JPH06128410A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant thermoplastic resin composition excellent in light resistance and heat resistance. CONSTITUTION:This composition is obtained by adding 2,4,6-tris(2,4,6- tribromophenoxy)-1,3,5-triazine, hydrotalcite, a benzotriazole-based compound as a light stabilizer and a phenolic compound having a hindered phenol group, a pentaerythritol type diphosphite-based compound or an organotin compound as a heat stabilizer to a thermoplastic resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition, and more particularly to a thermoplastic resin composition excellent in light resistance, heat resistance, mechanical strength and flame retardancy.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic resins have good processability and physical properties, and are used in large amounts for various purposes such as home appliances, upholstery and building materials.

However, since the present resin itself is flammable, its composition is required to have excellent flame retardance capable of complying with the stricter regulation of legal flame retardation against fire.

On the other hand, with the diversification of uses for this resin, the physical properties of the resin are being improved. Especially light resistance,
Improvements in heat resistance and mechanical strength, weight reduction, and resource saving are important goals for improvement.

By the way, as a method for making a thermoplastic resin flame-retardant, for example, JP-A-53-50255 discloses a specific brominated aromatic-S-triazine flame retardant and an ultraviolet absorber and / or an ultraviolet stabilizer. The method of addition is described.

However, since the above flame retardant has no melting property and does not uniformly mix with the thermoplastic resin, the resulting composition was not sufficiently flame retarded. In addition, the improvement of physical properties such as light resistance, heat resistance and mechanical strength, which are important goals for improvement today, have not been solved.

Therefore, as a result of intensive studies in view of the above circumstances, the present inventors have found that a thermoplastic resin containing a specific brominated aromatic-S-triazine flame retardant and hydrotalcite is good. It was found that the resin exhibits excellent flame retardancy and excellent physical properties such as light stability and heat stability, and the present invention has been accomplished.

[0008]

The gist of the flame-retardant thermoplastic resin of the present invention is 2,4 and mp having a melting point of 225 to 235 ° C.
6-tris (2,4,6-tribromophenoxy)-
The first invention is one containing 1,3,5-triazine and hydrotalcite, and the second invention is the combined use of a benzotriazole-based light stabilizer, and a phenol-based heat stabilizer and phosphite-based stabilizer. A third invention is to use at least one selected from the group consisting of a heat stabilizer and an organic tin heat stabilizer in combination.

The main items relating to the constitution of the invention will be described below item by item.

2,4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine (hereinafter referred to as
"TBP-TA") TBP-TA in the composition of the present invention has a melting point of 225 to 2
It is a compound having a temperature of 35 ° C. A substance having a melting point of less than 225 ° C. or a substance containing impurities that do not melt even at a temperature of more than 235 ° C. is a cause of deteriorating the light resistance and heat resistance of the resulting composition and further significantly reducing the mechanical strength of the molding resin. It cannot be used because it becomes.

High purity TB having a melting point of 225 to 235 ° C.
P-TA is obtained by adding, for example, an aqueous solution of tribromophenolate to a solution of a cyanuric chloride non-hydrophilic solvent to which a phase transfer catalyst is added, at a temperature not higher than the boiling point of the solvent used, and at a temperature not higher than the boiling point of the reaction system solvent composition. It is obtained by carrying out an aging reaction for 5 hours and then removing the hydrophilic solvent from the reaction system under reduced pressure or normal pressure.

Although the melting point of TBP-TA slightly varies depending on the measuring model, one sharp endothermic peak is observed in the range of 228 to 234 ° C. in the differential thermal analysis.

The hydrotalcite used in the present invention is, for example, a compound represented by the following composition formula (I).

(M ²⁺ ) _1-x (M ³⁺ ) _x (OH) ₂ (A ⁿ⁻ ) _{x / n} · mH ₂ O (I) (In the formula, M ²⁺ represents Mg or Zn. M ³⁺ Is Al
Indicates. A ⁿ⁻ is CO ₃ ²⁻ , HPO ₄ ²⁻ , SO ₄
^2- , or OH ⁻ . x is 0 to 0.5, m is 0
The numbers 1 are shown respectively. ).

The above-mentioned hydrotalcite includes natural ones and synthetic ones. Specifically, (M
g) _4.2 (Al) ₂ (OH) _12.4 (CO ₃ ),
(Mg) ₆ (Al) ₂ (OH) ₁₆ (CO ₃ ) .4H ₂
O and the like, and synthetic hydrotalcites that are easily available include magnesium, aluminum,
There are hydroxycarbonate hydrate and the like, but among them, (Mg) _4.2 (Al) ₂ (OH) _12.4 (C
O ₃ ) is preferable in terms of good heat resistance (small heating loss).

