Resin composition, pellet, and molded article

Abstract

To provide a resin composition with superior flame retardancy, as well as a pellet and a molded article produced from the resin composition.SOLUTION: A resin composition according to the present disclosure comprises 0.001 to 0.40 pt.mass of an ionic liquid containing an aromatic sulfonate per 100 pts.mass of a polycarbonate resin, and has a melt volume rate (MVR) of 5 cm3 / 10 min or more and 20 cm3 / 10 min or less, measured at 300°C under a load of 1.2 kg.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 polycarbonate resin as a main component. [Background technology]

[0002] Polycarbonate resin has excellent mechanical and thermal properties, and by imparting flame retardancy, it is used in a variety of applications, mainly in the fields of office automation equipment and electronic and electrical equipment. In recent years, with the trend toward thinner and lighter walls in applications such as office automation equipment and home appliances, there has been an increasing demand for resin materials with high impact resistance and high flame retardancy. Specifically, Patent Document 1 discloses a thermoplastic resin composition containing 3 to 30 parts by mass of a phosphate ester compound (C) and 0.01 to 2 parts by mass of a fluoropolymer (D) relative to a total of 100 parts by mass of a polycarbonate resin consisting of 60 to 95% by mass of a polycarbonate resin and 5 to 40% by mass of an ABS resin (B) produced by bulk polymerization, wherein the ABS resin (B) has a glass transition temperature in the range of 95 to 108°C. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-227436 Summary of the Invention [Problem to be solved by the invention]

[0004] The resin composition described in Patent Document 1 is said to have excellent flame retardancy. However, with recent technological innovations, new materials with excellent flame retardancy are required. The present invention aims to solve the above problems and to provide a resin composition having excellent flame retardancy, as well as pellets and molded articles formed from the resin composition. [Means for solving the problem]

[0005] In view of the above-mentioned problems, the present inventors have conducted research and found that the above-mentioned problems can be solved by blending an ionic liquid containing an aromatic sulfonate and adjusting the fluidity of a resin composition. Specifically, the above problems were solved by the following means. [1] A resin composition comprising 0.001 to 0.40 parts by mass of an ionic liquid containing an aromatic sulfonate per 100 parts by mass of a polycarbonate resin, The melt volume rate (MVR) of the resin composition measured at 300°C under a load of 1.2 kg is 5 cm 3 / 20cm for more than 10 minutes 3 / 10 minutes or less. [2] The resin composition according to [1], further comprising an anti-dripping agent in an amount of 0.01 to 3 parts by mass per 100 parts by mass of the polycarbonate resin. [3] The resin composition according to [1] or [2], wherein the ionic liquid containing an aromatic sulfonate contains a cation represented by formula (K): X + (R y )4(K) (In formula (K), X represents a nitrogen atom or a phosphorus atom, and R y each independently represents a hydrocarbon group. [4] The resin composition according to [3], wherein in formula (K), X represents a phosphorus atom. [5] The resin composition according to any one of [1] to [4], wherein the ionic liquid containing an aromatic sulfonate contains an anion represented by formula (A). [ka] (In formula (A), each R independently represents a hydrocarbon group, and n represents an integer of 0 to 5.) [6] The resin composition according to any one of [1] to [5], further comprising at least one selected from the group consisting of a stabilizer, an impact improver, a release agent, and a colorant. [7] The resin composition according to any one of [1] to [6], wherein the resin composition is molded into a thickness of 1.5 mm and has a flame retardancy of V-0 as measured according to the UL-94 standard. [8] Further, the anti-dripping agent is contained in an amount of 0.01 to 1 mass% per 100 mass parts of the polycarbonate resin, the aromatic sulfonate-containing ionic liquid contains a cation represented by formula (K), wherein X represents a phosphorus atom; the aromatic sulfonate-containing ionic liquid contains an anion represented by formula (A), Further, the composition contains at least one selected from the group consisting of a stabilizer, an impact modifier, a release agent, and a colorant, The resin composition according to any one of [1] to [7], wherein the resin composition is molded into a thickness of 1.5 mm and has a flame retardancy of V-0 as measured according to the UL-94 standard. X + (R y )4(K) (In formula (K), X represents a nitrogen atom or a phosphorus atom, and R y and each independently represents a hydrocarbon group. [ka] (In formula (A), each R independently represents a hydrocarbon group, and n represents an integer of 0 to 5.) Indicates an integer.) [9] Pellets of the resin composition according to any one of [1] to [8].

[10] A molded article formed from the resin composition according to any one of [1] to [8].

