Granular flame retardant composition and thermoplastic resin composition

Abstract

Provided is a granular flame retardant composition which has low mutual adhesion, has a certain degree of strength, and is capable of improving productivity. A granular flame retardant composition which contains a bromine-containing organic compound (A) and a binder (B), and which is characterized in that the bromine-containing organic compound (A) contains a bromine-containing organic compound (A1) that is selected from a 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-dibromo-2-alkylpropyl group, and a specific bromine-containing organic compound (A1-2) having a 2, 3-dibromo-2-alkylpropyl group. The binder (B) contains a fatty acid amide (B1) having a melting point of 40 DEG C to 90 DEG C, and the content of the fatty acid amide (B1) is 5 parts by mass to 15 parts by mass per 100 parts by mass of the bromine-containing organic compound (A).

Description

TECHNICAL FIELD

[0001] The present application relates to a granular flame retardant composition and a thermoplastic resin composition. BACKGROUND

[0002] Bromine-containing organic compounds are widely used as flame retardants for thermoplastic resins such as polystyrene resins, ABS resins, and the like. However, for example, in the case where the flame retardant is in the form of a powder, there are problems in that it is easy to scatter at the time of metering or at the time of charging into the resin, and the working environment is deteriorated to adversely affect the health of the worker, and there is a possibility of a dust explosion, and the like. In addition, due to the particle size and specific gravity of the flame retardant, there are sometimes problems in that the flowability is poor, the hopper is clogged at the time of charging from the hopper, air transport of the flame retardant is difficult, and the like. Therefore, a granular flame retardant composition which is not easy to scatter, has excellent flowability, and is easy to handle is desired.

[0003] For example, in Patent Literature 1, a granular flame retardant composition using an ethylene-vinyl acetate copolymer as an adhesive for a bromine-based flame retardant is disclosed.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open (kokai) No. 2007-70586 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, immediately after the granular flame retardant composition is just granulated, the particles immediately adhere to each other, and there is a problem in that the granular flame retardant composition is difficult to use. (Hereinafter, the property that the granular flame retardant composition after granulation and before cooling and solidification adheres to each other and cannot be separated is also referred to as "adhesion to each other.")

[0009] In addition, it is required that the granular flame retardant composition has a strength which is not easy to break even at a faster granulation speed, that is, has high productivity.

[0010] The present application was made in order to solve the above problems, and has an object to provide a granular flame retardant composition which has low adhesion to each other, has a certain degree of strength, and can improve productivity.

[0011] TECHNICAL MEANS FOR SOLVING THE PROBLEMS

[0012] The present application includes, for example, the embodiments shown below.

[0013] [1] A granular flame retardant composition, characterized in that it contains a bromine-containing organic compound (A) and an adhesive (B), wherein the bromine-containing organic compound (A) contains a bromine-containing organic compound (A1), wherein the bromine-containing organic compound (A1) is at least one selected from the group consisting of a bromine-containing organic compound (A1-1) having a 2,3-dibromo-2-alkylpropyl group and a bromine-containing organic compound (A1-2) having a 2,3-dibromopropyl group, wherein 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-S-bis(2,3-dibromo-2-methylpropyl ether). The bromine-containing organic compound (A1-2) is 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). The adhesive (B) contains a fatty acid amide (B1) with a melting point of 40°C to 90°C. The content of the fatty acid amide (B1) is 5 parts by mass to 15 parts by mass relative to 100 parts by mass of the bromine-containing organic compound (A).

[0014] [2] According to the granular flame retardant composition described above [2], the content of the fatty acid amide (B1) is 1% to 20% by weight of the granular flame retardant composition.

[0015] [3] According to the granular flame retardant composition described in [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.

[0016] [4] A thermoplastic resin composition comprising the granular flame retardant composition described in any one of [1] to [3] above and a thermoplastic resin.

