Thermoplastic resin composition, method for producing shaped object, and shaped object

Abstract

A thermoplastic resin composition for fused deposition modeling which comprises (A) a thermoplastic resin and (B) a polyphosphate ester compound, wherein the polyphosphate ester compound (B) is represented by formula (1) and has a melting point of 150°C or lower or is liquid at ordinary temperature, the amount of the polyphosphate ester compound (B) being 1-35 parts by mass per 100 parts by mass of the sum of the thermoplastic resin (A) and the polyphosphate ester compound (B) (with the proviso that in cases when the resin composition includes a plurality of compounds which are represented by general formula (1) and which are equal in R11, R12, R13, R14, and R15 but differ in r, then the requirement that the compound (B) has a melting point of 150°C or lower or is liquid at ordinary temperature includes a requirement that the mixture of the plurality of compounds has a melting point of 150°C or lower or is liquid at ordinary temperature). See the description as to definitions of the symbols in formula (1) See the description as to definitions of the symbols in formula (2) See the description as to definitions of the symbols in formulae (3) and (4)

Description

Thermoplastic resin composition, method for producing shaped body, and shaped body

[0001] The present invention relates to a thermoplastic resin composition for fused deposition modeling, a method for producing a shaped object by fused deposition modeling using the thermoplastic resin composition, and use of a resin material in producing the shaped object and a filament material for fused deposition modeling.

[0002] Three-dimensional modeling (also known as additive manufacturing or 3D printing) technology has been applied in various fields in recent years due to its advantages, such as the ability to manufacture resin products without using molds and a high degree of freedom in the shape of the manufactured products. In particular, additive manufacturing equipment using the fused deposition modeling (FDM) method is relatively inexpensive compared to other methods, and has therefore become popular not only for industrial use but also for home use. The FDM method is a method of forming three-dimensional objects by ejecting molten thermoplastic resin from a nozzle and layering it.

[0003] Traditionally, acrylonitrile-butadiene-styrene copolymer (ABS resin) and polylactic acid have been the mainstream thermoplastic resins used in FDM. However, these thermoplastic resins are flammable and therefore unsuitable for applications requiring high safety, such as aircraft components, automobile components, and home appliance components. To address this issue, Patent Document 1, for example, proposes a method using polyetherimide resin, a flame-retardant resin. However, FDM molding of polyetherimide requires a nozzle temperature of 350-400°C, and molding machines capable of operating in this temperature range are limited to some high-end models. Furthermore, polyetherimide resin is more expensive than mainstream materials such as ABS resin and polylactic acid, making it disadvantageous in terms of manufacturing costs.

[0004] One known method for solving these problems is to blend a flame retardant into an inexpensive thermoplastic resin material to make it flame-retardant. For example, Patent Document 2 proposes a glass fiber composite material for 3D printing, describing the use of waste plastics and triphenyl phosphate as its components. Patent Document 3 proposes a resin filament for creating three-dimensional objects, which is made of a resin composition containing an aromatic vinyl resin and a phosphate compound with a specific structure, and describes that objects created using the filament are less likely to experience delamination.

[0005] US Patent No. 10434705 Chinese Patent Application Publication No. 106433177 Japanese Patent Application Laid-Open No. 2017-149038

[0006] However, Patent Document 2 does not describe the creation of objects by three-dimensional modeling or their flame retardancy. As a result of the inventor's investigations, it was found that in FDM three-dimensional modeling of thermoplastic resin materials containing low-molecular-weight compounds such as triphenyl phosphate, the triphenyl phosphate volatilizes and emits smoke due to the heat generated during modeling, resulting in the three-dimensionally modeled object not exhibiting flame retardancy. Patent Document 3 does not describe the flame retardancy of the composition, nor does it describe or suggest the effect of the melting point of the phosphate ester on interlayer adhesion during three-dimensional modeling.

[0007] Under these circumstances, there has been a need for a thermoplastic resin composition for FDM that is excellent in flame retardancy, molding stability, and interlayer adhesion.

[0008] As a result of further investigation, the present inventors discovered that a three-dimensional object manufactured by FDM using a flame-retardant thermoplastic resin composition in which a condensed phosphate ester compound having a specific structure and a specific melting point range is blended with a thermoplastic resin as a flame retardant exhibits high flame retardancy, excellent modeling stability, and high interlayer adhesion of the object, thereby completing the present invention.

[0009] According to the present invention, there is provided a thermoplastic resin composition for fused deposition modeling, comprising: (A) a thermoplastic resin; and (B) a condensed phosphate ester compound, wherein the (B) condensed phosphate ester compound is represented by the following general formula (1) and has a melting point of 150°C or less or is liquid at room temperature, and the blending amount of the (B) condensed phosphate ester compound is 1 to 35 parts by mass per 100 parts by mass of the total of the (A) thermoplastic resin and the (B) condensed phosphate ester compound. １１ , R １２ , R １３ , R １４ and R １５ When the compound contains a plurality of compounds having the same r but different r's, the melting point of 150°C or less or being a liquid at room temperature includes a mixture of the plurality of compounds having a melting point of 150°C or less or being a liquid at room temperature.

[0010]

[0011] In general formula (1), R １１ , R １２ , R １３ and R １４ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group represented by the following general formula (2), R １５ represents a divalent aromatic hydrocarbon group represented by the following general formula (3) or (4), and r is a number from 1 to 30.

[0012]

[0013] In general formula (2), R ２１ and R ２２ each independently represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms, and * represents a bond.

[0014]

[0015] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R４４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitro group, a halogen atom, or a cyano group; X represents a direct bond, a divalent sulfur atom, a sulfonyl group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms; and * represents a bond.

[0016] The thermoplastic resin composition of the present invention preferably further contains one or more fluorine-containing polymers (C) in an amount of 0.03 to 5 parts by mass per 100 parts by mass of the thermoplastic resin (A).

[0017] The thermoplastic resin composition of the present invention is preferably in the form of a thread.

[0018] The thermoplastic resin composition of the present invention preferably has a filamentous shape with an average diameter of 1.55 to 1.95 mm.

