Thermoplastic resin composition, method for producing shaped body, shaped body and use of resin material

Abstract

A thermoplastic resin composition for fused deposition modeling, which contains 100 parts by mass of (A) a thermoplastic resin, 0.01 to 5 parts by mass of (B) a primary antioxidant and 0.01 to 1.4 parts by mass of (C) a secondary antioxidant, wherein: the component (A) is composed of a fused thermoplastic resin; the component (B) is composed of a phenolic antioxidant that has one or more structures represented by formula (1); and the component (C) is composed of one or more antioxidants that are selected from among phosphorus antioxidants represented by formulae (2) to (4) and thioether antioxidants represented by formulae (5) and (6). (See the description for details of formulae (2) to (6).)　In formula (1), each of R11 and R12 independently represents a hydrogen atom or a methyl group; and * represents a bonding hand.

Description

Thermoplastic resin composition, method for manufacturing shaped body, use of shaped body and resin material

[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 the use of a resin material in the production of 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, ABS and polylactic acid have been the main thermoplastic resins used as materials for the FDM method, but condensation thermoplastic resins such as polyamide, polycarbonate, and polyester have been attracting attention in order to improve processability and mechanical strength.

[0004] Thermoplastic resins are known to be subject to degradation due to heat and oxygen during processing and use, resulting in problems such as reduced mechanical properties and discoloration. In particular, additive manufacturing using FDM, unlike injection molding and extrusion molding, does not involve a screw-based kneading and plasticization process. Therefore, a higher amount of heat is required to impart fluidity to the material and achieve efficient molding. Furthermore, when molding crystalline resins, the molding furnace must be heated to suppress shrinkage during molding. However, this heat accelerates material degradation and worsens the color tone of the final molded product. To address this issue, the incorporation of antioxidants has been proposed. Patent Document 1 describes an example of incorporating antioxidants into resin materials for additive manufacturing technology, such as a resin powder for 3D modeling containing one or more antioxidants.

[0005] US2018 / 355144A1

[0006] However, the invention described in Patent Document 1 relates to a selective laser sintering (SLS) method in which a powdered material is sintered by irradiating it with a laser, and does not describe the application of the resin powder to the FDM method. Furthermore, as a result of the inventor's investigations, it was found that there is room for improvement in terms of color stability and long-term thermal stability of objects manufactured by the FDM method using the technology described in Patent Document 1.

[0007] As a result of further investigation, the present inventors have found that a thermoplastic resin composition obtained by using a primary antioxidant and a secondary antioxidant each having a specific structure in its molecule in combination is a resin material that exhibits excellent color stability and long-term thermal stability in objects manufactured by the FDM method, and have thus completed the present invention.

[0008] According to the present invention, there is provided a thermoplastic resin composition for fused deposition modeling, which contains an (A) thermoplastic resin and, relative to 100 parts by mass of the (A) thermoplastic resin, 0.01 to 5 parts by mass of a (B) primary antioxidant and 0.01 to 1.4 parts by mass of a (C) secondary antioxidant, wherein the (A) thermoplastic resin is a condensation thermoplastic resin, the (B) primary antioxidant is a phenolic antioxidant having one or more structures represented by the following formula (1), and the (C) component is one or more selected from phosphorus-based antioxidants represented by any of the following formulas (2), (3), and (4), and thioether-based antioxidants represented by any of the following formulas (5) and (6).

[0009] In formula (1), R １１ and R １２ each independently represents a hydrogen atom or a methyl group, and * represents a bond.

[0010] In formula (2), R ２１ and R ２２ each independently represents an alkyl group having 1 to 8 carbon atoms.

[0011] In formula (3), R ３１ and R ３２each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0012] In formula (4), R ４１ , R ４２ and R ４３ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４４ represents an alkyl group having 1 to 18 carbon atoms.

[0013] In formula (5), R ５１ and R ５２ each independently represents an alkyl group having 8 to 22 carbon atoms.

[0014] In formula (6), R ６１ ~R ６４ each independently represents an alkyl group having 8 to 22 carbon atoms.

[0015] The thermoplastic resin composition of the present invention preferably has a continuous filamentous shape.

[0016] The thermoplastic resin composition of the present invention preferably has a continuous filamentous shape with an average diameter of 1.55 to 1.95 mm.

[0017] In the thermoplastic resin composition of the present invention, the thermoplastic resin (A) is preferably a polyamide resin.

[0018] In the thermoplastic resin composition of the present invention, the thermoplastic resin (A) is preferably at least one selected from polyamide 6, polyamide 66, polyamide 11, and polyamide 12.

[0019] In the thermoplastic resin composition of the present invention, the component (B) is preferably a phenolic antioxidant having one or more structures represented by the following formula (7).

[0020] In the thermoplastic resin composition of the present invention, the component (B) is preferably a phenolic antioxidant having one or more structures represented by the following formula (8):

[0021] In formula (8), * represents a bond.

[0022] According to the present invention, in formula (3), R ３１ and R ３２ Preferably, each independently represents an alkyl group having 1 to 40 carbon atoms.

[0023] The present invention also provides a method for producing a shaped object by fused deposition modeling using the above-mentioned thermoplastic resin composition.

[0024] The present invention also provides a shaped body obtained by the above method.

[0025] The present invention also provides use of a resin material in the production of a filament material for fused deposition modeling, the resin material comprising: (A) a thermoplastic resin; (B) 0.01 to 5 parts by mass of a primary antioxidant per 100 parts by mass of the thermoplastic resin; and (C) 0.01 to 1.4 parts by mass of a secondary antioxidant per 100 parts by mass of the thermoplastic resin; the (A) thermoplastic resin is a condensation thermoplastic resin; the (B) primary antioxidant is a phenolic antioxidant having one or more structures represented by formula (1) above; and the (C) secondary antioxidant is one or more selected from phosphorus-based antioxidants represented by any of formulas (2), (3), and (4) above and thioether-based antioxidants represented by any of formulas (5) and (6) below.

[0026] According to the present invention, it is possible to provide a thermoplastic resin composition for fused deposition modeling that has excellent color stability and long-term thermal stability, and a method for producing a shaped object by fused deposition modeling using the thermoplastic resin composition.

[0027] Hereinafter, embodiments of the present invention will be described in detail.

[0028] The thermoplastic resin composition of the present invention is a thermoplastic resin composition for fused deposition modeling, containing (A) a thermoplastic resin (hereinafter sometimes referred to as "component (A)"), (B) a primary antioxidant (hereinafter sometimes referred to as "component (B)"), and (C) a secondary antioxidant (hereinafter sometimes referred to as "component (C)"). In this specification, fused deposition modeling refers to three-dimensional modeling using a fused deposition modeling method. The fused deposition modeling method is a modeling method for three-dimensional modeling, in which a 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 layer by layer while cooling and solidifying to form a three-dimensional object.