[0017] [5] The use of a composition as a particulate flame retardant composition, characterized in that the particulate flame retardant composition contains a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) contains a bromine-containing organic compound (A1), wherein the bromine-containing organic compound (A1) is at least one selected from the group consisting of a bromine-containing organic compound (A1-1) having 2,3-dibromo-2-alkylpropyl and a bromine-containing organic compound (A1-2) having 2,3-dibromopropyl, wherein 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... The bromine-containing organic compound (A1-2) is 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). The adhesive (B) contains a fatty acid amide (B1) with a melting point of 40°C to 90°C. The content of the fatty acid amide (B1) is 5 parts by mass to 15 parts by mass relative to 100 parts by mass of the bromine-containing organic compound (A).

[0018] Invention Effects

[0019] According to the granular flame retardant composition of the present invention, a granular flame retardant composition is provided that, when using 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 as a flame retardant, exhibits low mutual adhesion, a certain degree of strength, and improved productivity. Detailed Implementation

[0020] The preferred embodiments of the present invention will be described below.

[0021] The granular flame retardant composition of the present invention 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 bromine-containing organic compound (A1-1) having a 2,3-dibromo-2-alkylpropyl group and a bromine-containing organic compound (A1-2) having a 2,3-dibromopropyl group, wherein the bromine-containing organic compound (A1-1) is selected from 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 adhesive (B) contains at least one selected from the group consisting of phenol-F-bis(2,3-dibromo-2-methylpropyl ether), wherein 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 adhesive (B) contains a fatty acid amide (B1) with a melting point of 40°C to 90°C, wherein the content of the fatty acid amide (B1) is 5 parts by mass to 15 parts by mass relative to 100 parts by mass of the bromine-containing organic compound (A).

[0022] The following is a description of each component.

[0023] The bromine-containing organic compound (A) of the present invention, for example, contains 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). They can be used alone or in combination of two or more.

[0024] Furthermore, the bromine-containing organic compound (A) of the present invention, for example, contains 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). They can be used alone or in combination of two or more.

[0025] The bromine-containing organic compound (A) of the present invention may include bromine-containing organic compounds (A2) other than the bromine-containing organic compound (A1) described above. 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, polybrominated diphenyl ethers, polybrominated diphenyl ethanes, bis(polybrominated phenoxy ethanes), tri(polybrominated phenoxy triazines), polybrominated phenyl indenium, pentabromobenzyl polyacrylate, ethylene bis(tetrabromophthalimide), tris(tribromoneopentyl) phosphate, brominated epoxy oligomers, etc. They can be used alone or in combination of two or more.

[0026] In this invention, when the granular flame retardant composition is set to 100 parts by weight, the content of the bromine-containing organic compound (A) is preferably 70 to 98 parts by weight, more preferably 80 to 98 parts by weight. By keeping the content of the bromine-containing organic compound (A) within the above range, it has the advantage that even with a relatively small amount of the granular flame retardant composition added, the flame retardancy of the thermoplastic resin is superior.

[0027] From the viewpoint of improving productivity and strength, the content of bromine-containing organic compound (A1) is preferably 20% to 99% by weight of the total granular flame retardant composition, more preferably 40% to 97% by weight, more preferably 60% to 95% by weight, more preferably 80% to 93% by weight, and even more preferably 86% to 92% by weight.

[0028] From the viewpoint of improving productivity and strength, the content of bromine-containing organic compound (A1) is preferably 30% by weight or more, 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 can be 70% by weight or more, 80% by weight or more, or 90% by weight or more.

[0029] The adhesive (B) of the present invention contains a fatty acid amide (B1) with a melting point of 40°C to 90°C. From the viewpoint of improving productivity and strength and reducing inter-adhesion, the melting point of the fatty acid amide (B1) is more preferably 55°C to 88°C, more preferably 60°C to 85°C, more preferably 63°C to 83°C, and even more preferably 66°C to 80°C. Here, the melting point of the fatty acid amide (B1) is the melting point determined according to JIS K0064.

[0030] From the viewpoint of improving productivity and strength and reducing cross-adhesion, fatty acid amides (B1) preferably have one or more unsaturated bonds. Specifically, the fatty acids constituting fatty acid amides (B1) preferably have one or more unsaturated bonds. The number of unsaturated bonds is not particularly limited, but one is preferred.

