JP5679353B2 - Granular flame retardant composition and thermoplastic resin composition - Google Patents

Description

  The present invention relates to a granular flame retardant composition and a thermoplastic resin composition.

  Bromine-containing organic compounds are widely used as flame retardants for thermoplastic resins such as polystyrene resins and ABS resins. As a method of adding a flame retardant to a thermoplastic resin, it is possible to add a flame retardant as it is, but for the purpose of improving workability at the time of addition, a granular flame retardant composition in which a flame retardant is granulated in advance. Things are also used.

  For example, Patent Document 1 discloses a granular flame retardant composition using an ethylene vinyl acetate copolymer as a binder for a brominated flame retardant.

  Conventionally, hexabromocyclododecane (HBCD) having excellent flame retardancy has been used as a brominated flame retardant. However, since safety is a concern, in recent years, 2,3-dibromo-2 such as tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), which is excellent in flame retardancy like HBCD, is used. -Alternatives to bromine-containing organic compounds having an alkylpropyl group are being considered.

JP 2007-70586 A

  However, when a bromine-containing organic compound having a 2,3-dibromo-2-alkylpropyl group is used as a brominated flame retardant, when the binder of Patent Document 1 is used, the kneadability with a thermoplastic resin is reduced. There is.

  Therefore, the present invention provides a granular flame retardant composition excellent in kneadability with a thermoplastic resin when a bromine-containing organic compound having a 2,3-dibromo-2-alkylpropyl group is used as a flame retardant. Let it be an issue.

In order to solve the above problems, the particles comprising a flame retardant composition according to the present invention is a particle consisting of a flame retardant composition containing bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic Compound (A) is tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol-S-bis (2,3-dibromo-2-methylpropyl ether), and tetra 1 or more types (A1) selected from the group consisting of bromobisphenol-F-bis (2,3-dibromo-2-methylpropyl ether) , and the binder (B) contains the fatty acid ester (B1) It is characterized by containing.

According to this structure, when the binder (B) contains the fatty acid ester (B1), tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether), tetrabromobisphenol as a flame retardant One or more selected from the group consisting of -S-bis (2,3-dibromo-2-methylpropyl ether) and tetrabromobisphenol-F-bis (2,3-dibromo-2-methylpropyl ether) are used. The granular flame retardant composition thus obtained has excellent kneadability with the styrene resin .

Moreover, in the particle | grains which consist of a flame retardant composition of this invention, it is preferable that melting | fusing point is 40-80 degreeC for the said fatty acid ester (C1).

According to such a configuration, the kneading property with the styrene resin becomes more excellent.

Moreover, it is preferable that the particle | grains which consist of a flame retardant composition of this invention contain a heat stabilizer (C) further.

  According to the granular flame retardant composition of the present invention, when a bromine-containing organic compound having a 2,3-dibromo-2-alkylpropyl group is used as a flame retardant, the effect of being excellent in kneadability with a thermoplastic resin Play.

  Hereinafter, preferred embodiments of the present invention will be described. 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) is 2,3- A bromine-containing organic compound (A1) having a dibromo-2-alkylpropyl group is contained. Hereinafter, each component will be described.

  The bromine-containing organic compound (A) of the present invention contains a bromine-containing organic compound (A1) having a 2,3-dibromo-2-alkylpropyl group. Examples of such compounds include tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl ether) and 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.

  The content of the bromine-containing organic compound (A1) is preferably 10 to 100% by weight and more preferably 20 to 100% by weight in the bromine-containing organic compound (A). When the content of the bromine-containing organic compound (A1) is within the above range, there is an advantage that the flame retardancy of the thermoplastic resin is more excellent even if the amount of the granular flame retardant composition added is relatively small.

  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 tetrabromobisphenol-A-bis (2,3-dibromopropyl ether), tetrabromobisphenol-S-bis (2,3-dibromopropyl ether), and tetrabromobisphenol-F-bis. (2,3-dibromopropyl ether), tris (2,3-dibromopropyl) isocyanurate and tris (2,3-dibromopropyl) cyanurate, tetrabromobisphenol-A, hexabromobenzene, pentabromotoluene, polybromodiphenyl ether , Polybromodiphenylethane, bispolybromophenoxyethane, trispolybromophenoxytriazine, polybromophenylindane, polypentabromobenzyl acrylate, ethylenebistetrabromophthalimide Tris (tribromoneopentyl) phosphate, and the like brominated epoxy oligomer. These may be used alone or in combination of two or more.

