Resin composition, pellet, and molded article

Abstract

To provide a resin composition excellent in antibacterial property and surface impact resistance and capable of providing a white molded article, and to provide a pellet and a molded article.SOLUTION: A silver-containing antibacterial agent, and titanium oxide, wherein the intrinsic viscosity of the resin component is 1. 0dL / g or more.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 thermoplastic polyester resin as a main component. [Background technology]

[0002] Thermoplastic polyester resins have excellent mechanical strength, electrical properties, and other physical and chemical characteristics. Therefore, they are used as engineering plastics in a wide range of applications, including automobiles, electrical and electronic devices, and sanitary areas such as toilet seats and bathroom fixtures. In recent years, the harmful effects of bacteria on the human body caused by the growth of bacteria in products made from these materials have become a problem. Furthermore, the use of antibacterial properties to add value to products is becoming increasingly common. While kneading commercially available antibacterial agents into thermoplastic polyester resins is one method for imparting antibacterial properties, this has not always been sufficient depending on the type of antibacterial agent. For this reason, thermoplastic polyester resin compositions with excellent antibacterial properties are being investigated. Specifically, Patent Document 1 discloses a composition comprising (A) a thermoplastic polyester resin and (B) an alkali metal salt, alkaline earth metal salt, or ammonium salt of zirconium phosphate, in which the ratio of phosphate ions to zirconium ions is 3 / 2, carrying silver ions and hydrogen ions, and then calcining the composition at 500 to 1300°C, and containing 0.1 to 5% by weight (based on the total composition) of an antibacterial agent represented by general formula (I). Ag a A b H c Zr2(PO4)3·nH2O (I) (In the formula, A is at least one ion selected from an alkali metal ion, an alkaline earth metal ion, and an ammonium ion; q is the valence of A; a and c are positive numbers; b is 0 or a positive number; q, a, b, and c are numbers that satisfy a+qb+c=1; and n is a number that satisfies 0≦n≦6.) (C) 1 to 30% by weight (based on the total composition) of a halogenated aromatic bisimide compound represented by general formula (II) [ka] (wherein R1 represents a divalent organic acid group, and at least one of R2 and R3 represents a divalent organic group having one or more halogen atoms X; n=1 to 4, n'=0 to 4) is disclosed. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-348444 Summary of the Invention [Problem to be solved by the invention]

[0004] As described above, antibacterial properties can be imparted to a thermoplastic polyester resin by blending an antibacterial agent containing silver into the thermoplastic polyester resin. On the other hand, sanitary parts, such as toilet seats, are often required to have surface impact resistance. In order to impart thermal stability to thermoplastic polyester resins, it is common to blend a stabilizer into them. However, the inventors have conducted research and found that blending a stabilizer into a thermoplastic polyester resin containing a silver-containing antibacterial agent can result in significant discoloration of the resulting resin composition. On the other hand, many applications requiring antibacterial properties involve sanitary parts, which require parts with a white base. The present invention aims to solve these problems and to provide a resin composition that has excellent antibacterial properties and surface impact resistance and is capable of producing white molded articles, as well as pellets and molded articles. [Means for solving the problem]

[0005] In light of the above-mentioned problems, the present inventors have conducted research and found that the above-mentioned problems can be solved by blending a thermoplastic polyester resin having an intrinsic viscosity of 1.0 dL / g or more with a silver-containing antibacterial agent and titanium oxide. Specifically, the above problems were solved by the following means. [1] A thermoplastic polyester resin having an intrinsic viscosity of 1.0 dL / g or more. Antibacterial agents containing silver Titanium oxide, A resin composition for use in sanitary parts. [2] The thermoplastic polyester resin includes a polybutylene terephthalate resin. The resin composition according to [1]. [3] The resin composition according to [1] or [2], wherein the antibacterial agent containing silver includes an inorganic silver-based antibacterial agent. [4] The thermoplastic polyester resin includes a polybutylene terephthalate resin, The resin composition according to any one of [1] to [3], wherein the silver-containing antibacterial agent includes an inorganic silver-based antibacterial agent. [5] Pellets of the resin composition according to any one of [1] to [4]. [6] A molded article formed from the resin composition according to any one of [1] to [5]. [7] A molded article formed from the pellets described in [5]. [8] The molded product according to [6], which is a part for sanitary use. [Effects of the Invention]

[0006] The present invention makes it possible to provide a resin composition that has excellent antibacterial properties and surface impact resistance and is capable of producing white molded articles, 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, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. In this specification, various physical properties and characteristic values ​​are those at 23°C unless otherwise specified. In this specification, unless otherwise specified, the weight average molecular weight and number average molecular weight are values ​​measured by GPC (gel permeation chromatography) using a Tosoh HLC-8320GPC EcoSEC column, tetrahydrofuran as a solvent, and Shodex KF-G, KF-805L x 3, KF-800D columns at a column temperature of 40°C and a flow rate of 1.2 mL / min, and detected at a detection wavelength of 254 nm, in terms of polystyrene. If the measurement methods, etc. described in the standards shown in this specification vary from year to year, they will be based on the standards in effect as of January 1, 2023, unless otherwise stated.

