Polyolefin-based resin composition

Abstract

A polyolefin-based resin composition according to one embodiment of the present invention contains a polyolefin-based resin and a polymer-type bromine-based flame retardant. The polymer-type bromine-based flame retardant includes a structure represented by the following general formula (1). (In the formula, R1 represents a C1-C6 alkylene group, a C2-C6 alkylidene group, -S-, or -SO2-.)

Description

Polyolefin resin composition

[0001] The present invention relates to a polyolefin resin composition.

[0002] Brominated flame retardants are sometimes added to resin materials to impart flame retardancy. For example, Patent Document 1 discloses a polyamide resin composition containing, per 100 parts by weight of the polyamide resin, 1 to 80 parts by weight of a brominated flame retardant having a specific chemical structure, 10 to 100 parts by weight of glass fiber, and 1 to 30 parts by weight of an antimony-based flame retardant aid.

[0003] Furthermore, Patent Document 2 discloses a polyester resin composition containing a polyester resin, 1 to 80 parts by weight of a bromine-based flame retardant having a specific chemical structure, 10 to 100 parts by weight of glass fiber, and 1 to 30 parts by weight of an antimony-based flame retardant auxiliary, relative to 100 parts by weight of the polyester resin.

[0004] Japanese Patent Publication No. 2020-105432 Japanese Patent Publication No. 2020-105433

[0005] However, with the recent increase in environmental awareness, there is concern that when resin materials containing brominated flame retardants are released into the ocean, etc., they may be consumed by living organisms, resulting in the accumulation of toxic components in the organisms and adversely affecting the ecosystem. Therefore, there is a demand for new resin compositions that can suppress adverse effects on the ecosystem.

[0006] An object of one aspect of the present invention is to provide a novel resin composition that can suppress adverse effects on ecosystems.

[0007] In order to solve the above problems, a polyolefin-based resin composition according to one aspect of the present invention comprises a polyolefin-based resin and a polymeric brominated flame retardant, and the polymeric brominated flame retardant comprises a structure represented by the following general formula (1): (In the formula, R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ indicates -).

[0008] According to one aspect of the present invention, a novel polyolefin resin composition capable of suppressing adverse effects on ecosystems can be provided.

[0009] Hereinafter, one embodiment of the present invention will be described in detail. In this specification, unless otherwise specified, the expression "A to B" representing a range of numerical values ​​means "A or more and B or less."

[0010] <1. Polyolefin-Based Resin Composition> A polyolefin-based resin composition according to one aspect of the present invention (hereinafter may be simply abbreviated as "resin composition") contains a polyolefin resin and a polymeric brominated flame retardant, and the polymeric brominated flame retardant contains a structure represented by the following general formula (1): (In the formula, R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ indicates -).

[0011] A resin composition according to one embodiment of the present invention is a polyolefin resin composition containing a polyolefin resin as a main component, and further includes a polymeric brominated flame retardant, thereby reducing adverse effects on ecosystems. This is because, among brominated flame retardants, polymeric brominated flame retardants are less likely to accumulate in living organisms than non-polymeric brominated flame retardants. This effect contributes to the achievement of, for example, Goal 14 of the United Nations Sustainable Development Goals (SDGs), "Conserve and sustainably use the oceans and marine resources."

[0012] Furthermore, the resin composition according to one embodiment of the present invention has flame retardancy due to the inclusion of a polymeric brominated flame retardant. The level of flame retardancy of the resin composition according to one embodiment of the present invention is not particularly limited. For example, the resin composition according to one embodiment of the present invention preferably has a flame retardancy of V-2 or higher, more preferably V-1 or higher, and even more preferably V-0 or higher, in terms of a flammability rating according to the UL94V standard when used as a 0.8 mm thick test piece. Such a resin composition can be suitably used as a material for any article requiring flame retardancy.

[0013] (Polyolefin Resin) The polyolefin resin is a homopolymer or copolymer of an olefin.

[0014] The content of the polyolefin resin is preferably in the following range from the viewpoint of reducing adverse effects on mechanical properties such as impact strength. Specifically, the content of the polyolefin resin is preferably 40 parts by mass or more when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optionally contained inorganic filler, and the optionally contained flame retardant aid is 100 parts by mass. Furthermore, since the resin itself is easily combustible, the content of the polyolefin resin is preferably in the following range from the viewpoint of flame retardancy. Specifically, the content of the polyolefin resin is 75 parts by mass or less, preferably 50 parts by mass or less, and more preferably 45 parts by mass or less when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optionally contained inorganic filler, and the optionally contained flame retardant aid is 100 parts by mass.

