JPH09124839A - Flame-retardant, its production, flame-retardant thermoplastic resin composition containing the same flame-retardant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant to be mixed with a resin composition useful for housing of office automation devices, etc., excellent in adhesivity to metal while maintaining light resistance without lowering a bromine content in spite of a brominated epoxy oligomer type. SOLUTION: This flame-retardant is a bromine-containing flame retardant of formula I (X and Y are each a group of formula II or formula III); a compound comprising 15-30wt.% groups in which X=Y and are group of formula II, 40-60wt.% of groups in which X is the group of formula II and Y is the group of formula III and 20-35wt.% of groups in which X=Y and are group of formula III; (n) is the degree of polymerization and is an integer of 0<n<30)) and, for example, is obtained by reacting tetrabromobisphenol A with tribromophenol and epichlorohydrin in the presence of an alkali metal hydroxide. The flame-retardant can be mixed with a thermoplastic resin such as polystyrene and used. The mixed amount is preferably 1-30 pts.wt., more preferably 5-25 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant compounded in a thermoplastic resin, a method for producing the same, and a flame retardant-containing resin composition containing the flame retardant compound.

[0002]

2. Description of the Related Art High impact polystyrene (HIP)
S), styrene resins such as ABS have good mechanical properties, and excellent electrical insulation properties and moldability. PET, PB
Since engineering plastics such as T have added properties such as heat resistance and dimensional stability, in recent years OA
It is widely used for housings of appliances and home appliances, and automobile parts. However, since these resins are flammable, flame retardancy is required for safety. Furthermore, in the field of office automation equipment, home appliances, etc., it is used indoors, but it tends to yellow with the passage of time because it is exposed to fluorescent lamps and light entering from the outside, and improvement of light resistance is also emphasized. It's coming.

Conventionally, various halogenated organic compounds have been proposed for imparting flame retardancy to thermoplastic resins represented 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 deterioration of heat resistance, light resistance, and thermal stability. Things are becoming used. Examples of these are brominated bisphenol A epoxy oligomers whose both end groups are epoxy groups (commercially available products are YDB-406 and 408 manufactured by Tohto Kasei Co., Ltd.),
Modified brominated bisphenol A epoxy oligomer having both end groups blocked with an epoxy group with tribromophenol (commercially available TB-60, 62 manufactured by Tohto Kasei Co., Ltd.),
Examples include brominated polycarbonate oligomers.

To obtain a styrene resin composition having excellent impact resistance, light resistance and high flame retardancy by compounding an ABS resin with a halogen-containing compound having epoxy groups at both ends in JP-A-1-287132. It is shown. However, there is a drawback of adhesion to metals. Further, in JP-A-5-117463, a halogenated epoxy flame retardant containing a long-chain aliphatic carboxylic acid compound is blended with a styrene resin to obtain a flame retardant excellent in mold releasability from a mold. It is suggested to get. However, by containing a long-chain aliphatic carboxylic acid compound, it is difficult to obtain a flame-retardant styrene-based resin composition having an excellent quality balance due to the decrease in thermal stability and flame retardancy of the resin composition. It was the reality.

Further, in JP-A-64-2737 and JP-A-63-73749, 60% of the epoxy groups at both ends are contained.
It has been proposed to use a mixture of a halogenated epoxy modified product blocked with TBP (tribromophenol) and a halogenated epoxy resin containing 40% or less of one terminal epoxy group as a flame retardant. The method had the drawback of poor light resistance. Japanese Patent Laid-Open No. 1-1706
No. 30, it is proposed 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 poor due to the low molecular weight,
Moreover, there is a drawback that the light resistance is poor. As described above, the brominated epoxy oligomers and modified brominated epoxy oligomers, which have been used in increasing amounts recently, have many excellent characteristics, and in particular, although they have excellent light resistance, they have the following disadvantages, and their improvement is Was wanted.

That is, when a brominated epoxy oligomer is blended with a thermoplastic resin and melt-kneaded and molded by an extruder or an injection molding machine, it adheres to the screw of these molding machines, and when continuously produced, the adhered matter Since it is exposed to a high temperature for a long time, it has a drawback that it is discolored and deteriorated, and is mixed as a foreign matter into a compound or a molded product.
On the other hand, the modified brominated epoxy oligomer does not have adhesion to a metal like the brominated epoxy oligomer, but since the terminal is blocked with tribromophenol, it has poor light resistance and tends to yellow.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have conducted various studies to obtain a flame retardant having both the light resistance of the above-mentioned brominated epoxy oligomer and the metal non-adhesiveness equivalent to that of a modified brominated epoxy oligomer. The present invention has been completed, and an object of the present invention is to provide a novel flame retardant having light resistance and metal non-adhesion and a resin composition containing the flame retardant.

