Resin composition, pellet and molded product

Abstract

To provide a resin composition which comprises a polybutylene terephthalate resin, a polyethylene terephthalate resin, silicone and glass fibers and can provide a molded product having excellent slidability and appearance and to provide a pellet and a molded product.SOLUTION: There is provided a resin composition which comprises a polybutylene terephthalate resin, a polyethylene terephthalate resin, silicone and a glass fiber, wherein the ratio of polyethylene terephthalate resin is more than 50 pts.mass and 99 pts.mass or less and the ratio of the silicone in the resin composition is 0.3 to 1 mass% in 100 pts.mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a pellet, and a molded article, and more particularly to a resin composition containing a polybutylene terephthalate resin and a polyethylene terephthalate resin. [Background technology]

[0002] Polyalkylene terephthalate resins, such as polybutylene terephthalate resin and polyethylene terephthalate resin, are widely used in electrical and electronic equipment components, automotive interior and exterior components, other electrical components, machine components, and the like, due to their excellent mechanical strength, chemical resistance, and electrical insulation properties (Patent Document 1, Patent Document 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 165263 [Patent Document 2] International Publication No. 2016 / 117586 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, polyalkylene terephthalate resins, such as polybutylene terephthalate resins and polyethylene terephthalate resins, are used in various applications. However, resin compositions containing polyalkylene terephthalate resins and glass fibers may also be required to have good sliding properties. However, molded articles formed from polyalkylene terephthalate resin compositions containing glass fibers tend to have poor sliding properties because the glass fibers may get caught on other members, etc. Furthermore, molded articles formed from polyalkylene terephthalate resin compositions containing glass fibers and a sliding agent tend to have poor appearance. The present invention aims to solve these problems and to provide a resin composition containing polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, and glass fiber, which is capable of providing a molded article with excellent sliding properties and appearance, as well as pellets and a molded article. [Means for solving the problem]

[0005] In light of the above-mentioned problems, the present inventors have conducted studies and have found that the above-mentioned problems can be solved by increasing the blending ratio of polyethylene terephthalate resin among the polybutylene terephthalate resin and polyethylene terephthalate resin contained in the resin composition and precisely adjusting the blending ratio of silicone. Specifically, the above problems were solved by the following means. <1> A resin composition comprising a polybutylene terephthalate resin, a polyethylene terephthalate resin, silicone, and glass fibers, a ratio of the polyethylene terephthalate resin to the total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin is more than 50 parts by mass and 99 parts by mass or less; A resin composition, wherein the content of silicone in the resin composition is 0.3 to 1% by mass. <2> The proportion of the polyethylene terephthalate resin is 70 parts by mass or more and 90 parts by mass or less out of 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin. <1> The resin composition according to claim 1. <3> The proportion of glass fibers in the resin composition is 40 to 70 mass%. <1> or <2> The resin composition according to claim 1. <4> The silicone comprises silicone oil. <1> ~ <3> The resin composition according to any one of the above. <5> The proportion of the polyethylene terephthalate resin is 70 parts by mass or more and 90 parts by mass or less out of 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin, The proportion of glass fibers in the resin composition is 40 to 70 mass %, The silicone includes silicone oil. <1> ~ <4> The resin composition according to any one of the above. <6> <1> ~ <5> A pellet of the resin composition according to any one of the above. <7> <1> ~ <5> A molded article formed from the resin composition according to any one of the above items. <8> <6> A molded article formed from the pellets according to claim 1. <9> Vehicle exterior parts, <6> or <7> Molded products. <10> Door mirror components, <6> or <7> Molded products. [Effects of the Invention]

[0006] The present invention makes it possible to provide a resin composition containing polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, and glass fiber, which is capable of providing a molded article having excellent sliding properties and appearance, as well as pellets and molded articles. DETAILED DESCRIPTION OF THE INVENTION

[0007] Hereinafter, an embodiment for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. Note that the present embodiment is an example for explaining the present invention, and the present invention is not limited to only this embodiment. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification change from year to year, they will be based on the standards in effect as of January 1, 2024, unless otherwise specified. If the measurement methods, etc. described in the standards shown in this specification are abolished as of January 1, 2024, they will be based on the standards in effect at the time of abolition.

[0008] The resin composition of this embodiment is a resin composition containing polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, and glass fiber, and is characterized in that, out of a total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin, the proportion of the polyethylene terephthalate resin is more than 50 parts by mass and not more than 99 parts by mass, and the proportion of silicone in the resin composition is 0.3 to 1% by mass. By adopting such a configuration, it is possible to provide a resin composition that contains polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, and glass fiber, and that can provide molded articles with excellent sliding properties and appearance.

[0009] In this embodiment, the amount of silicone added to a resin composition containing polybutylene terephthalate resin, polyethylene terephthalate resin, and glass fiber is adjusted so that the amount added to the resin composition is 0.3 to 1 mass %. Silicone is known as a sliding agent, but if the amount of silicone added is low, it tends to be difficult to appear on the surface of a molded product, making it difficult to achieve sliding properties. On the other hand, if the amount of silicone added is high, it tends to deteriorate the surface appearance and cause deterioration of physical properties. Therefore, in this embodiment, the proportion of polyethylene terephthalate resin is set to more than 50 parts by mass and not more than 99 parts by mass, based on a total of 100 parts by mass of polybutylene terephthalate resin and polyethylene terephthalate resin. Polyethylene terephthalate resin is less likely to crystallize than polybutylene terephthalate resin, so by increasing the proportion of polyethylene terephthalate resin, it is more likely that silicone will be exposed to the surface when a molded product is formed, and it is presumed that excellent sliding properties were achieved even with the above amount of silicone. In particular, in molded articles formed from resin compositions containing glass fibers, the sliding properties tend to decrease because the glass fibers get caught, but in this embodiment, the appearance can be maintained even when a large amount of glass fibers is blended.

[0010] Hereinafter, the embodiments of the present invention will be described in detail. However, the explanation of the constituent elements described below is an example of an embodiment of the present invention, and the present invention is not limited to these contents.

[0011] <Polybutylene terephthalate resin> The resin composition of the present embodiment contains a polybutylene terephthalate resin. Polybutylene terephthalate resin is a resin obtained by polycondensation of terephthalic acid as the main acid component and 1,4-butanediol as the main diol component. "The main acid component is terephthalic acid" means that 50% by mass or more of the acid component is terephthalic acid, preferably 60% by mass or more, more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. "The main diol component is 1,4-butanediol" means that 50% by mass or more of the diol component is 1,4-butanediol, preferably 60% by mass or more, more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. When the polybutylene terephthalate resin contains other acid components, examples thereof include isophthalic acid and dimer acid, and when the polybutylene terephthalate resin contains other diol components, examples thereof include polyalkylene glycols such as polytetramethylene glycol (PTMG).

[0012] When a polybutylene terephthalate resin copolymerized with polytetramethylene glycol is used, the proportion of the tetramethylene glycol component in the copolymer is preferably 3 to 40 mass%, more preferably 5 to 30 mass%, and even more preferably 10 to 25 mass%.

