Resin composition and molded article

Abstract

The resin composition according to the present invention comprises a thermoplastic resin (A), a phosphorus-based flame retardant (B), and a copolymer (C) of an alpha-olefin and an unsaturated carboxylic acid, the proportion of the phosphorus-based flame retardant (B) with respect to the thermoplastic resin (A) is 5-400 mass%, and the proportion of the copolymer (C) with respect to the phosphorus-based flame retardant (B) is 10 mass% or less.

Description

This application is a divisional application based on the following Chinese patent application: Original filing date: May 27, 2021 Original application number: CN202180037245.X (PCT / JP2021 / 020189) Original application title: Resin composition and molded article Technical field

[0001] The present invention relates to a resin composition and a molded article. This application claims priority based on Japanese Patent Application No. 2020-93089 filed on May 28, 2020, and Japanese Patent Application No. 2021-44430 filed on March 18, 2021, and incorporates their contents by reference. Background art

[0002] Since polyolefin resins have excellent mechanical properties (such as bending properties and tensile properties), chemical resistance, and moldability, and are low in density and inexpensive, their molded articles can be used in various applications such as machinery, electrical and electronic equipment, office equipment, interior and exterior materials for motor vehicles, and electric vehicles. The molded articles in these applications sometimes require flame retardancy. For example, high flame retardancy is required for molded articles such as the casings (frames, housings, outer packages, lids, etc.) of electrical and electronic equipment and office equipment, and cables.

[0003] Since polyolefin resins are highly flammable, flame retardants are mixed to impart flame retardancy to their molded articles. In the past, as flame retardants, a system using a combination of brominated flame retardants and antimony compounds was used because of its low cost and high flame retardancy. However, due to the problem of bioaccumulation, phosphorus-based flame retardants have been used in recent years. In Patent Document 1, a polyolefin resin composition containing two specific phosphorus-based flame retardants is proposed.

[0004] On the other hand, in Patent Document 2, a resin composition containing a dispersant for polyolefin additives such as a flame retardant and a crystal nucleating agent, polyolefin additives, and a polyolefin resin is proposed. The dispersant uses a methacrylic acid alkyl ester-based polymer mainly composed of a methacrylic acid alkyl ester unit having an alkyl group with 2 or more carbon atoms.

[0005] In addition, in Patent Document 3, a flame-retardant resin composition composed of an olefin-based polymer, an ethylene-based polymer containing a maleic anhydride component, and a flame retardant is proposed. Further, in Patent Document 4, a halogen-free flame-retardant resin composition is proposed, which contains a specific amount of a terpolymer of ethylene and an α-olefin having a polar group and maleic anhydride and a specific amount of a halogen-free flame retardant of 180 to 250 parts by mass. Prior art documents Patent documents

[0006] [Patent Document 1] Japanese Patent Laid-Open No. 2013-119575 [Patent Document 2] International Publication No. 2011 / 96596 [Patent Document 3] Japanese Patent Laid-Open No. 5-117452 [Patent Document 4] Japanese Patent Laid-Open No. 2014-91753 Summary of the invention Problems to be solved by the invention

[0007] However, in the resin composition described in Patent Document 1, the dispersibility of the phosphorus-based flame retardant is poor, and there are problems of poor dispersion of the phosphorus-based flame retardant in the molded body, resulting in poor appearance. In the resin composition described in Patent Document 2, the addition amount of the dispersant is large, and there is a case where excellent physical properties such as the mechanical properties of the polyolefin resin are impaired.

[0008] In addition, in the compositions described in Patent Documents 3 and 4, it is understood that there are cases where a molded body having sufficient mechanical strength and flexural modulus of elasticity and high flame retardancy cannot be provided.

[0009] An object of the present invention is to provide a resin composition and a molded body thereof, in which a phosphorus-based flame retardant is well dispersed, and excellent flame retardancy can be exhibited while sufficiently maintaining the original physical properties of the polyolefin resin. Technical solutions for solving the problems

[0010] The present invention has the following aspects. [1] A resin composition, which comprises a thermoplastic resin (A), a phosphorus-based flame retardant (B), and a copolymer (C) of an α-olefin and an unsaturated carboxylic acid, wherein the proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) is 5% by mass or more and 400% by mass or less, and the proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) is 10% by mass or less. [2] The resin composition according to [1], wherein the proportion of the thermoplastic resin (A) relative to the total mass of the resin composition is 20% by mass or more and 85% by mass or less. [3] The resin composition according to [1] or [2], wherein the copolymer (C) is a copolymer of an α-olefin and maleic anhydride. [4] The resin composition according to any one of [1] to [3], wherein the thermoplastic resin (A) is a polyolefin resin. [5] A molded article is composed of the resin composition described in any one of [1] to [4]. Advantages of the Invention

[0011] According to the present invention, there is provided a resin composition and a molded article thereof, in which a phosphorus-based flame retardant is well dispersed, and excellent flame retardancy can be exhibited while sufficiently maintaining the original physical properties of the polyolefin resin. Detailed Description of the Invention

[0012] [Resin Composition] The resin composition according to one embodiment of the present invention (hereinafter also referred to as "the present resin composition") contains a thermoplastic resin (A), a phosphorus-based flame retardant (B), and a copolymer (C) of an α-olefin and an unsaturated carboxylic acid. The proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) (100% by mass) is 5% by mass or more and 400% by mass or less, and the proportion of the copolymer (C) relative to the flame retardant (B) (100% by mass) is 10% by mass or less.

[0013] By having this composition, the present resin composition can obtain a molded article with less reduction in mechanical properties and high flame retardancy. Since the copolymer (C) of an α-olefin and an unsaturated carboxylic acid has parts with high affinity for the thermoplastic resin (A) and the phosphorus-based flame retardant (B) respectively, by containing the copolymer (C) in an appropriate amount, the dispersion of the phosphorus-based flame retardant (B) in the thermoplastic resin (A) becomes good. Therefore, a reduction in mechanical properties due to the aggregation of the phosphorus-based flame retardant (B) can be prevented. On the other hand, due to the dispersion effect of the phosphorus-based flame retardant (B), an improvement in flame retardancy can also be expected. However, since the copolymer (C) of an α-olefin and an unsaturated carboxylic acid has a tendency to be easily combustible, if the copolymer (C) is too much, the copolymer (C) will be largely distributed on the surface of the molded article, and the flame retardancy of the molded article will instead become low. Therefore, by containing the thermoplastic resin (A), the phosphorus-based flame retardant (B), and the copolymer (C) of an α-olefin and an unsaturated carboxylic acid within an appropriate range, a resin composition capable of obtaining a molded article with less reduction in mechanical properties and high flame retardancy can be provided.

[0014] The present resin composition may further contain other flame retardants or flame retardant aids other than the phosphorus-based flame retardant (B). Within the range not impairing the effects of the present invention, the present resin composition may contain other components other than those described above as needed.

[0015] [Thermoplastic Resin (A)] As the thermoplastic resin, although there is no particular limitation, examples thereof include polyolefin resins, polycarbonate resins, polyester resins, acrylonitrile-styrene resins, ABS resins, polyamide resins, modified polyphenylene ethers, etc. It should be noted that one of these may be used, or two or more thereof may be used. For example, the thermoplastic resin (A) may be a composite resin of two or more of the above-mentioned thermoplastic resins.

