JP3510690B2 - Flame retardant ABS resin composition - 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 ABS resin composition in which the releasability of a flame-retardant ABS resin is improved.
The present invention relates to a flame-retardant ABS resin composition in which releasability at the time of molding is greatly improved when producing a resin molded product.

[0002]

2. Description of the Related Art ABS resin (acrylonitrile-butadiene-styrene copolymer) has excellent physical properties such as impact resistance, rigidity and moldability, and has a good surface appearance and easy secondary processing. It is widely used for interior and exterior materials for vehicles, communication office automation equipment, housing materials for home appliances, and miscellaneous goods.

In these applications, particularly for OA equipment and household appliances, there is an increasing demand for satisfying combustion standards such as UL standard and IEC standard. The flame retardancy of ABS resin can be improved by using flame retardants, but the effect of these additives reduces the releasability during injection molding and significantly deteriorates the production efficiency. Is used.

Examples of the lubricants that have been conventionally used include low molecular weight polyethylene wax, higher fatty acid esters such as stearic acid, higher fatty acid amides as internal lubricants, and dimethylpolysiloxane as external lubricants.

However, these lubricants are still unsatisfactory due to insufficient mold releasability and lubricity, and particularly when the processing temperature is high, the softening point is low, which causes deterioration of lubricity during processing, smoking, coloring. It has a drawback.
Amide stearate with a relatively high softening point (softening point 10
(0 to 105 ° C.) and ethylene bis-stearamide (softening point 142 to 145 ° C.) also have drawbacks such as insufficient fluidity as a lubricant and poor releasability.

[0006]

SUMMARY OF THE INVENTION The present invention was devised to solve the above-mentioned drawbacks of the prior art. The object of the present invention is to obtain excellent lubricity and separation during molding of flame-retardant ABS resin. It is to provide a flame-retardant ABS resin composition that gives moldability.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the physical properties are lowered by adding a specific silicone lubricant to a flame-retardant ABS resin. However, it was discovered that the releasability was improved and the production efficiency was improved, and the present invention was completed.

That is, the present invention is a flame-retardant ABS resin composition comprising a flame-retardant ABS resin and a silicone lubricant containing the following general formula [A] as a main component. In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 6 to 60 carbon atoms, and each may be a single type or a plurality of types. m is 0 to 1
000 is an integer, and n is an integer of 1 to 1000. R above
¹ is specifically a methyl, ethyl, propyl, butyl, pentyl or hexyl group, preferably a methyl group. R ² is an alkyl group having 6 to 60 carbon atoms,
It is preferably 12 to 40 alkyl groups.

The flame-retardant ABS resin composition of the present invention will be described in detail below. The above general formula [A] used in the present invention
The silicone-based lubricant represented by can be synthesized by a known method such as a hydrosilylation method or an equilibrium method. For example, methylhydrogenpolysiloxane, dimethylpolysiloxane-methylhydrogenpolysiloxane copolymer and the like are added with an unsaturated compound such as α-olefin by hydrosilylation using a catalyst such as chloroplatinic acid to obtain an alkyl compound. By introducing a group, the silicone compound used in the present invention can be synthesized.

The amount of the silicone lubricant used in the flame-retardant ABS resin composition of the present invention is 100 flame-retardant ABS resin.
It is preferably 0.1 to 5 parts by weight, more preferably 0.3 to 1 part by weight, based on parts by weight. If the amount of the lubricant used is less than 0.1 parts by weight, the desired molding processability cannot be obtained, and even if the amount exceeds 5 parts by weight, the effect remains unchanged, and in some cases, the mechanical properties deteriorate. It is not preferable because it may occur. Further, the silicone lubricant used in the present invention can be mixed with a conventional lubricant, and other additives such as an antioxidant, an antistatic agent and an ultraviolet absorber can be added depending on the purpose. .

The flame-retardant ABS resin used in the present invention is A
A flame retardant is added to BS resin. Any known ABS resin may be used as the ABS resin in the present invention, and its physical properties may be appropriately changed depending on the composition ratio of butadiene and acrylonitrile. Further, the flame retardant in the present invention refers to a substance which is added and mixed into a plastic, FRP or the like for the purpose of imparting flame retardancy, but any known one such as halogen type, inorganic type and phosphorus type can be used. . Specific examples thereof include tetrabromobisphenol A, octabromodiphenyl ether, decabromodiphenyl ether, tetrachlorophthalic acid, tetrabromophthalic acid, brominated epoxy oligomer, antimony trioxide, and paraffin chloride. These flame retardants can be used alone or in combination. The amount of flame retardant added is usually 0.1 to 40 parts by weight per 100 parts by weight of ABS resin.

[0012]

EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to the following examples.
All parts in the text are parts by weight.

Example 1 A reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer was charged with a methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer (Toshiba Silicone Co., Ltd.).
Manufactured by TSF483) (320 g, 0.0478 mol) and chloroplatinic acid (0.004 g) are charged, and the temperature is raised to 90 ° C. and kept constant. A solution prepared by dissolving 0.004 g of chloroplatinic acid in 432 g (2.3 mol) of 1-dodecene (Dialen 124, manufactured by Mitsubishi Kasei Co., Ltd.) was added dropwise while paying attention to heat generation. After the completion of the dropping, the temperature was raised to 110 ° C., the mixture was aged at the same temperature for 5 hours, the absorption of Si—H was confirmed to disappear by IR, the reaction was terminated, and a liquid compound was obtained at room temperature.

Example 2 A reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer was placed in a methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer (Toshiba Silicone Co., Ltd.).
Manufactured, TSF483) (280 g, 0.042 mol) and chloroplatinic acid (0.004 g) are charged, and the temperature is raised to 90 ° C. and kept constant. To this, 483 g of a mixture of 1-hexadecene and 1-octadecene (manufactured by Mitsubishi Kasei Co., Ltd., Dialen 168).
What melt | dissolved 0.004 g of chloroplatinic acid in (2.09 mol) was dripped, paying attention to heat generation. After completion of the dropping, the mixture was aged at the same temperature for 5 hours, IR was confirmed to eliminate absorption of Si-H, the reaction was terminated, and a liquid compound was obtained at room temperature.

Example 3 A reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer was charged in a methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer (Toshiba Silicone Co., Ltd.).
Manufactured by TSF483) (220 g (0.033 mol)) and chloroplatinic acid (0.004 g) are charged, and the temperature is raised to 90 ° C. and kept constant. 524 g of 1-octadecene and 1-eicosene mixture (Mitsubishi Kasei Co., Ltd., dialen 208)
What melt | dissolved 0.004 g of chloroplatinic acid in (1.64 mol) was dripped, paying attention to heat generation. After the completion of dropping, the mixture was aged at the same temperature for 5 hours, and it was confirmed by IR that absorption of Si-H had disappeared, and the reaction was terminated to obtain a waxy compound.

Example 4 A reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer was charged with a methylhydrogenpolysiloxane-dimethylpolysiloxane copolymer (Toshiba Silicone Co., Ltd.).
Manufactured by TSF483) (160 g, 0.024 mol) and chloroplatinic acid (0.004 g) are charged, and the temperature is raised to 90 ° C. and kept constant. 502 g (1.19 mol) of 1-triacontene mixture (Mitsubishi Kasei Co., Ltd., dialen 30).
What melt | dissolved 0.004 g of chloroplatinic acid was dripped while paying attention to heat generation. After completion of the dropping, the mixture was aged at the same temperature for 5 hours, and it was confirmed by IR that absorption of Si-H had disappeared, and the reaction was terminated to obtain a waxy compound.

Example 5 In a reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 200 g of methylhydrogen polysiloxane (TSF484 manufactured by Toshiba Silicone Co., Ltd.) (0.
066 mol) and 0.004 g of chloroplatinic acid,
The temperature is raised to ℃ and kept constant. A mixture of 1-dodecene and 1-tetradecene (manufactured by Mitsubishi Kasei Co., Ltd., dialen 12
4) 0.004 of chloroplatinic acid was added to 598 g (3.30 mol).
What melt | dissolved g was dripped, paying attention to heat generation. After completion of dropping, the mixture was aged at the same temperature for 5 hours, IR was confirmed to have absorbed Si-H, and the reaction was terminated to obtain a liquid compound.

