WO2023189877A1

WO2023189877A1 - Material for 3d printing

Info

Publication number: WO2023189877A1
Application number: PCT/JP2023/011078
Authority: WO
Inventors: 奈央山末
Original assignee: 三菱ケミカル株式会社
Priority date: 2022-03-31
Filing date: 2023-03-22
Publication date: 2023-10-05

Abstract

Provided is a material for 3D printing, the material containing a resin composition, wherein the resin composition comprises a thermoplastic resin (A) and a non-halogenated flame retardant (B), and the non-halogenated flame retardant (B) has a flow initiation temperature of 100-400°C.

Description

3D modeling materials

The present invention relates to a three-dimensional modeling material, and specifically relates to a three-dimensional modeling material containing a non-halogen flame retardant. In particular, the present invention relates to filaments for material extrusion processes and powders for powder bed fusion processes. The present invention also relates to a modeling method and a modeled article using these three-dimensional modeling materials.

Today, three-dimensional printers (hereinafter sometimes referred to as "3D printers") with various additive manufacturing methods (e.g., binder injection method, material extrusion method, liquid bath photopolymerization method, powder bed fusion method, etc.) are on the market. ing.
Among these, a 3D printer system (for example, a system manufactured by Stratasys, Inc. in the United States) using a material extrusion method (hereinafter sometimes referred to as "MEX") uses fluid raw materials through an extrusion head. It is used to construct three-dimensional objects in layers based on a computer-aided design (CAD) model by extruding them from a nozzle section provided in the computer. In this system, a raw material made of thermoplastic resin is inserted as a filament into an extrusion head, and while it is heated and melted, it is continuously extruded from a nozzle part provided in the extrusion head onto an XY plane base in a chamber, and the extruded resin is It is becoming widely used because it is a simple system in which it is deposited and fused onto an already deposited resin laminate and solidified as it cools. In material extrusion (MEX), a three-dimensional object resembling a CAD model is constructed by repeating the extrusion process, with the nozzle position relative to the substrate rising in the Z-axis direction perpendicular to the XY plane. .

In addition, a 3D printer system using a powder bed fusion method (hereinafter sometimes referred to as "PBF"), for example, a system manufactured by 3D Systems in the United States, uses a thin layer ( A powder bed) is heated and melted to a temperature near the melting point of the resin powder using a heating means such as a high-power CO ₂ laser, and a three-dimensional object is constructed in layers based on a computer-aided design (CAD) model. It is used to At this time, the laser used as a heating means scans the cross section in the XY direction on the surface of the powder bed to selectively melt the powder material. From 3D CAD data, a three-dimensional model can be obtained by laminating one layer at a time and repeating this process to form a laminate. This system has attracted attention in recent years because it does not require the use of molds, can use a variety of resin powders as raw materials as long as they have a certain degree of heat resistance, and the resulting molded products are highly reliable. It is a technology that

Thermoplastic resins used in 3D printers include acrylonitrile-butadiene-styrene (ABS) resins, polypropylene resins (PP), and polylactic acid (PLA), which have good moldability and fluidity as filament materials for 3D printers. Relatively good resins are commonly used.
In addition, polyamide resins such as nylon 12 and nylon 11 are widely used as materials for thermoplastic resin powder, but in recent years, polyamide resins such as nylon 12 and nylon 11 have become less absorbent of moisture and have higher heat resistance. Polybutylene terephthalate resin is also used as an aromatic polyester resin from which shaped articles can be obtained.

3D printers have been widely used for prototyping molded products, but in recent years, 3D printers are also being considered for application to functional parts used in actual applications. Assuming practical use, for example, when used as a member for home appliances, building materials, aircraft, automobile materials, etc., it is preferable that the shaped article has high heat resistance and flame retardancy. As a study on imparting flame retardancy to thermoplastic resin materials for 3D printers, for example, in Patent Document 1, a material with an oxygen index of 27 or more is melt-kneaded with a polyamide resin, and then pulverized to form a flame-retardant powder. A method for obtaining the is disclosed.
Furthermore, in Patent Document 2, water containing an emulsifier is added to a flame retardant-containing polymer solution in which a flame retardant, a thermoplastic resin, and an organic solvent are mixed under stirring to form an oil-in-water (O/W) emulsion. A method for precipitating flame-retardant polymer fine particles from an emulsion is disclosed.

WO2017/158688 JP 2020-7529 Publication

In Patent Document 1, the thermoplastic resin is limited to polyamide 12, and in Patent Document 2, since fine particles are precipitated from an oil-in-water (O/W) emulsion, the particle size is small, and the material for 3D printers is When used in large quantities, it takes time and effort to manufacture.

In order for 3D printers to be widely applied to functional parts that are used in practical applications, it is desirable that flame retardancy can be imparted to thermoplastic resin materials other than polyamide 12, and that the manufacturing method of the material is simple. It is preferable that

Furthermore, as the flame retardant, it is preferable to use a non-halogen compound such as a phosphorus compound. Conventionally, a method of blending a halogen compound, particularly a bromine compound, has been commonly used. However, it has been pointed out that halogen compounds can generate harmful gases such as dioxins when burned, which not only poses safety problems during waste incineration and thermal recycling, but also causes fires. There is also the possibility that the generation of harmful gases during this time may affect the human body.

The present invention solves the above problems, and is a three-dimensional modeling material containing a resin composition containing a thermoplastic resin and a non-halogenated flame retardant. An object of the present invention is to provide a material for 3D printing that maintains thermal properties such as oxidation temperature and has excellent formability on a 3D printer and color of a modeled product.

As a result of intensive studies aimed at solving the above problems, the present inventor discovered that these problems could be solved by using a non-halogen flame retardant that meets specific requirements, and thus developed the present invention. .

That is, the gist of the present invention is as follows.
[1] A three-dimensional modeling material containing a resin composition, the resin composition containing a thermoplastic resin (A) and a non-halogen flame retardant (B); ) has a flow start temperature of 100°C or more and 400°C or less.
[2] The three-dimensional modeling material according to [1] above, wherein the non-halogen flame retardant (B) is an organic phosphorus-containing compound.
[3] The three-dimensional modeling material according to [1] or [2] above, wherein the non-halogen flame retardant (B) is a phosphorus spiro compound or a phosphate ester compound.
[4] A three-dimensional modeling material containing a resin composition, the resin composition containing a thermoplastic resin (A) and a non-halogen flame retardant (B); ) is a compound represented by the following general formula (1), a three-dimensional modeling material.