[0013] When a dimer acid copolymerized polybutylene terephthalate is used as the polybutylene terephthalate resin, the proportion of the dimer acid component in all carboxylic acid components is preferably 0.5 to 30 mol %, more preferably 1 to 20 mol %, and even more preferably 3 to 15 mol %, in terms of carboxylic acid groups. By setting the copolymerization proportion in this range, it is preferable because it tends to have an excellent balance between long-term heat resistance and toughness.

[0014] When isophthalic acid copolymerized polybutylene terephthalate is used as the polybutylene terephthalate resin, the proportion of isophthalic acid components in all carboxylic acid components is preferably 1 to 30 mol %, more preferably 1 to 20 mol %, and even more preferably 3 to 15 mol %, in terms of carboxylic acid groups. By setting the copolymerization proportion in this range, a good balance of heat resistance, injection moldability, and toughness tends to be achieved, which is preferable.

[0015] The polybutylene terephthalate resin used in this embodiment is preferably a resin in which 90% by mass or more of the acid component is terephthalic acid and 90% by mass or more of the diol component is 1,4-butanediol (polybutylene terephthalate homopolymer), a copolymerized polybutylene terephthalate resin copolymerized with polytetramethylene glycol, or an isophthalic acid copolymerized polybutylene terephthalate resin.

[0016] The intrinsic viscosity of the polybutylene terephthalate resin is preferably 0.5 dL / g or more, more preferably 0.6 dL / g or more, and preferably 2.0 dL / g or less, more preferably 1.5 dL / g or less, and even more preferably 1.1 dL / g or less. By using a resin with an intrinsic viscosity of 0.5 dL / g or more, the mechanical strength of the resulting molded article tends to be improved. Furthermore, by using a resin with an intrinsic viscosity of 2 dL / g or less, the fluidity of the polybutylene terephthalate resin tends to be improved, and moldability tends to be improved. The intrinsic viscosity of the polybutylene terephthalate resin is a value measured at 30° C. in a mixed solvent of tetrachloroethane and phenol in a 1:1 (mass ratio). When two or more polybutylene terephthalate resins are contained, the intrinsic viscosity is that of the mixture.

[0017] The amount of terminal carboxy groups in the polybutylene terephthalate resin may be appropriately selected and determined, but is typically 60 eq / ton or less, preferably 50 eq / ton or less, and more preferably 30 eq / ton or less. By setting the amount of terminal carboxy groups to 50 eq / ton or less, gas generation during melt molding of the polybutylene terephthalate resin can be more effectively suppressed. Furthermore, the lower limit of the amount of terminal carboxy groups is not particularly specified, but is typically 5 eq / ton. When two or more types of polybutylene terephthalate resins are contained, the amount of terminal carboxy groups is the amount of terminal carboxy groups in the mixture.

[0018] The amount of terminal carboxy groups in a polybutylene terephthalate resin is determined by dissolving 0.5 g of polybutylene terephthalate resin in 25 mL of benzyl alcohol and titrating the solution with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. Methods for adjusting the amount of terminal carboxy groups include adjusting the polymerization conditions, such as the raw material charge ratio, polymerization temperature, and pressure reduction method, and reacting with a terminal blocking agent, and any other conventionally known methods.

[0019] The polybutylene terephthalate resin used in this embodiment may be a recycled polybutylene terephthalate resin product (including recovered products, material recycled products, chemical recycled products, etc.), a rejected product, or scrap material generated when molding a molded product from a polybutylene terephthalate resin composition.

[0020] <Polyethylene terephthalate resin> The resin composition of the present embodiment contains a polyethylene terephthalate resin. The polyethylene terephthalate resin used in this embodiment is a resin obtained by polycondensation of terephthalic acid as the main acid component and ethylene glycol as the main diol component. The term "the main acid component is terephthalic acid" means that 50% by mass or more of the acid component is terephthalic acid, preferably 60% by mass or more, more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or 95% by mass or more. The term "the main diol component is ethylene glycol" means that 50% by mass or more of the diol component is ethylene glycol, preferably 60% by mass or more, more preferably 70% by mass or more, and may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.

[0021] When the polyethylene terephthalate resin contains other acid components, examples thereof include phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-phenylenedioxydiacetic acid and structural isomers thereof, dicarboxylic acids such as malonic acid, succinic acid, and adipic acid and derivatives thereof, and oxyacids such as p-hydroxybenzoic acid and glycolic acid and derivatives thereof. Furthermore, when the polyethylene terephthalate resin contains other acid components, examples of the other diol components include aliphatic glycols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, pentamethylene glycol, hexamethylene glycol, and neopentyl glycol; alicyclic glycols such as cyclohexanedimethanol; and aromatic dihydroxy compound derivatives such as bisphenol A and bisphenol S.

[0022] Furthermore, the polyethylene terephthalate resin may be copolymerized with 1.0 mol % or less, preferably 0.5 mol % or less, and more preferably 0.3 mol % or less of a branched component, for example, a trifunctional acid capable of forming an ester, such as tricarballylic acid, trimellitic acid, trimellitic acid, or a tetrafunctional acid capable of forming an ester, such as pyromellitic acid, or an alcohol capable of forming an ester, such as glycerin, trimethylolpropane, or pentaerythritol.

[0023] The intrinsic viscosity of the polyethylene terephthalate resin is preferably 0.3 to 1.5 dL / g, more preferably 0.3 to 1.2 dL / g, and even more preferably 0.4 to 0.8 dL / g. The intrinsic viscosity of the polyethylene terephthalate resin is a value measured at 30° C. in a mixed solvent of tetrachloroethane and phenol in a 1:1 (mass ratio).

[0024] The concentration of terminal carboxy groups in the polyethylene terephthalate resin is preferably 3 to 60 eq / ton, more preferably 5 to 50 eq / ton, and even more preferably 8 to 40 eq / ton. By setting the terminal carboxy group concentration to 60 eq / ton or less, gas is less likely to be generated during melt molding of the resin material, and the mechanical properties of the resulting molded article tend to be improved. Conversely, by setting the terminal carboxy group concentration to 3 eq / ton or more, the heat resistance, retention heat stability, and color of the resulting molded article tend to be improved, which is preferable. The terminal carboxyl group concentration of the polyethylene terephthalate resin is a value determined by dissolving 0.5 g of polyethylene terephthalate resin in 25 mL of benzyl alcohol and titrating the solution with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

[0025] The polyethylene terephthalate resin used in this embodiment may be a recycled polyethylene terephthalate resin product (including recovered products, material recycled products, chemical recycled products, etc.), a rejected product, or scrap material generated when a molded product is formed from a polyethylene terephthalate resin composition.