[0015] The polyolefin resin is preferably a polypropylene resin containing at least propylene.

[0016] The polypropylene-based resin preferably contains at least one of polypropylene, which is a homopolymer of propylene, and a copolymer of propylene and another olefin. Examples of the copolymer of propylene and another olefin include a propylene-ethylene copolymer in which ethylene is copolymerized with propylene, a block copolymer containing a propylene-ethylene copolymer, and a random copolymer in which ethylene and butene-1 are copolymerized with propylene. From the viewpoint of strength, the polypropylene-based resin is preferably polypropylene.

[0017] The polypropylene resin is preferably an unmodified polypropylene resin. Here, "unmodified" means that the target compound has no substituents other than the basic structure, and an "unmodified polypropylene resin" is a polypropylene resin that has no substituents. An example of an unmodified polypropylene resin is a polypropylene resin that does not have a polar group such as maleic acid.

[0018] The polyolefin resin may be any commercially available polyolefin resin, and may be selected from those having suitable properties depending on the intended use and processing conditions of the composition.

[0019] From the viewpoint of moldability, the polyolefin resin preferably has a melt flow rate (MFR) measured under conditions of 230°C and 2.16 kg in the following range. Specifically, the MFR is preferably 1 g / 10 min or more, more preferably 10 g / 10 min or more, and even more preferably 20 g / 10 min or more. The MFR is also preferably 70 g / 10 min or less, more preferably 60 g / 10 min or less, even more preferably 55 g / 10 min or less, even more preferably 50 g / 10 min or less, and particularly preferably 45 g / 10 min or less.

[0020] MFR is measured in accordance with ASTM D-1238 (2013) under conditions of 230°C and 2.16 kg.

[0021] The decomposition temperature of the polyolefin resin is preferably higher than 400°C, more preferably higher than 420°C, and is preferably lower than 500°C, more preferably lower than 480°C.

[0022] (Polymer-type brominated flame retardant) The polymer-type brominated flame retardant is a polymer containing a structure represented by the following general formula (1) (hereinafter referred to as "structure (1)"). In the general formula (1), R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ Indicates -.

[0023] A resin composition according to one embodiment of the present invention contains a polymeric brominated flame retardant, thereby exhibiting flame retardancy. Furthermore, the resin composition according to one embodiment of the present invention becomes a polyolefin-based resin composition capable of suppressing adverse effects on ecosystems by containing a polymeric brominated flame retardant. Among polymeric brominated flame retardants, high-molecular-weight polymeric brominated flame retardants are particularly preferred because they are highly effective in suppressing adverse effects on ecosystems. Herein, "high-molecular-weight polymeric brominated flame retardants" refers to polymeric brominated flame retardants having a weight-average molecular weight of 1,000 or more in terms of standard polystyrene.

[0024] In the general formula (1), the C1 to C6 alkylene group is an alkylene group having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, etc. The C2 to C6 alkylidene group is an alkylidene group having 2 to 6 carbon atoms, such as an ethylidene group, an isopropylidene group, etc.

[0025] The polymeric brominated flame retardant may have a structure different from Structure (1) as long as it is a polymer containing Structure (1). In this case, the content (proportion) of Structure (1) in the polymeric brominated flame retardant can be appropriately adjusted and is not particularly limited. From the viewpoint of flame retardancy, the content (proportion) of Structure (1) relative to the total amount of polymer in the polymeric brominated flame retardant is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more.

[0026] The polymeric brominated flame retardant may contain a repeating structure of Structure (1). The molecular weight of the polymeric brominated flame retardant is not particularly limited. Considering a higher effect of suppressing adverse effects on ecosystems and higher heat resistance, the weight-average molecular weight of the polymeric brominated flame retardant, as calculated on standard polystyrene, is preferably 1,000 or more, more preferably 2,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and still more preferably 20,000 or more. Furthermore, if the weight-average molecular weight of the polymeric brominated flame retardant, as calculated on standard polystyrene, is 30,000 or less, this is preferable from the viewpoint that the polymeric brominated flame retardant can be decomposed in accordance with the decomposition of the polyolefin, thereby suppressing the combustion of olefin-derived gases.

