JPH04136060A - Flame-retarding styrene resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in light resistance, heat resistance and impact resistance by mixing a styrene resin comprising an ABS resin and an AS resin with an ether derivative of a halogenated aromatic diol. CONSTITUTION:A resin composition prepared by mixing 100 pts.wt. styrene resin comprising 10-90wt.% ABS resin (acrylonitrile/styrene copolymer) of a degree of grafting of 50% or above and 90-10wt.% AS resin (acrylonitrile/styrene copolymer) of an acrylonitrile content of 23% or above and a weight-average molecular weight of 80000 or above and 1-50wt.% ether derivative of a halogenated aromatic diol of the formula, having a weight-average molecular weight of 20000-100000. This composition is highly flame-retarding, ranks among the V-O materials in the UL standards when it is tested in a thickness of 1/16 inch and has impact resistance and excellent light resistance, so that is very useful as a housing material for OA machines, business machines, household electric appliances, etc.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a flame-retardant styrenic resin composite acid containing an ether derivative of a halogen-containing aromatic diol, and more particularly, to This relates to a flame-retardant styrene resin composition with excellent impact resistance, and is suitable for use in OA equipment,
It provides materials suitable for use in office equipment, enclosures, etc.

[Prior art and problems to be solved by the invention] Styrenic resin has excellent moldability and well-balanced mechanical properties, so it has been used as a housing material for home appliances, OA equipment, office equipment, etc. It is used.

However, in order to comply with the UL standard in the United States and the C3A standard in Canada, it is necessary to make the material flame retardant, and the method of doing so is to add organic and inorganic flame retardants.

Phosphorous compounds and halogen compounds are used as organic flame retardants, and antimony oxides are used as inorganic flame retardants.

Among these, halogen compounds are effective as flame retardants for styrene resins, and among them, from the viewpoint of physical properties and flame retardancy, tetrabromo bisphenol A, decabromodiphenyl ether, octabromodiphenyl ether, carbonate oligomers of tetrabromo bisphenol A, Bistribromophenoxyethane and the like are well known and are used depending on the purpose.

In recent years, with the development of industries such as OA equipment and office equipment, there has been a strong demand for housing materials to have heat deformation resistance and light discoloration resistance in addition to flame retardancy and mechanical properties. However, when conventionally used tetrabromobisphenol A is used as a flame retardant, the thermal stability and heat resistance of styrenic resins are significantly reduced, so there is a limit to its use as a heat-resistant grade, and its light resistance also decreases. Therefore, in order to improve the light resistance, it is necessary to add light stabilizers, ultraviolet absorbers, etc., which leads to significant cost increases and defects in mechanical properties and flame retardance. Ta.

When decabromodiphenyl ether is used as a flame retardant, the heat resistance and mechanical properties of styrenic resins are good, but the light resistance is extremely poor, and colored products that are exposed to ultraviolet rays are only colored black because of discoloration. It was used only as a material.

In the case of styrenic resins using octabromodiphenyl ether as a flame retardant, like decabromodiphenyl ether, the light resistance was extremely poor, and there was a problem that the flame retardant plated out in the mold during molding.

In the case of styrenic resins using bistribromophenoxyethane as a flame retardant, the light resistance is good, but the heat resistance of the resin is low, and there is also the problem that the flame retardant bleeds out on the surface of the molded product.

When a carbonate oligomer of tetrabromobisphenol A is used as a flame retardant, the heat resistance, mechanical properties, and light resistance of the styrenic resin are good, but due to poor thermal stability, it may cause flashes and flashes on the surface of the molded product during the molding process. The problem was that the failure rate due to flash and silver could not be completely eliminated even if molding manufacturers carefully controlled the conditions.

The present inventors discovered an ether derivative of a halogen-containing aromatic diol as a flame retardant that can solve the problems of the various flame retardants mentioned above, and as a result of blending evaluation with ABS resin, properties other than impact resistance and combustion level were found to be Although a satisfactory composition could be obtained, the impact resistance, which is an important characteristic of an enclosure, was low and at a level that could not be used in practical use.
Or it was difficult to reach the combustion level required for the enclosure.

[Means to solve the problem]

In view of this situation, the present inventor has developed flame retardancy, mechanical properties (impact resistance), heat resistance, heat creep resistance, light resistance,
It has excellent heat stability and no flash during molding.
The present invention was achieved as a result of intensive research aimed at providing a flame-retardant styrenic resin composition that is free from problems such as silver and the adhesion of flame retardants to the surfaces of molds and molded products. It is something.