(In formula (1), R ¹ and R ² are each a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Also, R ¹ and R ² are mutually They may be the same or different.)
[5] The above-mentioned [1] to [4] characterized in that the non-halogen flame retardant (B) is contained in a ratio of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A). ] The three-dimensional modeling material according to any one of the above.
[6] The thermoplastic resin (A) may be polyacetal, polyacrylate, polyacrylic acid, polyamide, polyamideimide, polyacid anhydride, polyarylate, polyarylene ether, polyarylene sulfide, polybenzoxazole, polyester, or polyester. Etheretherketone, polyetherimide, polyetherketoneketone, polyetherketone, polyethersulfone, polyimide, polymethacrylate, polyolefin, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine , polyurea, polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl ketone, polyvinylidene fluoride polyvinyl aromatic, polysulfone, polyarylene sulfone, polyaryletherketone, polylactic acid, polyglycolic acid, poly-3- Hydroxybutyrate, polyhydroxyalkanoate, starch, cellulose ester, poly(phenylene ether), poly(methyl methacrylate), styrene-acrylonitrile, poly(ethylene oxide), epichlorohydrin polymer, polycarbonate homopolymer, copolycarbonate, poly( ester carbonate), poly(ester-siloxane-carbonate), poly(carbonate-siloxane), vinyl polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin) ), polyvinyl chloride, modified polyphenylene ether, and any one or a mixture of two or more selected from the group consisting of olefin-based, styrene-based, and polyester-based thermoplastic elastomers [1] to [ 6], the three-dimensional modeling material according to any one of item 6].
[7] A three-dimensional modeling powder obtained using the three-dimensional modeling material according to any one of [1] to [6] above.
[8] The powder for three-dimensional modeling according to the above [7], which has a particle size distribution D50 of 20 μm or more and 100 μm or less.
[9] A molded article obtained using the three-dimensional modeling material according to any one of [1] to [6] above.
[10] A molded object obtained using the three-dimensional modeling powder described in [7] or [8] above.
[11] A method for producing a molded body, comprising a step of three-dimensionally shaping the molded body using the three-dimensional modeling material according to any one of [1] to [6] above.
[12] A powder bed fusion bonding method using the three-dimensional modeling material according to any one of [1] to [6] above, or the three-dimensional modeling powder according to [7] or [8] above. A method for producing a molded body, including a step of three-dimensionally shaping the molded body using (PBF).

According to the present invention, there is provided a three-dimensional printing material that contains a specific non-halogen flame retardant, has excellent flame retardancy, and is also excellent in printability in a 3D printer, and a three-dimensional printed object made from the material. I can do it.

(Reason why the present invention is effective)
The reason why the present invention is effective is not yet clear, but it can be assumed to be due to the following reasons. That is, the three-dimensional modeling material containing the resin composition of the present invention can be produced by adjusting the flow start temperature of the non-halogen flame retardant contained in the resin composition within a specific range. Because the fluid properties are maintained when heated, a uniform molten state is obtained when extruding the filament or when irradiating the powder layer with a heating medium such as a laser during modeling using a 3D printer, and the desired 3D modeling can be achieved. It can be inferred that the product can be manufactured with high precision.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. The present embodiment below is an illustration for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with various modifications within the scope of its gist.

[3D modeling materials]
The three-dimensional modeling material of the present invention contains a resin composition. The resin composition will be explained in detail below.

<Resin composition>
The resin composition used in the three-dimensional modeling material of the present invention contains a thermoplastic resin (A) and a non-halogen flame retardant (B), and the flow start temperature of the non-halogen flame retardant (B) is The temperature is 100°C or higher and 400°C or lower. Further, resins other than the thermoplastic resin (A), additives, reinforcing materials, etc. can be included to the extent that the effects of the present invention are not impaired.
The resin composition used in the three-dimensional modeling material of the present invention contains a thermoplastic resin (A) and a non-halogen flame retardant (B), but the flow start temperature of the non-halogen flame retardant (B) is 400°C or less. Therefore, it is considered that the present resin composition can maintain thermoplasticity equivalent to that of the thermoplastic resin (A). Since this resin composition can maintain thermoplasticity equivalent to that of the thermoplastic resin (A), unlike general thermoplastic molding methods such as extrusion molding and injection molding, this resin composition can be processed using heat or light. In 3D modeling, in which a molded product is produced by directly applying the resin to the material and laminating it layer by layer based on 3D-CAD or 3D-CG data, the inherent thermal properties of the thermoplastic resin (A) are significantly impaired. It is possible to impart flame retardancy to the molded product while maintaining formability.

<Thermoplastic resin (A)>
The thermoplastic resin (A) used in the present invention may be any material that exhibits thermoplasticity when exposed to heat or light from a 3D printer, and can be appropriately selected depending on the function to be imparted to the molded object to be modeled. For example, polyacetal, polyacrylate, polyacrylic acid, polyamide, polyamideimide, polyacid anhydride, polyarylate, polyarylene ether, polyarylene sulfide, polybenzoxazole, polyester, polyetheretherketone, polyetherimide, polyether Ketone ketone, polyether ketone, polyether sulfone, polyimide, polymethacrylate, polyolefin, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, polyurethane, polyvinyl alcohol, polyvinyl ester , polyvinyl ether, polyvinyl halide, polyvinyl ketone, polyvinylidene fluoride polyvinyl aromatic, polysulfone, polyarylene sulfone, polyaryletherketone, polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate, polyhydroxyalkanoate, starch , cellulose ester, poly(phenylene ether), poly(methyl methacrylate), styrene-acrylonitrile, poly(ethylene oxide), epichlorohydrin polymer, polycarbonate homopolymer, copolycarbonate, poly(ester carbonate), poly(ester-siloxane) carbonate), poly(carbonate-siloxane), vinyl polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), polyvinyl chloride, modified polyphenylene ether, Examples include olefin-based, styrene-based, and polyester-based thermoplastic elastomers.
These resins may be used in combination of two or more types as appropriate. Furthermore, additives such as fillers such as carbon black, carbon fibers, glass fibers, talc, mica, nanoclay, and magnesium, antioxidants, lubricants, and colorants may be appropriately mixed into the thermoplastic resin (A). .

In order to obtain a molded product with high heat resistance and flame retardancy using a 3D printer, the thermoplastic resin (A) must have a melting point or glass transition temperature of 50°C or higher when measured according to JIS K7121. From the viewpoint of excellent workability and heat resistance, those having a melting point or glass transition temperature of 100° C. or higher when measured according to JIS K7121 are more preferable. Specifically, vinyl polymers, polyesters (hereinafter sometimes referred to as "polyester resins"), polyolefins (hereinafter sometimes referred to as "polyolefin resins"), polyamides (hereinafter referred to as "polyamide resins"), ), polyarylene ether, polyarylene sulfide, polyether sulfone, polysulfone, polyether ketone, polyether ether ketone, polyurethane, polycarbonate (hereinafter sometimes referred to as "polycarbonate resin") ), polyamideimide, polyimide, polyetherimide, polyacetal, and copolymers thereof.

<Polyester resin>
The type of polyester resin used in the present invention is not particularly limited as long as it has an ester bond in its main chain. Examples of the polyester resin include dicarboxylic acids such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polytrimethylene terephthalate, poly-1,4-cyclohexylene dimethylene terephthalate, polyethylene succinate, and polybutylene succinate. Polyester resins derived from residues and diol residues, polyester resins polymerized with monomers having carboxylic acid residues and alcohol residues in one molecule such as polylactic acid, poly-ε-caprolactam, etc. Copolymers and the like can be mentioned. One type of these polyester resins may be used alone, or two or more types of polyester resins may be used.

The polyester resin used in the present invention is preferably an aromatic polyester resin from the viewpoint of thermal properties and mechanical properties, and the aromatic polyester resin is formed by condensation polymerization of an aromatic dicarboxylic acid component and a diol component. Any resin may be used, and among them, one in which one or both of the aromatic dicarboxylic acid component and the diol component is composed of a single compound is preferred. Among the aromatic polyester resins, polyethylene terephthalate resin, polypropylene terephthalate resin, and polybutylene terephthalate resin are preferred, polyethylene terephthalate resin and polybutylene terephthalate resin are more preferred, and polybutylene terephthalate resin (hereinafter referred to as polybutylene terephthalate) is particularly preferred.
Commercially available examples of the polybutylene terephthalate resin include the "Novaduran (registered trademark)" series manufactured by Mitsubishi Engineering Plastics Co., Ltd.

<Polyolefin resin>
The polyolefin resin used in the present invention is a polymer obtained by polymerizing monomers having an olefin skeleton. Olefins are monomers with hydrocarbon double bonds.
The polyolefin resin is not particularly limited, and homopolymers, block copolymers, random copolymers, etc. can be suitably used; polypropylene; propylene, ethylene, 1-butene, 1-hexene, 4-methyl; Propylene copolymer copolymerized with α-olefin such as -1-pentene; polyethylene such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, and high-density polyethylene; ethylene, 1-butene, 1 -Ethylene copolymers copolymerized with α-olefins such as hexene and 4-methyl-1-pentene; examples include poly(1-butene) and poly(4-methyl-1-pentene). One type of these may be used alone, or two or more types having different copolymer compositions, physical properties, etc. may be used as a mixture.

Among these, propylene-based polymers are preferred as the polyolefin-based resin from the viewpoint of obtaining molded products with excellent heat resistance. In addition, from the viewpoint of formability, in order to suppress deformation such as crystallization shrinkage during cooling and warping of the molded object during molding, propylene, ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, etc. More preferred are propylene-based copolymers copolymerized with α-olefins such as.
The propylene copolymers mentioned above include "Novatec PP", "Wintech", "Nucon", and "Wellnex" manufactured by Nippon Polypropylene Co., Ltd., "Vistamax" manufactured by ExxonMobil, and "Vistamax" manufactured by Dow Chemical Company. An example is the trademark name "Versify", and the product can be appropriately selected from these product groups and used alone or in combination.

<Polycarbonate resin>
As the polycarbonate resin used in the present invention, an aromatic polycarbonate resin is preferably used, but an aliphatic polycarbonate resin may also be used. Further, it may be either a homopolymer or a copolymer with other copolymerizable monomers. Further, the structure may be a branched structure, a linear structure, or a mixture of a branched structure and a linear structure. The polycarbonate resin used in the present invention may be produced by any known method such as the phosgene method, the transesterification method, or the pyridine method.

The weight average molecular weight of the polycarbonate resin used in the present invention is usually in the range of 10,000 to 100,000, preferably 20,000 to 40,000, particularly preferably 22,000 to 28,000. Can be used. The polycarbonate resins can be used alone or in combination of two or more. If the weight average molecular weight is within the above range, impact resistance is ensured and extrusion moldability is also good, which is preferable.
Note that the weight average molecular weight here was measured using GPC (HLC-8120GPC manufactured by Tosoh Corporation) and calculated in terms of polystyrene.

Commercial products can be used as the polycarbonate resin used in the present invention, and specific examples of aromatic polycarbonate resins include "SD POLYCA" manufactured by Sumika Polycarbonate Co., Ltd., and Mitsubishi Engineering Plastics. Examples include "Iupilon" and "NOVAREX" manufactured by Sustainability Co., Ltd., and "Panlite" manufactured by Teijin Ltd. Further, as a specific example of the aliphatic polycarbonate resin, there may be mentioned the product name "DURABIO" manufactured by Mitsubishi Chemical Corporation.

<Polyamide resin>
The polyamide resin used in the present invention may be either a crystalline polyamide resin or an amorphous polyamide resin. It can be polymerized by a known method, and commercially available products can be used.
Here, as the polymerization method, the following methods [1] to [6] can be exemplified. Moreover, either a batch type or a continuous type can be selected as appropriate.
[1] A method in which an aqueous solution or aqueous suspension of a dicarboxylic acid/diamine salt or a mixture thereof is heated and polymerized while maintaining the molten state (thermal melt polymerization method).
[2] A method of increasing the degree of polymerization of polyamide obtained by hot melt polymerization while maintaining the solid state at a temperature below the melting point (hot melt polymerization/solid phase polymerization).
[3] A method of heating an aqueous solution or suspension of dicarboxylic acid/diamine salt or a mixture thereof and melting the precipitated prepolymer again in an extruder such as a kneader to increase the degree of polymerization (prepolymer/extrusion polymerization method).
[4] A method of heating an aqueous solution or aqueous suspension of a dicarboxylic acid/diamine salt or a mixture thereof, and increasing the degree of polymerization while maintaining the precipitated prepolymer in a solid state at a temperature below the melting point of the polyamide ( Prepolymer/solid phase polymerization method).
[5] A method in which dicarboxylic acid, diamine salt, or a mixture thereof is polymerized in one step while maintaining it in a solid state (one-step solid phase polymerization method).
[6] A method of polymerizing using a dicarboxylic acid halide equivalent to a dicarboxylic acid and a diamine (solution method).

Although the crystalline polyamide resin is not particularly limited, specific examples include the following. Namely, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyundecamethylene adipamide (polyamide 116), polybis(4-aminocyclohexyl)methandodecamide (polyamide PACM12), polybis(3-methyl-4aminocyclohexyl)methandodecamide (polyamidedimethylPACM12), Nonamethylene terephthalamide (Polyamide 9T), polydecamethylene terephthalamide (Polyamide 10T), polyundecamethylene terephthalamide (Polyamide 11T), polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), polyundecamide (Polyamide 11) ), polydodecamide (polyamide 12), polytrimethylhexamethylene terephthalamide (polyamide TMDT), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene terephthal/isophthalamide (polyamide 6T/6I), polymethaxylylene adipamide ( Examples include polyamide MXD6) and copolymers thereof. These crystalline polyamide resins can be used alone or in combination of two or more.