[0008] The resin composition of this embodiment is characterized by containing a thermoplastic polyester resin having an intrinsic viscosity of 1.0 dL / g or more, an antibacterial agent containing silver, and titanium oxide, and is intended for use in sanitary parts. By adopting this configuration, a resin composition is obtained that has excellent antibacterial properties and surface impact resistance, and is capable of providing white molded products. Antibacterial agents containing silver are widely used in sanitary parts, but due to its high reactivity, it was thought that silver would discolor the resin composition when a stabilizer was added. In this embodiment, we discovered that by adding titanium oxide, it is possible to provide a white molded product even if a stabilizer is not added and thermal discoloration due to retention occurs. Furthermore, by using a thermoplastic polyester resin with a high intrinsic viscosity, it was possible to improve the surface impact resistance that is reduced by adding titanium oxide.

[0009] <Thermoplastic polyester resin> The resin composition of the present embodiment contains a thermoplastic polyester resin having an intrinsic viscosity of 1.0 dL / g or more. By using a thermoplastic polyester resin having a high intrinsic viscosity, a molded article having excellent surface impact resistance can be obtained. The thermoplastic polyester resin is not particularly limited in terms of type, but preferably contains a polyalkylene terephthalate resin, more preferably contains a polyethylene terephthalate resin and / or a polybutylene terephthalate resin, and even more preferably contains a polybutylene terephthalate resin.

[0010] The polyalkylene terephthalate resin is a polyester obtained by polycondensation of terephthalic acid as a dicarboxylic acid compound with a diol, and may be either a homopolyester or a copolyester.

[0011] As the dicarboxylic acid compound constituting the polyalkylene terephthalate resin, a terphthalic acid compound or an ester-forming derivative thereof is preferably used. Aromatic dicarboxylic acids other than terephthalic acid can also be used in combination. Examples include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylisopropylidene-4,4'-dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, anthracene-2,5-dicarboxylic acid, anthracene-2,6-dicarboxylic acid, p-terphenylene-4,4'-dicarboxylic acid, and pyridine-2,5-dicarboxylic acid. These can be used in the polycondensation reaction as ester-forming derivatives such as dimethyl esters in addition to free acids. Of the above, isophthalic acid or its ester-forming derivatives are particularly preferred.

[0012] In addition, a small amount of terephthalic acid or the above-mentioned aromatic dicarboxylic acid may be used in combination with one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, or alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.

[0013] Examples of dihydroxy compounds constituting the polyalkylene terephthalate resin include aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexylene glycol, neopentyl glycol, 2-methylpropane-1,3-diol, diethylene glycol, and triethylene glycol, alicyclic diols such as cyclohexane-1,4-dimethanol, and mixtures thereof. Among these, 1,4-butanediol and ethylene glycol are particularly preferred.

[0014] It is also possible to copolymerize one or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Also usable are aromatic diols such as hydroquinone, resorcinol, naphthalenediol, dihydroxydiphenyl ether, and 2,2-bis(4-hydroxyphenyl)propane.

[0015] In addition to the above-mentioned bifunctional monomers, a small amount of a trifunctional monomer such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, or trimethylolpropane can be used in combination to introduce a branched structure, or a monofunctional compound such as a fatty acid can be used in combination to adjust the molecular weight.

[0016] The polyalkylene terephthalate resin is preferably one formed by polycondensation of terephthalic acid and a diol, i.e., one in which the polycondensate accounts for more than 50% by mass of the entire resin, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 99% by mass or more. The diol is preferably an aliphatic diol, preferably 1,4-butanediol or ethylene glycol, and more preferably 1,4-butanediol.

[0017] The amount of terminal carboxyl groups in the thermoplastic polyester resin (preferably 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 to 60 eq / ton or less, gas generation during melt molding of the resin composition tends to be more effectively suppressed. There is no particular lower limit for the amount of terminal carboxyl groups, but it is typically 3 eq / ton or more, preferably 5 eq / ton or more, and more preferably 10 eq / ton or more.

[0018] The amount of terminal carboxyl groups in a thermoplastic polyester resin is determined by dissolving 0.5 g of the resin in 25 mL of benzyl alcohol and titrating the solution with a 0.01 mol / L benzyl alcohol solution of sodium hydroxide. The amount of terminal carboxyl groups can be adjusted by any conventional method, such as adjusting the polymerization conditions, such as the raw material charge ratio, polymerization temperature, and pressure reduction, or by reacting a terminal blocking agent.

[0019] The intrinsic viscosity of the thermoplastic polyester resin (preferably polybutylene terephthalate resin) is 1.00 dL / g or more, preferably 1.05 dL / g or more, and more preferably 1.10 dL / g or more. By setting it to the lower limit or more, deterioration of physical properties such as strength tends to be effectively suppressed. Furthermore, the intrinsic viscosity of the thermoplastic polyester resin (preferably polybutylene terephthalate resin) is preferably 1.30 dL / g or less, more preferably 1.25 dL / g or less, even more preferably 1.20 dL / g or less, and even more preferably 1.15 dL / g or less. By setting it to the upper limit or less, deterioration of fluidity tends to be effectively suppressed and thermal stability during retention tends to be further improved.

[0020] The intrinsic viscosity is measured by the following method. Thermoplastic polyester resin pellets are dissolved in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (1 / 1 by mass) by stirring at 110°C for 1 hour to a concentration of 1.00 g / dL. The solution is then cooled to 30°C. Using a fully automatic solution viscometer, the time it takes for the sample solution and the solvent alone to fall at 30°C is measured, and the intrinsic viscosity is calculated using the formula: Intrinsic viscosity=((1+4K H η sp ) 0.5 -1) / (2K H C) where η sp =η / η0-1, where η is the time it takes for the sample solution to fall, η0 is the time it takes for the solvent alone to fall, C is the concentration of the sample solution (g / dL), and K H is Huggins' constant. K H was set to 0.33. The fully automatic solution viscometer used is manufactured by Shibayama Scientific Co., Ltd. When the resin composition of the present embodiment contains two or more thermoplastic polyester resins, the intrinsic viscosity is the intrinsic viscosity of the mixture.

[0021] The catalyst used in carrying out the esterification reaction may be a conventionally known catalyst, such as a titanium compound, a tin compound, a magnesium compound, or a calcium compound. Among these, titanium compounds are particularly preferred. Specific examples of titanium compounds used as esterification catalysts include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

[0022] The polybutylene terephthalate resin may be a polybutylene terephthalate resin modified by copolymerization (hereinafter, also referred to as a "modified polybutylene terephthalate resin"), and specific preferred copolymers thereof include polyester ether resins copolymerized with polyalkylene glycols (particularly polytetramethylene glycol), dimer acid copolymerized polybutylene terephthalate resins, and isophthalic acid copolymerized polybutylene terephthalate resins.

[0023] When a polyester ether resin copolymerized with polytetramethylene glycol is used as the modified polybutylene terephthalate resin, 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%. When a dimer acid copolymerized polybutylene terephthalate resin is used as the modified 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. When an isophthalic acid copolymerized polybutylene terephthalate resin is used as the modified 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. Among the modified polybutylene terephthalate resins, polyester ether resins copolymerized with polytetramethylene glycol and isophthalic acid copolymerized polybutylene terephthalate resins are preferred.

[0024] The content of the thermoplastic resin (preferably a thermoplastic polyester resin, more preferably a polybutylene terephthalate resin) in the resin composition of this embodiment is preferably 70% by mass or more, more preferably 75% by mass or more, and even more preferably 80% by mass or more, based on 100% by mass of the resin composition. Depending on the application, etc., it may be 85% by mass or more, 90% by mass or more, or 95% by mass or more, or preferably 99% by mass or less, and may be 95% by mass or less, or 90% by mass or less, depending on the application, etc. The resin composition of the present embodiment may contain only one type of thermoplastic resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0025] <Antibacterial agent containing silver> The resin composition of the present embodiment contains an antibacterial agent containing silver. By including the antibacterial agent, a resin composition or molded article having excellent antibacterial properties can be obtained. The silver-containing antibacterial agent of this embodiment is preferably an inorganic antibacterial agent that releases silver ions. More specifically, the silver-containing antibacterial agent of this embodiment is preferably one in which silver (preferably silver ions) is supported on zeolite, glass, a phosphate compound, or the like, and the antibacterial effect is exhibited by the release of silver (preferably silver ions). The silver-containing antibacterial agent may carry metals other than silver in addition to silver (preferably silver ions), such as copper (preferably copper ions) and zinc (preferably zinc ions). The silver-containing antibacterial agent in this embodiment preferably includes a glass-based antibacterial agent.

[0026] The silver-containing antibacterial agent used in this embodiment is also preferably substantially free of zeolite. "Substantially free" means that the zeolite content is less than 10 parts by mass, preferably 1 part by mass or less, more preferably 0.1 parts by mass or less, and even more preferably 0.1 parts by mass or less, when the total silver-containing antibacterial agent is 100 parts by mass.

[0027] An example of a glass-based antibacterial agent is soluble glass that supports silver (preferably silver ions) so that the silver (preferably silver ions) can be eluted. Examples of soluble glass include P2O5-RO-R2O glass and B2O3-SiO2-R2O glass (RO is an oxide of an alkaline earth metal such as CaO or MgO, and R2O is an alkali metal oxide such as Li2O, Na2O, or K2O).

[0028] The average particle size of the silver-containing antibacterial agent in this embodiment is preferably 20 μm or less, more preferably 15 μm or less, and may be 1.5 μm or less, or may be 0.01 μm or more. The average particle size refers to the diameter of a sphere having the same volume as the silver-containing antibacterial agent, and this value is the number average particle size.

[0029] The silver-containing antibacterial agent may be blended into a resin composition as a masterbatch. When the silver-containing antibacterial agent is made into a masterbatch, the resin used for the masterbatch is preferably a thermoplastic polyester resin, more preferably a polyethylene terephthalate resin and / or a polybutylene terephthalate resin. The concentration of the silver-containing antibacterial agent when made into a masterbatch is preferably 1 to 50 mass %, more preferably 5 to 30 mass %. In particular, when the resin composition of the present embodiment contains a flame retardant, it is preferable to also form the silver-containing antibacterial agent into a masterbatch, which tends to further improve the productivity of the resin composition (e.g., pellets).