[0016] As the polyolefin resin, there is no particular limitation, and the resins described below can be cited. As the polyester resin, there is no particular limitation, and for example, polybutylene terephthalate can be cited. As the polyamide resin, there is no particular limitation, and for example, nylon 66 and nylon 6 can be cited. Among them, particularly in the present invention, the thermoplastic resin (A) is particularly useful when it is a polyolefin resin. It should be noted that in the present invention, "polyolefin resin" means a resin in which the proportion of olefin units or cycloolefin units is 90 mol% or more with respect to 100 mol% of all structural units constituting the resin. With respect to 100 mol% of all structural units constituting the polyolefin resin, the proportion of olefin units or cycloolefin units is preferably 95 mol% or more, more preferably 98 mol% or more.

[0017] As the polyolefin resin, for example, α-olefin polymers such as polyethylene, polypropylene, polybutene, poly(3-methyl-1-butene), poly(3-methyl-1-pentene), poly(4-methyl-1-pentene), etc. can be cited; α-olefin copolymers such as ethylene-propylene block or random copolymers, α-olefin-propylene block or random copolymers having 4 or more carbon atoms, ethylene-methyl methacrylate copolymers, ethylene-vinyl acetate copolymers, etc.; cycloolefin polymers such as polycyclohexene and polycyclopentene, etc. As polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, etc. can be cited. As polypropylene, isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene, stereoblock polypropylene, etc. can be cited. Among the α-olefin-propylene block or random copolymers having 4 or more carbon atoms, as the α-olefin having 4 or more carbon atoms, butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, etc. can be cited. These polyolefin resins can be used alone or in combination of two or more.

[0018] The polyolefin resin preferably contains polypropylene. Polypropylene and other polyolefin resins can also be used in combination. For example, as the polyolefin resin, a mixture of polypropylene and other α-olefin polymers such as ethylene-propylene block or random copolymers, α-olefin-propylene block or random copolymers having 4 or more carbon atoms can also be used. The polyolefin resin preferably has polypropylene as the main component. The proportion of polypropylene, relative to 100% by mass of the polyolefin resin, is preferably 50% by mass or more, more preferably 60% by mass or more. From the viewpoint of flame retardancy, the polyolefin resin is particularly preferably polypropylene.

[0019] The melt flow rate (MFR) of the thermoplastic resin (A) is preferably 0.1 g / 10 min or more, more preferably 0.5 g / 10 min or more. On the other hand, it is preferably 80 g / 10 min or less, more preferably 60 g / 10 min or less. If the MFR of the thermoplastic resin (A) is at or above the lower limit value, the molding processability is more excellent. If it is at or below the upper limit value, the bending properties, tensile properties, chemical resistance properties, etc. are more excellent. The preferred lower limit value and upper limit value can be appropriately combined (the same applies hereinafter). The MFR of the thermoplastic resin (A) can be, for example, 0.1 g / 10 min or more and 80 g / 10 min or less, or can be 0.5 g / 10 min or more and 60 g / 10 min or more. The melt flow rate of the thermoplastic resin (A) is measured according to JIS K7210 under the conditions of a temperature of 230 °C and a load of 2.16 kg.

[0020] Relative to the total mass of the resin composition, the proportion of the thermoplastic resin (A) is preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 40% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. On the other hand, it is preferably 85% by mass or less, more preferably 83% by mass or less, and further preferably 80% by mass or less. If the proportion of the thermoplastic resin (A) is at or above the lower limit value, the inherent physical properties of the thermoplastic resin (A) are likely to be exhibited. If it is at or below the upper limit value, the flame retardancy is more excellent. Relative to the total mass of the resin composition, the proportion of the thermoplastic resin (A) can be, for example, 20% by mass or more and 85% by mass or less, can be 30% by mass or more and 85% by mass or less, can be 40% by mass or more and 85% by mass or less, can be 50% by mass or more and 85% by mass or less, can be 55% by mass or more and 83% by mass or less, can be 60% by mass or more and 80% by mass or less.

[0021] [Phosphorus-based flame retardant (B)] The phosphorus-based flame retardant (B) is a phosphorus compound, that is, a compound containing a phosphorus atom in the molecule. The phosphorus-based flame retardant (B) exerts a flame retardant effect by forming a coke layer during the combustion of the resin composition. As the phosphorus-based flame retardant (B), it can be a known substance. For example, (poly)phosphates, (poly)phosphoric acid esters, etc. can be listed. "(Poly)phosphates" means phosphates or polyphosphates. "(Poly)phosphoric acid esters" means phosphoric acid esters or polyphosphoric acid esters. The phosphorus-based flame retardant (B) is preferably a solid at 80°C.

[0022] As the phosphorus-based flame retardant (B), (poly)phosphates are preferred from the viewpoint of flame retardancy. As the (poly)phosphates, for example, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, melamine orthophosphate, calcium phosphate, magnesium phosphate can be listed. In addition, in the above examples, compounds in which melamine or piperazine is replaced with other nitrogen compounds can also be used. As other nitrogen compounds, for example, N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, 1,4-bis(2-aminoethyl)piperazine, 1,4-bis(3-aminopropyl)piperazine, acetylguanamine, benzoguanamine, acryloylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, 2,4-diamino-6-hydroxy-1,3,5-triazine, 2-amino-4,6-dihydroxy-1,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-ethoxy-1,3,5-triazine, 2,4-diamino-6-propoxy-1,3,5-triazine, 2,4-diamino-6-isopropoxy-1,3,5-triazine, 2,4-diamino-6-mercapto-1,3,5-triazine, 2-amino-4,6-dimercapto-1,3,5-triazine, cyanurodiamide, benzoguanamine, acetylguanamine, phthalodiguanamine, cyanuric acid melamine, melamine pyrophosphate, butylidene biguanide, norbornene biguanide, methylene biguanide, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylidenebisimelamine can be listed. These (poly)phosphates can be used alone or in combination of two or more.

[0023] As the phosphorus-based flame retardant (B), among the above, it is preferably a salt of (poly)phosphoric acid and a nitrogen compound (hereinafter, also referred to as "compound (B1)"). "(Poly)phosphoric acid" means phosphoric acid or polyphosphoric acid. Compound (B1) is an intumescent flame retardant, and when the resin composition burns, it forms a foamed and charred surface intumescent layer. By forming the surface intumescent layer, the diffusion of decomposition products and heat transfer are suppressed, and excellent flame retardancy is exhibited. Examples of the nitrogen compound in compound (B1) include ammonia water, melamine, piperazine, and the other nitrogen compounds mentioned above.

[0024] Examples of the commercial products of the phosphorus-based flame retardant (B) include ADK STAB FP-2100J, FP-2200, and FP-2500S (manufactured by ADEKA Corporation).

[0025] As described above, the proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) (100% by mass) is 5% by mass or more and 400% by mass or less. By setting the proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) within this range, when copolymer (C) of an α-olefin and a carboxylic anhydride described later is used in combination, high flame retardancy can be obtained while preventing a significant decrease in mechanical properties and flexural modulus.