[0019] In the thermoplastic resin composition of the present invention, the thermoplastic resin (A) preferably contains one or more condensation polymer compounds.

[0020] In the thermoplastic resin composition of the present invention, the thermoplastic resin (A) preferably contains a polycarbonate resin.

[0021] The present invention also provides a method for producing a shaped object using the above-mentioned thermoplastic resin composition with a three-dimensional modeling device.

[0022] In the method of the present invention, the nozzle temperature of the three-dimensional modeling device is preferably 300° C. or less.

[0023] The present invention also provides a shaped body obtained by the above method.

[0024] Further, according to the present invention, there is provided a use of a resin material in the production of a filament material for fused deposition modeling, the resin material comprising: (A) a thermoplastic resin; and (B) a condensed phosphate ester compound; the (B) condensed phosphate ester compound is represented by the following general formula (1) and has a melting point of 150°C or less or is liquid at room temperature; and the blending amount of the (B) condensed phosphate ester compound is 1 to 35 parts by mass per 100 parts by mass of the total of the (A) thermoplastic resin and the (B) condensed phosphate ester compound (however, the use of the resin material is not limited to the use of the resin composition represented by the general formula (1) and R １１ , R １２ , R １３ , R １４ and R １５ When the compound contains a plurality of compounds having the same r but different r's, the melting point of 150°C or less or being a liquid at room temperature includes a mixture of the plurality of compounds having a melting point of 150°C or less or being a liquid at room temperature.

[0025] According to the present invention, it is possible to provide a thermoplastic resin composition for fused deposition modeling that has excellent flame retardancy, modeling stability, and interlayer adhesion, as well as a method for producing a shaped object by fused deposition modeling using the thermoplastic resin composition, and a shaped object obtained by the method.

[0026] Hereinafter, embodiments of the present invention will be described in detail. In this specification, fused deposition modeling (hereinafter also referred to as FDM) refers to three-dimensional modeling using the fused deposition modeling method. The FDM method is a modeling method for three-dimensional modeling, in which thermoplastic resin in a shape such as pellets or threads is heated and melted inside a modeling device, then ejected from a nozzle, and layered one by one while cooling and solidifying to form a three-dimensional object.

[0027] The thermoplastic resin composition of the present invention is a thermoplastic resin composition for fused deposition modeling, which contains (A) a thermoplastic resin and (B) a condensed phosphate ester compound.

[0028] The thermoplastic resin (A) used in the present invention will be described below. Hereinafter, the thermoplastic resin (A) may be referred to as "component (A)." Specific examples of the thermoplastic resin (A) used in the present invention include α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, and poly-4-methylpentene, and polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, and vinyl chloride-cyclohexylmaleimide copolymer. halogen-containing resins such as copolymers; petroleum resins, coumarone resins, polystyrene (PS), high-impact polystyrene (HIPS), polyvinyl acetate, acrylic resins, copolymers of styrene and / or α-methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (e.g., acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS resin), styrene-butadiene-styrene copolymer (SBS resin), heat-resistant ABS resin, methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), etc.); polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral;Polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polycyclohexanedimethylene terephthalate, aromatic polyester resins such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate, and linear polyester resins such as polytetramethylene terephthalate; polyester resins such as degradable aliphatic polyester resins such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone); polyamide resins such as polycaprolactam and polyhexamethylene adipamide; Examples of the resin include cellulose ester resins such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate; polycarbonate resins such as linear polycarbonate and branched polycarbonate, polycarbonate / ABS resins (polymer alloys of polycarbonate and ABS resin), polyacetal resins, polyphenylene sulfide resins, polyurethane resins, cellulose resins, polyimide resins, polyethersulfone (PES) resins, polysulfone resins, polyphenylene ether resins, polyether ketone resins, polyether ether ketone resins, and liquid crystal polymers, as well as blends thereof. The thermoplastic resin (A) may also be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyolefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, polyester-based thermoplastic elastomer, nitrile-based thermoplastic elastomer, nylon-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, polyamide-based thermoplastic elastomer, or polyurethane-based thermoplastic elastomer;

[0029] These thermoplastic resins (A) used in the present invention may be used alone or in combination of two or more. They may also be alloyed. These thermoplastic resins (A) can be used regardless of molecular weight, degree of polymerization, density, softening point, proportion of solvent-insoluble matter, degree of stereoregularity, presence or absence of catalyst residue, types and blending ratios of raw material monomers, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc.

[0030] Among these thermoplastic resins (A), from the viewpoint of significantly achieving the effects of the present invention, it is preferable to include one or more selected from condensation thermoplastic resins (condensation polymer compounds), more preferably a polycarbonate resin, and also preferably a polyphenylene ether resin. The condensation thermoplastic resin refers to a thermoplastic resin obtained by condensation polymerization. Condensation thermoplastic resins have high strength and are resistant to shrinkage, making them suitable as thermoplastic resins for use in FDM.

[0031] Examples of the condensation thermoplastic resin include polyester resin, polyamide resin, and polycarbonate resin. The condensation thermoplastic resin may also be an elastomer such as a polyester thermoplastic elastomer, a polyamide thermoplastic elastomer, or a polyurethane thermoplastic elastomer. In the present invention, these condensation thermoplastic resins may be used alone or in combination of two or more. The condensation thermoplastic resin may also be alloyed.

[0032] Examples of the polyester resin include the various aromatic polyester resins, linear polyester resins, and degradable aliphatic polyesters listed above. Among these, preferred examples include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, and polycyclohexanedimethylene terephthalate; polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone).

[0033] Examples of the polyamide resin include aliphatic polyamides such as polyamide 410, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 612, polyamide 11, and polyamide 12; and semi-aromatic polyamides such as polyamide 4T, polyamide 6T, polyamide 9T, and polyamide 10T.

