JPH0741621A - Flame-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition comprising a brominated bisphenol A type epoxy polymer and a styrene-butadiene block copolymer, capable of reducing the amount of a flame retardant, and improved in flame retardance and dripping. CONSTITUTION:The objective composition comprises (A) 100 pts.wt. of a styrenic resin, (B) 15-40 pts.wt. of a brominated bisphenol A type epoxy resin, (C) 2-10 pts.wt. of antimony trioxide, and (D) 2-15 pts.wt. of styrene-butadiene block copolymer. Examples of preferable component B include an epoxy resin having a structure of formula I (R1 is H, methyl; n is 1-30; k, m are 1-4; the end M is terminated with a group of formula II, etc.), etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin which is excellent in light resistance, heat resistance and impact resistance, and is used as a molding material for various molded products which require flame retardancy, such as home electric appliances and OA equipment. It relates to a composition.

[0002]

2. Description of the Related Art Styrenic resins are used in various applications because of their excellent workability and physical properties. Further, in recent years, the demand for flame retardancy of molded products mainly for electrical insulation applications has become stricter, and by adding a large amount of flame retardant, the demand of the market is met.
With respect to electric equipment parts, particularly housings, there is an increasing demand for improvement in light resistance and impact resistance in addition to flame retardancy. BACKGROUND ART Conventionally, a technique has been proposed in which a brominated bisphenol A type epoxy polymer is added to a styrene resin to impart flame retardancy. However, this composition is prone to dripping during combustion and its flame retardancy is unstable, and when a large amount of flame retardant is added, its impact resistance is lowered.

[0003]

Addition of a flame retardant of a brominated bisphenol A type epoxy polymer in order to impart flame retardancy to a styrene resin is sufficient in terms of flame retardancy, especially dripping. It is difficult to satisfy the above requirement, and a large amount of flame retardant must be blended, so that mechanical strength such as impact resistance decreases. However, the present invention can reduce the addition amount of the flame retardant, is not only excellent in mechanical strength such as impact resistance and light resistance, but also has good heat resistance and moldability (fluidity). It is also intended to obtain a composition which is excellent in flame retardancy and especially improved in dripping.

[0004]

The present invention comprises (a) 100 parts by weight of a styrene resin, (b) 15 to 40 parts by weight of a brominated bisphenol A type epoxy polymer, and (c) antimony trioxide 2. -10 parts by weight and (d) a block copolymer of styrene and butadiene 2 to 15 parts by weight of the flame-retardant resin composition.

The styrene resin which is the component (a) of the present invention is a homopolymer or copolymer of styrene or a styrene derivative such as α-methylstyrene or vinyltoluene, or a monomer thereof and acrylonitrile or methylmethacrylate. A copolymer obtained by graft-polymerizing a copolymer with a vinyl monomer such as a rate, a diene rubber such as polybutadiene, an ethylene / propylene rubber, an acrylic rubber or the like with styrene or a styrene derivative and another vinyl monomer. , Polystyrene, high-impact polystyrene, AS resin, ABS resin, AAS resin, AES resin and the like.

The brominated bisphenol A type epoxy polymer which is the component (b) of the present invention acts as a flame retardant and has the following structure.

[0007]

[Chemical 1] (In the formula, R1 represents hydrogen and / or a methyl group, and n = 1.
The integer of -30, k and m show the integer of 1-4. )
Also, the terminal M is

[Chemical 2] Has been stopped at.

Also, the terminal N is

[Chemical 3] Alternatively,

[Chemical 4] Has been stopped at.

(Wherein, R2 is an alkyl group having 1 to 4 carbon atoms, X is Br or Cl, i is an integer of 0 to 4, and j is
Represents an integer of 1 to 5. ) Such brominated bisphenol A type epoxy polymers (oligomers and polymers)
Preferably has a bromine content of 20% by weight or more. The brominated bisphenol A type epoxy polymer is
It can be produced by various methods, for example, a method of producing by condensation of brominated bisphenol A and epichlorohydrin, a reaction of diglycidyl ether of brominated bisphenol A and brominated bisphenol A. There are ways to do it. Alternatively, in addition to the brominated bisphenol A type epoxy polymer obtained as described above,
Those obtained by heating a halogenated phenol such as tribromophenol, trichlorophenol, dibromocresol and dichlorocresol in the presence of a basic catalyst and the like are also effective. In the present invention, such a thing is also called a brominated bisphenol A type epoxy polymer. The antimony trioxide which is the component (c) of the present invention is
Generally, it acts as a flame retardant aid and has an average particle size of 1 to 150 μm.

Styrene (S) which is the component (d) of the present invention
And a block copolymer of butadiene (B) are usually produced by block copolymerization by a method of anionic living polymerization, and have a total styrene content of 20 to 60% by weight and a total butadiene content of 80 to 40% by weight. It is a thing. The block copolymer is composed of styrene and butadiene. The block structure is optionally obtained by adding styrene or butadiene alone or a mixture thereof in a predetermined ratio to a polymerization system in a predetermined order. The structure of the block copolymer is S (B
-S) n (where n = 1 to 3) type is desirable.

In the resin composition of the present invention, the amount of the brominated bisphenol A type epoxy polymer as the component (b) is 15 to 40 parts by weight based on 100 parts by weight of the styrene resin as the component (a). Parts, preferably 20 to 30 parts by weight. If the blending amount of the brominated bisphenol A type epoxy polymer is less than 15 parts by weight, sufficient flame retardancy cannot be exhibited. On the other hand, if it exceeds 40 parts by weight, there is a problem in impact resistance. The compounding amount of the antimony trioxide as the component (c) is 2 with respect to 100 parts by weight of the styrene resin as the component (a).
-10 parts by weight, preferably 4-7 parts by weight are used. If the blending amount of antimony trioxide is less than 2 parts by weight, sufficient flame retardancy cannot be exhibited. On the other hand, if it exceeds 10 parts by weight, there is a problem in impact resistance. The compounding amount of the block copolymer of styrene and butadiene which is the component (d) is the same as in the above (a).
The amount is 2 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the styrene resin as a component. If the amount of the block copolymer of styrene and butadiene is less than 2 parts by weight, the impact resistance cannot be improved, and the dripping prevention effect cannot be fully exerted, resulting in a problem of flame retardancy. is there. On the other hand, if it exceeds 15 parts by weight, impact resistance can be greatly improved, but light resistance is deteriorated, and problems occur in flame retardancy unless the amount of flame retardant added is increased. The resin composition of the present invention can be obtained by blending these components in predetermined amounts, and the production method may be according to a conventional method. For example, the components (a) to (d) are pre-mixed by a mixer such as a Henschel mixer, a tumbler blender, or a kneader, and then kneaded by an extruder, or by melt kneading by a heating roll or a Banbury mixer. To manufacture. At this time, various additives which are generally blended with the styrene resin as required, for example, fillers, lubricants, reinforcing agents, stabilizers, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, A hue improver or the like may be added.

[0012]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

The flame-retardant styrene resin compositions of the following examples and comparative examples were evaluated in the following manner.

(1) Impact Strength The impact strength was measured using a notched Izod impact strength as a scale and in accordance with ASTM D256 using a 1/4 inch thick test piece.

(2) Fluidity As a fluidity evaluation scale, the melt flow rate was evaluated according to JIS K7210.

(3) Light discoloration resistance As an evaluation scale of light discoloration resistance, an Atlas kissenon weather ometer (Ci35A manufactured by Atlas Co., no rain) was used, and a test piece (natural color) was used for 100 hours at a black panel temperature of 63 ° C. After UV irradiation, the color difference (ΔE) from the unirradiated test piece was measured by a color difference meter (Nippon Denshoku Industries Co., Ltd. Σ
The color was measured in 80). The smaller the color difference (ΔE) is, the more excellent the light discoloration resistance is. The light discoloration resistance is determined according to the following criteria. ◯: ΔE ≦ 5 ×: ΔE> 5 XX: ΔE> 15 (4) Flame retardance As a flame retardancy evaluation scale, a thickness of 1 was obtained in accordance with the vertical flammability test stipulated in UL94 of the US UL standard. .67m
m test pieces were evaluated.

Examples 1 and 2 Daicel Styrol S85 (manufactured by Daicel Chemical Co., Ltd., high impact polystyrene) was used as a styrene resin.
As a block copolymer of styrene and butadiene, JS
RTR2000 (styrene-butadiene thermoplastic elastomer manufactured by Nippon Synthetic Rubber Co., Ltd.) was used. As the brominated bisphenol A type epoxy polymer, Platherm EP16 (flame retardant manufactured by Dainippon Ink and Chemicals, Inc.) is used, and as antimony trioxide, ANTIMONY BLOOM 5 is used.
00A (manufactured by Dowa Mining Co., Ltd.) was mixed in a tumbler blender in the combinations and ratios shown in Table 1, and then melt-kneaded by an extruder to obtain a pellet-shaped resin composition. Next, injection molding machine (cylinder temperature 220 ℃, mold temperature 5
A test piece for general physical properties was prepared at 0 ° C., and the physical properties were measured according to standard methods. The results are shown in Table 1.

Comparative Examples 1 to 6 The styrene resin, the block copolymer of styrene and butadiene, the brominated bisphenol A type epoxy polymer, and antimony trioxide were the same as those in Examples 1 and 2, and
Decabromodiphenyl ether (DBDP as flame retardant
As E), DE-83 (flame retardant manufactured by Great Lakes Co., Ltd.) is used in a tumbler blender in a combination and a ratio as shown in Table 1 and then melt-kneaded in an extruder to obtain a pelletized resin composition. Got Next, a test piece for general physical properties was prepared with an injection molding machine (cylinder temperature 220 ° C., mold temperature 50 ° C.), and physical properties were measured according to standard methods. The results are also shown in Table 1.

[0019]

[Table 1]

[0020]

That is, by combining a brominated bisphenol A type epoxy polymer with a block copolymer of styrene and butadiene, the amount of the flame retardant added can be reduced and a resin composition with well-balanced physical properties can be obtained. be able to. It also improves flame retardancy, especially dripping.

The resin composition obtained by the present invention is not only excellent in flame retardancy and impact resistance, but also exhibits the following effects (features).

1) Good moldability (flowability).

2) Excellent light resistance and little discoloration.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 63:00 53:02)

Claims (1)

[Claims] 1. (a) 100 parts by weight of styrene resin (b) brominated bisphenol A type epoxy polymer 15
-40 parts by weight (c) Antimony trioxide 2-10 parts by weight (d) Block copolymer of styrene and butadiene 2
A flame-retardant resin composition containing 15 parts by weight.