Resin composition and molded article thereof

Abstract

Provided are: a resin composition which has good fluidity when melted and has both excellent impact resistance and flame retardancy; and a molded article thereof. The resin composition contains a polycarbonate resin (A), a polyester resin (B), a core-shell elastomer (C), and a flame retardant (D), 90% by weight or more of the total amount of the polycarbonate resin (A) and the polyester resin (B) being recycled, and contains an amorphous polyester resin (B1) as the polyester resin (B). The polycarbonate resin composition contains, as a core-shell elastomer C, a core-shell elastomer C1 containing a phosphoric acid-based emulsifier and a core-shell elastomer C2 containing a sulfonic acid-based emulsifier, the total content of the core-shell elastomers C1 and C2 being more than 9.0 parts by weight and less than 11.5 parts by weight per 100 parts by weight of the total of the polycarbonate resin A and the polyester resin B, and the total content of the core-shell elastomers C1 and C2 being more than 9.0 parts by weight and less than 11.5 parts by weight per 100 parts by weight of the total of the polycarbonate resin A and the polyester resin The proportion of the core-shell elastomer C1 is more than 40 wt% and less than 100 wt% with respect to a total of 100 wt% of the core-shell elastomers C1 and C2.

Description

Technical Field

[0001] This invention relates to resin compositions and molded articles thereof, and more particularly to resin compositions and molded articles thereof using recycled materials, belonging to the field of recycled resins. Background Technology

[0002] With the rapid development of the plastics industry, the amount of waste plastics is increasing, leading to problems such as energy waste and environmental damage. Therefore, the recycling and reuse of waste plastics has become a global focus, and the use of recycled resins is being actively promoted. Recycled resins, also known as recycled resins or recyclable materials, are typically obtained through the recycling, sorting, cleaning, and crushing of post-consumer resin products and resin waste.

[0003] Polycarbonate / polyester alloys (typically polycarbonate / polyethylene terephthalate (PC / PET) alloys) are widely used in engineering plastics due to their combination of mechanical strength, heat resistance, solvent resistance, stress cracking resistance, and flowability. The use of recycled resins in polycarbonate / polyester alloys is also being actively promoted globally.

[0004] However, increasing the proportion of recycled resin in polycarbonate / polyester alloys often has adverse effects on mechanical properties and flame retardancy. For example, Patent Document 1 discloses a PC / PET alloy material prepared using waste PC and PET materials. This material is produced by recycling and improving waste PC and PET materials and adding additives; however, the mechanical properties, such as toughness, of this PC / PET alloy material are not yet sufficient. Patent Document 2 discloses a reinforced modified PC / PET alloy material, comprising, by weight percentage: 20-35% optical disc material, 45-70% crushed mineral water bottle material, 0.5-3.0% chain extender, 3-15% toughening agent, 0.5-10% reinforcing agent, 0.5-5% compatibilizer, 0.05-2% lubricant, and 0.01-1% antioxidant; however, the impact resistance of this reinforced modified PC / PET alloy material is insufficient, and it lacks flame retardancy.

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: CN105936744A

[0008] Patent Document 2: CN110628190A Summary of the Invention

[0009] The problem the invention aims to solve

[0010] The inventors have discovered that, in the prior art, there is currently no recycled polycarbonate / polyester alloy that combines good impact resistance and flame retardancy. The inventors have also found that when modifiers are added to improve the impact resistance and flame retardancy of recycled polycarbonate / polyester alloys, the melt flowability is sometimes impaired, resulting in poor processability and moldability. Therefore, the problem to be solved by the present invention is to provide a resin composition that exhibits good melt flowability, excellent impact resistance and flame retardancy, and allows for the use of recycled resins (e.g., polycarbonate / polyester alloys) in high amounts, as well as molded articles using the same.

[0011] Solution for solving the problem

[0012] In order to solve the above problems, the inventors conducted in-depth research and found that when more than 90% by weight of the resin component in the resin composition is recycled, the above problems can be solved by including an amorphous polyester resin in the resin composition and using a core-shell elastomer containing a phosphoric acid emulsifier and a core-shell elastomer containing a sulfonic acid emulsifier in a specific ratio. Thus, the present invention was completed.

[0013] Specifically, the present invention is based on the following structure.

[0014] [1] A resin composition comprising:

[0015] Polycarbonate resin (A)

[0016] Polyester resin (B)

[0017] Core-shell elastomers (C), and

[0018] Flame retardant (D),

[0019] More than 90% by weight of the total amount of the polycarbonate resin (A) and the polyester resin (B) is recycled.

[0020] As the polyester resin (B), it includes an amorphous polyester resin (B1).

[0021] The core-shell elastomer (C) comprises: a core-shell elastomer (C1) containing a phosphoric acid emulsifier and a core-shell elastomer (C2) containing a sulfonic acid emulsifier.

[0022] Relative to the total amount of 100 parts by weight of the polycarbonate resin (A) and the polyester resin (B), the combined content of the core-shell elastomer (C1) containing a phosphoric acid emulsifier and the core-shell elastomer (C2) containing a sulfonic acid emulsifier exceeds 9.0 parts by weight and is less than 11.5 parts by weight, and...