  The content of the bromine-containing organic compound (A) of the present invention is preferably 70 to 98 parts by weight and more preferably 80 to 98 parts by weight when the granular flame retardant composition is 100 parts by weight. preferable. When the content of the bromine-containing organic compound (A) is within the above range, there is an advantage that the flame retardancy of the thermoplastic resin is more excellent even if the amount of the granular flame retardant composition added is relatively small.

  The binder (B) of the present invention contains a fatty acid ester (B1). Here, the fatty acid ester is an esterification reaction product of a hydroxyl group-containing compound and a fatty acid.

  Examples of the hydroxyl group-containing compound include alcohols having 1 to 6 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol and hexanol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, butanediol, pentanediol, and hexane. Examples thereof include polyhydric alcohols such as diol, glycerin, diglycerin, polyglycerin, trimethylolpropane, pentaerythritol, sorbitan and sorbitol. Of these, polyhydric alcohols are preferred because the binding properties of the bromine-containing organic compound (A) are more excellent.

  Examples of the fatty acid 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. Of these, stearic acid is preferable because the binding property of the bromine-containing organic compound (A) is more excellent.

  The fatty acid ester (B1) preferably has a melting point measured by JIS K0064 of 40 to 80 ° C. When the melting point of the fatty acid ester (B1) is within the above range, there is an advantage that the mixing property and moldability are more excellent.

  Among the fatty acid esters (B1), examples of the compound having a melting point of 40 to 80 ° C. include glycerin monostearate, glycerin distearate, diglycerin stearate (melting point 55 to 61 ° C.), and propylene glycol monostearate. , Pentaerythritol stearate, sorbitan stearate (melting point 59 to 63 ° C.), stearyl stearate (melting point 53 to 57 ° C.), and the like.

  The content of the fatty acid ester (B1) is preferably 10 to 100% by weight, more preferably 20 to 100% by weight in the binder (B). When content of fatty acid ester (B1) exists in the said range, there exists an advantage that kneadability with a thermoplastic resin is more excellent.

  The binder (B) of the present invention may contain a binder (B2) other than the fatty acid ester (B1). Examples of such a compound include an ethylene-vinyl acetate copolymer and an acrylic resin.

  The content of the binder (B) of the present invention is preferably 1 to 10 parts by weight, and more preferably 2 to 8 parts by weight, when the granular flame retardant composition is 100 parts by weight. When the content of the binder (C) is within the above range, there is an advantage that granulation of the granular flame retardant composition becomes easier and kneadability with the thermoplastic resin is more excellent.

  The granular flame retardant composition of the present invention can further contain a stabilizer (C). The stabilizer (C) improves the durability of the thermoplastic resin and is generally solid. Therefore, the workability | operativity at the time of kneading | mixing with a thermoplastic resin can be improved more by mix | blending with the granular flame retardant composition of this invention previously.

  Examples of such stabilizer (C) include phosphite compounds, thioether compounds, hindered phenol compounds, hindered amine compounds, tin compounds, natural minerals, or synthetic minerals.

  Examples of the phosphite compound include tris (2,4-di-t-butylphenyl) phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, and bis [2,4-bis. (1,1-Dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphospho Knight, bis (nonylphenyl) pentaerythritol diphosphite, bisstearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2'-methylenebis (4,6-di-t-butyl-1-phenyloxy) (2-ethylhexyloxy) phosphorus, tetra Tridecyl) -4,4′-butylidene-bis (2-tert-butyl-5-methylphenyl) diphosphite, hexatridecyl-1,1,3-tris (3-tert-butyl-6-methyl-4-oxy) Phenyl) -3-methylpropane triphosphite, mono (dinonylphenyl) mono-p-nonylphenyl phosphite, tris (monononylphenyl) phosphite, tetraalkyl (C = 12-16) -4,4′-isopropyl Examples include redene- (bisphenyl) diphosphite, phosphorous acid mono- or diphenylmono- or dialkyl (or alkoxyalkyl, C = 8 to 13), diphenylisodecyl phosphite, trisdecyl phosphite, triphenyl phosphite, and the like.

  Examples of the thioether compound include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3 -Laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and the like.

  Examples of the hindered phenol compound include 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3- t-butyl-5-methyl-4-hydroxyphenyl) propionate], glycerol 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, thiodiethylenebis [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 diethylbis [[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, ethylenebis (oxyethylene) bis [3- (5-t-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 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-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.

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

  Examples of the tin compound include dioctyltin dilaurate and dioctyltin malate.

  Examples of natural minerals or synthetic minerals include hydrotalcite and zeolite.

