parts；Anophelifuge 10～20 parts；Sensitization discoloration toner 2～10 parts；Light diffusing agent 2～8 parts；Cross-linking agent 10～20 parts；Coupling agent 2～5 parts；Sodium lignin sulfonate 10～30 parts；Nano antibacterial agent 2～8 parts；Auxiliary agent 0.1～0.5 part.The present invention significantly enhances the network structure of material, is effectively improved the toughness of 3D printed product, and degradation rate is high, good anti-bacterial effect, photosensitive meeting variable color, has excellent mosquito repellent function concurrently；The most important thing is that the Mint flavone extract in anophelifuge and Herba Rosmarini Officinalis extract etc. are while having mosquito-repelling function, the antioxygenic property of the present invention, bactericidal performance and network structure is improve with other component synergism, interesting practicality is higher, and meaning is notable.
Description
Technical field
The invention belongs to 3D and print field, be specifically related to a kind of 3D printing material and preparation method and application.
Background technology
The development maked rapid progress along with 3D printing technique, the concept that 3D prints gradually is known by the public.FDM technology is to utilize ABS, polycarbonate (PC), polyphenylsulfone
(PPSF), PLA and the heated extruding of other thermoplastic become the filament of semi-molten state, by the mode being deposited on the basis of storehouse layer by layer, from 3D
CAD data direct construction prototype.This technology is commonly used to plastotype, assembling, functional test and conceptual design.Additionally, FDM technology can apply to draw a design and quickly manufacture.
Polylactic acid (PLA) is a kind of novel biodegradation material, and the starch material using reproducible plant resources (such as Semen Maydis) to be proposed is made.Mechanical performance and physical property are good.Polylactic acid is applicable to the various processing methods such as blowing, thermoplastic, easy to process, applies quite varied.The compatibility is good with degradability.Polylactic acid is applied the most widely at field of medicaments, and as produced disposable infusion apparatus, exempt to tear type operation suture thread etc. open, low molecular weight pdlla makees medicament slow release packaging agent etc..
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, Aero-Space, dentistry and medical industries, education, GIS-Geographic Information System, civil engineering, the fields such as gun, also begin to come into daily life, in order to make some living utensils or ornament, but the application in life is still embodied in the purposes that the shape of printed product is brought at present, and the Art Design etc. that its color and shape are formed, the application and development printing 3D there is also the biggest space, simultaneously in degradable rate, all need to be further improved in toughness and intensity.
Summary of the invention
Goal of the invention: the problem existed for prior art, first technical problem to be solved by this invention is to provide the 3D printed material with anophelifuge photosensitive effect.Second to be solved by this invention technical problem is that this has the preparation method of the 3D printed material of anophelifuge photosensitive effect.3rd technical problem to be solved by this invention has the application of 3D printed material of anophelifuge photosensitive effect described in being to provide.
Technical scheme: for solving above-mentioned technical problem, the invention provides a kind of 3D printed material with anophelifuge photosensitive effect, include that following components is made according to parts by weight: PLA110～145 parts；Anophelifuge 10～20 parts；Sensitization discoloration toner 2～10 parts；Light diffusing agent 2～8 parts；Cross-linking agent 10～20 parts；Coupling agent 2～5 parts；Sodium lignin sulfonate 10～30 parts；Nano antibacterial agent 2～8 parts；Auxiliary agent 0.1～0.5 part.
Preferably, according to parts by weight, described anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 2～4 parts；Herba Cymbopogonis Citrari cream 2～4 parts；Mint flavone extract 3～6 parts；Herba Rosmarini Officinalis extract 3～6 parts.
Preferably, described light diffusing agent is organosilicon light diffusing agent.
Preferably, one or both the mixture during described coupling agent is titanate coupling agent or silane coupler；Described cross-linking agent is one or both the mixture in trimesic acid or methyl acetoacetate.
Preferably, any one or the two or more mixture during described nano antibacterial agent is nano titanium oxide, nano zine oxide or nanometer silver.
Preferably, according to parts by weight, described auxiliary agent includes that following components is made: plasticizer 0.05～0.2 part；Toughener 0.05～0.3 part.
Invention also provides the preparation method for the above-mentioned 3D printed material with anophelifuge photosensitive effect, comprise the steps:
1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；
2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；
3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；
4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；
5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.
Invention also provides the application in printing the anophelifuge ornament with microcellular structure of the above-mentioned 3D printed material with anophelifuge photosensitive effect.