[0031] Examples of fatty acid amides (B1) include: palmitamide, oleamide, erucamide, eicosenoamide, purslane amide, transoleamide, trans-11-eicosenoamide, trans-13-docosaenoamide, linoleamide, linolenic acid amide, castor oil amide, N-stearyl erucamide, and N-oleyl palmitamide. These can be used alone or in combination of two or more. From the viewpoint of improving productivity and strength while reducing cross-adhesion, oleamide and erucamide are preferred.

[0032] From the viewpoint of improving productivity and strength and reducing tautomerism, the fatty acid that constitutes the fatty acid amide (B1) preferably has 10 to 28 carbon atoms, more preferably 14 to 26, even more preferably 16 to 24, and even more preferably 18 to 22.

[0033] From the viewpoint of improving productivity and strength and reducing cross-adhesion, the content of fatty acid amide (B1) is preferably 1% to 20% by weight of the total granular flame retardant composition, more preferably 2% to 20% by weight, more preferably 4 parts by weight to 15 parts by weight, more preferably 5 parts by weight to 11 parts by weight, and even more preferably 6 parts by weight to 10 parts by weight.

[0034] From the viewpoint of improving productivity and strength and reducing cross-adhesion, the content of fatty acid amide (B1) in the adhesive (B) is preferably 20% to 100% by weight, more preferably 40% to 100% by weight, more preferably 60% to 100% by weight, more preferably 70% to 100% by weight, and even more preferably 80% to 100% by weight.

[0035] From the viewpoint of improving productivity and strength and reducing cross-adhesion, the content of the adhesive (B) of the present invention is preferably 1% to 20% by weight of the total granular flame retardant composition, preferably 3% to 20% by weight, more preferably 5% to 15% by weight, and even more preferably 6% to 10% by weight.

[0036] The adhesive (B) of the present invention may contain an adhesive (B2) other than a fatty acid amide (B1). Examples of such compounds include ethylene-vinyl acetate copolymers and acrylic resins.

[0037] From the viewpoint of improving productivity and strength and reducing mutual adhesion, the mass ratio (A1 / B1) of the bromine-containing organic compound (A1) to the above-mentioned fatty acid amide (B1) is preferably 0.5 to 50, more preferably 1 to 40, more preferably 2 to 35, more preferably 5 to 30, even more preferably 7 to 20, even more preferably 8 to 15, and even more preferably 9 to 13.

[0038] The content of fatty acid amide (B1) is 5 to 15 parts by weight relative to 100 parts by weight of bromine-containing organic compound (A). From the viewpoint of improving productivity and strength and reducing cross-adhesion, this content is preferably 6 to 13 parts by weight relative to 100 parts by weight of bromine-containing organic compound (A), more preferably 6 to 12 parts by weight, and even more preferably 7 to 11 parts by weight.

[0039] From the viewpoint of improving productivity and strength and reducing cross-adhesion, the bromine-containing organic compound (A1-1) contained in the bromine-containing organic compound (A1) is preferably 30% to 100% by weight, more preferably 40% to 100% by weight, and even more preferably 50% to 100% by weight.

[0040] 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, which improves the durability of the thermoplastic resin.

[0041] Examples of such stabilizers (C) include: phosphite compounds, thioether compounds, hindered phenolic compounds, hindered amine compounds, tin compounds, natural or synthetic minerals, etc.

[0042] Examples of phosphite compounds include: tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl phosphite, tetra(2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphite, bis(nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and 2,2'-methylenebis(4,6-di-tert-butyl-1-phenoxy)(2-ethyl Phosphorus tridecyloxyphosphite, tetra(tetrazyl)-4,4'-butylene-bis(2-tert-butyl-5-methylphenyl)diphosphite, hexa(tetrazyl)-1,1,3-tris(3-tert-butyl-6-methyl-4-oxophenyl)-3-methylpropane triphosphite, mono(dinonylphenyl)mono-p-nonylphenyl phosphite, tri(monononylphenyl) phosphite, tetraalkyl(C=12~16)-4,4'-isopropylene-(bisphenyl)diphosphite, mono- or diphenyl mono- or dialkyl (or alkoxyalkyl, C=8~13) phosphite, diphenylisodecyl phosphite, tridecyl phosphite, triphenyl phosphite, etc.