[0023] Of the total 100% by weight of the core-shell elastomer (C1) containing phosphoric acid emulsifier and the core-shell elastomer (C2) containing sulfonic acid emulsifier, the proportion of the core-shell elastomer (C1) containing phosphoric acid emulsifier is more than 40% by weight but less than 100% by weight.

[0024] [2] According to the resin composition of [1], wherein 90% by weight or more of the polycarbonate resin (A) is recycled material.

[0025] The amorphous polyester resin (B1) is not a recycled material.

[0026] More than 90% by weight of the polyester resin (B) other than the amorphous polyester resin (B1) is recycled.

[0027] [3] According to the resin composition of [1] or [2], wherein the content of the polyester resin (B) is 5 to 35% by weight relative to 100% by weight of the total amount of the polycarbonate resin (A) and the polyester resin (B).

[0028] [4] The resin composition according to any one of [1] to [3], wherein the amorphous polyester resin (B1) comprises glycol-modified polyethylene terephthalate (b1),

[0029] In the amorphous polyester resin (B1) of 100% by weight, the content of the glycol-modified polyethylene terephthalate (B1) is 15-100% by weight.

[0030] [5] The resin composition according to any one of [1] to [4], wherein the core-shell elastomer (C1) containing a phosphoric acid emulsifier has: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene and butyl acrylate, wherein the core-shell elastomer (C1) containing a phosphoric acid emulsifier has a volume average particle size of 100 nm or more.

[0031] [6] The resin composition according to any one of [1] to [5], wherein the core-shell elastomer (C2) containing a sulfonic acid emulsifier has: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene and butyl acrylate, wherein the core-shell elastomer (C2) containing a sulfonic acid emulsifier has a volume average particle size of 100 nm or more.

[0032] [7] A molded body formed using any one of the resin compositions described in [1] to [6].

[0033] The effects of the invention

[0034] The resin composition according to the present invention can exhibit both excellent impact resistance and flame retardancy, even when using a high content of recycled resin, and can ensure good melt flowability, thus providing good processability and moldability. Detailed Implementation

[0035] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The term "exemplary" as used herein means "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior to or better than other embodiments.

[0036] Furthermore, to better illustrate the present invention, numerous specific details are set forth in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In other instances, methods, means, apparatus, and steps well known to those skilled in the art have not been described in detail in order to highlight the spirit of the present invention.

[0037] Unless otherwise stated, all units used in this specification are international standard units, and all numerical values ​​and ranges appearing in this invention should be understood to include systematic errors that are unavoidable in industrial production.

[0038] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0039] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "implementation," etc., refer to specific elements (e.g., features, structures, properties, and / or characteristics) related to that embodiment, which are included in at least one of the embodiments described herein and may or may not be present in other embodiments. Furthermore, it should be understood that these elements may be combined in any suitable manner in various embodiments.

[0040] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0041] Unless otherwise stated, in this specification, "parts by weight" and "% by weight" for polymers, copolymers, and resins refer to solid components and do not include solvents.

[0042] In this invention, "(meth)acrylic acid" refers to acrylic acid and / or methacrylic acid. Additionally, "(meth)acrylate" refers to acrylate and / or methacrylate.

[0043] In this invention, the weight-average molecular weight and number-average molecular weight were determined by gel permeation chromatography (GPC). The GPC-based molecular weight determination used a GPC HLC-8120 GPC manufactured by Tosoh Corporation as the measuring apparatus, and a Tosoh TSKgel SuperHM-M (15 cm) column manufactured by Tosoh Corporation, in tetrahydrofuran (THF) solvent. The weight-average molecular weight and number-average molecular weight were calculated from the determination results using a molecular weight calibration curve prepared from monodisperse polystyrene standard samples.

[0044] The resin composition of one embodiment of the present invention comprises:

[0045] Polycarbonate resin (A)

[0046] Polyester resin (B)

[0047] Core-shell elastomers (C), and

[0048] Flame retardant (D),

[0049] More than 90% by weight of the total amount of the polycarbonate resin (A) and the polyester resin (B) is recycled.

[0050] As the polyester resin (B), it includes an amorphous polyester resin (B1).

[0051] The core-shell elastomer (C) comprises: a core-shell elastomer (C1) containing a phosphoric acid emulsifier and a core-shell elastomer (C2) containing a sulfonic acid emulsifier.

[0052] Relative to the total amount of 100 parts by weight of the polycarbonate resin (A) and the polyester resin (B), the content of the core-shell elastomer (C1) and the core-shell elastomer (C2) is more than 9.0 parts by weight and less than 11.5 parts by weight, and...

[0053] Of the total 100% by weight of the core-shell elastomer (C1) containing phosphoric acid emulsifier and the core-shell elastomer (C2) containing sulfonic acid emulsifier, the proportion of the core-shell elastomer (C1) containing phosphoric acid emulsifier is more than 40% by weight but less than 100% by weight.

[0054] The following sections will describe each component of the resin composition in turn.

