JP2007002004A - Bromine-based flame retardant and flame retardant polyolefin-based resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bromine-based flame retardant containing a brominated bisphenol S derivative, having a sufficient flame retardant performance and also hardly forming blooming after kneading with a polyolefin-based resin. <P>SOLUTION: This bromine-based flame retardant contains a derivative having (m+n) of 4 and a derivative having (m+n) of 0-3 selected from the bisphenol S derivatives expressed by general formula (1) [wherein, R<SP>1</SP>, R<SP>2</SP>are each the same or different and H or a 1-3C alkyl which may have a substituent; (m), (n) are each the same or different and an integer of 0-2] by (90:10) to (60:40) weight ratio in the above order. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a brominated flame retardant and a flame retardant polyolefin resin composition containing the same.

  Conventionally, a flame retardant containing a bromine compound and an antimony compound is known as a flame retardant for polyolefin resins. As bromine compounds, for example, brominated bisphenol S derivatives are known as having high flame retardancy.

For example, Patent Document 1 discloses a flame retardant polyolefin resin composition having a ratio of (A) 70 to 98% by weight of a polyolefin resin and (B) 2 to 30% by weight of a bromine-containing flame retardant. Contains flame retardant, by weight,
(B1) The following formula:

（式中、Ｒは水素又はメチル、Ａは−Ｃ（ＣＨ_３）_２−、−ＳＯ_２−、−Ｓ−又は−ＣＨ_２−）で示される臭素化ビスフェノールエーテル誘導体３４〜９５％、
（Ｂ２）４０％以上の臭素含量を有するハロゲン化脂環族炭化水素５〜５０％、及び
（Ｂ３）２，４，６−トリス（モノ−，ジもしくはトリブロモフェノキシ）トリアジン０〜３３％を合計して１００％となる割合で含んでいる組成物が開示されている。また、特許文献１には、臭素含有難燃剤とともに、難燃助剤として三酸化アンチモンを併用しても良いことが記載されている（特許文献１［特許請求の範囲］）。

(Wherein R is hydrogen or methyl, A is —C (CH ₃ ) ₂ —, —SO ₂ —, —S— or —CH ₂ —) 34 to 95% of a brominated bisphenol ether derivative represented by the formula:
(B2) 5 to 50% of a halogenated alicyclic hydrocarbon having a bromine content of 40% or more, and (B3) 2,4,6-tris (mono-, di- or tribromophenoxy) triazine 0 to 33%. A composition containing 100% in total is disclosed. Patent Document 1 describes that antimony trioxide may be used in combination with a bromine-containing flame retardant as a flame retardant aid (Patent Document 1 [Claims]).

  On the other hand, a brominated flame retardant containing a brominated bisphenol S derivative is bloomed from the resin surface during and after preparation (including after molding) of a flame retardant polyolefin resin composition by kneading with a polyolefin resin. There is a drawback that it is easy to do. In particular, when the flame retardant blooms from the surface of the molded body, a problem of poor appearance occurs.

In view of the above, development of a brominated flame retardant containing a brominated bisphenol S derivative that has sufficient flame retardant performance and hardly causes blooming after kneading with a polyolefin resin is desired.
JP 2004-99780 A

  The main object of the present invention is to provide a brominated flame retardant containing a brominated bisphenol S derivative that has sufficient flame retardant performance and hardly causes blooming after kneading with a polyolefin resin.

  As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using two kinds of bisphenol S derivatives in a specific ratio, and have completed the present invention.

  That is, the present invention relates to the following brominated flame retardants and flame retardant polyolefin resin compositions containing the same.

  1. Brominated flame retardant having the following general formula (1)

〔式中、Ｒ^１及びＲ^２は、同一又は異なって、水素又は置換基を有していてもよい炭素数１〜３のアルキル基を示す。ｍ及びｎは、同一又は異なって、０〜２の整数を示す。〕
で示されるビスフェノールＳ誘導体から選択される、ｍ＋ｎが４である誘導体とｍ＋ｎが０〜３である誘導体とを、順に重量比で表して、９０：１０〜６０：４０の割合で含有することを特徴とする臭素系難燃剤。

[Wherein, R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a substituent. m and n are the same or different and represent an integer of 0 to 2. ]
A derivative having m + n of 4 and a derivative having m + n of 0 to 3 selected from the bisphenol S derivatives represented by the formula (1) in order of weight ratio and containing 90:10 to 60:40. Characteristic brominated flame retardant.