[0030] Commercially available products include "Bactekiller" manufactured by Fuji Chemical Co., Ltd. (BM-102NS(SB), BM-103CL, BM-103CK, BM-103NA, FK-68, etc.), "Million Guard" manufactured by Koa Glass Co., Ltd., and "Novalon" manufactured by Toagosei Co., Ltd.

[0031] The content of the silver-containing antibacterial agent in the resin composition of this embodiment is 0.1 parts by mass or more, preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.4 parts by mass or more, relative to 100 parts by mass of the total thermoplastic polyester resin. By setting the content at or above the lower limit, the antibacterial properties of the resulting molded article tend to be further improved. The upper limit of the content of the silver-containing antibacterial agent is 10.0 parts by mass or less, preferably 3.0 parts by mass or less, more preferably 2.5 parts by mass or less, more preferably 2.0 parts by mass or less, even more preferably 1.5 parts by mass or less, even more preferably 1.0 parts by mass or less, even more preferably 0.9 parts by mass or less, and even more preferably 0.6 parts by mass or less, relative to 100 parts by mass of the total thermoplastic polyester resin. Setting the content at or below the upper limit tends to more effectively suppress color tone changes in the resulting molded article, and also to further improve retention heat stability. In addition, when the antibacterial agent containing silver is made into a masterbatch, the amount of resin used in the masterbatch is not included in the above content. The resin composition of the present embodiment may contain only one type of silver-containing antibacterial agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0032] <Titanium oxide> The resin composition of the present embodiment contains titanium oxide, which allows the production of a white molded product.

[0033] In this embodiment, the titanium oxide may be rutile-type titanium oxide particles or anatase-type titanium oxide particles. The titanium oxide preferably has its surface treated with a surface treatment agent. The titanium oxide is typically titanium dioxide.

[0034] In this embodiment, the resin composition preferably contains 0.1 to 10 parts by mass of titanium oxide per 100 parts by mass of the thermoplastic polyester resin. By setting the content at or above the lower limit, the shielding properties tend to be improved. On the other hand, by setting the content at or below the upper limit, the deterioration of the physical properties of the molded product can be suppressed. In this embodiment, the content of titanium oxide is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.6 parts by mass or more, and even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of thermoplastic polyester resin. In this embodiment, the content of titanium oxide is preferably 10 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 6.0 parts by mass or less, even more preferably 5.0 parts by mass or less, and even more preferably 4.0 parts by mass or less, relative to 100 parts by mass of thermoplastic polyester resin. By setting the content at or above the lower limit, residence heat stability tends to be further improved. By setting the content at or below the upper limit, surface impact resistance tends to be further improved. The resin composition of the present embodiment may contain only one type of titanium oxide, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0035] <Halogen compounds> The resin composition of the present embodiment contains a halogen compound. By including a halogen compound, a resin composition or a molded article having excellent color stability can be obtained. The halogen compound used in the present embodiment preferably contains at least one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, more preferably contains at least one selected from the group consisting of a fluorine atom, a chlorine atom, and a bromine atom, and further preferably contains a bromine atom and / or a fluorine atom. An example of the halogen compound in this embodiment is one that contains a fluorine atom, and more preferably contains polytetrafluoroethylene. When a compound containing a fluorine atom is used as the halogen compound, the type thereof is not particularly limited, but examples thereof include homopolymers or copolymers of fluorine-containing monomers such as tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, perfluoroalkyl vinyl ether, etc. Specific examples include homopolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, and copolymers such as tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, and ethylene-chlorotrifluoroethylene copolymer. Another example of the halogen compound in this embodiment is one that contains a bromine atom, and more preferably contains a bromine-based flame retardant.

[0036] When a brominated flame retardant is used as the halogen compound, the type thereof is not particularly limited, but brominated phthalimide, brominated poly(meth)acrylate, brominated polycarbonate, brominated epoxy, and brominated polystyrene are preferred, brominated phthalimide, brominated poly(meth)acrylate, brominated polycarbonate, and brominated epoxy are more preferred, brominated poly(meth)acrylate, brominated polycarbonate, and brominated epoxy are even more preferred, and brominated poly(meth)acrylate is even more preferred. In particular, brominated poly(meth)acrylates are more easily mixed with antimony compounds and can achieve better flame retardancy.

[0037] The brominated flame retardant preferably has a free bromine content of 0.05% by mass or more, and preferably 0.20% by mass or less. By setting the content within these ranges, the heat resistance stability of the resin composition tends to be further improved. The brominated flame retardant also preferably has a bromine atom content of 0.001% by mass or more, and preferably 0.20% by mass or less. By setting the content within these ranges, the mold corrosion resistance during molding tends to be further improved.

[0038] The brominated phthalimide is preferably one represented by formula (1). [ka] (In formula (1), D represents an alkylene group, an arylene group, or a group formed by combining two or more of -S(=O)2-, -C(=O)-, and -O-. i is an integer of 1 to 4.)

