WO2021089898A1 - Filament antibactérien, insecticide, aromatisé et ayant une capacité virucide pour imprimantes 3d - Google Patents

Filament antibactérien, insecticide, aromatisé et ayant une capacité virucide pour imprimantes 3d Download PDF

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Publication number
WO2021089898A1
WO2021089898A1 PCT/ES2020/070677 ES2020070677W WO2021089898A1 WO 2021089898 A1 WO2021089898 A1 WO 2021089898A1 ES 2020070677 W ES2020070677 W ES 2020070677W WO 2021089898 A1 WO2021089898 A1 WO 2021089898A1
Authority
WO
WIPO (PCT)
Prior art keywords
filament
antibacterial
thermoplastic
tpu
printers
Prior art date
Application number
PCT/ES2020/070677
Other languages
English (en)
Spanish (es)
Inventor
Enrique OÑATE MOLINA
Pedro María ALONSO PÉREZ
Original Assignee
Onate Molina Enrique
Alonso Perez Pedro Maria
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from ES201931819U external-priority patent/ES1245650Y/es
Priority claimed from ES202031871U external-priority patent/ES1256211Y/es
Application filed by Onate Molina Enrique, Alonso Perez Pedro Maria filed Critical Onate Molina Enrique
Publication of WO2021089898A1 publication Critical patent/WO2021089898A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor

Definitions

  • ANTIBACTERIAL FILAMENT INSECT REPELLENT. AROMATIZED AND VIRUCIATED CAPACITY FOR 3D PRINTERS
  • the object of this utility model is a filament for 3D printers made from different polymers and elastomers such as polylactic acid (PLA), thermoplastic polyurethane (TPU), acrylonitrile butadiene styrene (ABS) or other elastomers (TPE s ), which is used essentially for the printing of three-dimensional figures or objects in printers designed for such use, the composition of which makes it possible to provide the materials with antibacterial, insect repellent and flavored properties.
  • PVA polylactic acid
  • TPU thermoplastic polyurethane
  • ABS acrylonitrile butadiene styrene
  • TPE s elastomers
  • the present invention relates to a filament with virucidal capacity and antibacterial properties for use in three-dimensional printers.
  • the filament of the invention makes it possible to print three-dimensional figures or objects in printers designed for such use, so that the object obtained has virucidal and antibacterial properties.
  • the applicant knows a multitude of solutions related to the printing of three-dimensional objects, an example of this is the European patent EP 1015215 that defines a method to carry out prototyping of solid models where the data corresponding to the desired shape of a prototype are transmitted to a rapid prototyping system.
  • the system calculates a sequence to extrude flowable material that is thermally solidified to create a desired geometric shape.
  • a heated, fluid modeling material is sequentially extruded at its deposition temperature into a building environment that maintains the volume close to the newly deposited material in a deposition temperature window between the material's solidification temperature and its yield point.
  • the newly extruded material gradually cools below its solidification temperature, while maintaining the temperature gradients in the geometric shape below a maximum value set by the geometric precision of the desired part.
  • European patent EP 1087862 defines a rapid prototyping system with control of the filament feed spool, where a spool of filament used in a rapid prototyping system carries a circuit that maintains data on the type and quantity of filament in The reel. And where, when the reel is mounted on a shaft in the rapid prototyping system, the circuit is connected to the electronic control of the system. Subsequently, the data indicating the amount of filament on the spool is updated as the system uses the filament. And finally, the filament spool has a central cylinder in which the filament can be wound and a sleeve inside the cylinder to receive the shaft, the circuit is mounted on the sleeve.
  • the European patent EP 1497093 describes a prototype injection molding system, where a method and an apparatus for making a prototype of an injection molded part are described. And where, an extruder of the type used for melt deposition modeling injects production thermoplastic material into a non-conductive plastic mold tool slowly heated at low pressure in an isothermal process.
  • the mold tool can be constructed from a CAD drawing using fused deposition modeling or other rapid prototyping technique.
  • an engineer in an office environment can make an injection molded prototype part from a digital representation of the part within 24 hours.
  • the technical problem solved by the present invention is to provide antibacterial, insect repellent and flavored properties to three-dimensionally printed objects.
  • the filament for 3D printers object of this utility model, is characterized by comprising a body materialized with a polylactic acid or polyacid lactic acid (PLA) and / or Thermoplastic Polyurethane (TPU) or other thermoplastic elastomers (TPE s, Abs ), which will provide the body shaped by 3D printing with antibacterial, aromatic and insect repellent properties.
  • PLA polylactic acid or polyacid lactic acid
  • TPU Thermoplastic Polyurethane
  • TPE s, Abs thermoplastic elastomers
  • thermoplastic polyurethane TPU
  • biodegradability barrier properties
  • biocompatibility a biocompatibility of polyurethane
  • This biopolymer finds numerous applications since it has an unusual wide range of properties, from the amorphous state to the crystalline state; properties that can be achieved by manipulating mixtures between the D (-) and L (+) isomers, molecular weights, and copolymerization.
  • Polylactic acid is a biodegradable polymer derived from lactic acid. It is a highly versatile material, which is made from 100% renewable resources, such as corn, beets, wheat and other products rich in starch. This acid has many equivalent and even better characteristics than many petroleum-based plastics, making it effective for a wide variety of uses.
  • the filament of the present invention is provided with virucidal and antibacterial properties in order to enable objects printed three-dimensionally from said filament to also offer virucidal and antibacterial capacity.
  • the filament for 3D printers object of this utility model is materialized by a body of a thermoplastic compound based on silver ions
  • the thermoplastic compound is constituted by a polylactic acid (PLA), a copolymer that combines the properties of PET (Polyethylene Terephthalate) and those of glycol (PET-G) , a polypropylene (PP), a thermoplastic polyurethane (TPU), thermoplastic elastomers (TPE) or a mixture of them.
  • thermoplastic body enables its virucidal capacity, as has been proven in the tests carried out and which are set out in the section on the preferred embodiment of the invention.
  • silver ions are known for their biocidal character.
  • silver ions act on the free radicals of the viral molecules, specifically SARS molecules, acting on the disulfide bridges that join the free radicals to the SARS molecule and causing the denaturation of the molecules and, therefore , its infectivity.
  • the plastic compound of the filament of the present invention is necessarily constituted by a thermoplastic compound that prevents the addition of silver ions from vitrifying them on the surface of the polymer and therefore their migration towards the virus is viable for its infectivity.
  • the body of the filament is a thermoplastic, it can be produced by extrusion.
  • the presence of silver ions in said plastic compound enables the silver ions of the filament to migrate towards the SARS viral molecule in the presence of ambient humidity.
  • the use of the filament of the present invention in three-dimensional printing makes it possible to provide the shaped body with virucidal and antibacterial properties.
  • the body of the filament is made up of a thermoplastic compound that has a saturation of silver ions in a range between 3% and 9%.
