JPS5865741A - Nonflammable resin composition - Google Patents

Abstract

PURPOSE:To provide a conflammable resin compsn. of favorable balance between mechanical properties and heat resistance, by mixing a halogenated diphenyl ether, a halogenated bisphenol polycarbonate oligomer, and Sb2O3, with a PS resin. CONSTITUTION:5-20pts.wt. one or more halogenated diphenyl ethers (A) (e.g. decabromodiphenyl ether), 1-15pts.wt. one or more halogenated bisphenol polycarbonate oligomers (B) (e.g. compds. of formulasI, II, or III), and 1-20pts.wt. Sb2O3 (C) are mixed together in the proportion such that the total amt. of compds. A and B is 6-35pts.wt., yielding a nonflammable PS resin compsn. The decrease in the amt. of compd. A having a high m.p. and unfavorable dispersibility and the use of compd. B together with A cause the dispersibility of both A and B to be improved synergistically. The combination has much more improved nonflammability, heat resistance, and mechanical properties than the case of each separate application.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant polystyrene resin composition with excellent mechanical properties and heat resistance buffing.

In recent years, the development of various office equipment has been remarkable, as is being called the office automation revolution. Most of these office equipment are electrical equipment with built-in live parts, and are subject to various regulations, such as self-extinguishing properties and prevention of dripping of decomposed molten material, etc. Due to usage conditions, the main body of the device and its surroundings are exposed to high temperatures, and heat resistance to the extent that the device does not collapse even under such conditions is now required.

Polystyrene resins such as polystyrene and AB8 resin are widely used for the above-mentioned purposes, and various means for making them flammable have been studied. Among them, it can impart relatively high flame retardancy to polystyrene resin,
As a flame retardant having heat resistance, (1) halogenated diphenyl ether compounds such as decaglom diphenyl μate A/(DBIC) (Japanese Patent Publication No. 32898/1989);
and (2) low-molecular-weight brominated polycarbonate (Japanese Patent Publication No. 56-25955) are known. However, the flame retardant in (1) above has a melting point of 500 to 515°C.
extremely high (poor dispersibility in polystyrene-based mM,
The mechanical properties and appearance of the molded product will be significantly impaired, so it is necessary to use a fairly high surface temperature during melt mixing. Although the flame retardant (2) has good heat resistance, it still has problems with its dispersibility in resins, and not only can it not be expected to have sufficient mechanical properties.
It has a fatal defect in that it sticks to one part of the mold during molding, degrading the surface appearance of the molded product.

Therefore, the present inventors investigated with the aim of obtaining a polystyrene-based resin composition with a high degree of flame retardancy, as well as excellent mechanical properties and heat resistance. The inventors have discovered that by blending both halogenated bisphenol type polycarbonate oligomers in a specific ratio, the drawbacks of both flame retardants can be mutually improved and the above object can be effectively achieved, and the present invention has been achieved.

That is, the present invention uses one part of 100 liters of polystyrene resin, (A) at least one type of halogenated diphenyl ether, (B) at least one type of halogenated bisphenol type polycarbonate oligomer, and (cl antimony dioxide). ) is 5 to 20 layers, (B) is 1 to 1
According to the present invention, which is characterized in that it is blended in a ratio of 5-fold part 1 and (C1 is 1 to b lid part), [Al halogenated diphenyl μ ether (TB)
By using a halogenated bisphenol-type polycarbonate oligomer in combination, the dispersibility of both (B) and (B) is synergistically improved, which is far more improved than when (A) and (B) are used individually. The polystyrene resin used in the present invention is a polymer containing an aromatic vinyl compound as a main component, such as polystyrene, etc.・・α-Methyl 7-V ・7-V′-acrylonitrile copolymer, styrene-methyl methacrylate co-summer polymer, styrene-acrylonitrile p-methacrylate
Examples include acid-methyl-μ copolymerized polymers and rubber-modified resins in which these hard resins are physically bonded to rubber components.