Example 6 In a reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 160 g of methylhydrogen polysiloxane (TSF484 manufactured by Toshiba Silicone Co., Ltd.) (0.
053 mol) and 0.004 g of chloroplatinic acid were charged, and 90
The temperature is raised to ℃ and kept constant. 1-hexadecene, 1
-Octadecene mixture (Mitsubishi Kasei Co., Ltd., dialen 168) 610g (2.64mol) in chloroplatinic acid 0.0
What melt | dissolved 04g was dripped, paying attention to heat generation.
After completion of the dropping, the mixture was aged at the same temperature for 5 hours, and it was confirmed by IR that absorption of Si-H had disappeared, and the reaction was terminated to obtain a waxy compound.

Example 7 A reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer was charged with 120 g (0.1%) of methylhydrogen polysiloxane (manufactured by Toshiba Silicone Co., Ltd., TSF484).
(04 mol) and 0.004 g of chloroplatinic acid were charged, and the temperature was 90 ° C.
The temperature is raised to and kept constant. 1-octadecene, 1-
Eicosene mixture (Mitsubishi Kasei Co., Ltd., dialen 20)
8) chloroplatinic acid 0.004 in 632 g (1.98 mol)
What melt | dissolved g was dripped, paying attention to heat generation. After completion of the dropping, the mixture was aged at the same temperature for 5 hours, and it was confirmed by IR that the absorption of Si-H had disappeared, and the reaction was terminated to obtain a waxy compound.

Example 8 In a reactor equipped with a thermometer, a condenser, a dropping funnel and a stirrer, 90 g (0.0%) of methylhydrogen polysiloxane (manufactured by Toshiba Silicone Co., Ltd., TSF484).
3 mol) and 0.004 g of chloroplatinic acid are charged, and the temperature is raised to 90 ° C. and kept constant. To this, 624 g of 1-triacontene mixture (manufactured by Mitsubishi Kasei Co., Ltd., dialen 30)
What dissolved 0.004 g of chloroplatinic acid in (1.48 mol) was added dropwise while paying attention to heat generation. After completion of the dropping, the mixture was aged at the same temperature for 5 hours, and it was confirmed by IR that absorption of Si-H had disappeared, and the reaction was terminated to obtain a waxy compound.

Comparative Example 1 Ethylenebisstearamide was used as a conventional internal lubricant.

Comparative Example 2 As a conventional external lubricant, dimethylpolysiloxane (TSF453-1000 manufactured by Toshiba Silicone Co., Ltd.) was used.

The following evaluation tests were carried out in order to show the remarkable effects of the flame-retardant ABS resin composition of the present invention.

Injection Molding Test A flame-retardant ABS resin having the following composition, to which the lubricants of Examples 1 to 8 and Comparative Examples 1 and 2 were added as shown in Table 1, was injection-molded under the following conditions to obtain a mold. The releasability of was investigated. Flame Retardant ABS Resin Blend: ABS Resin (Monsanto Kasei Co., Ltd., Tflex TFX-110) 100 parts Flame Retardant (Brominated Epoxy Organoma Type, DIC Co., 20 parts Flatherm EP-16) Trioxide Antimony Part 5

Table 1 shows the test results of the releasability from the mold.

[Table 1]

[0026]

EFFECTS OF THE INVENTION The flame-retardant ABS resin composition of the present invention contains a specific silicone lubricant, so that a remarkable releasing effect is recognized as compared with conventional lubricants, and the efficiency of molding process can be improved. It was

Continuation of the front page (56) Reference JP-A-4-356514 (JP, A) JP-A-5-186650 (JP, A) JP-A-50-123754 (JP, A) JP-A-8-104814 (JP , A) Tokuheihei 50-502097 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 55/02 C08L 83/04

Claims (2)

(57) [Claims] 1. A flame-retardant ABS resin composition comprising a flame-retardant ABS resin and a silicone lubricant containing the following general formula [A] as a main component. In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms, and R ² represents an alkyl group having 6 to 60 carbon atoms, and each may be a single type or a plurality of types may be present. m is 0
Is an integer from 1 to 1000, and n is an integer from 1 to 1000. 2. The flame-retardant ABS resin composition according to claim 1, wherein 0.1 to 5 parts by weight of the lubricant is mixed with 100 parts by weight of the flame-retardant ABS resin.