[0055] Polycarbonate resin (A)

[0056] The resin composition of the present invention uses polycarbonate resin (A) as the main component, and therefore typically contains 50% or more of polycarbonate resin (A) per 100% by weight of the resin composition. From the viewpoint of mechanical properties such as impact resistance, the content of polycarbonate resin (A) per 100% by weight of the resin composition of the present invention is preferably 55% or more by weight, more preferably 60% or more by weight, and even more preferably 65% ​​or more by weight.

[0057] The type of polycarbonate resin (A) used in this invention is not particularly limited, and examples include aliphatic polycarbonate resins, aromatic polycarbonate resins, and aliphatic-aromatic polycarbonate resins. From the viewpoint of mechanical properties such as impact resistance, aliphatic-aromatic polycarbonate resins and aromatic polycarbonate resins are preferred, and aromatic polycarbonate resins are more preferred. As an aromatic polycarbonate resin, for example, a branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic hydroxyl compound with phosgene or diester, or by reacting an aromatic hydroxyl compound and a small amount of polyhydroxyl compound with phosgene or diester, can be used. The method of manufacturing the polycarbonate resin is not particularly limited, and known methods such as interfacial polymerization and melt transesterification can be used.

[0058] The molecular weight of the polycarbonate resin (A) used in this invention can be appropriately selected within a range that does not impair the technical effect of this invention. For example, the number average molecular weight [Mn] of the polycarbonate resin (A) can be 10,000 or more and 80,000 or less. From the viewpoint of achieving a good balance between impact resistance and melt flowability, it is preferable to have a molecular weight of 12,000 or more and 60,000 or less, and more preferably 20,000 or more and 40,000 or less.

[0059] In this invention, for the purpose of achieving environmental protection and economy by using a high proportion of recycled resin, at least 90% by weight of the total amount of the resin components in the resin composition, namely polycarbonate resin (A) and polyester resin (B), are recycled. From the viewpoint of achieving a good balance between impact resistance and melt flowability of the resin composition even with a high proportion of recycled resin, it is preferable that at least 90% by weight of the polycarbonate resin (A) is recycled, and more preferably at least 95% by weight of the polycarbonate resin (A) is recycled. In some embodiments, all of the polycarbonate resin (A) may be recycled. In other words, when the impact resistance, flowability, and other properties are at the same level, a higher amount of recycled material is considered superior.

[0060] There are no specific limitations on the sources of recycled polycarbonate resins. For example, everyday items such as mineral water bottles, baby bottles, and CDs can be listed; automotive products such as car lights and dashboards; electrical equipment such as meter casings, meter boxes, and appliance housings; building materials such as slabs and hollow slabs; and industrial waste such as scrapped raw materials from virgin material plants and defective products from injection molding plants.

[0061] There are no particular limitations on the method for manufacturing recycled polycarbonate resins. Generally, recycled materials can be produced by collecting and sorting recovered waste, crushing and washing, separating foreign matter by color, and melt granulation. Alternatively, commercially available products can also be used as recycled polycarbonate resins. Examples of such commercially available products include MJ-311A and MJ-321 manufactured by MJ Materialtechnology SDN.BHD.

[0062] Polyester-based resin (B)

[0063] The resin composition of the present invention comprises a polyester resin (B) as a modifier for the aforementioned polycarbonate resin (A). Typically, the content of the polyester resin (B) is 1% by weight or more and 30% by weight or less relative to 100% by weight of the resin composition. From the viewpoint of mechanical properties such as impact resistance, the content of the polyester resin (B) is preferably 2.5% by weight or more and 20% by weight or less relative to 100% by weight of the resin composition of the present invention, more preferably 5% by weight or more and 15% by weight or less.

[0064] The aforementioned polyester resin (B) used in this invention refers to the general term for polymeric compounds and their modified or derivative products formed by the condensation polymerization of polyols and polyacids.

[0065] Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid, citracic acid, itaconic acid, pentenic acid, succinic acid, alkenyl succinic acid, adipic acid, and sebacic acid; alicyclic polycarboxylic acids such as cyclohexanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, trimellitic acid, and pyromellitic acid; and their anhydrides or their lower alkyl esters. Among these, aromatic polycarboxylic acids are preferred, and aromatic dicarboxylic acids are even more preferred. One of these polycarboxylic acids may be used alone, or two or more may be used in combination.

[0066] Examples of polyols include aliphatic polyols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, glycerol, trimethylolpropane, and pentaerythritol; alicyclic polyols such as cyclohexanediol, cyclohexanediol, and hydrogenated bisphenol A; and aromatic diols such as ethylene oxide adducts and propylene oxide adducts of bisphenol A. These polyols can be used individually or in combination of two or more.

[0067] The type of polyester resin (B) used in this invention is not particularly limited as long as it includes an amorphous polyester resin (B1). Examples of the aforementioned polyester resin (B) include polyethylene terephthalate (PET), polyethylene terephthalate (PEN), polybutylene terephthalate (PBT), and their alcohol-modified derivatives. From the viewpoint of achieving a good balance between impact resistance and the flowability of the resin composition when melted, the aforementioned polyester resin (B) preferably includes polyethylene terephthalate (PET) and / or its polyol-modified derivatives.