[0043] Examples of thioether compounds include: dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearate-3,3'-thiodipropionate, pentaerythritol tetra(3-lauryl thiopropionate), di(tetranyl)-3,3'-thiodipropionate, 2-mercaptobenzimidazole, etc.

[0044] Examples of hindered phenolic compounds include: 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], glyceryl tris[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and octadecyl-3-(3,5-di-tert-butyl)propionate. 3,4-hydroxyphenyl)propionate, thiodiethylidene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecanyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, calcium diethylbis[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate 1-Dimethylethyl)-4-hydroxyphenyl]methyl]phosphonate, 3,3',3'',5,5',5''-hexa-tert-butyl-a,a',a''-(trimethylbenzene-2,4,6-triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxoethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] Examples of such products include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris[(4-tert-butyl-3-hydroxy-2,6-dimethyl)methyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2-ylamino)phenol.

[0045] Examples of hindered amine compounds 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-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-n-butylmalonate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, and tetra(1,2,2,6,6-pentamethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate.

[0046] Examples of tin compounds include dioctyltin dilaurate and dioctyltin maleate.

[0047] Examples of natural or synthetic minerals include hydrotalcite and zeolite.

[0048] When the granular flame retardant composition is set to 100 parts by weight, the content of stabilizer (C) is preferably 0.1 parts by weight to 20 parts by weight, more preferably 0.3 parts by weight to 15 parts by weight, and even more preferably 0.8 parts by weight to 10 parts by weight.

[0049] The granular flame retardant composition of the present invention may further contain a phosphate ester (D). Examples of such phosphate esters include triphenyl phosphate, tricresyl phosphate, and tri(xylyl) phosphate.

[0050] Furthermore, without impairing the effects of the present invention, the granular flame retardant composition of the present invention may contain conventionally known additives. Examples of such additives include: fatty acid amides, fatty acids, waxes, pigments, etc. The fatty acid amide is, for example, a fatty acid amide other than fatty acid amide (B1).

[0051] Other fatty acid amides besides fatty acid amides (B1) include, for example, fatty acid monoamides such as caprylic acid amide, stearic acid amide, and behenic acid amide, and fatty acid diamides such as ethylene biscaprylic acid amide, ethylene bisstearic acid amide, hexamethylene bisstearic acid amide, and ethylene bisbenzyl acid amide.

[0052] Examples of fatty acids include: caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, benzyl acid, ceramide, 12-hydroxystearic acid, oleic acid, etc.

[0053] The thermoplastic resin composition of the present invention comprises a granular flame retardant composition and a thermoplastic resin. The thermoplastic resin is not particularly limited and can include various resins such as polystyrene resin, ABS resin, and polyurethane resin. Polystyrene resin is preferred as the thermoplastic resin. The thermoplastic resin composition containing polystyrene resin can be a foam or a non-foamed material.

[0054] The granular flame retardant composition of the present invention can be obtained, for example, by mixing a bromine-containing organic compound (A), a binder (B), and other compounds as needed, using a conventionally known extrusion granulator or compounding granulator, for example, at a temperature of 40°C to 80°C. Examples of extrusion granulators include, for example, screw extrusion granulators, roller extrusion granulators, paddle extrusion granulators, tablet extrusion granulators, and briquetting extrusion granulators.

[0055] Example

[0056] The invention is described in more detail based on embodiments and comparative examples, but is not limited thereto. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the invention.

[0057] The following details the raw materials used in the manufacture of granular flame retardant compositions.