That is, the present invention provides an ABS resin with a graft ratio of 50% or more (
a styrenic resin consisting of 10 to 90% by weight of an acrylonitrile-butadiene-styrene terpolymer) and 90 to 10% by weight of an AS resin (acrylonitrile-styrene copolymer) containing 23% or more of acrylonitrile and a weight average molecular weight of 80,000 or more; Or 100% by weight of BS resin with a graft ratio of 50% or more and a weight average molecular weight of 90,000 or more.
For 100 parts by weight of a styrenic resin consisting of
1 to 50 parts by weight of an ether derivative of a halogen-containing aromatic diol of 00, or 1 to 50 parts by weight of an ether derivative of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 1000 to 9000, Or it is represented by the following formula (I) and has a weight average molecular weight of 20,000 to 10
1 to 99% by weight of an ether derivative of a halogen-containing aromatic diol having a weight average molecular weight of 1000 to 9000 and 99 to 1% by weight of an ether derivative of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 1000 to 9000. This invention relates to a flame-retardant styrenic resin composition containing 1 to 50 parts by weight of an ether derivative of an aromatic diol.

CL 0H CH.

H is chlorine, J is an integer from 0 to 5).
or a different group, X is bromine or chlorine, i is 1-
An integer of 4, m is a natural number. ) Hereinafter, the present invention will be explained in detail.

The styrenic resin used in the present invention is a mixture of 10-90% by weight of ABS resin with a graft ratio of 50% or more and 90-10% by weight of AS resin with 23% or more acrylonitrile and a weight average molecular weight of 80,000 or more; Alternatively, it is made solely of ABS resin having a graft ratio of 50% or more and a weight average molecular weight of 90,000 or more. In the former styrenic resin, if the grafting rate of ABS (+) resin is less than 50%, the acrylonitrile content of AS resin is less than 23%, or the weight average molecular weight is less than 80,000, the resistance of the composition containing the flame retardant will decrease. Impact resistance decreases, making it difficult to use practically. In addition, in the latter styrene resin, if the grafting rate of the ABS resin is less than 50% or the weight average molecular weight is less than 90,000, the impact resistance of the composition containing the flame retardant will decrease, making it difficult to use it practically. It's tough. In the former styrene resin, especially ABS resin with a graft ratio of 70% or more, acrylonitrile of 27% or more and a weight average molecular weight of 1000
It is preferable to mix an AS resin of 00 or more. Also,
In the latter styrenic resin, the graft ratio is particularly high.
ABS resin having a weight average molecular weight of 0% or more and a weight average molecular weight of 90,000 or more is preferable.

Acrylonitrile-α-methylstyrene copolymer, acrylonitrile-butadiene-α-methylstyrene terpolymer, etc. may be added to the styrene resin used in the present invention, or two types may be mixed as necessary. May be used.

The ether derivative of the halogen-containing aromatic diol used in the present invention is represented by the above formula (+) and has a weight average molecular weight of 1,000 to 9,000, or a weight average molecular weight of 20,000 to 100,000. Weight average molecular weight is 20,000 to 1oooo
1 to 99% by weight of o.

It is a mixture consisting of 99 to 1% by weight of those having an average molecular weight of 1,000 to 9,000, and if the weight average molecular weight is more than 9,000 and less than 20,000, the impact resistance of the composition is significantly reduced. In addition, ether derivatives with a weight average molecular weight exceeding 100,000 or ether derivatives with a weight average molecular weight of less than too much will significantly reduce the heat resistance and thermal stability of molded products, and will also provide sufficient flame retardance in thin-walled molded products. It cannot be used because it cannot be used. Particularly preferred ether derivatives of halogen-containing aromatic diols are those having a weight average molecular weight of 1,400 to 5,000, or those having a weight average molecular weight of 30,000 to 80,000, each singly or a mixture thereof.