[0068] The proportion of the aforementioned amorphous polyester resin (B1) contained in the aforementioned polyester resin (B) is not particularly limited as long as at least 90% by weight of the total amount of polycarbonate resin (A) and polyester resin (B) is recycled. From the viewpoint of achieving a good balance between mechanical properties such as impact resistance and fluidity during melt flow, the proportion of the aforementioned amorphous polyester resin (B1) in 100% by weight of the aforementioned polyester resin (B) is preferably 10 to 100% by weight, more preferably 15 to 90% by weight, and even more preferably 20 to 75% by weight.

[0069] The weight-average molecular weight (Mw) of the aforementioned polyester resin (B) used in this invention is not particularly limited, and can be 5,000 or more and 800,000 or less, preferably 6,000 or more and 400,000 or less.

[0070] The amorphous polyester resin (B1) included in the aforementioned polyester resin (B) used in this invention may or may not be a recycled material, or it may be an amorphous polyester resin obtained by modifying a recycled polyester resin. From the viewpoints of achieving a good balance between mechanical properties such as impact resistance and melt flowability, as well as availability, the aforementioned amorphous polyester resin (B1) preferably does not use recycled materials.

[0071] Amorphous polyester resins (B1), which constitute component (B), can generally be identified by the absence of a distinct endothermic peak in differential scanning calorimetry (DSC). A distinct endothermic peak is specifically defined as a peak with a half-width of, for example, within 15° when measured at a heating rate of 10°C / min in DSC. Conversely, polyester resins exhibiting a distinct endothermic peak are referred to as crystalline polyester resins.

[0072] The aforementioned amorphous polyester resins typically have relatively high glass transition temperatures (Tg). Specifically, the Tg of the aforementioned amorphous polyester resins is preferably 40–90°C, more preferably 45–85°C. Tg can be measured using a differential scanning calorimeter.

[0073] The aforementioned amorphous polyester resin (B1) may, for example, be a copolyester resin containing two or more structural units derived from polyols, such as glycol-modified polyethylene terephthalate, glycol-modified polyethylene terephthalate, and glycol-modified polybutylene terephthalate. From the viewpoint of balancing mechanical properties such as impact resistance and melt flowability, the aforementioned amorphous polyester resin (B1) preferably contains glycol-modified polyethylene terephthalate (b1). From the same viewpoint, the content of glycol-modified polyethylene terephthalate (b1) in 100% by weight of the aforementioned amorphous polyester resin (B1) is preferably 15 to 100% by weight, more preferably 35 to 100% by weight, and even more preferably 55 to 100% by weight.

[0074] There are no particular limitations on the amount of the aforementioned glycol-modified polyethylene terephthalate (b1) in the resin composition. From the viewpoint of impact resistance, the content of the aforementioned glycol-modified polyethylene terephthalate (b1) relative to 100% by weight of the total amount of polycarbonate resin (A) and polyester resin (B) is preferably 5% by weight or less, more preferably 4% or less, and even more preferably 3% or less. As a lower limit for the content of glycol-modified polyethylene terephthalate (b1), from the viewpoint of exerting its effect, it is preferably 0.8% by weight or more, more preferably 1.8% by weight or more, and even more preferably 2.0% by weight or more.

[0075] The diol used for modification in the aforementioned diol-modified polyethylene terephthalate (b1) can be any one or more of the aforementioned polyols. From the viewpoint of combining impact resistance, flowability, and heat resistance, aromatic diols and alicyclic diols are preferred, and alicyclic diols are even more preferred. The aforementioned diol-modified polyethylene terephthalate (b1) can be synthesized by polycondensation of a polyacid with two or more polyols, or commercially available products can be used. Examples of such commercially available products include Eastman Chemical Company's Easter GN-001.

[0076] Regarding the content of recycled material in the aforementioned polyester resin (B), there is no particular limitation as long as at least 90% by weight of the total amount of polycarbonate resin (A) and polyester resin (B) is recycled material. From the viewpoint of achieving a good balance between impact resistance and fluidity of the resin composition when melted, it is preferable that the amorphous polyester resin (B1) is not recycled material, and that at least 90% by weight, more preferably at least 95% by weight, and even more preferably 100% by weight of the polyester resin (B) other than the amorphous polyester resin (B1) is recycled material.

[0077] There are no particular limitations on the sources of recycled polyester resins. For example, waste materials such as waste blocks and waste filaments generated in various processes of polyester and fiber production, as well as discarded polyester bottles, can be listed.

[0078] There are no particular limitations on the manufacturing method of recycled polyester resins. Generally, there are two types of methods: physical recycling and chemical recycling. Physical recycling is preferred from an economic perspective. Examples of physical recycling methods include: shredding waste polyester into flakes, separating impurities such as aluminum, paper, and adhesives, and then washing, drying, and granulating the waste polyester flakes; and separating impurities from waste polyester mechanically, followed by washing, crushing, and granulation. As recycled polyester resins, for example, recycled products obtained by recycling and granulating waste polyester can be used. Typically, recycled polyester with an intrinsic viscosity (IV) of 0.4–0.9 dL / g, preferably 0.5–0.8 dL / g, and more preferably 0.55–0.58 dL / g, obtained by granulating waste polyester film scraps, can be used. Alternatively, commercially available products can also be used as recycled polyester resins.