[11] A molded article formed from the pellets described in [9]. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a resin composition having excellent flame retardancy, as well as pellets and molded articles formed from the resin composition. 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 upper and lower limits. "A to B" means that the range is A or more and B or less. In addition, any combination of the upper and lower limit values ​​of the numerical values ​​in this specification is an example of this embodiment. 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 the present embodiment is a resin composition containing 0.001 to 0.40 parts by mass of an ionic liquid containing an aromatic sulfonate relative to 100 parts by mass of a polycarbonate resin, and the resin composition has a melt volume rate (MVR) of 5 cm or less measured at 300°C under a load of 1.2 kg. 3 / 20cm for more than 10 minutes 3 By using such a constitution, a resin composition having excellent flame retardancy can be obtained. In this embodiment, flame retardancy was improved by adjusting the MVR of the resin composition and adding an ionic liquid containing an aromatic sulfonate. The reason for this is presumably that the aromatic sulfonate contributed as a flame retardant, similar to known flame retardants such as sodium paratoluenesulfonate. However, sodium paratoluenesulfonate has a high melting point of over 300°C, and even when added to a polycarbonate resin and melt-kneaded, it exhibits poor dispersibility. Therefore, when mass-produced, there were cases where the flame retardancy varied from lot to lot. In this embodiment, it is presumed that the dispersibility in the polycarbonate resin can be improved by blending an ionic liquid containing an aromatic sulfonate. On the other hand, low molecular weight compounds may volatilize at high temperatures during extrusion, but in this embodiment, it is presumed that volatilization was suppressed by using an ionic liquid. Furthermore, it is believed that by adjusting the MVR of the resin composition, the ionic liquid containing aromatic sulfonate decomposes the polycarbonate resin to an appropriate degree, making it easier to form a charred layer and shortening the burning time (also known as afterflame time).

[0009] 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.

[0010] <Polycarbonate resin> The resin composition of the present embodiment contains a polycarbonate resin. The polycarbonate resin is not particularly limited as long as it contains an -[OR-OC(=O)]- unit containing a carbonate bond in the molecular main chain (wherein R is an organic group, preferably a hydrocarbon group, more preferably an aliphatic group, an aromatic group, or both an aliphatic group and an aromatic group, and further has a linear or branched structure). In this embodiment, the polycarbonate resin is preferably an aromatic polycarbonate resin, and more preferably a polycarbonate resin having a bisphenol skeleton. By using such a polycarbonate resin, the obtained molded article can achieve better heat resistance and toughness. In this embodiment, the polycarbonate resin having a bisphenol skeleton preferably contains 90 mol % or more of all structural units of structural units having a bisphenol skeleton, more preferably 90 mol % or more of all structural units of structural units having at least one skeleton of bisphenol A, bisphenol C, and bisphenol AP, and even more preferably 90 mol % or more of all structural units of structural units having a bisphenol A skeleton.

[0011] The viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 10,000 or more, more preferably 12,000 or more, even more preferably 15,000 or more, even more preferably 19,000 or more, and even more preferably 20,000 or more. By setting it to the above lower limit or above, the durability of the obtained molded article tends to be further improved. The upper limit of the viscosity average molecular weight (Mv) of the polycarbonate resin is preferably 50,000 or less, more preferably 40,000 or less, even more preferably 30,000 or less, and even more preferably 25,000 or less. By setting it to the above upper limit or below, the molding processability of the molded article tends to be further improved. The viscosity average molecular weight (Mv) was calculated by using methylene chloride as a solvent and an Ubbelohde viscometer to determine the intrinsic viscosity [η] (unit: dL / g) at a temperature of 25°C, and then using the Schnell viscosity formula, i.e., η = 1.23 × 10 -4 ×Mv 0.83 This means the value calculated from When two or more types of polycarbonate resins are used, the viscosity average molecular weight is the viscosity average molecular weight of the mixture.

[0012] The method for producing the polycarbonate resin is not particularly limited, and polycarbonate resins produced by the conventionally known phosgene method (interfacial polymerization method) or melt method (ester interchange method) can be used. When the melt method is used, a polycarbonate resin with an adjusted amount of OH groups at the terminal groups can be used.

