Resin composition and molded article

Abstract

The resin composition involved in the present invention comprises 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, and the proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) is 10% by mass or less.

Description

Technical Field

[0001] The present invention relates to a resin composition and a molded article.

[0002] 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

[0003] Since polyolefin resins have excellent mechanical properties (such as bending properties and tensile properties), chemical resistance, and moldability, and have a low density and low cost, 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.

[0004] 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.) for electrical and electronic equipment and office equipment, and cables.

[0005] Since polyolefin resins are highly flammable, flame retardants are mixed to impart flame retardancy to their molded articles.

[0006] 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.

[0007] In Patent Document 1, a polyolefin resin composition containing specific two phosphorus-based flame retardants is proposed.

[0008] 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 used is 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.

[0009] 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 containing 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 is proposed.

[0010] Prior Art Documents

[0011] Patent Documents

[0012]

Patent Document 1

[0013]

Patent Document 2

[0014]

Patent Document 3

[0015]

Patent Document 4

[0016] Problems to be Solved by the Invention

[0017] 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 article, resulting in poor appearance.

[0018] In the resin composition described in Patent Document 2, the addition amount of the dispersant is large, and there are cases where excellent physical properties such as the mechanical properties possessed by the polyolefin resin are impaired.

[0019] In addition, in the compositions described in Patent Documents 3 and 4, it is found that there are cases where a molded article having sufficient mechanical strength and flexural modulus of elasticity and high flame retardancy cannot be provided.

[0020] An object of the present invention is to provide 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.

[0021] Technical Solutions for Solving the Problems

[0022] The present invention has the following aspects.

[0023] [1] A resin composition, comprising 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.

[0024] [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.

[0025] [3] The resin composition according to [1] or [2], wherein the copolymer (C) is a copolymer of an α-olefin and maleic anhydride.

[0026] [4] The resin composition according to any one of [1] to [3], wherein the thermoplastic resin (A) is a polyolefin resin.

[0027] [5] A molded article comprising the resin composition according to any one of [1] to [4].

[0028] Advantages of the Invention

[0029] 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

[0030] 〔Resin Composition〕

[0031] 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.

[0032] By having this composition, the present resin composition can obtain a molded article with less reduction in mechanical properties and high flame retardancy.

[0033] Since the copolymer (C) of an α-olefin and an unsaturated carboxylic acid has parts with high affinity for both the thermoplastic resin (A) and the phosphorus-based flame retardant (B), by appropriately containing the copolymer (C), 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 excessive, the copolymer (C) will be largely distributed on the surface of the molded article, and the flame retardancy of the molded article will be rather 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.

[0034] The present resin composition may further contain other flame retardants or flame retardant aids other than the phosphorus-based flame retardant (B).

[0035] Within the range not impairing the effects of the present invention, the present resin composition may contain other components as needed in addition to the above.

[0036] [Thermoplastic resin (A)]

[0037] As the thermoplastic resin, there is no particular limitation, and 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.

[0038] 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.

[0039] Among them, in the present invention, particularly, when the thermoplastic resin (A) is a polyolefin resin, it is particularly useful. It should be noted that in the present invention, the "polyolefin resin" means a resin in which the proportion of olefin units or cycloolefin units is 90 mol% or more relative to 100 mol% of all the structural units constituting the resin.

[0040] The proportion of olefin units or cycloolefin units relative to 100 mol% of all the structural units constituting the polyolefin resin is preferably 95 mol% or more, more preferably 98 mol% or more.

[0041] 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.; 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, hemi-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.

[0042] The polyolefin resin preferably contains polypropylene.

[0043] It is also possible to use polypropylene and other polyolefin resins in combination. For example, as the polyolefin resin, a mixture of polypropylene and an ethylene-propylene block or random copolymer, an α-olefin-propylene block or random copolymer of an α-olefin having 4 or more carbon atoms, or other α-olefin polymers can also be used.

[0044] The polyolefin resin preferably has polypropylene as the main component. With respect to 100% by mass of the polyolefin resin, the proportion of polypropylene is preferably 50% by mass or more, more preferably 60% by mass or more.

[0045] From the viewpoint of flame retardancy, polypropylene is particularly preferred as the polyolefin resin.

[0046] 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.

[0047] The preferred lower limit value and upper limit value can be appropriately combined (the same applies hereinafter).