[0079] Core-shell elastomers (C)

[0080] The resin composition of the present invention includes a core-shell elastomer (C). The amount of the core-shell elastomer (C) is not particularly limited, but may be 1 to 30 parts by weight relative to 100 parts by weight of the total amount of polycarbonate resin (A) and polyester resin (B). From the viewpoint of achieving a good balance of impact resistance, flame retardancy, and melt flowability, it is preferable to include 3 to 25 parts by weight of the core-shell elastomer (C), and more preferably 5 to 20 parts by weight of the core-shell elastomer (C).

[0081] The core-shell elastomer (C) included in the resin composition of the present invention comprises a core-shell elastomer (C1) containing a phosphoric acid emulsifier and a core-shell elastomer (C2) containing a sulfonic acid emulsifier. In the resin composition of the present invention, relative to 100 parts by weight of the total amount of polycarbonate resin (A) and polyester resin (B), the total content of the aforementioned core-shell elastomer (C1) and the aforementioned core-shell elastomer (C2) is more than 9.0 parts by weight and less than 11.5 parts by weight. By using the aforementioned core-shell elastomer (C1) and the aforementioned core-shell elastomer (C2) at this content, a good balance of impact resistance, flame retardancy, and melt flowability is achieved. From the viewpoint of further improving impact resistance and flame retardancy, the total content of core-shell elastomer (C1) and core-shell elastomer (C2) is preferably 9.8 to 11.2 parts by weight, more preferably 9.5 to 10.8 parts by weight, and even more preferably 9.8 to 10.5 parts by weight, relative to 100 parts by weight of polycarbonate resin (A) and polyester resin (B).

[0082] In the resin composition of the present invention, the proportion of the core-shell elastomer (C1) is more than 40% by weight and less than 100% by weight relative to 100% by weight of the total amount of the core-shell elastomer (C1) and the core-shell elastomer (C2). By having the proportion of the core-shell elastomer (C1) within this range, a good balance is achieved between impact resistance, flame retardancy, and melt flowability. From the viewpoint of further improving impact resistance and melt flowability, the proportion of the core-shell elastomer (C1) is preferably 50-99% by weight, more preferably 52-97% by weight, and even more preferably 55-95% by weight relative to 100% by weight of the total amount of the core-shell elastomer (C1) and the core-shell elastomer (C2).

[0083] In this invention, a core-shell elastomer refers to an elastomer with a core-shell structure, which can be a graft copolymer with a core-shell structure formed by grafting the shell layer onto the core layer of a rubbery polymer.

[0084] Examples of rubber-like polymers used for the aforementioned core layer include diene polymers such as butadiene rubber, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, and butadiene / acrylate copolymer rubber; acrylic rubber polymers such as polybutyl acrylate and butyl acrylate / 2-ethylhexyl acrylate copolymer; and polyorganosiloxane rubber polymers such as organosilicon and organosilicon acrylics. From the viewpoint of impact resistance, diene polymers are preferred, and butadiene rubber and styrene / butadiene copolymer rubber are even more preferred.

[0085] The aforementioned shell layer can be obtained by graft polymerization of at least one vinyl monomer onto the core layer of the aforementioned rubbery polymer. As the vinyl monomer, any monomer capable of graft copolymerization with the aforementioned rubber is acceptable; examples include aromatic vinyl compounds, cyanide vinyl compounds, unsaturated carboxylic acids, and unsaturated carboxylic acid esters. Among aromatic vinyl compounds, styrene and α-methylstyrene are preferred; among cyanide vinyl compounds, acrylonitrile and methacrylonitrile are preferred; among unsaturated carboxylic acids, acrylic acid and methacrylic acid are preferred; and among unsaturated carboxylic acid esters, (meth)acrylates having alkyl groups of 1 to 12 carbons are preferred.

[0086] From the viewpoint of possessing both impact resistance and melt flowability, the aforementioned core-shell elastomer (C) preferably comprises: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate. Similarly, from the same viewpoint, the aforementioned core-shell elastomer (C1) containing a phosphoric acid emulsifier and the aforementioned core-shell elastomer (C2) containing a sulfonic acid emulsifier preferably each comprise: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene, and butyl acrylate.

[0087] The manufacturing method of the core-shell elastomer (C) used in this invention is not particularly limited; for example, it can be prepared by emulsion polymerization. In some embodiments, the aforementioned core-shell elastomer (C1) containing a phosphoric acid emulsifier can be prepared by emulsion polymerization using a phosphoric acid emulsifier. In some embodiments, the aforementioned core-shell elastomer (C2) containing a sulfonic acid emulsifier can be prepared by emulsion polymerization using a sulfonic acid emulsifier.

