WO2017158688A1 - Matériau en poudre de résine et procédé de production d'un article façonné à base de résine - Google Patents

Matériau en poudre de résine et procédé de production d'un article façonné à base de résine Download PDF

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WO2017158688A1
WO2017158688A1 PCT/JP2016/057995 JP2016057995W WO2017158688A1 WO 2017158688 A1 WO2017158688 A1 WO 2017158688A1 JP 2016057995 W JP2016057995 W JP 2016057995W WO 2017158688 A1 WO2017158688 A1 WO 2017158688A1
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powder
resin
resin powder
flame retardant
polyamide
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PCT/JP2016/057995
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English (en)
Japanese (ja)
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広毅 高橋
悦子 高根
聡 荒井
浩朗 古市
充 針替
邦彦 高尾
浩之 橘内
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株式会社日立ハイテクノロジーズ
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Priority to PCT/JP2016/057995 priority Critical patent/WO2017158688A1/fr
Publication of WO2017158688A1 publication Critical patent/WO2017158688A1/fr

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    • 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
    • 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
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/08—Organic materials containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/10—Organic materials containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/12—Organic materials containing phosphorus
    • 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
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B29B2009/125—Micropellets, microgranules, microparticles

Definitions

  • the present invention relates to a method for manufacturing a resin powder material and a resin model, and in particular, it is used for three-dimensional additive manufacturing for manufacturing a desired structure by laminating the cross-sectional shape based on three-dimensional data created by a computer.
  • the present invention relates to a resin powder material and a method for producing a resin molded article using the same.
  • three-dimensional additive manufacturing techniques have attracted attention in the fields of rapid prototyping and small-scale mass-production products, which are performed in the prototype stage of product design.
  • Three-dimensional additive manufacturing is roughly divided into four methods: powder lamination, stereolithography, melt deposition, and inkjet.
  • the powder lamination method can be applied with a thermoplastic resin or glass fiber, and has good dimensional accuracy, similar to the injection molding widely used in the resin molding technology. Therefore, the shaped article manufactured by the powder lamination method is advantageous in terms of quality and reliability as compared with the shaped article manufactured by the other three methods.
  • the powder laminating method is also called SLS (Selective Laser Sintering) method, and in order to avoid deformation phenomenon during production, the surface temperature of the material immediately before sintering is changed to the melting point of the material by preheating means such as a heater ( Hereinafter, it is necessary to set between Tm) and the crystallization temperature (hereinafter referred to as Tc). Therefore, as a powder material used in the powder lamination method, it is desirable to use a material having a Tm as low as possible and a temperature difference between Tm and Tc as large as possible.
  • ⁇ Hm melting enthalpy
  • Patent Document 1 mentions polyamide 12 powder as a powder material suitable for the powder lamination method using laser light.
  • the shaped object obtained as described above When the shaped object obtained as described above is applied to a specific application such as a home appliance, a building material, a part for electric / electronic use, an analysis device or a housing part of a medical device, it is ignited depending on the use environment. It is necessary not to promote the spread of fire. For this reason, it is necessary to manufacture the molded object used for these uses so that it may have a flame retardance or a nonflammability, and may satisfy
  • the particle size of the powder material used in the powder lamination method is generally larger than the particle size of the pellet-shaped material used for injection molding, the specific surface area of the material is increased, and the material surface is in contact with the molded object. Vaporization (combustible gasification) is promoted. For this reason, the modeled article by the powder lamination method is easier to burn than the molded article by injection molding, and this tendency becomes more prominent as the modeled article becomes thinner. Since the polyamide 12 described in Patent Document 1 is flammable, a molded article produced using the polyamide 12 by a powder lamination method has neither flame retardancy nor incombustibility.
  • an object of the present invention is to provide a resin powder material and a method for producing a resin shaped article that can obtain desired flame retardancy in a resin shaped article produced by a powder lamination method.
  • a preferred embodiment of the resin powder material according to the present invention is a resin powder material used for powder additive manufacturing, including polyamide 12 powder and at least one flame retardant material powder having an oxygen index of 27 or more, The oxygen index is 23 or more.