2. The brominated flame retardant according to item 1, wherein R ¹ and R ² are the same or different and are a bromine-substituted propyl group.

3. The brominated flame retardant according to item 1, wherein R ¹ and R ² are the same or different and are 2,3-dibromopropyl group or 2-hydroxy-3-bromopropyl group.

  4). 4. A flame retardant polyolefin resin composition comprising the brominated flame retardant according to any one of items 1 to 3 and a polyolefin resin.

  5. Item 5. The flame retardant polyolefin resin composition according to Item 4, wherein the polyolefin resin is polypropylene.

  6). Item 6. The flame retardant polyolefin resin composition according to item 4 or 5, comprising 1 to 50 parts by weight of a brominated flame retardant with respect to 100 parts by weight of the polyolefin resin.

  7). Item 7. The flame retardant polyolefin resin composition according to Item 6, further comprising 1 to 30 parts by weight of a flame retardant aid with respect to 100 parts by weight of the polyolefin resin.

8). Item 8. The flame retardant polyolefin resin composition according to Item 7, wherein the flame retardant aid is at least one selected from the group consisting of antimony trioxide, antimony pentoxide, boron trioxide, and zinc borate.

Hereinafter, the brominated flame retardant and the flame retardant polyolefin resin composition of the present invention will be described.

1. Brominated flame retardant The brominated flame retardant of the present invention has the following general formula (1):

〔式中、Ｒ^１及びＲ^２は、同一又は異なって、水素又は置換基を有していてもよい炭素数１〜３のアルキル基を示す。ｍ及びｎは、同一又は異なって、０〜２の整数を示す。〕
で示されるビスフェノールＳ誘導体から選択される、ｍ＋ｎが４である誘導体とｍ＋ｎが０〜３である誘導体とを、順に重量比で表して、９０：１０〜６０：４０の割合で含有することを特徴とする。

[Wherein, R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a substituent. m and n are the same or different and represent an integer of 0 to 2. ]
A derivative having m + n of 4 and a derivative having m + n of 0 to 3 selected from the bisphenol S derivatives represented by the formula (1) in order of weight ratio and containing 90:10 to 60:40. Features.

  The brominated flame retardant of the present invention is a derivative in which m + n is 4 among the above bisphenol S derivatives (that is, a compound in which the total number of bromines substituted on the phenyl group is 4, hereinafter referred to as “tetra body”). And m + n is a derivative of 0 to 3 (ie, the total number of bromines substituted on the phenyl group is 0 to 3; hereinafter referred to as “non-tetra form”), expressed in weight ratio in order, In the ratio of 90:10 to 60:40, sufficient flame retardancy is exhibited and blooming is suppressed after kneading with the polyolefin resin.

In the general formula (1), R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a substituent. Although it does not limit as a C1-C3 alkyl group which may have a substituent, A bromine substituted propyl group is preferable. Note that the bromine-substituted propyl group is not limited to one in which at least one of the substituents is bromine, and all the substituents are bromine. As such a bromine-substituted propyl group, a 2,3-dibromopropyl group or a 2-hydroxy-3-bromopropyl group is particularly preferable.

  In the said General formula (1), m and n are the same or different and show the integer of 0-2. Of these, when m + n is 4 (tetra), two (total 4) bromine atoms are substituted for each phenyl group. FIG. 1 shows a preferred specific example of a tetra-body.

  When m + n is 0 to 3 (non-tetra), the total number of bromine atoms substituted on the phenyl group is 3 or less. Specifically, the non-tetra isomers are classified into “tri isomers” in which m + n is 3, “di isomers” in which m + n is 2, “mono” in which m + n is 1, and “zero” in which m + n is 0. Specific examples of the bird body, di body, mono body and zero body are shown in FIGS.

  The brominated flame retardant of the present invention contains the tetra and non-tetra bodies in a ratio of 90:10 to 60:40 in this order. If it is in this range, a content rate will not be limited, However About 90: 10-70: 30 is more preferable. When the ratio of the tetra-body exceeds 90% by weight, the occurrence of blooming after kneading with the polyolefin resin may not be sufficiently suppressed. When the ratio of the tetra-body is less than 60% by weight, the flame retardancy may not be sufficiently exhibited.