[0048] 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 0.5 g / 10 min or more and 60 g / 10 min or more.

[0049] The melt flow rate of the thermoplastic resin (A) is measured under the conditions of a temperature of 230°C and a load of 2.16 kg in accordance with JIS K7210.

[0050] With respect 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 more easily exhibited. If it is at or below the upper limit value, the flame retardancy is more excellent.

[0051] The proportion of the thermoplastic resin (A), relative to the total mass of the present resin composition, 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.

[0052] [Phosphorus-based flame retardant (B)]

[0053] The phosphorus-based flame retardant (B) is a phosphorus compound, that is, a compound containing a phosphorus atom in its molecule.

[0054] The phosphorus-based flame retardant (B) exerts a flame retardant effect by forming a coke layer during the combustion of the resin composition.

[0055] 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.

[0056] The phosphorus-based flame retardant (B) is preferably solid at 80 °C.

[0057] As the phosphorus-based flame retardant (B), based on the point of flame retardancy, (poly)phosphates are preferred.

[0058] As the (poly)phosphate, for example, ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, melamine polyphosphate, melamine orthophosphate, calcium phosphate, and magnesium phosphate can be mentioned. In addition, in the above exemplification, 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, acetoguanamine, 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, cyanuramide, benzoguanamine, acetoguanamine, phthalodiguanamine, cyanuric acid melamine, melamine pyrophosphate, butylidenebiguanide, norbornenebiguanide, methylenebiguanide, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylidenebis(melamine). These (poly)phosphates can be used alone or in combination of two or more.

[0059] As the phosphorus-based flame retardant (B), among the above, a salt of (poly)phosphoric acid and a nitrogen compound (hereinafter, also referred to as "compound (B1)") is preferred. "(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 carbonized intumescent surface layer. By forming the surface expansion layer, the diffusion of decomposition products and heat transfer are suppressed, and excellent flame retardancy is exhibited.

[0060] As the nitrogen compound in compound (B1), ammonia water, melamine, piperazine, and the above other nitrogen compounds can be mentioned.

[0061] As commercial products of the phosphorus-based flame retardant (B), for example, ADK STAB FP-2100J, FP-2200, and FP-2500S (manufactured by ADEKA Corporation) can be cited.

[0062] 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.

[0063] Among them, 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, and 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, and particularly preferably 40% by mass or less.

[0064] 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, 5% by mass or more and 250% by mass or less, 5% by mass or more and 200% by mass or less, 5% by mass or more and 150% by mass or less, 5% by mass or more and 100% by mass or less, 10% by mass or more and 80% by mass or less, 15% by mass or more and 50% by mass or less, or 20% by mass or more and 40% by mass or less.

[0065] 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 at least the above lower limit value, the flame retardancy is more excellent, and if it is at most the above upper limit value, the original physical properties of the thermoplastic resin (A) are easily exhibited.

[0066] 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

[0067] or more and 50% by mass or less, 17% by mass or more and 45% by mass or less, or 20% by mass or more and 40% by mass or less.

[0068] [Copolymer (C) of α-olefin and unsaturated carboxylic acid]

[0069] The copolymer (C) improves the dispersibility of the phosphorus-based flame retardant (B) in the thermoplastic resin (A).

[0070] In the present invention, the “copolymer (C) of α-olefin and unsaturated carboxylic acid” means a copolymer in which the proportion of α-olefin units is 20 mol% or more and 80 mol% or less relative to a total of 100 mol% of α-olefin units and unsaturated carboxylic acid units.

[0071] In the copolymer (C), the proportion of α-olefin units is preferably 30 mol% or more and, on the other hand, preferably 70 mol% or less relative to a total of 100 mol% of α-olefin units and unsaturated carboxylic acid units. When the proportion of α-olefin units is at least the above lower limit value, in particular, the compatibility with polyolefin resins is more excellent, and when it is at most the above upper limit value, the compatibility with the phosphorus-based flame retardant (B) is more excellent.

[0072] In the copolymer (C), the α-olefin is preferably an α-olefin having 10 or more and 80 or less carbon atoms. When the number of carbon atoms of the α-olefin is 10 or more, in particular, the compatibility with polyolefin resins tends to become better, and when 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.

[0073] 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.