  • FIG. 1 is a diagram illustrating a resin powder material according to an example.
  • the resin powder material has (a) polyamide 12 powder 1a and (b) at least one flame retardant material powder 1b having an oxygen index of 27 or more.
  • (A) Polyamide 12 powder The polyamide 12 is obtained by a ring-opening polycondensation reaction of lauryl lactam, which is an ⁇ -amino acid having 12 carbon atoms, as shown in the following formula (1).
  • lauryl lactam which is an ⁇ -amino acid having 12 carbon atoms
  • the molecular weight distribution is controlled, and characteristics such as Tm, Tc, ⁇ Hm, particle size distribution, melt viscosity and the like are controlled.
  • the polyamide 12 will be described as including a plurality of types having different Tm, Tc, and ⁇ Hm depending on the molecular weight distribution.
  • the resin powder material of an Example should just contain the powder of the at least 1 sort (s) of polyamide 12 of these.
  • the polyamide 12 powder 1a it is desirable to use a material for a powder lamination method in which a temperature difference between Tm and Tc is relatively large and ⁇ Hm is relatively large (for example, see Patent Document 1). Further, as the polyamide 12 powder 1a, in addition to the above, after the pellet material of polyamide 12 commercial product for injection molding or extrusion molding is pulverized at low temperature, the pulverized product is classified to obtain an average particle size of 20 ⁇ m or more and 100 ⁇ m. You may use the powder adjusted to the following ranges. In that case, by adjusting preheating means (see FIG. 2) such as the heater 25 to be described later, it is possible to manufacture a resin molded article having a desired shape by suppressing variations in the surface temperature of the material immediately before sintering. become.
  • preheating means see FIG. 2 such as the heater 25 to be described later
  • polyamide 11 powder having characteristics relatively close to the polyamide 12 powder 1a may be used.
  • Polyamide 11 has a slightly higher Tm than polyamide 12 and a high crystallization speed, so that it is difficult to suppress deformation when manufacturing a molded article, but flexibility, low temperature impact resistance, heat resistance, gas barrier properties, wear resistance It is superior to polyamide 12 in terms of properties and bending fatigue resistance.
  • Polyamide 11 is desirable as a renewable raw material because it is obtained by a ring-opening polycondensation reaction of undecane lactam ( ⁇ -amino acid having 11 carbon atoms) synthesized from plant castor oil.
  • Table 1 shows the results of Tm, Tc, and ⁇ Hm measured by differential scanning calorimetry for polyamide 12 powder and polyamide 11 powder.
  • the polyamide 12 powder 1a may be used by appropriately mixing the polyamide 12 powders shown in Table 1 or may be used by mixing the polyamide 11 powder shown in Table 1.
  • polyamide 6 powder or polyamide 6,6 powder may be mixed with polyamide 12 powder.
  • a powder of a copolycondensation polymer obtained by copolycondensation of polyamide 12 with polyamide 11, polyamide 6 or polyamide 6,6 may be used in combination. In that case, Tm, Tc, ⁇ Hm and melt viscosity as the resin powder material can be freely controlled.
  • (B) Flame retardant material powder As a representative index relating to flammability, an oxygen index defined in JIS-K7201-2 or a classification according to UL94 standard established by the US Insurer Safety Laboratory is used. As the flame retardant material powder 1b of the examples, at least one of those having an oxygen index of 27 or more measured according to JIS-K7201-2 is used.
  • the oxygen index is an index indicating, as a percentage, the minimum oxygen concentration necessary for the combustion to continue in a state where the resin material is lit.
  • an oxygen index of less than 22 is classified as flammable
  • an oxygen index of 22 or more and less than 27 is self-extinguishing
  • an oxygen index of 27 or more is classified as flame retardant.
  • resin materials with an oxygen index of less than 26 fall under the category of designated combustible materials, and it is necessary to install fire extinguishing equipment stipulated by law for storage.
  • the UL94 standard mainly includes determination by a horizontal combustion test and determination by a vertical combustion test.
  • Table 2 shows the flammability classification according to the UL94 standard.
  • Table 3 shows the evaluation results of the combustibility of typical resin materials.
  • the conditions for determining V-2 are almost satisfied in the UL94 standard, and if the resin material has an oxygen index of 27 or more, the conditions for determining V-1 in the UL94 standard are satisfied. Is almost satisfied.
  • the difference in the combustibility of resin materials is thought to be due to the molecular structure of the resin materials.
  • polyethylene, polypropylene, polystyrene, and the like have only a carbon (C) and hydrogen (H) chemical component, and thus have a small oxygen index, and do not reach V-2 even in the UL94 standard.
  • polyvinyl chloride, flame-retardant chloroprene rubber, polyvinylidene fluoride and the like are at least one selected from halogen (F, Cl, Br, I) in addition to carbon (C) and hydrogen (H) in the molecule. Therefore, the oxygen index is large and is equivalent to V-0 in the UL94 standard. This is because the bond between carbon (C) and the halogen element suppresses combustion, which is an oxidation reaction.
  • the flame retardant material powder 1b is desirably adjusted to a mean particle size of 20 ⁇ m or more and 100 ⁇ m or less by low-temperature pulverization of a resin material having an oxygen index of 27 or higher and then classifying the pulverized product. Moreover, as the flame retardant material powder 1b, it is preferable to include at least one of those having a sublimation point or a vaporization temperature of 300 ° C. or higher. That is, since the sintering temperature in the powder lamination method reaches nearly 300 ° C., if the sublimation point or vaporization temperature of the flame retardant material powder 1b is low, the flame retardant material powder 1b sublimates or vaporizes during heating, and its concentration decreases.
  • the flame retardant material powder 1b the one having a sublimation point or vaporization temperature of 300 ° C. or higher is used. Concentration fluctuation due to sublimation or vaporization of 1b is suppressed. For this reason, the quality of the resin modeling thing manufactured is stabilized. Further, since the flame retardant material powder 1b remains in the unsintered resin powder material, the resin powder material can be reused.
  • the flame retardant material powder 1b instead of a resin material having an oxygen index of 27 or more, at least one kind selected from an organic material powder having an oxygen index of 27 or more or an inorganic material powder having an oxygen index of 27 or more is used. Also good.
  • an organic material powder or an inorganic material powder is used as the flame retardant material powder 1b, a commercially available flame retardant can be selected. However, in that case, there are side effects such as a decrease in mechanical strength such as tensile strength and bending strength in the resin molding, generation of bleed (precipitate on the surface of the resin molding), and generation of voids (cavities inside the resin molding). Need to be considered.
  • the resin material having an oxygen index of 27 or higher is preferably used in combination.
  • the organic material powder and the inorganic material powder are preferably adjusted to have an average particle size of 20 ⁇ m to 100 ⁇ m and a sublimation point or vaporization temperature of 300 ° C. or higher.
  • a material having a plurality of halogen atoms in the molecular structure and having an aromatic hydrocarbon or cyclic hydrocarbon as a basic skeleton that is easily liberated from the halogen atoms is difficult for polyamide 12. Desirable because of its good flammability effect.
  • a halogen compound having an aromatic hydrocarbon having a halogen atom or a cyclic hydrocarbon having a halogen atom as a basic skeleton has a halogen atom liberated from the aromatic hydrocarbon or the cyclic hydrocarbon so that the C—H of the polyamide 12 It acts on the bond and suppresses the combustion reaction.
  • strength can be acquired as a resin powder material by using the compound which has an aromatic hydrocarbon and cyclic hydrocarbon as a basic skeleton as a flame retardant material powder.
  • a resin powder material for example, brominated polyphenylene oxide, brominated polystyrene, pentabromobenzyl acrylate (polymer), brominated epoxy, polypentabromobenzyl acrylate, tetrabromobisphenol A diglycidyl ether / bromobisphenol A adduct (polymer), etc.
  • These halogen compounds are mentioned. From the viewpoint of ease of density management, it is desirable to use any one of these alone, but of course, two or more may be used in combination.
  • the following halogen compounds can be preferably used from the viewpoint of obtaining a good flame retarding effect on the polyamide 12.