  The brominated flame retardant of the present invention may further contain a flame retardant aid. As the flame retardant aid, one having a structure other than the bromine-substituted bisphenol S derivative is used. For example, at least one selected from the group consisting of antimony trioxide, antimony pentoxide, boron trioxide and zinc borate is preferable. It is. When these flame retardant aids are further contained, better flame retardant performance is exhibited. Among the above, at least one of antimony trioxide and antimony pentoxide is preferable. In addition, when using a flame retardant aid, it is not always necessary to include it in the brominated flame retardant. When kneading with a polyolefin resin to be described later, separately from the brominated flame retardant, an additive is added to the resin. It may be added. The amount of the flame retardant aid will be described later because it is defined as the amount of the polyolefin resin.

  The production method of the bisphenol S derivative (which contains a tetra-form and a non-tetra-form in a specific ratio and is referred to as “target product” in the following description) used in the brominated flame retardant of the present invention is not particularly limited. For example, it can be suitably manufactured by the following manufacturing method (1) or (2).

  The procedure of manufacturing method (1) is as follows. First, bisphenol S and bromine are mixed in a reaction vessel to perform bromine substitution on the phenyl group of bisphenol S. Here, by adjusting the amount of bromine to be mixed, the ratio of the tetra-form and the non-tetra-form in the target product can be adjusted within a desired range (90:10 to 60:40).

  Then sodium hydroxide is added to the reaction vessel. As a result, hydrogen bromide generated by the substitution reaction is neutralized, and the hydroxyl group of bromine-substituted bisphenol S is changed to a sodium salt.

  Next, diallyl ether of bromine-substituted bisphenol S is obtained by adding a lower alcohol having 1 to 6 carbon atoms and allyl halide to cause a dehydrohalogenation reaction.

  Next, after removing unnecessary components in the reaction vessel, an inert good solvent of diallyl ether is added to the reaction vessel to dissolve diallyl ether, and bromine is added to add bromine to the double bond of the allyl group.

  Finally, the solvent is distilled off under reduced pressure to obtain the desired product which is a mixture of tetra and non-tetra in a desired ratio.

  In the production method (2), a tetra-form and a non-tetra-form are separately prepared and then mixed in a desired ratio to obtain a desired target, and the procedure is as follows.

  First, bis (3,5-dibromo-4-hydroxyphenyl) sulfone (TBS) having a purity of 95% or more is used as a starting material, and diallyl ether is obtained by the same procedure as in the above (1) except for bromine substitution reaction. Then, a tetra-form is obtained by performing a bromine addition reaction.

  Next, using the procedure of (1) above, a reaction product containing a non-tetra isomer at a high concentration (substantially only the non-tetra isomer) is obtained (by adjusting the bromine mixing amount).

  Finally, the tetra-body and the non-tetra-body are mixed by melt mixing or powder mixing so that the ratio of both is in the range of 90:10 to 60:40 to obtain a desired target product.

  In any of the production methods (1) and (2) above, various reaction conditions, reagent amounts, and the like can be appropriately set according to conventional methods.

2. Flame Retardant Polyolefin Resin Composition The flame retardant of the present invention can be used as a flame retardant for various resins. In particular, it can be suitably used as a flame retardant for polyolefin resins. That is, it is suitable as a flame retardant for polyolefin resin. The flame-retardant polyolefin resin composition of the present invention (hereinafter abbreviated as “resin composition”) is obtained by kneading this and the polyolefin resin.

  Examples of the polyolefin resin include, but are not limited to, homopolymers or copolymers of olefins such as ethylene, propylene, and butene. Specifically, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-α-olefin copolymer , Ethylene-propylene copolymer, propylene-butene copolymer and the like. These resins can be used alone or in admixture of two or more. Among these resins, polypropylene is particularly preferable.

  The content of the flame retardant in the resin composition is not limited, but is preferably about 1 to 50 parts by weight, more preferably about 2 to 40 parts by weight, and most preferably about 3 to 15 parts by weight with respect to 100 parts by weight of the resin. preferable. When the blending amount is less than 1 part by weight, practical flame retardant performance cannot be obtained. When the blending amount exceeds 50 parts by weight, the mechanical properties and workability of the resin composition are degraded, the thermal stability is degraded, or Not only does it cause the inconvenience of blooming, but it also raises the uneconomical problem of not showing an increase in flame retardancy depending on the blending amount.