[0034] The polycarbonate resin is a resin having a carbonate bond, and is obtained, for example, by a polymerization reaction between a divalent hydroxy aromatic compound and a carbonate precursor. Examples of the divalent hydroxy aromatic compound include dihydroxybenzenes such as resorcinol and hydroquinone; bishydroxyaryls such as 4,4'-dihydroxydiphenyl; bis(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenoxy)ethane, and 2,2-bis(4-hydroxyphenyl)propane; dihydroxyarylketones such as bis(4-hydroxyphenyl)ketone and bis(4-hydroxy-3-methylphenyl)ketone; 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethylphenyl ether. dihydroxyaryl ethers such as 4,4'-thiodiphenol, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 2,2-bis(4-hydroxyphenyl)sulfone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and phenolphthalein. These may be used alone or in combination of two or more, and may also be used in combination with a polyvalent hydroxy aromatic compound having three or more hydroxy groups.

[0035] Specific examples of suitable carbonate precursors include phosgene, carbonic acid diesters, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof.

[0036] The polyphenylene ether resin may be used alone or in the form of an alloy. Examples of resins to be alloyed with polyphenylene ether include styrene-based resins, polyamides, polypropylenes, polyacetals, and polyphenylene sulfides. Among these, alloying with styrene-based resins is preferred because of their excellent compatibility with condensed phosphate ester compounds.

[0037] Specific examples of styrene-based resins include polystyrene (PS), styrene-butadiene-styrene copolymer (SBS resin), hydrogenated styrene-butadiene-styrene copolymer (hydrogenated SBS), hydrogenated styrene-isoprene-styrene copolymer (SEPS), high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), methyl methacrylate-acrylonitrile-styrene copolymer (MAS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), and styrene-IPN type rubber copolymer, as well as mixtures thereof. Furthermore, stereoregular resins such as syndiotactic polystyrene may also be used. Among these styrene-based resins, polystyrene and high-impact polystyrene are preferred.

[0038] On the other hand, a non-condensation polymer compound (non-condensation thermoplastic resin) may also be used as the thermoplastic resin. Such a polymer compound is a resin that basically does not have an amide bond, an ester bond, a urethane bond, a carbonate bond, or the like in its main skeleton, and examples thereof include α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polybutene-1, poly-3-methylpentene, and poly-4-methylpentene, polyolefin resins such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-propylene copolymer, and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride -Halogen-containing resins such as cyclohexylmaleimide copolymers; petroleum resins, coumarone resins, polystyrene, high impact polystyrene (HIPS), polyvinyl acetate, acrylic resins, copolymers of styrene and / or α-methylstyrene with other monomers (e.g., maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) (e.g., AS resin, ABS resin, ACS resin, SBS resin, MBS resin, MABS resin, heat-resistant ABS resin, etc.); isoprene rubber, butadiene Examples of elastomers include ethylene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyolefin-based thermoplastic elastomer, styrene-based thermoplastic elastomer, and vinyl chloride-based thermoplastic elastomer. Among these, polystyrene, HIPS, AS resin, ABS resin, MBS resin, MABS resin, heat-resistant ABS resin, and styrene-based thermoplastic elastomer are preferred from the viewpoints of modeling stability in FDM modeling, and particularly low shrinkage and low warpage.

[0039] From the viewpoint of mechanical properties, the amount of the thermoplastic resin in the thermoplastic resin composition is preferably 60% by mass or more, and more preferably 65% ​​by mass or more. From the viewpoint of increasing the amount of the condensed phosphate ester compound represented by general formula (1) added to enhance flame retardancy, the amount of the thermoplastic resin in the thermoplastic resin composition is preferably 95% by mass or less, and more preferably 93% by mass or less. From these viewpoints, the amount of the thermoplastic resin is, for example, preferably 60% by mass or more and 95% by mass or less, and more preferably 65% ​​by mass or more and 93% by mass or less, from the viewpoint of a balance between flame retardancy, molding stability, and interlayer adhesion.

[0040] Furthermore, when a condensation thermoplastic resin such as a polycarbonate resin is included, the amount of the condensation thermoplastic resin in the thermoplastic resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 65% ​​by mass or more, in order to easily obtain the above-mentioned effects of using the condensation thermoplastic resin. The amount of the condensation thermoplastic resin is preferably 95% by mass or less, more preferably 93% by mass or less, in order to increase the amount of the condensation phosphate ester compound represented by general formula (1) added in the thermoplastic resin composition to improve flame retardancy. From these viewpoints, the amount of the condensation thermoplastic resin in the thermoplastic resin composition is preferably 50% by mass or more but 95% by mass or less, in order to achieve a balance between flame retardancy, molding stability, and interlayer adhesion, more preferably 60% by mass or more but 95% by mass or less, and even more preferably 65% ​​by mass or more but 93% by mass or less.

[0041] Furthermore, when a condensation thermoplastic resin such as a polycarbonate resin is included, the amount of the condensation thermoplastic resin is preferably 1% by mass or more, more preferably 50% by mass or more, in the thermoplastic resin. The amount of the condensation thermoplastic resin is 100% by mass or less in the thermoplastic resin, but from the viewpoint of further improving the balance of flame retardancy, molding stability, and interlayer adhesion, it is preferably 95% by mass or less. From this viewpoint, the amount of the condensation thermoplastic resin is, for example, 1% by mass or more and 100% by mass or less in the thermoplastic resin, from the viewpoint of the balance of flame retardancy, molding stability, and interlayer adhesion, and more preferably 50% by mass or more and 95% by mass or less.

[0042] When the thermoplastic resin contains a non-condensation thermoplastic resin, it is not particularly limited, but from the viewpoint of moldability and impact resistance, the amount of the non-condensation thermoplastic resin in the thermoplastic resin composition is preferably 1% by mass or more, more preferably 3% by mass or more. From the viewpoint of flame retardancy, the amount of the non-condensation thermoplastic resin in the thermoplastic resin composition is preferably 50% by mass or less, more preferably 30% by mass or less. From these viewpoints, the amount of the non-condensation thermoplastic resin in the thermoplastic resin composition is, for example, preferably 1% by mass or more and 50% by mass or less, from the viewpoint of the balance between flame retardancy, molding stability, and interlayer adhesion, and more preferably 3% by mass or more and 30% by mass or less.

