JPS6017221B2 - Flame retardant polybutylene terephthalate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a flame-retardant polybutylene terephthalate resin which reduces the concentration of organic halogen flame retardant and antimony trioxide as much as possible, lowers the cost of the main flame retardant, and reduces toxicity. The present invention relates to a composition.

Polybutylene terephthalate resin is being used in a wide range of fields as an engineering plastic due to its excellent mechanical, electrical, and chemical properties.

However, since polybutylene terephthalate resin is combustible, various attempts have been made to make it flame retardant in response to flame retardant regulations that have recently become stricter. However, the organic halogen flame retardants and antimony trioxide used as scale flame retardants are expensive and have the drawback of an unavoidable increase in cost, as well as their toxicity, which limits their use. The present invention aims to improve such drawbacks, and uses melamine as a flame retardant aid in combination with a composition containing polybutylene terephthalate resin, an alicyclic chlorine flame retardant, and antimony trioxide as main components. By doing so, the addition rate of the main flame retardant is to be greatly reduced.

That is, in the present invention, the composition ratio of the chlorine atom of the chlorine-based alicyclic compound to the antimony atom of the antimony trioxide in the polybutylene terephthalate resin is about 0.7:1 to about 1.6:1.
(weight ratio), and the total of these main elutriation agents is 8 to 2% by weight.
In addition, melamine 4-4 is added as a flame retardant aid.
This is a flame-retardant polybutylene terephthalate resin composition characterized in that it contains 1% by weight of polybutylene terephthalate.

The polybutylene terephthalate resin referred to herein includes a polybutylene terephthalate homopolymer, a polybutylene terephthalate copolymer mainly consisting of tetraethylene terephthalate and having less than 40 mol % of copolymerized units.

The copolymerization components of the copolymer include aliphatic, aromatic, and alicyclic glycols such as ethylene glycol, propylene glycol, decamethylene glycol, neobentyl glycol, y-xylene glycol, cyclohexanediol, and cyclohexane methanol as diol components. , dicarboxylic acids such as isophthalic acid, phthalic acid, terephthalic acid, p-oxybenzoic acid, m-oxybenzoic acid, naphthalene dicarboxylic acid, oxalic acid, adipic acid, sebacic acid, cyclohexanedicarboxylic acid and other aromatic, alicyclic, and aliphatic acids. group dicarboxylic acids, etc. Furthermore, blends of polybutylene terephthalate and other thermoplastic polymers with an increase in weight of 4% or less can also be applied. Blend components and thermoplastic polymers include the above copolymers, polyethylene terephthalate, polycarbonate, and nylon 6.
, no. Examples include nylon 60, nylon 12, nylon 11, polymethylene oxide, polypropyne, polyethylene, polystyrene, and ABS resin. The chlorine-based alicyclic compound used as the main fuel agent has the general formula (W), (0
) There is a compound shown by Here, R is tetrahydrofuran, cyclobentane, cyclooctane, etc. connected on the left and right, and X is hydrogen, chlorine, and at least one
Preferably all chlorine is desired.

Examples of these compounds are perchlorbentacyclodecane, dote-juryoku chlorodode-juryoku hydrodimethanodibenzocyclooctane, and the like. Melamine used as a flame retardant aid can be used as a flame retardant for unreinforced polybutylene terephthalate resin, but has almost no key flame retardant effect on reinforced polybutylene terephthalate resin.

Examples of reinforcing agents that can be used here include glass fiber, carbon fiber, wollastonite (CaSi03), carrion (
N203, deprivation iC2, 210), calcium carbonate (Ca
C03) etc.

In addition to these reinforcing agents, various pigments, lubricants, stabilizers, mold release agents, etc. can also be appropriately blended. According to the present invention, by using a non-organic halogen elutriation agent, the concentration of the chlorine compound nada retardant and antimony trioxide required for pyrolysis of polybutylene terephthalate resin is kept much lower, thereby reducing costs. It is possible to significantly reduce the toxicity caused by the organic halogen scale retardant and to make it as low as possible, which is extremely useful in practice.

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 Additives were blended with the composition shown in Table 1 to polybutylene terephthalate having a melting point of 225 qo and an intrinsic viscosity (phenol/tetrachloroethane = 6/4, 30 q○) of 0.80, and the mixture was extruded using an extruder and pelletized. did.

Next, the resulting pellet was hydraulically dried and molded into a 1'32" thick UL-9 test piece using an injection molding machine.
-94 combustion test was conducted. Table 1 shows the results of combustion tests for each composition. Table 1 *: The numbers in parentheses are the weight ratio of CI atoms/Sb atoms.