[0027] A preferred embodiment of the polymer-type brominated flame retardant is a polymer containing a structure represented by the following general formula (2). In the general formula (2), R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ - indicates R ２ represents a C2 to C4 alkylene group, and n is an average value of 1 or more.

[0028] In the general formula (2), the C1 to C6 alkylene group and the C2 to C6 alkylidene group are as described above. The C2 to C4 alkylene group is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a trimethylene group, and a tetramethylene group.

[0029] The polymeric brominated flame retardant may be a condensation polymer obtained by condensation polymerization of a tetrabromobisphenol compound and an alkyl halide compound. Such a condensation polymer can be obtained, for example, by reacting a tetrabromobisphenol compound with an alkyl halide compound in the presence of a base, and can be produced, for example, according to the synthesis method described in Patent Document 1 or 2.

[0030] The tetrabromobisphenol compound is not particularly limited, but examples thereof include tetrabromobisphenol A and tetrabromobisphenol F. The alkyl halide compound is not particularly limited, but examples thereof include ethane dichloride, 1,3-dichloropropane, and 1,4-dichlorobutane. The base is not particularly limited, but examples thereof include sodium bicarbonate. These compounds can be used alone or in combination of two or more.

[0031] The polymeric brominated flame retardant is not particularly limited, but examples thereof include a polymer obtained by polymerizing tetrabromobisphenol F and dichloroethane, a polymer obtained by polymerizing tetrabromobisphenol A and dichloroethane, a polymer obtained by polymerizing tetrabromobisphenol F and 1,3-dichloropropane, a polymer obtained by polymerizing tetrabromobisphenol A and 1,3-dichloropropane, a polymer obtained by polymerizing tetrabromobisphenol F and 1,4-dichlorobutane, and a polymer obtained by polymerizing tetrabromobisphenol A and 1,4-dichlorobutane. Among these, in view of excellent recyclability of the resin composition, particularly preferred are those represented by the general formula (2) R １ is preferably a C3 isopropylidene group, and R ２ is preferably a C2-C4 alkylene group.

[0032] From the viewpoint of the effect of stabilizing the flowability of the resin composition, the polymeric brominated flame retardant is preferably a polymer obtained by polymerizing tetrabromobisphenol A and 1,4-dichlorobutane. １ is preferably a C3 isopropylidene group, and R ２ is more preferably a C4 alkylene group.

[0033] The polymer-type brominated flame retardants may be used alone or in combination of two or more.

[0034] From the viewpoint of exhibiting flame retardancy in the resin composition according to one embodiment of the present invention, the content of the polymeric brominated flame retardant is preferably in the following range. Specifically, the content of the polymeric brominated flame retardant is 20 parts by mass or more, for example, 21 parts by mass or more, 24 parts by mass or more, or 25 parts by mass or more, when the total amount of the polyolefin resin, the polymeric brominated flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, from the viewpoint of efficiently generating an inert gas for suppressing combustion, the content of the polymeric brominated flame retardant is preferably in the following range. Specifically, the content of the polymeric brominated flame retardant is preferably 30 parts by mass or less, when the total amount of the polyolefin resin, the polymeric brominated flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0035] (Inorganic Filler) The resin composition according to one aspect of the present invention may not contain an inorganic filler, but preferably further contains an inorganic filler. By including an inorganic filler, even better flame retardancy can be obtained. By further adding an inorganic filler to the resin composition according to one aspect of the present invention, it is possible to provide a resin composition having high flame retardancy even while using a polymeric brominated flame retardant. In other words, by further adding an inorganic filler to the resin composition according to one aspect of the present invention, it is possible to impart sufficient flame retardancy with the addition of a smaller amount of polymeric brominated flame retardant. Furthermore, by further including an inorganic filler in the resin composition according to one aspect of the present invention, the mechanical properties of the resin can be improved.

[0036] The inorganic filler is not particularly limited, and a general inorganic filler added to a resin can be used. The inorganic filler may be fibrous or powdery. Examples of such inorganic fillers include talc, calcium carbonate, glass fiber, and precipitated barium sulfate. The inorganic filler may be used alone or in combination of two or more. It is inexpensive and, being a natural mineral, requires less electricity and CO2 during production than synthetic substances. ２Talc is preferably used as the inorganic filler because of its low emission.