[0026] Among the above, the proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) is preferably 10% by mass or more, more preferably 15% by mass or more, particularly preferably 20% by mass or more. On the other hand, it is preferably 300% by mass or less, more preferably 250% by mass or less, more preferably 200% by mass or less, more preferably 150% by mass or less, more preferably 100% by mass or less, more preferably 80% by mass or less, further preferably 50% by mass or less, particularly preferably 40% by mass or less. The proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) can be, for example, 5% by mass or more and 300% by mass or less, can be 5% by mass or more and 250% by mass or less, can be 5% by mass or more and 200% by mass or less, can be 5% by mass or more and 150% by mass or less, can be 5% by mass or more and 100% by mass or less, can be 10% by mass or more and 80% by mass or less, can be 15% by mass or more and 50% by mass or less, can be 20% by mass or more and 40% by mass or less.

[0027] The proportion of the phosphorus-based flame retardant (B) relative to the total mass of the present resin composition is preferably 15% by mass or more, more preferably 17% by mass or more, and further preferably 20% by mass or more. On the other hand, it is preferably 50% by mass or less, more preferably 45% by mass or less, and further preferably 40% by mass or less. If the proportion of the phosphorus-based flame retardant (B) is above the above lower limit value, the flame retardancy is more excellent. If it is below the above upper limit value, the original physical properties of the thermoplastic resin (A) are likely to be exhibited. The proportion of the phosphorus-based flame retardant (B) relative to the total mass of the present resin composition can be, for example, 15% by mass or more and 50% by mass or less, can be 17% by mass or more and 45% by mass or less, and can be 20% by mass or more and 40% by mass or less.

[0028] [Copolymer (C) of α-olefin and unsaturated carboxylic acid] The copolymer (C) improves the dispersibility of the phosphorus-based flame retardant (B) in the thermoplastic resin (A). In the present invention, the "copolymer (C) of α-olefin and unsaturated carboxylic acid" means a copolymer in which the proportion of the α-olefin unit is 20 mol% or more and 80 mol% or less relative to the total of 100 mol% of the α-olefin unit and the unsaturated carboxylic acid unit. In the copolymer (C), the proportion of the α-olefin unit is preferably 30 mol% or more and, on the other hand, preferably 70 mol% or less relative to the total of 100 mol% of the α-olefin unit and the unsaturated carboxylic acid unit. If the proportion of the α-olefin unit is above the above lower limit value, particularly, the compatibility with the polyolefin resin is more excellent. If it is below the above upper limit value, the compatibility with the phosphorus-based flame retardant (B) is more excellent.

[0029] In the copolymer (C), as the α-olefin, an α-olefin having 10 or more and 80 or less carbon atoms is preferred. If the number of carbon atoms of the α-olefin is 10 or more, particularly, the compatibility with the polyolefin resin tends to become better. If it is 80 or less, the raw material cost tends to become better. The number of carbon atoms of the α-olefin is more preferably 12 or more and 70 or less, and further preferably 18 or more and 60 or less.

[0030] In the copolymer (C), examples of the unsaturated carboxylic acid include (meth)acrylic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, glutaric acid, norbornene-5-ene-2,3-dicarboxylic acid, and esters, acid anhydrides, imides, etc. of these unsaturated carboxylic acids. "(Meth)acrylic acid" means acrylic acid or methacrylic acid. Specific examples of the ester, acid anhydride or imide of the unsaturated carboxylic acid include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate; dicarboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride; maleimide compounds such as maleimide, N-ethylmaleimide, N-phenylmaleimide, etc. These can be used alone or in combination of two or more. Among the above, from the viewpoint of copolymerization reactivity, esters and dicarboxylic anhydrides are preferred. Among them, from the viewpoint of compatibility with the phosphorus-based flame retardant (B), dicarboxylic anhydrides are preferred, and maleic anhydride is particularly preferred.

[0031] The weight average molecular weight of the copolymer (C) is preferably 2,000 or more, more preferably 3,000 or more. On the other hand, it is preferably 50,000 or less, more preferably 30,000 or less. When the weight average molecular weight of the copolymer (C) is within the above upper and lower limit ranges, the dispersibility of the phosphorus-based flame retardant (B) is more excellent. The weight average molecular weight of the copolymer (C) can be, for example, 2,000 or more and 50,000 or less, or can be 3,000 or more and 30,000 or less. The weight average molecular weight of the copolymer (C) is the standard polystyrene conversion value measured by gel permeation chromatography after dissolving the copolymer (C) in tetrahydrofuran (THF).

[0032] Examples of the commercial products of the copolymer (C) include Licolub CE2 (manufactured by Kline Japan Co., Ltd.) and DIACARNA 30M (manufactured by Mitsubishi Chemical Corporation).

[0033] As described above, while the present resin composition contains the copolymer (C), the proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) is 10% by mass or less. Among them, relative to the phosphorus-based flame retardant (B) (100% by mass), the proportion of the copolymer (C) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, particularly preferably 0.3% by mass or more. On the other hand, it is preferably 8% by mass or less, further preferably 6% by mass or less, particularly preferably 5% by mass or less. When the proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) (100% by mass) is within the above range, a molded article having high flame retardancy can be obtained while maintaining high mechanical strength and high flexural modulus. The proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) (100% by mass) can be, for example, 0.01% by mass or more and 8% by mass or less, can be 0.05% by mass or more and 8% by mass or less, can be 0.1% by mass or more and 6% by mass or less, and can be 0.3% by mass or more and 5% by mass.

[0034] The proportion of the copolymer (C) relative to the total mass of the present resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.1% by mass or more. On the other hand, it is preferably 1.2% by mass or less, more preferably 1.1% by mass or less, and still more preferably 1.0% by mass or less. When the proportion of the copolymer (C) is at least the lower limit value, the phosphorus-based flame retardant (B) is well dispersed, and the flame retardancy and physical properties of the resin composition and the appearance of the obtained molded article become good. When the proportion of the copolymer (C) is at most the upper limit value, the influence of the copolymer (C) on the flame retardancy of the resin composition can be suppressed. The proportion of the copolymer (C) relative to the total mass of the present resin composition can be, for example, 0.01% by mass or more and 1.2% by mass or less, can be 0.03% by mass or more and 1.1% by mass or less, and can be 0.1% by mass or more and 1.0% by mass or less.

[0035] In addition, the proportion of the copolymer (C) relative to the total mass of the thermoplastic resin (A) and the phosphorus-based flame retardant (B) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% by mass or more. On the other hand, it is preferably 2.0% by mass or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less. When the proportion of the copolymer (C) is at least the lower limit value, the phosphorus-based flame retardant (B) is more well dispersed, and the flame retardancy and physical properties of the resin composition and the appearance of the obtained molded article become better. When the proportion of the copolymer (C) is at most the upper limit value, the influence of the copolymer (C) on the flame retardancy of the resin composition can be further suppressed. The proportion of the copolymer (C) relative to the total mass of the thermoplastic resin (A) and the phosphorus-based flame retardant (B) can be, for example, 0.01% by mass or more and 2.0% by mass or less, can be 0.05% by mass or more and 1.5% by mass or less, and can be 0.1% by mass or more and 1.0% by mass or less. The proportion of the thermoplastic resin (A), the phosphorus-based flame retardant (B), and the copolymer (C) relative to the total mass of the present resin composition is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and can also be 100% by mass.