Beneficial effect: the 3D printed material with anophelifuge photosensitive effect that the present invention provides, significantly enhances the network structure of material, is effectively improved the toughness of the 3D printed product made with this material, and degradation rate is high, good anti-bacterial effect；What is more important, the product that the anophelifuge type 3D printed material using the present invention to provide prints, there is moulding own and on the basis of basic function that shape is brought, the most photosensitive can variable color, i.e. under sunlight or ultraviolet irradiation change, produce molecular structure and the change of absorbing wavelength, thus produce the change of color or be reduced into original color, on the other hand have excellent mosquito repellent function concurrently, and while anophelifuge, antibacterial, antiinflammatory, effectively suppressing the breeding of worm's ovum, cleannes are high；The most important thing is, Mint flavone extract in anophelifuge and Herba Rosmarini Officinalis extract etc. are while having mosquito-repelling function, also there is antioxidation, work in coordination with further entirety with other components and significantly improve the antioxygenic property of the anophelifuge type 3D printed material that the present invention provides, bactericidal performance and network structure, diffusion effect is worked in coordination with good plus overall composition, make to the method can be widely used in printing pendant driving mosquitos, Toy watch, footwear, ornament etc., it is particularly suited for printing child, what old man carried with has the accessories having mosquito repellent function concurrently of microcellular structure, interesting practicality has concurrently, in terms of 3D printed material, it is greatly enlarged the application development space that 3D prints, meaning is notable.
Detailed description of the invention
According to parts by weight, embodiment 1: a kind of 3D printed material with anophelifuge photosensitive effect, includes that following components is made: PLA110 part；Anophelifuge 10 parts；Sensitization discoloration toner 2 parts；Light diffusing agent 2 parts；Cross-linking agent 10 parts；Coupling agent 2 parts；Sodium lignin sulfonate 10 parts；Nano antibacterial agent 2 parts；Auxiliary agent 0.1 part.
Wherein according to parts by weight, anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 2 parts；Herba Cymbopogonis Citrari cream 2 parts；Mint flavone extract 3 parts；Herba Rosmarini Officinalis extract 3 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is titanate coupling agent.
Wherein cross-linking agent is trimesic acid.
Wherein nano antibacterial agent is nano titanium oxide.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.05 part；Toughener 0.05 part.
Preparation method comprises the steps: 1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.After testing, the flexility of material reaches 81.5Mpa, notch impact strength reaches 46.9MJ/m2。
According to parts by weight, embodiment 2: a kind of 3D printed material with anophelifuge photosensitive effect, includes that following components is made: PLA145 part；Anophelifuge 20 parts；Sensitization discoloration toner 10 parts；Light diffusing agent 8 parts；Cross-linking agent 20 parts；Coupling agent 5 parts；Sodium lignin sulfonate 30 parts；Nano antibacterial agent 8 parts；Auxiliary agent 0.5 part.
Wherein according to parts by weight, anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 4 parts；Herba Cymbopogonis Citrari cream 4 parts；Mint flavone extract 6 parts；Herba Rosmarini Officinalis extract 6 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein said coupling agent is silane coupler.
Wherein cross-linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is nano zine oxide.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.2 part；Toughener 0.3 part.
Preparation method comprises the steps: 1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.After testing, the flexility of material reaches 82Mpa, notch impact strength reaches 47.7MJ/m2。
According to parts by weight, embodiment 3: a kind of 3D printed material with anophelifuge photosensitive effect, includes that following components is made: PLA130 part；Anophelifuge 15 parts；Sensitization discoloration toner 6 parts；Light diffusing agent 5 parts；Cross-linking agent 15 parts；Coupling agent 3 parts；Sodium lignin sulfonate 20 parts；Nano antibacterial agent 5 parts；Auxiliary agent 0.25 part.
Wherein according to parts by weight, anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 3 parts；Herba Cymbopogonis Citrari cream 3 parts；Mint flavone extract 5 parts；Herba Rosmarini Officinalis 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 coupler, and ratio is 2:3.
Mixture during wherein cross-linking agent is trimesic acid and methyl acetoacetate, ratio is 3:1.
Wherein nano antibacterial agent is nanometer silver.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.1 part；Toughener 0.15 part.
Preparation method comprises the steps: 1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.After testing, the flexility of material reaches 82.5Mpa, notch impact strength reaches 48.3MJ/m2。
According to parts by weight, embodiment 4: a kind of 3D printed material with anophelifuge photosensitive effect, includes that following components is made: PLA125 part；Anophelifuge 14 parts；Sensitization discoloration toner 5 parts；Light diffusing agent 5 parts；Cross-linking agent 12 parts；Coupling agent 3 parts；Sodium lignin sulfonate 15 parts；Nano antibacterial agent 4 parts；Auxiliary agent 0.2 part.
Wherein according to parts by weight, anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 3 parts；Herba Cymbopogonis Citrari cream 3 parts；Mint flavone extract 4 parts；Herba Rosmarini Officinalis extract 4 parts.
Wherein light diffusing agent is organosilicon light diffusing agent.
Wherein coupling agent is titanate coupling agent.
Wherein cross-linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is the mixture of nano titanium oxide, nano zine oxide and nanometer silver.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.1 part；Toughener 0.1 part.
Preparation method comprises the steps: 1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.After testing, the flexility of material reaches 79.8Mpa, notch impact strength reaches 47.5MJ/m2。
According to parts by weight, embodiment 5: a kind of 3D printed material with anophelifuge photosensitive effect, includes that following components is made: PLA135 part；Anophelifuge 18 parts；Sensitization discoloration toner 8 parts；Light diffusing agent 6 parts；Cross-linking agent 18 parts；Coupling agent 4 parts；Sodium lignin sulfonate 18 parts；Nano antibacterial agent 6 parts；Auxiliary agent 0.3 part.