[0013] The polycarbonate resin used in this embodiment may contain recycled products. Recycled products are polycarbonate resins derived from molded products formed from polycarbonate resin, meaning virgin polycarbonate resins that have been subjected to some kind of molding process, and include polycarbonate resin molded products, rejected polycarbonate resin molded products, scraps from the manufacture of polycarbonate resin molded products, etc. Molded products include injection molded products, extrusion molded products, and molded products formed by other manufacturing methods. Examples of recycled polycarbonate resin include those obtained by material recycling, in which recovered used polycarbonate resin molded products are crushed and alkaline washed to be reused as fibers, etc., those obtained by chemical recycling (chemical decomposition method), and those obtained by mechanical recycling. Chemical recycling involves chemically decomposing recovered used polycarbonate resin molded products, returning them to their raw material level, and resynthesizing the polycarbonate resin.Mechanical recycling, on the other hand, is a method that makes it possible to remove dirt from polycarbonate resin molded products more reliably than material recycling by carrying out alkaline washing more rigorously than in the material recycling described above, or by vacuum drying at high temperatures. For example, recycled polycarbonate resin can be obtained from used polycarbonate resin molded products by removing foreign matter, crushing and cleaning the product, and then pelletizing it using an extruder. Examples of used polycarbonate resin molded products include discs, sheets (including films), meter covers, headlamp lenses, water bottles, and face plates for gaming and pachinko machines. The recycled product is preferably a polycarbonate resin in which 90 mol % or more of all structural units are structural units having at least one skeleton of bisphenol A, bisphenol C, and bisphenol AP, and more preferably a polycarbonate resin in which 90 mol % or more of all structural units are structural units having a bisphenol A skeleton. Virgin products refer to products other than recycled products.

[0014] When blended, the proportion of recycled polycarbonate resins contained in the resin composition of this embodiment is preferably 1 part by mass or more per 100 parts by mass of polycarbonate resin (total of recycled and virgin polycarbonate resins), and may be 100 parts by mass or less. The resin composition of the present embodiment may contain only one type of recycled polycarbonate resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0015] In addition to the above, for details of the polycarbonate resin, please refer to the descriptions in paragraphs 0013 to 0041 of JP 2021-084942 A, the descriptions in paragraphs 0030 to 0035 of JP 2021-119211 A, and the descriptions in paragraphs 0008 to 0064 of JP 2023-012167 A, the contents of which are incorporated herein by reference.

[0016] The content of polycarbonate resin in the resin composition of this embodiment is preferably 80 mass % or more of the resin composition, more preferably 85 mass % or more, even more preferably 90 mass % or more, and even more preferably 95 mass % or more. In addition, all components other than the ionic liquid containing aromatic sulfonate may be polycarbonate resin. The resin composition of the present embodiment may contain only one type of polycarbonate resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0017] <Ionic liquids containing aromatic sulfonates> The resin composition of the present embodiment contains an ionic liquid containing an aromatic sulfonate. By including an ionic liquid containing an aromatic sulfonate, the flame retardancy of the resulting molded article can be improved. In this specification, an ionic liquid is a salt that exists in liquid form at 1 atmosphere and 100°C and is composed of cations and anions. Ionic liquids are liquids composed only of ions, have strong electrostatic interactions, and are non-volatile salts.

[0018] The ionic liquid containing an aromatic sulfonate used in this embodiment is preferably an ammonium salt and / or a phosphonium salt, and more preferably a phosphonium salt. Furthermore, the ionic liquid containing an aromatic sulfonate used in this embodiment is more preferably a salt containing a cation represented by formula (K). X + (R y )4(K) (In formula (K), X represents a nitrogen atom or a phosphorus atom, and R y each independently represents a hydrocarbon group.

[0019] In formula (K), X is preferably a phosphorus atom.

[0020] In formula (K), R y The type of R is not particularly limited as long as it is a hydrocarbon group that can be combined with an aromatic sulfonate anion to form an ionic liquid, but alkyl and / or aryl groups are preferred, with alkyl groups being more preferred. The alkyl group is preferably a linear or branched alkyl group, with linear alkyl groups being more preferred. The aryl group is preferably a phenyl group. y may be a benzyl group. The hydrocarbon group preferably has 2 or more carbon atoms, and preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, and even more preferably 5 or less. The Four Rs y Preferably, at least one of the R y One of the groups is an ethyl group, and the remaining three are n-butyl groups, etc.

[0021] Examples of cations of the ionic liquid containing an aromatic sulfonate that can be used in this embodiment are shown below, but it goes without saying that this embodiment is not limited to these. [ka]

[0022] The ionic liquid containing an aromatic sulfonate used in this embodiment preferably contains an anion represented by formula (A). [ka] (In formula (A), each R independently represents a hydrocarbon group, and n represents an integer of 0 to 5.)

[0023] In formula (A), R is not particularly limited to a specific type, provided that it is a hydrocarbon group that can be combined with an aromatic sulfonate cation to form an ionic liquid. However, R is preferably an alkyl group and / or an aryl group, and more preferably an alkyl group. The alkyl group is preferably a straight-chain or branched alkyl group, and more preferably a straight-chain alkyl group. When R is an alkyl group, it is preferably a methyl group, an ethyl group, an isopropyl group, an n-propyl group, an isobutyl group, or a t-butyl group, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. The aryl group is preferably a phenyl group. R may also be a benzyl group. The hydrocarbon group preferably has 1 or more carbon atoms, and preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, and even more preferably 5 or less. n represents an integer of 0 to 5, preferably an integer of 0 to 4, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, still more preferably 0 or 1, and still more preferably 1. When n is 1, the bonding position of R is preferably the para position relative to the sulfonyl group. An example of the anion represented by formula (A) is a toluenesulfonate anion (preferably, a paratoluenesulfonate anion).