[0036] [Other flame retardants or flame retardant aids] As other flame retardants or flame retardant aids, those preferably free of halogen, organic or inorganic flame retardants or flame retardant aids are used. As the relevant flame retardants or flame retardant aids, compounds containing a triazine ring, silicone-based flame retardants, metal hydroxides, metal oxides, boric acid compounds, expanded graphite, etc. can be cited.

[0037] As examples of the compounds containing a triazine ring, melamine, cyanuramide, benzoguanamine, acetylguanamine, phenyldiguanamine, melamine cyanurate, melamine pyrophosphate, butylidenebiguanamine, norbornenebiguanamine, methylenebiguanamine, ethylene bis-melamine, trimethylene bis-melamine, tetramethylene bis-melamine, hexamethylene bis-melamine, 1,3-hexylene bis-melamine, etc. can be cited. As examples of the silicone-based flame retardants, silicone oil, silicone rubber, silicone resin, etc. can be cited. As examples of the metal hydroxides, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, KISUMA 5A (magnesium hydroxide; manufactured by Kyowa Chemical Industry Co., Ltd.), etc. can be cited. As examples of the metal oxides, inorganic compounds such as zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, titanium dioxide, hydrotalcite and their surface-treated products can be cited. As specific examples of the metal oxides, TIPAQUE R-680 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.), KYOWAMAG 150 (magnesium oxide manufactured by Kyowa Chemical Industry Co., Ltd.), DHT-4A (hydrotalcite; manufactured by Kyowa Chemical Industry Co., Ltd.), ALCAMIZER 4 (zinc-modified hydrotalcite manufactured by Kyowa Chemical Industry Co., Ltd.), etc. can be cited. As examples of the boric acid compounds, zinc borate, etc. can be cited. These flame retardants or flame retardant aids can be used singly or in combination of two or more.

[0038] [Other components] This resin composition may contain at least one inorganic fiber filler (D) selected from the group consisting of glass fiber and carbon fiber. The inorganic fiber filler (D) can be used singly or in combination of two or more.

[0039] The type of the glass fiber is not particularly limited, and any glass fiber such as E glass, C glass, S glass, D glass, etc. can be used. The form of the glass fiber is not particularly limited either. Although any glass fiber such as chopped strands, rovings, yarns, glass wool, etc. can be used, based on the point of operability, chopped strands and glass wool are preferred.

[0040] The type of the carbon fiber is not particularly limited, and any carbon fiber such as polyacrylonitrile (PAN)-based carbon fiber, pitch-based carbon fiber, graphite fiber, etc. can be used. The method of using carbon fiber is not particularly limited. Although any carbon fiber such as filaments, regular tows, large tows, staple fiber yarns, and chopped strands can be used, chopped strands are preferred from the perspective of operability.

[0041] When the resin composition contains the inorganic fiber filler (D), the proportion of the inorganic fiber filler (D) relative to the total mass of the resin composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. On the other hand, it is preferably 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less, more preferably 25% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less. If the proportion of the inorganic fiber filler (D) is at least the lower limit value, it is easy to obtain an anti-tearing effect and a smoke suppression effect. If it is at most the upper limit value, it is not likely to damage the original physical properties of the thermoplastic resin (A).

[0042] When the resin composition contains the inorganic fiber filler (D), a surface strength improver (E) for the inorganic fiber filler (D) may be further contained. As the surface strength improver (E), particularly from the perspective of compatibility with the thermoplastic resin (A) such as polyolefin resin, a polymer having an olefin backbone (however, excluding polyolefin resin and copolymer (C)) is preferred. By making the olefin backbone compatible with the polyolefin resin, the surface strength is further improved.

[0043] The surface strength improver (E) preferably has an acidic group. The surface strength is improved by the reaction of the inorganic fiber filler (D) with the acidic group. Examples of the acidic group include a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group. It is preferably at least one selected from the group consisting of a carboxyl group, a carboxylic anhydride group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group, and a phosphinic acid group, more preferably at least one selected from the group consisting of a carboxyl group, a carboxylic anhydride group, and a phosphonic acid group, and particularly preferably at least one selected from the group consisting of a carboxyl group and a carboxylic anhydride group.

[0044] As a method for producing the surface strength improver (E) having an olefin backbone and an acidic group, there can be mentioned (1) a method of adding a compound or monomer having an acidic group after low molecular weightization by thermal decomposition of an olefin resin at a high temperature; (2) a method of adding a compound or monomer having an acidic group after polymerizing a low molecular weight olefin resin; (3) a method of copolymerizing an α-olefin and a compound or monomer having an acidic group, etc. As the polymerization method, radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization and living polymerization methods can be adopted. Further, a method of first forming a macromonomer and then performing polymerization can also be adopted. As a compound or monomer having an acidic group, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, citraconic anhydride, etc. can be mentioned, and maleic anhydride is particularly suitable.

[0045] As commercial products of the surface strength enhancer (E), for example, UMEX1001, 1010 (manufactured by Sanyo Chemical Industries, Ltd.), Kayabrid 002PP, 003PP (KAYAKU NOURYON Co., Ltd.) can be mentioned.

[0046] This resin composition may contain at least one selected from the group consisting of an antioxidant, an ultraviolet absorber, a light stabilizer, and an anti-aging agent.

[0047] As an antioxidant, for example, phenolic antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be mentioned. As phenolic antioxidants, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis[methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylene glycol bis[3,3-bis(4-hydroxy-3-tert-butylphenyl) butyrate], bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl]-2,4,8,10-tetraoxaspiro[5,5] undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], etc. can be cited. Relative to 100 parts by mass of the synthetic resin component in the resin composition, the content of the phenolic antioxidant is preferably 0.001 part by mass or more, more preferably 0.05 part by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

[0048] As phosphorus-based antioxidants, for example, trilauryl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl)-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetra(2,4-di-tert-butylphenyl) biphenyl diphosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenyl) fluorophosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butyl propylene glycol and 2,4,6-tri-tert-butylphenol, tris(2,4-di-tert-butylphenyl) phosphite, etc. can be cited. With respect to 100 parts by mass of the synthetic resin component in the resin composition, the content of the phosphorus-based antioxidant is preferably 0.001 part by mass or more, more preferably 0.05 part by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

[0049] As thioether-based antioxidants, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate and other dialkyl thiodipropionates, and pentaerythritol tetra(β-alkylthiopropionate) can be cited. With respect to 100 parts by mass of the synthetic resin component in the resin composition, the content of the thioether-based antioxidant is preferably 0.001 part by mass or more, more preferably 0.05 part by mass or more. On the other hand, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.

[0050] As ultraviolet absorbers, for example, 2-hydroxybenzophenone compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumenylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole and other 2-(2'-hydroxyphenyl)benzotriazole compounds; benzoic acid ester compounds such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, cetyl 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxyanilines such as 2-ethyl-2'-ethoxyaniline, 2-ethoxy-4'-dodecylaniline; cyanoacrylate compounds such as ethyl α-cyano-β,β-diphenylacrylate, methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; triaryltriazine compounds such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine can be cited. With respect to 100 parts by mass of the synthetic resin component in the resin composition, the content of the ultraviolet absorber is preferably 0.001 part by mass or more, more preferably 0.05 part by mass or more. On the other hand, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[0051] As a light stabilizer, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl)-4-piperidyl) sebacate, tetra(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-bis(tridecyl)-1,2,3,4-butane tetracarboxylate, bis(1,2,2,4,4-pentamethyl)-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate condensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine condensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine condensate, 1,5,8,12-tetra[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetra〔2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8-12-tetraazadodecane, 1,6,11-tri[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tri[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane and other hindered amine compounds can be cited. With respect to 100 parts by mass of the synthetic resin component in the resin composition, the content of the light stabilizer is preferably 0.001 part by mass or more, more preferably 0.05 part by mass or more. On the other hand, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less.