[0029] The thermoplastic resin (A) is a condensation thermoplastic resin. The condensation thermoplastic resin is a thermoplastic resin obtained by condensation polymerization. The condensation thermoplastic resin has high strength and is resistant to shrinkage, making it suitable as a thermoplastic resin for use in fused deposition modeling.

[0030] 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.

[0031] Examples of the polyester resin 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).

[0032] 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.

[0033] 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.

[0034] 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; dihydroxyaryl ketones 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 preferred examples of the carbonate precursor include phosgene, carbonic acid diester, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. These condensation thermoplastic resins 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, etc.

[0036] Among these condensation thermoplastic resins, polyamides are preferred from the viewpoints of versatility, color stability, and long-term thermal stability. Among them, aliphatic polyamides are more preferred from the viewpoints of their relatively low melting point and ease of fused deposition modeling at low temperatures, with at least one selected from polyamide 6, polyamide 66, polyamide 11, and polyamide 12 being even more preferred, and at least one selected from polyamide 11 and polyamide 12 being particularly preferred. In the present invention, when an aliphatic polyamide is used, other resins may be used, but it is preferable to use such that the mass proportion of the aliphatic polyamide in the thermoplastic resin is 50 mass% or more (or more than 50 mass%). In the present invention, for example, regardless of whether the thermoplastic resin composition contains a polyhydric alcohol, it is preferable to contain more than 100 parts by mass of aliphatic polyamide per 100 parts by mass of the total of the polyhydric alcohol and the semi-aromatic polyamide.

[0037] In terms of suitability for the applications of the present invention, the proportion of the thermoplastic resin in the thermoplastic resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, and may be 70% by mass or more. There is no particular upper limit, and it may be any upper limit necessary to contain the components (B) and (C), but it is preferably set to, for example, 99.9% by mass or less.

[0038] The following describes the (B) primary antioxidant and the (C) secondary antioxidant. Generally, primary antioxidants trap radicals and prevent autoxidation. Generally, secondary antioxidants decompose hydroperoxides into harmless compounds. In the present invention, component (C) does not have a structure represented by formula (1). In the following description, the number of carbon atoms in a group refers to the number of carbon atoms in the group after substitution when a hydrogen atom in the group is substituted with a substituent. For example, when a hydrogen atom in the alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms (1 to 20) refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted. In the following description, when a methylene group in a specific group may be replaced with a divalent group other than a methylene group, the divalent groups replacing the methylene groups are not adjacent to each other, regardless of whether they are identical or not.

[0039] (B) The primary antioxidant is a phenolic antioxidant having one or more structures represented by the following formula (1):

[0040] In formula (1), R １１ and R １２ each independently represents a hydrogen atom or a methyl group, and * represents a bond.

[0041] As the structure represented by the above formula (1), R １１ and R １２ Preferably, at least one of R １１ and R １２ It is particularly preferred that at least one of these is a methyl group and the other is a hydrogen atom.

[0042] Examples of the structure of the phenolic antioxidant having the structure represented by the above formula (1) include those represented by the following formula (A-1).

[0043] (In the formula, R １１ and R １２ is the same as in formula (1), m represents an integer of 1 to 10, and X １represents an m-valent bonding group.

[0044] The component (B) of the present invention preferably has 1 to 10 groups represented by formula (1) per molecule, and from the perspective of ease of synthesis, this is preferably an integer of 1 to 6, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 4. Similarly, the above m is an integer of 1 to 10, but from the perspective of ease of synthesis, it is preferably an integer of 1 to 6, of which an integer of 1 to 5 is more preferred, and particularly preferably an integer of 1 to 4.

[0045] The compound represented by the above formula (A-1) is X １ The m specific groups may be the same or different from one another.

[0046] Above X １ represents a linking group having a valence of m. １ Specific examples of the alkyl group include a direct bond, a hydrogen atom, a nitrogen atom, a sulfur atom, a carbon atom, an oxygen atom, a phosphorus atom, a group represented by the following formula (II-a), >C═O, and >NR ５３ , -OR ５３ , -SR ５３ , -NR ５３ R ５４ or represents a hydrocarbon group having 1 to 120 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms, each having the same valence as m. ５３ and R ５４ represents a hydrogen atom, a hydrocarbon group having 1 to 35 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms, and a methylene group in each of the hydrocarbon groups and heterocyclic ring-containing groups is -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８or a combination thereof, and the aromatic ring or heterocyclic ring may be fused with another ring. ５８ represents a hydrogen atom, a hydrocarbon group having 1 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. １ is a carbon atom, m is 4, and X １ is a nitrogen atom, a phosphorus atom, or a bonding group represented by the following (II-a), m is 3, and X １ is a direct bond, an oxygen atom, a sulfur atom, >C═O, —NH—CO—, —CO—NH— or >NR ５３ In the case of １ is a hydrogen atom, -OR ５３ , -SR ５３ or -NR ５３ R ５４ In the case of １ may form a ring together with a benzene ring.

[0047]

[0048] (* means that the * portion bonds to the adjacent group.)

[0049] The above bonding group X １Examples of the hydrocarbon group having 1 to 120 carbon atoms and a valence equal to m, represented by the formula (1), include an aliphatic hydrocarbon group having 1 to 120 carbon atoms and an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and a valence equal to m, where m is monovalent, include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an amyl group, an isoamyl group, a tert-amyl group, a cyclopentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a bicyclohexyl group, a 1-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, an ... Examples thereof include alkyl vinyl groups such as octyl, 2-ethylhexyl, nonyl, isononyl, and decyl groups; alkenyl groups such as 1-methylethenyl, 2-methylethenyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, eicosenyl, and tricosenyl groups; and groups in which these groups are substituted with substituents described below. Furthermore, examples of the aliphatic hydrocarbon group in which a methylene group has been replaced with -O- include alkoxy groups such as a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a sec-butyloxy group, a tert-butyloxy group, an isobutyloxy group, an amyloxy group, an isoamyloxy group, a tert-amyloxy group, a hexyloxy group, a cyclohexyloxy group, a heptyloxy group, an isoheptyloxy group, a tert-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a tert-octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, and a decyloxy group.

[0050] The above bonding group X １Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and a valence equal to m, where m is divalent, include those obtained by deleting one hydrogen atom from the monovalent aliphatic hydrocarbon groups exemplified above for 1 to 120 carbon atoms, such as alkylene groups such as methylene, ethylene, propylene, butylene, and butyldiyl; alkylene groups in which the methylene chain is replaced with -O-, -CO-O-, or -O-CO-; residues of diol groups such as ethanediol, propanediol, butanediol, pentanediol, and hexanediol; and groups in which these groups are substituted with the substituents described below.