Specific examples of the ether derivative of the halogen-containing aromatic diol represented by the formula (I) used in the present invention include reaction products of halogen-containing bisphenol A and halogen-containing bisphenol A type epoxy resin, halogen-containing bisphenol Examples include reaction products obtained by reacting A and epichlorohydrin according to a conventional method. By changing the reaction ratio of halogen-containing bisphenol A and halogen-containing bisphenol A type epoxy resin, the terminal can be made into an 10H group or an epoxy group, and the reaction product obtained in this way Both are suitable flame retardants. Furthermore, ether derivatives obtained by reacting a terminal epoxy group with tribromophenol, pentabromophenol, etc. are also flame retardants suitable for the purpose of the present invention.

Specific examples of halogen-containing bisphenol A include tetrabromobisphenol A and dibromobisphenol A. Further, as a specific example of the halogen-containing bisphenol A type epoxy resin, tetrabromobisphenol A
diglycidyl ether of dibromobisphenol A, diglycidyl ether of dibromobisphenol A, etc.

Particularly preferred ether derivatives of halogen-containing aromatic diols include the reaction product of tetrabromobisphenol A and diglycidyl ether to tetrabromobisphenol, the reaction product of tetrabromobisphenol A and epichlorohydrin, and among these reaction products. A compound with an epoxy group at the end can be converted into tribromophenol,
It is an ether derivative obtained by reacting with pentabromophenol etc.

In the composition of the present invention, the blending ratio of the ether derivative of the halogen-containing aromatic diol to 100 parts by weight of the styrene resin can be varied over a wide range from 1 to 50 parts by weight, but a particularly preferred blending ratio is from 10 to 35 parts by weight. Parts by weight.

In the present invention, the styrene resin and the ether derivative of the halogen-containing aromatic diol can be blended using common blending equipment, such as a tumbler, super mixer, floater, etc.

In addition, a general extruder can be used for the mixing and melting methods, and there are no special restrictions on the molding and processing methods.

If necessary, other types of flame retardant aids used in ordinary styrene resins, such as antimony trioxide and chlorinated polyethylene, can be added to the composition of the present invention.

In addition, various additives commonly added to styrene resins, such as fillers, lubricants, reinforcing agents, stabilizers, light stabilizers, ultraviolet absorbers, plasticizers, colorants, antistatic agents, and hue improvers. etc. may be added.

〔Effect of the invention〕

The flame-retardant styrenic resin composition of the present invention has a high degree of flame retardancy, has a thickness of 1/16 inch, and has a V-O rating of UL standard.
It is extremely useful as a housing material for office automation equipment, office equipment, home appliances, etc. because it has impact resistance and excellent light resistance.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail 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.

(I) Impact strength The impact strength was measured using a notched Izot impact strength as a scale and in accordance with ASTM D256 using a test piece having a thickness of 174 inches.

(2) Using a falling weight impact strength flat plate molded product (I20x120x 2t),
The falling weight impact strength was evaluated by changing the weight load and weight height.

(3) Heat deformation temperature based on ASTM 0648, fiber stress 18
．． 56 kg/cm'', measured without annealing treatment.

(4) Light discoloration resistance As an evaluation scale for light discoloration resistance, a standard ultraviolet long life fade meter (FAL-3 manufactured by Suga Test Instruments) was used.
After irradiating the test piece with ultraviolet light for 50 hours at a black panel temperature of 63°C, the color difference (ΔE) with the unirradiated test piece was measured using a color difference meter (Σ80 manufactured by Nippon Denshoku Kogyo ■). It was colored.

A small color difference (ΔE) indicates excellent light fastness to discoloration, but the light fastness to discoloration was judged based on the following criteria.

○: ΔE≦5 ×: ΔE>5 (5) Flame retardancy As a flame retardant evaluation scale, a test piece with a thickness of 1.61 was used in accordance with the vertical flammability test specified in UL94 of the American UL standard. evaluated.

(6) Fluidity As an evaluation measure of fluidity, melt flow rate was evaluated in accordance with ASTM 01238.

Examples 1 to 4 ABS resin (A) with a graft ratio of 55% (DP611 manufactured by Japan Synthetic Rubber Co., Ltd.), ABS resin (B) with a graft ratio of 90% (DP630A manufactured by Nippon Synthetic Rubber Co., Ltd.), acrylonitrile 27% by weight AS resin (A) with an average molecular weight of 120,000, AS resin (B) with 29% acrylonitrile and a weight average molecular weight of 105,000, and a flame retardant (A) ( EC20 manufactured by Dainippon Ink Chemical Industries, Ltd.
Weight average molecular weight 2000), flame retardant (B) (YPB43C manufactured by Tobu Kasei Co., Ltd., weight average molecular weight 80000), and antimony dioxide as a flame retardant aid were blended in the proportions shown in Table 1, and after mixing with a Hensel mixer, Pellets were produced using a 40 mmφ vented single screw extruder (cylinder temperature: 230°C).

