CH719359A2 - Process of fabricating and antimicrobial material per fabricating additiva per fabricating per fusion of filament. - Google Patents

Process of fabricating and antimicrobial material per fabricating additiva per fabricating per fusion of filament. Download PDF

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Publication number
CH719359A2
CH719359A2 CH000045/2022A CH452022A CH719359A2 CH 719359 A2 CH719359 A2 CH 719359A2 CH 000045/2022 A CH000045/2022 A CH 000045/2022A CH 452022 A CH452022 A CH 452022A CH 719359 A2 CH719359 A2 CH 719359A2
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Switzerland
Prior art keywords
recycled polymer
metal oxide
nylon
filament
fabricating
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CH000045/2022A
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French (fr)
Italian (it)
Inventor
Pezzini Giuseppe
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Pielleitalia Srl
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Priority to CH000045/2022A priority Critical patent/CH719359A2/en
Publication of CH719359A2 publication Critical patent/CH719359A2/en

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • 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
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/307—Handling of material to be used in additive manufacturing
    • B29C64/314—Preparation
    • 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
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/357—Recycling
    • 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
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/10—Pre-treatment
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/46—Post-polymerisation treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/34—Hot-melt inks
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B2017/042—Mixing disintegrated particles or powders with other materials, e.g. with virgin materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Environmental & Geological Engineering (AREA)
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  • Wood Science & Technology (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Composite Materials (AREA)
  • Civil Engineering (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Artificial Filaments (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

Procedimento di fabbricazione di un oggetto a partire da un polimero riciclato comprendente preferibilmente, nanoparticelle di TiO 2 che gli conferiscono proprietà antimicrobiche, in cui il polimero dériva dal riciclo d'un manufatto tessile a fine vita. Il procedimento utilizza indumenti a base di fibre sintetiche preferibilmente poliammidiche, ad esempio Nylon 6,6, Nylon 6,10 o Nylon 6. Il materiale riciclato, purificato e essiccato, viene plastificato assieme a un master carico di nanoparticelle di TiO 2 sino a ottenere un materiale utilizzabile per la fabbricazione avente la concentrazione di nanoparticelle desiderata. Preferibilmente, il materiale è condizionato sotto forma di filamenti o granuli per l'alimentazione di stampanti FFF tridimensionaliProcedure di fabrication di un oggetto a da a polymero riciclato comprehend preferibilmente, nanoparticle di TiO 2 che gli conferiscono proprietà antimicrobiche, in cui il polymero deriva dal riciclo d'un manufatto tessile a fine vita. The process used indumenti a base di synthetic fiber preferably polyammidiche, ad esempio Nylon 6.6, Nylon 6.10 or Nylon 6. a material that can be used for the manufacture of the concentration of the desired nanoparticle. Preferably, it materiale è condizionato sotto form di filamenti or granuli per l'alimentazione di stampanti FFF tridimensionali

Description

Campo dell'invenzioneField of invention

[0001] La presente invenzione riguarda un procedimento di fabbricazione d'un oggetto in materiale plastico riciclato avente proprietà antimicrobiche come anche un materiale per la fabbricazione additiva ottenuto come prodotto intermedio di detto procedimento. [0001] The present invention relates to a process for manufacturing an object made of recycled plastic material having antimicrobial properties as well as a material for additive manufacturing obtained as an intermediate product of said process.

Stato della tecnicaState of the art

[0002] Quasi tutti i materiali plastici utilizzati industrialmente sono non biodegradabili e causano gravi danni agli ecosistemi in cui si accumulano. La preoccupazione per l'inquinamento derivante dalla plastica s'accompagna ad un bisogno sempre più urgente di procedimenti economici ed ecologici per riutilizzare e riciclare i materiali plastici. [0002] Almost all plastic materials used industrially are non-biodegradable and cause serious damage to the ecosystems in which they accumulate. Concern about plastic pollution goes hand in hand with an increasingly urgent need for economical and environmentally friendly processes to reuse and recycle plastic materials.

