JPH01182342A - Styrene based resin composition - Google Patents

Abstract

PURPOSE:To obtain a styrene based resin composition having excellent flame retardance, heat and impact resistance, by blending a brominated bisphenol A type epoxy polymer with bis(tribromophenoxy)ethane and antimony trioxide in a specific proportion. CONSTITUTION:A composition obtained by blending (A) 100 pts.wt. styrene based resin with (B) 8-20 pts.wt. brominated bisphenol A type epoxy polymer obtained by condensing, e.g., tetrabromobisphenol A with epichlorohydrin, and expressed by formula I [R' is H and/or methyl; n is 1-30; k and m are 1-4) terminal M is terminated by formula II or III (R<2> is 1-4C alkyl; X is Br or Cl; i is 0-4; j is 1-5); terminal N is terminated by formula IV or V], (C) 15-3 pts.wt. bis(tribromophenoxy)ethane and (D) 3-10 pts.wt. antimony trioxide so as to provide >15-<=25 pts.wt. total amount of the components (B) and (C).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a styrene resin composition, and more specifically, a styrenic resin composition that has excellent flame retardancy, as well as excellent heat resistance and impact resistance. relating to things.

[Prior Art and Problems to be Solved by the Invention] Styrenic resins have excellent processability and physical properties and are used in a variety of applications. Demand for flame retardancy is increasing in applications such as

To make the styrene resin flame retardant, halogen-containing epoxy resin, bis(tribromophenoxy)ethane, tetrabromobisphenol A (TBA), etc.
) and other halogenated flame retardants are added, as disclosed in Japanese Patent Application Laid-open No.
This is disclosed in Japanese Patent Publication No. 4737-4737, Japanese Patent Publication No. 44298-1982, Japanese Patent Application Laid-open No. 192761-1984, and the like.

However, the above-mentioned TBA has the disadvantage that when blended with a thermoplastic resin, the heat resistance is greatly reduced.
Also, when bis(tribromophenoxy)ethane is blended, there is a drawback that the heat resistance similarly decreases.

Therefore, in JP-A-60-192761, heat resistance is achieved by using a combination of a carbonate oligomer of halogenated bisphenol A with a high molecular weight and bis(tribromophenoxy)ethane.

Although attempts have been made to maintain a balance in impact resistance, etc., it has not been possible to obtain a styrenic resin composition having sufficient impact resistance, heat resistance, light resistance, etc. Also TBA and TBA
It is also possible to use a high molecular weight compound of
Although it is disclosed in Japanese Patent No. 54, a resin composition with sufficient performance could not be obtained even when applied to polystyrene.
- [Means for Solving the Problems] Therefore, the present inventors solved the above-mentioned problems of the prior art and developed a styrene-based resin composition that has excellent flame retardancy, heat resistance, and impact resistance. As a result, it was discovered that this objective could be achieved by combining two specific types of halogenated flame retardants and a flame retardant aid in a styrene resin at a certain ratio. It was completed based on knowledge.

That is, in the present invention, (a) 100 parts by weight of styrene resin, (b) 8 to 20 parts by weight of brominated bisphenol A type epoxy polymer, and (c) 15 to 3 parts by weight of bis(tribromophenoxy)ethane. and (d) 3 to 10 parts by weight of antimony trioxide, and the above (b) and (
The present invention provides a styrenic resin composition characterized in that the total amount of c) is more than 15 parts by weight and not more than 25 parts by weight.

In the resin composition of the present invention, the base polymer (
As the styrene resin of component a), various kinds of styrene resins that are generally widely known can be used, and among them, rubber-modified styrenic resins are preferably used. This rubber-modified styrenic resin is obtained by dissolving or mixing a rubbery elastomer with a monovinyl aromatic monomer and polymerizing it, and has a rubber content of 2 to 15-t.
%.

It is preferable to use one having a melt index (Ml) of about 2 to 12 g/10 minutes.