[0037] From the viewpoint of improving the flame retardancy of the resin composition according to one embodiment of the present invention, the content of the inorganic filler is preferably in the following range. Specifically, the content of the inorganic filler is preferably 18 parts by mass or more, more preferably 20 parts by mass or more, even more preferably 21 parts by mass or more, and even more preferably 25 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the inorganic filler, and the optionally contained flame retardant aid is 100 parts by mass. Furthermore, from the viewpoint of improving the fluidity of the resin composition, the content of the inorganic filler is preferably in the following range. Specifically, the content of the inorganic filler is preferably 30 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the inorganic filler, and the optionally contained flame retardant aid is 100 parts by mass.

[0038] When the resin composition according to one aspect of the present invention further contains an inorganic filler, it is preferable to adjust the amount of polyolefin-based resin according to the amount of inorganic filler added. Specifically, it is preferable to adjust the amount of polyolefin-based resin so that the total amount of the polyolefin-based resin and the inorganic filler is 75 parts by mass or less when the total amount of the polyolefin-based resin, the polymeric bromine-based flame retardant, the inorganic filler, and the optionally contained flame retardant aid is 100 parts by mass. By increasing the amount of inorganic filler added and decreasing the amount of polyolefin-based resin, the effect of improving flame retardancy by adding the inorganic filler can be further obtained. Furthermore, when the inorganic filler is talc, talc generates water due to a dehydration reaction and inert gas (CO ) when it reaches a certain temperature. ２ These may contribute to improved flame retardancy.

[0039] When the resin composition according to an embodiment of the present invention further contains an inorganic filler, the blending ratio (parts by mass) of the inorganic filler to the total amount of the polymeric brominated flame retardant and the optionally contained flame retardant aid [inorganic filler / (polymeric brominated flame retardant + flame retardant aid)] is preferably 0.55 or more, more preferably 0.70 or more, from the viewpoint of improving the flame retardancy of the resin composition according to an embodiment of the present invention. Furthermore, the blending ratio of the inorganic filler to the total amount of the polymeric brominated flame retardant and the flame retardant aid [inorganic filler / (polymeric brominated flame retardant + flame retardant aid)] is preferably 0.85 or less, from the viewpoint of improving the fluidity of the resin composition.

[0040] (Flame retardant aid) The resin composition according to one aspect of the present invention may not contain a flame retardant aid, but preferably further contains a flame retardant aid. By further adding a flame retardant aid to the resin composition according to one aspect of the present invention, it is possible to provide a resin composition having high flame retardancy even when using a polymeric brominated flame retardant. In other words, by further adding a flame retardant aid to the resin composition according to one aspect of the present invention, it is possible to impart sufficient flame retardancy by adding a smaller amount of polymeric brominated flame retardant.

[0041] The flame retardant aid is not particularly limited, and examples thereof include antimony-based flame retardant aids such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, etc. From the viewpoint of the flame retardancy of the resin, the flame retardant aid is preferably antimony trioxide.

[0042] From the viewpoint of improving the flame retardancy of the resin composition according to one embodiment of the present invention, the content of the flame retardant aid is preferably in the following range. Specifically, the content of the flame retardant aid is preferably 6 parts by mass or more when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the flame retardant aid is 100 parts by mass. Furthermore, from the viewpoint of efficiently generating an inert gas for suppressing combustion, the content of the flame retardant aid is preferably in the following range. Specifically, the content of the flame retardant aid is preferably 8 parts by mass or less when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the flame retardant aid is 100 parts by mass.

[0043] When the resin composition according to an embodiment of the present invention further contains a flame retardant synergist, the blending ratio (parts by mass) of the polymeric brominated flame retardant to the flame retardant synergist [polymeric brominated flame retardant / flame retardant synergist] is preferably 2.5 or more, more preferably 3.0 or more, from the viewpoint of improving the flame retardancy of the resin composition according to an embodiment of the present invention. Furthermore, the mass ratio of the polymeric brominated flame retardant to the flame retardant synergist is preferably 4.5 or less, more preferably 4 or less, from the viewpoint of efficiently generating an inert gas for suppressing combustion.

[0044] (Other Additives) In addition to the above-described components, the resin composition according to one aspect of the present invention may further contain other additives within a range that does not impair the effects of the present invention. Examples of the additives include antioxidants, lubricants, anti-drip agents, weathering agents, antibacterial agents, pigments, crystal nucleating agents, molecular weight modifiers, foaming agents, dispersants, antistatic agents, neutralizing agents, metal deactivators, and inorganic fillers.