  The content of the stabilizer (C) of the present invention is preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, when the granular flame retardant composition is 100 parts by weight.

  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, trixylenyl phosphate, and the like.

  Moreover, the granular flame retardant composition of the present invention may contain a conventionally known additive as long as the effects of the present invention are not impaired. Such additives include fatty acid amides, fatty acids, waxes, pigments and the like.

  Examples of fatty acid amides include caprylic acid amide, capric acid amide, myristic acid amide, palmitic acid amide, lauric acid amide, erucic acid amide, stearic acid amide, arachidinic amide, behenic acid amide, lignoceric acid amide, and stearic acid monoester. Fatty acid monoamides such as ethanolamide, 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 Acid amide, butylene biscapric acid amide, hexamethylene biscapric acid amide, m-xylylene biscapric acid amide, ethylene bislauric acid amide, butylene bislauric acid amide, hexamethyl Bis lauric acid amide, m-xylylene bis lauric acid amide, ethylene bis stearic acid amide, butylene bis stearic acid amide, hexamethylene bis stearic acid amide, m-xylylene bis stearic acid amide, 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 , Ethylenebislignoceramide, butylene bisoleic acid amide, hexamethylene bislignoceric acid amide, m-xylylene bislignoceric acid amide, ethylene bisoleic acid amide, butylene bisoleic acid amide , Hexamethylene bis oleic acid amide, m-xylylene bis oleic acid amide, ethylene bis linoleic acid amide, butylene bis linoleic acid amide, hexamethylene bis linoleic acid amide, m-xylylene bis linoleic acid amide, ethylene bis arachidonic acid amide And fatty acid bisamides such as butylene bis arachidonic acid amide, hexamethylene bis arachidonic acid amide and m-xylylene bis arachidonic acid amide.

  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.

  The granular flame retardant composition of the present invention is prepared by, for example, mixing a bromine-containing organic compound (A), a binder (B), and other compounds as necessary, and using a conventionally known extrusion granulator or kneading granulator. For example, it can be obtained by kneading at 40 to 80 ° C.

  As the extrusion granulator, for example, a screw type extrusion granulator, a roll type extrusion granulator, a blade type extrusion granulator, a tablet type extrusion granulator, a briquette type extrusion granulator, etc. may be used. it can.

  The present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited to this. Those skilled in the art can make various changes, modifications, and alterations without departing from the scope of the present invention.

  Below, the detail of the raw material for manufacturing a granular flame retardant composition is demonstrated.

<Raw materials>
Bromine-containing organic compound (A1)
(A1-1): Tetrabromobisphenol-A-bis (2,3-dibromo-2-methylpropyl) ether (trade name: Pyroguard SR-130, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 66% by weight)

Bromine-containing organic compound (A2)
(A2-1): Tetrabromobisphenol-A-bis (2,3-dibromopropyl) ether (trade name: Pyroguard SR-720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 67% by weight)
(A2-2): Tris (2,3-dibromopropyl) isocyanurate (trade name: Pyroguard SR-750, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., bromine content: 65% by weight)
(A2-3): 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-containing) (Amount: 67% by weight)
(A2-4): Tris (tribromoneopentyl) phosphate (trade name: CR-900, manufactured by Daihachi Chemical Industry Co., Ltd., bromine content: 73% by weight)
(A2-5): Brominated epoxy compound (trade name: EPICLO153, manufactured by DIC Corporation, bromine content: 48% by weight)

Fatty acid ester (B1)
(B1-1): Glycerol monostearate (trade name: Riquemar S-100, manufactured by Riken Vitamin Co., Ltd., melting point 65 ° C.)
(B1-2): Glycerol mono-distearate Product name: Riquemar S-200, manufactured by Riken Vitamin Co., Ltd., melting point 60 ° C.)
(B1-3): Diglyceryl stearate (trade name: Riquemar S-71-D, manufactured by Riken Vitamin Co., Ltd., melting point 58 ° C.)
(B1-4): Propylene glycol monostearate (trade name: Riquemar PS-100, manufactured by Riken Vitamin Co., Ltd., melting point 45 ° C.)
(B1-5): Pentaerythritol stearate (trade name: EXCEPARL PE-MS, manufactured by Kao Corporation, melting point 52 ° C.)
(B1-6): Sorbitan stearate (trade name: Poem S-60V, manufactured by Riken Vitamin Co., Ltd., melting point 61 ° C.)
(B1-7): Stearyl stearate (trade name: Riquemar SL-900, manufactured by Riken Vitamin Co., Ltd., melting point 55 ° C.)