[0026] <Blend of polybutylene terephthalate resin and polyethylene terephthalate resin> In the resin composition of this embodiment, the proportion of the polyethylene terephthalate resin is more than 50 parts by mass and not more than 99 parts by mass, based on a total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin. The proportion of the polyethylene terephthalate resin is preferably not less than 55 parts by mass, more preferably not less than 60 parts by mass, even more preferably not less than 65 parts by mass, even more preferably not less than 70 parts by mass, and even more preferably not less than 72 parts by mass. It is also preferably not more than 90 parts by mass, more preferably not more than 85 parts by mass, even more preferably not more than 80 parts by mass, and even more preferably not more than 78 parts by mass. By setting the proportion at or above the lower limit, particularly high mechanical properties tend to be maintained, achieving both good mechanical properties and good appearance. Furthermore, by setting the proportion at or below the upper limit, moldability in injection molding and the like tends to be further improved. The resin composition of the present embodiment may contain only one polybutylene terephthalate resin and one polyethylene terephthalate resin, or may contain two or more of either or both. When two or more types are contained, the total amount is preferably in the above range.

[0027] The total content of the polybutylene terephthalate resin and the polyethylene terephthalate resin in the resin composition of this embodiment is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and even more preferably 33% by mass or more, based on 100% by mass of the resin composition. By making the total content equal to or greater than the lower limit, the surface appearance of the molded article tends to be improved. Furthermore, the total content of the polybutylene terephthalate resin and the polyethylene terephthalate resin is preferably 55% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 38% by mass or less, based on 100% by mass of the resin composition. By making the total content equal to or less than the upper limit, the mechanical properties tend to be improved.

[0028] <Silicone> The resin composition of the present embodiment contains silicone. The silicone used in the resin composition of this embodiment is not particularly limited, and a wide variety of known silicones can be used. By using silicone, a molded product with high sliding properties and excellent appearance can be obtained. The silicone used in the resin composition of this embodiment is preferably one with a high molecular weight. For example, it is preferable that the weight-average molecular weight is 5,000 or more, or 80,000 or less. It is more preferable that the silicone has a weight-average molecular weight of 5,000 or more, preferably 10,000 or more, and 80,000 or less, or even 70,000 or less, and that the silicone is blended in an extruder as a masterbatch containing the silicone and the thermoplastic resin, and melt-kneaded.

[0029] The weight average molecular weight can be measured by GPC (gel permeation chromatography) using, for example, Tosoh HLC-8320GPC EcoSEC, tetrahydrofuran as the solvent, three Shodex KF-G, KF-805L columns, and a KF-800D column, at a column temperature of 40°C and a flow rate of 1.2 mL / min, and can be measured as a polystyrene-equivalent value detected with a detector (UV-8320) at a detection wavelength of 254 nm. Alternatively, the average molecular weight of the silicone oil can be calculated by measuring the kinematic viscosity using an Ubbelohde viscometer according to ASTM D445-46T and then using the Warrik equation. In the case where the resin composition of the present embodiment contains two or more types of silicone, the weight average molecular weight is the weight average molecular weight of the mixture.

[0030] The silicone used in this embodiment is preferably an organosilicon compound having a siloxane bond as a skeleton, with organic groups directly bonded to the silicon. Known organic groups directly bonded to silicon include methyl, ethyl, phenyl, vinyl, trifluoropropyl, and combinations thereof, but methyl and / or phenyl groups are preferred. Also usable are siloxane compounds in which some of the organic groups are substituted with substituents having an epoxy group, an amino group, a polyether group, a carboxyl group, a mercapto group, an ester group, a chloroalkyl group, an alkyl group having 3 or more carbon atoms, a hydroxyl group, etc. Silicones can be used alone or in combination of two or more types.

[0031] The siloxane is preferably, for example, silicone oil and / or silicone resin. Specific examples of silicone oils include oily silicones such as dimethylsilicone oil, phenylmethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, polyether-modified silicone oil, aliphatic ester-modified silicone oil, amino-modified silicone oil, carboxylic acid-modified silicone oil, carbinol-modified silicone oil, epoxy-modified silicone oil, and mercapto-modified silicone oil.

[0032] When the silicone of this embodiment is a masterbatch, it is preferably masterbatched with a polyalkylene terephthalate resin, and more preferably masterbatched with a polybutylene terephthalate resin. When the silicone used in this embodiment is masterbatched with a thermoplastic resin, the content of the thermoplastic resin in the masterbatch is preferably 70 to 95% by mass. When the silicone used in this embodiment is masterbatched with a thermoplastic resin, the content of the silicone in the masterbatch is preferably 5 to 30% by mass.

[0033] The silicone content in the resin composition of this embodiment is preferably 0.3% by mass or more, and preferably 1% by mass or less, more preferably 0.9% by mass or less, even more preferably 0.7% by mass or less, even more preferably 0.6% by mass or less, and even more preferably 0.5% by mass or less, based on 100% by mass of the resin composition. By setting the content at or above the lower limit, sliding properties tend to be further improved. Meanwhile, by setting the content at or below the upper limit, deterioration of mechanical properties and deterioration of appearance tend to be more effectively suppressed. The resin composition of the present embodiment may contain only one type of silicone, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0034] <Glass fiber> The resin composition in this embodiment contains glass fibers. The glass fiber is selected from glass compositions such as A-glass, C-glass, E-glass, R-glass, D-glass, M-glass, and S-glass, with E-glass (alkali-free glass) being particularly preferred. Glass fiber refers to a fibrous material whose cross section, cut perpendicular to the longitudinal direction, is circular or polygonal. The number average fiber diameter of the single fiber of the glass fiber is usually 1 to 25 μm, preferably 5 to 17 μm. By making the number average fiber diameter 1 μm or more, the molding processability of the resin composition tends to be further improved. By making the number average fiber diameter 25 μm or less, the appearance of the obtained structure tends to be improved, and the reinforcing effect also tends to be improved. The glass fiber may be a single fiber or a plurality of single fibers twisted together. The glass fiber may be in the form of a glass roving obtained by continuously winding a single fiber or a plurality of twisted fibers, a chopped strand cut to a length of 1 to 10 mm (i.e., glass fiber having a number average fiber length of 1 to 10 mm), or a milled fiber pulverized to a length of about 10 to 500 μm (i.e., glass fiber having a number average fiber length of 10 to 500 μm), but chopped strand cut to a length of 1 to 10 mm is preferred. Glass fibers of different forms can also be used in combination. Glass fibers having an irregular cross-sectional shape are also preferred. The irregular cross-sectional shape has an oblateness, which is the ratio of the major axis to the minor axis of the cross section perpendicular to the longitudinal direction of the fiber, of, for example, 1.5 to 10, preferably 2.5 to 10, more preferably 2.5 to 8, and even more preferably 2.5 to 5.

[0035] The glass fiber may be surface-treated with, for example, a silane-based compound, an epoxy-based compound, a urethane-based compound, or the like, or may be oxidized, in order to improve its affinity with the resin component, as long as the properties of the resin composition in this embodiment are not significantly impaired.

[0036] The resin composition in this embodiment preferably contains 100 parts by mass or more of glass fiber, more preferably 120 parts by mass or more, even more preferably 130 parts by mass or more, and even more preferably 135 parts by mass or more, per 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin combined. By ensuring that the glass fiber content is equal to or greater than the lower limit, the mechanical strength of the resulting molded article tends to be further increased. Furthermore, the glass fiber content is preferably equal to or less than 200 parts by mass, more preferably equal to or less than 180 parts by mass, even more preferably equal to or less than 150 parts by mass, and even more preferably equal to or less than 140 parts by mass, per 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin combined. By ensuring that the glass fiber content is equal to or greater than the lower limit, the mechanical strength of the resin composition tends to be further improved. By ensuring that the glass fiber content is equal to or less than the upper limit, the appearance of the resulting molded article tends to be further improved.

