Granular flame retardant composition and thermoplastic resin composition

Abstract

To provide a granular flame retardant composition which has low mutual adhesion and a certain degree of strength, and can enhance productivity.SOLUTION: A granular flame retardant composition contains a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains at least one bromine-containing organic compound (A1) selected from the group consisting of a specific bromine-containing organic compound (A1-1) having a 2,3-dibromo-2-alkylpropyl group, and a specific bromine-containing organic compound (A1-2) having a 2,3-dibromopropyl group, and the binder (B) contains a sucrose fatty acid ester (B1) having a melting point of 40 to 90°C.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a granular flame retardant composition and a thermoplastic resin composition. [Background technology]

[0002] Bromine-containing organic compounds are widely used as flame retardants for thermoplastic resins such as polystyrene resins and ABS resins. However, for example, when the flame retardant is in powder form, it is likely to scatter when it is measured or added to the resin, which can cause problems such as worsening the working environment and adversely affecting the health of workers and the risk of dust explosion. In addition, depending on the particle size and specific gravity of the flame retardant, the flowability is poor, which can cause problems such as clogging of the hopper when it is added from the hopper and difficulty in pneumatic transport of the flame retardant. Therefore, a granular flame retardant composition that is less likely to scatter, has excellent flowability, and is easy to handle is desired.

[0003] For example, Patent Document 1 discloses a granular flame retardant composition that uses an ethylene-vinyl acetate copolymer as a binder for a brominated flame retardant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2007-70586 A Summary of the Invention [Problem to be solved by the invention]

[0005] However, there has been a problem in that particles of the granular flame retardant composition adhere to each other immediately after granulation, making it difficult to use the granular flame retardant composition. (Hereinafter, the property in which particles of the granular flame retardant composition adhere to each other after granulation and before cooling and solidifying, and cannot be separated thereafter, is also referred to as "mutual adhesion.")

[0006] In addition, the granular flame retardant composition is required to be granulatable even at a high granulation speed, i.e., to have high productivity, and to have a strength sufficient to prevent it from easily crumbling.

[0007] The present invention has been made to solve the above problems, and its object is to provide a granular flame retardant composition which has low mutual adhesion, a certain degree of strength, and enables increased productivity. [Means for solving the problem]

[0008] The present invention includes, for example, the embodiments shown below.

[0009] [1] A granular flame retardant composition containing a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains at least one bromine-containing organic compound (A1) selected from the group consisting of bromine-containing organic compounds (A1-1) having a 2,3-dibromo-2-alkylpropyl group and bromine-containing organic compounds (A1-2) having a 2,3-dibromopropyl group, and the bromine-containing organic compound (A1-1) is selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-B-bis(2,3-dibromo-2-methylpropyl ether). a bromobisphenol-A-bis(2,3-dibromopropyl ether), a bromobisphenol-F-bis(2,3-dibromo-2-methylpropyl ether), a bromobisphenol-S-bis(2,3-dibromopropyl ether), a bromobisphenol-F-bis(2,3-dibromopropyl ether), a bromobisphenol-A-bis(2,3-dibromo ...F-bis(2,3-dibromopropyl ether), a bromobisphenol-A-bis(2,3-dibromopropyl ether), a bromobisphenol-S-bis(2,3-dibromopropyl ether), a bromobisphenol-F-bis(2,3-dibromopropyl ether), a bromobisphenol-F-bis(2,3-dibromopropyl ether), a bromobisphenol-A-bis(2,3-dibromopropyl ether), a bromobisphenol-S-bis(2,3-dibromopropyl ether), a

[0010] [2] The granular flame retardant composition according to [1] above, wherein the content of the sucrose fatty acid ester (B1) is 1 to 20% by weight of the granular flame retardant composition.

[0011] [3] The granular flame retardant composition according to [1] or [2] above, wherein the content of the bromine-containing organic compound (A1) is 20 to 99% by weight of the granular flame retardant composition.

[0012] [4] A thermoplastic resin composition comprising the granular flame retardant composition according to any one of [1] to [3] above and a thermoplastic resin.

[0013] [5] A composition containing a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains at least one bromine-containing organic compound (A1) selected from the group consisting of bromine-containing organic compounds (A1-1) having a 2,3-dibromo-2-alkylpropyl group and bromine-containing organic compounds (A1-2) having a 2,3-dibromopropyl group, and the bromine-containing organic compound (A1-1) is selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether). the bromine-containing organic compound (A1-2) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-S-bis(2,3-dibromopropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromopropyl ether); and the binder (B) contains a sucrose fatty acid ester (B1) having a melting point of 40 to 90°C. Use of the composition as a granular flame retardant composition. Effect of the Invention

[0014] According to the granular flame retardant composition of the present invention, when at least one of a bromine-containing organic compound having a 2,3-dibromo-2-alkylpropyl group and a bromine-containing organic compound having a 2,3-dibromopropyl group is used as the flame retardant, a granular flame retardant composition can be provided which has low mutual adhesion, a certain degree of strength, and is capable of increasing productivity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Preferred embodiments of the present invention will now be described.

[0016] The granular flame retardant composition according to the present invention is a granular flame retardant composition containing a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains at least one bromine-containing organic compound (A1) selected from the group consisting of bromine-containing organic compounds (A1-1) having a 2,3-dibromo-2-alkylpropyl group and bromine-containing organic compounds (A1-2) having a 2,3-dibromopropyl group, and the bromine-containing organic compound (A1-1) is selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether), The bromine-containing organic compound (A1-2) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-S-bis(2,3-dibromopropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromopropyl ether), and the binder (B) contains a sucrose fatty acid ester (B1) having a melting point of 40 to 90° C. Each component will be described below.

[0017] The bromine-containing organic compound (A) of the present invention contains, for example, a bromine-containing organic compound (A1-1) having a 2,3-dibromo-2-alkylpropyl group. Specifically, the bromine-containing organic compound (A1-1) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromo-2-methylpropyl ether). These may be used alone or in combination of two or more.

[0018] The bromine-containing organic compound (A) of the present invention contains, for example, a bromine-containing organic compound (A1-2) having a 2,3-dibromopropyl group. Specifically, the bromine-containing organic compound (A1-2) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-S-bis(2,3-dibromopropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromopropyl ether). These may be used alone or in combination of two or more.

[0019] The bromine-containing organic compound (A) of the present invention may contain a bromine-containing organic compound (A2) other than the bromine-containing organic compound (A1). Examples of such compounds include tris(2,3-dibromopropyl)isocyanurate and tris(2,3-dibromopropyl)cyanurate, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromobisphenol-A, hexabromobenzene, pentabromotoluene, polybromodiphenylether, polybromodiphenylethane, bispolybromophenoxyethane, trispolybromophenoxytriazine, polybromophenylindane, polypentabromobenzyl acrylate, ethylenebistetrabromophthalimide, tris(tribromoneopentyl)phosphate, and brominated epoxy oligomers. These may be used alone or in combination of two or more.

[0020] The content of the bromine-containing organic compound (A) of the present invention is preferably 70 to 98 parts by weight, more preferably 80 to 98 parts by weight, based on 100 parts by weight of the granular flame retardant composition. By having the content of the bromine-containing organic compound (A) within the above range, there is an advantage that the flame retardancy of the thermoplastic resin is superior even if the amount of the granular flame retardant composition added is relatively small.

[0021] From the viewpoint of improving productivity and strength, the content of the bromine-containing organic compound (A1) is preferably 20 to 99% by weight, more preferably 40 to 97% by weight, even more preferably 60 to 95% by weight, still more preferably 80 to 93% by weight, and even more preferably 86 to 92% by weight, of the entire granular flame retardant composition.

[0022] From the viewpoint of increasing productivity and strength, the content of the bromine-containing organic compound (A1) is preferably 30% by weight or more of the bromine-containing organic compound (A), more preferably 40% by weight or more, more preferably 50% by weight or more, and even more preferably 60% by weight or more. This ratio may be 70% by weight or more, 80% by weight or more, or 90% by weight or more.

[0023] The binder (B) of the present invention contains a sucrose fatty acid ester (B1) having a melting point of 40 to 90° C. From the viewpoints of increasing productivity and strength and reducing mutual adhesion, the melting point of the sucrose fatty acid ester (B1) is more preferably 45 to 85° C., more preferably 48 to 80° C., even more preferably 50 to 75° C., even more preferably 52 to 70° C., and even more preferably 54 to 66° C. Here, the melting point of the sucrose fatty acid ester (B1) is a melting point measured according to JIS K0064.

[0024] Examples of the sucrose fatty acid ester (B1) include sucrose laurate, sucrose myristic acid ester, sucrose palmitate, sucrose stearate, sucrose oleate, sucrose behenate, and sucrose erucate. Examples of the sucrose fatty acid ester (B1) include sucrose mixed fatty acid esters produced by combining two or more fatty acids that are components of these sucrose fatty acid esters. These sucrose fatty acid esters may be used alone or in combination of two or more.

[0025] From the viewpoints of increasing productivity and strength and reducing mutual adhesion, the content of the sucrose fatty acid ester (B1) is preferably 1 to 20% by weight, more preferably 2 to 20% by weight, more preferably 4 to 15% by weight, more preferably 5 to 11% by weight, and even more preferably 5 to 10% by weight, of the entire granular flame retardant composition.

[0026] From the viewpoints of increasing productivity and strength and reducing mutual adhesion, the content of the sucrose fatty acid ester (B1) in the binder (B) is preferably 20 to 100% by weight, more preferably 40 to 100% by weight, even more preferably 60 to 100% by weight, and even more preferably 65 to 100% by weight.

[0027] From the viewpoints of increasing productivity and strength and reducing mutual adhesion, the content of the binder (B) of the present invention is preferably 1 to 20% by weight, more preferably 3 to 20% by weight, more preferably 5 to 15% by weight, and even more preferably 6 to 10% by weight, of the entire granular flame retardant composition.

[0028] The binder (B) of the present invention may contain a binder (B2) other than the sucrose fatty acid ester (B1). Examples of such compounds include ethylene-vinyl acetate copolymers and acrylic resins.

[0029] The weight ratio (A1 / B1) of the bromine-containing organic compound (A1) to the sucrose fatty acid ester (B1) is preferably 0.5 to 50, more preferably 1 to 40, more preferably 2 to 35, more preferably 5 to 30, and even more preferably 8 to 20, from the viewpoints of increasing productivity and strength and reducing mutual adhesion.

[0030] From the viewpoints of increasing productivity and strength and reducing mutual adhesion, the amount of the bromine-containing organic compound (A1-1) contained in the bromine-containing organic compound (A1) is preferably 30% by weight or more, more preferably 40% by weight or more, and even more preferably 50% by weight or more.

[0031] The granular flame retardant composition of the present invention may further contain a stabilizer (C). Specifically, the stabilizer (C) is, for example, a heat stabilizer that improves the durability of the thermoplastic resin.

[0032] Examples of such stabilizers (C) include phosphite compounds, thioether compounds, hindered phenol compounds, hindered amine compounds, tin compounds, natural minerals, and synthetic minerals.

[0033] Examples of the phosphite compound include tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis(2,4-di-t-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonite, bis(nonylphenyl)pentaerythritol diphosphite, bisstearylpentaerythritol diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyl) cyclopropyl)phosphorus, tetra(tridecyl)-4,4'-butylidene-bis(2-t-butyl-5-methylphenyl)diphosphite, hexatridecyl-1,1,3-tris(3-t-butyl-6-methyl-4-oxyphenyl)-3-methylpropane triphosphite, mono(dinonylphenyl)mono-p-nonylphenyl phosphite, tris(mononylphenyl)phosphite, tetraalkyl(C=12-16)-4,4'-isopropylidene-(bisphenyl)diphosphite, mono- or diphenyl mono- or dialkyl (or alkoxyalkyl, C=8-13) phosphite, diphenyl isodecyl phosphite, trisdecyl phosphite, triphenyl phosphite, and the like. Examples of thioether compounds include dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, pentaerythryltetrakis(3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, and 2-mercaptobenzimidazole.

[0034] Examples of the hindered phenol compound include 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], glycerin tris[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, thiodiethylene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, Calcium diethyl bis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3”,5,5',5”-hexa-t-butyl-a,a',a”-(mesitylene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-t-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-t-butyl-4- hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-t-butyl-3-hydroxy-2,6-xylyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-t-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, and the like.