Benzotriazole Light Stabilizer (Substance Corresponding to Claim 2) Examples of the benzotriazole light stabilizer usable in the present invention include 2- (2'-hydroxy-3'-t-butyl-5). '-Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole and the like can be mentioned.

Heat Stabilizer (Substance Corresponding to Claim 3) As the heat stabilizer usable in the present invention, the following compounds can be mentioned. That is, as a phenolic heat stabilizer, for example, tetrakis [methylene-3- (3 ', 5'-di-t
-Butyl-4-hydroxyphenyl) propionate]
Methane, n-octadecyl-β- (4'-hydroxy-
3 ', 5'-di-t-butylphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene, N, N'-bis-3- (3 ', 5'-di-t
A phenolic compound containing a hindered phenol group such as -butyl-4'-hydroxyphenyl) allopionylhexamethylenediamine is used as a phosphite heat stabilizer, for example, distearyl pentaerythritol diphosphite, bis (2,2, 4-di-t-butylphenyl)
-Pentaerythritol diphosphite, bis (2,6
A pentaerythritol-type diphosphite compound such as -di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite and dinonylphenyl pentaerythritol diphosphite is further used as an organotin heat stabilizer, for example, di-n- Octyl maleate polymer, di-n-butyl-tin maleate polymer, dibutyl tin-
3-mercaptopropionate, di-n-octyl-tin-3-mercaptopropionate, dibutyl-tinmercaptoacetate, diethylene glycol bis (butyltin thioacetate), dibutyltin sulfide, dioctyltin sulfide, dibutyltin dioctyl mercaptide, Examples thereof include organic tin compounds such as dimethyltin bis (ethylene glycol monothioglycolate) and dibutyltin bis (ethylene glycol monothioglycolate).

These may be used alone or in combination of two or more. Further, although it is possible to further use other stabilizers in combination, the light and heat stability may decrease due to the antagonism of the stabilizer and the resin composition.

Thermoplastic Resin As the thermoplastic resin to which the present invention is applied, polystyrene, acrylonitrile-butadiene-styrene (AB
S), polypropylene, polyethylene, polybutadiene, polyamide, polyethylene terephthalate (PE
T), polybutylene terephthalate (PBT), polycarbonate (PC) and the like. Further, these polymer alloys and the like (for example, polymer alloy of acrylonitrile-butadiene-styrene and polycarbonate (ABS-PC resin) can also be used.

Other auxiliary additives, etc. In the composition of the present invention, other halogen-based and / or phosphorus-based flame retardants, antimony-based flame retardant aids such as antimony trioxide and antimony pentoxide, flame-retardant resins, metals It is also possible to include oxides, metal hydroxides, alkyl metal compounds and the like.

Further, when used, other antioxidants and ultraviolet absorbers, infrared absorbers, antistatic agents, inorganic fillers, solvents, plasticizers, crystal nucleating agents, pigments and the like may be used in combination. However, an antagonism may occur depending on the compound added.

Blending method, blending ratio There is no particular limitation on the method of adding each component such as hydrotalcite, for example, a method of adding to TBP-TA,
Any method such as a method of directly adding to the resin may be used, but a method of adding to TBP-TA and then compounding with the resin is preferably adopted.

The amount to be blended is not particularly limited, but usually,
TBP-TA is 1 to 90 parts, preferably 5 to 50 parts, relative to 100 parts by weight of the thermoplastic resin (hereinafter, simply referred to as "parts"). If it is less than 1 part, the problem that sufficient flame retardancy cannot be obtained tends to occur, and if it exceeds 90 parts, the problem of causing deterioration of mechanical properties tends to occur.

When antimony trioxide is also used as a flame retardant aid, it is preferably added in a ratio of 1 to 30 parts, preferably 2 to 20 parts. If it is less than 1 part, the problem that a sufficient flame retardant effect cannot be obtained tends to occur, and if it exceeds 30 parts, the problem that the synergistic effect due to the compounding is impaired tends to occur.

Further, 0.001 to 30 parts, preferably 0.01 to 30 parts of various heat stabilizers such as hydrotalcite, benzotriazole type light stabilizer, and phenol type heat stabilizer.
It is recommended to add 10 parts. If less than 0.001 parts,
The problem that sufficient effect cannot be obtained easily occurs, and
If it exceeds 0 parts, problems such as deterioration of molding processability and physical properties are likely to occur.

Molding temperature The molding temperature of the composition of the present invention is suitably in the range of 200 to 280 ° C. If it is less than 200 ° C, the fluidity of the resin will be lowered, and if it exceeds 280 ° C, coloring and decomposition may occur.

The specific high purity T that constitutes the composition of the present invention.
Since BP-TA is compatible with the thermoplastic resin, the compound itself can be uniformly dispersed. Together with this and the combined use of hydrotalcite, not only excellent flame retardancy but also excellent light resistance, heat resistance and mechanical strength can be imparted to the thermoplastic resin.