[0051] The above bonding group X １ The aliphatic hydrocarbon group having 1 to 120 carbon atoms and a valence equal to m, where m is trivalent, includes those obtained by removing two hydrogen atoms from the monovalent aliphatic hydrocarbon groups having 1 to 120 carbon atoms listed above, such as alkylidine groups such as propylidine and 1,1,3-butylidinepropylidine; and groups in which these groups are substituted with the substituents described below. １ Examples of the aliphatic hydrocarbon group having 1 to 120 carbon atoms and a valence equal to m, where m is tetravalent, include groups in which three hydrogen atoms have been deleted from the monovalent aliphatic hydrocarbon groups exemplified above having 1 to 120 carbon atoms; and groups in which these groups are substituted with the substituents described below.

[0052] The above bonding group X １ Examples of aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and a valence equal to m, where m is monovalent, include arylalkyl groups such as benzyl, phenethyl, diphenylmethyl, triphenylmethyl, styryl, and cinnamyl; aryl groups such as phenyl, methylphenyl, ethylphenyl, and naphthyl; aryloxy groups such as phenoxy, methylphenoxy, and naphthyloxy; and groups in which these groups are substituted with the substituents described below.

[0053] The above bonding group X １Examples of aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and a valence equal to m, where m is divalent, include those obtained by removing one hydrogen atom from the monovalent aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms listed above. Examples include arylene groups such as a phenylene group, a naphthylene group, and a methylphenylene group; residues of bifunctional phenol groups such as a catechol group and a bisphenol group; and groups in which these groups are substituted with the substituents described below.

[0054] The above bonding group X １ The aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and a valence equal to m, represented by the formula (I), where m is trivalent, includes those obtained by removing two hydrogen atoms from the monovalent aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms listed above, such as a phenyl-1,3,5-trimethylene group and groups obtained by substituting this group with a substituent described below. １ Examples of aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms and a valence equal to m, where m is tetravalent, include groups in which three hydrogen atoms have been deleted from the monovalent aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms listed above; and groups in which these groups are substituted with the substituents described below.

[0055] The above bonding group X １The heterocycle-containing group having 2 to 35 carbon atoms and a valence equal to m, represented by the formula (I), where m is monovalent, includes a pyridyl group, a pyrimidyl group, a pyridazyl group, a piperidyl group, a pyranyl group, a pyrazolyl group, a triazyl group, a pyrrolyl group, a quinolyl group, an isoquinolyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a furyl group, a furanyl group, a benzofuranyl group, a thienyl group, a thiophenyl group, a benzothiophenyl group, a thiadiazolyl group, a thiazolyl group, a benzothiazolyl group, an oxazolyl group, Examples of heterocyclic groups include heterocyclic groups such as benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, 2-pyrrolidinon-1-yl, 2-piperidon-1-yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidin-3-yl, benzotriazolyl, and 2,4,8,10-tetraoxaspiro[5,5]undecane, as well as groups in which these heterocyclic groups are bonded to hydrocarbon groups, and groups in which these groups are substituted with the substituents described below. Examples of the hydrocarbon group in the group in which a heterocyclic group is bonded to a hydrocarbon group include the above-mentioned hydrocarbon groups having 1 to 120 carbon atoms, which satisfy the specified number of carbon atoms. In the group in which a heterocyclic group is bonded to a hydrocarbon group, the bond may be present on either the heterocyclic group or the hydrocarbon group.

[0056] The above bonding group X １ Examples of heterocycle-containing groups having 2 to 35 carbon atoms and a valence equal to m, where m is divalent, include those obtained by removing one hydrogen atom from the monovalent heterocycle-containing groups exemplified above having 2 to 35 carbon atoms, such as divalent groups having a pyridine ring, pyrimidine ring, piperidine ring, piperazine ring, triazine ring, furan ring, thiophene ring, indole ring, 2,4,8,10-tetraoxaspiro[5,5]undecane ring, etc., and groups in which these groups are substituted with a substituent described below.

[0057] R ５３ , R ５４ and R ５８ Among the hydrocarbon groups having 1 to 35 carbon atoms used in X, the aliphatic hydrocarbon groups include the above-mentioned １Among the groups listed as the aliphatic hydrocarbon groups having 1 to 120 carbon atoms used in R or groups in which such aliphatic hydrocarbon groups are substituted with the substituents described below, those having 1 to 35 carbon atoms can be mentioned, and those having 1 to 20 carbon atoms are preferred. ５３ , R ５４ and R ５８ Among the hydrocarbon groups having 6 to 35 carbon atoms used in X, the aromatic ring-containing hydrocarbon group is １ Examples of aromatic ring-containing hydrocarbon groups having 6 to 35 carbon atoms include those mentioned above as examples of aromatic ring-containing hydrocarbon groups used in R 1 or groups in which such aromatic ring-containing hydrocarbon groups are substituted with the substituents described below, and those having 6 to 20 carbon atoms are preferred. ５３ , R ５４ and R ５８ The heterocyclic group having 2 to 35 carbon atoms represented by the formula (I) is １ Examples of the heterocyclic ring-containing group having 2 to 35 carbon atoms and represented by the formula (I) include the groups listed above and groups in which these groups are substituted with the substituents described below, and those having 2 to 30 carbon atoms are preferred.

[0058] Each functional group, such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocycle-containing group, having the same valence as m described above may have a substituent, and the compound having a group represented by formula (1), which is component (B), includes both unsubstituted and substituted compounds, unless otherwise specified.

[0059] Examples of the substituent include ethylenically unsaturated groups such as vinyl, allyl, acrylic, and methacrylic groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; acetyl, 2-chloroacetyl, propionyl, octanoyl, acryloyl, methacryloyl, phenylcarbonyl (benzoyl), phthaloyl, 4-trifluoromethylbenzoyl, pivaloyl, salicyloyl, oxaloyl, stearoyl, methoxycarbonyl, ethoxycarbonyl, and t-butoxy groups. Acyl groups such as a carbonyl group, an n-octadecyloxycarbonyl group, and a carbamoyl group; acyloxy groups such as an acetyloxy group and a benzoyloxy group; amino group, ethylamino group, dimethylamino group, diethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, chlorophenylamino group, toluidino group, anisidino group, N-methyl-anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, methoxycarbonyl group, carbonylamino group, phenoxycarbonylamino group, acetylamino group, benzoylamino group, formylamino group, pivaloylamino group, lauroylamino group, carbamoylamino group, N,N-dimethylaminocarbonylamino group, N,N-diethylaminocarbonylamino group, morpholinocarbonylamino group, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino group, N-methyl-methoxycarbonylamino group Examples of the amino group include substituted amino groups such as a phenyl group, a phenoxycarbonylamino group, a sulfamoylamino group, an N,N-dimethylaminosulfonylamino group, a methylsulfonylamino group, a butylsulfonylamino group, and a phenylsulfonylamino group; a sulfonamide group, a sulfonyl group, a carboxyl group, a cyano group, a sulfo group, a hydroxyl group, a nitro group, a mercapto group, an imido group, a carbamoyl group, a sulfonamide group, a phosphonic acid group, a phosphoric acid group, and salts of a carboxyl group, a sulfo group, a phosphonic acid group, or a phosphoric acid group.

[0060] Above X １ When m is 1 to 4, a group represented by the following formula (1A) can be suitably used.

[0061]

[0062] (In the above formula (1A), m represents a number from 1 to 4, and Y １ represents a direct bond, a hydrogen atom, a nitrogen atom, a sulfur atom, a carbon atom, an oxygen atom, a phosphorus atom, a group represented by (II-a) above, >C═O, >NR ５３ , -OR ５３ , -SR ５３ , -NR ５３ R ５４ or a hydrocarbon group having 1 to 35 carbon atoms or a heterocyclic ring-containing group having 2 to 35 carbon atoms, and a methylene group in the hydrocarbon group having 1 to 35 carbon atoms and the heterocyclic ring-containing group having 2 to 35 carbon atoms is -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８ or a combination thereof, １ is a direct bond, -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８ , a hydrocarbon group having 1 to 20 carbon atoms, or a bonding group of a combination thereof; ５３ , R ５４ , R ５８ represents a hydrogen atom, a hydrocarbon group having 1 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms; Z １ When a plurality of R ５３ , R５４ , R ５８ When a plurality of Y are present, they may be the same or different, １ is a carbon atom, m is 4, and Y １ is a nitrogen atom, a phosphorus atom, or a bonding group represented by (II-a) above, m is 3, and Y １ is a direct bond, an oxygen atom, a sulfur atom, >C═O, —NH—CO—, —CO—NH— or >NR ５３ In the case of １ is a hydrogen atom, -OR ５３ , -SR ５３ or -NR ５３ R ５４ In the case of (I), m is 1, and * means that the * portion bonds to the adjacent group.)

[0063] Y in the group represented by the above formula (1A) １ Among the hydrocarbon groups having 1 to 35 carbon atoms represented by the formula (I), examples of the aliphatic hydrocarbon group include the same as those listed above as the aliphatic hydrocarbon groups having 1 to 120 carbon atoms and having the same valence as m, and those having the specified number of carbon atoms, with 1 to 20 carbon atoms being preferred. The methylene group in these groups is -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８ Or, it may be substituted with a bonding group that is a combination of these.

[0064] Y in the group represented by the above formula (1A) １Among the divalent hydrocarbon groups represented by the formula (I), examples of the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms include the same as those listed above as the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms and having the same valence as m, with 6 to 20 carbon atoms being preferred. The methylene group in these groups can be -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８ Or, it may be substituted with a bonding group that is a combination of these.

[0065] Y in the group represented by the above formula (1A) １ Examples of the divalent heterocyclic ring-containing group having 2 to 35 carbon atoms and represented by the formula (I) include the same as those listed above as the heterocyclic ring-containing group having 2 to 35 carbon atoms and a valence equal to m, and preferably have 6 to 20 carbon atoms. The methylene group in these groups is -O-, -CO-, -O-CO-, -CO-O-, -O-CO-O-, -O-CO-O-, -S-CO-, -CO-S-, -S-CO-O-, -O-CO-S-, -CO-NR ５８ -, -NR ５８ —CO—, —NR ５８ -CO-O-, -NR ５８ -CO-O-, -NR ５８ -, -S-S-, -SO ２ -, -S-O-, >PR ５８ Or, it may be substituted with a bonding group that is a combination of these.

[0066] Z in the group represented by formula (1A) １ Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include alkylene groups having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms.

[0067] Each functional group such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group may have a substituent, and unless otherwise specified, is unsubstituted or has a substituent. Examples of the substituents of such aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups include the same as those listed above as the substituents substituting hydrogen atoms of aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups having a valence equal to m.

[0068] The above bonding group X １ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent represented by the following formula (1-4) from the viewpoint of ease of production. For example, when m is 2, X １ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a substituent represented by the following formula (1-4): １ When m is 3, it is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

[0069]

[0070] (In the above formula (1-4), Y １ and Y ５ each independently represents an alkylene group having 1 to 4 carbon atoms; Y ２ and Y ４ are each independently an oxygen atom or —NR １１３ represents -, and R １１３ represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms; Y ３ is -CR １１４ R １１５ -, -NR １１６ -, a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, a divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, a divalent heterocyclic ring-containing group having 6 to 35 carbon atoms, or a substituent represented by the following formula (1-7), wherein a methylene group in the aliphatic hydrocarbon group, the aromatic ring-containing hydrocarbon group, and the heterocyclic ring-containing group may be replaced by -COO-, -O-, -OCO-, -NHCO-, -NH-, or -CONH-; R １１４ and R １１５each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms; R １１６ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 35 carbon atoms, an aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, or a heterocyclic ring-containing group having 2 to 35 carbon atoms. * represents a bond. ２ or Y ４ Ga-NR １１３ -, then Y ３ Ha-NR １１６ - It's not.) X １ is a substituent represented by (1-4), particularly, Y ２ and Y ４ are each independently preferably an oxygen atom in terms of bloom resistance, ease of production, and ease of availability of raw materials. １ is a substituent represented by (1-4), Y ３ is preferably a divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms, particularly preferably 3 to 20 carbon atoms, a group in which one or more methylene groups in the aliphatic hydrocarbon group have been substituted with -O-, or a substituent represented by the following formula (1-7) from the viewpoints of bloom resistance, ease of production, and ease of availability of raw materials; from this viewpoint, it is even more preferably a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms, in which one or more methylene groups have been substituted with -O-, or a substituent represented by the following formula (1-7), and in particular, it is preferably a group having 4 to 8 carbon atoms, particularly preferably 4 to 6 carbon atoms, in which ethylene groups or propylene groups and oxygen atoms are bonded alternately, or a substituent represented by the following formula (1-7), and most preferably a substituent represented by the following formula (1-7). Note that the aliphatic hydrocarbon group having 1 to 35 carbon atoms (particularly preferably 3 to 20 carbon atoms) in which a methylene group has been substituted with -O- may be linear or cyclic.

