TWI311578B - Fireproofing polyamide powders and their use in a sintering process - Google Patents

Description

1311578 (1) Description of the Invention [Technical Field] The present invention relates to a flame-retardant polyamide powder and its use in a sintering method, for example, a method of sintering under irradiation of radiation (e.g., laser light). The present invention relates to a composition mainly composed of a flame resistant powder (e.g., formed of polyamidamine π or ruthenium 2) which can be blended with a technique of sintering treatment (e.g., under laser light). Its purpose is to develop a flame resistance that does not φ and thus impairs other performance characteristics of the material (suitable for viscosity/rheology/flowability of the target application, satisfactory mechanical properties) and can be sintered by using radiation. The material that transforms the technique (especially the laser sintering technique). [Prior Art] The technique of sintering polyamine powder by laser light is used to manufacture three-dimensional objects such as prototypes or models. The fine layer of polyimide powder is deposited on a horizontal plate maintained in a bath having a temperature of φ heat between the crystallization temperature CP and the melting point MP of the polyamide powder. The powder particles are sintered by laser at different points of the powder layer according to the geometry corresponding to the object, for example, using a computer having a shape of the object in the memory and reconstructing it in a slice form. The horizontal plate is then lowered by a thickness corresponding to the thickness of the powder layer (for example, between 0.05 and 2 mm and typically about 0.1 mm), after which a fresh powder layer is deposited and according to the shape of the new article corresponding to this, The powder particles are sintered by laser. Repeat this procedure until you have a complete object. A powder block having an object inside is obtained. Therefore, the unsintered portion maintains the powder form. Thereafter, the combined product is slowly cooled, and the temperature of the composition is lowered to below the crystalline -4-(2) 卩11578 point CP, and the article solidifies. When completely cooled, the article is separated from the powder and the powder can be reused for another operation. It is recommended that the MP-CP difference of the powder used be as high as possible to avoid deformation (or curling) during the production process. This is because, at the tQ time point immediately after the action of the laser light, the sample temperature is greater than the crystallization point (CP) of the powder, but the introduction of a fresh, colder powder layer causes the temperature of the component to rapidly drop below the CP and cause The reason of the deformation. In addition, the AHf is required to be as high as possible so that the resulting assembly has good geometric definition. This is because, if the phlegm is too low, the energy introduced by the laser is sufficient to sinter the powder particles close to the growth wall due to heat conduction, so that the geometric accuracy of the assembly is no longer satisfactory. It is clear that all previous explanations for the use of laser-fired polyamide powders are suitable for any radiation that initiates melting. In special applications, the resulting article must be flame retardant, even flame resistant, but must also meet the criteria for smoke odour and toxicity. Hereinafter, for the sake of simplicity, the term 'flame resistant' is used for flame retardancy and flame resistance. It is known that metal organic phosphinates and organophosphorus additions based on ammonium polyphosphate are suitable for laser sintering. Dry blending of these products with the polyamide powder is sufficient. It has also been found that flame retardants which are generally used for polyamines are not suitable. For example, melamine cyanurate is not suitable. SUMMARY OF THE INVENTION The present invention relates to the use of a flame resistant polyamine powder in a method for preparing a polyamidide article by sintering the -5- (3) 1311578 powder by radiation. The powder comprises 2 to 4 0% by weight of at least one flame retardant and 98% to 60% by weight of at least one polyamine, the flame retardant being a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate. According to one system, the powder consists of the following components (to a total weight of the powder of 1% by weight):

• 2 to 40% by weight of at least one flame retardant, the flame retardant being a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate; • 98 to 60% by weight of at least one polyamine; And • at least one agent selected from the group consisting of UV stabilizers, antioxidants, dyes, pigments, bactericides, and rheological agents. According to one system, the phosphinate used is selected from the group consisting of a phosphinate represented by the formula (I) and a diphosphinate represented by the formula (Π):

Μ 〇 Ο II II - Ρ - R3 - P - o Ι (II)

Ri -Λ.- R2

Mxn wherein Ri and R2 are the same or different and are straight or branched Ci to C6 alkyl and/or aryl; R3 is straight or branched (2 to C1G alkyl, 〇6 to C1G aryl) , c6 to Cio alkyl extended aryl or c6 to CiG aryl extended base; -6- 1311578

M is a depletion, an imprint and/or a zinc ion; m is 2 or 3; η is 1 or 3; X is 1 or 2.