[0088] Alternatively, commercially available products can also be used for core-shell elastomers (C). Examples of commercially available products include Kane Ka Co., Ltd.'s KANE ACE (registered trademark) M-724, M-711, and M-732.

[0089] As the aforementioned core-shell elastomer (C), expanded versions of core-shell elastomers can also be used without impairing the technical effects of the present invention. Examples of expanded versions of core-shell elastomers include core-shell elastomers obtained by expanding acid-containing copolymer latex, i.e., acid latex expanded versions. It should be noted that the method of expanding using acid-containing copolymer latex is not particularly limited, and known methods can be used, such as those disclosed in Japanese Patent Application Publication No. 10-245468 and Japanese Patent Application Publication No. 8-12704.

[0090] There is no particular limitation on the size of the core-shell elastomer (C) used in this invention. For example, the volume average particle size of the core-shell elastomer (C) can be 20 nm or more and 10 μm or less, and from the viewpoint of combining impact resistance and melt flowability, it is preferably 100 nm or more and 5 μm or less. From the same viewpoint, the volume average particle size of the aforementioned core-shell elastomer (C1) containing a phosphoric acid emulsifier and the aforementioned core-shell elastomer (C2) containing a sulfonic acid emulsifier are preferably 100 nm or more and 5 μm or less, respectively.

[0091] In the aforementioned core-shell elastomer (C1) containing a phosphoric acid emulsifier, the content of the phosphoric acid emulsifier, relative to 100% by weight of the core-shell elastomer (C1), can be 50-2000 ppm, preferably 80-1500 ppm, more preferably 100-1200 ppm, and even more preferably 200-1000 ppm in terms of phosphoric acid element content. By having the content of the phosphoric acid emulsifier within this range, the impact resistance and flowability of the resin composition of the present invention are further improved. There is no particular limitation on the aforementioned phosphoric acid emulsifier; it can be selected from commonly used phosphoric acid emulsifiers. For example, alkyl phosphates and alkyl aryl phosphates can be listed. From the viewpoint of impact resistance, polyoxyalkylene alkylphenyl ether phosphates and polyoxyalkylene alkyl ether phosphates are preferred.

[0092] In the aforementioned core-shell elastomer (C2) containing a sulfonic acid emulsifier, the content of the sulfonic acid emulsifier, relative to 100% by weight of the core-shell elastomer (C2), can be 100-3000 ppm, preferably 200-2500 ppm, more preferably 400-2200 ppm, and even more preferably 800-1800 ppm in terms of sulfur content. By using this range of sulfonic acid emulsifier content, the impact resistance and flowability of the resin composition of the present invention are further improved. There is no particular limitation on the aforementioned sulfonic acid emulsifier; it can be selected from commonly used sulfonic acid emulsifiers, such as sodium alkyl diphenyl ether disulfonate, sodium alkylbenzene sulfonate, and sodium alkylnaphthalene sulfonate.

[0093] Flame retardant (D)

[0094] The resin composition of the present invention contains a flame retardant (D). There is no particular limitation on the type of flame retardant (D), and it can be appropriately selected from flame retardants commonly used to impart or improve the flame retardancy of resin compositions. Specific examples include halogen-based, phosphorus-based, nitrogen-based, silicon-based, magnesium-aluminum-based, and molybdenum-based flame retardants. From the viewpoint of improving the flame retardancy of the present invention without impairing mechanical properties such as impact resistance, the flame retardant (D) is preferably a phosphorus-based flame retardant, and more preferably a phosphate ester-based flame retardant.

[0095] Phosphorus-based flame retardants include ammonium polyphosphate, hydroquinone-bis-(diphenyl phosphate), bisphenol A bis-(diphenyl phosphate), tris(2-carboxyethyl)phosphine (TCEP), tri(chloroisopropyl) phosphate, trimethyl phosphate (TMP), dimethyl methylphosphonate (DMMP), resorcinol bis-(xylyl phosphate) (RDXP), phosphazene compounds, melamine polyphosphate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives or resins, diphenylphosphine oxide (DPPO) and its derivatives or resins, and aluminum phosphonate salts, etc.

[0096] The aforementioned flame retardant (D) can be a commercially available product. Specific examples include PX-200, PX-201, PX-202, SPB-100, SPH-100, and SPV-100 manufactured by Daihachi Chemical Industry Co., Ltd. of Japan; and Exolit OP-930 and OP-935 manufactured by Clariant Corporation.

[0097] There is no particular limitation on the amount of the aforementioned flame retardant (D) in the formulation, and it can be contained in the usual amount. From the viewpoint of achieving a good balance between impact resistance and flame retardancy, it is preferable to contain 5 to 30 parts by weight of the aforementioned flame retardant (D) relative to 100 parts by weight of the total amount of polycarbonate resin (A) and polyester resin (B), and more preferably 10 to 25 parts by weight of the aforementioned flame retardant (D).