[0008]

The gist of the present invention is a bromine-containing flame retardant represented by the following general formula (1), wherein the terminal groups X and Y consist of A or B shown in (2), X = Y
= A is 15 to 30%, X = A and Y = B is 40 to 60
%, X = Y = B is 20 to 35%, and
The degree of polymerization n is an integer and 0 <n <30.

[0009]

Embedded image

However, A and B are as follows.

[0011]

Embedded image

[0012]

The present invention will be described in more detail below. Several methods can be exemplified for obtaining the novel flame retardant represented by the formula (1) according to the present invention. That is, the first method is to use tetrabromobisphenol A (hereinafter abbreviated as TBA) with epichlorohydrin (hereinafter,
ECH) and tribromophenol (hereinafter T)
Abbreviated as BP) and methyl isobutyl ketone (hereinafter,
A mixture of abbreviated MIBK) can be reacted in the presence of an alkali metal hydroxide to obtain the formula (1) consisting of the terminal groups A and B. In this case, the degree of polymerization n can be controlled by the molar ratio of TBA and ECH, and the ratio of the terminal groups A and B can be controlled by the molar ratio of ECH and TBP. Alternatively, it can be manufactured by reacting TBP with the terminal group A after manufacturing the formula (1) of the terminal group A.

The second method is to use a glycidyl ether of tribromphenol (hereinafter abbreviated as TBPGE). That is, TB using MIBK as a solvent
In this method, A and a predetermined amount of TBPGE and ECH are charged and reacted in the presence of an alkali metal hydroxide to obtain the novel flame retardant represented by the formula (1). Also in this method, the polymerization degree n can be controlled by the molar ratio of TBA and (ECH + TBPGE) as in the first method, and the ratio of the terminal groups A and B can be controlled by the molar ratio of ECH and TBPGE. I can do things. Alternatively, TBA and TBPGE may be reacted first, and then ECH may be added to carry out the reaction.

The third method has an epoxy equivalent of 350 to 7
00g / eq, softening point 50 to 105 ° C, bromine content 5
This is a method of obtaining a flame retardant represented by the formula (1) by reacting 0 to 53% of tetrabromobisphenol A type epoxy resin with TBA and TBP in the presence of a catalyst. The tetrabromobisphenol A type epoxy resin used in this method has an epoxy equivalent of 350 to 700 g / eq, more preferably 380 to 420 and a softening point of 64 to 74.
A material having a bromine content of 46 to 50% at 0 ° C is desirable. Tetrabromobisphenol A with lower epoxy equivalent
The above diglycidyl ether is difficult to handle because it is a crystalline substance or very easily crystallized, and the manufacturing cost is high and the economy is low. On the other hand, if the epoxy equivalent is higher than this range, the degree of freedom in molecular design is insufficient, which is not preferable. Further, such an epoxy resin is preferable because the hue of the epoxy resin obtained by the direct reaction of TBA and ECH is good and there is no residue, but it is also used depending on the catalyst used in the addition reaction of the low molecular weight epoxy resin and TBA. You can do it. In the case of this method, n can be controlled by adjusting the molar ratio of the epoxy group and the phenolic hydroxyl group of TBA in consideration of the polymerization degree n of the raw material epoxy.
The ratio of the terminal groups A and B was the same as the initial epoxy group-TBA.
Of hydroxyl group-hydroxyl group of TBP (B) = A, and the number of moles of TBP charged = B.