The amorphous polyamide resin is preferably a polycondensate containing 30 to 70 mol%, more preferably 40 to 60 mol% of isophthalic acid as a dicarboxylic acid component.

Examples of such polycondensates include the following. That is, polycondensates of isophthalic acid/α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms/metaxylylene diamine, polycondensates of isophthalic acid/terephthalic acid/hexamethylene diamine, and isophthalic acid/terephthalic acid. Polycondensate of /hexamethylenediamine/bis(3-methyl-4-aminocyclohexyl)methane, polycondensate of terephthalic acid/2,2,4-trimethylhexamethylenediamine/2,4,4-trimethylhexamethylenediamine , isophthalic acid/bis(3-methyl-4-aminocyclohexyl)methane/ω-laurolactam polycondensate, isophthalic acid/2,2,4-trimethylhexamethylenediamine/2,4,4-trimethylhexamethylenediamine polycondensate of isophthalic acid/terephthalic acid/2,2,4-trimethylhexamethylenediamine/2,4,4-trimethylhexamethylenediamine, isophthalic acid/bis(3-methyl-4-aminocyclohexyl) ) Polycondensates of methane/ω-laurolactam and the like. Also included are those in which the benzene ring of the terephthalic acid component and/or isophthalic acid component constituting these polycondensates is substituted with an alkyl group or a halogen atom. Furthermore, two or more of these amorphous polyamide resins can also be used in combination.

Preferably, a polycondensate of isophthalic acid/α,ω-linear aliphatic dicarboxylic acid having 4 to 20 carbon atoms/methaxylylene diamine, isophthalic acid/terephthalic acid/hexamethylene diamine/bis(3-methyl-4- (aminocyclohexyl)methane polycondensate, terephthalic acid/2,2,4-trimethylhexamethylenediamine/2,4,4-trimethylhexamethylenediamine polycondensate, or isophthalic acid/terephthalic acid/hexamethylenediamine/bis A mixture of a polycondensate of (3-methyl-4-aminocyclohexyl)methane and a polycondensate of terephthalic acid/2,2,4-trimethylhexamethylenediamine/2,4,4-trimethylhexamethylenediamine is used. .

The relative viscosity of the polyamide resin used in the present invention is not particularly limited, but the relative viscosity measured using 96% by mass concentrated sulfuric acid as a solvent at a temperature of 25°C and a concentration of 1 g/dl is as follows: It is preferably in the range of 1.5 to 5.0. If it is within this range, it is preferable because it provides an excellent balance of take-up properties after melt-kneading, mechanical strength, moldability, etc. For these reasons, the relative viscosity is more preferably in the range of 2.0 to 4.0.

It is also possible to use commercially available polyamide resins for use in the present invention, and specific examples of crystalline polyamide resins include "DAIAMID" and "VESTOSINT" manufactured by Daicel-Evonik Ltd. )” can be exemplified.
Specific examples of the amorphous polyamide resin include "TROGAMID" manufactured by Daicel-Evonik Co., Ltd. and "Selar" manufactured by DuPont.

<Non-halogen flame retardant (B)>
The flame retardant in the present invention refers to a substance that is added to flammable materials such as plastics, rubber, fibers, and wood to make them difficult to burn or to make it difficult for flames to spread.

The non-halogen flame retardant (B) used in the present invention is required to have a flow start temperature of 100°C or more and 400°C or less. When the flow start temperature is below 100°C, the non-halogen flame retardant (B) tends to exhibit thermoplasticity when irradiated with heat or light during three-dimensional modeling, and the modeling material melts during stages such as powder dispersion. When printing a modeled object (resin molded object) using a 3D printer, it may cause defects in the shape of the object (resin molded object) due to the phenomenon of sticking (blocking) and difficulty in cooling and solidifying after printing. more likely to occur. In addition, if the flow start temperature exceeds 400°C, the non-halogen flame retardant (B) will not exhibit thermoplasticity when irradiated with heat or light during three-dimensional modeling, so it will not be possible to create it using a 3D printer. When shaping an object (resin molded body), materials (particularly powders) do not adhere sufficiently to each other, resulting in low interlayer adhesion in the shaped article.
The flow start temperature of the non-halogen flame retardant (B) is 100° C. or higher, more preferably 120° C. or higher, from the viewpoint of heat resistance of the molded product to which flame retardancy is desired. Further, from the viewpoint of formability with a 3D printer, the temperature is preferably 350°C or less, more preferably 300°C or less so that sufficient thermoplasticity can be expressed by irradiation with heat or light during three-dimensional modeling.
The above-mentioned flow start temperature is determined using Koka-type Flow Tester CFT-500 (manufactured by Shimadzu Corporation) under the conditions described in the Examples described later.

As the non-halogen flame retardant (B) used in the present invention, various known ones can be used, including phosphorus-based organic flame retardants (organic phosphorus-containing compounds), nitrogen-based organic flame retardants (melamine cyanurate, triazine compounds, guanidine compounds), silicon-based organic flame retardants (silicon polymers), and the like. These non-halogen flame retardants may be used in combination of two or more types as appropriate. Furthermore, the non-halogen flame retardant (B) may contain additives such as flame retardant-improving resins such as phenol resins, epoxy resins, or styrene resins, anti-dripping agents such as polytetrafluoroethylene (PTFE) particles, and fillers. The agents can be mixed as appropriate.
Moreover, as the non-halogen flame retardant (B), an inorganic flame retardant may be used as long as the flow start temperature is 400° C. or lower.

Among these, phosphorus-based flame retardants are preferred, and organic phosphorus-based flame retardants and inorganic phosphorus-based flame retardants (red phosphorus-based flame retardants, such as red phosphorus, stable Chemical red phosphorus, etc.). Further, phosphorus-based organic flame retardants (organic phosphorus-containing compounds) are preferable because they have excellent radical trapping effects and oxidation reaction suppressing effects. Examples of organic phosphorus-containing compounds include, but are not limited to, phosphates, polyphosphates, phosphazene compounds, phosphaphenanthrene compounds, phosphinate metal salts, phosphonic acid polymers, ammonium polyphosphates, melamine polyphosphates, and phosphoric acid. Examples include ester amides, phosphate ester compounds, condensed phosphate ester compounds, phosphate compounds, condensed phosphate compounds, phosphoric acid amide compounds, condensed phosphoric acid amide compounds, phosphorus spiro compounds, and the like.

Other phosphorus-based flame retardants include nitrogen-containing phosphates such as ammonium phosphate, melamine phosphate, guanylurea phosphate, melamine pyrophosphate, and piperazine pyrophosphate; nitrogen-containing condensed phosphoric acids such as ammonium polyphosphate and melamine polyphosphate. Examples include salts; phosphorus/nitrogen-containing compounds such as inorganic or organic phosphorus compounds such as phosphoric acid amide and condensed phosphoric acid amide; mixtures of phosphorus compounds and nitrogen compounds; or combinations thereof.