[0024] The content of the ionic liquid containing an aromatic sulfonate in the resin composition of this embodiment is, relative to 100 parts by mass of the polycarbonate resin, 0.001 parts by mass or more, preferably 0.025 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.04 parts by mass or more, even more preferably 0.055 parts by mass or more, even more preferably 0.06 parts by mass or more, even more preferably 0.07 parts by mass or more, and 0.40 parts by mass or less, preferably 0.30 parts by mass or less, more preferably 0.25 parts by mass or less, even more preferably 0.20 parts by mass or less, even more preferably 0.15 parts by mass or less, and even more preferably 0.10 parts by mass or less. By setting the content at or above the lower limit, the flame retardancy of the resulting molded article tends to be further improved. Meanwhile, by setting the content at or below the upper limit, the decomposition of the polycarbonate during heat processing tends to be further suppressed, and the number of drips during a combustion test tends to be effectively reduced. The resin composition of the present embodiment may contain only one type of ionic liquid containing an aromatic sulfonate, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0025] The resin composition of the present embodiment may or may not contain a flame retardant containing a fluorine atom (for example, perfluorobutanesulfonate). An example of the resin composition of this embodiment is one that is substantially free of a flame retardant containing a fluorine atom. "Substantially free" means that the content of the flame retardant containing a fluorine atom is less than 10% by mass, preferably less than 5% by mass, more preferably less than 3% by mass, and may even be less than 1% by mass of the ionic liquid containing an aromatic sulfonate contained in the resin composition of this embodiment. Another example of the resin composition of the present embodiment is that it is substantially free of perfluorobutanesulfonate. "Substantially free" means that the content of perfluorobutanesulfonate is less than 10% by mass, preferably less than 5% by mass, more preferably less than 3% by mass, and may even be less than 1% by mass of the content of the ionic liquid containing aromatic sulfonate contained in the resin composition of the present embodiment.

[0026] <Drip prevention agent> The resin composition of the present embodiment preferably contains an anti-dripping agent. The anti-dripping agent preferably contains a fluoropolymer having fibril-forming ability. Fibril-forming fluoropolymers are easily dispersed in resin compositions and tend to bond together to form fibrous structures. The fluoropolymer capable of forming fibrils preferably has an extremely high molecular weight of 1,000,000 to 10,000,000, and exhibits a tendency to bond together to form fibers under external action such as shear force. Preferred fluoropolymers include tetrafluoroethylene (PTFE) resin, perfluoroalkoxy (PFA) resin, and fluorinated ethylene propylene (FEP) resin, with polytetrafluoroethylene being particularly preferred.

[0027] Examples of fluoropolymers capable of forming fibrils include Teflon (registered trademark) 6J manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd. and Polyflon manufactured by Daikin Industries, Ltd.

[0028] It is also preferable to use the fluoropolymer in the form of an aqueous dispersion. This dispersion is an aqueous dispersion produced by adding a surfactant to a fluororesin latex obtained by ordinary emulsion polymerization, followed by concentration and stabilization. The content of the fluoropolymer in the aqueous dispersion is preferably 20 to 80% by mass, particularly 30 to 70% by mass. Examples of aqueous dispersions of polytetrafluoroethylene include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemicals Co., Ltd., Fluon D-1 manufactured by Daikin Industries, Ltd., and polytetrafluoroethylene polymers having a multilayer structure obtained by polymerizing vinyl monomers, such as Metablen A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

[0029] The fibril-forming fluoropolymer preferably has a primary particle size in the range of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. In the resin composition, the fluoropolymer is preferably in the form of fibrils having a thickness of 0.5 μm or less, and the fibrils preferably exist in a network structure and / or branched form.

[0030] The content of the anti-dripping agent in the resin composition of this embodiment is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, per 100 parts by mass of polycarbonate resin. By setting the content at or above the lower limit, the anti-dripping effect tends to be effectively exhibited. Furthermore, the content of the anti-dripping agent is preferably 3 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.8 parts by mass or less, and even more preferably 0.5 parts by mass or less, per 100 parts by mass of polycarbonate resin. By setting the content at or below the upper limit, the mechanical strength of the obtained molded article tends to be improved, and the appearance also tends to be improved. The resin composition of the present embodiment may contain only one type of anti-dripping agent, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0031] <Stabilizer> The resin composition of the present embodiment may contain a stabilizer. Examples of the stabilizer include a heat stabilizer, an antioxidant, and a light stabilizer. Examples of stabilizers include phenol-based, amine-based, phosphorus-based, and thioether-based stabilizers. Among these, in this embodiment, it is preferable to include a phosphorus-based heat stabilizer and / or a phenol-based antioxidant.