According to one system, the polyamine is selected from the group consisting of hydrazine 11, hydrazine 12, an aliphatic polyfluorene formed by the condensation reaction of an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having 9 to 18 carbon atoms. Amine, having more than 90% of 11 units or more than 90% of 12 units of copolymerized amidoxime/12. The invention also relates to an article made of a flame resistant polyamide powder comprising 2 to 40% by weight of at least one flame retardant and 98 to 60% by weight of at least one polyamine, the flame retardant being organic of at least one metal A blend of a phosphinate and at least one ammonium polyphosphate which is sintered by radiation.

It is also a method for preparing a polyamidide article by irradiating a polyimide powder with radiation, the powder comprising 2 to 40% by weight of at least one flame retardant and 98 to 60% by weight of at least one polyamine, the flame retardant It is a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate. According to one system, this radiation is derived from laser light. This powder can be obtained by simple dry blending of the components, which is a preferred system. It is also possible to add the flame retardant to the molten polyamine in the mixing device and to reduce the resulting product to a powder form, but in this case, there is a decrease in the hydrazine and a result of the aforementioned occurrence of the conversion of the powder by the sintering technique. Hey. The polyamine can be a homopolyamine or a copolymerized guanamine. It may be a blend of polyfluorene and at least one other polymer which forms a matrix of [5) 1311578 ί which also forms a phase dispersed in the matrix. Radiation can be supplied, for example, by a laser beam (thus 'this method is called "laser sintering"). The reticle in this method can be interposed between the powder layer and the source of radiation; the powder particles protected by the reticle are not sintered. DETAILED DESCRIPTION OF THE INVENTION As for polyamines, the term "polyamine" refers to the condensation products of:

One or more amino acids, such as: aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid, or one or more internal guanamines, such as: Amidoxime, heptanoin and laurylamine; a mixture of one or more salts or diamines (eg hexamethylenediamine, lauryldiamine, m-xylylenediamine, bis-(p-aminocyclohexyl) ) methane and trimethylhexamethylenediamine) and diacids (eg, isodecanoic acid, p-citric acid 'adipic acid, sebacic acid, suberic acid, sebacic acid and lauric acid, and Cm to C18 diacid) . Examples of polyamines are PA 6, PA 6-6, PA11, PA12, PA6-10, PA6-12 and PA6-14. Copolyamide can also be used. The copolymerized decylamine may be obtained by condensation reaction of at least two α,ω-amino carboxylic acids or two internal guanamines or an internal decylamine with an α,ω-aminocarboxylic acid. It may also be a copolymerized decylamine obtained by a condensation reaction of at least one α, ω-aminocarboxylic acid (or an internal guanamine), at least one diamine and at least one dicarboxylic acid. It may also be a copolymerization reaction of an aliphatic diamine with an aliphatic dicarboxylic acid and at least one aromatic diamine other than the above and another monomer other than the above aliphatic diacid. An example of the indoleamine may be one having 3 to 12 carbon atoms on the main ring -8 - (6) 1311578 and which may be substituted. Examples may be, for example, β,β-dimethylpropionamide, α,α-dimethylpropionamide, valeroinamine, caprolactam 'octeneamine and laurylamine.

Examples of the α,ω-aminocarboxylic acid may be aminoundecanoic acid and aminododecanoic acid. Examples of the dicarboxylic acid may be adipic acid, sebacic acid, isodecanoic acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, p-nonanoic acid, sodium or lithium salt of sulfisoisophthalic acid, and dimerization. Fatty acids (the dimer content of these dimerized fatty acids is at least 98% and preferably hydrogenated) and the lauric acid HOOC-(CH2) 10-CO〇H

The diamine may be an aliphatic diamine having 6 to 12 carbon atoms; it may be a saturated cyclic and/or aromatic group. Examples thereof may be hexamethylenediamine, piperazine, butanediamine, octanediamine, decanediamine, lauryldiamine, i,5-diaminohexane, 2,2,4-trimethyl-1,6. -diaminohexane, polyalcohol diamine, isophoronediamine (IPD), methylpentanediamine (MPDM), bis(aminocyclohexyl)methane (BCAM) or bis(3-methyl- 4-amino-cyclohexyl)methane (BMACM). An example of a copolymerized decylamine may be a copolymer of caprolactam and laurylamine (PA6/12), a copolymer of caprolactam, adipic acid and hexamethylenediamine (PA6/6-6), caprolactone. Copolymer of amine, laurylamine, adipic acid and hexamethylenediamine (PA6/12/6-6), caprolactam, laurylamine, 1丨-amino-carboic acid, bismuth Copolymer of acid and hexamethylene diamine (PA6/6-9/11-12), caprolactam, laurylamine, 11-aminoundecanoic acid, adipic acid and hexamethylenediamine (PA6/ 6-6/1 1-12 ), or a copolymer of laurylamine, sebacic acid and hexamethylene diamine (PA6-9/12). -9- (7) 1311578 A blend of polyamido can be used. These are, for example, blends of polyamines and semi-aromatic polyamines and blends of aliphatic polyamines and cycloaliphatic polyamines. For example, the composition disclosed in the patent application EP 1 2 2 7 1 3 1 contains the following components by weight, the total amount is 1: • 5 to 40% amorphous polyamine (B) , which is basically derived from the condensation reaction of the following species:

☆ at least one diamine selected from the group consisting of a cycloaliphatic diamine and an aliphatic diamine or at least one diacid selected from the group consisting of a cycloaliphatic diacid and an aliphatic diacid, at least one of which is at least one of Cycloaliphatic, ☆ or cycloaliphatic α,ω-amino carboxylic acid, ☆ or a combination of these two possibilities, ☆ and optionally selected from α, ω-amino carboxylic acid or related guilt At least one monomer of an amine, an aliphatic diacid and an aliphatic diamine, • 〇 to 40% of an elastomeric polyamine (C) selected from the group consisting of copolymers and copolymers comprising a polyamido agglomerate and a polyether mass Indoleamine, • 〇 to 20% for (A) and (Β) compatibilizer (D), • 〇 to 40% elastic modifier (Μ), • (C) + ( D ) + ( Μ ) Between 0 and 50% presupposes • The difference with 1〇〇% is complemented by semi-crystalline polyamine (Α). Patent application EP 1 227 1 3 2 also discloses compositions containing the following components by weight, in a total amount of 100%: 5 to 40% amorphous polyamine (Β), which is basically derived from To -10- 1311578

Condensation reaction of at least one selected cyclic diamine, at least one aromatic diacid and at least one of the following monomers selected: α, ω-amino carboxylic acid, aliphatic diacid, aliphatic diamine, • 0 to 4 〇% elastomeric polyamine (c) selected from the group consisting of copolymers of polyamidene agglomerates and polyether agglomerates and copolymerized guanamines,

• 〇 to 20% for (A) and (β) compatibilizers (d), • (C) + (D) between 2 and 50%, • ( B ) + ( C ) + ( D ) Not less than 30%, • The difference with 100% is complemented by semi-crystalline polyamine (A). A portion of the polyamine is replaced by a copolymer comprising a polyamidene agglomerate and a polyether agglomerate (ie, using a copolymer comprising at least one of the foregoing polyamines and at least one comprising a polyamido agglomerate and a polyether agglomerate) The blends do not depart from the scope of the invention.

The copolymer comprising a polyamine block and a polyether mass is derived from a copolymerization reaction of a polyamine sequence comprising a reactive end and a polyether sequence comprising a reactive end, for example, in particular: 1) comprising a diamine A polyamidene sequence at the end of the chain and a polyoxyalkylene sequence comprising a dicarboxy chain. 2) a polydecylamine sequence comprising a dicarboxy chain end and a polyoxyalkylene sequence comprising a diamine chain end, which is represented by an aliphatic α,ω-dihydroxylated polyoxyalkylene alkyl sequence (referred to as a polyether) Cyanide ethylation and hydrogenation of diols

-11 - 1311578

3) A polyamidole sequence comprising a dicarboxy chain end and a polyether diol, in which case the product is a polyether ester decylamine. It is preferred to use these copolymers. The polyamine sequence comprising a dicarboxy chain end is derived from the condensation reaction of an α,ω-aminocarboxylic acid, an indoleamine or a dicarboxylic acid and a diamine in the presence of a limiting chain dicarboxylic acid. This polyether can be, for example, polytetramethylene glycol (PTMG). The latter is also known as polytetrahydrofuran (PTHF).

