JP2005307219A - Flame retardant, method for producing the same and flame-retardant thermoplastic resin composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant to be compounded in a thermoplastic resin, to provide a method for producing the flame retardant, and to provide a flame retardant-containing resin composition compounded with the flame retardant. <P>SOLUTION: The bromine-containing flame retardant comprises a compound represented by general formula (1), wherein the end groups X and Y are represented by A or B shown in formula (2), and the flame retardant is the composition comprising compounds each comprising X=Y=A, X=A and Y=B or X=Y=B, the sum of the compounds is 100%, the bromine-containing flame retardant is obtained by a method selected from four methods including a production method reacting tetrabromobisphenol A, tribromophenol and epichlorohydrin in the presence of an alkali metal hydroxide, and polymerization degree n is an integer of 0<n<30. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant blended with a thermoplastic resin, a method for producing the same, and a flame retardant-containing resin composition blended with the flame retardant.

  Styrenic resins such as high impact polystyrene (HIPS) and ABS have good mechanical properties and are excellent in electrical insulation and molding processability. Furthermore, engineering plastics such as PET and PBT have been widely used in recent years for housings of OA equipment and home appliances, automobile parts, and the like because they have characteristics such as heat resistance and dimensional stability. However, since these resins are flammable, they are required to be flame retardant for safety. Furthermore, in fields such as OA equipment and home appliances, they are used indoors, but they tend to turn yellow over time because they are exposed to fluorescent light and light entering from outside, and improvement in light resistance is also regarded as important. It has become.

  Conventionally, various halogenated organic compounds have been proposed in order to impart flame retardancy to thermoplastic resins typified by styrene resins. These flame retardants were bromine-containing organic compounds having a relatively low molecular weight such as tetrabromobisphenol A (TBA) and polybromodiphenyl ether (PBDPE). However, although low molecular weight flame retardants are advantageous in terms of cost, they have problems such as bleed out and reduced heat resistance, light resistance, and thermal stability. Types of types are starting to be used. Examples of these are brominated bisphenol A epoxy oligomers whose both end groups are epoxy groups (commercially available products are YDB-406, 408, etc., manufactured by Tohto Kasei Co., Ltd.), both end groups are tribromophenol and the epoxy groups are blocked. Modified brominated bisphenol A epoxy oligomers (commercially available products such as TB-60, 62 manufactured by Tohto Kasei Co., Ltd.), brominated polycarbonate oligomers and the like.

  Patent Document 1 discloses that a halogen-containing compound having both terminal epoxy groups is blended in an ABS resin to obtain a styrene resin composition having excellent impact resistance and light resistance and high flame retardancy. However, there are drawbacks of adhesion to metals. Patent Document 2 proposes that a halogenated epoxy flame retardant containing a long-chain aliphatic carboxylic acid compound is blended with a styrene resin to obtain a flame retardant having excellent mold releasability from a mold. Has been. However, it is difficult to obtain a flame-retardant styrene-based resin composition having a superior balance of quality due to a decrease in thermal stability and flame retardancy of the resin composition by containing a long-chain aliphatic carboxylic acid compound. There was a real situation.

  Further, Patent Documents 3 and 4 describe a mixture of a halogenated epoxy modified product in which 60% or more of both terminal epoxy groups are blocked with TBP (tribromophenol) and a halogenated epoxy resin containing 40% or less of one terminal epoxy group. Has been proposed to be used as a flame retardant, but this method has the disadvantage of poor light resistance. Patent Document 5 proposes to use a modified brominated low molecular weight compound having one end and both ends blocked with 50% TBP as a flame retardant, but the heat resistance is inferior due to the low molecular weight and the light resistance is low. There was a disadvantage of being inferior. As described above, brominated epoxy oligomers and modified brominated epoxy oligomers that have been used in recent years have many excellent characteristics, and are particularly excellent in light resistance, but also have the following drawbacks. It was desired.