[0098] Anti-dripping agent (E)

[0099] In the resin composition of the present invention, an anti-dripping agent (E) may be incorporated for the purpose of preventing melt dripping during combustion. Examples of anti-dripping agents (E) include fluoroolefin resins with fluoroolefin resins as the main component. Fluoroolefin resins are polymers, copolymers, or composites containing a fluoroethylene structure. Examples of fluoroolefin resins include difluoroethylene polymers, tetrafluoroethylene polymers, tetrafluoroethylene-hexafluoropropylene copolymers, copolymers of tetrafluoroethylene with fluorine-free ethylene monomers, and composites of tetrafluoroethylene polymers with vinyl resins such as acrylic resins. Among these, polytetrafluoroethylene (PTFE) is preferred. The weight-average molecular weight of PTFE is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000.

[0100] Among polytetrafluoroethylene (PTFE), compounds with fibrillation-forming ability are preferred from the perspective of providing higher melt drip prevention. Examples of PTFE with fibrillation-forming ability include compounds classified as Type 3 in the ASTM standard. Examples of PTFE classified as Type 3 include Teflon 6-J (manufactured by DuPont-Mitsui Fluorochemicals Co., Ltd.), POLYFLON D-1, POLYFLON F-103, POLYFLON F201 (manufactured by Daikin Industries, Ltd.), CD1, and CD076 (manufactured by Asahi ICI Fluoropolymers Co., Ltd.).

[0101] Examples of polytetrafluoroethylene (PTFE) other than those classified as Type 3 compounds include Algoflon F5 (manufactured by Montefluos), POLYFLON MPA, and POLYFLON FA-100 (manufactured by Daikin Industries, Ltd.). These PTFEs can be used alone or in combination of two or more.

[0102] From the viewpoint of balancing melt dripping prevention during combustion with impact resistance, the amount of anti-dripping agent (E) is preferably 0.05 to 5 parts by weight, more preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the total amount of polycarbonate resin (A) and polyester resin (B). The amount of anti-dripping agent can be appropriately determined based on the required flame retardancy level of the molded article, such as UL94 V-0, V-1, V-2, etc., and further considering the amount of other components.

[0103] Other ingredients

[0104] The resin composition of the present invention may, without prejudice to the purpose of the present invention, include, as needed,: inorganic fillers such as glass fiber and carbon fiber; plate-like inorganic fillers such as glass flakes, talc, kaolin, mica, montmorillonite, and organic clay; impact-resistant modifiers such as various elastomers; nucleating agents; lubricants such as fatty amides and fatty amide compounds; antioxidants such as copper compounds, organic or inorganic halogen compounds, hindered phenols, hindered amines, hydrazines, sulfur compounds, and phosphorus compounds; anti-coloring agents; ultraviolet absorbers such as benzotriazoles; additives such as stabilizers, release agents, plasticizers, and colorants; and other components such as compounds containing oxidation reaction promoters, benzoquinones, anthraquinones, and naphthoquinones.

[0105] The method for manufacturing the resin composition of the present invention is not particularly limited, and the resin composition of the present invention can be manufactured by well-known methods for preparing resin compositions. For example, the components used to form the resin composition, along with additives added as needed, can be melt-mixed in a melt-mixing apparatus to obtain the resin composition of the present invention. The aforementioned melt mixing can be carried out in a batch or continuous manner. Examples of such melt-mixing apparatuses include extruders, kneaders, and Banbury mixers. The aforementioned resin composition can also be extruded after melt mixing and shredded using a cutter, granulator, or the like to produce a granular resin composition.

[0106] Another embodiment of the present invention provides a molded article formed using the aforementioned resin composition of the present invention. The molding method is not particularly limited; well-known molding methods can be used, typically injection molding. The molded article of the present invention can be widely used in the automotive, electronics, precision instrument, office equipment, packaging materials, and building materials industries.

[0107] Example

[0108] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0109] The components used in the examples and comparative examples are as follows:

[0110] (A)Ingredients:

[0111] • A-1: ​​Recycled polycarbonate (MJ Material Technology SDN.BHD, MJ-311A)

[0112] • A-2: Recycled polycarbonate (MJ Material Technology SDN.BHD, manufactured MJ-321)

[0113] (B) Ingredients

[0114] •B-1: Recycled polyethylene terephthalate, IV (intrinsic viscosity) of 0.55–0.58, granulated from scraps of polyethylene terephthalate film.

[0115] • B-2: Amorphous polyester resin (Eastman Chemical Company, Easter GN-111)

[0116] (C) Components

[0117] •C-1: Core-shell elastomer (KANE ACE M-724 manufactured by Kane Ka Co., Ltd., with a volume average particle size of 120 nm and a phosphoric acid emulsifier content of approximately 600 ppm based on phosphorus element).

[0118] •C-2: Core-shell elastomer (KANE ACE M-711 manufactured by Kane Ka Co., Ltd., with a volume average particle size of 200 nm and a sulfonic acid emulsifier content of approximately 1500 ppm based on sulfur content)

[0119] (D) Components

[0120] • Flame retardant (PX-200, an aromatic condensed phosphate ester manufactured by Daihachi Chemical Co., Ltd., Japan)

[0121] Other additives

[0122] • Stabilizer (Adekastab AO-60 manufactured by ADEKA Co., Ltd.)