[0032] Any known phosphorus-based heat stabilizer can be used. Specific examples include phosphorus oxoacids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid, and polyphosphoric acid; metal acid pyrophosphates such as sodium acid pyrophosphate, potassium acid pyrophosphate, and calcium acid pyrophosphate; phosphates of Group 1 or Group 2 metals such as potassium phosphate, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, and organic phosphonite compounds, with organic phosphite compounds being particularly preferred.

[0033] The organic phosphate compound is preferably a compound represented by the following formula: (R 1 O) 3-n P(=O)OH n (In the formula, R 1 are alkyl groups or aryl groups, and may be the same or different. n is an integer of 0 to 2. It is a compound represented by the formula: In the above formula, R 1 is more preferably an alkyl group having 1 or more, preferably 2 or more, and usually 30 or less, preferably 25 or less, carbon atoms, or an aryl group having 6 or more, usually 30 or less, carbon atoms. 1 is preferably an alkyl group rather than an aryl group. 1 If there are two or more, R 1 They may be the same or different. More preferably, R 1 and long-chain alkyl acid phosphate compounds having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include an octyl group, a 2-ethylhexyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an eicosyl group, and a triacontyl group. Examples of long-chain alkyl acid phosphates include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, and alkoxypolyethylene glycol acid phosphate. Acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, bisnonylphenyl acid phosphate, etc. Among these, octadecyl acid phosphate is preferred, and this is commercially available from ADEKA Corporation under the trade name "ADEKA STAB AX-71." In addition, organic phosphate compounds, including organic phosphate metal salts, can also be used. Specific examples include a mixture of zinc salt of distearyl acid phosphate and zinc salt of monostearyl acid phosphate. Specific examples of commercially available organic phosphate metal salts include "JP-518Zn" manufactured by Johoku Chemical Industry Co., Ltd.

[0034] Examples of organic phosphite compounds include triphenyl phosphite, tris(mononylphenyl)phosphite, tris(mononyl / dinonylphenyl)phosphite, tris(2,4-di-tert-butylphenyl)phosphite, monooctyldiphenyl phosphite, dioctylmonophenyl phosphite, monodecyldiphenyl phosphite, didecylmonophenyl phosphite, tridecyl phosphite, trilauryl phosphite, tristearyl phosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, distearyl pentaerythritol diphosphite, bis(decyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, and bis(nonylphenyl)pentaerythritol diphosphite. Specific examples of such organic phosphite compounds include "ADK STAB (registered trademark; the same applies hereinafter) 1178," "ADK STAB 2112," and "ADK STAB HP-10" manufactured by ADEKA CORPORATION, "JP-351," "JP-360," and "JP-3CP" manufactured by Johoku Chemical Industry Co., Ltd., and "IRGAFOS (registered trademark; the same applies hereinafter) 168" manufactured by BASF.

[0035] In addition to the above, the phosphorus-based heat stabilizer used in this embodiment can be found in paragraphs 0127 to 0133 of JP-A-2022-067329, the contents of which are incorporated herein by reference.

[0036] As the phenol-based antioxidant, a hindered phenol-based antioxidant is preferably used. Specific examples of hindered phenol antioxidants include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 4,6-bis(octyl methylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0037] 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. Specific examples of such hindered phenol antioxidants include "Irganox (registered trademark; the same applies hereinafter) 1010" and "Irganox 1076" manufactured by BASF, and "ADK STAB AO-50" and "ADK STAB AO-60" manufactured by ADEKA.

[0038] The content of the stabilizer in the resin composition of this embodiment is usually 0.001 part by mass or more, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, and even more preferably 0.05 part by mass or more, relative to 100 parts by mass of the polycarbonate resin, and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less. By setting the content of the stabilizer within this range, the effect of adding the stabilizer can be more effectively exerted. 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.

[0039] <Impact modifier> The resin composition of the present embodiment preferably contains an impact improver. The type of impact modifier is not particularly limited, and known impact modifiers can be used, with core-shell elastomers being preferred. The core-shell elastomer is particularly preferably a core-shell elastomer having 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 elastomer preferably contains 40% by mass or more of the rubber component, more preferably 60% by mass or more. Furthermore, the (meth)acrylic acid content is preferably 10% by mass or more. Note that the core-shell elastomer in this embodiment does not necessarily have a clearly distinguishable core layer and shell layer; it is intended to broadly include compounds obtained by graft-polymerizing a rubber component around the core portion.

[0040] Preferred specific examples of core-shell elastomers 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, and the like.

[0041] Examples of such core-shell elastomers include "Paraloid (registered trademark, the same applies hereinafter) EXL2602," "Paraloid EXL2603," "Paraloid EXL2655," "Paraloid EXL2311," "Paraloid EXL2313," "Paraloid EXL2315," "Paraloid KM330," "Paraloid KM336P," and "Paraloid KCZ201," manufactured by Rohm and Haas Japan Co., Ltd.; Examples of such adhesives include "Metablen (registered trademark, the same applies hereinafter) C-223A," "Metablen E-901," "Metablen S-2001," "Metablen SRK-200," "E-870A," and "E-860A" manufactured by the Company; "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," and "Kane Ace MR-01" manufactured by Kaneka Corporation; and "UBESTA XPA" manufactured by UBE Pharmaceuticals.

[0042] When the resin composition of this embodiment contains an impact modifier, the content thereof is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and even more preferably 1.5 parts by mass or more, relative to 100 parts by mass of the polycarbonate resin, and is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 4 parts by mass or less. By setting the content at or above the lower limit, the impact resistance of the obtained molded article tends to be further improved. On the other hand, by setting the content at or below the upper limit, the flame retardancy of the obtained molded article tends to be further improved. The resin composition of the present embodiment may contain only one type of impact modifier, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0043] <Release agent> The resin composition of the present embodiment may contain a release agent. Examples of the release agent include aliphatic carboxylic acids, salts of aliphatic carboxylic acids, esters of aliphatic carboxylic acids and alcohols, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15,000, polysiloxane-based silicone oils, ketone waxes, and light amides, and the like are preferred.

[0044] 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, tetratriacontanoic acid, montanic acid, adipic acid, and azelaic acid. Examples of salts of aliphatic carboxylic acids include sodium salts, potassium salts, calcium salts, and magnesium salts.

[0045] 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 described above. 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, a monohydric or polyhydric saturated alcohol having 30 or less carbon atoms is preferred, and an aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferred.

[0046] 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.

[0047] 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, and pentaerythritol tetrastearate.

[0048] 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. Among these, paraffin wax, polyethylene wax, partial oxide of polyethylene wax, and rice wax are preferred, with paraffin wax and polyethylene wax being more preferred.

[0049] For details about the release agent, please refer to paragraphs 0055 to 0061 of JP 2018-095706 A, the contents of which are incorporated herein by reference.

[0050] When the resin composition of the present embodiment contains a release agent, the content thereof in the resin composition is preferably 0.03 to 3 mass %, more preferably 0.05 to 0.8 mass %, and even more preferably 0.05 to 0.6 mass %. The resin composition of the present embodiment 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.

[0051] <Coloring agent> The resin composition of the present embodiment may contain a colorant. By containing a colorant, it is possible to impart color to the resulting molded article. The colorant may be a pigment or a dye, but is preferably a pigment. The colorant may be either an achromatic colorant or a chromatic colorant, with an achromatic colorant being preferred. Also preferred is a black colorant composed of two or more chromatic colorants. In this embodiment, preferred examples of the colorant include a black colorant (preferably a black pigment) and / or a white colorant (preferably a white pigment). An example of a black pigment is carbon black. An example of the white pigment is titanium oxide. The pigment such as carbon black may be made into a masterbatch with a thermoplastic resin (preferably a polycarbonate resin).

[0052] When the resin composition of the present embodiment contains a colorant, the content thereof is preferably more than 0 parts by mass, 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 polycarbonate 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 may contain only one type of colorant, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0053] <Other ingredients> The resin composition of the present embodiment may contain other components as needed, as long as the desired physical properties are not significantly impaired. Examples of the other components include resin components other than the polycarbonate resin and impact modifier, fillers (glass fibers), and various resin additives. Examples of resin additives include reactive compounds, ultraviolet absorbers, antistatic agents, antifogging agents, antiblocking agents, flow improvers, plasticizers, dispersants, and antibacterial agents. The resin composition may contain one type of resin additive, or two or more types in any combination and ratio. The content of these additives is preferably 0 to 5% by mass, more preferably 0 to 3% by mass, and may be 0 to 1% by mass. 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 this embodiment, the polycarbonate resin and the ionic liquid containing an aromatic sulfonate 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. If necessary, the resin composition may further contain at least one selected from the group consisting of a stabilizer, an impact modifier, a release agent, and a colorant. Furthermore, the total of the polycarbonate resin, the ionic liquid containing an aromatic sulfonate, and any anti-dripping agent, stabilizer, impact modifier, release agent, and colorant that are blended as needed preferably accounts for 95% by mass or more of the resin composition, more preferably 97% by mass or more, and even more preferably 99% by mass or more.