  When the flame retardant aid is contained in the resin composition, the amount is preferably about 1 to 30 parts by weight, more preferably 2 to 10 parts by weight, and most preferably 3 to 7 parts by weight with respect to 100 parts by weight of the resin. When the amount exceeds 30 parts by weight, not only the flame retardancy performance is not further improved, but also the flame retardancy performance may be lowered, and the mechanical properties of the flame retardant resin composition are lowered, which is not preferable. . As described above, the flame retardant aid may be contained in the brominated flame retardant of the present invention, and may be included in the resin composition as an additive different from the flame retardant.

  The method for preparing the resin composition is not particularly limited. For example, a predetermined amount of resin and flame retardant are premixed in a mixer such as a Henschel mixer, a tumbler mixer, a rotor mixer, etc., and then supplied to a kneader heated to the melting temperature of the resin, thereby forming a resin composition pellet. Is obtained. In addition, you may supply resin and a flame retardant separately to a kneading machine with a fixed quantity feeder, without pre-mixing. Moreover, you may supply each component of a flame retardant (for example, brominated bisphenol S derivative and flame retardant adjuvant in the case of including a flame retardant auxiliary) and resin separately to a kneader by a quantitative feeder.

  The said resin composition pellet turns into a resin molding (flame-retardant resin product) by shape | molding with a heat compression molding machine, an injection molding machine, etc. The molding conditions are not particularly limited, and can be set as appropriate according to the type of pellet.

  Resin composition is anti-glare stabilizer, antioxidant, anti-fogging agent, antistatic agent, antibacterial agent, impact resistance agent, foaming agent, carbon fiber, stainless fiber, conductive filler, nucleating agent, cross-linking as required Additives such as a colorant, a colorant, carbon black, and a lubricant; fillers such as talc, calcium carbonate, kaolin, clay, barium sulfate, and glass fiber. The content of these additives / fillers can be appropriately set according to the characteristics of the final product (flame retardant resin product).

  Examples of molded articles obtained from the resin composition include washing machines, refrigerators, tableware dryers, rice cookers, electric fans, televisions, personal computers, stereos, microwave ovens, heating toilets, irons and other parts and covers; mobile phones, personal computers And circuit boards of electronic equipment such as printers and facsimiles; parts and covers of air conditioners, stoves, stoves, fan heaters, water heaters, etc .; parts and interior materials of building materials, automobiles, ships, aircraft, etc.

  In particular, the brominated flame retardant of the present invention represents a derivative (tetra-form) in which m + n is 4 and a derivative (non-tetra-form) in which m + n is 0 to 3 in order of weight ratio, 90:10 to 60: By containing it at a ratio of 40, sufficient flame retardancy is exhibited and blooming is suppressed after kneading with the polyolefin resin.

It is a specific example of the brominated flame retardant (tetra body) in which m + n = 4. It is a specific example of a brominated flame retardant (tri body) in which m + n = 3. It is a specific example of a brominated flame retardant (di-form) in which m + n = 2. This is a specific example of a brominated flame retardant (mono) in which m + n = 1. It is a specific example of a brominated flame retardant (zero body) in which m + n = 0.

  The present invention will be specifically described below with reference to production examples, examples, comparative examples and reference examples. However, the present invention is not limited to the description of the examples.

In the production examples, LC / MS / MS ⁿ (manufactured by Thermo Electron, LCQ-DECA XP) is used for the total number of bromine atoms substituted on the phenyl group and the weight ratio of tetra: non-tetra. Identified.

≪Production of brominated flame retardant≫
Production Example 1 (Practical product)
A glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a heating / cooling device was prepared.

  In a reaction vessel, 1000 g of water and 250 g (1 mol) of bisphenol S were accommodated. While stirring the contents, 591 g (3.7 moles) of bromine was added dropwise over 2 hours to replace the phenyl group with bromine. Due to the dripping, the temperature of the contents increased from 5 ° C to 40 ° C. After completion of dropping, the reaction was continued for another hour. Here, since the reaction solution was reddish due to free bromine, sodium sulfite (reducing agent) was added until the reddish color disappeared. The reduction reaction was completed over an additional hour. The reason why the amount of bromine was 591 g in Production Example 1 was to set the weight ratio of the tetra-form: non-tetra-form after the substitution reaction to about 9: 1.

