JPS6026431B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition mainly composed of polyalkylene terephthalate, which has excellent flame retardancy, heat resistance, and mechanical properties.

Polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate have good moldability,
Due to its good mechanical properties, it has become widely used as an engineering plastic in recent years, but in fields such as electrical parts and automobile parts, it is necessary to have noisy properties, and such applications are expanding. There is.

So far, aromatic halogen compounds such as decabromobiphenyl oxide and hexabromobenzene, tetrabromobisphenol A diglycidyl ether, or polymers thereof have been proposed as elutriation agents for polyalkylene terephthalate. However, aromatic halogen compounds have a high sublimation property, and molded products containing these compounds may cause a "powdering phenomenon" in which the dyeing agent stands out on the surface of the molded product after long-term use, damaging the appearance of the molded product. Addition of a refractory agent has the disadvantage that the mechanical properties of the polyalkylene terephthalate contained in this pot are significantly reduced. As a solution to this problem, it has been proposed to use tetrapromobisphenol A diglycidyl ether or a polymer thereof as a dispersing agent. Although the disadvantages are improved to some extent, there are disadvantages in terms of mechanical properties, such as a decrease in tensile elongation and easy discoloration or gelation due to high temperature heating during molding. In this way, the use of conventional elutriation agents has the disadvantage of lowering the elongation rate, and on the other hand, the use of engineering plastics, especially for electronic parts, such as connectors, spacers, slot liners, bobbin switches, etc. If this is the case, a material that is scaled and has a good elongation rate is required. *The present invention solves these problems and provides a flame-retardant resin composition that is free from dusting, coloring, and gelling, and has a good elongation rate. .

That is, the present invention involves reacting a jepoxy compound obtained by reacting halogenated bisphenol A with epihalohydrin or methylepithalohydrin and a halogenated phenol or a halogenated alkylphenol for polyalkylene terephthalate 1, or C. To halogenated phenol glycidyl ether or halogenated hepta-alkyl phenol glycidyl ether.
After adding bisphenol A, it is obtained by subjecting epihalohydrin to a glycidyl etherification reaction or addition reaction with the above-mentioned dipoxy compound. means a methyl group or hydrogen, × means a bromine atom or chlorine, h
, i is an integer from 0 to 5 and h+i is 5 or less, or 0, j
and k is an integer from 0 to 4 such that j+k is 1 to 8; n is an average degree of polymerization and represents a number from 1 to 10;

) The present invention relates to a flame retardant resin composition containing 1 to 4 parts by weight of a scale flame-infecting agent represented by: Examples of the polyalkylene terephthalate used in the present invention include polybutylene terephthalate, which can be synthesized from 1,4-butadiol and dimethyl terephthalate, or polyethylene terephthalate, which can be synthesized from ethylene glycol and dimethyl phthalate. Also, at that time 1,3
Polymers obtained by cocondensation polymerization of polyhydric alcohols such as propanediol and neobentyl glycol, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, or aliphatic dicarboxylic acids may also be used. Furthermore, other polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polymethyl methacrylate, polypynyl chloride, A
Mixtures with BS resin, nylon, etc. are also used. The disturbing agent represented by the general formula (1) used in the present invention is:
A jepoxy compound obtained from halogenated bisphenol A such as tetrabromopisphenol A, epihalohydrin such as epichlorohydrin, or methylepihalohydrin such as methylepichlorohydrin, and a halogenated phenol or halogenated alkyl phenylene. It is easy to heat alcohol at 80 to 250°C using a catalyst such as an alkali metal hydroxide, halide, or tertiary amine, such as lithium hydroxide, lithium chloride, sodium hydroxide, triptylamine, or dibutylaniline. can be obtained.