  • polylactic acid is a biodegradable polymer derived from lactic acid. It is a highly versatile material, which is manufactured from resources 100% renewable, such as corn, beets, wheat and other starch-rich products. This acid has many equivalent and even better characteristics than many petroleum-based plastics, making it effective for a wide variety of uses.
  • polypropylene it should be noted that it is one of the most used plastic materials, along with polyethylene terephthalate. It is a thermoplastic, partially crystalline polymer that is obtained from the polymerization of propylene (or propene). Its uses range from textiles and packaging to medical devices, laboratory equipment or automotive components.
  • the thermoplastic compound that integrates the virucidal and antibacterial filament of the present invention is polylactic acid and / or polypropylene
  • the filament with virucidal and antibacterial capacity obtained will be, additionally, biodegradable, with barrier and biocompatible properties.
  • the biopolymer made up of polylactic acid and / or polypropylene finds numerous applications, since it has an unusual wide range of properties, from the amorphous state to the crystalline state; properties that can be achieved by manipulating mixtures between the D (-) and L (+) isomers, molecular weights, and copolymerization.
  • thermoplastic polyurethane is one of the existing varieties of polyurethanes. It is a linear elastomeric polymer and therefore thermoplastic. This elastomer can be shaped by the usual processes for thermoplastics, such as injection, extrusion and blow molding. As a urethane-based thermoplastic elastomer, it is abbreviated TPU.
  • thermoplastic polyurethane is characterized by its high resistance to abrasion, oxygen, ozone and low temperatures. This combination of properties makes thermoplastic polyurethane an engineering plastic; for this reason, it is used in special applications.
  • the antibacterial and virucidal filament of the invention optionally includes a universal polymeric resin which is introduced as an additive that is compatible with the thermoplastic compound.
  • the resin Polymeric universal facilitates the polymerization within an extrasolar chamber and subsequent migration to the surface of the silver ions to generate the virucidal and antibacterial capacity of the filament of the present invention.
  • the detailed filament allows three-dimensional printing of figures with virucidal and antibacterial properties, avoiding having to carry out subsequent processes and / or procedures that provide these characteristics, which increase the cost of the final product, and reduce profitability compared to the elements. materialized with the filament recommended here.
  • the solution provided in the present invention offers a configuration of the filament with virucidal capacity that does not differ from the filaments known in the state of the art in terms of weight or size, but does present virucidal and antibacterial properties that gives an appreciable advantage in its use
  • Figure 1.- Shows a schematic side view of the filament according to a preferred embodiment of the object of the invention.
  • Figure 2. Shows a graph of the results tested to verify the behavior of different samples of the filament with virucidal and antibacterial capacity of the present invention.
  • the filament for 3D printers object of the present invention is characterized by comprising a body (1) made entirely of polylactic acid (PLA) and / or thermoplastic polyurethanes (TPU / TPE), which in addition to the intrinsic characteristics of this biodegradable, hydrophilic and low flammability polymer, in the first case (PLA), and flexibility and durability, in the second case (TPU / TPE), it has antibacterial, aromatic and insect repellent properties.
  • PLA polylactic acid
  • TPU / TPE thermoplastic polyurethanes
  • the filament recommended here will not differ from the filaments present in the state of the art, in terms of weight or size, but in terms of the configuration of the properties (antibacterial, anti-repellent and flavored). , which will cause an appreciable advantage in its use.
  • the filament with virucidal and antibacterial capacity for three-dimensional printers is made up of a body (1) which is made entirely of polylactic acid (PLA), a copolymer that combines PET and glycol (PET -G), a polypropylene (PP), a thermoplastic polyurethane (TPU), elastomers thermoplastics (TPE) or a mixture of them.
  • PLA polylactic acid
  • PET -G copolymer that combines PET and glycol
  • PP polypropylene
  • TPU thermoplastic polyurethane
  • TPE thermoplastics
  • the aforementioned PLA and PP thermoplastics provide associated intrinsic characteristics as they are biodegradable, hydrophilic and low flammability polymers
  • TPU and TPE thermoplastics provide flexibility and durability.
  • the impregnation of the body of the thermoplastic compound with biocidal and antibacterial substances based on silver ions endow the filament with the ability to destroy, counteract and / or neutralize the inhibition of its growth or proliferation of viruses, bacterial agents, fungi and microorganisms harmful to the human being, without incurring damage to the object, environment or organism that carries it.
  • the silver ions present in the filament of the invention act at the level of the cell membrane of the microorganism they attack, causing the lysis of the protein wall of the microorganism and penetrating inside it, interrupting the biochemical reactions that sustain its life. .
  • TPU thermoplastic polyurethane
  • samples (C) and (D) are made up of a thermoplastic compound which is saturated with silver ions.
  • the procedure carried out consisted of incubating each of the aforementioned samples (A), (B), (C) and (D) with 200 ml_ of a coronavirus causative agent of the common cold in humans called HCoV-229E at 1,000 uff (focus-forming units) per ml_ (200 uff / sample) for 4 hours of exposure at room temperature.
  • Figure 2 shows the results obtained from the detailed test, where the ordinate axis collects the mean and standard deviation values of the infectivity percentages obtained for each of the samples (A), (B), (C) and (D ) represented on the abscissa axis.
  • the blank shows complete infectivity and the sample (B) - which does not contain silver ions - shows some infectivity due to the principle of contamination that takes place during the test.
  • samples (C) and (D) which are made up of a thermoplastic polyurethane (TPU) with silver ions, reduce the infectivity of the coronavirus after its co-incubation with respect to the control.
  • TPU thermoplastic polyurethane
  • sample (C) offers higher infectivity. Specifically, the infectivity of the coronavirus incubated with the sample (C) was only 22.7% compared to the control. In other words, sample (C) reduced the infectivity of the coronavirus by 77.3%.
  • the body of the filament is made up of a thermoplastic compound that has a saturation of silver ions with a percentage of 6%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Artificial Filaments (AREA)