[0045] The antioxidant is a substance that has the function of preventing oxidation of the resin composition according to one embodiment of the present invention. Examples of the antioxidant include phenolic, phosphorus-based, and thioether-based compounds. Examples of the phenolic antioxidant include 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)propionic acid amide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methyl ethylenebis(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[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate]methane , thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6-hexamethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butylic acid]glycol ester, 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. These may be used in combination of two or more. Examples of phosphorus-based antioxidants include trisnonylphenyl 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, 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)isopropylidenediphenol 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, tetrakis(2,4-ditert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl) 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropylene glycol and 2,4,Examples of antioxidants include 6-tri-tert-butylphenol phosphite, 3,9-bis[2-{3-(3-tert-butyl-4-methylphenoxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and tris(2,4-di-tert-butylphenyl)phosphite. These may be used in combination of two or more. Examples of thioether antioxidants include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-alkylmercaptopropionate esters). These may be used in combination of two or more. Among these, from the viewpoint of sufficiently preventing oxidation of the resin composition, it is preferable to use a phenol-based antioxidant and a phosphorus-based antioxidant in combination.

[0046] From the viewpoint of sufficiently preventing oxidation of the resin composition according to one embodiment of the present invention, the content of the antioxidant is preferably within the following range. Specifically, the content of the antioxidant is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the content of the antioxidant is preferably within the following range. Specifically, the content of the antioxidant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0047] The lubricant is a substance that has the function of improving the molding processability of the resin composition according to one embodiment of the present invention. Examples of lubricants include glycerin fatty acid esters and metal soaps. Among them, glycerin fatty acid esters are preferred from the viewpoint of improving the fluidity of the resin composition.

[0048] The content of the lubricant is preferably in the following range from the viewpoint of sufficiently improving the moldability of the resin composition according to one embodiment of the present invention. Specifically, the content of the lubricant is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the content of the lubricant is preferably in the following range from the viewpoint of preventing bleeding of the lubricant. Specifically, the content of the lubricant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0049] The anti-drip agent is a substance that prevents dripping during combustion of the resin composition according to one embodiment of the present invention and improves flame retardancy. Examples of the anti-drip agent include acrylic-modified polytetrafluoroethylene.

[0050] The content of the anti-drip agent is preferably in the following range from the viewpoint of sufficiently improving the moldability of the resin composition according to one embodiment of the present invention. Specifically, the content of the anti-drip agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the content of the anti-drip agent is preferably in the following range from the viewpoint of suppressing clogging of the mesh during kneading. Specifically, the content of the anti-drip agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0051] The weather resistance agent is a substance that imparts weather resistance to the resin composition according to one embodiment of the present invention. Examples of weather resistance agents that can be used include ultraviolet absorbers and hindered amine light stabilizers. Examples of ultraviolet absorbers include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and 2-(2' 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole, etc. benzoates 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, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; acrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; cyanoacrylates 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,Examples of the hindered amine light stabilizer include triaryltriazines such as 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-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate Methyl-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 polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino- s-Triazine polycondensate, 1,5,8,12-tetrakis[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-tetrakis[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,Examples of hindered amine compounds include 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane and 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane. These may be used in combination of two or more. Of these, from the viewpoint of imparting sufficient weather resistance, it is preferable to use an ultraviolet absorber and a hindered amine light stabilizer in combination.

[0052] The content of the weather resistant agent is preferably within the following range from the viewpoint of imparting sufficient weather resistance to the resin composition according to one embodiment of the present invention. Specifically, the content of the weather resistant agent is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.1 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the content of the weather resistant agent is preferably within the following range from the viewpoint of preventing gloss reduction due to bleed-out. Specifically, the content of the weather resistant agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0053] The antibacterial agent is a substance that imparts antibacterial properties to the resin composition according to one embodiment of the present invention. Examples of the antibacterial agent include, but are not limited to, organic compound-based antibacterial agents, natural organic antibacterial agents, and inorganic antibacterial agents.