[0035] Examples of the hindered amine compound include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperilidinyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate.

[0036] Examples of the tin compound include dioctyltin dilaurate and dioctyltin maleate.

[0037] Examples of natural or synthetic minerals include hydrotalcite and zeolite.

[0038] The content of the stabilizer (C) is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 15 parts by weight, and even more preferably 0.8 to 10 parts by weight, based on 100 parts by weight of the granular flame retardant composition.

[0039] The granular flame retardant composition of the present invention may further contain a phosphoric acid ester (D). Examples of such phosphoric acid ester include triphenyl phosphate, tricresyl phosphate, and trixylenyl phosphate.

[0040] The granular flame retardant composition of the present invention may contain conventionally known additives, such as fatty acid amides, fatty acids, waxes, and pigments, within the scope of not impairing the effects of the present invention.

[0041] Examples of fatty acid amides include fatty acid monoamides such as caprylic acid amide, capric acid amide, myristic acid amide, palmitic acid amide, lauric acid amide, erucic acid amide, stearic acid amide, arachidin amide, behenic acid amide, lignoceric acid amide, stearic acid monoethanolamide, oleic acid amide, linoleic acid amide, and arachidonic acid amide, ethylene biscaprylic acid amide, butylene biscaprylic acid amide, hexamethylene biscaprylic acid amide, m-xylylene biscaprylic acid amide, ethylene biscapric acid amide, butylene biscapric acid amide, hexamethylene biscapric acid amide, m-xylylene biscapric acid amide, ethylene bislauric acid amide, butylene bislauric acid amide, hexamethylene bislauric acid amide, m-xylylene bislauric acid amide, ethylene bisstearic acid amide, butylene bisstearic acid amide, hexamethylene bisstearic acid amide, m-xylylene bisstearic acid, Amides, ethylene bis arachidic acid amide, butylene bis arachidic acid amide, hexamethylene bis arachidic acid amide, m-xylylene bis arachidic acid amide, ethylene bis behenic acid amide, butylene bis behenic acid amide, hexamethylene bis behenic acid amide, m-xylylene bis behenic acid amide, ethylene bis lignoceric acid amide, butylene bis oleic acid amide, hexamethylene bis lignoceric acid amide, m-xylylene bis lignoceric acid amide, ethylene bis oleic acid amide Examples of the fatty acid bisamides include fatty acid bisamides such as linoleic acid amide, butylene bisoleic acid amide, hexamethylene bisoleic acid amide, m-xylylene bisoleic acid amide, ethylene bislinoleic acid amide, butylene bislinoleic acid amide, hexamethylene bislinoleic acid amide, m-xylylene bislinoleic acid amide, ethylene bisarachidonic acid amide, butylene bisarachidonic acid amide, hexamethylene bisarachidonic acid amide and m-xylylene bisarachidonic acid amide.

[0042] Examples of fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, 12-hydroxystearic acid, and oleic acid.

[0043] The thermoplastic resin composition of the present invention contains a granular flame retardant composition and a thermoplastic resin. The thermoplastic resin is not particularly limited, and various resins such as polystyrene resin, ABS resin, and polyurethane resin can be mentioned. The thermoplastic resin is preferably polystyrene resin. The thermoplastic resin composition containing polystyrene resin may be foamed or non-foamed.

[0044] The granular flame retardant composition of the present invention can be obtained, for example, by mixing the bromine-containing organic compound (A), the binder (B), and, if necessary, other compounds, and kneading the mixture using a conventionally known extrusion granulator or kneading granulator, for example, at 40 to 80° C. Examples of the extrusion granulator include a screw-type extrusion granulator, a roll-type extrusion granulator, a blade-type extrusion granulator, a tablet-type extrusion granulator, and a briquette-type extrusion granulator. EXAMPLES

[0045] The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

[0046] The raw materials for producing the granular flame retardant composition will be described in detail below.