[0037] The content of glass fibers in the resin composition in this embodiment is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 45% by mass or more, based on 100% by mass of the resin composition. The content of glass fibers in the resin composition is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 55% by mass or less. By setting the content at or above the lower limit, mechanical strength tends to be further increased. By setting the content at or below the upper limit, the appearance of the resulting molded article tends to be further improved. The resin composition in this embodiment may contain only one type of glass fiber, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0038] <Reactive compounds> The resin composition of the present embodiment may contain a reactive compound. By containing a reactive compound, the mechanical strength of the molded article is improved, and a resin composition having excellent hydrolysis resistance can be obtained. The reactive compound used in the present embodiment preferably includes at least one selected from the group consisting of a compound having an epoxy group, a carbodiimide compound, a compound having an oxazoline group, and a compound having an oxazine group, and more preferably includes a compound having an epoxy group.

[0039] <<Compounds with epoxy groups (epoxy resins)>> The compound having an epoxy group is a compound having one or more epoxy groups in one molecule, and examples thereof include a glycidyl compound, an aromatic ring-containing compound having an epoxy group, and an alicyclic compound having an epoxy group, and it is preferable that the compound contains at least an aromatic ring-containing compound having an epoxy group.

[0040] Specific examples of compounds having an epoxy group include bisphenol A type epoxy compounds (including bisphenol A diglycidyl ether), bisphenol F type epoxy compounds (including bisphenol F diglycidyl ether), biphenyl type epoxy compounds (including bis(glycidyloxy)biphenyl), resorcinol type epoxy compounds (including resorcinol diglycidyl ether), novolac type epoxy compounds, epoxy compounds having an aromatic ring such as benzoic acid glycidyl ester, terephthalic acid diglycidyl ester, orthophthalic acid diglycidyl ester, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and decyl glycidyl ether. (di)glycidyl ethers such as stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether, allyl glycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, and propylene glycol diglycidyl ether; paraffinic (e.g., saturated fatty acid) or olefinic (e.g., unsaturated fatty acid) (di)glycidyl esters such as sorbic acid glycidyl ester, adipic acid diglycidyl ester, epoxidized linseed oil, and epoxidized soybean oil; and alicyclic epoxy compounds such as vinylcyclohexene dioxide and dicyclopentadiene oxide. Among these, styrene-acrylic copolymers containing glycidyl groups in the side chains, bisphenol A type epoxy compounds, novolac type epoxy compounds, bisphenol F type epoxy compounds, biphenyl type epoxy compounds, etc. are preferred, and bisphenol A type epoxy compounds are more preferred.

[0041] The content of the reactive compound (preferably a compound having an epoxy group (epoxy resin)) in the resin composition of this embodiment is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, based on 100% by mass of the resin composition. By making the content equal to or greater than the lower limit, hydrolysis resistance tends to be further improved. Furthermore, the content of the reactive compound (preferably a compound having an epoxy group (epoxy resin)) in the resin composition is preferably 10.0% by mass or less, more preferably 5.0% by mass or less, even more preferably 3.0% by mass or less, and even more preferably 1.0% by mass or less. By making the content equal to or less than the upper limit, the melt viscosity tends to be more stable, and moldability tends to be improved. The resin composition of the present embodiment may contain only one type of reactive compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0042] <Stabilizer> The resin composition of the present embodiment may contain a stabilizer. By containing a stabilizer, a resin composition or a molded article having excellent thermal stability can be obtained. The stabilizer preferably contains one or more compounds selected from the group consisting of thioether compounds, hindered phenol compounds, and phosphite compounds, and more preferably contains a hindered phenol compound.

[0043] The thioether-based compound may be any conventionally known sulfur-containing compound, and among these, thioethers are preferred. By including the thioether-based compound in the resin composition of the present embodiment, the appearance of the molded article tends to be improved and color change tends to be suppressed. Specific examples include didodecylthiodipropionate, ditetradecylthiodipropionate, dioctadecylthiodipropionate, pentaerythritol tetrakis(3-dodecylthiopropionate), 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], thiobis(N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropyl xanthate, and trilauryl trithiophosphite. Among these, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate] is preferred. Commercially available products include Shipro Chemicals' product name "Seenox 412S" and ADEKA's product name "Adekastab AO-412S."

[0044] Examples of hindered phenol compounds include pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), pentaerythritol tetrakis(3-(3,5-di-neopentyl-4-hydroxyphenyl)propionate), and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene. Among these, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Commercially available products include ADEKA products under the trade names "ADK STAB AO-60" and "ADK STAB AO-330," EVERSPRING CHEMICAL products under the trade name "EVERNOX-10," and BASF products under the trade name "IRGANOX1010."

[0045] The phosphite compound is preferably a compound represented by the formula: R 2 OP(OR 3 )(OR 4 ) (In the formula, R 2 , R 3 and R 4 are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms, and R 2 , R 3 and R 4 At least one of the groups is an aryl group having 6 to 30 carbon atoms.) Examples of the compound include compounds represented by the following formula: Examples of the phosphite compound include triphenyl phosphite, tris(nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris(2-ethylhexyl) phosphite, tris(tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono(tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra(tridecyl) pentaerythritol tetraphosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis(3-methyl-6-tert-butylphenyl di(tridecyl) phosphite), tetra(tridecyl) 4,4'-isopropyl phosphate, tetra(tridecyl) ... propylidenediphenyl diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dilauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris(4-tert-butylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and the like. Among these, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is preferred. An example of a commercially available product is "ADEKA STAB PEP-36" manufactured by ADEKA Corporation.

[0046] Other examples of stabilizers include the descriptions in paragraphs 0067 to 0075 of JP 2021-063196 A, paragraphs 0046 to 0057 of JP 2018-070722 A, paragraphs 0030 to 0037 of JP 2019-056035 A, and paragraphs 0066 to 0078 of WO 2017 / 038949 A. The contents of these descriptions are incorporated herein by reference.

[0047] The stabilizer content in the resin composition of this embodiment is 0.01 parts by mass or more, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more, per 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin combined. By ensuring that the stabilizer content is above the lower limit, the effect of suppressing thermal and oxidative degradation of the resin during melt-kneading, molding, and use as a molded product tends to be more improved, and discoloration of the resin tends to be more effectively suppressed. Furthermore, the upper limit of the stabilizer content is preferably 2.0 parts by mass or less, more preferably 1.5 parts by mass or less, and even more preferably 1.0 part by mass or less, per 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin combined. By ensuring that the stabilizer content is below the upper limit, adverse effects on appearance and physical properties due to aggregation of additives such as stabilizers can be effectively suppressed. The resin composition of the present embodiment may contain only one stabilizer, or may contain two or more stabilizers. When two or more stabilizers are contained, the total amount is preferably in the above range.