*1 Triperchlorbentacyclodecamper Perchlorobentacyclodecane and antimony trioxide alone were used to convert polybutylene terephthalate to V-0, as shown in Comparative Example 1-2. When combined with melamine as a flame retardant, the required amounts of perchlorbentacyclodecane and antimony trioxide can be reduced to 8% by weight.

(Example 1-3). The total amount of flame retardant and combustion aid required is also 19. can be reduced to $wt% (Example 1
-4). In addition, Proportion 1-4 shows that it is possible to make polybutylene terephthalate from melamine alone, but as shown in Example 2 (Comparative Example 2-3), polybutylene terephthalate containing a large amount of glass fiber, It can be seen that it is difficult to make flame retardant using melamine alone.

Example 2 Additives were blended with the composition shown in Table 2 to polybutylene terephthalate with a melting point of 22,500 and an intrinsic viscosity (phenol/tetrachloroethane = 6/4, 30q○) of 0.80, and the mixture was extruded and pelletized using an extruder. did.

Next, the obtained pellet was dried under reduced pressure, and then molded into a UL-9 umbrella burnt test piece with a thickness of 1/32" using an injection molding machine.
The results of the -94 combustion test are shown in Table 2 along with the composition. Table 2 *: The value in parentheses is the weight ratio of CI atoms/Sb atoms.

*1: Perchlorbentacyclodecane For flame retardation using only perchlorbentacyclodecane and antimony trioxide, the total flame retardant was 26.5% as shown in Comparative Examples 2-4. Bamboo weight%
It is necessary to add something.

In the example, the amount of perchlorobentacyclodecane and antimony trioxide required is less than that of Comparative Example 2-4, and the amount of melamine, which is an auxiliary flame retardant, is added to 26~
19. The box weight% is decreasing.

By using memine as an auxiliary flame retardant in this way, the required amount of chlorine-based flame retardant can be significantly reduced compared to when no auxiliary flame retardant is used. Further, as can be seen from Comparative Examples 2-3, melamine alone has no scaling effect when the glass fibers are large. Comparative example 2-5
The bonito-burning effect of melamine comes into play only when the amount of glass fiber is extremely reduced. Example 3 Additives were blended with the composition shown in Table 3 to polybutylene terephthalate having a melting point of 225 qo and an intrinsic viscosity (phenol/tetrachloroethane = 6/4, 30°C) of 0.80, and the mixture was extruded using an extruder. Lettered.

After drying the obtained pellet under reduced pressure, it was molded into a 1/32" thick UL-94 lacquered test piece using an injection molding machine.
Table 3 shows the results of the 9-burning combustion test along with the composition. Table 3 *: Weight ratio of CI atoms/Sb atoms in parentheses *1:
Dodecachlorododecahydrodimethanodibenzocyclooctene By using melamine as the key additive, the amount of chlorine-based alicyclic compounds and antimony trioxide, which are the main flame retardant agents, is reduced compared to when no flame retardant additives are used. Even if the flame retardant additive and the main flame retardant are added together, it is still at a low level.

Example 4 Additives were blended with the composition shown in Table 4 to polybutylene terephthalate with a melting point of 225 qo and an intrinsic viscosity (phenol/tetrachloroethane = 6/4, 30 o 0) of 0.8000.
It was extruded and pelletized using an extruder.

Next, the obtained pellet was dried under reduced pressure, and then molded into a UL-9 umbrella window burnt test piece by 1/32" using an injection molding machine.
The inevitable corpse test was conducted. Table 4 Decabromidiphenyl ether was taken up as a representative example of the brominated aromatic compound, but as can be seen from Table 4, no synergistic effect was observed due to the addition of melamine.

Claims (1)

[Claims] 1. A polybutylene phthalate resin in which the composition ratio of chlorine atoms in a chlorine-based alicyclic compound to antimony atoms in antimony trioxide is about 0.7 to about 1.6: (weight ratio), and A flame-retardant polybutylene terephthalate resin composition containing 8 to 20% by weight of these main flame retardants in total and 4 to 10% by weight of melamine as a flame retardant aid. 2. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the chlorinated alicyclic compound is perchloropentacyclodecane or a modified product thereof. 3. The flame-retardant polybutylene terephthalate resin composition according to claim 1, wherein the chlorinated alicyclic compound is dodecachlorododecahydrodimethanodibenzocyclooctene or a modified product thereof.