Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
  • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
  • C08K5/5333—Esters of phosphonic acids
  • C08K5/5357—Esters of phosphonic acids cyclic
• • 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
  • B29C64/141—Processes of additive manufacturing using only solid materials
  • B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0066—Flame-proofing or flame-retarding additives

Definitions

• the present invention relates to a process for preparing flame-retardant parts by melting on a powder bed, in which the powder comprises at least one polyamide ef / or copolyamide and at least one flame retardant, as well as the corresponding powder.
• the flame retardancy of polymers is conventionally provided by the dispersion of mineral fillers or flame retardant additives, in particular based on halogenated compounds.
• patent application US 2010/0324190 describes a powder comprising polyamide 12 e ⁇ a flame retardant additive of ammonium polyphosphate type as well as its use in 3D printing.
• ammonium polyphosphate is responsible for a significant uptake of water in the parts that contain it, which adversely affects their dimensional stability in the event of a change in humidity.
• the present invention arises from the unexpected demonstration by the inventors that the addition to a powder for 3D printing of a flame retardant of the cyclic phosphonate ester type of the following formula (III):
• the mixture of a powder for 3D printing and the flame-retardant agent of the invention makes it possible to obtain well-sintered flame-retardant parts which do not exhibit any coalescence problem, thus guaranteeing good mechanical properties.
• the present invention relates to a process for preparing flame retardant parts by melting on powder li ⁇ , in which the powder comprises at least one polyamide and / or copolyamide and at least one flame retardant of the cyclic phosphonate ester type.
• the present invention also relates to a powder intended for the preparation of flame retardant parts by melting on powder li ⁇ , comprising at least one polyamide and / or copolyamide e ⁇ at least one flame retardant of cyclic phosphonate ester type.
• the present invention also relates to the use of a powder comprising at least one polyamide and / or copolyamide and at least one flame retardant of cyclic phosphonate ester type in a process for melting on powder, in particular a 3D printing process, more particularly by laser or infrared sintering, to produce a fireproof part.
• the present invention also relates to a process for preparing a powder as defined above, comprising the mixture of at least one polyamide and / or copolyamide e ⁇ of at least one cyclic phosphonate ester flame retardant.
• a powder bed smelting process is an additive manufacturing process in which an object or part is obtained by the selective fusion of certain areas of a powder bed according to the invention.
• the method according to the invention is a 3D printing method and the powder is a powder for 3D printing. More preferably, the process according to the invention is a 3D printing process by laser or infrared sintering of the powder.
• 3D printing or “additive manufacturing” within the meaning of the invention, is meant any process for manufacturing parts in volume by adding or agglomerating powder, layer by layer.
• the agglomeration of powders by fusion (hereinafter “sintering”) is caused by radiation, such as for example a laser beam (laser sinfering), infrared radiation, UV radiation, or any source of electromagnetic radiation allowing the powder to be melted layer by layer to make three-dimensional objects.
• laser beam laser sinfering
• infrared radiation infrared radiation
• UV radiation or any source of electromagnetic radiation
• 3D printing or “additive manufacturing” within the meaning of the invention, is also meant the selective sintering technologies using an absorber, in particular the technologies known under the names “High Speed Sinfering” (HSS) e ⁇ “Mulfi-Jef Fusion ”(MJF).
• HSS High Speed Sinfering
• MEF Mulfi-Jef Fusion
• the fabrication of 3D objects is also done layer by layer from a digital file, the process using a powder (for example a polymer) which is melted in a controlled manner for each layer constituting the 3D object: an absorber is deposited on the layer (by means for example of a liquid ink in the “ink process”) before the exposure of the layer to electromagnetic radiation (for example infrared ) which causes fusion of the areas containing said absorber.
• electromagnetic radiation for example infrared
• patent documents US9643359 and EP I 648686 describe such processes.
• 3D printing is generally used to produce prototypes, models of parts ("rapid protofyping") or to produce functional parts in small series (“rapid manufacturing”), for example in the fields: automotive, nautical, aeronautics , aerospace, medical (prostheses, hearing systems, cellular tissues ...), textiles, clothing, fashion, decoration, cases for electronics, telephony, home automation, IT, lighting , sport, industrial tools.
