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 (B1) having a melting point of 40 DEG C to 90 DEG C and having 16 to 22 carbon atoms, and at least one compound selected from the group consisting of specific bromine-containing organic compounds (A1-2) having a 1, 3-dibromopropyl group.

Description

Technical Field

[0001] This invention relates to granular flame retardant compositions and thermoplastic resin compositions. Background Technology

[0002] Bromine-containing organic compounds are widely used as flame retardants for thermoplastic resins such as polystyrene and ABS. However, when the flame retardant is in powder form, the following problems exist: it is prone to scattering during metering or addition to the resin, which can deteriorate the working environment and adversely affect the health of workers, potentially leading to dust explosions. Furthermore, due to the particle size and specific gravity of the flame retardant, it sometimes exhibits poor flowability, causing hopper blockage when added and difficulties in air delivery of the flame retardant. Therefore, granular flame retardant compositions that are not easily scattered, have excellent flowability, and are easy to handle are desirable.

[0003] For example, Patent Document 1 discloses a granular flame retardant composition that uses ethylene vinyl acetate copolymer as a brominated flame retardant in an adhesive.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2007-70586 Summary of the Invention

[0007] The technical problem that the invention aims to solve

[0008] However, immediately after granulation, the granules of the granular flame retardant composition adhere to each other, posing a problem of difficulty in using the granular flame retardant composition. (Hereinafter, the property of the granular flame retardant composition that cannot be separated after granulation and before cooling and curing is also referred to as "inter-adhesion.")

[0009] In addition, the granular flame retardant composition is required to have the ability to be granulated even at a relatively fast granulation rate, that is, to have high productivity and strength that is not easily broken.

[0010] The present invention was made to solve the above-mentioned problems, and its purpose is to provide a granular flame retardant composition with low mutual adhesion, a certain degree of strength, and improved productivity.

[0011] Technical means for solving problems

[0012] The present invention 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), ... The bromine-containing organic compound (A1-2) is selected from the group consisting of tetrabromobisphenol-S-bis(2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-F-bis(2,3-dibromo-2-methylpropyl ether), and the adhesive (B) contains at least one fatty acid (B1) with a melting point of 40°C to 90°C and having 16 to 22 carbon atoms.

[0014] [2] According to the granular flame retardant composition described above [1], wherein the content of the fatty acid (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- The bromine-containing organic compound (A1-2) 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-F-bis(2,3-dibromo-2-methylpropyl ether), and the adhesive (B) contains at least one fatty acid (B1) with a melting point of 40°C to 90°C and having 16 to 22 carbon atoms.

[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 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 (B1) with a melting point of 40°C to 90°C and having 16 to 22 carbon atoms. The components are described below.

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] The adhesive (B) of the present invention contains a fatty acid (B1) with a melting point of 40°C to 90°C and a carbon number of 16 to 22. From the viewpoint of improving productivity and strength and reducing inter-adhesion, the melting point of the fatty acid (B1) is more preferably 50°C to 80°C, more preferably 55°C to 75°C, and even more preferably 60°C to 72°C. Furthermore, from the viewpoint of improving productivity and strength and reducing inter-adhesion, the carbon number of the fatty acid (B1) is more preferably 16 to 20, and even more preferably 16 to 18. Here, the melting point of the fatty acid (B1) is the melting point determined according to JIS K0064.

[0029] Examples of fatty acids (B1) include palmitic acid, stearic acid, arachidic acid, behenic acid, 2-hydroxypalmitic acid, 10-hydroxypalmitic acid, 12-hydroxystearic acid, 2-hydroxyarachidic acid, and 2-hydroxybehenic acid. From the viewpoint of improving productivity and strength while reducing cross-adhesion, stearic acid and palmitic acid are preferred. They can be used alone or in combination of two or more.

[0030] From the viewpoint of improving productivity and strength and reducing cross-adhesion, the content of fatty acid (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 8 parts by weight.

[0031] From the viewpoint of improving productivity and strength and reducing mutual adhesion, the content of fatty acid (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, and even more preferably 65% ​​to 100% by weight.

[0032] 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.

[0033] The adhesive (B) of the present invention may contain an adhesive (B2) other than fatty acids (B1). Examples of such compounds include ethylene-vinyl acetate copolymers and acrylic resins.

[0034] From the viewpoint of improving productivity and strength and reducing mutual adhesion, the weight ratio (A1 / B1) of the bromine-containing organic compound (A1) to the fatty acid (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.

[0035] 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% by weight or more, more preferably 40% by weight or more, and more preferably 50% by weight or more.

[0036] 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.

[0037] Examples of such stabilizers (C) include: phosphite compounds, thioether compounds, hindered phenolic compounds, hindered amine compounds, tin compounds, natural or synthetic minerals, etc.

[0038] 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. 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.

[0039] 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. 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.

[0040] Examples of tin compounds include dioctyltin dilaurate and dioctyltin maleate.

[0041] Examples of natural or synthetic minerals include hydrotalcite and zeolite.

[0042] 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.

[0043] 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.

[0044] 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 is, for example, a fatty acid other than fatty acid (B1).

[0045] Examples of fatty acid amides include: caprylic acid amide, capric acid amide, myristic acid amide, palmitate amide, lauryl acid amide, erucic acid amide, stearic acid amide, arachidic acid amide, benzyl acid amide, tetracosyl acid amide, stearic acid monoethanolamide, oleic acid amide, linoleic acid amide, and arachidonic acid amide; ethylidene bis-caprylic acid amide, butylidene bis-caprylic acid amide, hexamethylene bis-caprylic acid amide, m-phenylene dimethyl bis-caprylic acid amide, ethylidene bis-decanoic acid amide, butylidene bis-decanoic acid amide, hexamethylene bis-decanoic acid amide, m-phenylene dimethyl bis-stearamide, ethylidene bis-stearamide, butylidene bis-stearamide, hexamethylene bis-stear ... Fatty acid diamides such as bisarachidamide, butylidene bisarachidamide, hexamethylene bisarachidamide, m-phenylene dimethyl bisarachidamide, ethylidene disorbate, butylidene bisarachidamide, hexamethylene disorbate, m-phenylene dimethyl bisarachidamide, ethylidene ditetracosamide, butylidene dioleamide, hexamethylene ditetracosamide, m-phenylene dimethyl bistetracosamide, ethylidene dioleamide, butylidene dioleamide, hexamethylene dioleamide, m-phenylene dimethyl bisarachidamide, ethylidene dilinoleamide, butylidene dilinoleamide, hexamethylene dilinoleamide, m-phenylene dimethyl bislinoleamide, ethylidene diarachidamide, butylidene diarachidamide, hexamethylene diarachidamide, and m-phenylene diarachidamide.

[0046] Fatty acids other than fatty acids (B1) that are used as additives include, for example, lauric acid, myristic acid, tetracosanoic acid, oleic acid, etc.

[0047] 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.

[0048] 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.

[0049] Example

[0050] 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.

[0051] The following details the raw materials used in the manufacture of granular flame retardant compositions.

[0052] <Ingredients Used>

[0053] [Brominated organic compounds (A1)]

[0054] (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)

[0055] (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)

[0056] [Brominated organic compounds (A2)]

[0057] (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)

[0058] (A2-2): Tris(2,3-dibromopropyl)isocyanurate (trade name: Pilogard SR-750, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., bromine content: 65% by weight)

[0059] (A2-3): Tris(tribromoneopentyl)phosphate (trade name: CR-900, manufactured by Daihachi Chemical Industry Co., Ltd., bromine content: 73% by weight)

[0060] [Fatty acid (B1)]

[0061] (B1-1): Stearic acid (trade name: stearic acid 98, manufactured by Miyoshi Oils Co., Ltd., melting point 68°C, 18 carbon atoms)

[0062] (B1-2): Palmitic acid (trade name: Palmitic acid 98, manufactured by Miyoshi Oils Co., Ltd., melting point 61°C, carbon number 16)

[0063] (B1-3): Arachidic acid (trade name: arachidic acid, manufactured by Tokyo Chemical Industry Co., Ltd., melting point 77°C, carbon number 20)

[0064] (B1-4): Bezoaric acid (trade name: Bezoaric acid 85, manufactured by Miyoshi Oils & Fats Co., Ltd., melting point 76°C, carbon number 22)

[0065] (b1-1): Lauric acid (trade name: Lauric acid 98, manufactured by Miyoshi Oils & Fats Co., Ltd., melting point 43°C, carbon number 12) (comparative material)

[0066] (b1-2): Myristic acid (trade name: Myristic acid 98, manufactured by Miyoshi Oils Co., Ltd., melting point 53°C, carbon number 14) (comparative material)

[0067] (b1-3): Oleic acid (trade name: Oleic acid D-100, manufactured by Shin Nippon Rikka Co., Ltd., melting point 17°C, carbon number 18) (comparative material)

[0068] (b1-4): Tetracosanoic acid (trade name: Tetracosanoic acid, manufactured by Tokyo Chemical Industry Co., Ltd., melting point 84°C, carbon number 24) (comparative material)

[0069] [Binder (B2) other than fatty acids (B1)]

[0070] (B2-1): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 684, manufactured by Tosoh Corporation, VA (vinyl acetate) = 20 mol%, MI (melt index) = 2000)

[0071] (B2-2): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 735, manufactured by Tosoh Co., Ltd., VA=28 mol%, MI=1000)

[0072] (B2-3): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 720, manufactured by Tosoh Co., Ltd., VA=28 mol%, MI=150)

[0073] (B2-4): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 760, manufactured by Tosoh Corporation, VA=42 mol%, MI=70)

[0074] (B2-5): Ethylene-ethyl methacrylate copolymer (trade name: NUC-6940, manufactured by ENEOS Corporation, EA (ethyl methacrylate) = 35 mol%, MI = 20)

[0075] (B2-6): Ethylene-methyl methacrylate copolymer (trade name: Acrylic CM5021, manufactured by Sumitomo Chemical Co., Ltd., MMA (methyl methacrylate) = 28 mol%, MI = 450)

[0076] (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)

[0077] [Stabilizer (C)]

[0078] (C-1): Tris(2,4-di-tert-butylphenyl)phosphite (trade name: Adeka 2112, manufactured by ADEKA Co., Ltd.)

[0079] (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.)

[0080] (C-3): Distearate-3,3'-thiodipropionate (trade name: Rasumit SG, manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd.)

[0081] (C-4): Pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (trade name: IRGANOX 1010, manufactured by BASF)

[0082] (C-5): Dioctyltin dilaurate (trade name: OL-1, manufactured by Tokyo Finkemica Co., Ltd.)

[0083] (C-6): Hydrotalcite (trade name: STABIACE HT-1, manufactured by Sakai Chemical Industry Co., Ltd.)

[0084] [Phosphate (D)]

[0085] (D-1): Triphenyl phosphate (trade name: TPP, manufactured by Daihachi Chemical Industry Co., Ltd.)

[0086] <Evaluation of Granular Flame Retardant Compositions>

[0087] The proportions (by weight), ratios, and evaluation results of the raw materials in each embodiment and comparative example are shown in the table below.

[0088] 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.

[0089] (Productivity)

[0090] 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.

[0091] 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.

[0092] A: It can granulate, with a maximum spraying speed of over 150 kg / h.

[0093] B: Capable of granulation, with a maximum spraying speed of over 100 kg / h and less than 150 kg / h.

[0094] C: Capable of granulation, with a maximum spraying speed of 50 kg / h or more but less than 100 kg / h.

[0095] 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.

[0096] (Mutual adhesion)

[0097] 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.

[0098] A: The granular flame retardant composition does not adhere to each other at all.

[0099] B: Part or all of the granular flame retardant composition adheres to each other but can be separated.

[0100] C: Some or all of the granular flame retardant composition adheres to each other and cannot be separated.

[0101] (strength)

[0102] 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.

[0103] A: Over 90% by weight

[0104] B: 80% by weight or more but less than 90% by weight

[0105] C: Less than 80% by weight

[0106] (Flame retardancy of thermoplastic resin compositions)

[0107] 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.

[0108] 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.

[0109] 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.

[0110] A: Oxygen index is above 26

[0111] B: Oxygen index less than 26

[0112] 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.

[0113] [Table 1]

[0114]

[0115] [Table 2]

[0116]

[0117] [Table 3]

[0118]

[0119] 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.

[0120] Additionally, in this specification, terms such as "XX~YY" refer to "XX and above and YY and below".

[0121] Industrial practicality

[0122] 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 (B1) with a melting point of 40°C to 90°C and 16 to 22 carbon atoms.

2. The granular flame retardant composition according to claim 1, wherein, The fatty acid (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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