[0047] <Raw materials used> [Bromi-containing organic compound (A1)] (A1-1): Tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether) (product name: Pyroguard SR-130, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 66% by weight) (A1-2): Tetrabromobisphenol-A-bis(2,3-dibromopropyl ether) (product name: Pyroguard SR-720N, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 67% by weight)

[0048] [Brome-containing organic compound (A2)] (A2-1): 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (trade name: Pyroguard SR-245, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 67% by weight) (A2-2): Tris(2,3-dibromopropyl)isocyanurate (product name: Pyroguard SR-750, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 65% by weight) (A2-3): Tris(tribromoneopentyl)phosphate (product name: CR-900, manufactured by Daihachi Chemical Industry Co., Ltd., bromine content: 73% by weight)

[0049] [Sucrose fatty acid ester (B1)] (B1-1): Sucrose fatty acid ester (product name: DK Ester F-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., melting point 64°C) (B1-2): Sucrose fatty acid ester (product name: DK Ester F-160, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., melting point 58°C) (B1-3): Sucrose fatty acid ester (product name: DK Ester F-110, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., melting point 55°C) (B1-4): Sucrose laurate (product name: Ryoto Sugar Ester L-1695, manufactured by Mitsubishi Chemical Corporation, melting point 47°C) (b1-1): Sucrose laurate (product name: Ryoto Sugar Ester L-195, manufactured by Mitsubishi Chemical Corporation, melting point 26°C) (comparative material) (b1-2): Sucrose erucic acid ester (product name: Ryoto Sugar Ester ER-290, manufactured by Mitsubishi Chemical Corporation, melting point 9°C) (comparative material) (b1-3): Glycerin monostearate (product name: Rikemal S-100, Riken Vita (Made by Minh Co., Ltd., melting point 65°C) (Comparative material) (b1-4): Stearyl stearate (product name: Rikemal SL-900, Riken Vitamin (manufactured by Epson Corporation, melting point 55°C) (comparison material)

[0050] [Binder (B2) other than sucrose fatty acid ester (B1)] (B2-1): Ethylene-vinyl acetate copolymer (product name: Ultrathene 684, Tosoh Corporation) (manufactured by Shimoda Co., Ltd., VA (vinyl acetate) = 20 mol%, MI (melt index) = 2000) (B2-2): Ethylene-vinyl acetate copolymer (product name: Ultrathene 735, Tosoh Corporation) (manufactured by Shimoda Co., Ltd., VA=28 mol%, MI=1000) (B2-3): Ethylene-vinyl acetate copolymer (product name: Ultrasen 720, Tosoh Corporation) (manufactured by Shimoda Co., Ltd., VA=28 mol%, MI=150) (B2-4): Ethylene-vinyl acetate copolymer (product name: Ultrasen 760, Tosoh Corporation) (manufactured by Shimoda Co., Ltd., VA=42 mol%, MI=70) (B2-5): Ethylene-ethyl methacrylate copolymer (product name: NUC-6940, manufactured by ENEOS Corporation, EA (ethyl methacrylate) = 35 mol%, MI = 20) (B2-6): Ethylene-methyl methacrylate copolymer (product name: Acryliff CM5021, manufactured by Sumitomo Chemical Co., Ltd., MMA (methyl methacrylate) = 28 mol%, MI = 450) (B2-7): Ethylene-methacrylic acid copolymer (product name: Nucrel N0200H, manufactured by Mitsui Dow Polychemicals Co., Ltd., MA (methacrylic acid) = 2 mol%, MI = 130)

[0051] [Stabilizer (C)] (C-1): Tris(2,4-di-t-butylphenyl)phosphite (trade name: ADEKA) Stub 2112, manufactured by ADEKA Corporation) (C-2): Tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2 ,3,4-Butanetetracarboxylate (product name: ADK STAB LA-57, Co., Ltd. (Manufactured by ADEKA) (C-3): Distearyl-3,3'-thiodipropionate (product name: Lasmit SG) (Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) (C-4): Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-phenyl] (hydroxyphenyl)propionate] (product name: IRGANOX 1010, BASF) (Manufacturer) (C-5): Dioctyltin dilaurate (product name: OL-1, Tokyo Fine Chemical Co., Ltd. (Manufactured by the company) (C-6): Hydrotalcite (product name: STABIACE HT-1, Sakai Chemical Industry Co., Ltd. (Manufactured by the company)

[0052] [Phosphate ester (D)] (D-1): Triphenyl phosphate (product name: TPP, manufactured by Daihachi Chemical Industry Co., Ltd.)