• the difference Tf l -Te of the PA powders used in sintering is in the range of 30 ° C to 50 ° C.
• polyamide powder with the following properties is also preferred:
• the molecular mass of the powder in the solid state is preferably sufficiently low, that is to say of inherent viscosity in solution of less than 3, both so that the fusion of the grains does not require too much energy e ⁇ so that the inter-grain coalescence is sufficient during the passage of the radiation so as to obtain an object as less porous as possible, with good mechanical properties.
• the inherent viscosity is measured by adapting the ISO 307: 2007 standard (measurement temperature at 20 ° C instead of 25 ° C) using an Ubbelhode tube; the measurement is carried out at 20 ° C on a sample of 75 mg at a concentration of 0.5% (w / w) in m-cresol.
• the inherent viscosity es ⁇ expressed in (g / 100 g) - l e ⁇ es ⁇ calculated according to the following formula:
• polyamide means the condensation products:
• amino acids such as aminocaproic, 7-aminoheptanoic, 1-amino-undecanoic and 12-amino-dodecanoic acids of one or more lactams such as caprolactam, enantholactam and lauryllactam;
• - one or more salts or mixtures of diamines such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylene diamine with diacids such as isophthalic, terephthalic, azelaic and adiphalic acids , sebacic and dodecanedicarboxylic.
• diamines such as hexamethylenediamine, decanediamine, dodecamethylenediamine, metaxylylenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylene diamine with diacids such as isophthalic, terephthalic, azelaic and adiphalic acids , sebacic and dodecanedicarboxylic.
• diamines such as hexamethylenediamine, decanediamine, dodecamethylenedi
• copolyamide By way of copolyamide according to the invention, mention may be made of the copolyamides resulting from the condensation of at least two different monomers, for example of at least two different alpha omega-aminocarboxylic acids or of two different lactams or of a lactam and d 'an alpha omega aminocarboxylic acid of different carbon numbers. We can also mention the copolyamides resulting from the condensation of at least one alpha omega-aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• copolyamides examples include copolymers of caprolactam e ⁇ of lauryllactam (PA 6/12), copolymers of caprolactam, of adipic acid and of hexamethylene diamine (PA 6/66), copolymers of caprolactam, lauryl lactam, adipic acid e ⁇ hexamethylene diamine (PA 6/12/66), copolymers of caprolactam, lauryllactam, amino 1 1 undecanoic acid, azelaic acid e ⁇ d 'hexamethylene diamine (PA 6/69/1 1/12), copolymers of caprolactam, lauryllactam, amino 1 1 undecanoic acid, adipic acid and hexamethylene diamine (PA 6/66/1 1 / 12), copolymers of lauryllactam, of azelaic acid e ⁇ of hexamethylene diamine (PA 69/12), copolymers of lauryll
• Standard NF EN ISO 1874-1: 201 1 defines ⁇ a nomenclature of polyamides.
• the firm "monomer” in the present description of powders based on polyamides should be taken in the sense of "repeating unit".
• the case where a repeating unit of the polyamide consists of the association of a diacid with a diamine is particular. It is considered that it is the association of a diamine and a diacid, that is to say the “diaminedacid” couple, also called “XY”, in an equimolar amount which corresponds to the monomer. This is because, individually, the diacid or diamine is only a structural unit, which is not enough on its own to form a polymer.
• diamine X By way of example of diamine X, mention may be made of aliphatic diamines having from 6 to 18 atoms, the diamine X possibly also being saturated aryl and / or cyclic. As examples, mention may be made of hexamethylenediamine, piperazine, tetra methylenediamine, octamethylene diamine, decamethylene diamine, dodeca methylenediamine, 1,5 diaminohexane, 2,2,4-trimethyl- l , 6-diamino-hexane, polyols diamine, isophorone diamine (IPD), methyl pentamethylenediamine (MPDM), bis (aminocyclohexyl) methane (BACM), bis (3-methyl-4 aminocyclohexyl) methane (BMACM) , methaxylyenediamine, bis-p-aminocyclohexylmethane and trimethylhexamethylene diamine.