[0071]

[0072] (In the above formula (1-7), Y ９ and Y １０ each independently represents an alkylene group having 1 to 8 carbon atoms. * represents a bond.

[0073] Y used as a substituent in the above formulas (1-4) and (1-7) １ , Y ５ , Y ９ and Y １０ Examples of the alkylene group used in Y include a methylene group, an ethylene group, a propylidene group, an isopropylidene group, and a butylidene group. ９ and Y １０ Each of the alkylene groups represented by the above formula (I) preferably has 1 to 4 carbon atoms. １１３ The aliphatic hydrocarbon group having 1 to 20 carbon atoms used in １ Among the aliphatic hydrocarbon groups having 1 to 120 carbon atoms used in the above formula, those having a predetermined number of carbon atoms can be mentioned, among those exemplified as those in which m is monovalent. ３ The divalent aliphatic hydrocarbon group having 1 to 35 carbon atoms and the divalent aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms represented by the formula (I) include the above-mentioned X １ It is possible to use those which satisfy the predetermined number of carbon atoms in the content exemplified as above.

[0074] The above R １１４ , R １１５ Examples of the alkyl group having 1 to 8 carbon atoms used in R include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, a t-butyl group, an isobutyl group, an amyl group, an isoamyl group, a t-amyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a t-heptyl group, a 1-octyl group, an isooctyl group, and a t-octyl group. １１４ and R １１５ The aryl group having 6 to 20 carbon atoms used in the formula (3) below includes R ３１ and R ３２ Among the groups listed as aryl groups represented by the formula (R), groups having a predetermined number of carbon atoms can be mentioned. １１４ and R １１５Examples of the arylalkyl group having 7 to 20 carbon atoms used in the above R include a benzyl group, a phenethyl group, a 2-phenylpropan-2-yl group, a diphenylmethyl group, a triphenylmethyl group, a styryl group, and a cinnamyl group. １１６ The aliphatic hydrocarbon group having 1 to 35 carbon atoms, the aromatic ring-containing hydrocarbon group having 6 to 35 carbon atoms, and the heterocyclic ring-containing group having 2 to 35 carbon atoms used in ５３ and R ５４ The same as the example given above can be used.

[0075] Each functional group such as the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group, and heterocyclic ring-containing group may have a substituent, and unless otherwise specified, is unsubstituted or has a substituent. Examples of the substituents of such aliphatic hydrocarbon groups, aromatic ring-containing hydrocarbon groups, and heterocyclic ring-containing groups include X １ The substituents which may be substituted on the aliphatic hydrocarbon group, aromatic ring-containing hydrocarbon group and heterocycle-containing group having the same valence as m represented by the following formula may be those listed above.

[0076] As described above, m is 2 or 3, and the bonding group X １ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, X １ is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms. Furthermore, this is because the compound can be easily produced.

[0077] From the viewpoints of color stability and long-term thermal stability, the (B) primary antioxidant is preferably a phenolic antioxidant having one or more structures represented by the following formula (7), and in this case, it is more preferable that the group represented by formula (1) is a group represented by formula (7).

[0078] In formula (7), * represents a bond.

[0079] From the viewpoints of color stability and long-term thermal stability, the (B) primary antioxidant is also preferably a phenolic antioxidant having one or more structures represented by the following formula (8), and in this case, it is more preferable that the group represented by formula (1) is a group represented by formula (8).

[0080] In formula (8), * represents a bond.

[0081] Specific examples of (B) the primary antioxidant include 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]. Among these, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] are preferred, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane is more preferred.

[0082] The (B) primary antioxidants may be used alone or in combination of two or more. The content of the (B) primary antioxidant is 0.01 to 5 parts by mass, preferably 0.03 to 3 parts by mass, more preferably 0.05 to 2 parts by mass, and even more preferably 0.05 to 1.5 parts by mass, per 100 parts by mass of the (A) thermoplastic resin. By setting the lower limit of the content to 0.01 parts by mass or more, it is possible to sufficiently obtain the effect of improving color stability and long-term thermal stability. By setting the upper limit of the content to 5 parts by mass or less, it is possible to suppress molding defects, poor appearance of the shaped product, and blooming.

[0083] The secondary antioxidant (C) is at least one selected from the group consisting of phosphorus-based antioxidants represented by any one of the following formulas (2), (3), and (4) and thioether-based antioxidants represented by any one of the following formulas (5) and (6).

[0084] In formula (2), R ２１ and R ２２ each independently represents an alkyl group having 1 to 8 carbon atoms.

[0085] In formula (3), R ３１ and R ３２ each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0086] In formula (4), R ４１ , R ４２ and R ４３ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R ４４ represents an alkyl group having 1 to 18 carbon atoms.

[0087] In formula (5), R ５１ and R ５２ each independently represents an alkyl group having 8 to 22 carbon atoms.

[0088] In formula (6), R ６１ ~R ６４ each independently represents an alkyl group having 8 to 22 carbon atoms.

[0089] R in formula (2) ２１ and R ２２ Examples of the alkyl group having 1 to 8 carbon atoms represented by the formula (R) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an isoheptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a tert-octyl group, and a 2-ethylhexyl group. ２１ and R ２２ As the alkyl group, from the viewpoints of color stability, long-term thermal stability, and hydrolysis resistance, an alkyl group having 1 to 4 carbon atoms is preferred, and a tert-butyl group is more preferred.

[0090] R in formula (3) ３１ and R ３２ Examples of the alkyl group having 1 to 40 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a 4-ethyl-2-methylheptyl group, a hexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 2,4-dimethylhexyl group, a cyclohexyl group, a 1 ... , 2,4-trimethylcyclohexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tert-heptyl group, 1-octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, icosyl group, adamantyl group, and norbornyl group.

[0091] R in formula (3) ３１ and R ３２Examples of the aryl group having 6 to 40 carbon atoms represented by the formula (I) include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-vinylphenyl group, a 3-isopropylphenyl group, a 4-isopropylphenyl group, a 4-butylphenyl group, a 4-isobutylphenyl group, a 4-tert-butylphenyl group, a 4-hexylphenyl group, a 4-cyclohexylphenyl group, a 4-octylphenyl group, a 4-(2-ethylhexyl)phenyl group, a 4-stearylphenyl group, a 2,3-dimethylphenyl group, and a 2,4-dimethylphenyl group. , 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-di-tert-butylphenyl group, 2,5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-di-tert-pentylphenyl group, 2,5-di-tert-amylphenyl group, 2,5-di-tert-octylphenyl group, 2,4-dicumylphenyl group, 4-cyclohexylphenyl group, (1,1'-biphenyl)-4-yl group, 2,4,5-trimethylphenyl group, 2,6-di-tert-butyl-4-methylphenyl group, and ferrocenyl group. ３１ and R ３２ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 10 to 24 carbon atoms, and even more preferably a 2,4-di-tert-butylphenyl group, a 2,4-dicumylphenyl group, or a 2,6-di-tert-butyl-4-methylphenyl group.

[0092] R ３１ and R ３２ As the group represented by the formula (I), from the viewpoints of compatibility with thermoplastic resins, resistance to volatilization during fused deposition modeling, and resistance to fogging from the fused deposition modeled product, an alkyl group is preferred, an alkyl group having 1 to 30 carbon atoms is preferred, an alkyl group having 8 to 22 carbon atoms is more preferred, and an octadecyl group is even more preferred.

[0093] R in formula (4) ４１ , R ４２ and R４３ The alkyl group having 1 to 4 carbon atoms represented by the formula (2) is R ２１ and R ２２ Among examples of alkyl groups having 1 to 8 carbon atoms represented by the formula: R ４１ and R ４２ As R, from the viewpoints of color stability, long-term thermal stability, and hydrolysis resistance, an alkyl group having 3 or 4 carbon atoms is preferred, and a tert-butyl group is more preferred. ４３ In terms of ease of production and thermal stability of the compound, a hydrogen atom, a methyl group, or an ethyl group is preferred, and a hydrogen atom is more preferred.

[0094] R in formula (4) ４４ The alkyl group having 1 to 18 carbon atoms represented by the formula (3) is R ３１ and R ３２ Among examples of alkyl groups having 1 to 40 carbon atoms represented by the formula: R ４４ As the alkyl group, from the viewpoints of compatibility with thermoplastic resins, color stability, long-term thermal stability, and hydrolysis resistance, alkyl groups having 4 to 12 carbon atoms are preferred, and alkyl groups having 6 to 10 carbon atoms are even more preferred.

[0095] R in formula (5) ５１ and R ５２ and R in formula (6) ６１ ~R ６４ The alkyl group having 8 to 22 carbon atoms represented by the formula (3) is R ３１ and R ３２ Among examples of alkyl groups having 1 to 40 carbon atoms represented by the formula: R ５１ and R ５２ As the R group, an alkyl group having 12 to 18 carbon atoms is preferred from the viewpoints of compatibility with thermoplastic resins, resistance to volatilization during fused deposition modeling, and resistance to fogging from the fused deposition modeled product. ６１ ~R ６４ As the alkyl group, an alkyl group having 10 to 15 carbon atoms is preferred, and an alkyl group having 12 to 13 carbon atoms is more preferred.

[0096] The (C) secondary antioxidants may be used alone or in combination of two or more. The content of the (C) secondary antioxidant is 0.01 to 1.4 parts by mass, preferably 0.03 to 1.2 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of the (A) thermoplastic resin. By setting the lower limit of the content to 0.01 parts by mass or more, the effect of improving color stability and long-term thermal stability can be sufficiently obtained. By setting the upper limit of the content to 1.4 parts by mass or less, molding defects, poor appearance of shaped products, blooming, etc. can be suppressed. The content ratio of the (B) primary antioxidant to the (C) secondary antioxidant in the thermoplastic resin composition of the present invention is preferably (B) / (C) = 99 / 1 to 25 / 75, more preferably (B) / (C) = 90 / 10 to 30 / 70, by mass ratio. This allows the effects of the present invention to be fully obtained.

[0097] The thermoplastic resin composition of the present invention is preferably in the form of a continuous filament. Being filament-like allows it to be suitably used as a filament material for a commercially available 3D modeling device using the fused deposition modeling method. In this specification, the filament material may be referred to as "filament."

[0098] When the thermoplastic resin composition of the present invention is in the form of a continuous filament, the average diameter thereof is preferably 1.55 to 1.95 mm, more preferably 1.65 to 1.85 mm, and even more preferably 1.70 to 1.80 mm. By having the average diameter within the above range, the composition can be suitably used as a filament material for commercially available three-dimensional modeling devices using the fused deposition modeling method.

[0099] Examples of methods for measuring the average diameter include physical measurement using digital calipers and measurement using infrared laser reflection. For example, when measuring the average diameter using digital calipers, diameters are measured at 20 or more locations and the average value is calculated. The measurement locations are preferably at least 100 mm apart in the longitudinal direction of the filamentous resin composition. Furthermore, when the filamentous resin composition is filamentous, cross-sectional shapes include circles and ellipses. When the cross-sectional shape is not circular, the diameter refers to the length of the longest line segment that intersects the cross section. The thermoplastic resin composition of the present invention can be obtained by molding a resin material obtained by mixing components (A), (B), and (C) into a filamentous shape using a known method. The resin material may contain any of the additives described above, if necessary. The optional additives may be premixed with the thermoplastic resin (A), mixed with the components (A) to (C), or mixed into the mixture of the components (A) to (C). The above-mentioned descriptions of the preferred components (A), (B), and (C) and their respective amounts in the thermoplastic resin composition of the present invention, as well as the following descriptions of other optional components and their preferred amounts, can all be applied to a resin material in which the components (A), (B), and (C) are mixed.

[0100] The method for mixing the resin materials is not particularly limited, and known methods can be applied, such as a method of mixing using a mixer such as a tumbler mixer, a Henschel mixer, a ribbon blender, a V-type mixer, a W-type mixer, a Super Mixer, or a Nauta mixer, a method of melt-kneading using an extruder, or a method of mixing together with a solvent and then solution-casting.

[0101] 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.

[0102] 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.

[0103] The resin composition of the present invention may further contain, as necessary, resin additives such as a phenolic antioxidant other than component (B), a phosphorus-based antioxidant other than component (C), a thioether-based antioxidant other than component (C), an ultraviolet absorber, or a hindered amine-based light stabilizer, within a range that does not significantly impair the effects of the present invention.

[0104] Examples of phenolic antioxidants other than component (B) 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], 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and 2,2'-methylenebis(4-ethyl-6-tert-butylphenol). 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], thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene Examples of suitable phenolic antioxidants include olefin bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, and 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate. When a phenolic antioxidant other than these components (B) is used, the amount 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).

[0105] Examples of phosphorus-based antioxidants other than component (C) include tris(nonylphenyl)phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, tetrakis(tridecyl)isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol)diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxyphenyl)- Examples of phosphorus-based antioxidants include tetrakis(2,4-di-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 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. When a phosphorus-based antioxidant other than these component (C) is used, the amount 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). The amount of the phosphorus-based antioxidant other than component (C) is preferably 100 parts by mass or less per 100 parts by mass of component (C).

[0106] Examples of the thioether-based antioxidant other than component (C) include dialkylthiodipropionates other than component (C) and pentaerythritol tetrakis(β-alkylmercaptopropionates other than component (C). When these thioether-based antioxidants other than component (C) are used, the amount 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). Furthermore, the amount of the thioether-based antioxidant other than component (C) is preferably 100 parts by mass or less per 100 parts by mass of component (C).

[0107] 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.When these ultraviolet absorbers are used, the amount 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.

[0108] 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 such 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. When these hindered amine light stabilizers are used, the amount 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.

[0109] The resin composition of the present invention may contain a filler as an optional component within a range that does not significantly impair the effects of the present invention.

[0110] Examples of 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, clay, dolomite, silica, alumina, potassium titanate whiskers, wollastonite, fibrous magnesium oxysulfate, and hydrotalcite. These fillers can be used by appropriately selecting the particle size (fiber diameter, fiber length, and aspect ratio in the case of fibrous fillers). These fillers may be used alone or in combination of two or more. Furthermore, fillers that have been surface-treated may be used as needed. When these fillers are used, the amount of filler added is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight, and even more preferably 5 to 50 parts by weight, per 100 parts by weight of the thermoplastic resin.

[0111] If necessary, the 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, within the range that does not impair the effects of the present invention.

[0112] The thermoplastic resin composition of the present invention can be used as a filament material to produce the shaped object of the present invention by fused deposition modeling. The present invention provides a method for producing a shaped object, which includes a step of producing a shaped object by fused deposition modeling using the thermoplastic resin composition as a filament material. The modeling device used for fused deposition modeling includes a fused deposition modeling type three-dimensional modeling device (3D printer), and commercially available devices can be used.

[0113] The shaped object of the present invention has excellent color stability and long-term thermal stability, and can therefore be suitably used in a wide range of industrial fields, including electricity, electronics, 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.

[0114] 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, window materials, and other materials for automobiles, rolling stock, ships, aircraft, buildings, houses, and construction; 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.

[0115] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0116] [Examples 1-12, Comparative Examples 1-8] <Method for Producing Thermoplastic Resin Composition> The thermoplastic resin compositions listed in Table 1 were dry-blended and then melt-kneaded using a single-screw extruder (D3038, manufactured by Toyo Seiki Seisakusho) at an extrusion temperature of 210°C and a screw rotation speed of 25 rpm to produce a filament-like thermoplastic resin composition (hereinafter also referred to as filament). The strand discharged from the extruder was cooled with water and wound to an average diameter of 1.65-1.85 mm using a strand 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 according to the method described above. The filament was wound around a filament reel and then dried under reduced pressure at 80°C. The blending amounts shown in Tables 1 and 2 are in parts by mass.

[0117] <Method of Preparing Evaluation Test Pieces> The reel wound with the filament obtained above was attached to a 3D printer (H+1 manufactured by Afinia 3D), and fused deposition modeling was performed under the following conditions to obtain a multipurpose test piece (thickness 4 mm) conforming to ISO 527. Nozzle temperature: 285°C Stage temperature: 95°C Layer pitch: 0.2 mm Filling rate: 99% or more (solid) Raster orientation: 0° / 90° Layer direction: X-Y (Flat)

[0118] <Accelerated Heat Degradation Treatment> The test piece obtained above was left to stand in a 120°C blast gear oven for 2,000 hours and then removed from the gear oven. This operation is referred to as accelerated heat degradation treatment.

[0119] <Method for evaluating color stability> The coloring of the test piece obtained above was measured. The coloring of the test piece was measured using a spectrophotometer (XRite manufactured by X-Rite Corporation) ＊ a ＊ b ＊ The color space was measured and then converted to ΔE76. Furthermore, the test pieces obtained above were subjected to accelerated thermal aging treatment, and the colorability of the test pieces after the accelerated thermal aging treatment was measured in the same manner as above. The difference (ΔE) between the measured values ​​of the test pieces that were not subjected to the accelerated thermal aging treatment and the test pieces that were subjected to the accelerated thermal aging treatment is shown in Tables 1 and 2 as an evaluation value of color stability. The smaller the ΔE, the more excellent the color stability.

[0120] <Method for evaluating long-term thermal stability> The tensile elongation of the test specimen obtained above was measured. The tensile elongation of the test specimen was measured at 23°C in accordance with ISO 527. Furthermore, the test specimen obtained above was subjected to accelerated thermal aging treatment, and the tensile elongation of the test specimen after the accelerated thermal aging treatment was measured in the same manner as above. The ratio of the tensile elongation of the test specimen that had been subjected to accelerated thermal aging treatment to the tensile elongation of the test specimen that had not been subjected to accelerated thermal aging treatment (tensile elongation retention) is shown in Tables 1 and 2 as an evaluation value of long-term thermal stability. The closer the tensile elongation retention rate is to 100 (%), the more excellent the long-term thermal stability.

[0121] <Evaluation of Blooming Properties> After the test pieces obtained above were subjected to accelerated heat aging treatment, the presence or absence of blooming on the surface of the test pieces was visually confirmed. The presence or absence of blooming is shown in Tables 1 and 2.

[0122] Details of each component in Tables 1 and 2 are as follows: Component (A) PA12: Polyamide 12, trade name UBESTA3024U, manufactured by Ube Industries, Ltd. Component (B) B-1: 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane (phenolic antioxidant having a structure represented by formula (8)) Component (B) B-2: 4,4'-butylidenebis(6-tert-butyl-m-cresol) (phenolic antioxidant having a structure represented by formula (8)) Component (B) B-3: 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane (phenolic antioxidant having a structure represented by formula (7)) Component (B) B-4: Triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] (phenolic antioxidant having a structure represented by formula (7)) Comparative component of (B) BX-1: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate Comparative component of (B) BX-2: Stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate Comparative component of (B) BX-3: Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Comparative component of (B) BX-4: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene Comparative component of (B) BX-5: N,N'-bis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl}hydrazine Component (C) C-1: Tris(2,4-di-tert-butylphenyl)phosphite (phosphorus-based antioxidant represented by formula (2)) Component (C) C-2: 2,2'-methylenebis(4,(6-di-tert-butylphenyl)-2-ethylhexyl phosphite (phosphorus-based antioxidant represented by formula (4)) component (C) C-3: bis(octadecyl)pentaerythritol diphosphite (phosphorus-based antioxidant represented by formula (3)) component (C) C-4: tetrakis[methylene-3-(dodecylthio)propionate]methane (thioether-based antioxidant represented by formula (6)) component (C) C-5: di(lauryl)-3,3'-thiodipropionate (thioether-based antioxidant represented by formula (5)) Comparative components for (C) CX-1: tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite,

[0123]

[0124]

[0125] As shown in Tables 1 and 2, the compositions of the present invention (Examples 1 to 12) showed a small change in color tone (ΔE) before and after accelerated thermal degradation treatment and a high retention of tensile elongation. On the other hand, the compositions of the present invention that did not use the (B) primary antioxidant or (C) secondary antioxidant (Comparative Examples 1 to 7) showed a poorer change in color tone (ΔE) before and after accelerated thermal degradation treatment, and many also showed poorer retention of tensile elongation, compared to Examples 1 to 12. Furthermore, the composition containing 1.5 parts by mass of (C) secondary antioxidant (Comparative Example 8) showed a small change in color tone, but blooming was observed on the surface of the shaped article.