[0052] This resin composition may also contain other fillers other than the inorganic fiber filler (D). As other fillers, fibrous, flaky, granular, and powdery materials can be used. Specifically, inorganic fibrous reinforcing materials such as asbestos fiber, metal fiber, potassium titanate whisker, aluminum borate whisker, magnesium whisker, silicon whisker, wollastonite, sepiolite, asbestos, slag fiber, cristobalite, perovskite, gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, and boron fiber can be mentioned; organic fibrous reinforcing materials such as polyester fiber, nylon fiber, acrylate fiber, regenerated cellulose fiber, acetate fiber, kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, manila hemp, sugarcane, wood pulp, waste paper, waste paper, and wool; and plate-like and granular reinforcing materials such as glass sheet, non-swelling mica, graphite, metal foil, ceramic beads, clay, mica, sericite, zeolite, bentonite, dolomite, kaolin, fine silica, feldspar powder, potassium titanate, white sand balls, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, alumina, titanium oxide, titanium dioxide, aluminum silicate, gypsum, novaculite, dawsonite, and white clay. These fillers can be covered or bundled with thermoplastic resins such as ethylene-vinyl acetate copolymer or thermosetting resins such as epoxy resin, or can be treated with coupling agents such as amino silane and epoxy silane. With respect to 100 parts by mass of the synthetic resin component in the resin composition, the content of other fillers is preferably 10 parts by mass or more, more preferably 20 parts by mass or more. On the other hand, it is preferably 60 parts by mass or less, more preferably 50 parts by mass or less.

[0053] This resin composition may contain a crystallization nucleating agent. As the crystallization nucleating agent, those generally used as crystallization nucleating agents for polyolefin resins can be appropriately used. For example, inorganic crystallization nucleating agents and organic crystallization nucleating agents can be mentioned.

[0054] Specific examples of the inorganic crystallization nucleating agent include metal salts such as kaolinite, synthetic mica, clay, zeolite, graphite, carbon black, magnesium oxide, titanium oxide, calcium sulfide, boron nitride, calcium carbonate, barium sulfate, alumina, neodymium oxide, and phenylphosphonate. In order to improve the dispersibility in the composition, these inorganic crystallization nucleating agents can be modified with an organic substance.

[0055] Specific examples of the organic crystallization nucleating agent include metal salts of organic carboxylic acids such as sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, potassium terephthalate, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octacosanoate, calcium octacosanoate, sodium stearate, potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate, aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium β-naphthalenedicarboxylate, sodium cyclohexanecarboxylate, etc.; organic sulfonates such as sodium p-toluenesulfonate, sodium sulfoisophthalate; carboxamides such as stearamide, ethylene bislauramide, palmamide, hydroxystearamide, erucamide, tris(tert-butylamide) benzene-1,3,5-tricarboxylate, etc.; benzylidene sorbitol and its derivatives; metal salts of phosphorus compounds such as sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate; and sodium 2,2-methylenebis(4,6-di-tert-butylphenyl), etc.

[0056] The resin composition may contain a plasticizer. As the plasticizer, those commonly used as plasticizers for polyolefin resins can be appropriately used. For example, polyester plasticizers, glycerol plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, epoxy plasticizers, etc. can be cited. These plasticizers can be used alone or in combination of two or more.

[0057] Specific examples of the polyester plasticizer include polyesters composed of acid components such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, rosin, etc. and glycol components such as propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, etc., or polyesters composed of hydroxycarboxylic acids such as polycaprolactone. The chain ends of these polyesters can be blocked with monofunctional carboxylic acids or monofunctional alcohols, or can be capped with epoxy compounds, etc.

[0058] Specific examples of the glycerol plasticizer include glycerol monoacetyl monolaurate, glycerol diacetyl monolaurate, glycerol monoacetyl monostearate, glycerol diacetyl monooleate, and glycerol monoacetyl monomontanate, etc.

[0059] Specific examples of the polycarboxylic acid ester plasticizer include phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, and butyl benzyl phthalate; trimellitic acid esters such as tributyl trimellitate, trioctyl trimellitate, and trihexyl trimellitate; adipic acid esters such as diisodecyl adipate, n-octyl n-decyl adipate, methyl glycol butyl glycol adipate, benzyl methyl glycol adipate, and benzyl butyl glycol adipate; citric acid esters such as acetyl triethyl citrate and acetyl tributyl citrate; azelaic acid esters such as di-2-ethylhexyl azelate; sebacic acid esters such as dibutyl sebacate and di-2-ethylhexyl sebacate, etc.

[0060] Specific examples of the polyalkylene glycol plasticizer include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, poly(ethylene oxide·propylene oxide) block and / or random copolymers, polybutylene glycol, bisphenol-based ethylene oxide addition polymers, bisphenol-based propylene oxide addition polymers, bisphenol-based tetrahydrofuran addition polymers, and their end-capped compounds such as end-epoxy modified compounds, end-ester modified compounds, and end-ether modified compounds.

[0061] Epoxy plasticizers generally refer to epoxy triglycerides composed of epoxy stearic acid alkyl esters and soybean oil. In addition, so-called epoxy resins mainly composed of bisphenol A and epichlorohydrin can also be used.

[0062] Specific examples of other plasticizers include benzoates of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, and triethylene glycol di-2-ethylbutyrate; fatty acid amides such as stearamide; aliphatic carboxylic acid esters such as butyl oleate; hydroxy acid esters such as methyl acetyl ricinoleate and butyl acetyl ricinoleate; pentaerythritol, various sorbitols, polyacrylates, and paraffins.

[0063] This resin composition may also contain a fluorine-containing anti-dripping agent. Examples of the fluorine-containing anti-dripping agent include fluorine-containing polymers having fibril-forming ability. Examples of related fluorine-containing polymers include polytetrafluoroethylene (hereinafter referred to as "PTFE"), tetrafluoroethylene copolymers (e.g., tetrafluoroethylene / hexafluoropropylene copolymers), partially fluorinated polymers as shown in U.S. Patent No. 4,379,910, polycarbonate resins made from fluorinated bisphenols, etc. Among them, PTFE is preferred.

[0064] PTFE with fibril-forming ability refers to PTFE having an extremely high molecular weight. When subjected to external actions such as shear force, PTFE shows a tendency to combine with each other to form fibrils. Among the number-average molecular weights obtained from the standard specific gravity, this molecular weight is preferably 1 million or more, more preferably 2 million or more. On the other hand, it is preferably 10 million or less, more preferably 9 million or less. PTFE with fibril-forming ability can be used in the form of an aqueous dispersion in addition to the solid shape.