[0074] Specific examples of the ester, acid anhydride or imide of the unsaturated carboxylic acid include (meth)acrylic 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.

[0075] 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.

[0076] The weight-average molecular weight of 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 copolymer (C) is within the above upper and lower limit ranges, the dispersibility of the phosphorus-based flame retardant (B) is more excellent.

[0077] The weight-average molecular weight of copolymer (C) can be, for example, 2,000 or more and 50,000 or less, and can be 3,000 or more and 30,000 or less.

[0078] The weight-average molecular weight of copolymer (C) is a standard polystyrene conversion value measured by gel permeation chromatography after dissolving copolymer (C) in tetrahydrofuran (THF).

[0079] Examples of commercially available products of copolymer (C) include Licolub CE2 (manufactured by Kline Japan Co., Ltd.) and DIACARNA 30M (manufactured by Mitsubishi Chemical Corporation).

[0080] As described above, while this resin composition contains copolymer (C), the proportion of copolymer (C) relative to the phosphorus-based flame retardant (B) is 10% by mass or less.

[0081] Among them, relative to the phosphorus-based flame retardant (B) (100% by mass), the proportion of 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 copolymer (C) relative to the phosphorus-based flame retardant (B) (100% by mass) is within the above range, a molded article with high flame retardancy can be obtained while maintaining high mechanical strength and high flexural modulus.

[0082] The proportion of 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.

[0083] 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, 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, 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.

[0084] 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, can be 0.1% by mass or more and 1.0% by mass or less.

[0085] 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, 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, 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.

[0086] 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, can be 0.1% by mass or more and 1.0% by mass or less.

[0087] 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.

[0088] [Other flame retardants or flame retardant aids]

[0089] As other flame retardants or flame retardant aids, those that are preferably halogen-free, organic or inorganic flame retardants or flame retardant aids are preferred. 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.

[0090] Examples of the compound containing a triazine ring include melamine, cyanuric diamide, 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, and the like.

[0091] Examples of the silicone-based flame retardant include silicone oil, silicone rubber, silicone resin, and the like.

[0092] Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, KISUMA 5A (magnesium hydroxide; manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.

[0093] Examples of the metal oxide include inorganic compounds such as zinc oxide, titanium oxide, aluminum oxide, magnesium oxide, titanium dioxide, hydrotalcite, and surface-treated products thereof. Specific examples of the metal oxide include 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.), and the like.

[0094] Examples of the boric acid compound include zinc borate and the like.

[0095] These flame retardants or flame retardant aids can be used singly or in combination of two or more.

[0096] [Other components]

[0097] 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.

[0098] 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.

[0099] The form of the glass fiber is not particularly limited either. Although any glass fiber such as chopped strand, roving, yarn, glass wool, etc. can be used, based on the point of operability, chopped strand and glass wool are preferred.

[0100] 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.

[0101] The method of the carbon fiber is not particularly limited, and although any carbon fiber such as filament, regular tow, large tow, staple fiber yarn, chopped roving, etc. can be used, chopped roving is preferred from the viewpoint of operability.

[0102] 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 above the lower limit value, it is easy to obtain an anti-tearing effect and a smoke suppression effect. If it is below the upper limit value, it is not easy to damage the original physical properties of the thermoplastic resin (A).

[0103] When the resin composition contains the inorganic fiber filler (D), a surface strength improver (E) for the inorganic fiber filler (D) can be further contained.

[0104] As the surface strength improver (E), particularly from the viewpoint 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.

[0105] 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.

[0106] Examples of the acidic group include carboxyl group, carboxylic anhydride group, sulfonic acid group, sulfinic acid group, phosphonic acid group, and hypophosphonic acid group, etc. It is preferably at least one selected from the group consisting of carboxyl group, carboxylic anhydride group, sulfonic acid group, sulfinic acid group, phosphonic acid group, and hypophosphonic acid group, more preferably at least one selected from the group consisting of carboxyl group, carboxylic anhydride group, and phosphonic acid group, and particularly preferably at least one selected from the group consisting of carboxyl group and carboxylic anhydride group.

[0107] As a method for manufacturing a surface strength enhancer (E) having an olefin skeleton and an acidic group, there can be mentioned (1) a method of low-molecularizing an olefin resin by thermal decomposition at a high temperature and then adding a compound or monomer having an acidic group; (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 a polymerization method, radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization, and living polymerization can be adopted. Further, a method of first forming a macromonomer and then performing polymerization can also be adopted.

[0108] 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.

[0109] As a marketed product 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.

[0110] 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.

[0111] As an antioxidant, for example, phenolic antioxidants, phosphorus-based antioxidants, and thioether-based antioxidants can be mentioned.

[0112] 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.

[0113] With respect 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.

[0114] As phosphorus-based antioxidants, for example, tris(nonylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, bis(decyl) monophenyl phosphite, bis(tridecyl) pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(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'-ethylidenebis(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-butylpropanediol and 2,4,6-tri-tert-butylphenol, tris(2,4-di-tert-butylphenyl) phosphite, etc. can be cited.

[0115] Relative 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.

[0116] As thioether-based antioxidants, for example, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate and other dialkyl thiodipropionates, and pentaerythritol tetra(β-alkylthiopropionate) can be cited.

[0117] Relative 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.

[0118] As ultraviolet absorbers, for example, 2-hydroxybenzophenone compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 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 esters 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; cyanoacrylates such as ethyl α-cyano-β,β-diphenylacrylate, methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; triaryltriazines such as 2-(2-hydroxy-4-octyloxyphenyl)-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.

[0119] 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.

[0120] 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-butanetetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-bis(tridecyl)-1,2,3,4-butanetetracarboxylate, 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-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-

[0121] (1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane and other hindered amine compounds.

[0122] 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.

[0123] This resin composition may also contain other fillers other than the inorganic fiber filler (D).

[0124] As other fillers, fibrous, flaky, granular, and powdery materials can be used. Specifically, examples include 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; organic fibrous reinforcing materials such as polyester fiber, nylon fiber, acrylate fiber, regenerated cellulose fiber, acetate fiber, ambary, ramie, cotton, jute, hemp, sisal, flax, linen cloth, 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 aminosilane and epoxy silane.

[0125] 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.

[0126] This resin composition may contain a crystallization nucleating agent.

[0127] As the crystallization nucleating agent, those commonly 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 cited.

[0128] 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 organic substances.

[0129] As specific examples of the organic crystallization nucleating agent, there can be mentioned 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, etc.; carboxamides such as stearamide, ethylene bislauramide, palmitamide, hydroxystearamide, erucamide, tris(tert-butylamide) trimellitate, 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.

[0130] This resin composition may contain a plasticizer.

[0131] As the plasticizer, those generally used as plasticizers for polyolefin resins can be suitably used. For example, there can be mentioned polyester plasticizers, glycerol plasticizers, polycarboxylic acid ester plasticizers, polyalkylene glycol plasticizers, epoxy plasticizers, etc.

[0132] These plasticizers can be used singly or in combination of two or more.

[0133] As specific examples of the polyester plasticizer, there can be mentioned 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, etc. The chain ends of these polyesters can be blocked with monofunctional carboxylic acids or monofunctional alcohols, or can be capped with epoxy compounds, etc.

[0134] As specific examples of the glycerol plasticizer, there can be mentioned glycerol monoacetyl monolaurate, glycerol diacetyl monolaurate, glycerol monoacetyl monostearate, glycerol diacetyl monooleate, and glycerol monoacetyl monomontanate, etc.

[0135] As specific examples of polycarboxylic acid ester plasticizers, phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diheptyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, etc.; trimellitic acid esters such as tributyl trimellitate, trioctyl trimellitate, trihexyl trimellitate, etc.; adipic acid esters such as diisodecyl adipate, n-octyl n-decyl adipate, methyl glycol butyl glycol adipate, benzyl methyl glycol adipate, benzyl butyl glycol adipate, etc.; citrate esters such as acetyl triethyl citrate, acetyl tributyl citrate, etc.; azelaic acid esters such as di-2-ethylhexyl azelate, etc.; sebacic acid esters such as dibutyl sebacate and di-2-ethylhexyl sebacate, etc. can be cited.

[0136] As specific examples of polyalkylene glycol plasticizers, 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, or their end-epoxy modified compounds, end-ester modified compounds, and end-ether modified compounds such as capped compounds can be cited.