[0043] Furthermore, when a non-condensation thermoplastic resin is contained, from the viewpoint of moldability and impact resistance, the amount of the non-condensation thermoplastic resin in the thermoplastic resin is preferably 1% by mass or more, more preferably 5% by mass or more. From the viewpoint of flame retardancy, the amount of the non-condensation thermoplastic resin in the thermoplastic resin is preferably 50% by mass or less, more preferably 40% by mass or less. From these viewpoints, the amount of the non-condensation thermoplastic resin in the thermoplastic resin is, for example, 1% by mass or more to 50% by mass or less, from the viewpoint of the balance between flame retardancy, molding stability, and interlayer adhesion, and more preferably 5% by mass or more to 40% by mass or less.

[0044] In the present invention, when the thermoplastic resin composition contains an aromatic vinyl resin, the amount of the aromatic vinyl resin selected from the group consisting of PS resin, HIPS resin, MS resin, ABS resin, AS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and mixtures thereof, which contains a rubber component in an amount of 5 to 15% by weight based on the weight of the aromatic vinyl resin, may be less than 85% by mass in the resin composition.

[0045] The condensed phosphate ester compound (B) used in the present invention will be explained below: The condensed phosphate ester compound (B) used in the present invention is a condensed phosphate ester compound represented by the following general formula (1).

[0046]

[0047] In general formula (1), R １１ , R １２ , R １３ and R １４ may be the same or different and represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group represented by the following general formula (2), R １５ represents a divalent aromatic hydrocarbon group represented by the following general formula (3) or (4), and r is a number from 1 to 30.

[0048]

[0049] In general formula (2), R ２１ and R ２２ each independently represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms, and * represents a bond.

[0050]

[0051] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R ４４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitro group, a halogen atom, or a cyano group; X represents a direct bond, a divalent sulfur atom, a sulfonyl group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms; and * represents a bond.

[0052] In general formula (1), R １１ , R １２ , R １３ and R １４ Examples of the alkyl group having 1 to 10 carbon atoms that may be taken by include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a tert-pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, and a 2-propylheptyl group.

[0053] In general formula (1), R １１ , R １２ , R １３ and R １４ are each preferably an aromatic hydrocarbon group represented by general formula (2) from the viewpoint of flame retardancy. In general formula (1), r is a number from 1 to 30. When the lower limit of r is 1 or more, the interlayer adhesion and additive manufacturing stability of a three-dimensional object manufactured using the thermoplastic resin composition of the present invention tend to be improved. The upper limit of r is preferably 10 or less, and more preferably 7 or less. This improves the handleability of the (B) condensed phosphate ester compound. The (B) condensed phosphate ester compound is a compound represented by general formula (1) that has a different r but has another structure (R １１ , R １２ , R １３ , R １４ and R １５ ) may be a mixture of compounds having the same structure.

[0054] In general formula (2), R ２１ and R ２２ The alkyl group having 1 to 10 carbon atoms that can be taken by R in general formula (1) is １１ ~R １４ In general formula (2), R ２１ and R ２２ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0055] Specific examples of the aromatic hydrocarbon group represented by general formula (2) include a phenyl group, a tolyl group, a xylyl group, a 2,6-xylyl group, a 2,4,6-trimethylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 2,4-di-tert-butylphenyl group, a 2,6-di-tert-butyl-4-methylphenyl group, and a nonylphenyl group, with a phenyl group, a tolyl group, a xylyl group, and a 2,6-xylyl group being preferred, a phenyl group and a 2,6-xylyl group being more preferred, and a phenyl group being even more preferred. This improves the handleability and storage stability of the (B) condensed phosphate ester compound.

[0056] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R ４４ The alkyl group having 1 to 4 carbon atoms that can be taken by R in general formula (1) is １１ ~R １４ Examples of the alkyl group having 1 to 10 carbon atoms that can be taken by include those having 1 to 4 carbon atoms among those listed above.

[0057] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R ４４ Examples of the alkoxy group having 1 to 4 carbon atoms that can be taken by include alkoxy groups corresponding to the alkyl groups having 1 to 4 carbon atoms listed above.

[0058] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R ４４ The cycloalkyl group having 3 to 8 carbon atoms that can be taken by R in general formula (1) is １１ ~R １４Examples of the alkyl group having 1 to 10 carbon atoms that can be taken by include cycloalkyl groups corresponding to the alkyl groups having 3 to 8 carbon atoms among the alkyl groups listed above, such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, and those substituted with an alkyl group.

[0059] In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ and R ４４ Examples of the aryl group having 6 to 10 carbon atoms that may be taken by include a phenyl group, a tolyl group, a xylyl group, a 2,4,6-trimethylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.

[0060] In general formula (4), examples of the alkylidene group having 1 to 5 carbon atoms which X may represent include ethylidene, propylidene, isopropylidene, butylidene, and isobutylidene, and examples of the alkylene group having 1 to 5 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, an isobutylene group, and a pentylene group.

[0061] In general formula (4), X is preferably a direct bond, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms in terms of thermal stability, ease of adjusting the melting point, and ease of raw material availability.

[0062] Specific examples of the divalent aromatic hydrocarbon group represented by formula (3) include a 1,4-phenylene group and a 1,3-phenylene group.

[0063] Specific examples of the divalent aromatic hydrocarbon group represented by general formula (4) include a 4,4'-biphenylene group, a 4,4'-isopropylidenediphenylene group, a 4,4'-thiodiphenylene group, and a 4,4'-sulfonyldiphenylene group.

[0064] The melting point of the (B) condensed phosphate ester compound is 150°C or lower, preferably 125°C or lower, and more preferably 110°C or lower. In this specification, the (B) condensed phosphate ester compound may be liquid at room temperature. Hereinafter, a condensed phosphate ester compound represented by general formula (1) and having a melting point of 150°C or lower or being liquid at room temperature may be referred to as "component (B)". The "component (B)" includes (1) a compound represented by general formula (1) and having a melting point of 150°C or lower when measured alone, (2) a compound represented by general formula (1) and having a melting point of 150°C or lower when measured alone, and (3) a compound represented by general formula (1) and having a melting point of 150°C or lower when measured alone, and １１ , R １２ , R １３ , R １４ and R １５ (3) a compound represented by general formula (1) which is a liquid at room temperature; and (4) a compound represented by general formula (1) which is a compound having R １１ , R １２ , R １３ , R １４ and R １５ The present invention also includes a mixture of compounds having the same r and different r's, which is liquid at room temperature. When the (B) condensed phosphate ester compound is liquid at room temperature, the interlayer adhesion and additive manufacturing stability of a three-dimensional object produced using the thermoplastic resin composition of the present invention are improved. The room temperature is, for example, 25°C.

[0065] The melting point in the present invention is measured by the following melting point measurement method. Here, when multiple compounds represented by formula (1) are present in a resin composition, the melting points of those compounds are measured for each compound. However, when multiple compounds represented by formula (1) that have the same structure except for the difference r are present in a resin composition, the melting points of those multiple compounds are measured as a mixture of multiple compounds represented by formula (1) that have the same structure except for the difference r. <Melt Point Measurement Method> The melting point is measured using a differential thermal thermogravimetric analyzer. 10±0.5 mg of a sample is weighed into an aluminum pan, and the temperature is raised from 25°C to 450°C at a rate of 10°C / min in an air atmosphere, and the melting point is determined to be the peak top of the melting peak.

[0066] Specific examples of the (B) condensed phosphate ester compound include the following Compounds No. 1 to 5. Note that r in the following Compounds No. 1 to 5 each represents a number from 1 to 30.

[0067] Furthermore, being a liquid at room temperature means being a liquid at 25°C. Being a liquid means having a viscosity that can be measured with a Brookfield viscometer. From the viewpoint of handleability, the viscosity measured with a Brookfield viscometer (25°C) is preferably 150,000 mPa·s or less, more preferably 100,000 mPa·s or less, even more preferably 80,000 mPa·s or less, and particularly preferably 60,000 mPa·s or less. Furthermore, it is preferable that there is no turbidity, crystallization, or solid precipitation.

[0068]

[0069] These compounds may be used alone or in combination of two or more. From the viewpoints of interlayer adhesion and additive manufacturing stability, the (B) condensed phosphate ester compound is preferably one or more of the above-mentioned compounds No. 1, No. 2, No. 3, and No. 5, and from the viewpoint of flame retardancy, it is more preferably one or more of the compounds No. 1 and No. 2.

[0070] The lower limit of the amount of component (B) in the thermoplastic resin composition of the present invention is 1 part by mass or more per 100 parts by mass of the total of components (A) and (B), and from the viewpoint of flame retardancy, it is preferably 7 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 12 parts by mass or more. On the other hand, the upper limit of the amount of component (B) is 35 parts by mass or less per 100 parts by mass of the total of components (A) and (B), and from the viewpoint of interlayer adhesion and additive manufacturing stability, it is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less.

[0071] The method for producing the condensed phosphate compound (B) of the present invention is not particularly limited, but for example, the above-mentioned compound No. 1 can be produced by reacting 4,4′-dihydroxybiphenyl, phenol, and phosphorus oxychloride in the presence of a catalyst such as magnesium chloride, followed by dehydrochlorination.

[0072] The thermoplastic resin composition of the present invention may contain components other than (A) the thermoplastic resin and (B) the condensed phosphate ester compound, as long as the effects of the present invention are not impaired. As the other components, any of the additives described below as components that can be blended in the thermoplastic resin composition of the present invention can be used.

[0073] The thermoplastic resin composition of the present invention preferably contains one or more fluorine-containing polymers (C) in order to suppress dripping during combustion. Examples of the fluorine-containing polymers (C) include polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, polyvinylidene fluoride, and polychlorotrifluoroethylene. Among these, polytetrafluoroethylene is preferred from the viewpoint of drip prevention performance.

[0074] When a fluorine-containing polymer is contained, the content of the fluorine-containing polymer (C) is preferably 0.03 to 5 parts by mass, more preferably 0.05 to 3 parts by mass, and even more preferably 0.1 to 1 part by mass, relative to 100 parts by mass of the thermoplastic resin (A). By setting the content to 0.03 part by mass or more, a sufficient drip prevention effect can be achieved, and by setting the content to 5 parts by mass or less, deterioration of the resin properties can be easily prevented.

[0075] Furthermore, it is preferable to further add a phenol-based antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, an ultraviolet absorber, a hindered amine-based light stabilizer, or the like to the thermoplastic resin composition of the present invention, as necessary, to stabilize the resin composition.

[0076] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butyl-m-cresol ... 2,2'-ethylidenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3 ,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate nate)], thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butylic acid]glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris[(3,Examples of suitable phenolic antioxidants include 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. The amount of these phenolic antioxidants used is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0077] Examples of the phosphorus-based antioxidant include tris(nonylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyl diphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-te tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-te tert-butyl-5-methylphenol) diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2, Examples of suitable phosphorus-based antioxidants include 2'-methylenebis(4,6-tert-butylphenyl)octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, and phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol. The amount of these phosphorus-based antioxidants used is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0078] Examples of the thioether-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetrakis(β-alkylmercaptopropionates). The amount of these thioether-based antioxidants used is preferably 0.001 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0079] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-butylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-tert-octylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl salicylate , resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, and other benzoates; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β,β-diphenylacrylate and cyanoacrylates such as methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine.The amount of these ultraviolet absorbers used is preferably 0.001 to 30 parts by mass, and more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0080] Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2 ,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxybenzyl)- polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidinol) / diethyl succinate, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine, polycondensation product of 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine, polycondensation product of 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino]hexane / 2,4-dichloro-6-tert-octylamino-s-triazine, 1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,Examples of suitable hindered amine light stabilizers include bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)amino)-s-triazin-6-yl)aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl)decanedioate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl)carbonate, and TINUVINNOR 371 manufactured by BASF. The amount of these hindered amine light stabilizers used is preferably 0.001 to 30 parts by mass, and more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin (A).