Abstract

La présente invention concerne un filament pour imprimantes 3D ayant des propriétés antibactériennes, antimoustiques et aromatisé qui présente facultativement également une capacité virucide. Ainsi le corps du filament est matérialisé par un polymère qui est sélectionné entre l'acide polylactique (PLA) et le polyuréthane thermoplastique (TPU) ou d'autres élastomères (TPE) avec des constituants antibactériens. Facultativement, le corps du filament est constitué d'un composite thermoplastique à base d'ions argent pour assurer son pouvoir virucide et antibactérien, lequel composite thermoplastique est constitué de PLA, PET-G, PP, TPU, TPE ou un mélange de ceux.ci.
PCT/ES2020/070677 2019-11-05 2020-11-04 Filament antibactérien, insecticide, aromatisé et ayant une capacité virucide pour imprimantes 3d WO2021089898A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ESU201931819 2019-11-05
ES201931819U ES1245650Y (es) 2019-11-05 2019-11-05 Filamento antibacteriano, repelente de insectos y aromatizado para impresoras 3D
ESU202031871 2020-08-24
ES202031871U ES1256211Y (es) 2020-08-24 2020-08-24 Filamento con capacidad virucida y antibacteriana para impresoras tridimensionales

Publications (1)

Publication Number Publication Date
WO2021089898A1 true WO2021089898A1 (fr) 2021-05-14

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WO (1) WO2021089898A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060019574A (ko) * 2003-06-06 2006-03-03 리메이 인크. 부직포 인쇄 매질 및 그 제조방법
CN104530668A (zh) * 2014-12-17 2015-04-22 广州飞胜高分子材料有限公司 具有自清洁抗菌功能的3d打印材料及制备方法与应用
WO2015064877A1 (fr) * 2013-11-04 2015-05-07 화인케미칼 주식회사 Composition pour filament d'imprimante tridimensionnelle
WO2016035949A1 (fr) * 2014-09-05 2016-03-10 (주)비앤케이 Procédé de fabrication de filament antibactérien pour imprimante 3d et filament antibactérien pour imprimante 3d fabriqué en faisant appel à celui-ci
CN105585830A (zh) * 2016-02-25 2016-05-18 广州飞胜高分子材料有限公司 具有木质属性的改性聚乳酸复合3d打印材料及制备方法与应用
WO2016080573A1 (fr) * 2014-11-19 2016-05-26 퓨처사이버 주식회사 Composition de filament pour imprimante 3d
EP3067389A1 (fr) * 2013-11-04 2016-09-14 Fine Chemical Co., Ltd. Composition polymère pour imprimante 3d
KR101794985B1 (ko) * 2016-09-09 2017-12-01 청주대학교 산학협력단 항균기능을 갖는 삼차원 프린팅용 옻 필라멘트의 제조방법 및 이에 의해 제조된 삼차원 프린팅용 옻 필라멘트
WO2018150599A1 (fr) * 2017-02-14 2018-08-23 ホッティーポリマー株式会社 Filament et son procédé de production

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060019574A (ko) * 2003-06-06 2006-03-03 리메이 인크. 부직포 인쇄 매질 및 그 제조방법
WO2015064877A1 (fr) * 2013-11-04 2015-05-07 화인케미칼 주식회사 Composition pour filament d'imprimante tridimensionnelle
EP3067389A1 (fr) * 2013-11-04 2016-09-14 Fine Chemical Co., Ltd. Composition polymère pour imprimante 3d
WO2016035949A1 (fr) * 2014-09-05 2016-03-10 (주)비앤케이 Procédé de fabrication de filament antibactérien pour imprimante 3d et filament antibactérien pour imprimante 3d fabriqué en faisant appel à celui-ci
WO2016080573A1 (fr) * 2014-11-19 2016-05-26 퓨처사이버 주식회사 Composition de filament pour imprimante 3d
CN104530668A (zh) * 2014-12-17 2015-04-22 广州飞胜高分子材料有限公司 具有自清洁抗菌功能的3d打印材料及制备方法与应用
CN105585830A (zh) * 2016-02-25 2016-05-18 广州飞胜高分子材料有限公司 具有木质属性的改性聚乳酸复合3d打印材料及制备方法与应用
KR101794985B1 (ko) * 2016-09-09 2017-12-01 청주대학교 산학협력단 항균기능을 갖는 삼차원 프린팅용 옻 필라멘트의 제조방법 및 이에 의해 제조된 삼차원 프린팅용 옻 필라멘트
WO2018150599A1 (fr) * 2017-02-14 2018-08-23 ホッティーポリマー株式会社 Filament et son procédé de production

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