[0003] Il riciclo dei materiali sintetici a fine vita, e in particolare il riciclo di manufatti e indumenti in tessile sintetico présenta difficoltà particolari. Da una parte per il lungo impiego degli indumenti che contribuisce inevitabilmente al degrado dei polimeri, dall'altra perché il materiale riciclato proviene da una moltitudine di capi di età, caratteristiche e storie diverse e quindi présenta una grande dispersione delle sue proprietà. [0003] The recycling of synthetic materials at the end of their life, and in particular the recycling of synthetic textile articles and garments presents particular difficulties. On the one hand due to the long use of clothing which inevitably contributes to the degradation of polymers, on the other because the recycled material comes from a multitude of garments of different ages, characteristics and histories and therefore presents a great dispersion of its properties.

[0004] Le poliammidi, tra cui si annoverano il Nylon 6 (PA6) il Nylon 6,6 (PA66) sono tra i materiali plastici più usati per la produzione di fibre e sono anche largamente impiegati come materiali strutturali nell'industria dell'automobile, della costruzione, in aviazione e nell'industria elettronica. [0004] Polyamides, which include Nylon 6 (PA6) and Nylon 6.6 (PA66) are among the most used plastic materials for the production of fibers and are also widely used as structural materials in the automotive industry , construction, aviation and electronics industries.

[0005] Nell'ambito delle fibre poliammidiche, sono noti dei procedimenti di riciclaggio che permettono d'ottenere una poliammide riciclata, per esempio di Nylon 6 (PA6) a partire da scarti tessili. Si tratta perlopiù di scarti di lavorazione (i cosiddetti rifiuti pre-consumer). Questi materiali riciclati sono di regola filati una seconda volta per ricavarne nuovi prodotti. Il riciclo di capi usati è assai meno rappresentato nella tecnica in quanto questi sono degradati dall'uso e il prodotto che se ne ottiene è molto inferiore. Anche se qualche caso di riciclo di manufatti tessili postconsumer esiste, questi sono un'esigua minoranza. [0005] In the field of polyamide fibres, recycling processes are known which make it possible to obtain a recycled polyamide, for example Nylon 6 (PA6) starting from textile waste. It is mostly processing waste (so-called pre-consumer waste). These recycled materials are usually spun a second time into new products. The recycling of used garments is much less represented in the technique as these are degraded by use and the product obtained is much lower. Even if there are some cases of post-consumer textile recycling, these are a small minority.

[0006] I procedimenti di fabbricazione additivi sono sempre più utilizzati per la produzione di prototipi e piccole serie di oggetti in alternativa ai metodi convenzionali come lo stampaggio, l'estrusione o la laminazione. Tra questi si conoscono processi di fabbricazione per fusione di filamento, denotati anche con l'abbreviazione „FFF“ (Fused Filament Fabrication) ovvero processi di fabbricazione additiva per deposizione d'un materiale plastico nello stato di fluido viscoso attraverso un ugello che viene mosso serialmente in modo da modellizzare la forma voluta. Sono noti anche processi di fabbricazione additiva basati sulla tecnologia delle polveri, come ad esempio i processi „PBF“ (Powder Bed Fusion) o „SLS“ (Selective Laser Sintering) in cui si usano polimeri termoplastici sotto forma di polveri che vengono depositate in uno strato uniforme e sinterizzate mediante l'applicazione di energia termica iterativamente, uno strato dopo l'altro. [0006] Additive manufacturing processes are increasingly used for the production of prototypes and small series of objects as an alternative to conventional methods such as moulding, extrusion or lamination. Among these are known manufacturing processes for filament fusion, also denoted by the abbreviation "FFF" (Fused Filament Fabrication) or additive manufacturing processes by deposition of a plastic material in the viscous fluid state through a nozzle which is moved serially in order to model the desired shape. Additive manufacturing processes based on powder technology are also known, such as for example the "PBF" (Powder Bed Fusion) or "SLS" (Selective Laser Sintering) processes in which thermoplastic polymers are used in the form of powders which are deposited in a uniform layer and sintered by applying thermal energy iteratively, one layer after another.