[0065] As vendible products of PTFE with fibril-forming ability, for example, Teflon (registered trademark) 6J of Mitsui DuPont Fluorochemical Co., Ltd., Polyflon (registered trademark) MPA FA500 and F-201L of Daikin Industries, Ltd. can be cited. As vendible products of the aqueous dispersion of PTFE, Fluon AD-939E manufactured by AIF Co., Ltd., Fluon D-310, D-210C manufactured by Daikin Industries, Ltd., Teflon31JR manufactured by Mitsui DuPont Fluorochemical Co., Ltd., etc. can be cited.

[0066] In order to improve the dispersibility of PTFE with fibril-forming ability in the resin composition, and further in order to obtain good flame retardancy, mechanical properties and flexural modulus of elasticity, a PTFE mixture in the form of a mixture of PTFE with fibril-forming ability and other resins can be used. Relative to the total mass of the PTFE mixture, the proportion of PTFE is preferably 1% by mass or more, more preferably 5% by mass or more. On the other hand, it is preferably 60% by mass or less, more preferably 55% by mass or less. When the proportion of PTFE is within the above range, good dispersibility of PTFE can be achieved.

[0067] PTFE mixtures, for example, can use the methods of (1) mixing and co-precipitating an aqueous dispersion of PTFE and an aqueous dispersion or solution of other resins to obtain a co-condensed mixture (methods described in Japanese Patent Laid-Open No. Sho 60-258263, Japanese Patent Laid-Open No. Sho 63-154744, etc.); (2) mixing an aqueous dispersion of PTFE with particles of other dried resins (methods described in Japanese Patent Laid-Open No. Hei 4-272957); (3) uniformly mixing an aqueous dispersion of PTFE and a solution of other resins, and simultaneously removing each solvent from the mixture (methods described in Japanese Patent Laid-Open No. Hei 06-220210, Japanese Patent Laid-Open No. Hei 08-188653, etc.); (4) polymerizing monomers of other resins in an aqueous dispersion of PTFE (methods described in Japanese Patent Laid-Open No. Hei 9-95583); or (5) uniformly mixing an aqueous dispersion of PTFE with a dispersion of other resins, polymerizing vinyl-based monomers in the obtained mixed dispersion to obtain a subsequent mixture (methods described in Japanese Patent Laid-Open No. Hei 11-29679, etc.). Examples of PTFE mixture products for sale include "METABLEN A3000" of Mitsubishi Chemical Corporation, "BLENDEX B449" of GESPECIALTY CHEMICALS, etc.

[0068] With respect to 100 parts by mass of the present resin composition, the content of the fluorine-containing anti-dripping agent is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and further preferably 0.1 part by mass or more in terms of the amount of PTFE. On the other hand, it is preferably 1 part by mass or less, more preferably 0.8 part by mass or less, and further preferably 0.5 part by mass or less.

[0069] In the present resin composition, in addition to the above, within the range not impairing the effects of the present invention, additives commonly used in synthetic resins can be included, such as crosslinking agents, antistatic agents, metal soaps, fillers, antifogging agents, anti-bleeding agents, surface treatment agents, fluorescent agents, mildew-proof agents, bactericides, foaming agents, metal passivators, mold release agents, pigments, processing aids, etc.

[0070] [Manufacturing method of resin composition] When manufacturing the present resin composition, any method can be adopted. For example, it can be mentioned that the thermoplastic resin (A), phosphorus-based flame retardant (B), copolymer (C), and other flame retardants and flame retardant aids, and other components as required are fully mixed using a V-type mixer, Henschel mixer, mechanochemical device, extrusion mixer, etc. pre-mixing unit, and can be granulated by an extrusion granulator or a briquetting machine as the case may be, and then melt-kneaded by a melt-kneading machine and extruded. Examples of the melt kneading machine include twin-screw extruders such as a vented twin-screw extruder, a Banbury mixer, a kneading roll, a single-screw extruder, and a multi-screw extruder having three or more screws. The temperature during melt kneading is, for example, 170 to 260°C. The resin composition extruded as described above may be directly cut by a pelletizer or the like to be pelletized, or may be cooled to form strands, and then the strands may be cut by a pelletizer or the like to be pelletized.

[0071] The resin composition described above contains the copolymer (C) together with the thermoplastic resin (A) and the phosphorus-based flame retardant (B), and can exhibit excellent flame retardancy while fully maintaining the original physical properties (e.g., mechanical strength and flexural modulus) of the polyolefin resin (A). The copolymer (C) is used to improve the dispersibility of the phosphorus-based flame retardant (B) in the thermoplastic resin (A) such as the polyolefin resin. Since the dispersibility of the phosphorus-based flame retardant (B) is improved, it becomes easier to form a char layer during combustion, thereby improving the flame retardancy. Although the mechanism is not yet clear, it is considered as follows. In particular, when the thermoplastic resin (A) is a polyolefin resin, the polyolefin resin is classified as a low-polarity resin among thermoplastic resins, and it is difficult to disperse polar additives such as phosphorus-based flame retardants (B). On the other hand, the low-polarity α-olefin part of the copolymer (C) has excellent compatibility with the polyolefin resin, and the polar unsaturated carboxylic acid part has excellent compatibility with the phosphorus-based flame retardant (B). When the resin composition is melt-kneaded, the presence of the copolymer (C) between the polyolefin resin and the phosphorus-based flame retardant (B) improves the dispersibility of the phosphorus-based flame retardant (B) in the polyolefin resin.

[0072] Examples of the effects of the copolymer (C) include (1) improving the dispersibility of the phosphorus-based flame retardant (B) (fine dispersion); (2) promoting the formation of a coke layer during combustion; and (3) improving physical properties (tensile breaking point strain). As the effect during combustion, specifically, when the flat test piece obtained by molding the resin composition including thermoplastic resin (A) and phosphorus flame retardant (B) is roasted with a flamethrower, the resin composition, when not including copolymer (C), forms small and many coke pieces on the surface, but when the resin composition includes copolymer (C), the size of the coke pieces is enlarged, and the heat transfer inhibition effect is improved. In addition, in the cone calorimeter test, the 3mm thick flat plate obtained by molding the resin composition including thermoplastic resin (A) and phosphorus flame retardant (B), when burned by radiant heat, when copolymer (C) is not included in the resin composition, more coke piece gaps are generated, and the molded body burns, and when the resin composition includes copolymer (C), the gap of the coke piece is reduced, and the coke piece is formed in the combustion of the side and becomes dome-shaped. Although the mechanism is not yet clear, by adding the copolymer (C), a more stable coke layer is formed, heat transfer is inhibited, and V-0 can be achieved in the UL94 test. Even a small amount of the copolymer (C) (for example, 1.2% by mass or less relative to the total mass of the resin composition) can achieve the above effects.

[0073] According to this resin composition, since the phosphorus-based flame retardant (B) is well dispersed, a molded article having a dispersibility of, for example, 22% or less, further 21% or less, calculated according to the following formula can be obtained. Dispersibility [%] = 4,000 μm 2 Sum of the area values of particles of the above size [μm 2 ÷ Flame retardant area (threshold 3%, 136,331) [μm 2 × 100 Here, the sum of the area values of particles of 4,000 μm 2 or more in size and the flame retardant area are obtained by image processing of the optical microscope image of the molded article. Details are as described in the examples below.

[0074] 〔Molded article〕 The molded article according to one embodiment of the present invention is composed of this resin composition. The shape of the molded article is not particularly limited, and can be various shapes such as resin plates, sheets, films, cables, and irregular objects.

[0075] The molded article can be obtained by molding this resin composition. The molding method is not particularly limited, and examples include extrusion processing, calendering processing, injection molding, winding into a roll, compression molding, blow molding, and the like. The temperature at the time of molding this resin composition is, for example, 170 to 260 °C.

Examples

[0076] Hereinafter, specific descriptions will be made through examples of the present invention. However, the present invention is not limited by the following examples. In addition, in the following examples and the like, unless otherwise specified, % is based on mass standards. The following items were evaluated.

[0077] (1) Flame retardancy (UL94) Using the obtained molded article (1 / 16-inch test bar), the flame retardancy was judged based on the UL94 standard.

[0078] (2) Evaluation of dispersibility of flame retardant 1 The number of undispersed flame retardants present in the obtained molded article (a sheet with a thickness of 0.5 mm) was evaluated. As the evaluation process, the sheet was irradiated with transmitted light using an optical microscope (manufactured by Nikon, product name: ECLIPSE E600W POL), and observed at a magnification of 50 times (eyepiece 10 times, objective lens 5 times). Based on this optical microscope image, using image processing software (Image J, Ver 1.52a), 5 images of 640×480 pixels were randomly selected and converted into 8-bit format. When observing at 50 times magnification, since 1,000 μm is 260 pixels, 640×480 pixels is 4,454,379 μm 2 . After that, through Bandpass filter processing, the flame retardants in the sheet were emphasized and the concentration was measured. Since the flame retardants have the strongest contrast in the image, the area with a value of 3% after binarization from the minimum value (0) was used as the threshold to extract the flame retardant area. Then, among the particles in the binarized image, the area of particles with a size of 4,000 μm 2 or more was summed up, and the dispersibility [%] was calculated using the following formula, and the average value of the dispersibility of the 5 images was obtained respectively. Dispersibility [%] = Area value sum of particles with a size of 4,000 μm 2 or more [μm 2 ÷ Flame retardant area (threshold 3%, 136,331) [μm 2 × 100

[0079] (3) Evaluation of flame retardant dispersibility 2 The same operation as the (2) Evaluation of flame retardant dispersibility 1 was performed, and the dispersibility was compared based on the following criteria from the observed images. A: The number of flame retardant particles observed in the picture is 100 or more. B: The number of flame retardant particles in the picture is 50 or more and less than 100. C: The number of flame retardant particles in the picture is less than 50. D: The number of flame retardant particles in the picture is less than 30. It should be noted that in this evaluation, the dispersibility is better as it goes from A to D. (4) Bending characteristics The obtained molded article (JIS K7139-A1 dumbbell-shaped test piece) was cut into a length of 80 mm, and the flexural modulus (GPa) was measured based on JIS K7171.

[0080] (5) Tensile characteristics Using the obtained molded body (JIS K7139-A1 dumbbell-shaped test piece), the tensile yield point strength (MPa) and the tensile fracture point strain (%) were measured based on JIS K7161-1.

[0081] (6) Heat of combustion (cone calorimeter) For a test piece of 100 mm × 100 mm × 3 mm thick, using the Toyo Seiki Co., Ltd. model: C3 cone calorimeter III, based on ISO5660-1 (2002), under the condition of radiant heat of 50 kW / m 2 , the maximum heat release rate (kW / m 2 ) and the total heat of combustion (MJ / m 2 ) were measured.

[0082] The following were used as raw materials. <Polyolefin resin> A-1: Polypropylene resin (manufactured by Nippon PolyPro Co., Ltd., NOVATEC PP FY-4, melt flow rate 5 g / 10 min). A-2: Polypropylene resin (manufactured by Nippon PolyPro Co., Ltd., NOVATEC PP SA06GA, melt flow rate 60 g / 10 min). <Flame retardant> B: Phosphorus-based flame retardant composition (manufactured by ADEKA Corporation, ADK STAB FP-2200, containing 50 - 60% of piperazine pyrophosphate, 35 - 45% of melamine pyrophosphate, and 3 - 6% of zinc oxide relative to the total mass of the phosphorus-based flame retardant composition).

[0083] <Dispersant> C-1: α-olefin·maleic anhydride copolymer (manufactured by Mitsubishi Chemical Corporation, DIACARNA 30M, weight average molecular weight 7,800). C-2: α-olefin·maleic anhydride copolymer (manufactured by Clariant Japan K.K., Licolub CE2, weight average molecular weight 13,500). C-3: Maleic anhydride-modified polyethylene (manufactured by Mitsui Chemicals, Inc., Hi-WAX 1105A). C-4: Acid-modified polyethylene (manufactured by Clariant Japan K.K., Licolub H12).

[0084] [Examples 1 - 7, Comparative Examples 1 - 4] The raw materials shown in Table 1 were mixed in the proportions described in Table 1 and mixed by hand. After that, using Co-rotating twin-screw extruder (equipment name "BT-30", manufactured by Plastics Engineering Research Institute Co., Ltd., L / D = 30), melt-kneaded under the conditions of a screw rotation speed of 250 rpm and a barrel temperature of 200 °C to obtain a resin composition. "L / D" represents the ratio of the length (L) to the diameter (D) of the screw.

[0085] The obtained resin composition was injection-molded using a 100t injection molding machine (equipment name "SE-100DU", manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 200 °C to obtain a molded article (a 1 / 16-inch test bar). This molded article (1 / 16-inch test bar) was used as a test piece for UL94 evaluation. In addition, the obtained resin composition was injection-molded using a 100t injection molding machine (equipment name "SE-100DU", manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 200 °C to obtain a molded article (JIS K7139-A1 dumbbell-shaped test piece). This molded article (JIS K7139-A1 dumbbell-shaped test piece) was used as a test piece for evaluating bending properties and tensile properties.

[0086] In addition, the obtained resin composition was injection-molded using a 100t injection molding machine (equipment name "SE-100DU", manufactured by Sumitomo Heavy Industries, Ltd.) at a molding temperature of 200 °C to obtain a molded article (a 100×100×3 mm square plate). This molded article (100×100×3 mm square plate) was extruded using a hydraulic molding machine (manufactured by Shoji Iron Works Co., Ltd.) under the conditions of a molding temperature of 200 °C, a molding pressure of 10 MPa, and a process of preheating for 5 minutes, pressurizing for 5 minutes, and cooling for 5 minutes to obtain a molded article (sheet) with a thickness of 0.5 mm. This molded article (sheet) was used as a test piece for evaluating the dispersibility of the flame retardant.

[0087] The respective properties of these molded articles were measured. The results are shown in Table 1. It should be noted that regarding the dispersibility, Dispersibility Evaluation 1 was evaluated for Examples 1 to 7 and Comparative Examples 1 to 3, and Dispersibility Evaluation 2 was evaluated for Examples 4, Comparative Example 1, and 4. In addition, the ratios (%) of the dispersibility (value obtained from Dispersibility Evaluation 1), flexural modulus of elasticity, and tensile fracture point strain of each example and comparative example to the dispersibility (value obtained from Dispersibility Evaluation 1), flexural modulus of elasticity, and tensile fracture point strain of Comparative Example 1 were calculated. These values are shown in Table 1 as the dispersibility ratio, flexural modulus ratio, and tensile fracture point strain.

[0088] [Example 8] Using a composition of A-2: NOVATEC PP, 39.18% by mass of SA06GA as the polypropylene resin, B: 58.78% by mass of ADK STAB FP-2200 as the phosphorus-based flame retardant composition, C-1: 1.96% by mass of DIACARNA 30M as the dispersant, and 0.04% by mass of ADK STAB AO-60, 2112 as the antioxidant, use A co-rotating twin-screw extruder (equipment name "BT-30", manufactured by Plastics Engineering Institute Co., Ltd., L / D = 30) was used to melt and knead at a screw speed of 250 rpm and a barrel temperature of 200 °C to produce flame retardant masterbatch-1. Using a composition of 50% by mass of this masterbatch-1 and 50% by mass of the polypropylene resin A-1 NOVATEC PP FY4, mixing was carried out, and using a 100 t injection molding machine (equipment name "SE-100DU", manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was carried out under the condition of a molding temperature of 200 °C, and the same evaluation as in Example 1 was carried out. The obtained results are shown in Table 1.

[0089] [Example 9] Except for using a composition of A-2: NOVATEC PP, 29.31% by mass of SA06GA as the polypropylene resin, B: 68.39% by mass of ADK STAB FP-2200 as the phosphorus-based flame retardant composition, C: 2.25% by mass of DIACARNA 30M as the dispersant, and 0.03% by mass of ADK STAB AO-60, 2112 as the antioxidant, masterbatch-2 was obtained under the same conditions as in Example 8. After mixing using a composition of 47% by mass of the obtained masterbatch-2 and 53% by mass of the polypropylene resin A-1 NOVATEC PP FY4, injection molding was carried out under the same conditions as in Example 8, and the same evaluation as in Example 1 was carried out. The obtained results are shown in Table 1.

[0090]

Table 1

[0091] In Table 1, B / A is the proportion (%) of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) (100%). C / B is the proportion (%) of the copolymer (C) relative to the phosphorus-based flame retardant (B) (100%) (the same applies hereinafter).

[0092] The molded bodies of the resin compositions of Examples 1 to 9 containing the copolymer (C) (C-1 or C-2) of an α-olefin and an unsaturated carboxylic acid are excellent in flame retardancy and dispersibility of the flame retardant compared to the molded bodies of the resin composition of Comparative Example 1 that does not contain the copolymer (C). In addition, sufficient flexural modulus of elasticity and tensile yield point strength are exhibited. Further, due to the improved dispersibility of the flame retardant, the tensile break point strain is also improved. In addition, in Examples 1 to 9, since the test results of the UL94 standard all reached V-0, the resin compositions of Examples 1 to 9 are resin compositions capable of suppressing dripping during combustion.

[0093] On the other hand, for the molded body of the resin composition of Comparative Example 2 in which maleic anhydride-modified polyethylene was mixed instead of copolymer (C), although the flame retardancy was excellent, the dispersibility of the flame retardant was poor. In addition, the tensile fracture point strain ratio was small and the mechanical strength was poor. For the molded body of the resin composition of Comparative Example 3 in which acid-modified polyethylene was mixed instead of copolymer (C), the flame retardancy and the dispersibility of the flame retardant were poor. In addition, the tensile fracture point strain ratio was small and the mechanical strength was poor. In Comparative Example 4 where the proportion of copolymer (C) relative to the phosphorus-based flame retardant (B) was too large, although the dispersion of the flame retardant was good compared to Example 4, the flexural modulus of elasticity decreased significantly, seriously damaging the original properties of polypropylene.

[0094] [Combustion heat release comparison test based on a cone calorimeter] The raw materials shown in Table 2 were mixed in the proportions described in Table 2 by hand mixing. Then, using a co-rotating twin-screw extruder (equipment name "BT-30", manufactured by Plastic Engineering Research Institute Co., Ltd., L / D = 30), melt-kneaded at a screw rotation speed of 250 rpm and a barrel temperature of 200 °C to obtain a resin composition. For the obtained resin composition, in the same manner as in Example 1, a test piece for evaluating the dispersibility of the flame retardant was produced, and Dispersion Evaluation 1 was carried out to obtain the dispersibility and the dispersion ratio. The results are shown in Table 2. In addition, the obtained resin composition was injection-molded using a 100 t injection molding machine (equipment name "SE-100DU", manufactured by Sumitomo Heavy Industries, Ltd.) under the condition of a molding temperature of 200 °C to obtain a molded body (a square plate of 100 × 100 × 3 mm). For the obtained molded body, the combustion heat release was evaluated using a cone calorimeter. The results are shown in Table 2.

[0095] [Table 2]

[0096] Even in the comparison of the combustion heat release according to the cone calorimeter shown in Table 2, Examples 3, 10, and 11 containing the copolymer (C) (C-1 or C-2) of an α-olefin and an unsaturated carboxylic acid had a lower total heat release and maximum heat release rate compared to Comparative Examples 1 and 5 without the copolymer (C), and had excellent flame retardancy. Industrial availability

[0097] The resin composition according to the present invention can provide a molded article in which a phosphorus-based flame retardant is well dispersed, and which has excellent flame retardancy, mechanical strength, and flexural modulus of elasticity. The molded article obtained by using the resin composition of the present invention can be used as a molding material for applications in the fields of motor vehicles, office equipment such as printers, and electrical and electronic fields such as mobile phones, as well as for cables and the like due to its excellent flame retardancy, mechanical strength, and flexural modulus of elasticity.

Claims

1. A resin composition, wherein, It contains a thermoplastic resin (A), a phosphorus-based flame retardant (B), and a copolymer (C) of an α-olefin and an unsaturated carboxylic acid. The proportion of the phosphorus-based flame retardant (B) relative to the thermoplastic resin (A) is 5% by mass or more and 400% by mass or less. The thermoplastic resin (A) is a polyolefin resin. The phosphorus-based flame retardant (B) is a salt of (poly)phosphoric acid and a nitrogen compound. As the nitrogen compound, it contains melamine or piperazine. The α-olefin in the copolymer (C) has 10 or more and 80 or fewer carbon atoms. The proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) is 10% by mass or less.

2. The resin composition according to claim 1, wherein, Relative to the total mass of the resin composition, the proportion of the thermoplastic resin (A) is 20% by mass or more and 85% by mass or less.

3. The resin composition according to claim 1 or 2, wherein The copolymer (C) is a copolymer of an α-olefin and maleic anhydride.

4. The resin composition according to claim 1 or 2, wherein, The α-olefin in the copolymer (C) has 18 or more and 60 or fewer carbon atoms.

5. The resin composition according to claim 1 or 2, wherein In the copolymer (C), relative to a total of 100 mol% of the α-olefin unit and the unsaturated carboxylic acid unit, the proportion of the α-olefin unit is 30 mol% or more and 70 mol% or less.

6. The resin composition according to claim 1 or 2, wherein The weight-average molecular weight of the copolymer (C) is 2,000 or more and 50,000 or less.

7. The resin composition according to claim 1 or 2, wherein, It contains a metal oxide.

8. The resin composition according to claim 7, wherein, The metal oxide contains zinc oxide.

9. The resin composition according to claim 1 or 2, wherein In the polyolefin resin, relative to 100 mol% of all the structural units constituting the resin, the proportion of the olefin unit or the cycloolefin unit is 90 mol% or more.

10. A molded article composed of the resin composition according to any one of claims 1 to 9.

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