[0054] The content of the antibacterial agent is preferably within the following range from the viewpoint of sufficiently imparting antibacterial properties to the resin composition according to one embodiment of the present invention. Specifically, the content of the antibacterial agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.3 parts by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the content of the antibacterial agent is preferably within the following range from the viewpoint of preventing a deterioration in impact properties and further increase in costs. Specifically, the content of the antibacterial agent is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0055] The pigment prevents deterioration of the resin composition by blocking ultraviolet light. The pigment is preferably an inorganic pigment. Examples of inorganic pigments include TiO ２ , carbon black, iron oxide, chromium oxide, zinc oxide, etc. In particular, TiO ２ is preferred.

[0056] The pigment content is preferably within the following range from the viewpoint of sufficiently preventing deterioration of the resin composition. Specifically, the pigment content is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, when the total amount of the polyolefin resin, the polymeric brominated flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass. Furthermore, the pigment content is preferably within the following range from the viewpoint of exhibiting sufficient flame retardancy in the resin composition according to one aspect of the present invention. Specifically, the pigment content is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and even more preferably 5 parts by mass or less, when the total amount of the polyolefin resin, the polymeric brominated flame retardant, the optional inorganic filler, and the optional flame retardant aid is 100 parts by mass.

[0057] The total amount of the other additives is preferably within the following range from the viewpoint of the performance expression of the additives. Specifically, the total amount of the other additives is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optionally contained inorganic filler, and the optionally contained flame retardant aid is taken as 100 parts by mass. Furthermore, the total amount of the other additives is preferably within the following range from the viewpoint of reducing the effect on the physical properties and flame retardancy of the resulting molded article. Specifically, the total amount of the other additives is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the optionally contained inorganic filler, and the optionally contained flame retardant aid is taken as 100 parts by mass.

[0058] (Shape and Properties) The shape of the resin composition according to one aspect of the present invention can be pellets, etc. The resin composition according to one aspect of the present invention is preferably thermoplastic.

[0059] [Method for Producing Resin Composition] The resin composition according to one embodiment of the present invention can be produced by blending and melt-kneading, for example, a polyolefin resin, a polymeric bromine-based flame retardant, and, if necessary, at least one of an inorganic filler, a flame retardant aid, and an additive. For example, the above components can be blended and kneaded using a Henschel mixer, a Banbury mixer, a single-screw extruder, a twin-screw extruder, a multi-screw extruder, a co-kneader, or the like. The heating temperature during kneading is usually 160°C or higher and 250°C or lower.

[0060] Alternatively, the above components may be compounded and pre-mixed (pre-blended) using a commonly used device (for example, a ribbon blender, a drum tumbler, etc.), and then kneaded using the above device.

[0061] [Molded Article] The molded article according to one aspect of the present invention can be produced using the resin composition described above. The molded article according to one aspect of the present invention can be produced by, for example, injection molding, injection compression molding, extrusion molding, blow molding, press molding, vacuum molding, foam molding, or the like.

[0062] The molded article according to one aspect of the present invention can be used, for example, in home appliances, electrical installation materials, and the like.

[0063] [Summary] The polyolefin resin composition according to aspect 1 of the present invention comprises a polyolefin resin and a polymeric brominated flame retardant, and the polymeric brominated flame retardant comprises a structure represented by the following general formula (1): (In the formula, R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ - indicates.)

[0064] In the polyolefin resin composition according to Aspect 2 of the present invention, in Aspect 1, the polymeric brominated flame retardant preferably has a weight average molecular weight of 1,000 or more in terms of standard polystyrene.

[0065] In the polyolefin resin composition according to Aspect 3 of the present invention, in Aspect 1 or 2, the polymeric brominated flame retardant may contain a structure represented by the following general formula (2): (In the formula, R １ represents a C1 to C6 alkylene group, a C2 to C6 alkylidene group, -S-, or -SO ２ - indicates R ２ represents a C2 to C4 alkylene group, and n is an average value of 1 or more.

[0066] The polyolefin resin composition according to Aspect 4 of the present invention is any one of Aspects 1 to 3, wherein the polymeric brominated flame retardant is a condensation polymer obtained by condensation polymerization of a tetrabromobisphenol compound and an alkyl halide compound.

[0067] A polyolefin resin composition according to a fifth aspect of the present invention is the polyolefin resin composition according to any one of the first to fourth aspects, further comprising an inorganic filler.

[0068] A polyolefin-based resin composition according to a sixth aspect of the present invention is the polyolefin-based resin composition according to the fifth aspect, wherein the inorganic filler is at least one selected from the group consisting of talc, calcium carbonate, glass fiber, and precipitated barium sulfate.