The rubber-modified resin referred to here is a two-layer or three-layer resin in which the above-mentioned hard resin is bonded to a rubber component such as polybutadiene, styrene-butadiene rubber, acrylonitrile loosetadiene rubber, acrylic rubber, ethylene-globulinage, and en-rubber. A specific example is acrylonitrium μ
m-butadiene-styrene copolymer (AB8 Tochiko), acrylonitrile p-getadiene-styrene-a-methylstyrene copolymer, acrylonitrile-methacrylic acid p
-Butadiene-styrene copolymer, acrylonitrium μm
Examples include acrylic rubber-styrene co-electrolyte and acrylonitri-fi/-ethylene rubber-styrene copolymer.

These polystyrene resins are produced by conventional suspension polymerization methods, bulk polymerization methods, emulsion polymerization methods, bulk-suspension polymerization methods, and the like.

The (mu)halogenated diphenyl ether used in the present invention is a compound represented by the following general formula (I).

However, in the above intermediate formation, X is cl or Bre and f
each represents an integer from 2 to 5.

Examples of the compound represented by the above general formula (1) include pentabromodiphenyl ether, octabromodiphenyl ether, and octabromodiphenyl ether! Examples include ether, decabromodiphenyl ether, etc. Among them, decabromodiphenyl ether IL/(DDE
) is recommended.

The amount of halogenated diphenyl μ added is 1 part for polystyrene resin.
5 to 20 parts by weight, preferably 6 to 1 parts by weight per 00 parts by weight
It has a 5-layer lid. If it is less than 5 parts by weight, a sufficient flame retardant effect cannot be obtained, and if it exceeds 20 parts by weight, poor dispersion occurs and sufficient mechanical properties and heat resistance cannot be obtained, which is not preferable.

Further, (B) halogenated bispheno-)V used in the present invention
The type polycarbonate oligomer is a compound represented by the following general formula or (2).

However, in the above (1) or formula 1, X is cl or Br, R is cl, 6 alkyl μ group, carbonyl group, -〇-1-s-1-so, -1g is 1 to 4, h is 1 to 5 k
is the number i, l indicates that there are mXm in repeating units 1 to 5o, and m and n indicate extra numbers satisfying 11.75<<L199 and ≦m + n <50. Here, Mm is a repeating unit xg xg.

-6-n i5-oc-mit, M n G!
The weight of the repeating unit -o-Q-R0-0-C- is shown respectively.

The halogenated bisphenol type polycarbonate oligomer represented by the above general formula (1) or I) is produced by reacting a halogenated bispheno-p compound with phosgene and/or a halogenated bisphenol compound, a bisphenol compound, a halogenated phenol compound, and phosgene. This is the compound obtained.

The amount of the halogenated bisphenol type polycarbonate oligomer represented by the above general formula (1) or I is 1 to 15 coulometric parts per 100 coulometric parts of the polystyrene resin;
Preferably, the amount is from 2 to 12 parts by weight; if it is less than 1 part by weight, the desired effect cannot be obtained, and if it is more than 15 parts by weight, not only will the mechanical properties deteriorate, but the surface appearance of the molded product will be 1l11*. This is not desirable because it causes

In addition, the total blending amount of the above fc*fuel agent fA) and (B) is 6 to 35 parts by weight, especially 10 to 25 parts by weight, based on 100 parts by weight of polystyrene resin, for electrical equipment, and 6 parts or less. If the amount is 35 parts or more, the mechanical properties and heat resistance of the polystyrene resin will be impaired, which is not preferable.

The flame retardant effect when the above flame retardant Nl (A) and (B) are used together can be further enhanced by using antimony trioxide in combination. The amount added is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of the polystyrene resin; if it is less than 1 part by weight, the flame retardance is insufficient, and if it is more than 20 parts by weight, the polystyrene resin This is undesirable because the mechanical properties of the material are impaired. At the same time, other flame retardant aids such as boron oxide, zirconium oxide, iron oxide, etc. may be used in combination.

A flame-retardant polystyrene resin composition containing a primary flame retardant and antimony trioxide has sufficient flame retardancy3, but if necessary, chlorinated polyethylene may be further added to prevent combustion. 08A (OANAD AN8T, ANDA, RD8.
A380qIATION) The specified performance can be improved.

Further, the heat resistance, particularly the thermochromic property, of the flame-retardant polystyrene resin composition of the present invention is improved by adding a stabilizer. These stabilizers include phosphorus compounds such as trisnoniμphosphite and sialkylaryl phosphite;
Sulfur-containing compounds such as hindered phenol compounds, thioethers, mercaptobenzimidazoles, and thiodipropionic acid esters, and tin-based compounds such as tin malate, tin laurate, and digtyltin monooxide can be used. The amount of these stabilizers added is 0.01 to 2 parts by weight per 100 parts by weight of the polystyrene resin.