The number average molecular weight Μη of the polyamine sequence is between 300 and 1,500, preferably between 650 and 50,000. The mass Μη of the polyether sequence is preferably between 100 and 6,000, preferably between 200 and 30,000. The polymer comprising a polyamine block and a polyether mass may also comprise randomly distributed units. These polymers can be prepared by simultaneous reaction of polyether and polyamido agglomerates. For example, a polyether diol, an indoleamine (or an α,ω-amino acid) and a chain-limiting diacid can be reacted in the presence of a small amount of water. The resulting polymer essentially has a polyether mass and a polyamidene agglomerate, the length of which varies widely, but there are also a variety of reactants that react in an irregular manner, which extend the polymer chain distribution in a statistically acceptable manner. These polymers comprise a polyamidene agglomerate and a polyether agglomerate, whether they are derived from a copolymerization reaction of a polyamine sequence and a polyether sequence prepared in advance or derived from a single-stage reaction, such as, Shore D Hardness between 20 and 75 (preferably between 30 and 70), internal viscous viscosity (measured at 25 ° C in p-cresol, initial concentration 0.8 g / 100 ml) Between .8 and 2.5. MFI値 is between 5 and 50 (23 5 °C, loading 1 kg-12-(10) 1311578 polyether diol agglomerates are used in this form and copolymerized with a polyamido oxime block containing a carboxyl terminal or Aminated to be converted to a polyether diamine' and condensed with a polyamine group comprising a carboxyl terminus. They may also be blended with a polyamine precursor and a chain limiting agent to prepare a polymer comprising statistically distributed units. a polymer of a guanamine agglomerate and a polyether mass.

Polymers comprising a polyamine block and a polyether mass are disclosed in US 4 33 1 786, US 4 115 475, US 4 1 95 015, US 4 83 9 441, US 4 864 0 1 4, US 4 230 8 3 8 and US 4 3 3 2 9 2 0. The weight ratio of the copolymer comprising the polyamide block and the polyether block to the amount of polyamine may be between 1/99 and 15/85.

As for the blend of polyamine and at least one other polymer', it may be in the form of a blend comprising a polyamine substrate and other one or more polymer forms which form a phase dispersed in the matrix. Examples of such other polymers are polyabidocarbons, polyesters, polycarbonates, PPO (abbreviation for polyphenylene oxide), PPS (abbreviation for polyphenylene sulfide) or elastomers. The particularly useful polyamine of the present invention is selected from the group consisting of PA1 1, PA12 'aliphatic polyamines derived from an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having 9 to 18 carbon atoms. The condensation reaction, and the copolymerized decylamine 11/12 has more than 90% of 11 units or more than 90% of I2 units. An example of an aliphatic polyamine derived from the condensation reaction of an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic diacid having 9 to 18 carbon atoms is PA 6-12, which is derived from Condensation of amine and 1,12-lauric acid-13- (11) 1311578 PA 9-12 'from the condensation reaction of C9 diamine and lauric acid, PA 10-10' is derived from C1G diamine and The condensation reaction of 1,10-sebacic acid, PA 10-12, is derived from the condensation reaction of C9 diamine and 1,12-lauric acid.

As for copolyamine 1 1 /1 2 having more than 90% of 11 units or more than 90% of 12 units, they are derived from 1 1 -aminoundecanoic acid and laurylamine (or α,ω-amino group (Ci2) The condensation reaction of acid). Blends using polyamido are also within the scope of the invention. Prior to blending with the flame retardant, the polyamine is treated with water and steam according to the method disclosed in the patent EP 1 4 1 3 5 95. In this patent, the disclosed method is used to enhance at least one of the following two parameters of polyamine: (i) its melting point and (Π) its hydrazine AHf, in which: • the polyamine The solid is contacted with water or water vapor at a temperature near its crystallization point CP for a time sufficient to initiate this increase. • Thereafter, water (or water vapor) is separated from the polyamine and the polyamine is dried. The polyamine can be a homopolyamine or a copolymerized guanamine. It may be a blend of polyamidamine and at least one other polymer which forms a matrix and the other polymer or polymers form a dispersed phase. Advantageously, the polyamine is in isolated form, such as a powder or granule. The granules thus treated can be honed to form a powder. -14- (12) 1311578 Treatment with water or steam may also be carried out by routine treatment of the extraction of oligomers which may be present in the polyamide. According to another form, the water or water vapor may comprise methanol. Thereby, oligomers and impurities present in the treated polyamine can be simultaneously extracted. In this form of the invention, it is recommended to rinse prior to drying the polyamide to completely remove any methanol present. As for the flame retardant or the flame retardant, the ratio is between 2 and 40% by weight, preferably between 5 and 35 % by weight, which are 98 to 60% by weight and 95 to 65% by weight, respectively. Guanamine. Preferably, it is between 5 and 30% by weight, corresponding to 95 to 70% by weight of polyamine. In addition to the metal organic phosphinate and ammonium polyphosphate, zinc borate is added as a synergist. The proportion of zinc borate may be between 0 and 10% by weight, which corresponds to from 1 to 0% by weight of the flame retardant or flame retardant, and the total (synergistic agent + flame retardant) constitutes 100% by weight. As for the powder, they can be of different sizes. For example, the powder used in the laser sintering method has a size of up to 3 50 μm and preferably has a size between 10 and 1 μm. Preferably, the D50 is 60 microns (i.e., 50% of the particles are less than 60 microns in size). As for its preparation, it can be carried out by a simple dry blending constitution. Mixers of commonly used powdered products (eg Henschel® mixers) can be used. Blend at standard temperature and pressure. The blending time must be sufficient to make the blend uniform; this time can be between 2 and 15 minutes. It is also possible to add the flame retardant to the molten polyamine in a mixing device and to reduce the resulting product to a powder form. The blending time must be sufficient to make the -15-(13) 1311578 blend uniform. Use ', for example, an extruder. At the extrusion exit, the product is recovered in the form of granules which are then honed to the same particle size as the polyammonium powder used in the dry blending process. The powder of the present invention may also contain additives: UV stabilizers, antioxidants, dyes, pigments or bactericides. These products are preferably incorporated into the polyamine prior to the addition of the flame retardant.

[Embodiment] The present invention will now be described in detail. Percentages are expressed in weight percent. 1) Preparation of PA powder with flame resistance

Using a Henschel® rapid mixer, incorporating PA 1 1 suitable for sintering under laser light (D50 is 48 microns and treated according to patent FR 2 8 4 6 3 3 3 A1, melting point 2 0 1 °C,焓1〇5 joules/gram), flame retardant blend (added according to the ratio defined below), 0.6% phenolic φ antioxidant, and 0.1% fumed vermiculite (as rheological agent) Polyamide powder blend. The blending time was 15 〇s. The blend thus obtained was sieved through a cloth having an opening of 160 μm. The flame retardant properties, ratios, and PA ratios are shown in the examples below and in the comparative examples. 2) Conversion of PA powder with flame resistance The powder blend prepared according to the above Process 1) is introduced to be used to deposit a layer of polyamidamine powder by being heated to a temperature at a crystallization point and dissolved -16 - (14) A laser sintering device for the manufacture of three-dimensional objects on a horizontal surface in a groove between 1311578 points. This laser sinters the powder particles according to the geometry corresponding to the object', e.g., using a 3D System Vanguard® device, the memory of which is shaped and reconstituted in slices.

The flame test was carried out on a sample having a size of 12 x 3 inches and a thickness of 0.05 inch. The burning time (seconds) and the burning length (inch) were measured using these samples. When the burning length is <6 inches and the burning time is as short as possible, the ignition property is considered to be satisfactory. Three comparative examples (Cpl to Cp3) having a PA blend which is not suitable for the flame retardant of the present invention will now be described: • having melamine cyanurate (Cpl) according to the method described in the above 1), Made of 89.3% PA 1 1, 10% melamine cyanurate (for example, Melapur C25) (as a flame retardant), 0.6% phenolic antioxidant and 0.1% fumed vermiculite (as a rheological agent) Powder blend. But during the conversion of the powder (the method is disclosed in 2)

) During the manufacturing period of laser sintering, component deformation was observed. • Ammonium phosphate (Cp2) according to the method described in the above 1), containing 89.3% PA1 1, 10% ammonium phosphate (for example, Exolit AP 752) (as a flame retardant), 0.6% phenolic antioxidants and A powder blend of 0.1% fumed vermiculite (as a rheological agent). However, during the conversion of the powder (the method of which is disclosed in 2)), it was found that the composition sublimed in the manufacturing bath, so that the laser light weakened and soiled the construction groove, so it was not very suitable for constructing the assembly. Further, the burning time of the obtained component was 1,29 seconds, and the flame resistance was unsatisfactory. -17- (15) 1311578 • With ammonium polyphosphate (CP3), according to the method described in 1) above, it is made to contain 8 9 · 3 % PA 1 1