[0081] The thermoplastic resin composition of the present invention may contain a filler as an optional component, provided that the effects of the present invention are not significantly impaired. Examples of such fillers include talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, carbon fiber, clay, dolomite, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, and hydrotalcite. The particle size (fiber diameter, fiber length, and aspect ratio in the case of fibrous forms) may be appropriately selected. These fillers may be used alone or in combination of two or more. Furthermore, surface-treated fillers may be used as needed. When these fillers are added, the amount is preferably 1 to 50 parts by weight, more preferably 3 to 45 parts by weight, and even more preferably 5 to 43 parts by weight, per 100 parts by weight of the thermoplastic resin (A), from the viewpoints of ejection stability of the resin composition from the nozzle of an FDM printer and maintaining interlayer adhesion strength of the molded object.

[0082] If necessary, the thermoplastic resin composition of the present invention may further contain additives that are commonly used in synthetic resins, such as crosslinking agents, antistatic agents, antifogging agents, anti-plate-out agents, surface treatment agents, plasticizers, lubricants, reinforcing agents, flame retardants, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, release agents, pigments, silicone oils, and silane coupling agents, as optional components, within the range that does not impair the effects of the present invention.

[0083] The thermoplastic resin composition of the present invention can be obtained by mixing component (A) and component (B). If necessary, the above-mentioned optional additives may be mixed. The optional additives may be mixed in advance with component (A) or component (B), may be mixed when component (A) and component (B) are mixed, or may be mixed into a mixture of component (A) and component (B).

[0084] The method for mixing the above components is not particularly limited, and known methods can be applied. Examples include a method of mixing using a mixer such as a tumbler mixer, Henschel mixer, ribbon blender, V-type mixer, W-type mixer, Supermixer, or Nauta mixer, a method of melt-kneading using an extruder, or a method of mixing together with a solvent and solution-casting. When component (B) is a liquid at room temperature, from the viewpoint of handleability, it is preferable to integrate component (A) and component (B) by a method such as melt-kneading using an extruder, and mix them so as to form a resin composition that is solid at room temperature.

[0085] The shape of the thermoplastic resin composition of the present invention is not particularly limited, and may be in the form of threads, pellets, powder, granules, or flakes, and from the viewpoint of handleability, threads, pellets, or granules are preferred.

[0086] The thermoplastic resin composition of the present invention is preferably in the form of a thread. Being in the form of a thread makes it suitable for use as a filament material for commercially available FDM-based three-dimensional modeling devices. When the thermoplastic resin composition of the present invention is in the form of a thread, the length thereof is preferably 10 cm or more, and more preferably 200 cm or more.

[0087] When the thermoplastic resin composition of the present invention is in the form of a filament, its average diameter is preferably 1.55 to 1.95 mm, and more preferably 1.65 to 1.85 mm. Having an average diameter within the above range makes it suitable for use as a filament material for commercially available FDM-based three-dimensional modeling devices. Examples of methods for measuring the average diameter include physical measurement using digital calipers.

[0088] For example, when measuring the average diameter using a digital caliper, the diameter is measured at 20 or more different locations along the longitudinal direction of the filament material, and the average value is calculated. The measurement locations are preferably at least 100 mm apart along the longitudinal direction of the filament-shaped resin composition. Furthermore, when the filament-shaped resin composition is in the form of a filament, the cross-sectional shape may be a circle, an ellipse, or the like. When the cross-sectional shape is not a circle, the diameter refers to the length of the longest line segment that crosses the cross section.

[0089] The method for producing the filamentous thermoplastic resin composition is not particularly limited, and known methods can be applied. For example, the thermoplastic resin composition of the present invention may be extruded using an extruder, cooled with water or air, and then wound up using a winder. The filamentous resin composition of the present invention may be stretched or unstretched.

[0090] Methods for adjusting the average diameter of the filamentous thermoplastic resin composition include appropriately selecting the feed rate of the resin material to the extruder, the screw rotation speed of the extruder, the diameter of the extruder die hole, the winding speed of the winder, etc.

[0091] The filamentous thermoplastic resin composition can be obtained by molding a resin material obtained by mixing components (A) and (B) into a filamentous form using a known method. The resin material may contain any of the additives described above, if necessary. The additives may be premixed with the thermoplastic resin (A), may be mixed when mixing components (A) and (B), or may be mixed into a mixture of components (A) and (B). The composition of the resin material is the same as that of the thermoplastic resin composition described above, and all of the descriptions of the composition of the thermoplastic resin composition of the present invention described above can also be applied to a resin material obtained by mixing components (A) and (B).

[0092] The shaped object of the present invention can be produced by a three-dimensional modeling device using the thermoplastic resin composition of the present invention as a filament material. Examples of the modeling device include FDM three-dimensional modeling devices (3D printers), and commercially available devices can be used. When producing the shaped object of the present invention by FDM, the nozzle temperature of the modeling device is preferably 300°C or lower. In the present invention, by using a specific condensed phosphate ester compound, three-dimensional modeling by FDM is possible with a wide range of thermoplastic resins (e.g., general-purpose plastics and engineering plastics) even at this relatively low temperature range. The present invention, which allows three-dimensional modeling even at such a relatively low temperature range and can produce shaped objects with excellent flame retardancy, has excellent industrial applicability.

[0093] The shaped object of the present invention has excellent flame retardancy, interlayer adhesion, and additive manufacturing stability, and can therefore be suitably used in a wide range of applications, including electrical, electronic, and communications, agriculture, forestry, and fisheries, mining, construction, food, textiles, clothing, medicine, coal, petroleum, rubber, leather, automobiles, railways, aviation, precision instruments, wood, building materials, civil engineering, furniture, printing, and musical instruments. More specifically, they are used in office automation equipment such as printers, personal computers, word processors, keyboards, PDAs (personal digital assistants), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic organizers, cards, holders, and stationery; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game consoles, irons, and kotatsu tables; audio-visual equipment such as TVs, VTRs, video cameras, radio cassette players, tape recorders, minidiscs, CD players, speakers, and liquid crystal displays; electrical and electronic components and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, and clocks.