[0069] In the polyolefin resin composition according to Aspect 7 of the present invention, in Aspect 5 or 6, the inorganic filler is preferably talc.

[0070] A polyolefin resin composition according to an eighth aspect of the present invention is the polyolefin resin composition according to any one of the first to seventh aspects, which comprises the polyolefin resin and the polymeric brominated flame retardant, and optionally comprises an inorganic filler and a flame retardant aid, and when the total amount of the polyolefin resin, the polymeric brominated flame retardant, the inorganic filler, and the flame retardant aid is 100 parts by mass, the polyolefin resin comprises 40 parts by mass or more and 75 parts by mass or less and 20 parts by mass or more and 30 parts by mass or less of the polymeric brominated flame retardant, and the total amount of the polyolefin resin and the inorganic filler may be 75 parts by mass or less.

[0071] The polyolefin resin composition according to Aspect 9 of the present invention, in accordance with Aspect 8, may contain 18 parts by mass or more and 30 parts by mass or less of the inorganic filler.

[0072] A polyolefin-based resin composition according to Aspect 10 of the present invention is the polyolefin-based resin composition according to Aspect 8 or Aspect 9, wherein the inorganic filler is one or more selected from the group consisting of talc, calcium carbonate, glass fiber, and precipitated barium sulfate.

[0073] In the polyolefin resin composition according to an eleventh aspect of the present invention, in the eighth or ninth aspect, the inorganic filler is preferably talc.

[0074] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in the embodiments are also included in the technical scope of the present invention.

[0075] The present invention will be explained in more detail below with reference to examples and reference examples, but the present invention is not limited to these examples.

[0076] [Raw Materials for Polyolefin Resin Composition] The raw materials for the polyolefin resin composition used in the Examples and Reference Examples are as follows.

[0077] <Polyolefin resin> Product name: "J-700GP" (manufactured by Prime Polymer Co., Ltd., polypropylene (PP) resin)

[0078] <Brominated flame retardants> Product name: "Scitex 8010" (manufactured by Albemale Corporation, brominated polystyrene (weight average molecular weight in standard polystyrene equivalent: 971.2)) Product name: "FLAMECUT (registered trademark) 210HR" (manufactured by Tosoh Corporation, polymeric brominated flame retardant containing a structure represented by the general formula (1) above, weight average molecular weight in standard polystyrene equivalent: 8,661)

[0079] <Flame retardant synergist> Product name: "PATOX (registered trademark)-MK" (antimony trioxide, manufactured by Nihon Seiko Co., Ltd.)

[0080] <Inorganic filler> Product name: Mistron 950JSA (talc, manufactured by Imerys) Product name: JM305P-G7 (talc, manufactured by Asada Flour Milling Co., Ltd.)

[0081] <Other additives> (Antioxidants) The following two types of phenolic antioxidants were used: ＴＭ20" (manufactured by SI Group, compound name: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]) - Product name: Adekastab (registered trademark) 2112" (manufactured by ADEKA Corporation, compound name: Tris(2,4-ditert-butylphenyl) phosphite) (lubricant) Product name: Rheostat (registered trademark) GS-95P" (manufactured by Lion Corporation, compound name: glycerin fatty acid ester) (anti-drip agent) Product name: Metablen (registered trademark) A3800" (manufactured by Mitsubishi Chemical Corporation, compound name: acrylic-modified polytetrafluoroethylene).

[0082] Example 1 (Production of Resin Composition) The components and blending amounts shown in Table 1 were weighed and pre-blended. In Table 1, the blending amounts are in parts by mass, and represent values ​​when the total amount of the polyolefin resin, polymeric brominated flame retardant, inorganic filler, and flame retardant aid is taken as 100 parts by mass. The pre-blended mixture was melt-kneaded using a twin-screw extruder TEM37-SX (manufactured by Shibaura Machine Co., Ltd.) with a screw diameter of 37 mm and a cylinder temperature set to 220°C, and the strand extruded from the die was cooled in a cooling bath and cut with a pelletizer to obtain pellets (resin composition).

[0083] (Preparation of Test Pieces) The obtained pellets were injected into an injection molding machine EC100SX (manufactured by Toshiba Machine Co., Ltd.) under conditions of a cylinder temperature of 210°C and a mold temperature of 50°C to prepare test pieces for evaluating flame retardancy having a size of 125 mm x 12.7 mm and a thickness of 0.8 mm.