The reaction of tribromophenol with an epoxy group preferably uses a catalyst whose reaction rate is slow due to steric hindrance because a bromine atom is present in the ortho position with respect to the hydroxyl group of tribromophenol. As the catalyst, conventionally known alkali metal salts such as caustic alkali and caustic potash, tertiary amines such as tributylamine and triethylamine, and quaternary amine salts such as tetrabutylammonium bromide can be used. Later, when it is used as a flame retardant for polyester or polycarbonate, problems such as easy hydrolysis occur.
Further, the amine-based catalyst has a drawback that the product is severely colored and is not suitable for a white molded product, and the molded product lacks light resistance. In practicing the present invention, preferably phosphines such as triphenylphosphine, ethyltriphenylphosphonium iodide, ethyltriphosphonium bromide, ethyltriphenylphosphonium acetate, n-butyltriphenylphosphine. Phosphorus-based catalysts such as phonium bromide are excellent in reaction rate, hue of products, thermal stability and the like. Such a catalyst has a ratio of 2 to the phenol component of the reaction product.
From 00 to 5000 PPM, preferably 400 to 3
It is preferably used in the range of 000 PPM.

The fourth method is to use an epoxy equivalent of 600 to 13
A novel compound represented by the formula (1) by a method of reacting a tetrabrom bisphenol A type epoxy resin having a bromine content of 50 to 53% with a tribromphenol in the presence of a catalyst. It is a method of obtaining a flame retardant. The tetrabromobisphenol A type epoxy resin used in this method has an epoxy equivalent of 600 to 1300 g / that is obtained by the direct reaction of TBA and ECH.
eq, more preferably 600 to 770 g / eq, softening point 95 to 115 ° C., bromine content 50 to 52%
Are preferred. This is because the flame retardant represented by the formula (1) obtained by adding a target amount of TBP to an epoxy resin having such an epoxy equivalent has an appropriate n number and is versatile.
Also in this method, the reaction catalyst is preferably a phosphorus-based catalyst.

The fifth method has an epoxy equivalent of 350 to 7
00g / eq, softening point 50-105 ° C, bromine content 4
This is a method for obtaining a novel flame retardant represented by the formula (1) by reacting 6 to 52% of a tetrabromobisphenol A type epoxy resin with tribromophenol A and a glycidyl ether of tribromophenol in the presence of a catalyst. This method replaces the TBP used in the third method with T
Although BPGE is used, in this method, T
Unless the method of reacting BA with TBPGE and then reacting with an epoxy resin, unreacted TBPGE remains, resulting in defects such as lowering of the softening point and generation of gas components.

Formula (1) is an oligomer and has a molecular weight distribution. The average degree of polymerization n is 0 to 30,
It should be selected so as to obtain the optimum physical properties depending on the resin of the target partner. Generally, a degree of polymerization of about n = 0 to 5 is recommended for styrenic resins, and a degree of polymerization of about n = 3 to 30 is recommended for PET / PBT.

The terminal group A of the formula (1) is to introduce B in order to improve the metal adhesion, which is a drawback, while maintaining the light resistance which is an advantage of the brominated epoxy oligomer.
In the flame retardant of the present invention, the terminal groups X and Y are X = Y = A
15 to 30% for X = A, Y = B for 40%
If it is not 60%, the effect of light resistance cannot be expected. Also,
If the content of X = Y = B is not 20 to 35% and the content of X = A and Y = B is not 40 to 60%, the excellent effect of improving the metal adhesion cannot be exhibited.

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

When the flame retardant of the present invention is used by blending it with a thermoplastic resin, the amount is preferably 1 to 30 parts by weight, 5 to 5 parts by weight.
More preferably 25 parts by weight. Further, the flame retardant of the present invention may be used in combination with another flame retardant unless the effect of the present invention is impaired. Further, as required, antimony trioxide, antimony pentoxide, flame retardant aids such as molybdenum oxide, lubricants, ultraviolet absorbers, antioxidants, coloring pigments, dyes, release agents, fillers, and other additives. There is no particular limitation on the combined use of.

[0022]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples. In the examples, all parts and percentages are based on weight. Further, 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: Test before and after an exposure test (without rain) at 62 ± 2 ° C. for 48 hours using a sunshine weather meter. The color difference of the piece was measured with a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.). (4) Flammability test: Based on UL-94 test method. (5) Metal adhesion: The first roll of the 6-inch metal hot roll was set to 200 ° C. and the second roll was set to 60 ° C., and the test piece was lightly pressure-bonded to the first roll for 3 minutes and kneaded for 3 minutes. The kneading resin was peeled off and the state of adhesion to the roll was observed. Evaluation a It does not adhere to the roll. b It was easily peeled off from the roll. c It adheres to the roll and does not come off. (6) Terminal group composition: Liquid chromatography (LC)
Tetrahydrofuran (THF) / water (H ₂ O) / acetonitrile (ACN) as the mobile phase, the column is Tosoh Corp. TSKgel ODS-120T, measured with a UV detector at 280 nm, and the average area ratio of each peak is used. Represent