[0054] The resin composition of this embodiment may also be configured to be substantially free of an antistatic agent. "Substantially free" means that the content of the antistatic agent contained in the resin composition of this embodiment is less than 10 parts by mass, preferably less than 5 parts by mass, more preferably less than 3 parts by mass, even more preferably less than 1 part by mass, and may even be less than 0.1 parts by mass, per 100 parts by mass of the polycarbonate resin. In particular, the resin composition of this embodiment may be configured to be substantially free of a polymeric antistatic agent. "Substantially free" means that the content of the polymeric antistatic agent contained in the resin composition of this embodiment is less than 10 parts by mass, preferably less than 5 parts by mass, more preferably less than 3 parts by mass, even more preferably less than 1 part by mass, and may even be less than 0.1 parts by mass, per 100 parts by mass of the polycarbonate resin. Components that are specified in this specification and that also fall under the category of antistatic agents are considered to be the components specified therein.

[0055] <Physical properties of resin composition> The resin composition of this embodiment has a melt volume rate (MVR) of 5 cm when measured at 300°C under a load of 1.2 kg. 3 / 20cm for more than 10 minutes 3 By making the MVR equal to or greater than the lower limit, the flowability of the resin composition tends to be good, and moldability tends to be further improved. On the other hand, by making the MVR equal to or less than the upper limit, the flame retardancy (particularly, the drip prevention effect) tends to be further improved. 3 / 10 minutes or more is preferable, 8cm 3 / 10 minutes or more is more preferable, and 10cm 3 / 10 minutes or more is more preferable, and 12 cm 3 / 10 minutes or more is more preferable, and 19 cm 3 / 10 minutes or less is preferable, 18cm 3 / 10 minutes or less is more preferable, 17cm 3 It is more preferable that the time is 10 minutes or less. In addition, the resin composition of the present embodiment preferably has excellent flame retardancy. Specifically, it is preferable that the resin composition is molded into a thickness of 1.5 mm, and the flame retardancy measured in accordance with the UL-94 standard satisfies V-0. In particular, the resin composition of this embodiment is preferably molded to a thickness of 1.5 mm and has a burning time (total burning time of five pieces) measured in accordance with the UL-94 standard of 40 seconds or less, more preferably 30 seconds or less, even more preferably 20 seconds or less, even more preferably 15 seconds or less, and even more preferably 10 seconds or less. The MVR and flame retardancy are measured as described in the Examples below.

[0056] <Method of manufacturing resin composition> The method for producing the resin composition of this embodiment is not limited, and a wide variety of known methods for producing resin compositions can be used. For example, a polycarbonate resin, an ionic liquid containing an aromatic sulfonate, and other components that are added as needed may be premixed using a mixer such as a tumbler or a Henschel mixer, and then melt-kneaded using a mixer such as a Banbury mixer, a roll, a Brabender mixer, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The melt-kneading temperature is not particularly limited, but is typically in the range of 240 to 320°C. Inorganic fillers such as glass fibers may be side fed.

[0057] <Molded products> The molded article of this embodiment is formed from the resin composition or pellets of this embodiment. The resin composition of this embodiment can also be molded directly without first going through the pellet state. The resin composition (e.g., pellets) described above can be molded into a molded article by various molding methods. The shape of the molded article is not particularly limited and can be appropriately selected depending on the application and purpose of the molded article. Examples of the shape include film, rod, cylinder, ring, circle, ellipse, polygon, irregular shape, hollow, frame, box, panel, button, etc.

[0058] The method for forming the molded article is not particularly limited, and conventionally known molding methods can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating) molding, rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, and pressure molding. The resin composition of this embodiment is particularly suitable for molded articles obtained by injection molding, injection compression molding, and extrusion molding. However, it goes without saying that the resin composition of this embodiment is not limited to molded articles obtained by these methods.

[0059] The molded article of this embodiment can be widely used for molded articles containing polycarbonate resin. Specifically, it is preferably used in electrical and electronic equipment / components, office automation equipment / components, information terminal equipment / components, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and sundries, lighting equipment, etc. It is particularly preferably used for thin-walled molded products (for example, thin-walled molded products with a thickness of 1 μm or more and 1 mm or less at the thinnest part). [Example]

[0060] 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 performed using other instruments with equivalent performance.