[0094] Furthermore, the shaped object of the present invention can be used for a variety of applications, including seats (padding, outer fabric, etc.), belts, ceiling coverings, convertible tops, armrests, door trim, rear package trays, carpets, mats, sun visors, wheel covers, mattress covers, airbags, insulating materials, hand straps, hand straps, wire covering materials, electrical insulating materials, paints, coating materials, upholstery materials, flooring materials, bulkheads, carpets, wallpaper, wall coverings, exterior materials, interior materials, roofing materials, decking materials, wall materials, pillar materials, flooring boards, fence materials, frames and moldings, window and door profiles, shingles, paneling, terraces, balconies, soundproofing boards, heat insulating boards, and window materials for automobiles, rolling stock, railway vehicles, ships, aircraft, buildings, houses, and construction materials; civil engineering materials; clothing; curtains, sheets, plywood, synthetic fiberboards, carpets, entrance mats, sheets, buckets, hoses, containers, eyeglasses, bags, cases, goggles, skis, rackets, tents, musical instruments, and other daily necessities and sporting goods.

[0095] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

[0096] [Examples 1-12, Comparative Examples 1-9] <Method for Producing Thermoplastic Resin Composition> After blending the thermoplastic resin compositions listed in Table 1, the blends were melt-kneaded using a single-screw extruder (D3038, manufactured by Toyo Seiki Seisakusho) at an extrusion temperature of 250°C and a screw rotation speed of 25 rpm to produce a filament-like thermoplastic resin composition (hereinafter also referred to as filament). The filament extruded from the extruder was cooled with water and wound to an average diameter of 1.65-1.85 mm using a filament winder (manufactured by Nippon Placon Co., Ltd.) equipped with a length measuring device (manufactured by Filameasure, manufactured by Filabot). The average diameter of the filament-like thermoplastic resin composition was measured using a digital caliper using the method described above. The filament was wound around a filament reel and then dried under reduced pressure at 80°C. Note that all blending amounts shown in Tables 1 and 2 are based on parts by mass.

[0097] <Method of Preparing Test Pieces for Evaluation> The reel wound with the filament obtained above was attached to a 3D printer (H+1 manufactured by Afinia 3D) and modeled using the FDM method under the following conditions to obtain test pieces of 125 mm x 13 mm x 1.6 mm and 80 mm x 10 mm x 4 mm. Nozzle temperature: 280°C Stage temperature: 90°C Layer pitch: 0.2 mm Filling rate: 99% or more (solid) Raster orientation: 0° / 90° Layer direction: X-Y (Flat)

[0098] <Evaluation of interlayer adhesion> Interlayer adhesion was evaluated based on the degree of adhesion between the resin extruded from the nozzle and the previous layer surface during additive manufacturing. The evaluation results were expressed in the following two stages: A: The resin extruded from the nozzle and the previous layer surface adhered well, and the desired shape could be molded without any problems. B: The resin extruded from the nozzle and the previous layer surface adhered poorly, and peeled off during molding, making it impossible to mold the desired shape.

[0099] <Evaluation of additive manufacturing stability> Additive manufacturing stability was evaluated based on the stability of the resin extrusion behavior from the nozzle during modeling. The evaluation results are expressed in the following three levels: A: The resin extrusion speed is constant, there is no variation in the resin thickness during layering, and it is stable. B: The resin extrusion speed is somewhat unstable, and there is some variation in the resin thickness during layering, but the desired shape can be obtained. C: The resin extrusion speed is unstable, and there is large variation in the resin thickness during layering. Layering is not completed in some parts, and the desired shape cannot be obtained.

[0100] <Flame Retardancy Evaluation 1: Extinguishing Time After Flame Contact> The resulting 125 mm x 13 mm x 1.6 mm test specimens were placed in a thermo-hygrostat at 23°C and 50% RH for two days, then held vertically. A burner flame was applied to the bottom of the specimen for 10 seconds, after which the flame was removed and the time (unit: seconds) for the flame to extinguish on the test specimen was measured. The shorter this time, the higher the flame retardancy. The results are shown in Tables 1 and 2.

[0101] <Flame Retardancy Evaluation 2: Oxygen Index> The resulting 80 mm x 10 mm x 4 mm test specimens were placed in a thermo-hygrostat chamber at 23°C and 50% RH for two days, and then the oxygen index of the test specimens was measured in accordance with JIS K7201-2. The oxygen index is the minimum oxygen concentration at which a small, vertical test specimen can sustain combustion in a nitrogen and oxygen gas mixture; the higher this value, the more difficult it is to burn. The results are shown in Tables 1 and 2.

[0102] <Method for measuring melting point> The melting point was measured using a differential thermal thermogravimetry analyzer (TG-DTA8122 manufactured by Rigaku Corporation). 10±0.5 mg of a sample was weighed out and placed in an aluminum pan. The sample was heated from 25°C to 450°C at a rate of 10°C / min in an air atmosphere, and the peak top of the melting peak was taken as the melting point.

[0103] Details of each component in Tables 1 and 2 are as follows: (A) Component A-1: ​​Polycarbonate resin (Iupilon S-3000F, manufactured by Mitsubishi Engineering Plastics) (A) Component A-2: ABS resin (acrylonitrile-butadiene-styrene copolymer, AT-05, manufactured by Nippon A&L) (B) Component B-1: Compound represented by the following formula (a mixture of compounds in which r1 is 1 to 7, liquid at room temperature (viscosity of 28,000 mPa·s at 25°C))

[0104]

[0105] Component (B) B-2: Compound represented by the following formula (a mixture of compounds in which r2 is 1 to 7, liquid at room temperature (viscosity at 25°C: 19,000 mPa·s))

[0106]

[0107] (B) Component B-3: Compound represented by the following formula (solid at room temperature, melting point 95°C)

[0108]

[0109] Comparative component of (B) BX-1: Compound represented by the following formula (solid at room temperature, melting point 185°C)

[0110]

[0111] Comparative component of (B) BX-2: Triphenyl phosphate

[0112]

[0113] (C) Component C-1: Polytetrafluoroethylene (Polyflon MPAFA-500H manufactured by Daikin Industries, Ltd.)