[0137] Epoxy plasticizers generally refer to epoxy glycerol triesters composed of epoxy stearic acid alkyl esters and soybean oil, etc. In addition, so-called epoxy resins mainly composed of bisphenol A and epichlorohydrin can also be used.

[0138] As specific examples of other plasticizers, benzoates of aliphatic polyols such as neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol di-2-ethylbutyrate, etc.; fatty acid amides such as stearamide, etc.; aliphatic carboxylic acid esters such as butyl oleate, etc.; hydroxy acid esters such as methyl acetyl ricinoleate, butyl acetyl ricinoleate, etc.; pentaerythritol, various sorbitols, polyacrylates, and paraffins, etc. can be cited.

[0139] This resin composition may also contain a fluorine-containing anti-dripping agent.

[0140] As the fluorine-containing anti-dripping agent, fluorine-containing polymers having fibril-forming ability can be cited. As related fluorine-containing polymers, polytetrafluoroethylene (hereinafter referred to as "PTFE"), tetrafluoroethylene-based copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymer), partially fluorinated polymers as shown in U.S. Patent No. 4379910, polycarbonate resins manufactured from fluorinated bisphenols, etc. can be cited. Among them, PTFE is preferred.

[0141] PTFE with fibril-forming ability refers to PTFE having an extremely high molecular weight. When subjected to external forces such as shear force, PTFE shows a tendency to combine with each other to form fibrils. In terms of the number-average molecular weight 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.

[0142] PTFE with fibril-forming ability can be used not only in solid form but also in the form of an aqueous dispersion.

[0143] As commercial 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 commercial products of the aqueous dispersion of PTFE, Fluon AD-939E manufactured by AIF Co., Ltd., Fluon D-310 and D-210C manufactured by Daikin Industries, Ltd., Teflon 31JR manufactured by Mitsui-DuPont Fluorochemical Co., Ltd., etc. can be cited.

[0144] In order to improve the dispersibility of PTFE with fibril-forming ability in the resin composition, and further 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.

[0145] 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.

[0146] PTFE mixtures, for example, can be obtained by the following methods: (1) a method of co-precipitating a co-condensed mixture by mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of other resins (methods described in Japanese Patent Laid-Open No. Sho 60-258263, Japanese Patent Laid-Open No. Sho 63-154744, etc.); (2) a method of mixing an aqueous dispersion of PTFE with particles of other dried resins (method described in Japanese Patent Laid-Open No. Hei 4-272957); (3) a method of 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) a method of polymerizing a monomer of other resins in an aqueous dispersion of PTFE (method described in Japanese Patent Laid-Open No. Hei 9-95583); or (5) a method of uniformly mixing an aqueous dispersion of PTFE with a dispersion of other resins, polymerizing a vinyl monomer in the resulting mixed dispersion, and obtaining a subsequent mixture (methods described in Japanese Patent Laid-Open No. Hei 11-29679, etc.).

[0147] Examples of commercially available PTFE mixtures include "METABLEN A3000" from Mitsubishi Chemical Corporation and "BLENDEX B449" from GESPECIALTY CHEMICALS.

[0148] 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 PTFE amount. 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.

[0149] In the present resin composition, in addition to the above, additives commonly used in synthetic resins can be included within the range that does not impair the effects of the present invention. For example, 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.

[0150] [Manufacturing method of resin composition]

[0151] When manufacturing this 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 blender, Henschel mixer, mechanochemical device, extrusion mixer, etc. Depending on the situation, granulation can also be carried out through an extrusion granulator or a briquetting machine, etc. Then, melt mixing is carried out through a melt mixer, and the extrusion method.

[0152] As the melt mixer, twin-screw extruders such as vented twin-screw extruders, Banbury mixers, mixing rolls, single-screw extruders, multi-screw extruders with 3 or more screws, etc. can be mentioned.

[0153] The temperature during melt mixing is, for example, 170 to 260 °C.

[0154] The resin composition extruded as described above can be directly granulated by cutting through equipment such as a granulator, or after cooling to form strand materials, the strand materials are cut through equipment such as a granulator to be granulated.

[0155] In the resin composition described above, since the copolymer (C) is contained simultaneously with the thermoplastic resin (A) and the phosphorus-based flame retardant (B), excellent flame retardancy can be exhibited while fully maintaining the original physical properties of the polyolefin resin (A) (for example, mechanical strength and flexural modulus of elasticity).