Such flame retardants are called intumescent flame retardants, and are compounds that contain a phosphorus component that promotes carbonization and a nitrogen component that promotes fire extinguishing and foaming, or compounds that contain a phosphorus component and a nitrogen component that promotes fire extinguishing and foaming. It is a flame retardant mixture obtained by mixing a compound containing a nitrogen component.

In the present invention, from the viewpoint of flame retardancy and thermal properties, it is preferable to use phosphoric acid ester compounds, phosphorus spiro compounds, intumescent flame retardants, and phosphonic acid polymers. It is further preferable to use compounds, and it is particularly preferable to use phosphorus-based spiro compounds.

The phosphorus-based spiro compound is not particularly limited as long as it is a spiro compound having a phosphorus atom. A spiro compound is a compound having a structure in which two cyclic skeletons share one carbon, and a spiro compound having a phosphorus atom is a compound in which at least one of the elements constituting the two cyclic skeletons is a phosphorus atom. Preferably, each cyclic skeleton has a phosphorus atom. Among these, aryl spirodiphosphinate condensed with a polyhydric alcohol is preferred.

An example of the aryl spiro diphosphinate is a pentaerythritol diphosphinate compound. Specifically, 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-dibenzyl-3,9-dioxide, 2,4,8,10-tetraoxa-3 , 9-diphosphaspiro[5.5]undecane, 3,9-diα-methylbenzyl-3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, 3,9-di(2-phenylethyl)-3,9-dioxide, 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane,3,9-bis(diphenylmethyl) Examples include -3,9-dioxide. Two or more types of these compounds may be contained.

Among the aryl spirodiphosphinates, aryl spirodiphosphinates represented by the following general formula (1) are preferred.

In the above formula, R ¹ and R ² are each a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Further, R ¹ and R ² may be the same or different. When the aryl spirodiphosphinate has an aromatic ring such as a phenyl group, a naphthyl group, or an anthryl group, the thermal properties of the aryl spirodiphosphinate are increased, and the aryl spirodiphosphinate has a preferred flow initiation temperature of the present invention.

The phosphonic acid polymer is a polymer compound having a phosphorus atom in its main chain, and includes, for example, a copolymer of bisphenol A-diphenyl methylphosphonate.

Examples of commercially available phosphorus-based spiro compounds include, but are not limited to, Fireguard FCX-210 manufactured by Teijin Ltd. Commercially available phosphonic acid polymers include, but are not limited to, Nofia HM1100 manufactured by FRX.

The amount of non-halogen flame retardant (B) to be used may be determined by selecting an amount that satisfies the sufficient flame retardancy and physical properties required for the situation in which it is used, and specifically, 100 parts by mass of thermoplastic resin (A). On the other hand, from the viewpoint of imparting flame retardancy, it is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, and particularly preferably 15 parts by mass or more. Further, from the viewpoint of formability, the amount is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.

<Flame retardant aid>
The resin composition according to the present invention may contain a flame retardant aid. The flame retardant aid is not particularly limited as long as it improves flame retardancy when combined with the above flame retardant. Examples include fluorine-based flame retardant aids, phosphate ester-based flame retardant aids, nitrogen-based flame retardant aids, and the like. Among these, fluorine-based flame retardant aids are preferred, fluoroolefin resins are preferred, and tetrafluoroethylene resins are exemplified. The fluorine-based flame retardant aid may be in any form, such as a powder, a dispersion, or a powder obtained by coating a fluororesin with another resin.
The content of the flame retardant aid is preferably in the range of 0.001 to 1 part by mass, more preferably in the range of 0.01 to 0.5 part by mass, per 100 parts by mass of the flame retardant. .

<Other ingredients>
Furthermore, in the present invention, the resin composition of the present invention may appropriately contain commonly used additives within a range that does not significantly impede the effects of the present invention. The additives include inorganic particles such as silica, alumina, and kaolin, acrylic resin particles, etc., which are added for the purpose of improving and adjusting the formability, stability of the three-dimensional model, and various physical properties of the three-dimensional model. Organic particles such as melamine resin particles, pigments such as titanium oxide and carbon black, weathering stabilizers, heat resistant stabilizers, antistatic agents, melt viscosity improvers, crosslinking agents, lubricants, nucleating agents, plasticizers, anti-aging agents , antioxidants, light stabilizers, ultraviolet absorbers, neutralizing agents, antifogging agents, antiblocking agents, slip agents, and coloring agents.

The content of the additive in the resin composition of the present invention is not particularly specified, but from the viewpoint of stability of the three-dimensional modeling material to be modeled and its three-dimensional model, the content of the additive in the resin composition of the present invention is 100 parts by mass in total of the three-dimensional modeling material. The amount is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.08 parts by mass or more, and 0.1 parts by mass or more. It is particularly preferable. Further, from the viewpoint of suppressing a decrease in interlayer adhesion of the three-dimensional structure to be modeled, the upper limit of the content of the additive is preferably 30 parts by mass or less, more preferably 28 parts by mass or less, More preferably, it is 25 parts by mass or less.

Furthermore, the resin composition of the present invention may appropriately contain, in addition to the above-mentioned components, a reinforcing material that is generally blended within a range that does not significantly impede the effects of the present invention. Specific examples of reinforcing materials include inorganic fillers and inorganic fibers. Specific examples of inorganic fillers include calcium carbonate, zinc carbonate, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, potassium titanate, glass balloon, glass flakes, glass powder, Silicon carbide, silicon nitride, boron nitride, gypsum, calcined kaolin, zinc oxide, antimony trioxide, zeolite, hydrotalcite, wollastonite, silica, talc, metal powder, alumina, graphite, carbon black, carbon nanotubes, etc. It will be done. Specific examples of inorganic fibers include glass cut fibers, glass milled fibers, glass fibers, gypsum whiskers, metal fibers, metal whiskers, ceramic whiskers, carbon fibers, cellulose nanofibers, and the like.

Here, the content when containing the reinforcing material is not particularly specified, but from the viewpoint of the strength of the three-dimensional object to be modeled, it should be 1% by mass or more based on the total 100% by mass of the three-dimensional modeling material. It is preferably 5% by mass or more, more preferably 10% by mass or more. Moreover, from the viewpoint of suppressing a decrease in interlayer adhesion of the three-dimensional structure to be modeled, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less.