Example 1 In a 3 liter separable flask equipped with a thermometer, a stirrer, a dropping device and a condenser, 544 g of TBA and EC
H138.8g, Methyl isobutyl ketone (MIBK)
210 g was charged, and the mixture was heated and dissolved while purging with nitrogen.
37.5 g of 48% aqueous NaOH solution was added dropwise at 5 ° C. in 30 minutes, and after the reaction for 4 hours, 160 g of TBP and MIBK5
After diluting with 5 g, 150 g of 48% NaOH aqueous solution was added to 3 g.
Drop in 0 minutes, then react for another 12 hours MIBK5
30 g and 320 g of water were added, and the solution was allowed to stand still to separate by-product salt. After further washing with the same amount of water 5 times, the solution was filtered and then the solvent was recovered under reduced pressure of 150 ° C. and 5 Torr to obtain the intended flame retardant A. The physical properties of this are shown in Table 1.

Example 2 Epotote YDB-in a 1 liter separable flask.
400 (Toto Kasei Co., Ltd., epoxy equivalent 400g / eq, softening point 67 ° C, bromine content 49%) 800g, TBA136
g, TBP224g, triphenylphosphine (hereinafter,
0.25 g of TPP) was charged and reacted at 160 ° C. for 5 hours while purging with nitrogen to obtain a target flame retardant B. The physical properties of this are shown in Table 1.

Example 3 Flame retardant C was obtained in the same manner as in Example 2 except that the amount of TBP was changed to 273 g. Table 1 shows the physical properties.

Reference Example 1 The same reaction as in Example 2 was repeated except that the amount of TBP was changed to 137 g. Table 1 shows the physical properties of the obtained flame retardant D.

Reference Example 2 The same reaction as in Example 2 was repeated except that the amount of TBP was changed to 347 g. Table 1 shows the physical properties of the obtained flame retardant E. For comparison, YDB-406 is an example of a brominated epoxy oligomer and TB-62 is an example of a modified brominated epoxy oligomer (all manufactured by Tohto Kasei Co., Ltd.).
The physical properties of are shown in Table 1.

[0028]

[Table 1]

Example 4 The same apparatus as in Example 1 was used, except that TBA544g, ECH97.
1 g, epoxy equivalent 395 g / eq, bromine content 60.
8% glycidyl ether of tribromophenol (T
BPGE) 177.8 g, MIBK 205 g,
Dissolve at elevated temperature while purging with nitrogen, and use NaOH 48 at 95 ° C
% Aqueous solution 87.5 g in 90 minutes, then 2 more
After reacting for a time, 350 g of MIBK and 230 g of water were added, and the mixture was allowed to stand to separate by-product salt. After further washing 5 times with the same amount of water, the solution was filtered and then at 150 ° C. for 5 To
The solvent was recovered under reduced pressure of rr to obtain the target flame retardant F.
The physical properties of this are shown in Table 2.

Example 5 Epotote YDB-in a 1-liter separable flask.
408 (Epoxy equivalent of Toto Kasei Co., Ltd. 720 g / eq,
Softening point 110 ° C, bromine content 51%) 1440 g, TB
P331 g and 0.33 g of ethyltriphenyl iodide as a catalyst were charged, and the reaction was carried out at 130 ° C. for 1 hour and at 160 ° C. for 5 hours while purging with nitrogen to obtain a target flame retardant G. The physical properties of this are shown in Table 2.

Example 6 TBA 816 g, epoxy equivalent 395 g / eq, glycidyl ether of tribromphenol glycidyl ether (TBPGE) having a bromine content of 60.8% (TBPGE) 592.5 g, methyl isobutyl ketone 600 g, in a 3 liter separable flask equipped with a reflux condenser. Charge TPP 0.8g, MIB
The reaction was carried out at the reflux temperature of K for 2 hours. Next, Epotote YD
B-400 (Epoxy equivalent of Toto Kasei Co., Ltd. 400g / e
q, softening point 67 ° C., bromine content 49%) 1200 g was added, and the reaction was carried out at 170 ° C. for 5 hours while distilling off MIBK as a solvent to obtain a target flame retardant H. The physical properties of this are shown in Table 2.