Wherein according to parts by weight, anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 4 parts；Herba Cymbopogonis Citrari cream 4 parts；Mint flavone extract 5 parts；Herba Rosmarini Officinalis 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 coupler.
Wherein cross-linking agent is methyl acetoacetate.
Wherein nano antibacterial agent is the mixture of nano titanium oxide and nanometer silver.
Wherein according to parts by weight, auxiliary agent includes that following components is made: plasticizer 0.15 part；Toughener 0.15 part.
Preparation method comprises the steps: 1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；2) it is cooled to 20 DEG C ~ 30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize and obtain preparing the PLA powder of graft crosslinking agent；3) by step 2) obtain by PLA powder, sodium lignin sulfonate, nano antibacterial agent, coupling agent and the auxiliary agent of corresponding parts by weight, add hot mixing and high-speed stirred be uniform；4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then add sensitization discoloration toner and the light diffusing agent of corresponding parts by weight, continue to be mixed and stirred for uniformly；5) it is cooled to 50 DEG C ~ 55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.After testing, the flexility of material reaches 81.6Mpa, notch impact strength reaches 48.1MJ/m2。
The 3D printed material with anophelifuge and sensitization discoloration effect that above-described embodiment provides is applied in printing anophelifuge ornament, especially apply in printing ornament or the apparatus with microcellular structure, as in apparatus of camping, gardens decoration or the anophelifuge accessories carried with etc., have a wide range of applications market and significant Practical significance, can widely promote.
More than implementing row and the present invention does not constitute restriction, relevant staff is in the range of without departing from the technology of the present invention thought, and carried out various changes and modifications, and all falls within protection scope of the present invention.
Claims (6)
1. a 3D printed material with anophelifuge photosensitive effect, it is characterised in that include following group according to parts by weight
Divide and make: PLA110～145 parts；Anophelifuge 10～20 parts；Sensitization discoloration toner 2～10 parts；Light diffusing agent 2～8
Part；Cross-linking agent 10～20 parts；Coupling agent 2～5 parts；Sodium lignin sulfonate 10～30 parts；Nano antibacterial agent 2～8 parts；
Auxiliary agent 0.1～0.5 part；
Described light diffusing agent is organosilicon light diffusing agent；
According to parts by weight, described anophelifuge includes that following components is made: Radix Buddlejae Butterflybush extract 2～4 parts；Herba Cymbopogonis Citrari cream 2～4
Part；Mint flavone extract 3～6 parts；Herba Rosmarini Officinalis extract 3～6 parts.
The 3D printed material with anophelifuge photosensitive effect the most according to claim 1, it is characterised in that described idol
Connection agent is one or both the mixture in titanate coupling agent or silane coupler；Described cross-linking agent is trimesic acid
Or the mixture of one or both in methyl acetoacetate.
The 3D printed material with anophelifuge photosensitive effect the most according to claim 1, it is characterised in that described in receive
Nano antibacterial agent is any one or two or more mixing in nano titanium oxide, nano zine oxide or nanometer silver
Thing.
The 3D printed material with anophelifuge photosensitive effect the most according to claim 1, it is characterised in that described in help
According to parts by weight, agent includes that following components is made: plasticizer 0.05～0.2 part；Toughener 0.05～0.3 part.
5. the preparation side of the 3D printed material with anophelifuge photosensitive effect described in Claims 1 to 4 any claim
Method, it is characterised in that comprise the steps:
1) PLA particle high-temperature is melted, add cross-linking agent and mix, grafting；
2) it is cooled to 20 DEG C～30 DEG C after stirring, puts into extruder, heating, extrusion, pulverize to obtain preparing being grafted and hand over
The PLA powder of connection agent；
3) by step 2) the PLA powder of corresponding parts by weight that obtains, sodium lignin sulfonate, nano antibacterial agent, idol
Connection agent and auxiliary agent, add hot mixing and high-speed stirred be uniform；
4) it is subsequently adding the anophelifuge of corresponding parts by weight, continues to be mixed and stirred for uniformly；Then corresponding weight portion is added
The sensitization discoloration toner of number and light diffusing agent, continue to be mixed and stirred for uniformly；
5) it is cooled to 50 DEG C～55 DEG C, puts in extruder, add hot-extrudable, vacuum drying, prepare target product.
6. the 3D printed material with anophelifuge photosensitive effect described in Claims 1 to 4 any claim is printing tool
There is the application in the anophelifuge ornament of microcellular structure.
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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 |
| CN201610197367.6A Division CN105733218A (en) | 2015-05-29 | 2015-05-29 | 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 |
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| 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 |
| 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 |
| 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 |
| 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 |
| CN105994404A (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 |
| 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 |
| 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 |
| 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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| CN104177803A (en) * | 2014-08-19 | 2014-12-03 | 珠海天威飞马打印耗材有限公司 | Color three-dimensional printing molding material and preparation method thereof |
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| CN104310948B (en) * | 2014-09-10 | 2016-01-20 | 济南大学 | A kind of three D print the preparation method of rapid shaping inorganic powder materials |
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