[0058] <Ingredients Used>

[0059] [Brominated organic compounds (A1)]

[0060] (A1-1): Tetrabromobisphenol-A-bis(2,3-dibromo-2-methylpropyl ether) (Trade name: Pilogard SR-130, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., bromine content: 66% by weight)

[0061] (A1-2): Tetrabromobisphenol-A-bis(2,3-dibromopropyl ether) (Trade name: Pilogard SR-720N, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., bromine content: 67% by weight)

[0062] [Brominated organic compounds (A2)]

[0063] (A2-1): 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (trade name: Pilogard SR-245, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., bromine content: 67% by weight)

[0064] (A2-2): Tris(2,3-dibromopropyl)isocyanurate (trade name: Pilogard SR-750, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., bromine content: 65% by weight)

[0065] (A2-3): Tris(tribromoneopentyl)phosphate (trade name: CR-900, manufactured by Daihachi Chemical Industry Co., Ltd., bromine content: 73% by weight)

[0066] [Fatty acid amide (B1)]

[0067] (B1-1): Oleamide (trade name: Fatty acid amide ON, manufactured by Kao Corporation, melting point 73℃)

[0068] (B1-2): Erucamide (trade name: fatty acid amide E, manufactured by Kao Corporation, melting point 82℃)

[0069] (B1-3): Palmitamide (trade name: (9Z)-9-hexadeceneamide, Aaron Chemicals LLC., melting point 69℃)

[0070] (B1-4): Linolenic acid amide (trade name: 9,12,15-octadecanetrienamide, Aaron Chemicals LLC., melting point 59℃)

[0071] (B1-5): N-Stearylerucamide (trade name: SNT-F, manufactured by Nippon Seika Co., Ltd., melting point 75°C)

[0072] (b1-1): N,N'-Ethylene dioleoamide (trade name: N,N'-Ethylene dioleoamide, manufactured by Wako Pure Chemical Industries, Ltd., melting point 115°C) (comparative material)

[0073] (b1-2): Stearamide (trade name: fatty acid amide S, manufactured by Kao Corporation, melting point 03℃) (comparative material)

[0074] [Adhesives other than fatty acid amides (B1) (B2)]

[0075] (B2-1): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 684, manufactured by Tosoh Corporation, VA (vinyl acetate) = 20 mol%, MI (melt index) = 2000)

[0076] (B2-2): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 735, manufactured by Tosoh Co., Ltd., VA=28 mol%, MI=1000)

[0077] (B2-3): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 720, manufactured by Tosoh Co., Ltd., VA=28 mol%, MI=150)

[0078] (B2-4): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 760, manufactured by Tosoh Corporation, VA=42 mol%, MI=70)

[0079] (B2-5): Ethylene-ethyl methacrylate copolymer (trade name: NUC-6940, manufactured by ENEOS Corporation, EA (ethyl methacrylate) = 35 mol%, MI = 20)

[0080] (B2-6): Ethylene-methyl methacrylate copolymer (trade name: Acrylic CM5021, manufactured by Sumitomo Chemical Co., Ltd., MMA (methyl methacrylate) = 28 mol%, MI = 450)

[0081] (B2-7): Ethylene-methacrylic acid copolymer (trade name: Nycleru N0200H, manufactured by Mitsui Dow Polymethyl methacrylate Co., Ltd., MA (methacrylic acid) = 2 mol%, MI = 130)

[0082] [Stabilizer (C)]

[0083] (C-1): Tris(2,4-di-tert-butylphenyl)phosphite (trade name: Adeka 2112, manufactured by ADEKA Co., Ltd.)

[0084] (C-2): Tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate (trade name: Abeka LA-57, manufactured by ADEKA Co., Ltd.)

[0085] (C-3): Distearate-3,3'-thiodipropionate (trade name: Rasumit SG, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.)

[0086] (C-4): Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF)

[0087] (C-5): Dioctyltin dilaurate (trade name: OL-1, manufactured by Tokyo Finkemica Co., Ltd.)

[0088] (C-6): Hydrotalcite (trade name: STABIACE HT-1, manufactured by Sakai Chemical Industry Co., Ltd.)