Reference Example 5 Flame retardant I was obtained in the same manner as in Example 2 except that triphenylphosphine was replaced with tributylamine (1.08 g). Table 2 shows the physical properties.

[0033]

[Table 2]

Examples 7 to 9 and Comparative Examples 1 to 4 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 Examples 7 to 9, when the flame retardants A to C obtained in Examples 1 to 3 were added,
And Comparative Examples 1-4 are flame retardant D obtained in Reference Examples 1-2.
To E and commercially available YDB-406 and TB-62 (described above) were blended in the compositions shown in Table 3 and mixed in a Henschel mixer, and then a twin-screw extruder (PCM-30 manufactured by Ikegai Tekko Co., Ltd.).
) To obtain a compound. A test piece was prepared from the obtained compound by injection molding. Using this test piece, the flammability, adhesion, and light resistance were measured. Table 3 shows the results.

[0035]

[Table 3]

Examples 10-12, Comparative Example 5 Examples 10-12 are flame retardants F obtained in Examples 4-6.
When H is added, and in Comparative Example 5, the flame retardant I of Reference Example is used.
Were blended in the compositions shown in Table 4, mixed with a Henschel mixer in the same manner as in Examples 7 to 9, and then melt-kneaded with a twin-screw extruder (PCM-30 type manufactured by Ikegai Tekko Co., Ltd.) to obtain compounds. . A test piece was prepared from the obtained compound by injection molding. Using this test piece, the flammability, adhesion, and light resistance were measured. The results are shown in Table 4.

[0037]

[Table 4]

[0038]

As is clear from Tables 3 and 4, the flame retardant of the present invention is a brominated epoxy oligomer type, but has improved metal adhesion while maintaining light resistance without lowering the bromine content. It has an excellent effect of being performed. Therefore, the resin composition containing the flame retardant is
With high flame retardancy, light resistance, heat resistance and fluidity, it has improved properties with no adhesion to metal parts such as screws, cylinders, and molds of injection molding machines and extruders. It is possible to provide a thermoplastic resin composition used in fields requiring flame retardancy, such as housings for office automation equipment and home electric appliances, and automobile parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09K 21/08 C09K 21/08 21/14 21/14 (72) Inventor Junko Morikawa Edogawa, Tokyo 3-17-14 Higashikasai-ku, Tochikasei Co., Ltd. Research Institute

Claims (8)

[Claims] 1. A bromine-containing flame retardant represented by the following general formula (1), wherein the terminal groups X and Y consist of A or B shown in (2), and X = Y = A is 15 to 30%. , X = A and Y = B are 40 to 60%, and X = Y = B is 20 to 35%, and the degree of polymerization n is an integer 0 <n <30.
It is. Embedded image However, A and B are as follows. Embedded image 2. A flame-retardant thermoplastic resin composition comprising the bromine-containing flame retardant shown in claim 1. 3. The method for producing a flame retardant according to claim 1, wherein tetrabromobisphenol A, tribromophenol and epichlorohydrin are reacted in the presence of an alkali metal hydroxide. 4. The method for producing a flame retardant according to claim 1, wherein tetrabromobisphenol A, tribromophenol glycidyl ether and epichlorohydrin are reacted in the presence of an alkali metal hydroxide. 5. The epoxy equivalent is 350 to 700 g / e.
q, softening point 50 to 105 ° C., bromine content 46 to 52
% Of tetrabromobisphenol A type epoxy resin, tetrabromobisphenol A and tribromophenol are reacted in the presence of a catalyst, The method for producing a flame retardant according to claim 1. 6. Epoxy equivalent of 600 to 1300 g / e
q, softening point 95-140 ° C, bromine content 50-53
% Of tetrabromobisphenol A type epoxy resin and tribromophenol are reacted in the presence of a catalyst, The method for producing a flame retardant according to claim 1. 7. Epoxy equivalent of 350 to 700 g / e
q, softening point 50 to 105 ° C., bromine content 46 to 52
% Of tetrabromobisphenol A type epoxy resin and tetrabromobisphenol A and glycidyl ether of tribromophenol are reacted in the presence of a catalyst, The method for producing a flame retardant according to claim 1. 8. The method for producing a flame retardant according to claim 5, wherein the catalyst used in the reaction is a phosphorus-based catalyst.