[0039] In formula (1), D represents a group consisting of a combination of two or more of an alkylene group, an arylene group, -S(=O)2-, -C(=O)-, and -O-; a group consisting of a combination of an alkylene group or an arylene group with at least one of -S(=O)2-, -C(=O)-, and -O- is preferred; a group consisting of a combination of an alkylene group or an arylene group with one of -S(=O)2-, -C(=O)-, and -O- is more preferred; and an alkylene group is even more preferred. The group consisting of a combination of an alkylene group and -O- is intended to include, for example, a combination of two alkylene groups and one -O- (the same applies to other combinations). The alkylene group represented by D is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group or a butylene group. The arylene group is preferably a phenylene group. i is an integer of 1 to 4, and is preferably 4.

[0040] Examples of the brominated phthalimide represented by formula (1) include N,N'-(bistetrabromophthalimide)ethane, N,N'-(bistetrabromophthalimide)propane, N,N'-(bistetrabromophthalimide)butane, N,N'-(bistetrabromophthalimide)diethyl ether, N,N'-(bistetrabromophthalimide)dipropyl ether, N,N'-(bistetrabromophthalimide)dibutyl ether, N,N'-(bistetrabromophthalimide)diphenylsulfone, N,N'-(bistetrabromophthalimide)diphenyl ketone, and N,N'-(bistetrabromophthalimide)diphenyl ether.

[0041] The brominated phthalimide represented by formula (1) is preferably a brominated phthalimide represented by formula (2). [ka] (In formula (2), i is an integer of 1 to 4.) i is an integer of 1 to 4, and is preferably 4.

[0042] The brominated poly(meth)acrylate is preferably a polymer obtained by polymerizing a bromine atom-containing benzyl (meth)acrylate alone, copolymerizing two or more types of bromine atom-containing benzyl (meth)acrylate, or copolymerizing the bromine atom with another vinyl monomer. The bromine atoms are attached to benzene rings, and the number of bromine atoms attached is preferably 1 to 5, and more preferably 4 to 5, per benzene ring.

[0043] Examples of the benzyl acrylate containing a bromine atom include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromobenzyl acrylate, and mixtures thereof. Examples of the benzyl methacrylate containing a bromine atom include methacrylates corresponding to the above-mentioned acrylates.

[0044] Specific examples of other vinyl monomers that can be copolymerized with the bromine atom-containing benzyl (meth)acrylate include acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and benzyl acrylate; methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and benzyl methacrylate; unsaturated carboxylic acids or anhydrides thereof such as styrene, acrylonitrile, fumaric acid, and maleic acid; vinyl acetate; and vinyl chloride.

[0045] These are usually used in an equimolar amount or less, particularly preferably 0.5 times or less, of the amount of benzyl (meth)acrylate containing a bromine atom.

[0046] Furthermore, vinyl monomers such as xylene diacrylate, xylene dimethacrylate, tetrabromxylene diacrylate, tetrabromxylene dimethacrylate, butadiene, isoprene, and divinylbenzene can also be used, and these can usually be used in an amount of 0.5 times or less by mole relative to the bromine atom-containing benzyl acrylate or benzyl methacrylate.

[0047] The brominated poly(meth)acrylate is preferably a polymer obtained by polymerizing a bromine atom-containing (meth)acrylate monomer, particularly benzyl (meth)acrylate, alone or by copolymerizing two or more of them, or by copolymerizing them with other vinyl monomers. The bromine atoms are attached to the benzene ring, and the number of bromine atoms attached is preferably 1 to 5, more preferably 4 to 5, per benzene ring.

[0048] As the brominated poly(meth)acrylate, pentabromobenzyl poly(meth)acrylate is preferred because of its high bromine content.

[0049] The molecular weight of the brominated poly(meth)acrylate is optional and may be appropriately selected and determined, but the weight-average molecular weight (Mw) is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 15,000 or more, even more preferably 20,000 or more, and even more preferably 25,000 or more. By setting the weight-average molecular weight at or above the lower limit, molded articles with higher mechanical strength tend to be obtained. Furthermore, the upper limit of the weight-average molecular weight (Mw) is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, even more preferably 50,000 or less, and even more preferably 35,000 or less. By setting the weight-average molecular weight at or below the upper limit, the flowability of the resin composition tends to be further improved.

[0050] Specifically, the brominated polycarbonate is preferably a brominated polycarbonate obtained from brominated bisphenol A, particularly tetrabromobisphenol A. Examples of the terminal structure include a phenyl group, a 4-t-butylphenyl group, and a 2,4,6-tribromophenyl group, and particularly, those having a 2,4,6-tribromophenyl group in the terminal group structure are preferred.

[0051] The average number of carbonate structural units in the brominated polycarbonate may be appropriately selected and determined, but is preferably 2-30, more preferably 3-15, and even more preferably 3-10.

[0052] The molecular weight of the brominated polycarbonate is optional and may be appropriately selected and determined, but preferably has a viscosity average molecular weight of 1,000 to 20,000, more preferably 2,000 to 10,000.

[0053] The brominated polycarbonate obtained from the above brominated bisphenol A can be obtained, for example, by a conventional method of reacting brominated bisphenol with phosgene. The end-capping agent includes an aromatic monohydroxy compound, which may be substituted with a halogen or an organic group.

[0054] Specific preferred examples of the brominated epoxy include bisphenol A type brominated epoxy compounds, such as tetrabromobisphenol A epoxy compounds and glycidyl brominated bisphenol A epoxy compounds.