[0053] <Evaluation of Granular Flame Retardant Composition> The amounts (by weight) of the raw materials used in each Example and Comparative Example, the ratios of the amounts used, and the evaluation results are shown in the table below.

[0054] According to the compounding amounts shown in the table, the bromine-containing organic compound (A) and the binder (B), and other compounds as necessary, were mixed for 5 minutes at a rotation speed of 600 rpm using a mixer (product name: high-speed mixer, manufactured by Fukae Powtec Co., Ltd.). Hereinafter, the mixture thus obtained is also referred to as the "evaluation composition". Using the evaluation compositions of each Example and Comparative Example, evaluations were performed on the productivity, mutual adhesion, and strength. In addition, the flame retardancy of the thermoplastic resin composition obtained by adding each evaluation composition to a thermoplastic resin was evaluated.

[0055] (Productivity) Using an extrusion granulator (product name: EXDF-100, manufactured by Dalton Co., Ltd.) set at a temperature of 70° C., the composition for evaluation was used as a material, and granulation was performed while adjusting the discharge speed from the extrusion granulator, to determine the productivity of the granular flame retardant composition. Specifically, the highest discharge speed (hereinafter also referred to as the "maximum discharge speed") within the range of discharge speeds at which granulation is possible was used to determine the productivity.

[0056] Here, the discharge rate is the weight of the flame retardant composition (whether granular or not) discharged from the extrusion granulator per unit time, and its unit is [kg / h]. Although there is some variation, the granular flame retardant composition obtained by granulation with the extrusion granulator is typically cylindrical, with a bottom diameter of 3 mm and a height of 5 mm (the same applies to the evaluation of mutual adhesion and strength described below). The productivity evaluation criteria are as follows. Note that evaluation "A" is the most productive and is preferable. Note that evaluation of mutual adhesion and strength described below was not performed on the evaluation composition with evaluation "D". A: Granulation is possible, and the maximum discharge speed is 150 kg / h or more. B: Granulation is possible, and the maximum discharge speed is 100 kg / h or more and less than 150 kg / h C: Granulation is possible, and the maximum discharge speed is 50 kg / h or more and less than 100 kg / h D: Granulation is possible but the maximum discharge speed is less than 50 kg / h, or granulation is not possible regardless of the discharge speed.

[0057] (mutuality) The mutual adhesion of the granular flame retardant composition was determined by the following method. That is, the above-mentioned extrusion granulator was set at a temperature of 70°C, and the composition for evaluation was used as a material to perform granulation. The discharge speed from the extrusion granulator at this time was the maximum discharge speed obtained in the above-mentioned evaluation of productivity. A horizontal wooden board was placed 20 cm below the discharge port of the extrusion granulator, and the discharged granular flame retardant composition was piled up on the wooden board. The composition for evaluation used in this evaluation was 1 kg. The granular flame retardant composition was left to stand in a room temperature (25°C) atmosphere for 30 minutes after granulation to sufficiently cool and solidify, and the mutual adhesion was evaluated using the composition. The criteria for the mutual adhesion are as follows. Note that the evaluation "A" is the lowest mutual adhesion and is preferable. In addition, the following "capable of being separated" means that, for example, each of the granular flame retardant compositions gathered in a lump shape can be broken apart without using tools or the like while maintaining its original shape. A: The granular flame retardant composition does not adhere to each other at all. B: Part or all of the granular flame retardant composition is attached to each other but can be separated C: Part or all of the granular flame retardant composition is adhered to each other and cannot be separated.