Alternatively, halogenated bisphenol A is added to halogenated phenol glycidyl ether or halogenated alkylphenol glycidyl ether as a starting material, and then a glycidyl etherification reaction is performed using epihalohydrin and sodium hydroxide or potassium hydroxide. Alternatively, it can also be obtained by addition reaction with the above jepoxy compound. In the above, halogenated bisphenol A and epihalohydrin or methylephalohydrin are used in a molar ratio of about 1:1, and halogenated phenol glycidyl ether or halogenated alkylphenol glycidyl ether and halogenated pisphenol are used in a molar ratio of about 1:1. A and epihalohydrin or halogenated bisphenol A are used in a molar ratio of about 1:1:2.

The number n in general formula (1) represents the average degree of polymerization, which can be adjusted by changing the raw material blending ratio during synthesis, and has a softening point of 1
Although it is possible to synthesize up to 5-C solids, those with n of 1 to 5 are preferred from the viewpoint of workability.

Further, the halogenation rate of the straightening agent represented by the general formula (1) is preferably in the range of 40 to 7% by weight. 40% by weight
If the amount is less than that, the amount to be blended will increase in order to obtain sufficient visual properties, which is not preferable.

It is used in an amount of 1 to 40 parts by weight based on 10 parts by weight of the refractory agent polyalkylene terephthalate represented by the general formula (1).

If it is less than 1 part by weight, scaling will be insufficient, and if it exceeds 4 parts by weight, there will be problems with compatibility.

Preferably 5 to 2 parts by weight are used. When carrying out the present invention, the disintegrating agent represented by general formula (1) can be mixed during the polymerization reaction of polyalkylene terephthalate or in a molten state after the completion of the reaction, or it can be mixed into chips of polyalkylene terephthalate. Mixing can be carried out at room temperature or by heating using a rear V-type blender, mixer**, or roll. In addition, if necessary for the composition of the present invention,
Elutriation aids such as antimony trioxide, pigments, antioxidants,
Various additives such as thickeners and reinforcing agents such as glass fibers can also be blended. When using antimony trioxide 1
It is preferable to use up to 24 parts by weight for the properties and elutriation of the molded article. Next, an example of producing a naturalizing agent will be shown. In addition,
Hereinafter, parts refer to parts by weight. Production example 1 Tetrabromobisphenol A diglycidyl ether (
Epoxy equivalent: 400) 10 base solids, 42 parts of tribromophenol, and 0.5 parts of lithium hydroxide were charged into a flask, and reacted in a nitrogen stream at 160 pm for 7 hours.

After the reaction was completed, the mixture was cooled and the solidified product was ground to obtain a white to pale yellow powder. The molar ratio of tetrabisphenol A diglycidyl ether and tribromophenol used above is 0.125:0.127.

The product had a softening point of 8 pi, an epoxy equivalent of 1180, and an average degree of polymerization in general formula (1) of about 1. It was confirmed by IR spectrum and high performance gel permeation chromatography that the main product had the following structure. Flame retardant (1) production example 2 zips.

After reacting 92 parts of moffyl glycidyl ether, tetrabromobisphenol AI muscle, and 0.05 part of dibutylaniline in a nitrogen stream at 14 p○ for 2 hours, tetrabromobisphenol A diglycidyl ether (epoxy equivalent of 400 ), 0.05 part of dibutylaniline was added, and the mixture was further reacted at 140°C for 3 hours. After the reaction was completed, the mixture was cooled and the solidified product was ground to obtain a white to pale yellow powder. The molar ratio of dipromophenol glycidyl ether, tetrabromobisphenol A and tetrabromobisphenol A diglycidyl ether used above is about 1:1:2. The product has a softening point of 114q0
The epoxy equivalent was 1 and 0, and the average degree of polymerization in general formula (1) was about 2. According to IR spectroscopy and high performance gel permeation chromatography, the main product is
It was confirmed that it has the following structure. Flame retardant (0) Flame retardants (1) and (0) obtained in Production Examples 1 and 2 were placed in a metal Petri dish, heated at 270° C. for 10 minutes, and then the degree of coloring was observed.