[0089] [Phosphate (D)]

[0090] (D-1): Triphenyl phosphate (trade name: TPP, manufactured by Daihachi Chemical Industry Co., Ltd.)

[0091] <Evaluation of Granular Flame Retardant Compositions>

[0092] The proportions (by weight), ratios, and evaluation results of the raw materials in each embodiment and comparative example are shown in the table below.

[0093] According to the proportions shown in the table, the bromine-containing organic compound (A), the binder (B), and other compounds as needed were mixed for 5 minutes using a mixer (trade name: high-speed mixer, manufactured by Fukae Powertech Co., Ltd.). Hereinafter, the mixture obtained in this way will also be referred to as the "evaluation composition". The productivity, inter-adhesion, and strength were evaluated using the evaluation compositions of each example and each comparative example. In addition, the flame retardancy of the thermoplastic resin compositions obtained by adding each evaluation composition to a thermoplastic resin was evaluated.

[0094] (Productivity)

[0095] Using an extrusion granulator (trade name: EXDF-100, manufactured by Darton Co., Ltd.) with a set temperature of 70°C, and using the evaluation composition as material, granulation was performed while adjusting the ejection speed from the extrusion granulator to determine the productivity of the granulated flame retardant composition. Specifically, the highest ejection speed (hereinafter also referred to as "maximum ejection speed") within the range of ejection speeds that can be granulated was used to determine productivity.

[0096] Here, the ejection rate is the weight of the flame retardant composition (whether granular or not) ejected from the extruder per unit time, expressed in kg / h. Furthermore, the granular flame retardant composition obtained by extrusion granulation exhibits some deviations, typically being cylindrical with a base diameter of 3 mm and a height of 5 mm (this also applies to the evaluation of inter-adhesion and strength described later). The productivity criteria are shown below. It should be noted that a rating of "A" indicates the highest productivity and is preferred. Additionally, for compositions rated "D," the evaluations of inter-adhesion and strength, as described later, were not performed.

[0097] A: It can granulate, with a maximum spraying speed of over 150 kg / h.

[0098] B: Capable of granulation, with a maximum spraying speed of over 100 kg / h and less than 150 kg / h.

[0099] C: Capable of granulation, with a maximum spraying speed of 50 kg / h or more but less than 100 kg / h.

[0100] D: Capable of granulation but with a maximum ejection speed of less than 50 kg / h, or unable to complete granulation regardless of extrusion rate.

[0101] (Mutual adhesion)

[0102] The inter-adhesion of the granular flame retardant composition was determined by the following method. Specifically, the evaluation composition was granulated using the aforementioned extrusion granulator at a set temperature of 70°C. The ejection speed from the extrusion granulator was the maximum ejection speed obtained during the evaluation of productivity. A horizontal wooden board was placed 20 cm below the nozzle of the extrusion granulator, and the ejected granular flame retardant composition was piled on the board. 1 kg of the evaluation composition was used in this evaluation. The granular flame retardant composition was allowed to stand at room temperature (25°C) for 30 minutes from the start of granulation to fully cool and solidify, and its inter-adhesion was determined. The criteria for determining inter-adhesion are shown below. It should be noted that the lowest inter-adhesion is preferred for evaluation "A". Furthermore, "ability to separate" as described below means, for example, the ability to separate the granular flame retardant composition aggregated into clumps while maintaining its original shape, without the use of any tools or similar equipment.

[0103] A: The granular flame retardant composition does not adhere to each other at all.

[0104] B: Part or all of the granular flame retardant composition adheres to each other but can be separated.

[0105] C: Some or all of the granular flame retardant composition adheres to each other and cannot be separated.

[0106] (strength)

[0107] The granular flame retardant composition is required to have a strength that prevents it from easily breaking. The strength of the granular flame retardant composition is determined by the following method: Granulation is performed using the aforementioned extrusion granulator at a set temperature of 70°C, using the evaluation composition as the material. The ejection speed from the extrusion granulator at this time is the maximum ejection speed obtained when evaluating the productivity. 20g of the obtained granular flame retardant composition is placed on a 1mm mesh sieve and vibrated for 10 minutes using a vibrator (AS200tap percussion sieve, manufactured by Rech. Co., Ltd.). The weight of the granular flame retardant composition remaining on the sieve is then measured, and the ratio (wt%) relative to the weight (20g) before the test is calculated. Using this calculated ratio, the strength of the granular flame retardant composition is determined based on the following criteria. Furthermore, a strength rating of "A" is the highest and preferred.

[0108] A: Over 90% by weight

[0109] B: 80% by weight or more but less than 90% by weight

[0110] C: Less than 80% by weight

[0111] (Flame retardancy of thermoplastic resin compositions)

[0112] It was confirmed that the thermoplastic resin compositions obtained by adding the granular flame retardant compositions of the various embodiments and comparative examples to the thermoplastic resin have flame retardant properties.

[0113] Specifically, a styrene-based resin (trade name: PSJ polystyrene G9305, manufactured by PS Japan) and a granular flame retardant composition are fed into an extruder with a 65mm diameter. The mixture is heated to 200°C inside the extruder to melt and plasticize, and then further compounded to prepare the styrene-based resin composition within the extruder. The ratio of the styrene-based resin to the granular flame retardant composition is adjusted so that the bromine-containing organic compound (A) in the granular flame retardant composition is 3% by weight of the total. A two-stage extruder with diameters of 65mm to 90mm connected in series is used.

[0114] Next, at the front end of a 65mm extruder (on the side opposite to the die of a 90mm diameter extruder), a specified amount of foaming agent is forced in using another production line, and the resin temperature (internal temperature) is cooled to 120°C using a 90mm diameter 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) are used. Then, the resin composition is extruded into the atmosphere from a die lip with a rectangular cross-section of 2.5mm in the thickness direction and 45mm in the width direction, located at the front end of the 90mm diameter extruder, thereby obtaining a cuboid-shaped extruded foamed styrene-based resin. The resulting extruded foamed styrene is then tested for its flame retardancy according to JIS K-7201, measuring the oxygen index. The criteria for determining flame retardancy are shown below. It should be noted that an evaluation of "A" indicates high flame retardancy, which is preferred. Furthermore, when the oxygen index is 26 or higher, the designated combustibles under the Japanese Fire Protection Law are not applicable.

[0115] A: Oxygen index is above 26

[0116] B: Oxygen index less than 26

[0117] Here, the flame retardancy of foamed styrene resin is described as an example, but when using other thermoplastic resins (such as non-foamed styrene resin and ABS resin), the desired flame retardancy of the thermoplastic resin composition can also be confirmed.

[0118] [Table 1]

[0119]

[0120] [Table 2]

[0121]

[0122] [Table 3]

[0123]

[0124] As can be seen from the tables, the granular flame retardant compositions of the present invention, namely the granular flame retardant compositions shown in the various embodiments, have excellent manufacturability, low mutual adhesion, and excellent strength.

[0125] Additionally, in this specification, terms such as "XX~YY" refer to "XX and above and YY and below".

[0126] Industrial practicality

[0127] The granular flame retardant composition of the present invention can be used as a flame retardant in thermoplastic resins.

Claims

1. A granular flame retardant composition, characterized in that, The granular flame retardant composition contains a bromine-containing organic compound (A) and a binder (B). The bromine-containing organic compound (A) contains a bromine-containing organic compound (A1), which is at least one selected from the group consisting of a bromine-containing organic compound (A1-1) having a 2,3-dibromo-2-alkylpropyl group and a bromine-containing organic compound (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). The adhesive (B) contains a fatty acid amide (B1) with a melting point of 40°C to 90°C. The content of fatty acid amide (B1) is 5 to 15 parts by mass relative to 100 parts by mass of bromine-containing organic compound (A).

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

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

4. A thermoplastic resin composition, characterized in that, The thermoplastic resin composition comprises the granular flame retardant composition according to any one of claims 1 to 3 and the thermoplastic resin.

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