Next, a test piece for film physical properties was prepared using an injection molding machine (cylinder temperature: 240° C., mold temperature: 50° C.), and the physical properties were measured according to a standard method. The results are shown in Table-1.

Comparative Examples 1 to 7 BS resin (C) with a grafting rate of 40% (DP606 manufactured by Japan Synthetic Rubber Co., Ltd.), ABS resin (D) with a grafting rate of 45% (DP 615A manufactured by Nippon Synthetic Rubber Co., Ltd.), a grafting rate of 50% ABS resin (E) (manufactured by Japan Synthetic Rubber Co., Ltd. D)
P608), AS resin (C) with 26% acrylonitrile and a weight average molecular weight of 9200, acrylonitrile 20
% and a weight average molecular weight of 92000 AS resin (D),
The flame retardant (^) and the flame retardant (
B) Alternatively, TBA (tetrabromobisphenol A) and DB-83 (tecabromodiphenyl ether) manufactured by Great Lakes are blended in the proportions shown in Table 1,
Berets were produced in the same manner as in Examples 1-4.

Next, the physical properties were evaluated in the same manner as in Examples 1 to 4, and the results are shown in Table 1.

Examples 5-9 ABS resin (B) and AS resin (B) used in Examples 1-4, flame retardant (A) and flame retardant (B) used in Examples 1-4, and flame retardant (C ) (manufactured by Dainippon Ink & Chemicals Co., Ltd. EP16. Weight average molecular weight 1600), flame retardant (D
) (manufactured by Hanhon Yakuhin Kogyo Co., Ltd., 5RT20000, weight average molecular weight 30000), antimony trioxide was blended as a flame retardant aid in the proportion shown in Table 2, mixed in a Hensel mixer, and then mixed in a 40ma+φ vented uniaxial extruder ( Pellets were produced at a cylinder temperature of 230°C.

Next, a grain test piece and a falling weight impact test piece were prepared using an injection molding machine (cylinder temperature: 240° C., mold temperature: 50° C.), and their physical properties were measured according to a standard method.

The results are shown in Table-2.

Comparative Examples 8-9 The ABS resin (B) and AS resin (B) used in Examples 1-4 were added with the flame retardant (8) and flame retardant (B) used in Examples 1-4, and the flame retardant ( E) (Dainippon Ink Chemical Co., Ltd. εP100. Weight average molecular weight 10000) and flame retardant (F) (Hanhon Yakuhin Kogyo Co., Ltd. 5RT5040. Weight average molecular weight 10000) were blended in the proportions shown in Table 2 and carried out. Pellets were produced in the same manner as in Examples 5-9.

Next, the physical properties were evaluated in the same manner as in Examples 5 to 9, and the results are shown in Table 2.

Claims (1)

[Scope of Claims] ABS resin (acrylonitrile-butadiene-styrene terpolymer) with a graft ratio of 50% or more and 10 to 90% by weight, and an AS resin (acrylonitrile-butadiene-styrene terpolymer) with a graft ratio of 23% or more and a weight average molecular weight of 80,000 or more. Styrene copolymer) Styrenic resin consisting of 90 to 10% by weight, or with a graft ratio of 50% or more and a weight average molecular weight of 9
1 to 50 parts by weight of an ether derivative of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 20,000 to 100,000 to 100 parts by weight of a styrene resin consisting of 100% by weight of ABS resin of 0,000 or more. , or 1 to 50 parts by weight of an ether derivative of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 1000 to 9000;
) and the weight average molecular weight is 20,000 to 100,000
Ether derivatives of halogen-containing aromatic diols 1 to 9
1 to 50 parts by weight of an ether derivative of a halogen-containing aromatic diol consisting of 9% by weight and 99 to 1% by weight of an ether derivative of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 1000 to 9000. A flame-retardant styrene resin composition. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) {In the formula, R_1 and R_2 are -H, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(
Y is the same or different groups selected from bromine or chlorine, j is an integer of 0 to 5), X is bromine or chlorine, and i is 1 to
An integer of 4, m is a natural number. }