At the same time, a scale-forming agent (m) having the following structure was also tested as a comparative example. The results are shown in Table 1. Flame retardant (m) Table 1 Test results Next, examples and comparative examples of the present invention are shown.

Example 1 Polybutylene terephthalate (Mitsubishi Rayon brand name,
Tough bet ■N-looo) 122 anchorage, locking agent (1
), 183 parts of antimony trioxide and Nada part of antimony trioxide are mixed in a mixer, a pellet is made using a twin-screw extruder at a temperature of 170 to 25 pi○, and injection molded at a temperature of 170 to 25 pi by a conventional method. A tensile test, a bending test, an impact test, a bushing test, and a heating test were conducted using the test pieces.

Example 2 and Comparative Examples 1 to 3 Tests were conducted in the same manner as in Example 1 using the formulations shown in Table 2 using deconcentrating agents (0), (m), decabromobiphenyl oxide, and hexafromobenzene. I did this.

The test results of Examples 1-2 and Comparative Examples 1-3 are shown in Table 2.

Table 2 Test Results Comparative Example 4 Tetrabromobisphenol AO. 3 mol, epichlorohydrin 0.3 mol, 50% NaOH aqueous solution 4 total, water 2
50 cc and 200 cc of toluene were mixed, and the mixture was heated under reflux for 6 hours.

Thereafter, the reaction solution was washed several times with water, dried over anhydrous sodium sulfate, heated in an oven, and then the toluene was removed. The resulting product was then ground. It has a softening point (ring and ball method) of 1520 and a bromine content of I. It was 3%. When this product was placed in a metal Petri dish and heated at 270°C for 10 minutes, it turned dark brown. 183 parts of this product,
The same polybutylene terephthalate 122 base and 98 parts of antimony trioxide used in Example 1 were added to Example 1.
A pellet was made in the same manner as above, and a test piece was obtained.

When this test piece was heated at 200° C. for 5 hours, it changed color to brown. The test pieces obtained in Examples 1 and 2, the test pieces obtained in Comparative Examples 1 and 4, the reference test pieces, and the test pieces obtained by heating these test pieces at 25,000 °C for 1 hour were measured using a color difference meter (
The degree of coloration was measured using a model HD-101DC (manufactured by Nippon Denshoku Co., Ltd.). The results are shown in Table 3. Note that the L value, A value, and B value of the reference test piece before heating were 93.
2, 12.10 and 4. I, and the values of the other test pieces were also similar to this. Table 3 Degree of Coloration (After Heating) The Z value represents the brightness, the A value represents the degree of reddish tone (negative value represents the green color tone), and the B value represents the degree of yellowish tone.

(Note) As shown by heating at 200°C for 5 hours or more, the flame-retardant resin composition according to the present invention has an excellent elongation rate, does not have a large decrease in properties such as bending strength, and does not cause dusting or discoloration. There is no need to worry about gelling.

Claims (1)

[Claims] 1. For 100 parts by weight of polyalkylene terephthalate, halogenated bisphenol A
A diepoxy compound obtained by reacting epihalohydrin or methyl epihalohydrin with a halogenated phenol or a halogenated alkyl phenol, or a halogenated bisphenol A is added to a halogenated phenol glycidyl ether or a halogenated alkyl phenol glycidyl ether. After that, it is obtained by subjecting epihalohydrin to a glycidyl etherification reaction or addition reaction with the above diepoxy compound, and has the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 is an alkyl group, R_2, R_3 are a methyl group or hydrogen, X means a bromine atom or a chlorine atom, h and i are integers from 0 to 5 and h+1 is 5 or less, or 0
, j and k are integers from 0 to 4 and j+k is from 1 to 8, n
represents the average degree of polymerization and is a number from 1 to 10. ) A flame retardant resin composition containing 1 to 40 parts by weight of a flame retardant represented by: