JPH04136053A - Flame-retarding styrene resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition improved in flame retardancy, mechanical properties, heat resistance, etc., while preventing the flame retardant from adhering to the mold or the molding by mixing a styrene resin with two specified halogenated aromatic diol ether derivatives and Sb2O3. CONSTITUTION:100 pts.wt. styrene resin (e.g. acrylonitrile/butadiene/styrene terpolymer) is mixed with 5-35 pts.wt. halogenated aromatic diol ether derivative of a weight-average molecular weight of 20000-100000, represented by formula I (wherein R1 and R2 are each H or a group of formula II or III; Y is Br; j is 0-5; X is Br or Cl; i is 1-4; and m is natural number), 5-35 pts.wt. another halogenated aromatic diol ether derivative of a weight-average molecular weight of 1000-9000, represented by formula I (the total of components B and C is 10-50 pts.wt.), 1-20 pts.wt. Sb2O3 of a mean particle diameter of 3mum or below, and optionally a flame-retarding aid, a filler, a lubricant, etc.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a flame-retardant styrenic resin composition containing an ether derivative of a halogen-containing aromatic diol, and more specifically, to a flame-retardant styrenic resin composition that has excellent light resistance, heat resistance, and impact resistance. This relates to a flame-retardant styrene resin composition with excellent properties, 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 resins have excellent moldability and well-balanced mechanical properties, so they have traditionally been used as housing materials for home appliances, OA equipment, office equipment, equipment, etc. is used as.

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.

As organic flame retardants, phosphorus compounds and ologen compounds are used, and as inorganic flame retardants, antimony oxides are used.

Among these, halogen compounds are effective as flame retardants for styrene resins, and among them, from the viewpoint of physical properties and flame retardancy, carbonate oligomers of tetrafluorobisphenol A1 decabromodiphenyl ether, octabromodiphenyl ether, and tetrabromobisphenol A , bistribromophenoxyethane, etc. 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. Silher defects were likely to occur, and even if molding manufacturers carefully controlled conditions, it was impossible to completely eliminate the defective rate due to flash and silver.

Recently, halogenated epoxy type flame retardants have attracted attention.
Ether derivatives of halogen-containing aromatic diols with a weight average molecular weight of 1,000 to 10,000 are blended with styrene resins and used as housing materials for office automation equipment and office equipment, but they have poor flame retardancy and low heat resistance. However, its use has been limited due to its poor thermal creep properties.

[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, in the present invention, based on 100 parts by weight of the styrene resin, the compound is expressed by the following formula N) and has a weight average molecular weight of 20,000 to 1.
5 to 35 parts by weight of an ether derivative (A) of a halogen-containing aromatic diol having a weight average molecular weight of 1000 to 9000, and 5 to 35 parts by weight of an ether derivative (B) of a halogen-containing aromatic diol represented by the following formula (I) and having a weight average molecular weight of 1000 to 9000. 35 parts by weight (
However, if the total amount of ether derivative (8) and (B) is 10 or more,
The present invention relates to a flame-retardant styrenic resin composition characterized in that it contains 1 to 20 parts by weight of antimony trioxide having an average particle size of 3 pm or less (30 parts by weight).

C) If OH H3 0H or chlorine, j is an integer from O to 5)
or a different group, X is bromine or chlorine, i is 1-
An integer of 4, l is a natural number. ) Hereinafter, the present invention will be explained in detail.

Examples of the styrenic resin used in the present invention include polystyrene, rubber-reinforced polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-α-methylstyrene copolymer, acrylonitrile-butadiene-styrene ternary copolymer, and acrylonitrile-butadiene copolymer. −α
Examples include methylstyrene terpolymer, etc., and these can be used alone or in polymers with good compatibility,
If necessary, two or more types can be used as a mixture.

The ether derivative of halogen-containing aromatic diol used in the present invention is represented by the above formula (I), and specific examples thereof include a reaction product of halogen-containing bisphenol A and halogen-containing bisphenol A type epoxy resin, Examples include reaction products obtained by reacting bisphenol 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 OH group or an epoxy group, and the reaction product obtained in this way can be are also 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 A1 and dibucomobisphenol A. Specific examples of halogen-containing bisphenol A type epoxy resins include diglycidyl ether of tetrabromobisphenol and diglycidyl ether of dibromobisphenol A.

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.

The ether derivative of halogen-containing aromatic diol used in the present invention has a weight average molecular weight of 20,000 to 100.
000 ether derivative (A) and weight average molecular weight 1110
It is a combination of ether derivatives (B) of 00 to 9000. Weight average molecular weight is 20,000 to 1oooo.

The ether derivative (A) alone has excellent heat-resistant creep properties and thermal stability, but has poor moldability and low impact resistance. In addition, the ether derivative (B) having a weight average molecular weight of 1000 to 9000 alone has excellent moldability, but has poor heat-resistant creep properties and thermal stability of molded products.
Furthermore, sufficient flame retardancy cannot be imparted to thin-walled molded products.

Ether derivatives having a weight average molecular weight of more than 9,000 and less than 20,000 cannot be used because they significantly reduce the impact resistance of molded products. Also, ether derivatives with a weight average molecular weight of over 100,000, or ether derivatives with a weight average molecular weight of 100,000
Ether derivatives with less than 0 can not be used because they significantly reduce the heat resistance and thermal stability of molded products, and cannot provide sufficient flame retardance to thin-walled molded products. Particularly preferred ether derivatives (A), ( The combination B) has a weight average molecular weight in the range of 23,000 to 5ooo.

The ether derivative (A) and the weight average molecular weight range of 140
0 to 3000 ether derivative (B).

The blending ratio of these ether derivatives to 100 parts by weight of the styrene resin can be varied over a wide range, with the ether derivatives (A) and (B) of halogen-containing aromatic diols each ranging from 5 to 35 parts by weight, but a particularly preferred blend is The ratio is ether derivative of halogen-containing aromatic diol (A
), (B) each in an amount of 10 to 25 parts by weight. However, it is necessary that the total amount of the ether derivatives (A) and (B) be 10 to 30 parts by weight.

The average particle diameter of antimony trioxide used in the present invention is 3 or less, preferably 1 or less is effective. If the average particle diameter exceeds 3, the mechanical properties will be significantly reduced.

The amount of antimony trioxide to be blended is 1 to 20 parts by weight per 100 parts by weight of the styrene resin, and if it exceeds 20 parts by weight, the mechanical properties will be significantly reduced. A particularly preferred blending ratio is 3 to 15 parts by weight.

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

If necessary, other types of flame retardant additives used in common styrenic resins, such as 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 improving agents. 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, and has a thickness of 1/16 inch that meets the UL standard v-0.
Corresponds to the material and ball pressure temperature is 95℃
It has the above heat resistance level, and also has impact resistance, heat creep deformation resistance, and excellent light resistance, so it is extremely useful as a housing material for office automation equipment, office equipment, home appliances, etc.

〔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 Resistance Strength Impact strength was measured using Izot impact strength with non-chips as a measure and in accordance with ASTM D256 using a test piece having a thickness of 174 inches.

(2) Heat distortion temperature based on ASTM D648, fiber stress 18
．． 56 kg/c+*z, measured without annealing treatment.

(3) Ball pressure temperature (B, P, T,) 301
After annealing a 101 square, 3 mm thick sample at 70°C for 96 hours, and conditioning it in a desiccator,
Using a φ steel ball, a static load of 2ON was applied to the heated sample for one hour, and the temperature at which the diameter of the recessed hole became 2mm+ was determined.

(4) Heat-resistant creep deformability A sample with a thickness of 5" x l/2" x l/8" was
Set to I, fiber stress 100kg/cm2
The deformation rate was measured after 1000 hours at a temperature of 70°C. The following criteria were used to determine the deformation rate.

○: Deformation rate of 1% or less ×: Deformation rate of over 1% (5) Light discoloration resistance As an evaluation scale for light discoloration resistance, a standard ultraviolet long life fade meter (PAL - manufactured by Suga Test Instruments ■) was used.
After irradiating the test piece with ultraviolet rays for 30 hours at a black panel temperature of 63°C, the color difference (ΔE) from the unirradiated test piece was measured using a color difference meter (Σ80 manufactured by Nippon Heavy Industries Ltd.). did.

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 ×: ΔB>5 (6) Flame retardancy As a flame retardant evaluation scale, the vertical flammability test specified in UL94 of the U.S. UL standard was used, and the thickness was 1.6sn.
The test piece was evaluated.

(7) Fluidity As a fluidity evaluation scale, melt flow rate was evaluated in accordance with ASTM [+1238].

(8) Appearance of molded product The appearance of the molded product (60x90x 3t) was evaluated.

Appearance evaluation: ≮ ○, somewhat good Δ bad Commercially available flame retardants made of ether derivatives of halogen-containing aromatic diols include flame retardant (a) (manufactured by Tobu Kasei Co., Ltd., YPB43C, weight average molecular weight 80,000), flame retardant (b) (printed version). 5RT100OO (manufactured by Yakuhin Kogyo Co., Ltd., weight average molecular weight t60000), flame retardant (C) (manufactured by Dainippon Ink Chemical Co., Ltd. EP300, weight average molecular weight 40000), flame retardant (d) (manufactured by Dainippon Ink Chemical Co., Ltd. EC20, weight average molecular weight 2000)
, and antimony trioxide with an average particle diameter of 0.5 am were blended in the proportions shown in Table 1, mixed in a Hensel mixer, and then pellets were produced in a single screw extruder with a 40 mtaφ hent (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: 30° C.), and the physical properties were measured according to a standard method. The results are shown in Table-1.

Comparative Examples 1 to 6 The same ABS resin and AS tree as in Examples 1 to 4 were used as the styrene resin, and the above flame retardant (d) consisting of an ether derivative of a halogen-containing aromatic diol was used as the flame retardant, and the flame retardant (
e) (EP100 manufactured by Dainippon Ink & Chemicals Co., Ltd. Weight average molecular weight 10000) or TBA manufactured by Great Lakes Co., Ltd.
(tetrabromobisphenol A), DH-83 (decabromodiphenyl ether), and average particle size 4ρ
Antimony dioxide was blended in the proportions shown in Table 1, and pellets were produced in the same manner as in Examples 1 to 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.

Claims (1)

[Claims] For 100 parts by weight of styrene resin, the following formula (I)
5 to 35 parts by weight of an ether derivative (A) of a halogen-containing aromatic diol represented by the formula (I) and having a weight average molecular weight of 20,000 to 100,000, and a halogen-containing aromatic diol having the weight average molecular weight of 1,000 to 9,000 and represented by the following formula (I). 5 to 35 parts by weight of the ether derivative (B) (however, the total amount of the ether derivatives (A) and (B) is 10 to 30 parts by weight), and 1 to 35 parts by weight of antimony trioxide with an average particle size of 3 μm or less.
A flame-retardant styrene resin composition characterized by containing 20 parts by weight. ▲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. )