The resin composition used in the present invention can be produced by adding and mixing the thermoplastic resin (A), the non-halogen flame retardant (B), and the other components mentioned above. The method for producing the resin composition is not particularly limited as long as it contains each component. For example, after pre-mixing the thermoplastic resin (A) and other components such as additives blended as necessary using various mixers such as a tumbler or Henschel mixer, The resin composition of the present invention can be produced by melt-kneading using a single-screw kneading extruder, a twin-screw kneading extruder, a kneader, or the like.
When using 3D modeling materials in the form of powder or pellets, non-halogen flame retardants (B), inorganic particles, organic particles, reinforcing materials should be combined with thermoplastic resin (A), additives, etc. It may be mixed with powder produced by the method described below to form a powder mixture without kneading.

<3D modeling materials>
The three-dimensional modeling material of the present invention is a material used for modeling a three-dimensional object (resin molded object) using a 3D printer. The three-dimensional modeling material may be made of the above-mentioned resin composition for three-dimensional printing alone, or may have a single layer structure consisting of a single resin layer made of the above-mentioned resin composition for three-dimensional printing. Moreover, the three-dimensional modeling material of the present invention may have a multilayer structure including at least a resin layer made of the above-mentioned resin composition for three-dimensional modeling.

The shape of the three-dimensional modeling material may be any shape that can be applied to 3D printers of various methods such as material extrusion method (MEX), powder bed fusion method (PBF), and multi-jet fusion method. Specific shapes of the three-dimensional modeling material include powder, pellets, granules, filaments, and the like.

<3D modeling powder>
The three-dimensional modeling powder of the present invention is a modeling material used in powder bed fusion bonding (PBF). Hereinafter, the manufacturing method, physical properties, etc. of the powder for three-dimensional modeling will be explained in detail.

<Method for manufacturing powder for three-dimensional modeling>
Powdering means for producing the powder for three-dimensional modeling of the present invention include melt granulation, in which the resin composition of the present invention is melted near the melting point and cut into fibers, and the resin composition of the present invention is cut into fibers. There is pulverization, in which the material is cut or destroyed by applying impact or shear to it. In order to improve the powder applicability in powder bed fusion bonding modeling, it is preferable not to contain fine powder of around 10 μm and to have a constant particle size and particle size distribution, so that powder with such a suitable shape can be obtained. Therefore, it is preferable to select a suitable powder format.

As the crushing means, for example, a stamp mill, a ring mill, a stone mill, a mortar, a roller mill, a jet mill, a high-speed rotation mill, a hammer mill, a pin mill, a container-driven mill, a disc mill, a medium stirring mill, etc. can be adopted. .

In addition, in order to prevent stretching of the resin material due to shear heat generated during crushing, liquid nitrogen is used to cool the inside of the powder system to lower the resin temperature during crushing, resulting in brittle fracture rather than ductile fracture. There is a method to create . This is called cryogenic grinding or freeze grinding.
In particular, by using a high-speed rotary mill for pulverization, which can obtain powder with a particle size distribution and shape suitable for powder bed fusion bonding modeling, fluidity and powder applicability during modeling are improved. Therefore, it is preferable. In addition, in order to suppress changes in the physical properties and color of the resin material due to pulverization, it is preferable to use liquid nitrogen to produce powder by brittle fracture of the resin material.

In addition, from the viewpoint of removing stretched powder from the pulverized powder to increase circularity, and from the viewpoint of removing fine powder and preventing powder from flying up during handling, it is preferable to perform a classification process after pulverization. . In this case, examples of the classification method include wind classification, sieve classification, and the like. In addition, the above-mentioned inorganic particles and reinforcing material of the obtained powder may be added and mixed as necessary.

<Physical properties of powder for 3D modeling>
When used as a material for powder bed fusion bonding (PBF), D50, which accounts for 50% of the volume ratio of the particle size distribution of the powder measured by laser diffraction, is used as a material for resin molding by powder bed fusion bonding (PBF). Although it depends on the specifications of the system used for modeling the body, from the viewpoint of applying the powder to a thickness within a predetermined range during modeling, the thickness is preferably 20 μm or more, more preferably 30 μm or more, even more preferably 40 μm or more, and especially Preferably it is 50 μm or more, most preferably 55 μm or more, preferably 100 μm or less, more preferably 80 μm or less, still more preferably 75 μm or less, particularly preferably 70 μm or less.

The above D50 is determined by weighing 5 g of powder and measuring the particle size distribution (volume basis) of the powder using a particle size distribution measuring device (Horiba, Ltd., LA-960).The frequency distribution of the powder is 50% of the detected particle size distribution. The particle size located at is determined as D50.

<Filament for 3D modeling>
The filament for three-dimensional modeling of the present invention can be used as either a modeling material or a support material, which are broadly classified as raw materials used in material extrusion (MEX), but it is preferable to use it as a modeling material. Note that the material that becomes the main body of the modeled object is the modeling material, and the material that supports the stacked building materials until they harden into a desired shape is the support material.

<Method for manufacturing filament for 3D modeling>
The filament for three-dimensional modeling of the present invention is produced by melt-kneading a thermoplastic resin (A) and a non-halogen flame retardant (B). The kneading method is not particularly limited, but known methods such as melt kneading devices such as a single screw extruder, a multi-screw extruder, a Banbury mixer, and a kneader can be used. In the present invention, it is preferable to use a co-directional twin-screw extruder from the viewpoint of dispersibility and miscibility of each component. It is preferable that the dispersibility and miscibility are excellent because the accuracy and circularity of the filament diameter can be improved.

The method for producing the filament for three-dimensional modeling of the present invention is not particularly limited, but a thermoplastic resin (A), a non-halogen flame retardant (B), etc. are molded by a known molding method such as extrusion molding. It can be obtained by a method etc. For example, when the filament for three-dimensional modeling of the present invention is obtained by extrusion molding, the conditions are adjusted as appropriate depending on the flow characteristics and molding processability of the thermoplastic resin (A) and non-halogenated flame retardant (B) used. However, the temperature is usually 200°C or more and 400°C or less, preferably 220°C or more and 350°C or less.

<Physical properties of filament for 3D modeling>
The diameter of the filament for three-dimensional modeling of the present invention depends on the specifications of the system used for molding a resin molded body by material extrusion method (MEX), but is usually 1.0 mm or more, preferably 1.5 mm or more, and more preferably is 1.6 mm or more, particularly preferably 1.7 mm or more, while the upper limit is 5.0 mm or less, preferably 4.0 mm or less, more preferably 3.5 mm or less, particularly preferably 3.0 mm or less. Furthermore, it is preferable from the viewpoint of stability of raw material supply that the accuracy of the diameter is within ±5% for any measurement point on the filament. In particular, the filament for three-dimensional modeling of the present invention preferably has a standard deviation of diameter of 0.07 mm or less, particularly 0.06 mm or less.