In other words, brominated epoxy oligomers are blended into thermoplastic resins, melted and kneaded with an extruder or injection molding machine, and then adhered to the screws of these molding machines. Due to exposure to high temperatures, discoloration deteriorates, and there is a drawback in that it is mixed into a compound or molded product as a foreign substance. On the other hand, the modified brominated epoxy oligomer has no adhesion to the metal like the brominated epoxy oligomer, but its end is blocked with tribromophenol, so that it has poor light resistance and tends to yellow.
JP-A-1-287132 JP-A-5-117463 JP-A-62-2737 JP-A-63-73749 JP-A-1-170630

  As a result of various investigations to obtain a flame retardant having both the light resistance of the brominated epoxy oligomer described above and the non-sticking property of metal to the degree of the modified brominated epoxy oligomer, the present inventor completed the present invention. The object of the present invention is to provide a novel flame retardant having light resistance and non-metal adhesion and a resin composition containing the flame retardant.

  The gist of the present invention is a bromine-containing flame retardant containing a compound composed of the general formula (1) represented by A or B in which the end groups X and Y are represented by the following formula (2), wherein the bromine-containing flame retardant is X = Y = A compound 15-30%, X = A and Y = B compound 40-60%, X = Y = B compound 20-35%, X = Y = A, X = A And Y = B, X = Y = B is a composition comprising a total of 100%, according to any one of the production methods described in (a), (b), (c) and (d) below. A bromine-containing flame retardant characterized by being obtained.

但し、重合度ｎは整数で０＜ｎ＜３０である。

However, the degree of polymerization n is an integer 0 <n <30.

(A) A method for producing tetrabromobisphenol A, tribromophenol, and epichlorohydrin by reacting them in the presence of an alkali metal hydroxide.
(B) A process for producing tetrabromobisphenol A, tribromophenol glycidyl ether and epichlorohydrin in the presence of an alkali metal hydroxide.
(C) Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 350 to 700 g / eq, a softening point of 50 to 105 ° C., and a bromine content of 46 to 52%, and glycidyl ether of tetrabromobisphenol A and tribromophenol. A method of producing by reacting in the presence.
(D) Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 350 to 700 g / eq, a softening point of 50 to 105 ° C. and a bromine content of 46 to 52%, and glycidyl ether of tetrabromobisphenol A and tribromophenol in a phosphorus system A process for producing by reacting in the presence of a catalyst.

  Although the flame retardant of the present invention is a brominated epoxy oligomer type, it exhibits an excellent effect that metal adhesion is improved while maintaining light resistance without reducing bromine content. Therefore, the resin composition containing the flame retardant has excellent flame resistance, light resistance, heat resistance, and fluidity, and adheres to metal parts such as screws, cylinders, and molds of injection molding machines and extruders. As a result, it is possible to provide a thermoplastic resin composition used in fields requiring flame retardancy, such as housings for office automation equipment, home appliances, and automobile parts.

The novel flame retardant represented by the formula (1) according to the present invention is obtained by any of the methods (A), (B), (C) or (D) as defined above. This will be described in detail.
Method (a): Tetrabromobisphenol A (hereinafter abbreviated as TBA), epichlorohydrin (hereinafter abbreviated as ECH), tribromophenol (hereinafter abbreviated as TBP), and methyl isobutyl ketone (hereinafter abbreviated as MIBK). ) Can be reacted in the presence of an alkali metal hydroxide to obtain the formula (1) consisting of the end groups A and B. In this case, the polymerization degree n can be controlled by the molar ratio of TBA and ECH, and the ratio of the end groups A and B can be controlled by the molar ratio of ECH and TBP. Or it can manufacture by making TBP react with the terminal group A after manufacturing Formula (1) of the terminal group A.

Method (b): A method using glycidyl ether of tribromophenol (hereinafter abbreviated as TBPGE). That is, it is a method of preparing TBA, a predetermined amount of TBPGE and ECH using MIBK as a solvent, and reacting them in the presence of an alkali metal hydroxide to obtain a novel flame retardant represented by the formula (1). In this method, the degree of polymerization n can be controlled by the molar ratio of TBA and (ECH + TBPGE), and the ratio of end groups A and B can be controlled by the molar ratio of ECH and TBPGE. I can do it. Alternatively, a method may be used in which TBA and TBPGE are reacted first, and then ECH is added to perform the reaction.