Examples of the monovinyl aromatic monomer include not only styrene alone but also a mixture of styrene and other vinyl monomers that can be copolymerized with styrene. Examples of vinyl monomers include methyl methacrylate, methyl acrylate, ethyl methacrylate, methacrylonitrile, halogen-containing vinyl heptamer 9α-methylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, and the like. can. These vinyl monomers are usually used in a proportion of 30-t% or less, preferably 10-t% or less of the total monomers.

Further, as the rubber-like elastic body, polybutadiene is particularly preferable, and other rubber-like elastic bodies containing acrylate and/or methacrylate, SBS resin, ASB resin,
AS resin and the like are also suitable.

The above polybutadiene is a low cis polybutadiene.

Any high cis polybutadiene may be used or a mixture may be used. In addition, examples of rubber-like elastic bodies containing acrylate and/or methacrylate include MAS resin,
MS resin, MABS resin.

Examples include MBS resin.

In the resin composition of the present invention, it is necessary to blend a brominated bisphenol A type epoxy polymer as the component (b) with the above-mentioned styrene resin as the component (a).

This brominated bisphenol A type epoxy polymer acts as a flame retardant and has the following structure.

(In the formula, R1 represents hydrogen and/or a methyl group, and n is 1
an integer of ~30, and m represents an integer of 1 to 4), and its terminal M is terminated with.

Also, the terminal N is or, has been stopped.

(In the formula, R2 represents an alkyl group having 1 to 4 carbon atoms, X represents Br or Cl, i represents an integer of 0 to 4, and j represents an integer of 1 to 5.) Such brominated bisphenol A type Epoxy polymer (
Oligomers or polymers) have a bromine content of 20% by weight.
The above are preferred. In addition, this brominated bisphenol A type epoxy polymer can be produced by various methods, such as a method of producing by condensation of TBA and epichlorohydrin, a method of producing by reacting diglycidyl ether of TBA and TBA. and so on.

Alternatively, the brominated bisphenol A type epoxy polymer obtained as described above is further heated to react with halogenated phenol such as tribromophenol, trichlorophenol, dibromocresol, dichlorocresol, etc. in the presence of a basic catalyst or the like. What you get is also valid. In the present invention, such a polymer is also referred to as a brominated bisphenol A type epoxy polymer.

In addition, as this brominated bisphenol A type epoxy polymer, a commercially available one can also be used, for example, a product name: EC-20, EC- manufactured by Dainippon Ink Chemical Industry ■
Product name manufactured by 36 and Matsunaga Chemical ■: EBR700, EBR7
34 etc. can also be used.

In the resin composition of the present invention, the blending amount of the brominated bisphenol A type epoxy polymer, which is the component (b), is as described above (
8 to 2 parts per 100 parts by weight of the styrene resin of component a)
0 parts by weight, preferably 10 to 15 parts by weight. If it is less than 8 parts by weight, the heat resistance of the resulting resin composition will decrease,
If it exceeds 0 parts by weight, impact resistance will decrease, which is not preferable.

In addition, in the resin composition of the present invention, bis(tribromophenoxy)ethane is blended as the component (c), but this also has the same difficulty as the brominated bisphenol A type epoxy polymer, which is the component (b). It acts as a fuel. This screw (tripro.

Normally, commercially available moff'enoxy)ethane may be used, such as FF680 manufactured by Great Lakes Co., Ltd.
(product name) etc. are used. The blending amount of this bis(tribromophenoxy)ethane is 15 to 3 parts by weight based on 100 parts by weight of the styrene resin which is the component (a).
Preferably it is 13 to 7 parts by weight. If the amount exceeds 15 parts by weight, the heat resistance of the resulting composition will decrease, and if it is less than 7 parts by weight, the impact resistance will decrease.