[0055] The molecular weight of the brominated epoxy compound is optional and may be appropriately selected and determined. However, the weight-average molecular weight (Mw) is preferably 3,000 or more, more preferably 10,000 or more, even more preferably 13,000 or more, even more preferably 15,000 or more, and even more preferably 18,000 or more. By setting the Mw at or above the lower limit, molded articles with higher mechanical strength tend to be obtained. The upper limit of the weight-average molecular weight (Mw) is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 78,000 or less, even more preferably 75,000 or less, even more preferably 70,000 or less, and may even be 50,000 or less, 30,000 or less, or 25,000 or less. Setting the Mw at or below the upper limit tends to further improve the flowability of the resin composition. The brominated epoxy compound preferably has an epoxy equivalent of 3,000 to 40,000 g / eq, more preferably 4,000 to 35,000 g / eq, and particularly preferably 10,000 to 30,000 g / eq.

[0056] Brominated epoxy oligomers can also be used in combination with the brominated epoxy. In this case, for example, by using an oligomer with an Mw of 5,000 or less in a proportion of about 50% by mass or less, flame retardancy, mold releasability, and flowability can be appropriately adjusted. The bromine atom content in the brominated epoxy compound is optional, but to provide sufficient flame retardancy, it is usually 10% by mass or more, preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit is 60% by mass, and preferably 55% by mass or less.

[0057] The brominated polystyrene preferably includes a brominated polystyrene containing a constitutional unit represented by formula (3). [ka] (In formula (3), t is an integer of 1 to 5, and n is the number of constitutional units.)

[0058] Brominated polystyrene can be produced by either brominating polystyrene or polymerizing brominated styrene monomers. Polymerization of brominated styrene is preferred because it contains a smaller amount of free bromine atoms. In formula (3), the CH group to which the brominated benzene is bonded may be substituted with a methyl group. Brominated polystyrene may also be a copolymer copolymerized with other vinyl monomers. Examples of vinyl monomers in this case include styrene, α-methylstyrene, (meth)acrylonitrile, methyl (meth)acrylate, butadiene, and vinyl acetate. Brominated polystyrene may be used alone or as a mixture of two or more different structures, and may contain units derived from styrene monomers with different bromine numbers in a single molecular chain.

[0059] Specific examples of brominated polystyrene include poly(4-bromostyrene), poly(2-bromostyrene), poly(3-bromostyrene), poly(2,4-dibromostyrene), poly(2,6-dibromostyrene), poly(2,5-dibromostyrene), poly(3,5-dibromostyrene), poly(2,4,6-tribromostyrene), poly(2,4,5-tribromostyrene), poly(2,3,5-tribromostyrene), and poly(4-bromo-α-methylstyrene). Examples of suitable styrene copolymers include poly(2,4-dibromostyrene), poly(2,4-dibromo-α-methylstyrene), poly(2,5-dibromo-α-methylstyrene), poly(2,4,6-tribromo-α-methylstyrene), and poly(2,4,5-tribromo-α-methylstyrene), and poly(2,4,6-tribromostyrene), poly(2,4,5-tribromostyrene), and polydibromostyrene and polytribromostyrene containing an average of 2 to 3 bromine groups in the benzene ring are particularly preferred.

[0060] The brominated polystyrene preferably has the number n (average degree of polymerization) of structural units in formula (3) of 30 to 1,500, more preferably 150 to 1,000, and particularly preferably 300 to 800. If the average degree of polymerization is less than 30, blooming is likely to occur, while if it exceeds 1,500, poor dispersion is likely to occur and mechanical properties are likely to deteriorate. The weight-average molecular weight (Mw) of the brominated polystyrene is preferably 5,000 to 500,000, more preferably 10,000 to 500,000, even more preferably 10,000 to 300,000, even more preferably 10,000 to 100,000, and even more preferably 10,000 to 70,000. In particular, in the case of the above-mentioned brominated polystyrene, the weight average molecular weight (Mw) is preferably 50,000 to 70,000, and in the case of brominated polystyrene produced by a polymerization method, the weight average molecular weight (Mw) is preferably about 10,000 to 30,000.

[0061] The bromine concentration in the brominated flame retardant is preferably 45% by mass or more, more preferably 48% by mass or more, even more preferably 50% by mass or more, and may be 55% by mass or more, or may be 60% by mass or more. By setting the bromine concentration at or above the lower limit, the flame retardancy of the molded article tends to be effectively improved. The upper limit of the bromine concentration is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and may be 73% by mass or less.

[0062] The content of the halogen compound in the resin composition of this embodiment is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 0.7 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of the total thermoplastic polyester resin. When flame retardancy is to be imparted to the resin composition, the content is more preferably 5 parts by mass or more, even more preferably 8 parts by mass or more, and even more preferably 10 parts by mass or more. By setting the content at or above the lower limit, the flame retardancy of the resulting molded article tends to be further improved and color change tends to be more effectively suppressed. Furthermore, the upper limit of the content of the halogen compound is 30 parts by mass or less, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of the total thermoplastic polyester resin. When the resin composition is used for applications that do not require high flame retardancy, the content is more preferably 10 parts by mass or less, even more preferably 7 parts by mass or less, even more preferably 5 parts by mass or less, particularly preferably 4 parts by mass or less, and even particularly preferably 3 parts by mass or less. By ensuring that the content is equal to or less than the upper limit, changes in color tone of the resulting molded product tend to be more effectively suppressed, and decreases in physical properties such as strength tend to be effectively suppressed. The resin composition of the present embodiment may contain only one halogen compound or may contain two or more halogen compounds. When two or more halogen compounds are contained, the total amount is preferably in the above range.