Method (c): Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 350 to 700 g / eq, a softening point of 50 to 105 ° C., and a bromine content of 46 to 52%, tribromophenol A, and glycidyl ether of tribromophenol Is a method for obtaining a novel flame retardant represented by the formula (1) by reacting in the presence of a catalyst. In this method, first, TBA and TBPGE are reacted, and then the epoxy resin is reacted, unreacted TBPGE remains, resulting in problems such as a decrease in softening point and generation of gas components.

Method (d): In the method (c), a phosphorus catalyst is used as the catalyst.

  Formula (1) is an oligomer and has a molecular weight distribution. The average degree of polymerization n is from 0 to 30, and should be selected so as to obtain optimum physical properties depending on the target partner resin. In general, a degree of polymerization of about n = 0 to 5 is recommended for styrene resins, and a degree of polymerization of n = 3 to 30 is recommended for polyester resins such as polyethylene terephthalate and polybutylene terephthalate.

  In the flame retardant of the present invention, the terminal group A of the formula (1) introduces B in order to improve the metal adhesion which is a defect while maintaining the light resistance which is an advantage of the brominated epoxy oligomer. Unless the terminal groups X and Y are compounds containing 15 to 30% of a compound having X = Y = A and 40 to 60% of a compound having X = A and Y = B, an effect of light resistance cannot be expected. Moreover, the effect which was excellent in the adhesive improvement of a metal cannot be exhibited unless it is a composition containing 20 to 35% of the compound of X = Y = B and 40 to 60% of the compound of X = A and Y = B.

  The thermoplastic resin compounded with the flame retardant of the present invention includes polystyrene resins, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polypropylene, polyamide resins such as nylon, polycarbonate resins, and polyacetal (POM). Examples thereof include polyether resins such as resins, polyarylate (PAR) resins, and modified polyphenylene (PPO) resins.

  The amount of the flame retardant according to the present invention used in the thermoplastic resin is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight. Further, the combined use of the flame retardant of the present invention and another flame retardant is not particularly limited as long as the effects of the present invention are not impaired. In addition, flame retardant aids such as antimony trioxide, antimony pentoxide, and molybdenum oxide, lubricants, UV absorbers, antioxidants, color pigments, dyes, mold release agents, fillers, and other additives as necessary There is no restriction | limiting in particular also using together.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to an Example. In the examples, both parts and% are based on weight. Furthermore, the following test method was used in the present invention.
(1) Epoxy equivalent: JIS K-7234
(2) Softening point: JIS K-7236
(3) Light resistance ΔE: A color difference meter (manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the color difference between test pieces before and after a 62 ± 2 ° C. × 48 hour exposure test (no rain) using a sunshine weather meter.

(4) Flammability test: Conforms to UL-94 test method.
(5) Metal adhesion: After setting the first roll of a 6 mm metal hot roll at 200 ° C. and the second roll at 60 ° C., the test piece was lightly pressed on the first roll for 3 minutes and then kneaded for 3 minutes. The kneaded resin was peeled off and the state of adhesion to the roll was observed.
Evaluation a Does not adhere to the roll.
b Easily peeled off from the roll.
c It adheres to the roll and does not peel off.
(6) End group composition: Using liquid chromatography (LC), the mobile phase is tetrahydrofuran (THF) / water (H ₂ O) / acetonitrile (ACN), the column is Tosoh Corporation TSKgel ODS-120T, UV detector Measured at 280 nm, expressed as the average value of the area ratio of each peak.

Example 1
A 3 liter separable flask equipped with a thermometer, a stirrer, a dropping device and a condenser was charged with 544 g of TBA, 138.8 g of ECH, and 210 g of methyl isobutyl ketone (MIBK), dissolved at a temperature while purging with nitrogen, and NaOH 48% at 95 ° C. 37.5 g of aqueous solution was added dropwise over 30 minutes, and after 4 hours of reaction, diluted with 160 g of TBP and 55 g of MIBK, 150 g of 48% NaOH aqueous solution was added dropwise over 30 minutes, and then further reacted for 12 hours. Was separated for separation. Further, after washing 5 times with the same amount of water, the solution was filtered and the solvent was recovered under reduced pressure at 150 ° C. and 5 Torr to obtain the desired flame retardant A. The physical properties are shown in Table 1.

Reference Example Table 1 shows the physical properties of YDB-406 as an example of a brominated epoxy oligomer and TB-62 (both manufactured by Tohto Kasei Co., Ltd.) as an example of a modified brominated epoxy oligomer for comparison.