[0061] 1. Raw materials The following raw materials were used: [Table 1]

[0062] [Table 2]

[0063] 2. Examples 1 to 4, Comparative Examples 1 and 2 <Preparation of resin pellets> The components listed in Table 1 or 2 were blended in the proportions shown in Table 4 (each component is in parts by mass) and mixed in a tumbler for 20 minutes. This mixture was fed into an extruder (TEM26SX) manufactured by Shibaura Machine Co., Ltd., kneaded at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 280°C, and extruded into a strand shape. This was cooled with water and pelletized using a pelletizer.

[0064] <Melt Volume Rate (MVR)> The MVR of the resin composition was measured in accordance with ISO1133 at 300°C under a load of 1.2 kg. Unit: cm 3 / 10 minutes.

[0065] <Flammability> The obtained pellets were dried at 120°C for 5 hours, and then injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd., "SE100DUHP") under conditions of a set temperature of 280°C and a mold temperature of 80°C, to obtain a molded test piece (UL test piece) with a length of 127 mm, a width of 12.7 mm, and a thickness of 1.5 mm. The UL test specimens prepared as described above were conditioned for 48 hours in a temperature-controlled room at a temperature of 23°C and a relative humidity of 50%, and then their flame retardancy was evaluated in accordance with the UL94 test (combustion test for plastic materials for equipment parts). This test is a method for evaluating flame retardancy based on the afterflame time and dripping properties after a test specimen held vertically is exposed to a burner flame for 10 seconds, according to the following criteria. Afterflame time is the length of time the test specimen continues to burn with a flame after the burner is removed. Cotton ignition by dripping is a test to determine whether or not a cotton marker located approximately 300 mm from the bottom of the test specimen is ignited by dripping (also called dripping) from the test specimen. If even one of the five specimens does not meet the above criteria, it is deemed not to meet V-2 and is rated NR (not rated).

[0066] [Table 3]

[0067] [Table 4]

[0068] As is clear from the above results, the molded articles formed from the resin compositions of the present invention were excellent in flame retardancy (Examples 1 to 4). In contrast, when the MVR of the resin composition was outside the range of the present invention, the flame retardancy was poor (Comparative Examples 1 and 2).

[0069] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.

Claims

1. A resin composition comprising 0.001 to 0.40 parts by mass of an ionic liquid containing an aromatic sulfonate relative to 100 parts by mass of a polycarbonate resin, The melt volume rate (MVR) of the resin composition measured at 300°C under a load of 1.2 kg is 5 cm ３ / 20cm for 10 minutes or more ３ / 10 minutes or less.

2. The resin composition according to claim 1, further comprising an anti-dripping agent in an amount of 0.01 to 3 parts by mass per 100 parts by mass of the polycarbonate resin.

3. The resin composition according to claim 1 or 2, wherein the ionic liquid containing an aromatic sulfonate contains a cation represented by formula (K): X ＋ (R ｙ ) ４ (K) (In formula (K), X represents a nitrogen atom or a phosphorus atom, and R ｙ each independently represents a hydrocarbon group.

4. The resin composition according to claim 3 , wherein in formula (K), X represents a phosphorus atom.

5. The resin composition according to claim 1 or 2, wherein the ionic liquid containing an aromatic sulfonate contains an anion represented by formula (A): 【Chemistry 1】 (In formula (A), each R independently represents a hydrocarbon group, and n represents an integer of 0 to 5.)

6. The resin composition according to claim 1 or 2, further comprising at least one selected from the group consisting of a stabilizer, an impact modifier, a release agent, and a colorant.

7. The resin composition according to claim 1 or 2, wherein the resin composition is molded into a thickness of 1.5 mm and has a flame retardancy of V-0 as measured according to the UL-94 standard.

8. Further, the anti-dripping agent is contained in an amount of 0.01 to 1 mass % relative to 100 mass parts of the polycarbonate resin, The ionic liquid containing an aromatic sulfonate contains a cation represented by formula (K), wherein X represents a phosphorus atom: the aromatic sulfonate-containing ionic liquid contains an anion represented by formula (A), Further, the composition contains at least one selected from the group consisting of a stabilizer, an impact modifier, a release agent, and a colorant, The resin composition according to claim 1, wherein the resin composition is molded to a thickness of 1.5 mm and has a flame retardancy of V-0 as measured according to the UL-94 standard. X ＋ (R ｙ ) ４ (K) (In formula (K), X represents a nitrogen atom or a phosphorus atom, and R ｙ each independently represents a hydrocarbon group. 【Chemistry 2】 (In formula (A), each R independently represents a hydrocarbon group, and n represents an integer of 0 to 5.) Indicates an integer.)

9. Pellets of the resin composition according to claim 1, 2 or 8.

10. A molded article formed from the resin composition according to claim 1, 2 or 8.

11. A molded article formed from the pellets of claim 9.

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