[0063] <Other ingredients> The resin composition of the present embodiment may contain other components in addition to those described above, as necessary, as long as the desired physical properties are not significantly impaired. The other components may be contained alone or in any combination and ratio of two or more. Examples of other components include reinforcing fillers and resin additives. Specific examples of resin additives include flame retardant aids, release agents, colorants (pigments, dyes), nucleating agents, reactive compounds, antistatic agents, antifogging agents, antiblocking agents, flow improvers, plasticizers, and dispersants. The total amount of these other components is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, and even more preferably 0 to 3% by mass, based on 100% by mass of the resin composition. In the resin composition of this embodiment, the total amount of the thermoplastic polyester resin, the antibacterial agent containing silver, titanium oxide, and other components that are blended as necessary is 100% by mass. In the resin composition of this embodiment, the thermoplastic polyester resin, the silver-containing antibacterial agent, and the titanium oxide preferably account for 90% by mass or more of the resin composition, more preferably 95% by mass or more, even more preferably 97% by mass or more, and even more preferably 99% by mass or more, and is 100% by mass or less.

[0064] The resin composition of the present embodiment may or may not contain a stabilizer. The stabilizer preferably contains one or more compounds selected from the group consisting of thioether compounds, hindered phenol compounds, and phosphite compounds, and examples thereof include one or more compounds selected from the group consisting of hindered phenol compounds and phosphite compounds. The resin composition of the present embodiment is preferably substantially free of stabilizers, which means, for example, that the stabilizer content is less than 0.001 parts by mass, or may be less than 0.0001 parts by mass, or may be 0 parts by mass, per 100 parts by mass of the thermoplastic polyester resin. If a stabilizer is not blended, discoloration occurs due to retention of the resin composition, but this can be compensated for by blending titanium oxide. In particular, in this embodiment, by blending titanium oxide in order to achieve whiteness, a configuration can be made that is substantially free of stabilizers.

[0065] <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. A masterbatch may be prepared by melt-kneading some of the components of the silver-containing antibacterial agent or flame-retardant auxiliary with a thermoplastic resin, and then blending the remaining components with this to melt-knead. The reinforcing filler (particularly glass fiber) is preferably fed from a side feeder midway through the cylinder of the extruder. The heating temperature during melt-kneading can usually be selected appropriately from the range of 220 to 300°C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration that takes shear heat generation, etc. into consideration.

[0066] <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.

[0067] <Application> The resin composition of the present 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 as materials for manufacturing parts in home appliances, electrical and electronic equipment, automobiles, housing, and other industrial fields. More specifically, it is preferably used for sanitary use parts such as kitchens, washrooms, toilets and other wet area parts. [Example]

[0068] 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.

[0069] 1.Raw materials The following raw materials were used: [Table 1]

[0070] <Free bromine content> The free bromine content was quantified by the combustion ion chromatography method described in paragraph 0083 of JP 2013-057009 A. Specifically, the brominated flame retardant or resin composition was heated under an argon atmosphere at 270°C for 10 minutes, and the amount of bromine generated was measured. The resin composition was heated using an automatic sample combustion apparatus "AQF-100" manufactured by Mitsubishi Chemical Analytech Co., Ltd., and the amount of bromine generated by heating the resin composition was measured using an apparatus "ICS-90" manufactured by Nippon Dionex Co., Ltd.

[0071] 2. Examples 1 to 8 and Comparative Examples 1 to 13 <Compound> The components shown in Table 1 were uniformly mixed in a tumbler mixer in the proportions shown in Tables 2 to 4 (each component in Tables 2 to 4 is shown in parts by mass). The resulting mixture was fed to a twin-screw extruder ("TEX30α" manufactured by The Japan Steel Works, Ltd.) through the main feed port. The resin composition was melt-kneaded in the first kneading section under conditions of a cylinder temperature setting of 260°C and a screw rotation speed of 200 rpm, and then quenched in a water bath and pelletized using a pelletizer to obtain pellets of the resin composition.

[0072] <color tone> The pellets obtained above were used in an injection molding machine (NEX-80, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce molded pieces (length 100 mm x width 100 mm x thickness 2 mm) under the conditions of a resin temperature of 250 °C, a mold temperature of 80 °C, and a cycle time of 45 s. The color tone of the obtained plate was measured using a spectrophotometer CM-36dg manufactured by Konica Minolta. * , a * , b * ) was measured. * The value of is 87 or more, a * The value of is in the range of -1.0 to 1.0, b * The values ​​were categorized as A if they were in the range of -1.0 to 1.0, B if two values ​​were within the range but one value was outside the range, and C if two or more values ​​were outside the range.