[0007] Questi procedimenti si basano sull'uso di materiali plastici specialmente preparati e condizionati per essere stampabili, sia su forma di filamento pellets o polvere, sia a partire di polimeri vergini che di polimeri riciclati. [0007] These processes are based on the use of plastic materials specially prepared and conditioned to be printable, both in the form of pellets or powder, both from virgin polymers and from recycled polymers.

[0008] Il documento WO 2017109741 A1 divulga un procedimento di fabbricazione d'un articolo in un polimero termoplastico antibatterico comprendente nanoparticelle di biossido di titanio. Document WO 2017109741 A1 discloses a method of manufacturing an article from an antibacterial thermoplastic polymer comprising titanium dioxide nanoparticles.

Brève descrizione dell'invenzioneBrief description of the invention

[0009] Uno scopo della presente invenzione è di proporre un procedimento per riciclare dei polimeri in articoli aventi proprietà antimicrobiche. Un altro scopo dell'invenzione è quello di proporre un prodotto intermedio riciclato e antibatterico che può essere usato per alimentare una stampante tridimensionale. [0009] An object of the present invention is to propose a process for recycling polymers into articles having antimicrobial properties. Another object of the invention is to propose a recycled and antibacterial intermediate product which can be used to feed a three-dimensional printer.

[0010] Secondo l'invenzione, tali scopi sono raggiunti dall'oggetto della rivendicazione principale allegata, e in particolare da un procedimento di fabbricazione di un oggetto, comprendente le fasi di: fornitura di un manufatto tessile a fine vita, ottenimento di un polimero riciclato a partire dal manufatto tessile, funzionalizzazione del polimero riciclato in modo da renderlo antimicrobico, fabbricazione di detto oggetto a partire da detto polimero riciclato funzionalizzato. [0010] According to the invention, these aims are achieved by the object of the attached main claim, and in particular by a process for manufacturing an object, comprising the steps of: supplying a textile article at the end of its life, obtaining a polymer recycled starting from the textile article, functionalisation of the recycled polymer so as to make it antimicrobial, manufacturing of said object starting from said functionalised recycled polymer.

[0011] Le rivendicazioni dipendenti riguardano delle caratteristiche addizionali che, benché utili e vantaggiose, non sono essenziali all'invenzione, tra cui la funzionalizzazione attraverso l'aggiunta di una carica di nano particelle di diossido di Titanio ad una percentuale massica compresa tra lo 0.1 % e il 20%, preferibilmente compresa tra lo 0.5% e il 5% e con una dimensione média inferiore a 1 µm, preferibilmente inferiore a 150 nm, più preferibilmente compreso tra 10 nm e 30 nm. [0011] The dependent claims relate to additional characteristics which, although useful and advantageous, are not essential to the invention, including the functionalization through the addition of a filler of titanium dioxide nano particles at a mass percentage ranging from 0.1 % and 20%, preferably between 0.5% and 5% and with an average size of less than 1 µm, preferably less than 150 nm, more preferably between 10 nm and 30 nm.

[0012] L'attività antimicrobica del biossido di titanio si ritiene dovuta a un'azione fotocatalitica attivata da una certa lunghezza d'onda UV-A. Questa materia ha dato ottimi risultati nei test di attività antibatterica ed antimicrobica effettuati su materiali della stessa natura di quelli in oggetto seppur processati diversamente e non présenta rischi per la salute alle concentrazioni impiegate. Si tratta d'una variante preferita, ma non è l'unica scelta possibile. L'ossido di titanio potrebbe essere sostituito da altre nanoparticelle di ossidi metallici, ad esempio di ossido di zinco. [0012] The antimicrobial activity of titanium dioxide is believed to be due to a photocatalytic action activated by a certain UV-A wavelength. This material has given excellent results in antibacterial and antimicrobial activity tests carried out on materials of the same nature as those in question, albeit processed differently and does not present health risks at the concentrations used. This is a preferred variant, but it is not the only possible choice. Titanium oxide could be replaced by other metal oxide nanoparticles, such as zinc oxide.

