JP3518026B2 - Flame retardant and flame retardant resin composition containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant which imparts a high degree of flame retardancy to a resin, and a flame retardant resin composition containing the flame retardant, and particularly to a housing of OA equipment and home appliances, an automobile. The present invention relates to a thermoplastic resin composition and a thermosetting resin composition used in fields requiring flame retardancy such as parts.

[0002]

2. Description of the Related Art High-impact polystyrene (HIP
Styrenic resins such as S) and ABS have good mechanical properties, electrical insulation and molding processability. Also, PET, P
In recent years, engineering plastics such as BT have been added with properties such as heat resistance and dimensional stability.
It is widely used for housings of A appliances and home appliances, automobile parts, etc. However, since these resins are flammable, flame retardancy is required for safety reasons. Furthermore, OA
In the field of equipment, home appliances, etc., it is used indoors, but it tends to turn yellow over time because it is exposed to fluorescent lights and light entering from the outside, and improvement of light resistance is becoming more important. It was

Conventionally, various halogenated organic compounds have been proposed for imparting flame retardancy to thermoplastic resins represented by styrene resins. These flame retardants are bromine-containing organic compounds having a relatively low molecular weight such as tetrabromobisphenol A (TBA) and polybromodiphenyl ether (PBDPE). Although these 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. Oligomeric types have been used. Examples of these are brominated epoxy oligomers whose both end groups are epoxy groups (commercially available YDB-406, 408 manufactured by Tohto Kasei Co., Ltd.), both end groups being modified by blocking the epoxy group with tribromophenol. Brominated epoxy oligomer (hereinafter referred to simply as modified brominated epoxy oligomer, commercially available as TB-produced by Tohto Kasei Co., Ltd.)
60, 62, etc.) and brominated polycarbonate oligomers. In the field of thermosetting resins typified by phenol resins, epoxy resins, and polyester resins, there is a demand for flame retardants as excellent as the above. In the field of paper phenolic laminates, which is a typical application, brominated epoxy oligomers (commercially available Toto Kasei Co., Ltd.) as flame retardants.
YDB-400, etc.) and modified brominated epoxy oligomers have been used.

As described above, the brominated epoxy oligomers and modified brominated epoxy oligomers, which have been used in increasing amounts recently, have many excellent characteristics. However, although they are particularly excellent in light resistance and fluidity, they are as follows. There are drawbacks, and improvements have been desired. That is, when a brominated epoxy oligomer is mixed with a thermoplastic or thermosetting resin and molded,
These resin compositions adhere to the screw of an extruder at the time of melt-kneading or the injection molding machine at the time of molding, and when continuous production is performed, the adhered matter is exposed to high temperatures for a long time, resulting in discoloration and deterioration, and as a foreign substance. It gets mixed into compounds and moldings. On the other hand, the modified brominated epoxy oligomer does not have adhesion to metals like brominated epoxy oligomer, but its terminal is blocked with tribromophenol, so it is inferior in light resistance, and the resin composition containing it is yellowed. It tends to be easy.

[0005]

The problem to be solved by the present invention is that it is difficult to combine both the light resistance of the above-mentioned brominated epoxy oligomer and the non-adhesiveness to a metal such as a modified brominated epoxy oligomer. It is to obtain a flame retardant, and an object of the present invention is to provide a novel flame retardant having the above-mentioned light resistance and metal non-adhesiveness, and a resin composition containing the flame retardant.

[0006]

That is, the invention of the present application is
A bromine-containing flame retardant represented by the following general formula (1):
The terminal groups X and Y consist of A and B or C, in which A is 10 mol% to 25.1 mol%, and the residue is a single or a combination of two or more selected from B and C. Where n is an integer and 0 ≦ n <30.

[0007]

[Chemical 2]

That is, the bromine-containing flame retardant represented by the general formula (1) in the present invention 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 resin of the target partner. Generally, a low degree of polymerization of about n = 0 to 2 is used for thermosetting resins, and n = for styrene resins.
N = 3 for medium polymerization degree of 1 to 4 and PET / PBT etc.
A high degree of polymerization of about 30 is recommended.

One of the features of the flame retardant of the present invention is that
At least one of the terminal groups X and Y in the general formula (1) has A. That is, the terminal group A is introduced 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, and the terminal groups X and Y are at least 10 mol% of A. Must be Below that, no effect can be expected. Also ,
Since the bromine content decreases as it approaches 100 mol%, it is not necessary to increase it unnecessarily.