[0058] (strength) The granular flame retardant composition is required to have a strength that does not easily crumble. The strength of the granular flame retardant composition was determined by the following method. That is, the above-mentioned extrusion granulator with a set temperature of 70°C was used to granulate the composition for evaluation as a material. The discharge speed from the extrusion granulator at this time was the maximum discharge speed obtained in the above-mentioned evaluation of productivity. 20 g of the obtained granular flame retardant composition was placed on a sieve with a mesh size of 1 mm and shaken for 10 minutes using a shaker (tap-type sieve shaker AS200tap, manufactured by Recce Co., Ltd.), and the weight of the granular flame retardant composition remaining on the sieve was measured, and the ratio (wt%) to the weight (20 g) before the test was calculated. Using the calculated ratio, the strength of the granular flame retardant composition was judged according to the following criteria. The evaluation "A" is the highest strength and is preferable. A: 90% by weight or more B: 80% by weight or more and less than 90% by weight C: Less than 80% by weight

[0059] (Flame retardancy of thermoplastic resin composition) It was confirmed that the thermoplastic resin compositions obtained by adding the granular flame retardant compositions of each of the Examples and Comparative Examples to a thermoplastic resin had flame retardancy.

[0060] Specifically, a styrene-based resin (product name: PSJ Polystyrene G9305, manufactured by PS Japan Co., Ltd.) and a granular flame retardant composition were put into an extruder with a caliber of 65 mm, and the inside of the extruder was heated to 200°C to melt and plasticize the composition, and kneading was continued to prepare a styrene-based resin composition in the extruder. The blending ratio of the styrene-based resin and the granular flame retardant composition was adjusted so that the bromine-containing organic compound (A) in the granular flame retardant composition was 3% by weight of the total. The extruder used was a two-stage extruder connected in series from a caliber of 65 mm to a caliber of 90 mm.

[0061] Next, a predetermined amount of foaming agent was injected into the tip of the 65 mm extruder (opposite the nozzle of the 90 mm extruder) on a separate line, and the resin temperature (temperature inside the machine) was cooled to 120 ° C. with the 90 mm extruder. As the foaming agent, 3 parts by weight of isobutane and 3 parts by weight of dimethyl ether (per 100 parts by weight of styrene-based resin) were used. Then, the resin composition was extruded into the atmosphere from a die lip with a rectangular cross section of 2.5 mm in the thickness direction and 45 mm in the width direction provided at the tip of the 90 mm extruder, to obtain a rectangular shaped extruded foam of styrene-based resin. The oxygen index of the obtained extruded foam was measured according to JIS K-7201, and the flame retardancy of the extruded foam was judged. The flame retardancy judgment criteria are as follows. Note that evaluation "A" is preferable because it has higher flame retardancy. In addition, if the oxygen index is 26 or more, it is not subject to the application of designated flammable materials under the Fire Service Act of Japan. A: Oxygen index is 26 or higher B: Oxygen index less than 26

[0062] Here, the flame retardancy of expanded styrene resin has been confirmed as an example, but it was also confirmed that the thermoplastic resin composition had the desired flame retardancy when other thermoplastic resins (such as non-expanded styrene resin and ABS resin) were used.

[0063] [Table 1]

[0064] [Table 2]

[0065] [Table 3]

[0066] It can be seen from each table that the granular flame retardant composition of the present invention, that is, the granular flame retardant composition shown in each Example, has excellent productivity, low mutual adhesion, and excellent strength.

[0067] In this specification, for example, the description "XX to YY" means "XX or more and YY or less." [Industrial Applicability]

[0068] The granular flame retardant composition of the present invention can be used as a flame retardant for thermoplastic resins.

Claims

1. A granular flame retardant composition containing a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains at least one bromine-containing organic compound (A1) selected from the group consisting of bromine-containing organic compounds (A1-1) having a 2,3-dibromo-2-alkylpropyl group and bromine-containing organic compounds (A1-2) having a 2,3-dibromopropyl group; The bromine-containing organic compound (A1-1) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromo-2-methylpropyl ether); the bromine-containing organic compound (A1-2) is at least one selected from the group consisting of tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-S-bis(2,3-dibromopropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromopropyl ether); A granular flame retardant composition, characterized in that the binder (B) contains a sucrose fatty acid ester (B1) having a melting point of 40 to 90°C.

2. The granular flame retardant composition according to claim 1, wherein the content of the sucrose fatty acid ester (B1) is 1 to 20% by weight of the granular flame retardant composition.

3. The granular flame retardant composition according to claim 1, wherein the content of the bromine-containing organic compound (A1) is 20 to 99% by weight of the granular flame retardant composition.

4. A thermoplastic resin composition comprising the granular flame retardant composition according to any one of claims 1 to 3 and a thermoplastic resin.

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