By blending the light stabilizer according to claim 2 and the heat stabilizer according to claim 3, the above physical properties can be further improved.

[0029]

EXAMPLES Examples and effects of the present invention will be described below with reference to examples, but these are merely for the purpose of explanation and are not intended to limit or limit the inventive idea. In addition, "%" is shown as a weight standard in the examples.

Production Example A (of TBP-TA in the present invention)
Production) A reactor equipped with a stirrer, cooling condenser, thermometer, dropping funnel, 206.5 g of methylene chloride, 1 cyanuric chloride
After 8.4 g (0.10 mol) was added and dissolved, triphenylethylphosphonium bromide 0.7 g was added. Next, 173.9 g of water and 12.8 g of caustic soda
(0.32 mol) and tribromophenol 102.
An aqueous tribromophenolate solution prepared from 3 g (0.31 mol) was added dropwise while maintaining the reaction temperature at 30 ° C. After completion of the dropping, an aging reaction was performed for 3 hours under reflux of methylene chloride, and then methylene chloride was distilled off under normal pressure. The product was washed once with methanol, filtered off and dried to give 2,4,6-
Tris (2,4,6-tribromophenoxy) -1,
103.1 g (yield 96.5%) of 3,5-triazine was obtained.

Production Example B (Production of low melting point TBP-TA) 30.5 g of acetone and 18.4 g of cyanuric chloride were placed in a reactor having a stirrer, a cooling condenser, a thermometer and a dropping funnel.
(0.10 mol) was added and dissolved. Then water 30
5.5 g, caustic soda 12.8 g (0.32 mol) and tribromophenol 102.6 g (0.31 mol)
The tribromophenolate aqueous solution prepared above was added dropwise while maintaining the reaction temperature at 30 ° C. After dripping, at 4 ℃ at 4
After aging reaction for 8 hours, it is filtered and dried,
6-tris (2,4,6-tribromophenoxy)-
80.7 g of 1,3,5-triazine (yield 75.6%)
Got

Production Example C (Brominated Aromatic S-without Meltability)
Production of triazine) 206.5 g of methylene chloride, 1 cyanuric chloride in a reactor having a stirrer, a cooling condenser, a thermometer, and a dropping funnel.
After 8.4 g (0.10 mol) was added and dissolved, triphenylethylphosphonium bromide 0.7 g was added. Next, water 332.7g, caustic soda 12.0g
(0.30 mol), 56.3 g of tribromophenol
(0.17 mol) and tetrabromobisphenol A
An aqueous solution in which 38.1 g (0.07 mol) was dissolved was added dropwise while maintaining the reaction temperature at 30 ° C. After completion of the dropping, an aging reaction was performed for 3 hours under reflux of methylene chloride, and then methylene chloride was distilled off under normal pressure. The product was washed once with methanol, filtered and dried to obtain 93.3 g of a white powder.

TBP-T obtained by Production Examples A to C
The physical properties of A or the brominated aromatic S-triazine compound are shown in [Table 1] below.

[0034]

[Table 1]

Example 1 TBP-T obtained in Production Example A, Production Example B or Production Example C
A or a brominated aromatic S-triazine compound, and hydrotalcite, a benzotriazole-based light stabilizer and a heat stabilizer shown in the following [Table 2] at a ratio shown in the table for 3 minutes in a vertical mixer. After mixing, antimony trioxide and HI-polystyrene resin (Estyrene H-
65; Nippon Steel Chemical Industry Co., Ltd.) was added and mixed at the ratio shown in the table, and then the inner diameter was adjusted to 220 ° C. and the inner diameter was 20.
After kneading with an m / mφ extruder, it was extruded from a die having a diameter of 3 m / mφ, and the obtained strand was cut to obtain pellets. The pellets were supplied to an injection molding machine whose temperature was adjusted to 230 ° C., and immediately injection-molded to prepare a test piece.
Using this test piece, the light resistance, heat resistance, and flame retardancy were examined, and the impact strength was measured. The results are also shown in [Table 2].