Furthermore, in the present invention, the total amount of the brominated bisphenol A type epoxy polymer as the component (b) and (tribromophenoxy)ethane as the component (c) is in the range of more than 15 parts by weight and not more than 25 parts by weight. It is necessary to adjust so that If the total amount is less than 15 parts by weight, sufficient flame retardancy will not be obtained, and if it exceeds 25 parts by weight, mechanical properties such as impact resistance will be significantly reduced.

Furthermore, antimony dioxide, which is the component (d) of the resin composition of the present invention, acts as a flame retardant auxiliary agent, and usually a commercially available product may be used. -3 etc. are used. The blending amount of antimony trioxide is 100% of the styrene resin of component (a).
The amount is 1 to 10 parts by weight, preferably 3 to 7 parts by weight. If it is less than 1 part by weight, flame retardancy cannot be imparted to the resulting glued composition, and if it exceeds 10 parts by weight, the impact resistance will be significantly reduced, which is not preferable.

□ The resin composition of the present invention can be obtained by dispensing a predetermined amount of each of these components, and the production method may be according to a conventional method. For example, each component (a) to (d) may be premixed using a mixer such as a Henschel mixer, tumbler blender, or Nigu, and then kneaded using an extruder, or melt-kneaded using a heated roll or Banbury mixer. Manufactured by. At this time, colorants and plasticizers may be added as necessary.

Appropriate amounts of stabilizers, ultraviolet absorbers, mold release agents, inorganic fillers, etc. can also be blended.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Synthesis example (preparation of brominated bisphenol A type epoxy polymer) Brominated bisphenol A type epoxy polymer (111154% per epoxy, bromine content 51 wt%, general formula (1)
) with n of 2.7) and 331 g (1 mol) of tribromophenol were placed in a reaction vessel of 22, and after purging the inside with nitrogen, the contents were heated and melted to -140 0.4 g of tri-n-butylamine was added with stirring.

After reacting at 160-180° C. for 10 hours, the reaction product was cooled and ground to obtain a pale yellow powder.

The softening point of this product is 144°C and the bromine content is 55.1
%, n in general formula (1) was 2.7 (average degree of polymerization).

Examples 1 to 5 and Comparative Examples 1 to 6 Polybutadiene-modified polystyrene (rubber content 9 wt%
, M12g/10min) to 100 parts by weight of the brominated bisphenol A type epoxy polymer (having a tribromophenoxy group at the end) obtained in the above synthesis example, bis(tribromophenoxy)ethane, and trioxide. Mix the prescribed amount of antimony in the proportion shown in the table and add it to the super floater.
(manufactured by Yoda Seisakusho) for preliminary blending. Thereafter, the mixture was melt-kneaded using a single-screw extruder (cylinder temperature set at 210° C.) and injection molded to prepare a test piece.

Using this test piece, Izod impact strength, heat distortion temperature, and flammability to determine flame retardance were measured. The results are shown in the table.

Examples 6 to 8 Pratherm (registered trademark) EC- manufactured by Dainippon Ink and Chemicals Co., Ltd. as a brominated bisphenol A type epoxy polymer
A test piece was prepared in the same manner as in the above example except that No. 36 was used, and its various physical properties were measured. The results are shown in the table.

(The following is a blank space) [Effects of the invention] Like soft clay, the resin composition of the present invention is a combination of styrene resin and two specific flame retardants, as well as antimony trioxide in a specific ratio. Because it is a thing,
It has excellent flame retardancy, as well as heat resistance, impact resistance,
Furthermore, it has excellent weather resistance.

Therefore, the resin composition of the present invention is expected to be particularly useful as a product material in fields where flame retardancy is required, specifically in fields such as electricity, electronics, and vehicles.

Claims (1)

[Claims] (1) (a) For 100 parts by weight of styrene resin, (
b) Brominated bisphenol A type epoxy polymer 8-20
Parts by weight, (c) bis(tribromophenoxy)ethane 1
5 to 3 parts by weight and (d) 3 to 10 parts by weight of antimony trioxide, and the total amount of (b) and (c) is more than 15 parts by weight and not more than 25 parts by weight. A styrenic resin composition.