[0048] <Release agent> The resin composition of the present embodiment preferably contains a release agent. A wide variety of known release agents can be used as the release agent, and examples thereof include aliphatic carboxylic acid amides, aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, and polysiloxane-based silicone oils, with aliphatic carboxylic acid amides being preferred.

[0049] Examples of the aliphatic carboxylic acid amides include compounds obtained by a dehydration reaction between a higher aliphatic monocarboxylic acid and / or a polybasic acid and a diamine. As the higher aliphatic monocarboxylic acid, saturated aliphatic monocarboxylic acids and hydroxycarboxylic acids having 16 or more carbon atoms are preferred, and examples thereof include palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. Examples of polybasic acids include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid; aromatic dicarboxylic acids such as phthalic acid and terephthalic acid; and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and cyclohexylsuccinic acid. Examples of diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylenediamine, metaxylylenediamine, tolylenediamine, paraxylylenediamine, phenylenediamine, and isophoronediamine. The carboxylic acid amide compound is preferably a compound obtained by polycondensation of stearic acid, sebacic acid, and ethylenediamine, and more preferably a compound obtained by polycondensation of 2 moles of stearic acid, 1 mole of sebacic acid, and 2 moles of ethylenediamine. In addition to bisamide compounds obtained by reacting diamines with aliphatic carboxylic acids, such as N,N'-methylenebisstearamide and N,N'-ethylenebisstearamide, dicarboxylic acid amide compounds such as N,N'-dioctadecylterephthalamide can also be suitably used.

[0050] Examples of aliphatic carboxylic acids include saturated or unsaturated aliphatic mono-, di-, or tri-carboxylic acids. Aliphatic carboxylic acids also include alicyclic carboxylic acids. Among these, preferred aliphatic carboxylic acids are mono- or di-carboxylic acids having 6 to 36 carbon atoms, with saturated aliphatic mono-carboxylic acids having 6 to 36 carbon atoms being more preferred. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, tetralinic acid, montanic acid, adipic acid, and azelaic acid.

[0051] The aliphatic carboxylic acid in the ester of an aliphatic carboxylic acid and an alcohol can be, for example, the same as the aliphatic carboxylic acid. On the other hand, the alcohol can be, for example, a saturated or unsaturated monohydric or polyhydric alcohol. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic or alicyclic saturated monohydric alcohols or aliphatic saturated polyhydric alcohols having 30 or less carbon atoms are more preferred. Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, and dipentaerythritol. Specific examples of esters of aliphatic carboxylic acids and alcohols include beeswax (a mixture containing myricyl palmitate as a main component), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin distearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, and esters of montanic acid and polyfunctional alcohols.

[0052] Examples of aliphatic hydrocarbons having a number average molecular weight of 200 to 15,000 include liquid paraffin, paraffin wax, microcrystalline wax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomers having 3 to 12 carbon atoms. Note that the aliphatic hydrocarbons herein also include alicyclic hydrocarbons. The number average molecular weight of the aliphatic hydrocarbons is preferably 5,000 or less.

[0053] Examples of polyolefin waxes include polyethylene wax, polypropylene wax, and polyethylene propylene wax, with polyethylene wax being preferred. The polyolefin wax may be unmodified or modified. Examples of modified polyolefin waxes include vinyl ester-modified polyolefin wax, acid-modified polyolefin wax, and oxidized polyolefin wax, with oxidized polyolefin wax being preferred. Oxidized polyolefin waxes have excellent compatibility with polyalkylene terephthalate resins and tend to effectively suppress mold deposits in the resulting resin composition.

[0054] Oxidized polyolefin waxes can be obtained by oxidizing the corresponding unmodified polyolefin waxes. Examples of oxidized polyethylene waxes include Licowax (registered trademark) PED521, PED522, and PED121 manufactured by Clariant Chemicals; Ceridust (registered trademark) 3715, etc. In addition to the above, commercially available polyolefin waxes can be found in paragraph 0028 of JP-A-2022-140470, the contents of which are incorporated herein by reference.

[0055] The weight-average molecular weight of the polyolefin wax is preferably 800 or more, more preferably 1,000 or more, even more preferably 1,500 or more, even more preferably 2,000 or more, and even more preferably 2,500 or more. By setting it to the lower limit or above, glowing time tends to be further shortened. Furthermore, the weight-average molecular weight of the polyolefin wax is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 15,000 or less, and even more preferably 10,000 or less. By setting it to the upper limit or below, the fluidity of the resin composition during molding tends to be further improved. The weight average molecular weight can be measured by GPC (gel permeation chromatography) using a Tosoh HLC-8320GPC EcoSEC with tetrahydrofuran as the solvent and three Shodex KF-G, KF-805L, and KF-800D columns at a column temperature of 40°C and a flow rate of 1.2 mL / min, and can be measured as a polystyrene-equivalent value detected with a detector (UV-8320) at a detection wavelength of 254 nm. When the resin composition of the present embodiment contains two or more types of polyolefin waxes, the weight average molecular weight is the weight average molecular weight of the mixture.

[0056] The dropping point of the polyolefin wax is preferably 165°C or lower, more preferably 160°C or lower, even more preferably 155°C or lower, even more preferably 150°C or lower, even more preferably 145°C or lower, even more preferably 140°C or lower, even more preferably 135°C or lower, particularly more preferably 130°C or lower, and preferably 80°C or higher, more preferably 85°C or higher, even more preferably 85°C or higher, even more preferably 90°C or higher, and even more preferably 95°C or higher. The dropping point is the temperature at which a polyolefin wax is heated to change from a solid to a liquid state and the first drop of molten material falls from a standard cup with a 2.8 mm opening.

[0057] In addition to the above, the release agent can be found in paragraphs 0063 to 0077 of JP 2018-070722 A and paragraphs 0090 to 0098 of JP 2019-123809 A, the contents of which are incorporated herein by reference.

[0058] The resin composition of this embodiment preferably contains 0.01 parts by mass or more of the release agent, per 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin combined, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 0.7 parts by mass or more, and even more preferably 1.0 parts by mass or more. It is also preferable that the amount is 5 parts by mass or less, more preferably 4 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less. By setting the amount at or above the lower limit, the releasability of the resulting molded article tends to be further improved. Furthermore, by setting the amount at or below the upper limit, bleed-out of the resulting molded article can be effectively suppressed. The resin composition may contain only one type of release agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0059] <Elastomer> The resin composition of the present embodiment preferably contains an elastomer. By containing an elastomer, the impact resistance of the resulting molded article tends to be further improved. The type of elastomer is not particularly limited, and known elastomers can be used. In this specification, a compound that falls under the category of an elastomer and also falls under the category of a siloxane or a reactive compound will be referred to as a siloxane or a reactive compound.

[0060] An example of an elastomer is an elastomer containing an epoxy group. By including an elastomer containing an epoxy group, a molded product tends to have higher impact resistance.