[0123] • Stabilizer (Adekastab 2112 manufactured by ADEKA Co., Ltd.)

[0124] • Anti-dripping agent (SN3310 manufactured by Guangzhou Shine Polymer Technology Co., Ltd., polytetrafluoroethylene)

[0125] Examples 1-4 and Comparative Examples 1-10

[0126] Manufacturing of resin composition particles

[0127] The above components were mixed according to the mixing ratio shown in Table 1. The resulting mixture was then compounded and extruded in a twin-screw extruder (TEX44SS manufactured by Nippon Steel) with the barrel temperature heated to 230-260°C and the screw speed at 100 rpm to obtain resin composition particles for each example.

[0128] Production of test pieces

[0129] The resin composition particles obtained in Examples 1-4 and Comparative Examples 1-10 were dried in a dryer at 100°C for 12 hours, and then molded in an injection molding machine (FAS100B manufactured by FANUC Corporation of Japan) at a molding temperature of 270-290°C and a mold temperature of 50°C to produce test pieces.

[0130] Evaluation methods

[0131] (1) Melt Flow Rate (MFR)

[0132] For the resin composition particles, the MFR (5s) was determined according to JIS K7210 A method at a test temperature of 265°C and a load of 2.16 kg.

[0133] (2) Impact resistance

[0134] For the test piece with a length of 63.5 mm, a width of 12.7 mm, and a thickness of 3.2 mm, and featuring a V-notch, prepared using the aforementioned method, the Izod impact strength (kJ / m²) was determined according to the method specified in JIS K7110 standard. 2 ).

[0135] (3) Flame retardancy

[0136] The resin composition particles obtained in Examples 1-4 and Comparative Examples 1-10 were dried at 100°C for 8 hours, and then injection molded using an injection molding machine (TOYO (100i), clamping pressure: 100 tons) at a barrel temperature of 235-260°C and a mold temperature of 50°C to obtain strip-shaped test pieces with a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm. The flame retardancy of these test pieces was evaluated according to the UL94 standard V test.

[0137] Table 1

[0138]

[0139] As can be seen from the above examples and comparative examples, the resin composition according to the present invention, provided that more than 90% by weight of the total resin component in the resin composition is recycled, has good fluidity when melted, is suitable for the production of molded articles, and can also have excellent impact resistance and flame retardancy.

[0140] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is chosen to best explain the principles, practical application, or technical improvements to the embodiments in the market, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A resin composition comprising: Polycarbonate resin (A) Polyester resin (B) Core-shell elastomers (C), and Flame retardant (D), More than 90% by weight of the total amount of the polycarbonate resin (A) and the polyester resin (B) is recycled. As the polyester resin (B), it includes an amorphous polyester resin (B1). The core-shell elastomer (C) comprises: a core-shell elastomer (C1) containing a phosphoric acid emulsifier and a core-shell elastomer (C2) containing a sulfonic acid emulsifier. Relative to the total amount of 100 parts by weight of the polycarbonate resin (A) and the polyester resin (B), the combined content of the core-shell elastomer (C1) containing a phosphoric acid emulsifier and the core-shell elastomer (C2) containing a sulfonic acid emulsifier exceeds 9.0 parts by weight and is less than 11.5 parts by weight, and... Of the total 100% by weight of the core-shell elastomer (C1) containing phosphoric acid emulsifier and the core-shell elastomer (C2) containing sulfonic acid emulsifier, the proportion of the core-shell elastomer (C1) containing phosphoric acid emulsifier is more than 40% by weight but less than 100% by weight.

2. The resin composition according to claim 1, wherein, More than 90% by weight of the polycarbonate resin (A) is recycled material. The amorphous polyester resin (B1) is not a recycled material. More than 90% by weight of the polyester resin (B) other than the amorphous polyester resin (B1) is recycled.

3. The resin composition according to claim 1 or 2, wherein, The content of the polyester resin (B) is 5 to 35% by weight relative to 100% of the total amount of the polycarbonate resin (A) and the polyester resin (B).

4. The resin composition according to any one of claims 1 to 3, wherein, The amorphous polyester resin (B1) comprises glycol-modified polyethylene terephthalate (b1). In the amorphous polyester resin (B1) of 100% by weight, the content of the glycol-modified polyethylene terephthalate (B1) is 15-100% by weight.

5. The resin composition according to any one of claims 1 to 4, wherein, The core-shell elastomer (C1) containing a phosphoric acid emulsifier has: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene and butyl acrylate, wherein the volume average particle size of the core-shell elastomer (C1) containing a phosphoric acid emulsifier is 100 nm or more.

6. The resin composition according to any one of claims 1 to 5, wherein, The core-shell elastomer (C2) containing a sulfonic acid emulsifier has: a core layer comprising butadiene rubber or styrene / butadiene copolymer rubber; and a shell layer comprising a polymer containing at least one monomer unit selected from the group consisting of methyl methacrylate, styrene and butyl acrylate, wherein the volume average particle size of the core-shell elastomer (C2) containing the sulfonic acid emulsifier is 100 nm or more.

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

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