[0073] <Surface impact resistance> The pellets obtained above were used in an injection molding machine (NEX-80, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce molded pieces (length 100 mm × width 100 mm × thickness 2 mm) under conditions of a resin temperature of 250° C. and a mold temperature of 80° C. The impact resistance of the obtained plates was confirmed in accordance with ASTM D2794 using a DuPont impact tester (H-200, manufactured by Toyo Seiki Co., Ltd.). A 2000g weight was used to check the impact resistance from a drop distance of 150cm. The test was conducted with N=5, and specimens that showed no damage were rated A, specimens that showed damage in 1-2 specimens were rated B, and specimens that showed damage in 3 or more specimens were rated C.

[0074] <Antibacterial> The pellets obtained above were used in an injection molding machine (NEX-80, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce molded pieces (length 100 mm × width 100 mm × thickness 2 mm) under conditions of a resin temperature of 250° C. and a mold temperature of 80° C. The obtained molded pieces were cut into lengths of 50 mm × width 50 mm to obtain test pieces. Antibacterial testing was conducted in accordance with JIS Z 2801. A test specimen was placed in a petri dish, 0.4 mL of Escherichia coli or Staphylococcus epidermidis test bacteria solution was dropped on it, and a film (40 mm x 40 mm) was placed over the dish, which was then covered with a lid. The dish was then left to stand at 35°C and 90% RH or higher for 24 hours for incubation. Then, 10 mL of lecithin-sorbate 80-added soybean-casein-digest agar (SCDLP) medium was added, and the test bacteria were washed out from the film and test specimen. The number of bacteria in the liquid was measured using the agar plate culture method, and the antibacterial activity value was calculated according to formula (a). Formula (a) Antibacterial activity value = log(1cm of untreated sample) 2 Number of viable bacteria per 1cm of processed sample after incubation) - log(1cm of processed sample) 2 (number of viable bacteria per 100ml after incubation) Antibacterial activity value ≧ 2.0:+ Antibacterial Antibacterial activity value < 2.0: No antibacterial activity

[0075] Before conducting the above antibacterial test, the test piece was (Water resistance) Immerse in 50±10mL of deionized or distilled water at room temperature for 16 to 18 hours, or (Light resistance) 10±0.5 hours of exposure to light using a xenon weather meter, or 8±0.5 hours of exposure to light using a sunshine weather meter Pre-processing of (1) E. coli, water-resistant (2) E. coli, light-resistant (3) Staphylococcus aureus, water-resistant (4) Staphylococcus aureus, light-resistant In the four conditions, Those whose antibacterial activity value was ≥ 2.0 under all conditions were rated as A, and those whose antibacterial activity value was < 2.0 under any condition were rated as B.

[0076] <Retention thermal stability> The pellets obtained above were used in an injection molding machine (NEX-80, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce a "retention molded plate" (length 100 mm x width 100 mm x thickness 2 mm) under conditions of a cylinder temperature of 270°C, a mold temperature of 80°C, and a cycle time of 150 s. The pellets obtained above were also used in an injection molding machine (NEX-80, manufactured by Nissei Plastic Industrial Co., Ltd.) to produce a "reference plate" (length 100 mm x width 100 mm x thickness 2 mm) under conditions of a cylinder temperature of 270°C, a mold temperature of 80°C, and a cycle time of 45 s. The color tone of the obtained plate was measured using a spectrophotometer (CM-36dg, manufactured by Konica Minolta) to determine the color tone (L * , a * , b * The color difference ΔE of the "retention molded plate" relative to the "reference plate" was calculated, and a ΔE of less than 2 was rated A, a ΔE of 2 or more but less than 4 was rated B, and a ΔE of 4 or more was rated C.

[0077] [Table 2]

[0078] [Table 3]

[0079] [Table 4]

[0080] As is clear from the above results, the resin compositions of the present invention were excellent in antibacterial properties and surface impact resistance, and were able to provide white molded articles (Examples 1 to 8). In particular, by precisely adjusting the type of antibacterial agent, the intrinsic viscosity of the polyester resin, and the amount of titanium oxide blended, molded products with excellent retention stability during molding were obtained (comparison of Examples 3, 4, and 5 with other Examples). Furthermore, by precisely adjusting the amount of titanium oxide blended, molded products with excellent surface impact resistance were obtained while maintaining whiteness (comparison of Examples 7 and 8 with other Examples).

[0081] In the above table, the content of "antibacterial agent" means the content of the antibacterial agent itself in the resin composition, and does not include resin components in which the antibacterial agent is masterbatched.

Claims

1. a thermoplastic polyester resin having an intrinsic viscosity of 1.0 dL / g or more; Antibacterial agents containing silver Titanium oxide, A resin composition for use in sanitary parts.

2. The thermoplastic polyester resin includes a polybutylene terephthalate resin. The resin composition according to claim 1.

3. The resin composition according to claim 1 , wherein the silver-containing antibacterial agent comprises an inorganic silver-based antibacterial agent.

4. the thermoplastic polyester resin includes a polybutylene terephthalate resin, The resin composition according to claim 1 , wherein the silver-containing antibacterial agent comprises an inorganic silver-based antibacterial agent.

5. Pellets of the resin composition according to any one of claims 1 to 4.

6. A molded article formed from the resin composition according to any one of claims 1 to 4.

7. A molded article formed from the pellets of claim 5.

8. The molded article according to claim 6, which is a part for sanitary use.