[0114]

[0115]

[0116] As shown in Tables 1 and 2, the compositions of the present invention (Examples 1 to 12) were confirmed to have good interlayer adhesion, additive manufacturing stability, and flame retardancy. On the other hand, compositions in which the blending amount of component (B) was outside the range of the present invention (Comparative Examples 1, 2, and 7) showed poor interlayer adhesion, additive manufacturing stability, and flame retardancy. Furthermore, compositions using condensed phosphate ester compounds that are solid at room temperature and have melting points outside the range of the present invention (Comparative Examples 3, 4, and 8) showed poor interlayer adhesion and inferior additive manufacturing stability compared to the corresponding Examples 1, 3, 11, and 12. Furthermore, compositions using phosphate ester compounds with structures different from the component (B) of the present invention (Comparative Examples 5, 6, and 9) showed poor interlayer adhesion and additive manufacturing stability.

Claims

1. (A) a thermoplastic resin, and (B) a condensed phosphate ester compound, wherein the thermoplastic resin composition contains: the (B) condensed phosphate ester compound is represented by the following general formula (1) and has a melting point of 150°C or lower or is a liquid at room temperature, and the blending amount of the (B) condensed phosphate ester compound is 1 to 35 parts by mass with respect to a total of 100 parts by mass of the (A) thermoplastic resin and the (B) condensed phosphate ester compound.

2. A thermoplastic resin composition for hot melt additive manufacturing (provided that the resin composition is represented by the general formula (1) and R １１ , R １２ , R １３ , R １４ and R １５ are the same and when the composition contains a plurality of compounds with different r values, the melting point of 150 °C or lower or being liquid at room temperature includes that the mixture of the plurality of compounds has a melting point of 150 °C or lower or is liquid at room temperature.). 【Chemical 1】 In the general formula (1), R １１ , R １２ , R １３ and R １４ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group represented by the following general formula (2), and R １５ represents a divalent aromatic hydrocarbon group represented by the following general formula (3) or (4), and r is a number from 1 to 30. [Chemical 2] In the general formula (2), R ２１ and R ２２ each independently represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms, and * represents a bond. 【Chemical Formula 3】 In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ , and R ４４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitro group, a halogen atom, or a cyano group, X represents a direct bond, a divalent sulfur atom, a sulfonyl group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms, and * represents a bond. The thermoplastic resin composition according to claim 1, further containing (C) one or more fluorine-containing polymers in an amount of 0.03 to 5 parts by mass with respect to 100 parts by mass of the (A) thermoplastic resin.

3. The thermoplastic resin composition according to claim 1, having a filamentous shape.

4. The thermoplastic resin composition according to claim 3, having a filamentous shape with an average diameter of 1.55 to 1.95 mm.

5. The thermoplastic resin composition according to claim 1, wherein the (A) thermoplastic resin contains one or more condensation polymer compounds.

6. The thermoplastic resin composition according to claim 5, wherein the (A) thermoplastic resin contains a polycarbonate resin as a condensation polymer compound.

7. A method for manufacturing a shaped body by a three-dimensional shaping apparatus using the thermoplastic resin composition according to any one of claims 1 to 6.

8. The method according to claim 7, wherein the nozzle temperature of the three-dimensional shaping apparatus is 300°C or lower.

9. A shaped body obtained by the method according to claim 7.

10. Use of a resin material for manufacturing a filament material for hot melt deposition modeling, wherein the resin material contains:

11. A flame retardant used in a thermoplastic resin composition for hot melt deposition modeling containing (A) a thermoplastic resin, containing (B) a condensed phosphate ester compound, wherein the (B) condensed phosphate ester compound is represented by the following general formula (1) and has a melting point of 150°C or lower or is a liquid at room temperature. ​ ​ (B) The compounding amount of the condensed phosphate ester compound is 1 to 35 parts by mass with respect to 100 parts by mass in total of (A) the thermoplastic resin and (B) the condensed phosphate ester compound (however, the resin material is represented by the general formula (1), and R １１ , R １２ , R １３ , R １４ and R １５ are the same and r is different, and when it contains a plurality of compounds, the melting point of 150 ° C or lower, or being a liquid at room temperature, includes that the mixture of the plurality of compounds has a melting point of 150 ° C or lower, or is a liquid at room temperature.). 【Chemical Formula 4】 In the general formula (1), R １１ , R １２ , R １３ and R １４ may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group represented by the following general formula (2), and R １５ represents a divalent aromatic hydrocarbon group represented by the following general formula (3) or (4), and r is a number from 1 to 30. 【Chemical Formula 5】 In general formula (2), R ２１ and R ２２ each independently represents a hydrogen atom, a hydroxy group, or an alkyl group having 1 to 10 carbon atoms, and * represents a bond. 【Chemical Formula 6】 In general formulas (3) and (4), R ３１ , R ３２ , R ４１ , R ４２ , R ４３ , and R ４４ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitro group, a halogen atom, or a cyano group; X represents a direct bond, a divalent sulfur atom, a sulfonyl group, an alkylidene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms; and * represents a bond. ​ ​ ​ For adding in such a range that the blending amount of the (B) condensed phosphate ester compound in the thermoplastic resin composition is 1 to 35 parts by mass with respect to 100 parts by mass in total of the (A) thermoplastic resin and the (B) condensed phosphate ester compound, a flame retardant (however, when the (B) condensed phosphate ester compound is represented by the general formula (1) and is a plurality of compounds in which R11, R12, R13, R14 and R15 are the same and r is different, whether the melting point is 150°C or lower or it is a liquid at normal temperature includes whether the mixture of the plurality of compounds has a melting point of 150°C or lower or is a liquid at normal temperature). 【Chemical Formula 7】 In the general formula (1), R11, R12, R13 and R14 may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group represented by the following general formula (2), R15 represents a divalent aromatic hydrocarbon group represented by the following general formula (3) or (4), and r is a number from 1 to 30. 【Chemical 8】 In the general formula (2), R21 and R22 each independently represent a hydrogen atom, a hydroxy group or an alkyl group having 1 to 10 carbon atoms, and * represents a bond. 【Chemical Formula 9】 In the general formulas (3) and (4), R31, R32, R41, R42, R43 and R44 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a nitro group, a halogen atom or a cyano group, X represents a direct bond, a divalent sulfur atom, a sulfonyl group, an alkylidene group having 1 to 5 carbon atoms or an alkylene group having 1 to 5 carbon atoms, and * represents a bond.

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