Binders (B2) other than fatty acid esters (B1)
(B2-1): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 684, manufactured by Tosoh Corporation)
(B2-2): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 735, manufactured by Tosoh Corporation)
(B2-3): Ethylene-vinyl acetate copolymer (trade name: Ultrasen 720, manufactured by Tosoh Corporation)
(B2-4): Ethylene-vinyl acetate copolymer (trade name: Sumitate RB-11, manufactured by Sumitomo Chemical Co., Ltd.)

Stabilizer (C)
(C-1): Tris (2,4-di-t-butylphenyl) phosphite (trade name: ADK STAB 2112, manufactured by ADEKA Corporation)
(C-2): Tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) -1,2,3,4-butanetetracarboxylate (trade name: ADK STAB LA-57, manufactured by ADEKA Corporation)
(C-3): Distearyl-3,3′-thiodipropionate (trade name: Rasmit SG, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C-4): Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010, manufactured by BASF)
(C-5): Dioctyltin dilaurate (trade name: OL-1, manufactured by Tokyo Fine Chemical Co., Ltd.)
(C-6): Hydrotalcite (trade name: STABIACE HT-1, manufactured by Sakai Chemical Industry Co., Ltd.)

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

(Examples 1-15, Comparative Examples 1-2)
According to the blending amount shown in Table 1, bromine-containing organic compound (A), binder (B), and other compounds as necessary, with a mixer (trade name: high speed mixer, manufactured by Fukae Powtech Co., Ltd.) at a rotation speed of 600 rpm And mixed for 5 minutes. The obtained mixture was granulated using an extrusion granulator (trade name: EPDS-60, manufactured by Fuji Powder Co., Ltd.) at a set temperature of 70 ° C. to obtain a granular flame retardant composition.

<Evaluation of granular flame retardant composition>
The granular flame retardant composition was evaluated by the method described below. The evaluation results are shown in Table 1.

(Formability)
20 g of the granular flame retardant composition is placed on a 1 mm sieve and shaken for 10 minutes using a shaker (tap type sieve shaker AS200 tap, manufactured by Lecce Co., Ltd.), and then the granular flame retardant remaining on the sieve The weight of the composition was measured, the ratio (% by weight) to the weight (20 g) before the test was calculated, and the moldability was evaluated. It shows that a moldability is excellent, so that a ratio is large.

(Kneadability)
A polystyrene resin (trade name: PSJ polystyrene G9305, manufactured by PS Japan Co., Ltd.) and a granular flame retardant composition were introduced from the inlet of a 65 mm diameter extruder connected in series from a diameter of 65 mm to a diameter of 90 mm. A polystyrene resin composition was obtained by melt-kneading at 200 ° C. At this time, the mixing ratio of the polystyrene resin and the granular flame retardant composition was such that the bromine-containing organic compound (A) was 3% by weight with respect to a total of 100 parts by weight of the polystyrene resin and the granular flame retardant composition. .
The bromine content of the obtained polystyrene resin composition was determined by substituting the formula amount of chlorine with the formula amount of bromine according to JIS K7229, and then the bromine-containing organic compound corresponding to the obtained bromine content. The content (% by weight) of (A) was calculated and the kneadability was evaluated. The closer the content of the bromine-containing organic compound (A) is to 3% by weight, the better the kneadability.

  As shown in Examples 1-15, it turns out that the granular flame retardant composition of this invention is excellent in a moldability, and is excellent also in the kneadability with the polystyrene resin which is a thermoplastic resin.

  On the other hand, as shown in Comparative Examples 1 and 2, when the fatty acid ester (B1) of the present invention is not contained, granulation cannot be performed, so that the moldability cannot be evaluated, and a polystyrene resin that is a thermoplastic resin and The kneadability was also inferior.

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

Claims (4)

Particles comprising a flame retardant composition containing a bromine-containing organic compound (A) and a binder (B), wherein the bromine-containing organic compound (A) is 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) Containing one or more selected from the group (A1),
Particles comprising a flame retardant composition, wherein the binder (B) contains a fatty acid ester (B1). The fatty acid ester (B1) has a melting point of 40 to 80 ° C.
Particles comprising the flame retardant composition described in 1. Furthermore, the heat stabilizer (C) is contained, The particle | grains which consist of a flame retardant composition of Claim 1 or 2 characterized by the above-mentioned. Containing particles consisting of a flame retardant composition according to any one of claims 1 to 3 and a styrene resin set Narubutsu.