The method for producing the novel flame retardant represented by the general formula (1) according to the present invention is not particularly limited,
Some methods are illustrated below. The first method is to react tetrabromobisphenol A (hereinafter abbreviated as TBA) with a mixture of epichlorohydrin (hereinafter abbreviated as ECH) and glycidol (hereinafter abbreviated as GD) in the presence of an alkali metal hydroxide. Thus, the compound of the general formula (1) having the terminal groups A and B can be obtained. In this case T
The degree of polymerization n can be controlled by the molar ratio of BA and ECH, and the ratio of the terminal groups A and B can be controlled by the molar ratio of ECH and GD. To introduce the terminal group C, tribromophenol (hereinafter abbreviated as TBP) is mixed with TBA in advance and reacted, or the terminal groups A and B are mixed.
The compound of the general formula (1) can be produced by reacting TBP with the terminal group B after the production.

In the second method, TBA and ECH are reacted in the presence of an alkali metal hydroxide to synthesize a compound of the general formula (1) having a terminal group B, which is reacted in the presence of an acid or alkali catalyst. The compound of the general formula (1) consisting of the terminal groups A and B can be obtained by hydrolysis. The terminal group C can be introduced in the same manner as the first method. As the catalyst used for this hydrolysis, acids such as phosphoric acid, sulfuric acid, oxalic acid and acetic acid, and alkalis such as caustic soda and caustic potash can be used. Further, in the second method, a low molecular weight brominated epoxy resin consisting of a low molecular weight terminal group B is synthesized in advance, and after hydrolyzing it to introduce the terminal group A, the remaining terminal group B (epoxy group) It is also possible to react T) with TBA to obtain a desired degree of polymerization. This second method has a cost advantage over the first method using expensive glycidol.

The third method is to react a low molecular weight brominated epoxy resin with 2 mol of TBA to make the terminal group a phenolic OH.
And Next, a predetermined amount of glycidol is reacted and the remaining phenolic OH is reacted with a low molecular weight brominated epoxy resin to obtain the compound of the general formula (1). Although the third method requires a slightly longer process, it is a method that can be recommended because it involves only a simple addition reaction. The content of the terminal group A of the flame retardant according to the present invention obtained by these methods can be known by quantifying the α-glycol group. The terminal group B can be known by quantifying the epoxy group. Although the terminal group C cannot be directly quantified, it can be determined by measuring the bromine content and calculating it together with the quantitative results of the terminal groups A and B.

The flame-retardant resin composition of the present invention is a resin composition containing the above flame retardant. The resin may be either a thermoplastic resin or a thermosetting resin, and as the thermoplastic resin, styrene resin, polyethylene terephthalate (PET), polybutylene terephthalate (P
Examples of the thermosetting resin such as BT) include phenol resin, epoxy resin, unsaturated polyester resin and the like. When the flame retardant according to the present invention is used by being mixed with a resin, it is selected so as to obtain optimum characteristics depending on the type of the target resin as described above. The amount added is preferably 0.1 to 30 parts by weight, and more preferably 5 to 25 parts by weight, based on 100 parts by weight of the total resin composition. 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.

[0014]

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 addition, all parts and% in the examples 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) α-glycol: GASTENMARK., ANAL.CHEM.Vol3
0, No3,381-383,1958 (4) Light resistance ΔE: Using a sunshine weather meter, using a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.) It was measured. (5) Flammability test: Based on UL-94 test method. (6) Metal adhesion: The first roll of the 6-inch metal heat 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.