  Subsequently, 464 g of a 50% aqueous sodium hydroxide solution (5.8 mol as sodium hydroxide) was added to the reaction mixture over 30 minutes. The pH of the reaction solution after the addition was 9 or more. By the addition, the temperature of the reaction solution rose from 5 ° C to 40 ° C. This addition was performed for the purpose of neutralizing hydrogen bromide generated by the substitution reaction and making bromine-substituted bisphenol S into a water-soluble alkali metal salt (Na salt).

  Next, 400 g of isopropyl alcohol (IPA) (boiling point 82.5 ° C.) and 187.4 g (2.45 mol) of allyl chloride were added to the reaction solution and refluxed. The liquid temperature rose from 40 to 83 ° C. by refluxing. This operation is an allyl etherification of bromine-substituted bisphenol S. When the pH of the reaction solution became acidic during the reaction, an aqueous sodium hydroxide solution was added until it showed alkalinity. The end point of the reaction was judged as follows. That is, a small amount of the reaction solution was taken out, and when the aqueous hydrochloric acid solution was added and no cloudiness or milky white color was exhibited, the end point was set. In Production Example 1, it took 8 hours until no cloudiness to milky white color was exhibited. In the reaction vessel after completion of the reaction, needle-like crystals of diallyl ether were generated.

  Next, after removing the liquid components from the reaction vessel, water was added to the reaction vessel to wash the vessel and the reaction product, and unnecessary alkali salts, IPA, allyl chloride, and the like were dissolved and removed. Further, the reaction product was transferred to a magnetic filter, and then 1000 ml of water was poured to completely dissolve and remove unnecessary alkali salts, IPA, allyl chloride, and the like. The reaction product after washing was transferred to a glass eggplant flask having a volume of 2 liters, and the eggplant flask was connected to an evaporator at a hot water temperature (60 ° C.) and dried under reduced pressure at a reduced pressure of 20 Torr.

  Next, a glass reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a heating / cooling device was prepared. The reaction product after drying was placed in a reaction vessel, and further 600 g of methylene chloride (solvent) was added and completely dissolved. To this solution, 2 mol of bromine was dropped little by little with a dropping funnel. By this dropping, bromine is added to the unsaturated bond of the allyl group of the bromine-substituted bisphenol S derivative. Since this reaction was accompanied by a rapid exotherm, stirring and cooling were sufficiently performed. The liquid temperature during the reaction was controlled so as not to exceed 40 ° C. The end point of the bromine addition reaction was when the reaction solution became reddish after completion of the dropwise addition of a predetermined amount of bromine. In Production Example 1, it took 2 hours from the start of dropping of bromine. Thereafter, the reaction was continued for another hour for aging.

  Next, 1000 ml of water was added to the reaction solution, and the mixture was vigorously stirred to dissolve unnecessary unreacted bromine in the aqueous phase, and then the decantation was repeated to remove the aqueous phase. Thereafter, the reaction product was poured into 2000 ml of methanol with strong stirring over 5 minutes to cause reprecipitation. The precipitate was pulverized once and further allowed to stand in methanol for 10 hours for crystallization. Thereafter, most of methanol was removed by filtration, and then transferred to a glass 2000 ml eggplant flask. The eggplant flask was connected to an evaporator of hot water (70 ° C.), and unnecessary solvents (methanol, water, etc.) were distilled off at a reduced pressure of 10 Torr.

The yield of the reaction product (brominated flame retardant) was 745 g. As a result of identifying the weight ratio of the tetra-form: non-tetra-form of the reaction product from LC / MS / MS ⁿ , it was 89:11. Moreover, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 122 ° C.

Production Example 2 (Comparative product)
As bromine-substituted bisphenol S, tetrabromobisphenol S (TBS, trade name EB400S, manufactured by Manac Co., Ltd.) containing 95% by weight or more of bisphenol S having a bromine substitution number of 4 (tetra) as a starting material for allyl etherification, A brominated flame retardant was obtained in the same manner as in Production Example 1 except that 412 g (4 mol) of sodium bromide was dissolved in the reaction solution as a reaction catalyst for allyl etherification.

The yield of the reaction product (brominated flame retardant) was 765 g. The weight ratio of the tetra-form: non-tetra-form of the reaction product was identified from LC / MS / MS ^n, and as a result, it was 99: 1. Moreover, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 120 ° C.

Production Example 3 (Comparative product)
Production Example, except that 479.4 g (3 mol) of bromine was added to bisphenol S and the amount of 50% aqueous sodium hydroxide solution added for the allyl etherification reaction was 408 g (5.1 mol as sodium hydroxide). In the same manner as in Example 1, a brominated flame retardant was obtained.

The yield of the reaction product (brominated flame retardant) was 656 g. As a result of identifying the weight ratio of the tetra-form: non-tetra-form of the reaction product from LC / MS / MS ⁿ , it was 54:46. Moreover, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 96 ° C.

Production Example 4 (Comparative product)
250 g (1 mol) of bisphenol S not substituted with bromine is used as a starting material for allyl etherification, 2000 g of water as a reaction solvent is used, and 172 g of 50% aqueous sodium hydroxide solution added for the allyl etherification reaction ( A brominated flame retardant was obtained in the same manner as in Production Example 1 except that 2.15 mol) was used as sodium hydroxide.

The yield of the reaction product (brominated flame retardant) was 536 g. The weight ratio of the tetra-form: non-tetra-form of the reaction product was identified from LC / MS / MS ⁿ . As a result, it was 0: 100. Moreover, as a result of measuring the melting endothermic peak temperature of the reaction product with a differential scanning calorimeter, a melting point peak was confirmed at 75 ° C.

Production Example 5 (Practical product)
140 g of the reaction product obtained in Production Example 2 and 160 g of the reaction product obtained in Production Example 3 were mixed with a tumbler mixer to obtain 300 g of a brominated flame retardant.

  The tetra-body: non-tetra-body weight ratio of this product was calculated to be 75:25. When the melting endothermic peak temperature of this product was determined with a differential scanning calorimeter, melting point peaks were confirmed at 96 ° C and 120 ° C.

Production Example 6 (Practical product)
73 g of the reaction product obtained in Production Example 2 and 220 g of the reaction product obtained in Production Example 3 were mixed with a tumbler mixer to obtain 300 g of a brominated flame retardant.

  The weight ratio of the tetra-body: non-tetra-body of this product was determined to be 65:35 by calculation. When the melting endothermic peak temperature of this product was determined with a differential scanning calorimeter, melting point peaks were confirmed at 94 ° C and 118 ° C.

≪Production and property evaluation of flame retardant polyolefin resin composition≫
Example 1
The following materials were kneaded and granulated using a twin screw extruder (Hyper KTX30, manufactured by Kobe Steel Co., Ltd.) to obtain a flame retardant polyolefin resin composition pellet.
-100 parts by weight of homopolymer polypropylene (Y101, MFR = 15, manufactured by Sumitomo Mitsui Polyolefin Co., Ltd.)
-10 parts by weight of brominated flame retardant obtained in Production Example 1,
-5 parts by weight of antimony trioxide (antimony trioxide MSF, manufactured by Yamanaka Sangyo Co., Ltd.)
-1 part by weight of carbon black masterbatch (RB9904P, 10% carbon black product, manufactured by Hitec Chem Co., Ltd.).

  The characteristics of the resin composition were evaluated. The characteristic evaluation was performed from the following viewpoints.

(1) Flammability Evaluation of the flammability of the resin composition was performed according to the safety standard “UL-94 flammability test” of US Underwriter Laboratories. The dimensions of the test piece were 1.5 mm in thickness, 13 mm in width, and 150 mm in length. The UL94 combustion test is roughly divided into two types: a horizontal test (HB method) and a vertical test (V method). The comprehensive evaluation of flammability increases in the order of FAIL <HB <V-2 <V-1 <V-0.

  Moreover, it evaluated also by the limiting oxygen index (LOI value) measuring method (JIS K7201-1976) which measures the oxygen concentration required for a test piece to continue burning for 5 cm or 3 minutes. The dimensions of the test piece are 3 mm thick, 6 mm wide, and 150 mm long. The evaluation numerical value is referred to as a LOI value, and the larger the value, the higher the flame retardancy.

Each test piece is compression-molded with a pressure of 10 MPa (100 kgf / cm ² ) using a heat compression molding machine (manufactured by Shintan Metal Industry Co., Ltd., set at 200 ° C.), and has a thickness of 1.5 mm and 3 mm. It was produced by cutting each plate into a predetermined dimension.

(2) Processability The processability of the resin composition was evaluated from the viewpoint of whether or not the components were successfully kneaded and molded in the pellet production process. The case where the kneading and forming of the components were successfully performed was evaluated as “good”. The case where kneading and molding of the components were difficult was evaluated as x.