• a diacid (or dicarboxylic acid) Y By way of example of a diacid (or dicarboxylic acid) Y, mention may be made of acids having between 4 and 36 carbon atoms. Mention may be made, for example, of adipic acid, sebacic acid, azelaic acid, suberic acid, isophthalic acid, butanedioic acid, 1, 4 cyclohexyldicarboxylic acid, terephthalic acid, sodium or lithium salt of sulfo-isophthalic acid, dimerized fatty acids (these dimerized fatty acids have a dimer content of at least 98% and are preferably hydrogenated) and dodecanedioic acid HOOC- (CH2 ) io-COOH.
• Lactam or amino acid monomers are said to be of type "Z":
• lactams By way of example of lactams, mention may be made of those having from 3 to 12 carbon atoms on the main cycle and which may be substituted. Mention may be made, for example, of b, b-dimethylpropriolactam, a, a-dimethylpropriolactam, amylolactam, caprolactam, capryllactam, oenantholactam, 2-pyrrolidone and lauryllactam.
• an amino acid mention may be made of alpha-omega amino acids, such as aminocaproic, amino-7-heptanoic, amino-1 1 -undecanoic, n-heptyl-1 1 -aminoundecanoic and amino-12-. dodecanoic.
• the powder comprising a polyamide and / or copolyamide of the invention comprises at least one polyamide and / or copolyamide chosen from polyamides and copolyamides comprising at least one of the following XY or Z monomers: 46, 4T, 56, 59 , 510, 512, 513, 514, 51 6, 518, 536, 6, 69, 610, 612, 613, 614, 61 6, 618, 636, 6T, 9, 109, 1010, 1012, 1013, 1014, 101 6, 1018, 1036, 10T, 11, 12, 129, 1210, 1212, 1213, 1214, 121 6, 1218, 1236, 12T, MXD6, MXD 10, MXD 12, MXD 14, and their mixtures; in particular chosen from PA 1 1, PA 12, PA 1010, PA 6, PA 6/10, PA 6/12, PA 10/12, PA 1 1/1010, and their mixtures .
• the polyamide and / or copolyamide according to the invention can be a mixture of polyamides and / or copolyamides. Mention may be made, by way of mixture, of mixtures of aliphatic polyamides / coplyamides and of semi-aromatic polyamides / copolyamides and of mixtures of aliphatic polyamides and of cycloaliphatic polyamides.
• the polyamide and / or copolyamide according to the invention can be a polyamide block copolymer, in particular a polyamide block copolymer and polyether blocks.
• Polyamide block copolymers and polyether block copolymers result from the copolycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, among others:
• Polyamide sequences having dicarboxylic chain ends with polyoxyalkylene sequences having diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic alpha-omega dihydroxylated polyoxyalkylene sequences called polyetherdiols.
• the polyamide sequences containing dicarboxylic chain ends originate, for example, from the condensation of alpha-omega-aminocarboxylic acids, lactams or dicarboxylic acids e ⁇ diamines in the presence of a dicarboxylic acid chain limiter.
• the polyether can be, for example, a polytetramethylene glycol (PTMG). The latter is also called polytetrahydrofuran (PTHF).
• the molar mass in number of the polyamide blocks is between 300 and 15000 and preferably between 600 and 5000 g / mol.
• the molar mass of the polyether blocks is between 100 and 6000 and preferably between 200 and 3000 g / mol.
• Polymers containing polyamide blocks and polyether blocks can also comprise units distributed randomly. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
• polyetherdiol for example, one can react polyetherdiol, a lactam (or an alpha-omega amino acid) and a chain-limiting diacid in the presence of water.
• a polymer is obtained having essentially polyether blocks, polyamide blocks of very variable length, but also the various reactants having reacted randomly which are distributed randomly along the polymer chain.
• the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated in order to be transformed into polyether diamines and condensed with polyamide blocks having carboxylic ends. They can also be mixed with polyamide precursors and a chain limiter to make polymers containing polyamide blocks and polyether blocks having units distributed in a statistical manner.
• the ratio of the amount of polyamide block and polyether block copolymer to the amount of polyamide is advantageously between 1/99 and 1 5/85 by weight.