[0013] Questa divulgazione présenta un esempio dell'invenzione in cui la matrice polimerica è composta da Nylon 6 (PA6) riciclato. Questa non è tuttavia la sola possibilità. L'invenzione può essere estesa anche ad altre matrici polimeriche proveniente dal riciclo di capi di abbigliamento, ad esempio di altre forme di poliammide alifatica, come il Nylon 6,6. In generale si preferisce l'utilizzo d'un masterbatch ad alta concentrazione di nanocarica ed una diluzione in fase di preparazione del granulo finale con la PA6 riciclata per ottenere un prodotto avente la concentrazione di TiO2 voluta. This disclosure presents an example of the invention wherein the polymer matrix is made from recycled Nylon 6 (PA6). However, this is not the only possibility. The invention can also be extended to other polymeric matrices deriving from the recycling of clothing items, for example other forms of aliphatic polyamide, such as Nylon 6,6. In general, the use of a masterbatch with a high concentration of nanofiller and a dilution in the preparation phase of the final granule with the recycled PA6 is preferred to obtain a product having the desired TiO2 concentration.

[0014] Il prodotto intermedio può essere condizionato sotto forma di filamento con un diametro precisamente calibrato e adatto all'alimentazione di stampanti tridimensionali FFF, ovvero in polvere per la stampa SLS o in pellets o polvere utilizzabili per alimentare qualunque procedimento di messa in forma di materie plastiche, ad esempio stampa a iniezione, estrusione, filatura, laminatura, eccetera. [0014] The intermediate product can be conditioned in the form of a filament with a precisely calibrated diameter and suitable for feeding FFF three-dimensional printers, or in powder for SLS printing or in pellets or powder which can be used to feed any process of shaping plastics, e.g. injection molding, extrusion, spinning, lamination, etc.

[0015] Il polimero riciclato funzionalizzato può subire delle operazioni di essiccamento prima delle diverse operazioni di plastificazione e/o stampa 3D e/o messa in forma per contrastare la sua naturale igroscopicità. Nell'ambito di questa divulgazione il termine „plastificazione“ designa un processo nel quale una materia plastica viene riscaldata fino a portarla alla fusione mentre viene rimescolata per ottenere un fluido visco-elastico omogeneo. Sovente, queste operazioni avvengono all'interno di camere cilindriche a profilo di temperatura controllato entro le quali ruota una vite con un profilo opportuno. La rotazione della vite porta al rimescolamento voluto e contemporaneamente spinge il prodotto verso un ugello estrusore o un iniettore. [0015] The functionalized recycled polymer can undergo drying operations before the various plasticizing and/or 3D printing and/or shaping operations to counteract its natural hygroscopicity. In the context of this disclosure, the term "plastification" designates a process in which a plastic material is heated until it melts while being stirred to obtain a homogeneous visco-elastic fluid. Often, these operations take place inside cylindrical chambers with a controlled temperature profile within which a screw with a suitable profile rotates. The rotation of the screw brings about the desired mixing and simultaneously pushes the product towards an extruder nozzle or an injector.

[0016] Rispetto a quanto noto nell'arte, Il procedimento dell'invenzione porta alla realizzazione di un oggetto di polimero riciclato funzionalizzato in modo da conferirgli proprietà antimicrobiche, intendendosi per antimicrobico una sostanza o una composizione che decompone i microorganismi fino ad ottenere acqua ed anidride carbonica o ne inibisce la crescita. A seconda dei microorganismi che ne subiscono l'azione e dell'effetto ottenuto si distinguere tra battericidi, fungicidi, virucidi, batteriostatici, fungistatici, virostatici, tutti compresi nell'ambito dell'invenzione. [0016] With respect to what is known in the art, the process of the invention leads to the creation of an object of recycled polymer functionalized so as to give it antimicrobial properties, meaning by antimicrobial a substance or a composition which decomposes microorganisms to obtain water and carbon dioxide or inhibit its growth. Depending on the microorganisms which undergo its action and the effect obtained, a distinction can be made between bactericides, fungicides, virucides, bacteriostatics, fungistatics, virostatics, all included in the scope of the invention.

[0017] Una variante preferita dell'invenzione comporta la produzione intermedia di un filamento di alimentazione di stampante 3D costituito da poliammide PA6 riciclata funzionalizzata con un nanomateriale con proprietà antibatteriche e virucida. [0017] A preferred variant of the invention involves the intermediate production of a 3D printer feed filament made of recycled polyamide PA6 functionalised with a nanomaterial with antibacterial and virucidal properties.

[0018] La poliammide riciclata (re-PA) viene ottenuta a partire da un processo innovativo che ha tra gli altri, come input, abbigliamento a finevita. Grazie al nuovo processo si potranno realizzare parti o dispositivi ad alto grado tecnologico, caratterizzate da elevata leggerezza rispetto ai materiali tradizionali, migliore robustezza, resistenza ad agenti chimici, estrema regolarità superficiale, elevate opportunità di personalizzazione. [0018] Recycled polyamide (re-PA) is obtained starting from an innovative process which has, among others, end-of-life clothing as an input. Thanks to the new process, it will be possible to create high-tech parts or devices, characterized by high lightness compared to traditional materials, better strength, resistance to chemical agents, extreme surface regularity, high customization opportunities.

[0019] L'adozione delle tecnologie di fabbricazione additiva favorisce anche l'adozione di processi circolari in quanto le stampanti 3D sono localizzate nel mondo e solo il filamento funzionalizzato viene trasportato da un sito all'altro. Tali processi che non dipendono in modo eccessivo da catene logistiche lunghe e complesse possono messi in opera con rapidità anche in situazioni di emergenza ed epidemie. [0019] The adoption of additive manufacturing technologies also favors the adoption of circular processes as 3D printers are located in the world and only the functionalized filament is transported from one site to another. Such processes that are not overly dependent on long and complex supply chains can be implemented quickly even in emergency situations and epidemics.

[0020] Il processo prevede l'adattamento del polimero riciclato alla lavorazione con tecnologie di „additive manufacturing“, necessario ad ottenere il grado di viscosità richiesto dalla efficace lavorazione del filamento in fase di stampa. Inoltre, il processo prevede la fase di funzionalizzazione con nanomateriale con proprietà antibatteriche e virucida, attraverso la miscelazione di polimero riciclato con un masterbatch specifico. Tale master è preferibilmente realizzato con lo stesso polimero a base riciclata caricato con il nanomateriale di riferimento. Una volta avvenuta la miscelazione della PA riciclata con il master, il preparato viene alimentato ai processi di manifattura additiva modificandone opportunamente le caratteristiche per consentire una sua efficace lavorabilità su attrezzature di stampa 3D. [0020] The process provides for the adaptation of the recycled polymer to processing with "additive manufacturing" technologies, necessary to obtain the degree of viscosity required by the effective processing of the filament in the printing phase. Furthermore, the process involves the functionalization phase with nanomaterial with antibacterial and virucidal properties, through the mixing of recycled polymer with a specific masterbatch. This master is preferably made with the same recycled-based polymer loaded with the reference nanomaterial. Once the recycled PA has been mixed with the master, the preparation is fed to the additive manufacturing processes by appropriately modifying its characteristics to allow its effective workability on 3D printing equipment.

[0021] I manufatti ottenibili dal filamento innovativo presentano proprietà antibatteriche e virucide e sono pertanto particolarmente adatti all'impiego in ambito „protezione personale“, oltre ad essere caratterizzati da elevata leggerezza, robustezza, maggiore resistenza agli agenti chimici, regolarità superficiale, opportunità di personalizzazione elevata e inimitabili complessità geometriche. [0021] The products obtainable from the innovative filament have antibacterial and virucidal properties and are therefore particularly suitable for use in the field of "personal protection", as well as being characterized by high lightness, sturdiness, greater resistance to chemical agents, surface regularity, high customization and inimitable geometric complexity.

Breve descrizione della figuraBrief description of the figure

[0022] La figura annessa illustra schematicamente un procedimento di fabbricazione secondo l'invenzione. Il procedimento comporta come prodotto intermedio un prodotto antimicrobico utilizzabile per la stampa tridimensionale. [0022] The attached figure schematically illustrates a manufacturing process according to the invention. The process involves as an intermediate product an antimicrobial product which can be used for three-dimensional printing.

Divulgazione di un modo di realizzazione dell'invenzioneDisclosure of an embodiment of the invention

[0023] Riferendosi alla figura, il materiale di partenza del procedimento inventivo proviene manufatti tessili 20 sintetici, per esempio una poliammide 6 (PA6), per mezzo di procedimenti noti 25, sino a ottenere un prodotto riciclato rigranulato 30. I mezzi 25 usati per il riciclo della poliammide possono includere delle fasi di lavaggio, taglio, triturazione, separazione dei materiali estranei, vaglio, fusione e via di seguito. [0023] Referring to the figure, the starting material of the inventive process comes from synthetic textile products 20, for example a polyamide 6 (PA6), by means of known processes 25, until a regranulated recycled product 30 is obtained. The means 25 used for Polyamide recycling may include stages of washing, cutting, shredding, separation of foreign materials, screening, melting and so on.

[0024] Una parte del prodotto rigranulato 30 è destinata alla produzione di un masterbatch ad alta concentrazione di TiO2. A questo scopo, la poliammide riciclata è mescolata ad una quantità opportuna di nanoparticelle di biossido di titanio 32 con una dimensione média inferiore a un micrometro. Preferibilmente, le particelle di biossido di titanio impiegate hanno una dimensione massima inferiore o uguale a 150 nm, meglio se compresa tra 5 nm e circa 100 nm, idealmente compresa tra 10 nm e circa 30 nm. [0024] A part of the regranulated product 30 is intended for the production of a masterbatch with a high concentration of TiO2. For this purpose, the recycled polyamide is mixed with a suitable amount of titanium dioxide nanoparticles 32 with an average size of less than one micrometer. Preferably, the titanium dioxide particles used have a maximum size lower than or equal to 150 nm, better if between 5 nm and about 100 nm, ideally between 10 nm and about 30 nm.

[0025] A causa della loro spiccata igroscopicità, si preferisce utilizzare un procedimento di macinazione criogenica per trasformare i granuli di polimero riciclato in polvere. Questo processo garantisce un miglior controllo della fase successiva di lavorazione: la realizzazione del masterbatch. [0025] Due to their marked hygroscopicity, it is preferred to use a cryogenic grinding process to transform the recycled polymer granules into powder. This process ensures better control of the next processing stage: the creation of the masterbatch.

[0026] Dopo aver premiscelato il polimero riciclato polverizzato alla nanocarica nella concentrazione desiderata, il masterbatch viene realizzato con un processo di estrusione tramite estrusore bivite e successiva pellettizzazione. [0026] After premixing the pulverized recycled polymer with the nanofiller in the desired concentration, the masterbatch is made with an extrusion process using a twin-screw extruder and subsequent pelletisation.

[0027] In una possibile variante, il master arricchito di nanoparticelle di TiO2 può essere prodotto a partire da un polimero vergine invece che da una parte del polimero riciclato. [0027] In a possible variant, the master enriched with TiO2 nanoparticles can be produced starting from a virgin polymer instead of from a part of the recycled polymer.

[0028] Nella tappa di produzione 60, il polimero riciclato 52 e il master 51 sono usati in miscela per alimentare un estrusore 60 con una vite di plastificazione con profilo per materiali speciali. Alla fuoriuscita del polimero allo stato fuso (gelificato) lo stesso è prelevato e accompagnato a una stazione di tiro in cui si ricava un filamento 65 di diametro adatto all'alimentazione di stampanti tridimensionali. [0028] In the production step 60, the recycled polymer 52 and the master 51 are used in mixture to feed an extruder 60 with a plasticizing screw with a profile for special materials. When the polymer comes out in the molten (gelled) state, it is taken and accompanied to a drawing station where a 65 diameter filament suitable for feeding three-dimensional printers is obtained.

[0029] Il filamento 65 viene infine utilizzato per alimentare una stampante FFF 80 e ottenere in questo modo un prodotto finale stampato 100. In ragione dell'igroscopicità e delle poliammidi e per evitare deformazioni alla stampa, è opportuno utilizzare una stampante dotata di una camera di essiccazione 68 direttamente comunicante con un involucro a temperatura controllata 66 che racchiude il volume attivo di stampa. [0029] The filament 65 is finally used to feed an FFF 80 printer and thus obtain a final printed product 100. Due to the hygroscopicity and polyamides and to avoid deformation during printing, it is advisable to use a printer equipped with a chamber drying chamber 68 communicating directly with a temperature-controlled casing 66 which encloses the active print volume.

Simboli utilizzati nella figuraSymbols used in the figure

[0030] 20 prodotto tessile a fine vita 25 procedimento di riciclo 30 poliammide riciclata granulata 31 polverizzazione criogenica 32 nanocarica di ossido metallico 40 estrusore bivite 52 polimero riciclato 60 estrusore 65 filamento 66 involucro a temperatura controllata 68 camera d'essiccazione 80 stampante FFF 100 prodotto stampato [0030] 20 end-of-life textile product 25 recycling process 30 granulated recycled polyamide 31 cryogenic pulverization 32 metal oxide nanofiller 40 twin-screw extruder 52 recycled polymer 60 extruder 65 filament 66 temperature-controlled casing 68 drying chamber 80 FFF printer 100 product printed

Claims (15)

1. Procedimento di fabbricazione di un oggetto, comprendente le fasi di: – fornitura di un manufatto tessile, in particolare un manufatto tessile a fine vita, – ottenimento di un polimero riciclato a partire dal manufatto tessile, – funzionalizzazione del polimero riciclato in modo da renderlo antimicrobico, – fabbricazione di detto oggetto a partire da detto polimero riciclato funzionalizzato.1. Manufacturing process of an object, including the steps of: – supply of a textile product, in particular a textile product at the end of its life, – obtaining a recycled polymer starting from the textile product, – functionalisation of the recycled polymer in order to make it antimicrobial, – manufacture of said object starting from said functionalized recycled polymer. 2. Il procedimento della rivendicazione precedente, in cui la funzionalizzazione comporta la miscelazione di una matrice di polimero riciclato e d'una carica di nanoparticelle di un ossido metallico ad una percentuale massica compresa tra lo 0.1 % e il 20%, preferibilmente compresa tra lo 0.5% e il 5%.2. The process of the preceding claim, wherein the functionalization involves mixing a recycled polymer matrix and a filler of nanoparticles of a metal oxide at a mass percentage ranging from 0.1% to 20%, preferably ranging from 0.5% and 5%. 3. Il procedimento della rivendicazione precedente in cui le nanoparticelle di ossido metallico sono nanoparticelle di diossido di titanio.The process of the preceding claim wherein the metal oxide nanoparticles are titanium dioxide nanoparticles. 4. Il procedimento della rivendicazione 2, in cui le nanoparticelle di ossido metallico hanno una dimensione média inferiore a 1 µm, preferibilmente inferiore a 150 nm, più preferibilmente compreso tra 10 nm e 30 nm.4. The process of claim 2, wherein the metal oxide nanoparticles have an average size of less than 1 µm, preferably less than 150 nm, more preferably between 10 nm and 30 nm. 5. Il procedimento d'una delle rivendicazioni 2-4 in cui la miscelazione comporta la preparazione d'un master contenente una prima concentrazione di nanoparticelle di ossido metallico in una matrice di polimero e la plastificazione del master insieme al polimero riciclato.The process of one of claims 2-4 wherein the mixing involves preparing a master containing a first concentration of metal oxide nanoparticles in a polymer matrix and plasticizing the master together with the recycled polymer. 6. Il procedimento d'una delle rivendicazioni precedenti, in cui i manufatti tessili contengono fibre poliammidiche e la matrice di polimero riciclato è una poliammide alifatica, per esempio una matrice di Nylon 6,6 o di Nylon 6.6. The process of one of the preceding claims, wherein the textile articles contain polyamide fibers and the recycled polymer matrix is an aliphatic polyamide, for example a matrix of Nylon 6,6 or Nylon 6. 7. Il procedimento d'una delle rivendicazioni precedenti, in cui la fabbricazione dell'oggetto comporta dei procedimenti additivi o di stampa tridimensionale per fabbricazione per fusione di filamento (FFF).The process of one of the preceding claims, wherein the manufacturing of the object involves additive or three-dimensional printing processes by fusion filament manufacturing (FFF). 8. Il procedimento della rivendicazione precedente, comprendente la tappa di adattamento delle caratteristiche del polimero riciclato, e in particolare della sua viscosità, in modo che il filamento sia adatto a realizzare la stampa tridimensionale.8. The process of the preceding claim, comprising the step of adapting the characteristics of the recycled polymer, and in particular of its viscosity, so that the filament is suitable for carrying out the three-dimensional printing. 9. Il procedimento d'una delle rivendicazioni da 1 a 6, in cui la fabbricazione dell'oggetto comporta uno stampaggio.9. The process of one of claims 1 to 6, wherein the manufacture of the object involves moulding. 10. Il procedimento secondo una delle rivendicazioni precedenti, comprendente delle operazioni di essiccamento del polimero riciclato funzionalizzato.10. The process according to one of the preceding claims, comprising drying operations of the functionalized recycled polymer. 11. Materiale antimicrobico per la fabbricazione additiva per fabbricazione per fusione di filamento (FFF) comprendente una matrice di polimero riciclato e una carica di nano particelle di ossido metallico ad una percentuale massica compresa tra lo 0.1 % e il 20%, preferibilmente compresa tra lo 0.5% e il 5%.11. An antimicrobial material for fusion filament manufacturing (FFF) additive manufacturing comprising a recycled polymer matrix and a filler of metal oxide nano particles at a mass percentage of between 0.1% and 20%, preferably between 0.5% and 5%. 12. Il materiale della rivendicazione precedente, in cui le nanoparticelle di ossido metallico sono nanoparticelle di diossido di titanio.The material of the preceding claim, wherein the metal oxide nanoparticles are titanium dioxide nanoparticles. 13. Il materiale d'una delle rivendicazioni 11 o 12, in cui le nanoparticelle di ossido metallico hanno una dimensione média inferiore a 1 µm, preferibilmente inferiore a 150 nm, più preferibilmente compreso tra 10 nm e 30nm.The material of any one of claims 11 or 12, wherein the metal oxide nanoparticles have an average size of less than 1 µm, preferably less than 150 nm, more preferably between 10 nm and 30nm. 14. Il materiale d'una delle rivendicazioni da 11 a 13, in cui la matrice di polimero riciclato è una poliammide alifatica, per esempio una matrice di Nylon 6,6 o di Nylon 6 proveniente dal riciclo di capi di abbigliamento contenenti fibre poliammidiche.14. The material of one of claims 11 to 13, wherein the recycled polymer matrix is an aliphatic polyamide, for example a matrix of Nylon 6,6 or Nylon 6 coming from the recycling of garments containing polyamide fibres. 15. Il materiale d'una delle rivendicazioni da 11 a 14, condizionato come un filamento di diametro adatto all'alimentazione di stampanti tridimensionali.15. The material of one of claims 11 to 14, conditioned as a filament with a diameter suitable for feeding three-dimensional printers.
CH000045/2022A 2022-01-14 2022-01-14 Process of fabricating and antimicrobial material per fabricating additiva per fabricating per fusion of filament. CH719359A2 (en)

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