Further, it is preferable that the filament for three-dimensional modeling of the present invention has a roundness of 0.93 or more, particularly 0.95 or more. The upper limit of roundness is 1.0. In this way, if the standard deviation of the diameter is small and the filament for 3D printing has high roundness, uneven discharge during printing will be suppressed, and resin molded objects with excellent appearance and surface properties can be stably produced. However, by using the resin composition described above, it is possible to relatively easily produce a filament for three-dimensional modeling that satisfies such standard deviation and circularity.

[Molded object]
The molded article of the present invention is made of the above-mentioned three-dimensional modeling material. As a method for manufacturing the molded body, it is preferable to mold the molded body using a 3D printer. The detailed manufacturing method will be described below.

<Method for manufacturing 3D objects>
In the method for manufacturing a molded body made of the three-dimensional modeling material of the present invention, a resin molded body is obtained by molding with a 3D printer using the three-dimensional modeling material of the present invention. Examples of molding methods using a 3D printer include material extrusion (MEX), powder bed fusion bonding (PBF), material jetting, and liquid bath photopolymerization. Among these, it is preferable to use the material extrusion method (MEX) and the powder bed fusion bonding method (PBF) in which a molded article is manufactured by melting a thermoplastic resin.

In addition, in the material extrusion method (MEX), a filament-shaped resin composition melted or softened at high temperature is extruded from a nozzle and arranged in a flat shape, and a molded article is created by forming each layer divided in the height direction. This is the way to obtain.
In addition, powder bed fusion bonding (PBF) involves irradiating particles of a resin composition spread on a stage with a laser or electron beam to sinter or fuse the particles to form a layer in the height direction. . Next, the next layer is formed by spreading particles of the resin composition in contact with the formed layer and irradiating it with a laser or an electron beam. By sequentially laminating the layers in this manner, it is a method of obtaining a molded body of a desired shape.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

<Physical property measurement method>
(Flow starting temperature)
Regarding the flame retardant (B), the flow start temperature was measured by the following method.
Using a sophisticated flow tester manufactured by Shimadzu Corporation, product name "Flow Tester CFT-500C", 1.0 g of the measurement sample was heated at a constant rate of 3°C/min through the nozzle (inner diameter 1 mm, length 2 mm) and a load of 40 kg/cm ² , the temperature at which the sample to be measured starts to flow from the nozzle was measured, and this was determined as the flow start temperature.

(Melting point Tm or glass transition temperature Tg)
The melting point (Tm) or glass transition temperature (Tg) of the flame retardant (B) was measured by the following method.
Using a differential scanning calorimeter manufactured by PerkinElmer Co., Ltd. under the trade name "Pyris1 DSC", approximately 10 mg of a powder sample was heated from room temperature to the crystal melting temperature (melting point Tm) +20 at a heating rate of 10°C/min in accordance with JIS K7121. From the thermogram measured when the temperature was raised to ℃, held at that temperature for 1 minute, then lowered to 30℃ at a cooling rate of 10℃/min, and then raised again to 280℃ at a heating rate of 10℃/min. Based on the detected endothermic peak, the crystal melting temperature (melting point Tm) (°C) (reheating process) or glass transition temperature (Tg) was determined. When multiple endothermic peaks were detected, the one with the largest peak area was selected. In addition, each value was rounded to the second decimal place.

(Color)
When the thermoplastic resin (A) and non-halogenated flame retardant (B) etc. were compounded, the color of the pellets of the resulting resin composition was visually observed and the color was evaluated based on the following criteria. . Evaluation criteria A: Same whiteness as thermoplastic resin (A) alone B: More yellowish than thermoplastic resin (A) alone

(particle size distribution)
5 g of the powder material was weighed, and the particle size distribution of the powder was measured on a volume basis using a particle size distribution measuring device (manufactured by Horiba, Ltd.) using a laser diffraction method. Among the detected particle size distributions, the particle size D50 located at 50% of the frequency distribution of the powder was determined, and the particle size distribution was evaluated based on the following criteria.
A: D50 is less than 100 μm B: D50 is 100 μm or more

(Formability)
Using a powder bed fusion bonding (PBF) printer Lisa Pro (Sinterit), the printing area (Print bed) is heated to a temperature above the cooling crystallization temperature of the powder sample and below the crystal melting temperature, and the material supply section (Feed bed) was set at a temperature equal to or higher than the cooling crystallization temperature of the powder sample, and a 1BA type tensile test piece conforming to JIS K7161 was molded under the conditions of a lamination pitch of 0.125 mm, and the presence or absence of molding defects was determined by external observation. Formability was evaluated based on the following criteria.
A: Possible to print, mechanical properties can be evaluated using the obtained sample B: Possible to print, but very brittle C: Printing defects such as defects are observed, or printing is not possible

(Flame retardance)
Using a powder bed fusion bonding (PBF) printer Lisa Pro (Sinterit), the printing area (Print bed) is heated to a temperature above the cooling crystallization temperature of the powder sample and below the crystal melting temperature, and the material supply section (Feed bed) was set to a temperature equal to or higher than the cooling crystallization temperature of the powder sample, and a test piece with a thickness of 5.0 mm, a width of 13.0 mm, and a length of 125 mm was formed under the conditions of a lamination pitch of 0.125 mm. In accordance with the evaluation criteria of UL94 vertical test, the obtained test piece was vertically attached to a clamp, and indirect flame was applied twice for 10 seconds using a 20 mm flame to measure the combustion time. Flame retardancy was evaluated based on the following criteria.
A: The combustion time for each test is 10 seconds or less, and the total combustion time is less than 50 seconds. B: The combustion time for each test is 20 seconds or less, and the total combustion time is less than 50 seconds. C: Total combustion time is 50 seconds or more

(comprehensive evaluation)
The above-mentioned color, particle size distribution, formability, and flammability were evaluated based on the following criteria.
A: Formability evaluation is “B” or higher, and any two or more are “A”
B: Formability evaluation is "B" or higher. However, none of them are "C".
C: Formability evaluation is “C”

[Example 1]
Fireguard FCX-210 (manufactured by Teijin) (B-1) as a non-halogen flame retardant was added to 100 parts by mass of polybutylene terephthalate (A-1) (Tm: 195°C, ΔHc: 34.6 J/g). 15 parts by mass was added to form a compound. Further, the compound product was pulverized by freeze pulverization using liquid nitrogen and high speed rotary pulverization. In addition, the obtained powder was 100 parts by mass, and 0.3 parts by mass of alumina particles (Alu CRK, manufactured by AEROSIL, average particle size 20 nm) was added as a flow aid, and carbon powder was added as an electromagnetic wave absorber. (Fine Powder SGP-10, manufactured by SEC Carbon Co., Ltd., average particle size 10 μm) was used to evaluate moldability using 0.3 parts by mass. Table 1 shows the evaluation results of the non-halogen flame retardant used and the properties, color, particle size distribution, formability, etc. of the obtained powder.