• the polyamide and / or copolyamide according to the invention is selected from the group consisting of polyamide 6 (PA6), polyamide 66 (PA66), poyamide 610 (PA 610), polyamide 612 (PA 612), polyamide 1 1 (PA 1 1) and polyamide 12 (PA 12).
• the polyamide and / or copolyamide according to the invention is PA11.
• the cyclic phosphonate ester type flame retardant is of general formula (I):
• j, k, I e ⁇ m identical or different, represent an integer from 1 to 3;
• a 1 e ⁇ A 2 identical or different, represent an alkyl group of 1 to 4 carbon atoms or an aryl group of 5 to 7 carbon atoms.
• the cyclic phosphonate ester flame retardant is of the general formula (II):
• a 1 e ⁇ A 2 identical or different, represent an alkyl group of 1 to 4 carbon atoms or an aryl group of 5 to 7 carbon atoms.
• the cyclic phosphonate ester flame retardant is of the following formula (III):
• the flame retardant is a powder, which typically has a volume median diameter D50 in the range of 1 to 40 miti, preferably 5 to 30 miti.
• the powder according to the invention typically has a volume median diameter D50 in the range of 5 to 200 mi.
• the powder has a volume median diameter D50 comprised in the range of 10 to 150 miti, preferably 20 to 100 miti, and 25 to 80 miti.
• the median diameter by volume (D50) of the powder particles is measured according to the ISO 9276 standard - parts 1 to 6: “Representation of data obtained by particle size analysis”.
• the powder can in particular be obtained by mixing the flame retardant of cyclic phosphonate ester type with at least one polyamide and / or copolyamide. Any method known to those skilled in the art can be used.
• the process for preparing the powder according to the invention is carried out by a dry mixing of the flame retardant and at least one polyamide and / or copolyamide.
• a mixer known to those skilled in the art, for example a Henschel, MAGIMIX, or LOEDIGE mixer.
• the mixture is advantageously carried out at room temperature. The speed of rotation can be easily adjusted.
• the powders can optionally be sieved after mixing.
• the powder comprises 5 to 40% by mass, preferably 5 to 35% by mass, more preferably 5 to 30% by mass, preferably 5 to 25% by mass, based on the total mass powder, cyclic phosphonate ester flame retardant.
• the powder comprises at least 40%, 50%, 60%, 70%, 80%, 90% or 95% by mass of polyamide and / or copolyamide relative to the total mass of the powder.
• the powder comprises at most 95%, 90%, 80%, 70%, 60%, 50% by mass of polyamide and / or copolyamide relative to the total mass of the powder.
• the powder may also contain at least one other polymer.
• this ⁇ other polymer we can mention polyolefins, polyesters, polycarbonate, PPO (abbreviation of polyphenylene oxide), PPS (abbreviation of polyphenylene sulfide), elastomers.
• the powder according to the invention does not comprise any polymer other than the polyamide and / or copolyamide according to the invention.
• the powder according to the invention comprises at least one other additive, in particular selected from the group consisting of a synergizer of the flame retardant of the cyclic phopshonate ester type, of a pigment, of a dye, a plasticizer, an antioxidant, a flow agent, and a UV absorber.
• a synergizer of the flame retardant of the cyclic phopshonate ester type of a pigment, of a dye, a plasticizer, an antioxidant, a flow agent, and a UV absorber.
• the synergizer of the cyclic phopshonate ester type flame retardant is selected from the group consisting of aluminum diethylphosphinate (DEPAL), melamine cyanurate, pyrophosphate, red phosphorus, phosphates, melamine polyphosphate, and ammonium polyphosphate.
• DEPAL diethylphosphinate
• melamine cyanurate pyrophosphate
• red phosphorus red phosphorus
• phosphates melamine polyphosphate
• ammonium polyphosphate ammonium polyphosphate
• the powder according to the invention does not include a synergizer of the cyclic phopshonate ester flame retardant.
• the powder of the present invention exhibits good recyclability, in particular when it is prepared by a dry mixing process.
• the invention makes it possible to recycle the unprocessed powder into part following 3D printing, that is, to reuse the unconverted powder in a subsequent 3D printing process to obtain flame retardant objects with reproducible mechanical properties and flame retardant properties.
• the invention relates to a process for preparing flame-retardant parts by melting on a powder bed, in particular by 3D printing, more particularly by 3D printing by laser sintering, using a recycled powder as defined above.