[0036]

[Table 2]

However, the meanings of the abbreviations in [Table 2] (the same applies to the following [Tables 3 to 5]) and the physical property evaluation methods are as follows. That is, (a): a synthetic hydrotalcite having the following structure; D
HT4A-2 (Kyowa Chemical Co., Ltd. product) (Mg) _4.2 (Al) ₂ (OH) _12.4 (CO ₃ ) (b): Hydrotalcite-containing inorganic compound; MC-6
1 (Sankoki Gosei Co., Ltd. product) (C): benzotriazole-based light stabilizer 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole (d): phenol-based Thermal Stabilizer Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane (e): Phosphite thermal stabilizer Bis (2,6-di-t-) Butyl-4-methylphenyl)
-Pentaerythritol diphosphite (f): Organotin-based heat stabilizer di-n-butyltin malate polymer Light resistance (△ E): The prepared test piece was xenon weather meter (80 ° C), illuminance 0.39W / 30 in m ²
After irradiation for 0 hours, the change in color tone was measured with a color difference meter. The smaller the value, the better the light resistance. Heat resistance (ΔE): After the resin is retained in the cylinder for 30 minutes under the injection molding temperature condition, the change in color tone is measured with a color difference meter.
The smaller the value, the better the heat resistance. Flame retardance: Carried out according to UL-94 (1/16 inch).
The smaller the value, the better the flame resistance. Impact strength: Carried out according to JIS-K6871. The larger the value, the better the impact strength.

Example 2 TBP-T obtained in Production Example A, Production Example B or Production Example C
A or a brominated aromatic S-triazine compound, and hydrotalcite, a benzotriazole-based light stabilizer, and a heat stabilizer shown in the following [Table 3] are mixed in a vertical mixer for 3 minutes at the ratios shown in the table. Then, antimony trioxide and an ABS resin (Cycolac T; manufactured by Ube Saikon Co., Ltd.) were added at a ratio shown in the table and mixed,
After kneading with an extruder having an inner diameter of 20 m / mφ adjusted to 230 ° C., the mixture was extruded from a die having a caliber of 3 m / mφ. The obtained strand was cut into pellets. The pellets were supplied to an injection molding machine whose temperature was adjusted to 230 ° C., and immediately injection-molded to prepare a test piece. Using this test piece, the light resistance, heat resistance, and flame retardancy were examined, and the impact strength was measured. The results are also shown in [Table 3].

[0039]

[Table 3]

Example 3 TBP-T obtained in Production Example A, Production Example B or Production Example C
A or a brominated aromatic S-triazine compound, and hydrotalcite, a benzotriazole-based light stabilizer, and a heat stabilizer shown in the following [Table 4] are mixed in a vertical mixer for 3 minutes at the ratios shown in the table. In addition, antimony trioxide and ABS-PC resin (Iupilon MB-221
0: Mitsubishi Gas Chemical Co., Ltd.) was added and mixed in the ratio shown in the table, and then the inner diameter was adjusted to 250 ° C. and the inner diameter was 20 m / mφ.
After kneading with the extruder, the product was extruded from a die having a diameter of 3 m / mφ, and the obtained strand was cut to obtain pellets. After supplying the pellets to an injection molding machine whose temperature was adjusted to 250 ° C., they were immediately injection-molded to prepare test pieces. Using this test piece, the light resistance, heat resistance, and flame retardancy were examined, and the impact strength was measured. The results are also shown in [Table 4].

[0041]

[Table 4]

Example 4 TBP-T obtained in Production Example A, Production Example B or Production Example C
A or brominated aromatic S-triazine compound was mixed with hydrotalcite, benzotriazole-based light stabilizer and heat stabilizer shown in the following [Table 5] at a ratio shown in the table for 3 minutes with a vertical mixer. In addition, antimony trioxide and PBT resin (Novadul 5010G-30
Mitsubishi Kasei Co., Ltd.) was added and mixed in the proportions shown in the table, and after kneading with an extruder having an inner diameter of 20 m / mφ adjusted to 250 ° C., the mixture was extruded from a 3 m / mφ die. The obtained strand was cut into pellets. After supplying the pellets to an injection molding machine whose temperature was adjusted to 250 ° C., they were immediately injection-molded to prepare test pieces. Using this test piece, the light resistance, heat resistance, and flame retardancy were examined, and the impact strength was measured. The results are also shown in [Table 5].

[0043]

[Table 5]

[0044]

As described and demonstrated above, the present invention provides a thermoplastic resin composition having good flame retardancy and excellent light stability, heat stability, and mechanical strength. It was

A flame-retardant heat which gives a light-resistant and heat-resistant molded product with little heat deterioration and without corrosion of the molding die at a general working temperature for injection molding, extrusion molding or rolling of a thermoplastic resin. By providing a plastic resin, we will contribute to the industry using this resin and disaster prevention.

Claims (3)

[Claims] 1. 2,4,6-Tris (2,4,6-tribromophenoxy) -1,3,5 having a melting point of 225 to 235 ° C.
-A flame-retardant thermoplastic resin composition containing triazine and hydrotalcite. 2. The flame-retardant thermoplastic resin composition according to claim 1, wherein a benzotriazole-based light stabilizer is added. 3. The flame retardant according to claim 1, wherein at least one selected from the group consisting of a phenol-based heat stabilizer, a phosphite-based heat stabilizer, and an organotin-based heat stabilizer is added. Thermoplastic resin composition.