(3) Blooming property Pellet is molded by injection molding machine (Nissei Plastic Industry Co., Ltd., FE80S 18ASE, mold temperature 40 ° C.) (width 35 × length 48 × thickness 1.5 mm) and blooming test plate It was. This plate was placed in an oven at 70 ° C., and the surface state after 150 hours was evaluated by visual observation. The case where blooming was not confirmed was evaluated as “good”. What was confirmed was evaluated as x.

  These evaluation results are also shown in Table 1.

Example 2
Pellets were produced in the same manner as in Example 1 except that the brominated flame retardant obtained in Production Example 5 was used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 1 and shown.

Example 3
Pellets were produced in the same manner as in Example 1 except that the brominated flame retardant obtained in Production Example 6 was used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 1 and shown.

Example 4
Pellets were produced in the same manner as in Example 1 except that 30 parts by weight of brominated flame retardant and 15 parts by weight of antimony trioxide were used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 1 and shown.

Example 5
Pellets were produced in the same manner as in Example 1 except that 3 parts by weight of the brominated flame retardant obtained in Production Example 5 and 1.5 parts by weight of antimony trioxide were used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 1 and shown.

Comparative Example 1
Pellets were produced in the same manner as in Example 1 except that the brominated flame retardant obtained in Production Example 2 was used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 2 and shown.

Comparative Example 2
Pellets were produced in the same manner as in Example 1 except that the brominated flame retardant obtained in Production Example 3 was used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 2 and shown.

Comparative Example 3
Pellets were produced in the same manner as in Example 1 except that the brominated flame retardant obtained in Production Example 4 was used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 2 and shown.

Comparative Example 4
Pellets were produced in the same manner as in Example 1 except that 3 parts by weight of the brominated flame retardant obtained in Production Example 3 and 1.5 parts by weight of antimony trioxide were used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 2 and shown.

Reference example 1
Pellets were produced in the same manner as in Example 1 except that 0.5 parts by weight of the brominated flame retardant obtained in Production Example 1 and 0.3 parts by weight of antimony trioxide were used.

Each specific (characteristic) evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 3, and is shown.

Reference example 2
Pellets were produced in the same manner as in Example 1 except that 60 parts by weight of the brominated flame retardant obtained in Production Example 1 and 30 parts by weight of antimony trioxide were used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 3, and is shown.

Reference example 3
Pellets were produced in the same manner as in Example 1 except that 15 parts by weight of the brominated flame retardant obtained in Production Example 1 and 35 parts by weight of antimony trioxide were used.

  Each characteristic evaluation procedure / evaluation method is the same as in the first embodiment.

  Each evaluation result is combined with Table 3, and is shown. In addition, since the workability was extremely difficult and the test plate could not be obtained, and the evaluation of the flammability and the blooming property could not be carried out, “***” is shown in the evaluation column.

Claims (8)

Brominated flame retardant having the following general formula (1)

[Wherein, R ¹ and R ² are the same or different and represent hydrogen or an alkyl group having 1 to 3 carbon atoms which may have a substituent. m and n are the same or different and represent an integer of 0 to 2. ]
A derivative having m + n of 4 and a derivative having m + n of 0 to 3 selected from the bisphenol S derivatives represented by the formula (1) in order of weight ratio and containing 90:10 to 60:40. Characteristic brominated flame retardant. The brominated flame retardant according to claim ^1, wherein R ¹ and R ² are the same or different and are bromine-substituted propyl groups. The brominated flame retardant according to claim ^1, wherein R ¹ and R ² are the same or different and are 2,3-dibromopropyl group or 2-hydroxy-3-bromopropyl group.   A flame retardant polyolefin resin composition comprising the brominated flame retardant according to any one of claims 1 to 3 and a polyolefin resin.   The flame retardant polyolefin resin composition according to claim 4, wherein the polyolefin resin is polypropylene.   The flame-retardant polyolefin resin composition according to claim 4 or 5, comprising 1 to 50 parts by weight of a brominated flame retardant with respect to 100 parts by weight of the polyolefin resin.   The flame retardant polyolefin resin composition according to claim 6, further comprising 1 to 30 parts by weight of a flame retardant aid with respect to 100 parts by weight of the polyolefin resin.   The flame retardant polyolefin resin composition according to claim 7, wherein the flame retardant aid is at least one selected from the group consisting of antimony trioxide, antimony pentoxide, boron trioxide, and zinc borate.

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