  • the following non-halogen compounds can be suitably used from the viewpoint of obtaining a good flame retarding effect on the polyamide 12.
  • melamine compounds such as melamine polyphosphate and melamine cyanurate, for example ammonium polyphosphate, bisphenol A bis (diphenyl phosphate ester), resorcinol bis (diphenyl phosphate ester), triisopropylphenyl phosphate ester
  • phosphorus compounds such as triphenyl phosphate, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris (chloroisopropyl) phosphate, and phosphazene compounds.
  • the molecular structure is a material having a cyclic CN unsaturated bond group as a basic skeleton and a nitrogen compound easily generated as an inert gas. Thereby, the dilution effect with respect to combustible gas and oxygen gas is fully acquired.
  • phosphorus compounds those having a functional group of phosphoric acid having a radical trapping effect in the molecular structure are desirable.
  • production and the suppression effect of gas diffusion by promoting the carbonization of a combustible material is good.
  • an inorganic material having an oxygen index of 27 or more from the viewpoint of obtaining a good flame retardant effect on the polyamide 12, for example, metal compounds such as magnesium hydroxide, aluminum hydroxide, zinc borate, antimony trioxide, expanded graphite, etc. Is mentioned.
  • antimony trioxide it is desirable to use in combination with the above-mentioned resin material or organic material having a halogen atom. Thereby, a coating of antimony halide is formed on the surface of the combustible material, and liberation of halogen atoms is promoted.
  • Magnesium hydroxide, aluminum hydroxide, and zinc borate can provide effects such as suppression of exothermic reaction of combustibles by endothermic action, that is, suppression of combustible gas generation and reduction of combustible concentration by dehydrated product water.
  • magnesium hydroxide, aluminum hydroxide, and zinc borate in combination with the above-described resin material having an oxygen index of 27 or higher or an organic material having an oxygen index of 27 or higher.
  • Expanded graphite expands in volume when exposed to high temperatures and covers the surface of the combustible material, thereby preventing the reaction between the combustible gas and the oxygen gas and preventing combustion. Furthermore, expanded graphite also has an effect of suppressing the generation of combustible gas by an endothermic action during volume expansion. Expanded graphite alone exhibits a sufficient flame retarding effect, but it may be used in combination with the above-described resin material having an oxygen index of 27 or more and an organic material having an oxygen index of 27 or more.
  • the melamine compound also has an effect as a lubricant. For this reason, when a melamine compound is mix
  • the resin powder material As the resin powder material, excellent flame retardancy can be obtained by having the above-described polyamide 12 powder 1a and flame retardant material powder 1b.
  • the resin powder material preferably has an oxygen index defined by JIS-K7201-2 of 23 or more.
  • the resin powder material achieves V-2 determination, V-1 determination, and V-0 determination according to the UL94 standard.
  • the average particle size of the resin powder material is preferably 20 ⁇ m or more and 100 ⁇ m or less. As a result, it is possible to achieve both the stable deposition of the resin powder material and the improvement of the dimensional accuracy of the resin molded article to be manufactured. When the average particle diameter of the resin powder material is less than 20 ⁇ m, it is difficult to stably deposit the resin powder material. Moreover, when the average particle diameter of resin powder material exceeds 100 micrometers, the dimensional accuracy of a resin molded article will fall.
  • the crystallization temperature of the resin powder material is preferably 144 degrees or more and 161 degrees or less.
  • the crystallization temperature is in the above range, a sufficient temperature difference between Tm and Tc as the resin powder material is ensured. For this reason, the tolerance of the process which sets the surface temperature of the resin powder material just before sintering is ensured.
  • a resin powder material having an oxygen index of 23 or more By uniformly mixing the polyamide 12 powder 1a and the flame retardant material powder 1b having an oxygen index of 27 or more in a desired blending amount, a resin powder material having an oxygen index of 23 or more can be obtained.
  • the means for uniformly mixing include a method using a dry powder mixer (dry blending).
  • dry powder mixer any of rotary mixing, rocking mixing, and V-type mixing can be selected according to the type of powder.