[0156] The copolymer (C) is used to improve the dispersibility of the phosphorus-based flame retardant (B) in the thermoplastic resin such as the polyolefin resin (A). Since the dispersibility of the phosphorus-based flame retardant (B) is improved, it becomes easier to form a coke layer during combustion, and the flame retardancy is improved. Although the mechanism is not yet clear, the following is considered.

[0157] 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 the phosphorus-based flame retardant (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-mixed, the dispersibility of the phosphorus-based flame retardant (B) in the polyolefin resin is improved by the presence of the copolymer (C) between the polyolefin resin and the phosphorus-based flame retardant (B).

[0158] As the effects of the copolymer (C), it can be mentioned (1) improving the dispersibility of the phosphorus-based flame retardant (B) (finely dispersing); (2) promoting the formation of a coke layer during combustion; (3) improving physical properties (tensile fracture point strain), etc.

[0159] 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.

[0160] Although the mechanism is not clear, by adding the copolymer (C), a more stable coke layer is formed, heat transfer is suppressed, and V-0 can be achieved in the UL94 test.

[0161] 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-mentioned effects.

[0162] According to the present resin composition, since the phosphorus-based flame retardant (B) is well dispersed, a molded article having a dispersibility of, for example, 22% or less, or further 21% or less as calculated by the following formula can be obtained.

[0163] Dispersion [%] = 4,000 μm 2 The sum of the area values ​​of particles of the above sizes [μm 2 ]÷flame retardant area (threshold 3%, 136, 331) [μm 2 ]×100

[0164] Here, 4,000 μm 2 The sum of the area values ​​of the particles of the above size and the flame retardant area are obtained by processing the optical microscope image of the molded body. The details are described in the examples below.

[0165] [molded body]

[0166] A molded article according to one embodiment of the present invention is composed of the present resin composition.

[0167] The shape of the molded body is not particularly limited, and can be various shapes such as a resin plate, a sheet, a film, a cable, and a foreign object.

[0168] The molded article can be obtained by molding the present resin composition.

[0169] The forming method is not particularly limited, and examples include extrusion processing, calendering, injection molding, winding into rolls, compression molding, blow molding, etc.

[0170] The temperature during the forming of this resin composition is, for example, 170 to 260 °C.

[0171]

Examples

[0172] Hereinafter, specific descriptions will be made through the examples of the present invention. However, the present invention is not limited by the following examples. In addition, in the following examples, etc., unless otherwise specified, % is based on mass standards. The following items were evaluated.

[0173] (1) Flame retardancy (UL94)

[0174] Using the obtained formed body (1 / 16-inch test bar), the flame retardancy was judged based on the UL94 standard.

[0175] (2) Evaluation of the dispersibility of the flame retardant 1

[0176] The number of undispersed substances of the flame retardant present in the obtained formed body (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 retardant in the sheet was emphasized and the concentration was measured. Since the flame retardant has the strongest contrast in the image, the area value with a binarized value of 3% 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 sum of the areas of particles with a size of 4,000 μm 2 or more was calculated, and the dispersibility [%] was calculated by the following formula, and the average value of the dispersibility of the 5 images was obtained respectively.

[0177] Dispersibility [%] = 4,000 μm 2 Sum of the area values of particles with a size of or more [μm 2 ÷ Flame retardant area (threshold 3%, 136,331) [μm 2 × 100

[0178] (3) Evaluation of the dispersibility of the flame retardant 2

[0179] Perform the same operation as the dispersion evaluation (2) of the flame retardant, and compare the dispersion based on the following criteria from the observed images.

[0180] A: There are 100 or more flame retardant particles observed in the picture.

[0181] B: There are 50 or more and less than 100 flame retardant particles in the picture.

[0182] C: There are less than 50 flame retardant particles in the picture.

[0183] D: There are less than 30 flame retardant particles in the picture.

[0184] It should be noted that in this evaluation, the dispersion is better from A to D.

[0185] (4) Flexural properties

[0186] Cut the obtained molded body (JIS K7139-A1 dumbbell-shaped test piece) into 80 mm in length, and measure the flexural modulus (GPa) based on JIS K7171.

[0187] (5) Tensile properties

[0188] Use the obtained molded body (JIS K7139-A1 dumbbell-shaped test piece) to measure the tensile yield point strength (MPa) and the tensile fracture point strain (%) based on JIS K7161-1.