[0061] A first embodiment of the epoxy group-containing elastomer is a copolymer obtained by copolymerizing an α-olefin, a glycidyl ester of an α,β-unsaturated acid, and, if necessary, an unsaturated monomer copolymerizable therewith. Of all the copolymerization components in the copolymer, the α-olefin and the glycidyl ester of an α,β-unsaturated acid preferably account for 60 mass % or more.

[0062] Examples of α-olefins include ethylene, propylene, butene-1, and pentene-1. Two or more of these may be used. Examples of glycidyl esters of α,β-unsaturated acids include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate. Two or more of these may be used. Examples of vinyl monomers copolymerizable with the above components include vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic and methacrylic esters such as methyl, ethyl, propyl, and butyl, acrylonitrile, and styrene. Two or more of these may be used.

[0063] Preferred examples of the epoxy group-containing elastomer of the first embodiment include ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate / vinyl acetate copolymer, ethylene / glycidyl methacrylate / alkyl acrylate copolymer, and ethylene / alkyl acrylate / vinyl acetate copolymer. In particular, from the viewpoint of excellent toughness and further improving the moist heat resistance and impact resistance of molded articles, ethylene / glycidyl methacrylate / alkyl acrylate (preferably butyl acrylate) copolymer is preferred. Specific examples of the epoxy group-containing elastomer of the first embodiment are available from Arkema under the trade names "Rotader" (registered trademark) AX8900 and AX8700.

[0064] A second embodiment of the epoxy group-containing elastomer is a core-shell elastomer. The use of a core-shell elastomer facilitates dispersion in polybutylene terephthalate resin due to its small molecular size, and the reaction of reactive groups tends to increase welding strength. An example of a core-shell elastomer is one in which a monomer component is graft-copolymerized onto a core polymer. The core is preferably a rubbery polymer, and examples thereof include acrylonitrile-acrylic rubbery polymer-styrene graft copolymer (ASA resin), methyl methacrylate-acrylic rubbery polymer-styrene graft copolymer (MSA resin), methyl methacrylate-acrylonitrile-acrylic rubbery polymer-styrene graft copolymer (MASA resin), polyorganosiloxane-containing rubbery polymer, etc., with polyorganosiloxane-containing rubbery polymer being preferred. The polyorganosiloxane-containing rubbery polymer usually has a glass transition temperature of 0° C. or lower, preferably −20° C. or lower, and more preferably −30° C. or lower. Specific examples of the rubber component are not particularly limited as long as it contains polyorganosiloxane rubber, and examples thereof include polyorganosiloxane rubber, and composite rubber (IPN type) of polyorganosiloxane rubber and polyalkyl acrylate rubber.

[0065] Specific examples of the monomer component graft-copolymerizable with the core include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, (meth)acrylic acid compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate, maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and anhydrides thereof (for example, maleic anhydride, etc.).

[0066] Specific examples of rubber polymers, aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid ester compounds can be found in paragraphs 0042 to 0046 of JP 2019-059813 A, the contents of which are incorporated herein by reference.

[0067] The epoxy group-containing elastomer of the second embodiment is preferably a compound obtained by graft polymerizing an epoxy group-containing (meth)acrylic acid ester compound onto a polyorganosiloxane-containing rubbery polymer (preferably a composite rubber of polyorganosiloxane rubber and polyalkyl acrylate rubber).

[0068] Specific examples of the elastomer containing an epoxy group according to the second embodiment include "Metablen (registered trademark, the same applies hereinafter) S-2002" and "Metablen S-2200" manufactured by Mitsubishi Rayon Co., Ltd.

[0069] Another example of the elastomer is a graft copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. The graft copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc., and the copolymerization method may be either single-stage grafting or multi-stage grafting.

[0070] The rubber component typically has a glass transition temperature of 0°C or lower, preferably -20°C or lower, and more preferably -30°C or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polyalkyl acrylate rubbers such as polybutyl acrylate, poly(2-ethylhexyl acrylate), and butyl acrylate-2-ethylhexyl acrylate copolymers, silicone rubbers such as polyorganosiloxane rubber, butadiene-acrylic composite rubber, IPN (Interpenetrating Polymer Network) composite rubbers consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubbers such as ethylene-propylene rubber, ethylene-butene rubber, and ethylene-octene rubber, ethylene-acrylic rubber, and fluororubber. These may be used alone or in combination. Among these, polybutadiene rubber, polyalkyl acrylate rubber, polyorganosiloxane rubber, IPN type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferred in terms of mechanical properties and surface appearance.

[0071] Specific examples of the monomer component capable of graft copolymerization with the rubber component include the epoxy group-containing elastomer, and are the same as the specific examples of the monomer component capable of graft copolymerization with the rubber component described above.

[0072] The graft copolymer obtained by copolymerizing a rubber component is preferably a core / shell graft copolymer in terms of impact resistance and surface appearance. Among these, a core / shell graft copolymer is particularly preferred, which comprises a core layer made of at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, polyorganosiloxane rubber, and an IPN-type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and a shell layer formed by copolymerizing a (meth)acrylic acid ester around the core layer. The core / shell graft copolymer preferably contains 40% by mass or more of the rubber component, more preferably 60% by mass or more. Furthermore, it is preferable that the (meth)acrylic acid content be 10% by mass or more. Note that the core / shell type in this embodiment does not necessarily have to be one in which the core layer and the shell layer are clearly distinguishable; it broadly includes compounds obtained by graft polymerizing a rubber component around the core portion.

[0073] Preferred specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber-styrene copolymer, methyl methacrylate-(acrylic-silicone IPN rubber) copolymer, etc. Such rubbery polymers may be used alone or in combination of two or more.

[0074] Examples of such elastomers include Paraloid (registered trademark, the same applies hereinafter) EXL2602, Paraloid (registered trademark, the same applies hereinafter) EXL2603, Paraloid (registered trademark, the same applies hereinafter) EXL2655, Paraloid (registered trademark, the same applies hereinafter) EXL2311, Paraloid (registered trademark, the same applies hereinafter) EXL2313, Paraloid (registered trademark, the same applies hereinafter) EXL2315, Paraloid (registered trademark, the same applies hereinafter) KM330, Paraloid (registered trademark, the same applies hereinafter) KM336P, Paraloid (registered trademark, the same applies hereinafter) KCZ201, Metablen (registered trademark, the same applies hereinafter) C-223A, Metablen (registered trademark, the same applies hereinafter) E-901, Metablen (registered trademark, the same applies hereinafter) S-2001, Metablen (registered trademark, the same applies hereinafter) SRK-200, Kaneka Corporation Kane Ace (registered trademark, the same applies hereinafter) M-511, Kane Ace M-600, Kane Ace M-400, Kane Ace M-580, Kane Ace M-711, Kane Ace MR-01, Kane Ace M-580, Kane Ace M-711, Kane Ace MR-01, Ube Industries UBESTA XPA, and the like.

[0075] Another example of the elastomer is an acrylic block copolymer. Examples of acrylic block copolymers include block copolymers containing a hard segment made of a methyl methacrylate block and a soft segment made of an alkyl acrylate block.