[Example 2]
When compounding polybutylene terephthalate (A-1) and Fireguard FCX-210 (B-1), 0.2 mass of IT-1105-D (manufactured by ITAFlon) (C-1) was used as an anti-dripping agent. A powder was prepared in the same manner as in Example 1, except that 100% of the powder was further added, and various evaluations were performed.

[Example 3]
Polybutylene terephthalate (A-1) (Tm: 195°C, ΔHc: 34.6 J/g) was pulverized by freeze pulverization using liquid nitrogen and high speed rotation pulverization, and based on 100 parts by mass of the obtained powder, A dry blended powder was prepared by adding 15 parts by mass of Fireguard FCX-210 (B-1) as a non-halogen flame retardant. The composition of the obtained powder was the same as in Example 1, and the same results were obtained in terms of the color and shapeability of the powder. Table 1 shows the results of various evaluations.

[Example 4]
Powders were prepared in the same manner as in Example 1, except that Nofia HM1100 (manufactured by FRXpolymers) (B-2) was used as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1), and various We conducted an evaluation.

[Example 5]
Fireguard FCX-210 (B) was added as a non-halogen flame retardant to 100 parts by mass of polypropylene powder (A-2) (Tm: 135°C, ΔHc: 64.6 J/g), which is a powder material for LisaPro 3D printer manufactured by Sinterit. -1) A dry blended powder was prepared by adding 15 parts by mass, and various evaluations were performed.

[Comparative example 1]
Powder was prepared in the same manner as in Example 1, except that 7 parts by mass of Exolit AP422 (manufactured by Clariant) (B-3) was used as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1). It was manufactured and various evaluations were performed.

[Comparative example 2]
Powder was prepared in the same manner as in Example 1, except that 10 parts by mass of Exolit OP1240 (manufactured by Clariant) (B-4) was used as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1). It was manufactured and various evaluations were performed.

[Comparative example 3]
A powder was produced in the same manner as in Example 3, except that Exolit OP1240 (manufactured by Clariant) (B-4) was used as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1). , and conducted various evaluations.

[Comparative example 4]
In the same manner as in Example 3, except for using PX-200 (manufactured by Daihachi Kagaku Kogyo Co., Ltd.) (B-5) as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1). A powder was prepared and various evaluations were performed.

[Comparative example 5]
A powder was produced in the same manner as in Example 5, except that Exolit OP1240 (manufactured by Clariant) (B-4) was used as a non-halogen flame retardant instead of Fireguard FCX-210 (B-1). , and conducted various evaluations.

As is clear from the above results, if the flow start temperature of the non-halogenated flame retardant is 400°C or lower, the thermal properties of the thermoplastic resin can be maintained while the moldability and color of the molded product can be excellent in 3D printers. We were able to provide materials for dimensional modeling.

According to the three-dimensional printing material of the present invention, it is possible to provide a three-dimensional printing material that maintains the thermal properties of a thermoplastic resin and has excellent printability in a 3D printer and color tone of a printed product, and can be used for prototype production. It can also be used for practical purposes such as electric/electronic parts, home appliances, building materials, aircraft, and automobile materials.
Examples of automotive materials include various control units, various sensors, ignition coils, cases for vehicle components such as ECU boxes, connector boxes, and vehicle electrical components. Examples of electrical and electronic components include connectors, switches, relays, coils, actuators, sensors, transformer bobbins, terminal blocks, covers, sockets, and plugs.

Claims

A three-dimensional modeling material containing a resin composition, wherein the resin composition includes a thermoplastic resin (A) and a non-halogen flame retardant (B), and the resin composition contains a thermoplastic resin (A) and a non-halogen flame retardant (B). A three-dimensional modeling material characterized by a starting temperature of 100°C or higher and 400°C or lower.
The three-dimensional modeling material according to claim 1, wherein the non-halogen flame retardant (B) is an organic phosphorus-containing compound.
The three-dimensional modeling material according to claim 1, wherein the non-halogen flame retardant (B) is a phosphorus spiro compound or a phosphate ester compound.
A three-dimensional modeling material containing a resin composition, wherein the resin composition includes a thermoplastic resin (A) and a non-halogen flame retardant (B), and the non-halogen flame retardant (B) A three-dimensional modeling material that is a compound represented by the following general formula (1).

(In formula (1), R 1 and R 2 are each a phenyl group, a naphthyl group, or an anthryl group, and may have a substituent on the aromatic ring. Also, R 1 and R 2 are mutually They may be the same or different.)
3-dimensional modeling according to claim 1, characterized in that the non-halogen flame retardant (B) is contained in a ratio of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin (A). material.
The thermoplastic resin (A) is polyacetal, polyacrylate, polyacrylic acid, polyamide, polyamideimide, polyacid anhydride, polyarylate, polyarylene ether, polyarylene sulfide, polybenzoxazole, polyester, polyether ether ketone. , polyetherimide, polyetherketoneketone, polyetherketone, polyethersulfone, polyimide, polymethacrylate, polyolefin, polyphthalide, polysilazane, polysiloxane, polystyrene, polysulfide, polysulfonamide, polysulfonate, polythioester, polytriazine, polyurea, Polyurethane, polyvinyl alcohol, polyvinyl ester, polyvinyl ether, polyvinyl halide, polyvinyl ketone, polyvinylidene fluoride polyvinyl aromatic, polysulfone, polyarylene sulfone, polyaryletherketone, polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate , polyhydroxyalkanoate, starch, cellulose ester, poly(phenylene ether), poly(methyl methacrylate), styrene-acrylonitrile, poly(ethylene oxide), epichlorohydrin polymer, polycarbonate homopolymer, copolycarbonate, poly(ester carbonate) , poly(ester-siloxane-carbonate), poly(carbonate-siloxane), vinyl polymer, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), methyl methacrylate-butadiene-styrene copolymer resin (MBS resin), poly The three-dimensional structure according to claim 1, which is any one selected from the group consisting of vinyl chloride, modified polyphenylene ether, and olefin-based, styrene-based, and polyester-based thermoplastic elastomers, or a mixture of two or more thereof. Materials for use.
A three-dimensional modeling powder obtained using the three-dimensional modeling material according to any one of claims 1 to 6.
The powder for three-dimensional modeling according to claim 7, having a particle size distribution D50 of 20 μm or more and 100 μm or less.
A molded object obtained using the three-dimensional modeling material according to any one of claims 1 to 6.
A molded object obtained using the three-dimensional modeling powder according to claim 7.
A method for producing a molded body, comprising the step of three-dimensionally modeling the molded body using the three-dimensional modeling material according to any one of claims 1 to 6.
Using the three-dimensional modeling material according to any one of claims 1 to 6 or the three-dimensional modeling powder according to claim 7, a molded body is three-dimensionally formed by powder bed fusion bonding (PBF). A method for manufacturing a molded body, including a step of shaping it into a molded body.