• the flame-retardant part according to the invention can be of a crazy type capable of being produced by fusion on a powder bed, in particular by 3D printing, more particularly by 3D printing by laser sintering.
• the powder according to the invention is such that it makes it possible to obtain parts classified V-2, more advantageously Vl and even more advantageously V-0 according to the UL 94 V and IEC 60695-1 1 -10 standards, in particular described in the examples. Description of flaws
• Figure 1 is a photograph of a part obtained by 3D printing from a powder according to the invention.
• Figure 2 is a photograph of a part obtained by 3D printing from a comparative powder.
• a powder according to the invention is produced by dry mixing ("dry blend", using a Henschel mixer) 83% by mass relative to the total mass of the polyamide powder 1 1 (Rilsan Invent Natural ( RIN), Arkema) and 17% by mass relative to the total mass of the powder of flame retardant of cyclic phosphonate ester type of formula (III) below:
• a comparative powder is produced which comprises 80% by mass relative to the total mass of the polyamide powder 1 1 (Rilsan Inven ⁇ Natural (RIN), Arkema) e ⁇ 20% by mass relative to the total mass of the melamine polyphosphate flame retardant powder (Melapur TM 200, BASF).
• the powders are ⁇ used to power a Formiga® P 100 (Eos) e ⁇ 3D printer to print a bar-type part with the following dimensions: length 127mm, width 12.7mm and ⁇ thickness 2.5mm. Photographs of the parts obtained are presented in Figure 1 (powder according to the invention) and in Figure 2 (comparative powder).
• the powder according to the invention makes it possible to obtain a perfectly smooth part
• the part obtained with the comparative powder exhibits coalescence problems.
• the comparative powder is therefore unsuitable for use in 3D printing.
• Tests were carried out with a commercial flame retardant Technirez® FR-001, exhibiting a viscous liquid appearance, which has the same molecule as the flame retardant Antiblaze 1045®.
• Test 1 Technirez® FR-001 flame retardant agen ⁇ was introduced into the polyamide powder using a Henschel mixer.
• a very flaky powder is obtained. It is impossible to use it in the 3D printing machine, i.e. part sintering could not be performed.
• Test 2 The flame retardant Technirez® FR-001 is heated beforehand to 70 ° C before introducing it into a Flenschel mixer with the polyamide powder with stirring.
• Example 1 The part obtained from the powder according to the invention as defined in Example 1 was tested according to UL 94V standard.
• the length of the sample is 127 mm and its width is 12.7 mm. Its thickness must not exceed 12.7mm.
• the specimen is fixed at 1/4 of its upper end in a vertical position.
• a metal wire ⁇ covered with surgical cotton is placed 305 mm below the sample.
• the burner is set to form a 19mm blue flame which heats up from 100 to 700 ° C in 44 ⁇ 2 seconds. This flame is directed from below over the lower edge of the plastic sample at a distance of 9.5 mm. It is applied for 10 seconds, then removed.
• the burn time of the sample is measured. As soon as the combustion stops, the flame is reapplied for 10 seconds. As soon as it is removed, the burn time e ⁇ of incandescence is measured again.
• the full test is performed on five samples.
• the material tested is UL 94 V-O classified if:
• the material tested is UL 94 V-l classified if:
• the material tested is UL 94 V-2 classified if:
• test results according to UL 94V standard The part according to the invention is classified V-0 according to UL 94 standard measured with a thickness of 1.3 mm on the samples
• the mechanical properties of maximum stresses e ⁇ of elongation at break of the parts obtained using the powder according to the invention are ⁇ equivalent to those of parts obtained with the comparative FR-106 powder comprising an agent halogenated flame retardant.
• Young's modulus measured according to the ISO 527-2: 2012-1 A standard with approximately 2000 MPa for the parts of the invention against 1750 for the parts obtained with the comparative FR-106 powder.
• the present invention thus provides a powder without halogenated additives, easy to prepare and to use in 3D machines, making it possible to manufacture a part having a better flame retardant property while maintaining the mechanical properties.

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• 2019
  • 2019-03-18 FR FR1902769A patent/FR3093945B1/fr active Active
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