[0076] The acrylic block copolymer is preferably a triblock copolymer having two hard segment blocks on either side of a soft segment block, or a diblock copolymer having one soft segment block and one hard segment block. That is, the acrylic block copolymer in this embodiment preferably has a triblock structure consisting of a methyl methacrylate block-alkyl acrylate block-methyl methacrylate block, or a diblock structure consisting of a methyl methacrylate block-alkyl acrylate block.

[0077] Examples of alkyl acrylates constituting the soft segment include n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, phenyl acrylate, toluyl acrylate, benzyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, stearyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, and γ-(acryloyloxypropyl)trimethicone. Examples of suitable acrylates include xysilane, γ-(acryloyloxypropyl)dimethoxymethylsilane, ethylene oxide adduct of acrylic acid, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, 2-perfluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, and 2-perfluorohexadecylethyl acrylate, and among these, butyl acrylate or butyl acrylate / 2-ethylhexyl acrylate is preferred.

[0078] The acrylic block copolymer is not particularly limited as long as it can exhibit the effects of the present invention. However, among the above, it is preferable that the acrylic block copolymer has a diblock structure consisting of a methyl methacrylate block-butyl acrylate block or a methyl methacrylate block-butyl acrylate / 2-ethylhexyl acrylate block, or a triblock structure consisting of a methyl methacrylate block-butyl acrylate block-methyl methacrylate block or a methyl methacrylate block-butyl acrylate / 2-ethylhexyl acrylate block-methyl methacrylate block.

[0079] In the acrylic block copolymer, the ratio of hard segments to soft segments is preferably in the range of 3:97 to 40:60 by mass, more preferably 5:95 to 35:65. The greater the proportion of soft segments, the more the vinyl chloride resin can be softened. However, if the proportion of hard segments is too low, the compatibility with vinyl chloride resin decreases as described above, resulting in poor moldability. On the other hand, the smaller the proportion of soft segments, the less efficient the vinyl chloride resin softening.

[0080] Examples of commercially available acrylic block copolymers include LA1892, LA4285, LA2270, LA2250, LA2140, LA2330, and LA3320, which are part of the LA series of Kuraray's Kurary (registered trademark), and M51, M52, and M22, which are part of the Nanostrength (registered trademark) series, manufactured by Arkema. Acrylic copolymers using butyl acrylate / 2-ethylhexyl acrylate as the soft segment are also commercially available as LK9243 and KL-LK9333, which are part of the LK series of Kuraray's Kurary (registered trademark).

[0081] The elastomer used in this embodiment preferably has a melt mass flow rate (MFR) measured in accordance with ISO 1133 at 190°C under a load of 2.16 kgf of 1 g / 10 min or more, more preferably 2 g / 10 min or more, and preferably 15 g / 10 min or less, and even more preferably 10 g / 10 min or less. When the resin composition of the present embodiment contains two or more elastomers, the MFR of the elastomers is a weighted average value.

[0082] In addition to the above, the elastomers that can be used include the elastomers described in paragraphs 0075 to 0088 of JP 2012-251061 A, the elastomers described in paragraphs 0101 to 0107 of JP 2012-177047 A, the elastomers described in paragraphs 0076 to 0087 of JP 2016-98242 A, and the elastomers described in paragraphs 0080 to 0087 of JP 2019-11514 A, the contents of which are incorporated herein by reference.

[0083] In this embodiment, it is preferable to use an epoxy group-containing elastomer (preferably the epoxy group-containing elastomer of the first embodiment) in combination with an acrylic block copolymer, which tends to improve fluidity and impact resistance in a well-balanced manner.

[0084] When the resin composition of the present embodiment contains an elastomer, the content thereof is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 7 parts by mass or more, still more preferably 10 parts by mass or more, relative to 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 20 parts by mass or less, and may be 15 parts by mass or less. By setting the content at or above the lower limit, impact resistance tends to be further improved, while by setting the content at or below the upper limit, fluidity tends to be improved. The resin composition of the present embodiment may contain only one type of elastomer, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0085] <Coloring agent> The resin composition of the present embodiment may contain a colorant. The colorant may be a pigment or a dye, but from the viewpoint of flame retardancy, a pigment is preferred, and carbon black is more preferred. For details of carbon black, please refer to paragraph 0021 of JP 2011-57977 A, the contents of which are incorporated herein by reference. Furthermore, when a colorant such as carbon black is blended into the resin composition of the present embodiment, it is preferable to form a masterbatch and then knead it with a polybutylene terephthalate resin, a polyethylene terephthalate resin, etc. For the masterbatch, a polyester resin is preferably used, a polyalkylene terephthalate resin is more preferably used, a polyethylene terephthalate resin and / or a polybutylene terephthalate resin is even more preferably used, and a polybutylene terephthalate resin is even more preferably used. The proportion of the colorant in the masterbatch is preferably 5% by mass or more, more preferably 10% by mass or more, and is preferably 50% by mass or less, more preferably 40% by mass or less.

[0086] When the resin composition of the present embodiment contains a colorant (preferably carbon black), the content thereof is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.4 parts by mass or more, and even more preferably 0.6 parts by mass or more, relative to 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin, and is preferably 5 parts by mass or less, and more preferably 4 parts by mass or less. The resin composition of the present embodiment preferably contains a colorant (preferably carbon black) in an amount of 0.8 to 1.5% by mass relative to 100% by mass of the resin composition. The resin composition of the present embodiment may contain only one colorant (preferably carbon black), or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0087] <Other ingredients> The resin composition of this embodiment may contain other components in addition to those described above, as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include thermoplastic resins other than polybutylene terephthalate resin and polyethylene terephthalate resin, and various resin additives. One type of other component may be contained, or two or more types may be contained in any combination and ratio. The total amount of these other components is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass, based on 100% by mass of the resin composition. Specific examples of the additives include ultraviolet absorbers, antistatic agents, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, and antibacterial agents. In addition, the resin composition of this embodiment can be blended with additives described in paragraphs 0047 to 0103 of WO 2021 / 241471 within the scope of the present invention, the contents of which are incorporated herein by reference. In the resin composition of the present embodiment, the total of the polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, and glass fiber preferably accounts for 80% by mass or more of the resin composition, more preferably 85% by mass or more, and may be 100% by mass or less. Furthermore, in the resin composition of the present embodiment, the polybutylene terephthalate resin, polyethylene terephthalate resin, silicone, glass fiber, and optionally blended reactive compound, stabilizer, release agent, elastomer, and colorant preferably account for 90% by mass or more of the resin composition, more preferably 95% by mass or more, and even more preferably 97% by mass or more. They may also account for 99% by mass or more, or 100% by mass or less.

[0088] The resin composition of this embodiment is molded into an ISO tensile test piece (4 mm thick) and subjected to a reciprocating sliding test under a load of 300 g. When this test piece is subjected to a reciprocating sliding test, the static friction coefficient is preferably 0.40 or less, more preferably 0.35 or less, and even more preferably 0.30 or less. There is no particular lower limit for the static friction coefficient, but a practical value is 0.10 or more. The resin composition of this embodiment is molded into an ISO tensile test piece (4 mm thick) and subjected to a reciprocating sliding test under a load of 300 g. When this test piece is subjected to a reciprocating sliding test, the coefficient of dynamic friction is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. There is no particular lower limit for the coefficient of dynamic friction, but a practical value is 0.05 or more. The static friction coefficient and dynamic friction coefficient are measured according to the description in the examples below.

[0089] <Method of manufacturing resin composition> The resin composition of this embodiment can be produced by a conventional method for preparing a resin composition (e.g., pellets). Typically, the components and various optional additives are thoroughly mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Alternatively, the resin composition of this embodiment can be prepared without premixing the components, or by premixing only a portion of the components, feeding the mixture into an extruder using a feeder and melt-kneading the mixture. For example, it is preferable to feed glass fibers into an extruder using a side feeder and melt-knead them. Alternatively, a masterbatch may be prepared by melt-kneading some of the components, such as silicone or a colorant, with a thermoplastic resin, and then blending the remaining components with the masterbatch and melt-kneading the resulting mixture. The thermoplastic resin to be used for the masterbatch is preferably a polyalkylene terephthalate resin, more preferably a polybutylene terephthalate resin and / or a polyethylene terephthalate resin, and even more preferably a polybutylene terephthalate resin.

[0090] <Method of manufacturing molded products> The resin composition or pellets of this embodiment are molded according to a known method. The method for producing the molded article is not particularly limited, and any molding method generally used for resin compositions can be used. Examples thereof include injection molding, ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted or other hollow molding, molding using a heat-insulating mold, molding using a rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding), extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding, blow molding, etc., among which injection molding is preferred. For details of the injection molding method, please refer to the description in paragraphs 0113 to 0116 of Japanese Patent No. 6183822, the contents of which are incorporated herein by reference. Furthermore, the mold temperature during molding such as injection molding is preferably 40 to 150°C.

[0091] <Application> The resin composition of this embodiment is used as a molded article formed from the resin composition or pellets. The uses of the resin composition and pellets are not particularly limited, and they can be widely used in applications where sliding properties are required. For example, they can be widely used indoors or outdoors as materials for electrical and electronic devices, vehicles, housing, and materials for manufacturing parts in other industrial fields. In this embodiment, vehicle exterior parts are preferred. Examples of vehicle exterior equipment parts include lamp housings, door mirrors, reflectors, bezels, extensions, connectors, ECU cases, housings for in-vehicle cameras and millimeter-wave radars, battery cases, sensor housings, etc. In this embodiment, the present invention can be preferably used for door mirror members. [Example]

[0092] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. If the measuring instruments used in the examples are difficult to obtain due to discontinuation or the like, measurements can be made using other instruments with equivalent performance.

[0093] 1.Raw materials The following raw materials were used: [Table 1]

[0094] Example 1, Comparative Examples 1 to 3 <Compound> The components shown in Table 1 were mixed uniformly in a tumbler mixer in the proportions shown in Table 2 (each component in Table 2 is expressed in mass %), with the exception of the glass fiber. The resulting mixture was fed into a twin-screw extruder ("TEX30α" manufactured by The Japan Steel Works, Ltd.) through the main feed port. The cylinder temperature of the first kneading section was set to 260°C, and the glass fiber was fed through a side feeder. The resin composition was melt-kneaded under conditions of a cylinder temperature setting of 260°C and a screw rotation speed of 200 rpm after the addition of the glass fiber, and then quenched in a water bath and pelletized using a pelletizer to obtain pellets of the resin composition.

[0095] <Bending properties> The pellets obtained above were dried at 110°C for 5 hours, and then injection-molded into 4 mm thick ISO tensile test specimens using an injection molding machine ("J85AD" manufactured by The Japan Steel Works, Ltd.) at a cylinder temperature of 265°C and a mold temperature of 80°C. In accordance with ISO178, the flexural strength (unit: MPa) and flexural modulus (unit: MPa) were measured at a temperature of 23°C using the above ISO tensile test pieces (4 mm thick).

[0096] <Reciprocating sliding test> The pellets obtained above were dried at 110°C for 5 hours and then injection-molded into 3.5 mm thick plate-shaped test specimens using an injection molding machine (Japan Steel Works, Ltd., "J50-ADS") at a cylinder temperature of 270°C and a mold temperature of 110°C. Furthermore, pin-shaped test specimens with a tip R2 (arc-shaped tip with a radius of 2 mm) were injection-molded using the same injection molding machine at a cylinder temperature of 280°C and a mold temperature of 130°C, using Reny N252-UX75 (polyamide MXD6) as the material to be slid against the plate-shaped test specimens. Using these test specimens, a load of 300 g was applied to the pin-shaped test specimen side, and the surface of the plate-shaped test specimen was slid back and forth 2000 times using a Tribogear Surface Property Tester Type: 38 (Shintokagaku Co., Ltd.). The static and dynamic friction coefficients at the final run were measured.

[0097] <Appearance> The pellets obtained above were dried at 110°C for 5 hours, and then injection-molded into a 2 mm thick grained (GR503) plate using an injection molding machine (Japan Steel Works, Ltd., "J100") at a cylinder temperature of 270°C and a mold temperature of 110°C. The appearance of the grained surface of this plate was visually evaluated. The evaluation was performed by five experts and judged by majority vote. A: It had an excellent appearance. B: Other than A above (poor appearance, etc.)

[0098] [Table 2]

[0099] As is clear from the above results, molded articles formed from the resin composition of the present invention maintained high mechanical strength while exhibiting excellent sliding properties and appearance (Example 1). In contrast, when no silicone was blended, or when the silicone content was low even if it was blended (Comparative Examples 1 to 3), the sliding properties were poor.

Claims

1. A resin composition comprising a polybutylene terephthalate resin, a polyethylene terephthalate resin, silicone, and glass fibers, a proportion of the polyethylene terephthalate resin in the total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin is more than 50 parts by mass and 99 parts by mass or less; A resin composition, wherein the proportion of silicone in the resin composition is 0.3 to 1 mass%.

2. The resin composition according to claim 1, wherein the proportion of the polyethylene terephthalate resin is 70 parts by mass or more and 90 parts by mass or less, based on 100 parts by mass of the total of the polybutylene terephthalate resin and the polyethylene terephthalate resin.

3. The resin composition according to claim 1 or 2, wherein the proportion of glass fibers in the resin composition is 40 to 70 mass%.

4. The resin composition according to claim 1 or 2, wherein the silicone comprises silicone oil.

5. a ratio of the polyethylene terephthalate resin to the total of 100 parts by mass of the polybutylene terephthalate resin and the polyethylene terephthalate resin is 70 parts by mass or more and 90 parts by mass or less; The proportion of glass fibers in the resin composition is 40 to 70% by mass, The resin composition according to claim 1 , wherein the silicone comprises a silicone oil.

6. Pellets of the resin composition of claim 1, 2 or 5.

7. A molded article formed from the resin composition of claim 1, 2 or 5.

8. A molded article formed from the pellets of claim 6.

9. 8. The molded article of claim 7, which is an exterior vehicle component.

10. The molded article according to claim 7, which is a door mirror member.

Images