In order to further improve the heat resistance and rigidity of the composition of the present invention, fibrous substances such as glass fiber, asbestos, calcium metasilicate, potassium titanate, and ceramic tweiber can be added, and the amounts of these additions are limited. Usually, the amount is in the range of 5 to 70 parts by weight based on 10G of polystyrene thread resin. In addition, fillers such as glass peas, lipolyme, calcium urate, aluminum oxide, etc. can also be added in the same manner.

Furthermore, in order to improve the moldability of the composition of the present invention, stearin t
II! W (calcium, barium, aluminum, lithium), silicone oil 1 monoclic acid wax (ester, Hafester 1 salt), stearate ester,
A lubricant such as ethylene bis-stearylamide can be blended. The amount of these additions is usually Llas~! for 100 layers of polystyrene resin. This is lLO subfilament.

Additionally, dyes, pigments, plasticizers,
Known FS additives such as ultraviolet absorbers and foaming agents can be added.

The method for producing the composition of the present invention is not particularly limited. (For example, polystyrene resin, flame retardant (A), extrusion with or without premixing of polystyrene resin, flame retardant (A), and antimony trioxide. It is prepared by feeding it into a machine and melting and mixing it.

The polystyrene resin composition of the present invention thus obtained has a high degree of flame retardancy as well as excellent heat resistance and mechanical properties, and is useful for various uses such as office equipment and electrical equipment.

The present invention will be explained in detail below using examples.

Note that all percentages and parts in the examples are based on weight.

Examples 1 to 15 and Comparative Examples 1 to 4 Acryloni) μm butadiene-styrene copolymer resin 1
1 TOYOWOTSUKU U1GO (general-purpose ABS resin manufactured by Toshiku Co., Ltd.) 100 parts by weight, flame retardant (A) D B E% flame release agent (B) CB-1) and (B-2) shown by the following structural formula. ) and antimony trioxide in the proportions shown in Table 1 were mixed in a ribbon blender, and further mixed in a 40φ baking sheet.
The mixture was melt-kneaded and pelletized at 250°C using an extruder equipped with a vent. In each of the Idi products, one amount of Djibouti μ brown difurate was added as a heat stabilizer. Next, using this pellet, a combustion test piece (U
1/8” x 1/2” x 5” for L and 1/16” x 1/2” x 5” rod and CS” 1 for A.
/8″
2"X1/2)'X2.1/2" bars] and heat deformation test pieces (172"XI'/2"X5") were molded.

Combustion test is UL-95 and C8A 022.2 A1
The test was carried out according to the method specified in 451. In addition, the cylinder impact strength is A8TM D-256, and the heat distortion temperature is ASTM D-6.
48.

These results are shown in Table 1.

Table 1 also shows a comparative example in which flame retardant (Al or (B) was used alone).

As is clear from Table 1, flame retardant (A) and (Bl)
1. The composition of the present invention comprises flame retardants (A) and (B).
Compared to the case where each is used alone, excellent flame retardance can be obtained with a small amount of addition, and the balance between impact resistance and heat resistance is also excellent.

Example 16 The same test F as in Example 6 was carried out by adding 5 parts of chlorinated polyethylene (trade name: Dysolac G-255) to the same formulation as in Example 6. However, the flammability is UL
-94,1/8"V-0,1'/16"v-o, CBA
A composition with improved mechanical properties of I/8" OK, impact strength of 20 kg-ffi, heat distortion temperature of 83 DEG C., and excellent external line properties was obtained.

Claims (1)

[Claims] For the polystyrene resin 100-layer base, (A) at least one type of halogenated bisphenol type polycarbonate oligomer and (10) antimony trioxide with a small amount of IAI halogenated diphenylene
is 5 to 20 parts by weight, (B) is 1 to 15 parts by weight, TO) is 1 to 20 parts by weight, and the total lid of (A) and (B) is 6 to 3 parts by weight.
A flame-retardant resin composition characterized in that it is blended in a ratio of 5 parts.