[0084] [Examples 2 to 9, Reference Examples] In Examples 2 to 9 and Reference Examples, pellets (resin compositions) and test pieces were prepared in the same manner as in Example 1, except that the compositions were changed to those shown in Table 1, and the flame retardancy was evaluated.

[0085] Flame retardancy evaluation test was carried out using the obtained test pieces of Examples 1 to 9 and Reference Example. Flame retardancy was evaluated by a vertical combustion test in accordance with the UL94V standard using an HVUL plastic UL combustion test chamber "Atlas" (manufactured by Toyo Seiki Seisakusho, Ltd.).

[0086] The five test pieces were ranked for flammability in accordance with the UL94V standard based on the first and second burning times and whether or not the cotton ignited, and the flame retardancy was evaluated.

[0087] The highest flammability rating is V-0, with flame retardancy decreasing as the rating progresses to V-1 and V-2.

[0088] <Results> The results are shown in Table 1.

[0089]

[0090] The above results demonstrate that a polyolefin resin composition containing a polyolefin resin and a polymeric brominated flame retardant, wherein the polymeric brominated flame retardant contains a structure represented by general formula (1), has flame retardancy despite the use of a polymeric brominated flame retardant that can suppress adverse effects on ecosystems.

[0091] When a polymer-type brominated flame retardant was simply added to a polyolefin-based resin as in Example 9, the flame retardancy was at V-2 level. However, by further adding an inorganic filler as in Examples 1 to 8, it was possible to provide a polyolefin-based resin composition that, despite using a polymer-type brominated flame retardant, has high flame retardancy comparable to that of the reference examples that used conventional brominated flame retardants.

[0092] The polyolefin resin composition according to one aspect of the present invention can be suitably used as a resin composition for any molded article that requires flame retardancy.

Claims

1. A polyolefin resin composition comprising a polyolefin resin and a polymeric bromine-based flame retardant, the polymeric bromine-based flame retardant having a structure represented by the following general formula (1): (In the formula, R １ represents a C1-C6 alkylene group, a C2-C6 alkylidene group, -S-, or -SO ２ - indicates.) 2. The polyolefin resin composition according to claim 1, wherein the polymer-type brominated flame retardant has a weight average molecular weight of 1,000 or more in terms of standard polystyrene.

3. The polyolefin resin composition according to claim 1 or 2, wherein the polymer-type bromine-based flame retardant comprises a structure represented by the following general formula (2): (In the formula, R １ represents a C1-C6 alkylene group, a C2-C6 alkylidene group, -S-, or -SO ２ - indicates R ２ represents a C2 to C4 alkylene group, and n is an average value of 1 or more.

4. A polyolefin resin composition according to any one of claims 1 to 3, wherein the polymeric bromine-based flame retardant is a condensation polymer obtained by condensation polymerization of a tetrabromobisphenol compound and an alkyl halide compound.

5. The polyolefin resin composition according to any one of claims 1 to 4, further comprising an inorganic filler.

6. The polyolefin resin composition according to claim 5, wherein the inorganic filler is at least one selected from the group consisting of talc, calcium carbonate, glass fiber and precipitated barium sulfate.

7. The polyolefin resin composition according to claim 5 or 6, wherein the inorganic filler is talc.

8. The polyolefin resin composition according to any one of claims 1 to 7, comprising the polyolefin resin and the polymeric bromine-based flame retardant, and optionally comprising an inorganic filler and a flame retardant auxiliary, wherein, when the total amount of the polyolefin resin, the polymeric bromine-based flame retardant, the inorganic filler and the flame retardant auxiliary is 100 parts by mass, the polyolefin resin comprises 40 parts by mass or more and 75 parts by mass or less, and 20 parts by mass or more and 30 parts by mass or less of the polymeric bromine-based flame retardant, and the total amount of the polyolefin resin and the inorganic filler is 75 parts by mass or less.

9. The polyolefin resin composition according to claim 8, comprising 18 parts by mass or more and 30 parts by mass or less of the inorganic filler.

10. The polyolefin resin composition according to claim 8 or 9, wherein the inorganic filler is at least one selected from the group consisting of talc, calcium carbonate, glass fiber and precipitated barium sulfate.

11. The polyolefin resin composition according to claim 8 or 9, wherein the inorganic filler is talc.