[0189] (6) Heat of combustion (cone calorimeter)

[0190] For a test piece of 100 mm × 100 mm × 3 mm in thickness, use the Toyo Seiki Co., Ltd. model: C3 cone calorimeter III, and based on ISO5660-1 (2002), measure the maximum heat release rate (kW / m 2 under the condition of radiant heat of 50 kW / m 2 ) and the total heat of combustion (MJ / m 2 ).

[0191] Use the following as raw materials.

[0192] <Polyolefin resin>

[0193] A-1: Polypropylene resin (manufactured by Nippon PolyPro Co., Ltd., NOVATEC PP FY-4, melt flow rate 5 g / 10 min).

[0194] A-2: Polypropylene resin (manufactured by Nippon PolyPro Co., Ltd., NOVATEC PP SA06GA, melt flow rate 60 g / 10 min).

[0195] <Flame Retardant>

[0196] B: Phosphorus-based flame retardant composition (manufactured by ADEKA CORPORATION, ADK STAB FP-2200, containing 50 - 60% piperazine pyrophosphate, 35 - 45% melamine pyrophosphate, and 3 - 6% zinc oxide based on the total mass of the phosphorus-based flame retardant composition).

[0197] <Dispersant>

[0198] C-1: α-olefin·maleic anhydride copolymer (manufactured by Mitsubishi Chemical Corporation, DIACARNA 30M, weight-average molecular weight 7,800).

[0199] C-2: α-olefin·maleic anhydride copolymer (manufactured by Clariant Japan K.K., Licolub CE2, weight-average molecular weight 13,500).

[0200] C-3: Maleic anhydride-modified polyethylene (manufactured by Mitsui Chemicals, Inc., Hi-WAX 1105A).

[0201] C-4: Acid-modified polyethylene (manufactured by Clariant Japan K.K., Licolub H12).

[0202] [Examples 1 - 7, Comparative Examples 1 - 4]

[0203] Mix the raw materials shown in Table 1 in the proportions described in Table 1 and mix them by hand. After that, use A co-rotating twin-screw extruder (equipment name "BT-30", manufactured by Plastic Engineering Research Institute Co., Ltd., L / D = 30) to melt and knead at a screw 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.

[0204] Inject mold the obtained resin composition 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 body (a 1 / 16-inch test bar). Use this molded body (a 1 / 16-inch test bar) as a test piece for UL94 evaluation.

[0205] In addition, inject mold the obtained resin composition 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 body (a JIS K7139-A1 dumbbell-shaped test piece). Use this molded body (a JIS K7139-A1 dumbbell-shaped test piece) as a test piece for evaluating bending properties and tensile properties.

[0206] 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). This molded body (a square plate of 100 × 100 × 3 mm) was extruded using a hydraulic molding machine (manufactured by Shoji Iron Works Co., Ltd.) under the conditions of a molding temperature of 200 °C and a molding pressure of 10 MPa, with a process of preheating for 5 minutes, pressurizing for 5 minutes, and cooling for 5 minutes, to obtain a molded body (sheet) with a thickness of 0.5 mm. This molded body (sheet) was used as a test piece for evaluating the dispersibility of the flame retardant.

[0207] Each property of these molded bodies was 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.

[0208] In addition, the ratios (%) of the dispersibility (the value obtained from Dispersibility Evaluation 1), flexural modulus, and tensile fracture point strain of each example and comparative example to the dispersibility (the value obtained from Dispersibility Evaluation 1), flexural modulus, and tensile fracture point strain of Comparative Example 1 were calculated respectively. These values are shown in Table 1 as the dispersibility ratio, flexural modulus ratio, and tensile fracture point strain.

[0209] [Example 8]

[0210] Using the composition of A-2: NOVATEC PP, SA06GA 39.18 mass% as the polypropylene resin, B: ADK STAB FP-2200 58.78 mass% as the phosphorus-based flame retardant composition, C-1: DIACARNA 30M 1.96 mass% as the dispersant, and ADK STAB AO-60, 2112 0.04 mass% as the antioxidant, a co-rotating twin-screw extruder (equipment name "BT-30", manufactured by Plastic Engineering Research Institute Co., Ltd., L / D = 30) was used for melt mixing under the conditions of a screw rotation speed of 250 rpm and a barrel temperature of 200 °C to produce a flame retardant masterbatch-1. Mixing was carried out with the composition of 50 mass% of this masterbatch-1 and 50 mass% of the polypropylene resin A-1 NOVATEC PP FY4, and injection molding was carried out 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, and the same evaluation as in Example 1 was carried out. The obtained results are shown in Table 1.

[0211] [Example 9]

[0212] Except for the composition of using A-2: NOVATEC PP at 29.31% by mass as the polypropylene resin, B: ADK STAB FP-2200 at 68.39% by mass as the phosphorus-based flame retardant composition, C: DIACARNA 30M at 2.25% by mass as the dispersant, and ADK STAB AO-60, 2112 at 0.03% by mass as the antioxidant, masterbatch-2 was obtained under the same conditions as in Example 8. After mixing with the 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 conducted. The obtained results are shown in Table 1.

[0213]

Table 1

[0214]

[0215] 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 hereinafter).

[0216] 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 the 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 breaking point strain is also improved.

[0217] In addition, since the test results of the UL94 standard in Examples 1 to 9 all reached V-0, the resin compositions of Examples 1 to 9 are resin compositions that can suppress dripping during combustion.

[0218] On the other hand, the molded body of the resin composition of Comparative Example 2 in which maleic anhydride-modified polyethylene was mixed instead of the copolymer (C) is excellent in flame retardancy but poor in the dispersibility of the flame retardant. In addition, the ratio of the tensile breaking point strain is small and the mechanical strength is poor.

[0219] The molded body of the resin composition of Comparative Example 3 in which acid-modified polyethylene was mixed instead of the copolymer (C) is poor in flame retardancy and the dispersibility of the flame retardant. In addition, the ratio of the tensile breaking point strain is small and the mechanical strength is poor.

[0220] In Comparative Example 4 where the proportion of the copolymer (C) relative to the phosphorus-based flame retardant (B) is excessive, although the dispersion of the flame retardant is good compared to Example 4, the flexural modulus of elasticity is greatly reduced, seriously damaging the original properties of polypropylene.

[0221] [Combustion Heat Comparison Test Based on Cone Calorimeter]

[0222] 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-kneading was carried out under the conditions of a screw rotation speed of 250 rpm and a barrel temperature of 200 °C to obtain a resin composition.

[0223] Regarding the obtained resin composition, in the same manner as in Example 1, test pieces for evaluating the dispersibility of the flame retardant were produced, and Dispersibility Evaluation 1 was carried out to obtain the dispersibility and the dispersibility ratio. The results are shown in Table 2.

[0224] 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.) under the condition of a molding temperature of 200 °C to obtain a molded body (a square plate of 100 × 100 × 3 mm). Regarding the obtained molded body, the combustion heat release was evaluated using a cone calorimeter. The results are shown in Table 2.

[0225]

Table 2

[0226]

[0227] 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 and excellent flame retardancy compared to Comparative Examples 1 and 5 that did not contain the copolymer (C).

[0228] Industrial Applicability

[0229] With the resin composition of the present invention, a molded body with good dispersion of the phosphorus-based flame retardant, excellent flame retardancy, excellent mechanical strength, and flexural modulus can be obtained. The molded body obtained using the resin composition of the present invention, due to its excellent flame retardancy, excellent mechanical strength, and flexural modulus, can be applied to molding materials in the fields of motor vehicles, office equipment such as printers, and electrical and electronic fields such as mobile phones, as well as cables, etc.

Claims

1. A resin composition, wherein, it contains a thermoplastic resin (A), a phosphorus-based flame retardant (B), a copolymer (C) of an α-olefin and an unsaturated carboxylic acid, and a metal oxide, 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 α-olefin in the copolymer (C) has 10 or more and 80 or less carbon atoms, the copolymer (C) has a weight-average molecular weight of 2,000 or more and 50,000 or less, 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, 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 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 phosphorus-based flame retardant (B) is a salt of (poly)phosphoric acid and a nitrogen compound.

5. The resin composition according to claim 1 or 2, wherein, the phosphorus-based flame retardant (B) is an intumescent flame retardant.

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

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

8. The resin composition according to claim 1 or 2, wherein, the metal oxide is zinc oxide.

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

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

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