  • inert gas or dry air In order to prevent an increase in the average particle size due to aggregation of powder particles and to prevent a non-uniform mixing state due to sedimentation of components with high density in the resin powder material, it is filled with inert gas or dry air. It is desirable to mix immediately before carrying out powder additive manufacturing in an atmosphere where the humidity is as low as possible.
  • a pellet (resin compound) obtained by melting and mixing the polyamide 12 powder or the polyamide 12 pellet and the flame retardant material powder is manufactured once, and this resin compound is produced.
  • a resin powder material having an oxygen index of 23 or more can be obtained by low-temperature pulverization and classification. This method makes the mixed state of the resin powder material more uniform as compared with dry blending, while Tc is higher than that of the polyamide 12 before melt mixing. As a result, the temperature difference between Tm and Tc becomes small, and it is necessary to suppress variations in the surface temperature of the material just before sintering by adjusting the preheating means.
  • the blending amount of the flame retardant material powder 1b having an oxygen index of 27 or more is preferably 5% by mass or more and less than 50% by mass, more preferably 10% by mass or more and less than 40% by mass. If the blending amount of the flame retardant material powder 1b is too small, the oxygen index of the resin powder material becomes less than 23 and flame retardancy is lost. Moreover, when there are too many compounding quantities of the flame retardant material powder 1b, side effects, such as the fall of mechanical strength, generation
  • FIG. 2 is a diagram illustrating an example of a process of manufacturing a resin molded article using the resin powder material manufactured based on the above [Preparation of resin powder material].
  • the powder additive manufacturing apparatus raises a part cartridge (hereinafter referred to as a powder bed) 21 for arranging a powder material and a model, a feed cartridge 22 for supplying the part cartridge and the powder material, and a feed cartridge.
  • a piston 23 for newly supplying a powder material, a heater 25 for heating the powder bed and the material supply portion, and a laser irradiator 26 for selectively heating a part of the surface of the powder bed with a laser beam, Consists of.
  • a layer of the resin powder material 20 is laid on the powder bed 21 with the roller 24 (FIG. 2A).
  • laser light is irradiated from the laser irradiator 26 to selectively sinter and solidify the resin powder material of the powder bed 21 (FIG. 2 ( b)).
  • the feed cartridge 22a near the roller 24 is raised by the piston 23a, and the powder bed 21 and the other feed cartridge 22b are lowered by the pistons 23c and 23b (FIG. 2C).
  • the resin powder material is supplied (powder laying by roller movement) (FIG.
  • the resin molded material manufactured by the powder lamination method using laser light using the above-described resin powder material can ensure the desired flame retardancy even if the resin molded product is thinned. It becomes possible.
  • the polyamide 12 powder As the polyamide 12 powder, a pulverized product (average particle diameter of 65 ⁇ m) of the commercially available polyamide 12 for injection molding listed in Table 1 was used.
  • the flame retardant powder is a mixture of 75% by mass of tetrabromobisphenol A diglycidyl ether / brominated bisphenol A adduct, which is a halogen-based resin material, and 25% by mass of antimony trioxide, and then pulverized. Were used to adjust the average particle size to 67 ⁇ m.
  • a polyamide 12 powder was mixed in an amount of 60% by mass and a flame retardant material powder was mixed in an amount of 40% by mass to prepare a combustion test piece, a tensile test piece, and a bending test piece.
  • the polyamide 12 powder is the same as the polyamide 12 powder described in Example 1.
  • the flame retardant material powder is obtained by subjecting a mixture of 5% by mass of brominated polystyrene, which is a halogen-based resin material, and 95% by mass of antimony trioxide, to low temperature pulverization, and then classifying the pulverized material to obtain an average particle size of 21 ⁇ m. The adjusted one was used.
  • a polyamide 12 powder was mixed in an amount of 60% by mass and a flame retardant material powder was mixed in an amount of 40% by mass to prepare a combustion test piece, a tensile test piece, and a bending test piece.
  • the polyamide 12 powder is the same as the polyamide 12 powder described in Example 1.
  • melamine polyphosphate (average particle size of less than 5 ⁇ m), which is an organic material and is a non-halogen compound, was used.
  • a polyamide 12 powder was mixed in a blending amount of 90% by mass and a flame retardant material powder was mixed in an amount of 10% by mass to prepare a combustion test piece, a tensile test piece, and a bending test piece.
  • the polyamide 12 powder is the same as the polyamide 12 powder described in Example 1.
  • As the flame retardant material powder melamine cyanurate (average particle size: 14 ⁇ m), which is an organic material and is a non-halogen compound, was used.
  • a polyamide 12 powder and a flame retardant material powder were mixed in a blending amount of 70% by mass, and a combustion test piece, a tensile test piece, and a bending test piece were prepared.
  • the polyamide 12 powder is the same as the polyamide 12 powder described in Example 1.
  • the flame retardant material powder was an inorganic material and was adjusted to an average particle size of less than 100 ⁇ m by classifying expanded graphite powder, which is a non-halogen compound.
  • a polyamide 12 powder and a flame retardant material powder were mixed in a blending amount of 70% by mass, and a combustion test piece, a tensile test piece, and a bending test piece were prepared.
  • Combustion test pieces, tensile test pieces, and bending test pieces were produced using only the polyamide 12 powder described in Example 1.
  • the UL94 vertical combustion test, the tensile test, and the bending test were performed on the combustion test piece, the tensile test piece, and the bending test piece prepared for each of Examples 1 to 6 and the comparative example.
  • the evaluation results are shown in Table 4.
  • the tensile test was performed in accordance with the ISO 3167 standard.
  • the bending test was performed in accordance with ISO178 standard. Since all the components of the flame retardant material powder in Examples 1 to 6 have a vaporization temperature of 300 ° C. or higher, it is clear that the concentration is hardly lowered in the process of preparing the test piece.
  • test piece of the comparative example had a V-Not determination with no flame retardancy because the maximum burning time exceeded 30 seconds.
  • the test piece of Example 1 had a maximum burning time of 10 seconds or less, a total burning time of 50 seconds or less, and the lower cotton was not ignited, so it was determined as V-0 and exhibited particularly good flame retardancy. Moreover, tensile strength and bending strength were higher than the comparative example, and favorable mechanical strength was shown.
  • the test piece of Example 2 had a maximum combustion time of 10 seconds or less, a total combustion time of 50 seconds or less, and the lower cotton was not ignited.
  • the test piece of Example 3 had a maximum burning time of 30 seconds or less and a total burning time of 250 seconds or less. However, since the lower cotton ignited, it was judged as V-2 and showed a slight flame retardancy.
  • the test piece of Example 4 had a maximum burning time of 10 seconds or less, a total burning time of 50 seconds or less, and the lower cotton was not ignited, so it was determined as V-0 and exhibited particularly good flame retardancy.
  • the test piece of Example 5 had a maximum burning time of 10 seconds or less, a total burning time of 50 seconds or less, and the lower cotton was not ignited, so it was determined as V-0 and exhibited particularly good flame retardancy.
  • the test piece of Example 6 had a maximum combustion time of 10 seconds or less and a total combustion time of 50 seconds or less. However, since the lower cotton ignited, it was judged as V-2 and showed a slight flame retardancy.
  • test pieces described in Examples 1 to 6 have a shorter burning time and exhibit flame retardancy than the test pieces described in Comparative Examples.
  • the test piece of Example 1 has the highest concentration of the halogen-based resin material whose basic skeleton is an aromatic hydrocarbon in which halogen atoms are easily liberated, it can achieve both good flame retardancy and mechanical strength. did it.
  • the polyamide 12 powder most commonly used in the powder laminating method using laser light has been described as an example, but the polyamide is a low melting crystalline resin having a Tm of 200 degrees or less. 11. Even if powder, such as 11, polyethylene, a polypropylene, polyoxymethylene, is used with polyamide 12 powder, it can implement similarly. Further, for example, by improving the preheating means (heater 25 in FIG. 2), polybutylene terephthalate, polyphenylene sulfide, polyamide 6, polyamide 6,6, polyamide 6T, which are crystalline resins having a high melting point exceeding Tm of 200 degrees.
  • polyamide 9T polyetheretherketone
  • liquid crystal polymer polyethylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polytetrafluoroethylene and the like together with polyamide 12 powder.

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Abstract

La présente invention concerne : un matériau en poudre de résine qui permet de conférer à un article façonné, qui est produit par un procédé de stratification de poudre, un caractère ignifuge désiré ; et un procédé de production d'un article façonné à base de résine. Un matériau en poudre de résine est utilisé dans le façonnage par stratification de poudre et comprend une poudre (1a) de polyamide (12) et au moins une poudre de matériau ignifuge (1b) présentant un indice d'oxygène supérieur ou égal à 27.
PCT/JP2016/057995 2016-03-14 2016-03-14 Matériau en poudre de résine et procédé de production d'un article façonné à base de résine WO2017158688A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019068659A1 (fr) * 2017-10-04 2019-04-11 Basf Se Poudre adaptée au frittage, contenant un retardateur de flamme minéral, pour la fabrication de corps façonnés
JP2021532244A (ja) * 2018-08-01 2021-11-25 ブラスケム・アメリカ・インコーポレイテッド 向上した堅牢性を有する熱可塑性組成物、その物品、及びその方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11216779A (ja) * 1997-10-27 1999-08-10 Huels Ag 粉末状材料の選択的レーザー焼結により成形体を製造する方法
JP2005048187A (ja) * 2003-07-29 2005-02-24 Degussa Ag 積層方法において加工するためのポリマー粉末、その製造方法、成形体を製造する方法、およびその成形体
JP2007529340A (ja) * 2004-03-16 2007-10-25 デグサ ゲーエムベーハー レーザ技術およびインキジェット法による吸収体の塗布によって３次元の対象物を製造するための方法および装置
JP2007534524A (ja) * 2004-04-27 2007-11-29 デグサ ゲーエムベーハー インクジェット法により吸収剤を塗布し電磁放射を照射する３次元物体の製造方法および３次元物体の製造装置
JP2008505243A (ja) * 2004-07-20 2008-02-21 アルケマ フランス 不燃性ポリアミド粉末と、その溶融凝結法での使用
JP2010514855A (ja) * 2006-12-21 2010-05-06 ザ・ボーイング・カンパニー 難燃性材料を加工する方法及びシステム

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11216779A (ja) * 1997-10-27 1999-08-10 Huels Ag 粉末状材料の選択的レーザー焼結により成形体を製造する方法
JP2005048187A (ja) * 2003-07-29 2005-02-24 Degussa Ag 積層方法において加工するためのポリマー粉末、その製造方法、成形体を製造する方法、およびその成形体
JP2007529340A (ja) * 2004-03-16 2007-10-25 デグサ ゲーエムベーハー レーザ技術およびインキジェット法による吸収体の塗布によって３次元の対象物を製造するための方法および装置
JP2007534524A (ja) * 2004-04-27 2007-11-29 デグサ ゲーエムベーハー インクジェット法により吸収剤を塗布し電磁放射を照射する３次元物体の製造方法および３次元物体の製造装置
JP2008505243A (ja) * 2004-07-20 2008-02-21 アルケマ フランス 不燃性ポリアミド粉末と、その溶融凝結法での使用
JP2010514855A (ja) * 2006-12-21 2010-05-06 ザ・ボーイング・カンパニー 難燃性材料を加工する方法及びシステム

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019068659A1 (fr) * 2017-10-04 2019-04-11 Basf Se Poudre adaptée au frittage, contenant un retardateur de flamme minéral, pour la fabrication de corps façonnés
CN111183015A (zh) * 2017-10-04 2020-05-19 巴斯夫欧洲公司 用于生产成型体的包含矿物阻燃剂的烧结粉末
JP2020535996A (ja) * 2017-10-04 2020-12-10 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 成形体の製造のための無機難燃剤を含む焼結粉末
US11613074B2 (en) 2017-10-04 2023-03-28 Basf Se Sinter powder containing a mineral flame retardant for producing moulded bodies
JP2021532244A (ja) * 2018-08-01 2021-11-25 ブラスケム・アメリカ・インコーポレイテッド 向上した堅牢性を有する熱可塑性組成物、その物品、及びその方法

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