A powder blend of 10% ammonium polyphosphate (e.g., Exolit AP 423) (as a flame retardant), 0.6% phenolic antioxidant, and 0.1% fumed vermiculite (as a rheological agent). However, during the conversion period in 2), it was found that this composition was very unsuitable for constructing components because it formed smoke in the manufacturing tank and caused the laser light to be weakened. Further, the burned length of the obtained component was 8.9 inches, the target to be achieved was <6 inches, and the burning time was 126 seconds, so that the flame resistance was unsatisfactory. Thus, it has been found that the use of melamine cyanurate, ammonium phosphate and ammonium polyphosphate alone will not provide a composition suitable for the intended use. Two examples of the PA blend blended with the flame retardant suitable for use in the present invention (Examples 1 and 2) will now be described: • 10% phosphinate/ammonium polyphosphate blend (Example 1) The formulation as described in 1) comprises 89.3% PA1 1, 10% phosphorus compound admixture (Exolit OP1311, Clariant) (as a flame retardant), 0.6% phenolic antioxidant and 〇. 1% fumed vermiculite ( A powder blend as a rheological agent). After the powder thus obtained was converted according to the conversion method described in 2), the obtained assembly had satisfactory combustion properties, and its burning length was 3 inches, and the burning time was 36 seconds. The elongation at break was 49% and the tensile strength was 40 MPa (ASTM 63 8). • Blend with 15% hypophosphite/polyammonium phosphate (Example 2) as described in 1) contains 84.3% PA1 1, 15% phosphorus compound blend (EX ο 1 it 0 P 1 3 1 1 , C1 ariant ) (as a flame retardant), a powder blend of 0.6% -18- (16) 1311578 phenolic antioxidant and 0.1% fumed vermiculite (as a rheological agent). The combustion properties of the assembly obtained in accordance with 2) were satisfactory, with a burn length of 3.6 inches and a burn time of 23 seconds. The elongation at break was 32% and the tensile strength was 36 MPa (ASTM 638).

The powder prepared according to 1) contains 99.3% PA11, 0.6% phenolic antioxidant and 0.1% fumed vermiculite (as a rheological agent) and 0% flame retardant, which burns more than 1 〇 吋, when pulled The elongation is 52% and the tensile strength is 3 9 MPa (ASTM 63 8). It was found that the burning time was remarkably lowered, but the mechanical properties of the articles produced by the sintering method according to the composition of the present invention were not impaired.

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Claims (1)

X. Patent Application Range 1. Use of a flame resistant polyamide powder for producing a polyamide material by sintering the powder by radiation, the powder comprising 2 to 40% by weight of at least one flame retardant and 98 to 60% by weight of at least A polyamine which is a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate. 2. For the use of the scope of claim 1, wherein the powder consists of the following φ components (1% by weight of the total weight of the powder: • 2 to 40% by weight of at least one flame retardant, the flame retardant) Is a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate; • 98 to 60% by weight of at least one polyamine; and • 0 to 38% by weight of at least one selected from the group consisting of UV stabilizers, An agent for an oxidizing agent, a dye, a pigment, a bactericide, and a rheological agent. 3 _ The use of the phosphinate in the application of the second aspect of the application, wherein the phosphinate is selected from the group consisting of the phosphinates of the formula (I) (Π) The two sub-φ phosphonates: Wherein Ri and Rz are the same or different and are straight or branched <^ to C6 alkyl and -20-(2) 1311578 / or aryl; R3 is straight or branched (: 2 to C1Q alkyl) 〇6 to C1Q aryl, C6 to c1G alkyl aryl or c6 to C1G aryl alkyl; hydrazine is calcium, aluminum and/or zinc ion; m is 2 or 3; η is 1 or 3; X is 1 or 2. 4. The use according to any one of the claims 1 to 3 wherein the polyamine is selected from the group consisting of ruthenium 11 , ruthenium 12 , an aliphatic diamine having 6 to 12 carbon atoms and having 9 to 18 carbons An aliphatic polyamine formed by the condensation reaction of an aliphatic diacid of an atom, having more than 90% of 11 units or more than 90% of 12 units of copolymerized decylamine 11/12. 5. An article made of a flame resistant polyamide powder, the powder comprising 2 to 40% by weight of at least one flame retardant and 98 to 60% by weight of at least one polyamine, the flame retardant being at least one metal A blend of an organic phosphinate and at least one ammonium polyphosphate which is sintered by radiation. 6. A method for preparing a polyamidide article by irradiating a polyimide powder with radiation, the powder comprising 2 to 40% by weight of at least one flame retardant and 98 to 60% by weight of at least one polyamine, the flame retardant being a blend of at least one metal organic phosphinate and at least one ammonium polyphosphate. 7. The method of claim 6, wherein the radiation is derived from laser light. -twenty one -