Example 1 In a 2 liter separable flask equipped with a thermometer, a stirrer, a dropping device and a condenser, 544 g (1 mol) of TBA, 127.2 g (1.375 mol) of ECH and GD were added.
9.3 g (0.125 mol) and 170 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) were charged and dissolved by heating while purging with nitrogen.
An aqueous solution of H (25 g, 0.3 mol) was added dropwise over 30 minutes, followed by reaction for 4 hours and further dilution with 280 g of MIBK.
% NaOH aqueous solution 125 g (1.5 mol) in 30 minutes, and after reacting for another 4 hours, MIBK 230 g,
320 g of water was added and the solution was allowed to stand 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 A low molecular weight brominated epoxy resin Epotote YDB-400 (manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 400 g / eq, softening point 69) was placed in a separable flask similar to Example 1.
℃, bromine content 48%) 800 g (1 mol), MIBK
After 310 g and 35 g of n-butanol were added and dissolved by heating at 95 ° C., 240 g of a 10% aqueous oxalic acid solution was added and reacted at the same temperature for 8 hours to hydrolyze the epoxy group. afterwards,
Neutralize with 5% caustic soda, MIBK 450g, water 20
0 g was added and the mixture was allowed to stand and separate. After washing with water 5 times in the same manner, the solvent was recovered by filtration. Obtained flame retardant intermediate B
-1 was 635.2 g / eq of epoxy equivalent and 0.059 mol / 100 g of alpha diol. This means that 36% of the terminal epoxy groups of the group are hydrolyzed. Further, 406.5 g (0.5 mol) of this B-1 was mixed with TBA.
Using 44.4 g (0.1 mol) as a catalyst, 0.05 g of triphenylphosphonium bromide (hereinafter abbreviated as TPPB) was added, and 160 g of nitrogen was added while purging with nitrogen.
The desired flame retardant B was obtained by reacting at 5 ° C. for 5 hours. The physical properties of this are shown in Table 1.

[0017]

Example 3 A separable flask similar to that used in Example 1 was charged with Epotote YD.
B-400 (previous) 400 g (0.5 mol), TBA5
44 g (1.0 mol) and 0.272 g of TPPB were charged and reacted at 150 ° C. for 5 hours while purging with nitrogen.
Then, 22.2 g (0.3 mol) of GD was added and reacted for 1 hour, and then 560 g of YDB-400.
(0.7 mol) was added and the mixture was reacted at 170 ° C. for 2 hours to obtain the intended flame retardant C. Table 1 shows these physical properties. For comparison, YD was used as an example of a brominated epoxy oligomer.
Table 1 shows the physical properties of B-406 and TB-62 (all manufactured by Tohto Kasei Co., Ltd.) as an example of the modified brominated epoxy oligomer.
It was shown to.

[0019]

[Table 1]

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. Examples 5 to 7 and Comparative Examples 1 to 2 The flame retardants A to C obtained in Examples 1 to 3 and Y for comparison.
DB-406 and TB-62 (previously described) were blended in the compositions shown in Table 2, mixed with a Henschel mixer, and then melt-kneaded with a twin-screw extruder (PCM-30 type manufactured by Ikegai Tekko Co., Ltd.), I got a compound. A test piece was prepared from the obtained compound by injection molding. Using this test piece, flammability, adhesion, and light resistance were measured. The results are shown in Table 2.

[0021]

[Table 2]

[0022] For Example 9及 beauty Comparative Example 3-4 obtained in Example 1 was flame retardant A及 beauty compared YDB-
Each of 406 and TB-62 (described above) was adjusted to a 65% toluene solution. In addition, a 50% methanol solution of tung oil-modified phenol resin (commercial product) was mixed with toluene solution of each flame retardant and triphenyl phosphate in a solid content ratio of 75/20.
/ 5 (phenol resin / flame retardant / phosphate) were mixed and dissolved, and the kraft paper for paper lamination was impregnated with the resin amount of 50% and dried. Eight sheets of the obtained paper base materials were heated and pressed to be laminated to obtain a laminated board having a thickness of 1.6 mm. Table 3 shows the physical properties of the obtained resin varnish and the paper base laminate.

[0023]

[Table 3]

From the results shown in Tables 1, 2 and 3, the flame retardant of the present invention is a brominated epoxy oligomer type, but the reduction of the bromine content is minimized and the metal adhesion is maintained while maintaining the light resistance. Were able to impart improved properties.

[0025]

As described above, the resin composition containing the flame retardant according to the present invention has high flame retardancy, light resistance and
It has excellent heat resistance and fluidity and does not adhere to metal parts such as screws, cylinders, and molds of injection molding machines and extruders.

Continuation of the front page (56) Reference JP-A-6-145533 (JP, A) JP-A-54-3900 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 1 / 00-101/16

Claims (2)

(57) [Claims] 1. A bromine-containing flame retardant represented by the following general formula (1), wherein the terminal groups X and Y consist of A and B or C, in which A is at least 10 mol% to 25.1 mol%. And the residue may be a single or a combination of two selected from B and C, n is an integer and 0 ≦ n <
Thirty. [Chemical 1] 2. A flame-retardant resin composition containing the bromine-containing flame retardant shown in claim 1.