Claims

1. (A) a thermoplastic resin, (B) 0.01 to 5 parts by weight of a primary antioxidant per 100 parts by weight of the thermoplastic resin; and (C) 0.01 to 1.4 parts by mass of secondary antioxidant per 100 parts by mass of thermoplastic resin A thermoplastic resin composition comprising: The (A) thermoplastic resin is a condensation thermoplastic resin, The (B) primary antioxidant is a phenol-based antioxidant having one or more structures represented by the following formula (1): The (C) secondary antioxidant is at least one selected from the group consisting of phosphorus-based antioxidants represented by any one of the following formulas (2), (3), and (4) and thioether-based antioxidants represented by any one of the following formulas (5) and (6): A thermoplastic resin composition for fused deposition modeling. 【Chemistry 1】 In formula (1), R 11 and R 12 each independently represents a hydrogen atom or a methyl group, and * represents a bond. 【Chemistry 2】 In formula (2), R 21 and R 22 each independently represents an alkyl group having 1 to 8 carbon atoms. 【Chemistry 3】 In formula (3), R 31 and R 32 each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms. 【Chemistry 4】 In formula (4), R 41 , R 42 and R 43 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 44 represents an alkyl group having 1 to 18 carbon atoms. 【Chemistry 5】 In formula (5), R 51 and R 52 each independently represents an alkyl group having 8 to 22 carbon atoms. 【Chemistry 6】 In formula (6), R 61 , R 62 , R 63 and R 64 each independently represents an alkyl group having 8 to 22 carbon atoms.

2. The thermoplastic resin composition according to claim 1, A thermoplastic resin composition having a continuous filamentous shape.

3. The thermoplastic resin composition according to claim 2, A thermoplastic resin composition having a shape of continuous filaments with an average diameter of 1.55 to 1.95 mm.

4. The thermoplastic resin composition according to claim 1, (A) A thermoplastic resin composition, wherein the thermoplastic resin is a polyamide resin.

5. The thermoplastic resin composition according to claim 1, (A) A thermoplastic resin composition, wherein the thermoplastic resin is one or more selected from polyamide 6, polyamide 66, polyamide 11, and polyamide 12.

6. The thermoplastic resin composition according to claim 1, A thermoplastic resin composition, wherein the component (B) is a phenol-based antioxidant having one or more structures represented by the following formula (7): 【Chemistry 7】 In formula (7), * represents a bond.

7. The thermoplastic resin composition according to claim 1, (B) A thermoplastic resin composition, wherein the primary antioxidant is a phenolic antioxidant having one or more structures represented by formula (8). 【Chemistry 8】 In formula (8), * represents a bond.

8. In formula (3), R 31 and R 32 The thermoplastic resin composition according to claim 1, wherein each independently represents an alkyl group having 1 to 40 carbon atoms.

9. A method for producing a shaped object, comprising the step of producing a shaped object by fused deposition modeling using the thermoplastic resin composition according to any one of claims 1 to 8.

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

11. Use of a resin material in the manufacture of a filament material for fused deposition modeling, The resin material is (A) a thermoplastic resin, (B) 0.01 to 5 parts by weight of a primary antioxidant per 100 parts by weight of the thermoplastic resin; and (C) 0.01 to 1.4 parts by mass of secondary antioxidant per 100 parts by mass of thermoplastic resin Contains The (A) thermoplastic resin is a condensation thermoplastic resin, The (B) primary antioxidant is a phenol-based antioxidant having one or more structures represented by the following formula (1): The (C) secondary antioxidant is at least one selected from the group consisting of phosphorus-based antioxidants represented by any one of the following formulas (2), (3), and (4) and thioether-based antioxidants represented by any one of the following formulas (5) and (6). 【Chemistry 9】 In formula (1), R 11 and R 12 each independently represents a hydrogen atom or a methyl group, and * represents a bond. 【Chemistry 10】 In formula (2), R 21 and R 22 each independently represents an alkyl group having 1 to 8 carbon atoms. 【Chemistry 11】 In formula (3), R 31 and R 32 each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms. 【Chemistry 12】 In formula (4), R 41 , R 42 and R 43 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; R 44 represents an alkyl group having 1 to 18 carbon atoms. 【Chemistry 13】 In formula (5), R 51 and R 52 each independently represents an alkyl group having 8 to 22 carbon atoms. 【Chemistry 14】 In formula (6), R 61 , R 62 , R 63 and R 64 each independently represents an alkyl group having 8 to 22 carbon atoms.

12. (B) a primary antioxidant; and (C) a secondary antioxidant, The (B) primary antioxidant is a phenol-based antioxidant having one or more structures represented by the following formula (1): The (C) secondary antioxidant is at least one selected from the group consisting of phosphorus-based antioxidants represented by any one of the following formulas (2), (3), and (4) and thioether-based antioxidants represented by any one of the following formulas (5) and (6), For thermoplastic resin compositions for fused deposition modeling, The thermoplastic resin composition for fused deposition modeling contains (A) a thermoplastic resin, The additive, wherein the thermoplastic resin (A) is a condensation thermoplastic resin. 【Chemistry 15】 In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and * represents a bond. 【Chemistry 16】 In formula (2), R 21 and R 22 each independently represent an alkyl group having 1 to 8 carbon atoms. 【Chemistry 17】 In formula (3), R 31 and R 32 each independently represent an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms. 【Chemistry 18】 In formula (4), R 41 , R 42 and R 43 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 44 represents an alkyl group having 1 to 18 carbon atoms. 【Chemistry 19】 In formula (5), R 51 and R 52 each independently represent an alkyl group having 8 to 22 carbon atoms. 【Chemistry 20】 In formula (6), R 61 , R 62 , R 63 and R 64 each independently represent an alkyl group having 8 to 22 carbon atoms.

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