Example 2
In the same apparatus as in Example 1, 544 g of TBA, 97.1 g of ECH, epoxy equivalent of 395 g / eq, 177.8 g of glycidyl ether (TBPGE) of tribromophenol having a bromine content of 60.8%, and 205 g of MIBK were added, and the temperature was increased while purging with nitrogen. Dissolved in warm, 87.5 g of a 48% NaOH solution was added dropwise at 95 ° C. over 90 minutes, and after further reaction for 2 hours, 350 g of MIBK and 230 g of water were added, and the mixture was allowed to stand for separation to separate by-product salt. Further, after washing with the same amount of water five times, the solution was filtered and the solvent was recovered under reduced pressure at 150 ° C. and 5 Torr to obtain the desired flame retardant F. The physical properties are shown in Table 2.

Example 3
A 3 liter separable flask with a reflux condenser was charged with 816 g of TBA, 395 g / eq of epoxy equivalent, 592.5 g of glycidyl ether (TBPGE) of bromine content of 60.8%, 600 g of methyl isobutyl ketone, and 0.8 g of TPP. , And reacted at the reflux temperature of MIBK for 2 hours. Next, 1200 g of Epototo YDB-400 (Toto Kasei Co., Ltd. epoxy equivalent 400 g / eq, softening point 67 ° C., bromine content 49%) was added and reacted at 170 ° C. for 5 hours while distilling off the solvent MIBK. The target flame retardant H was obtained. The physical properties are shown in Table 2.

Example 4, Comparative Examples 1-2
Next, in order to see the effect of the obtained flame retardant, the physical properties of the composition blended with the thermoplastic resin were examined. That is, in Example 4, when the flame retardant A obtained in Example 1 was added, and in Comparative Examples 1 and 2, commercially available YDB-406 and TB-62 (supra) were respectively shown in Table 3. After compounding and mixing with a Henschel mixer, a compound was obtained by melt-kneading with a twin-screw extruder (PCM-30 type manufactured by Ikekai Tekko). A test piece was prepared from the obtained compound by injection molding. Using this test piece, combustibility, adhesion, and light resistance were measured. The results are shown in Table 3.

Examples 5-6
Examples 5 to 6 were prepared by adding the flame retardants F and H obtained in Examples 2 to 3 with the compositions shown in Table 4, respectively, and after mixing with a Henschel mixer in the same manner as Example 4, A compound was obtained by melt-kneading with an extruder (Ikegai Iron Works PCM-30 type). A test piece was prepared from the obtained compound by injection molding. Using this test piece, combustibility, adhesion, and light resistance were measured. The results are shown in Table 4.

Claims (2)

A bromine-containing flame retardant containing a compound represented by the general formula (1) represented by A or B of the following formula (2) in which the end groups X and Y are the bromine-containing flame retardant, wherein X = Y = A Is 15-30%, X = A and Y = B are 40-60%, X = Y = B is 20-35%, X = Y = A, X = A and Y = B, X = Y = B is a composition comprising a total of 100% of each compound, and obtained by any one of the production methods described in the following (a), (b), (c), and (d) Bromine-containing flame retardant.

However, the degree of polymerization n is an integer 0 <n <30.

(A) A method for producing tetrabromobisphenol A, tribromophenol, and epichlorohydrin by reacting them in the presence of an alkali metal hydroxide.
(B) A process for producing tetrabromobisphenol A, tribromophenol glycidyl ether and epichlorohydrin in the presence of an alkali metal hydroxide.
(C) Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 350 to 700 g / eq, a softening point of 50 to 105 ° C., and a bromine content of 46 to 52%, and glycidyl ether of tetrabromobisphenol A and tribromophenol. A method of producing by reacting in the presence.
(D) Tetrabromobisphenol A type epoxy resin having an epoxy equivalent of 350 to 700 g / eq, a softening point of 50 to 105 ° C. and a bromine content of 46 to 52%, and glycidyl ether of tetrabromobisphenol A and tribromophenol in a phosphorus system A process for producing by reacting in the presence of a catalyst. A flame retardant thermoplastic resin composition comprising the bromine-containing flame retardant shown in claim 1.