JPH05148391A - Flame-retardant styrene resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Halogenated bisphenol type epoxy containing styrene resin (A) (HIPS, etc.) and having a degree of polymerization of 15 to 40% by weight and a weight average molecular weight of 1000 to 3000. Contains resin (B) (tetrabromobisphenol A type epoxy resin, etc.). [Effect] The molded product is excellent in heat resistance, weather resistance and impact resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant styrene resin composition having excellent heat resistance and light resistance of a molded article and having good impact resistance.

[0002]

2. Description of the Related Art Conventionally, a flame retardant composed of a halogenated bisphenol type epoxy resin and a flame retardant auxiliary such as antimony trioxide are added and blended with a styrene-based resin to obtain non-bleeding property, heat resistance and light resistance. A technique for obtaining a flame-retardant styrene resin composition having excellent properties and the like is disclosed.
For example, as an example where such technology is described,
JP-A-50-27843 can be mentioned.
On the other hand, a flame-retardant styrene-based resin composition obtained by blending a halogenated bisphenol-type epoxy resin with a styrene-based resin is excellent in heat resistance, light resistance, etc., but is not necessarily good in impact resistance. In order to improve this point, an attempt has been made to use a halogenated bisphenol type epoxy resin having a range of weight average molecular weight as a flame retardant. (Japanese Patent Laid-Open No. 1-287132)

[0003]

However, the flame-retardant styrene-based resin composition obtained by blending the halogenated bisphenol-type epoxy resin described in those publications with the styrene-based resin is heat-resistant and light-resistant. Although excellent in
Still, there was a problem in practical impact resistance.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that halogenated bisphenol epoxy resins used as flame retardants have the same weight average molecular weight. Also, they found that the impact resistance of the flame-retardant styrene resin composition using the same greatly changed depending on the proportion of the specific polymer in the polymers constituting the same, and completed the present invention.

That is, the present invention comprises a styrene resin (A),
Flame-retardant containing 15 to 30% by weight of a polymerization degree of 1 and a halogenated bisphenol type epoxy resin (B) having a weight average molecular weight of 1,000 to 3,000. Styrene-based resin composition.

Examples of the styrene resin which can be used in the present invention include polystyrene and styrene-butadiene copolymer (H
IPS resin), styrene-acrylonitrile copolymer (AS resin), acrylonitrile-styrene-butadiene copolymer (ABS resin), phenylmaleimide-acrylonitrile-styrene-butadiene copolymer (heat resistant ABS resin), acrylonitrile-acrylic rubber -Styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin)
And the like, alloys of ABS resin and polycarbonate, alloys of ABS resin and PBT resin, polymer alloys of polystyrene and PPO resin, and the like.

Among them, styrene-butadiene copolymer (HIPS resin), acrylonitrile-styrene-butadiene copolymer (ABS resin), phenylmaleimide-, from the viewpoint of excellent impact resistance, heat resistance, light resistance, and gloss.
Acrylonitrile-styrene-butadiene copolymer (heat resistant ABS resin), alloy of ABS resin and polycarbonate are preferable, and styrene-butadiene copolymer (HIPS resin) and acrylonitrile-styrene-butadiene copolymer (ABS resin) are particularly preferable. .

The halogenated bisphenol type epoxy resin (B) used in the present invention is not particularly limited in its structure, but is generally represented by the following structural formula.

[0009]

[Chemical 1] However, X is a bromine atom or a chlorine atom, and l and m
Represents the number of substituents, each is an integer of 1 to 4, and n
Is a natural number indicating a repeating unit.

The halogenated bisphenol type epoxy resin (B) having a degree of polymerization of 1 contained in the range of 15 to 30% by weight means that the halogenated bisphenol skeleton is 2
For example, those having n = 1 in the structural formula represented by the above general formula can be mentioned.

The halogenated bisphenol type epoxy resin used in the present invention can be obtained, for example, by subjecting a halogenated bisphenol and epichlorohydrin to a dehydrochlorination reaction in the presence of an alkali.

By changing the reaction molar ratio of the halogenated bisphenol and epichlorohydrin, the amount of the polymer in which n is 1 and the weight average molecular weight can be variously changed. In order to obtain the halogenated bisphenol type epoxy resin of the present invention, the reaction molar ratio of halogenated bisphenol and epichlorohydrin is from 1 / 1.9 to 1 / 1.19.
The range of 1 / 1.7 to 1 / 1.3 is preferable from the viewpoint of obtaining a halogenated bisphenol type epoxy resin having an excellent balance between impact resistance and heat resistance. Specific examples of the halogenated bisphenol include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, tetrabromobisphenol F, dichlorobisphenol F and tetrachlorobisphenol F. , Dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S, tetrachlorobisphenol S, and the like, preferably, the halogenated bisphenol type epoxy resin (B) of the present invention which can include tetrabromobisphenol A, The weight average molecular weight thereof is 1,000 to 3,000 and the degree of polymerization is 1 to 15 to 30 in the epoxy resin (B).
The epoxy resin (B), which is contained by weight,
From the viewpoint of improving the balance between impact resistance and heat resistance, the weight average molecular weight is 1,200 to 2,300,
An epoxy resin (B) having a degree of polymerization of 1 is preferably contained in an amount of 17 to 25% by weight.

The weight average molecular weight and the amount of the polymer in which the repeating unit n is 1 are not the average value but are those measured by gel permeation chromatography.

The compounding amount of the epoxy resin (B) of the present invention with respect to the styrene resin (A) is not particularly limited, but is 5 to 35 parts by weight with respect to 100 parts by weight of the styrene resin. It is preferable. That is, when the blending amount is within this range, appropriate flame retardancy can be obtained while maintaining the heat resistance and impact resistance obtained by the present invention.

Further, in the present invention, antimony trioxide can be preferably used as a flame retardant aid in a system containing a styrene resin (A) and an epoxy resin (B). The compounding amount of antimony trioxide is preferably 2 to 10 parts by weight with respect to 100 parts by weight (A) of the styrene resin from the viewpoint that the heat resistance and impact resistance of the resin composition are remarkably improved.

If necessary, the flame-retardant styrene resin composition of the present invention further comprises antimony compounds such as antimony tetroxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, and molybdenum oxide. Flame retardant effect by blending flame retardant aids such as molybdenum-based compounds such as ammonium molybdate, zirconium oxide and zirconium hydroxide, and boron-based compounds such as zinc borate and barium metaborate. Can be increased.

The styrene-based resin composition of the present invention may further contain other known bromine-based flame retardants, phosphorus-based flame retardants, if necessary, as long as the light resistance, heat resistance and impact resistance are not significantly impaired. An inorganic flame retardant may be used in combination, and if necessary, an ultraviolet absorber, a light stabilizer, an organic phosphite, a heat stabilizer such as an organic tin compound, a release agent, a lubricant, a colorant, a plasticizer, A filler, a foaming agent, a glass fiber, a carbon fiber, a reinforcing agent such as an aramid fiber, and the like can be mixed.

As a method of blending the above-mentioned respective components, for example, there is a method of premixing with a mixer such as a Henschel mixer or a tumbler mixer, and then melt-kneading with an extruder, a kneader, a heat roll, a Banbury mixer or the like.

[0019]

EXAMPLES The present invention will be described more specifically below with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

All parts and% in the examples are based on weight, and various evaluations are based on the following measuring methods. (1) Softening point test (ring-and-ball type) It was measured according to JIS K-2077. (2) Epoxy group content test It is the reciprocal of the epoxy equivalent (g / eq) measured according to JIS K-7236, and is the value expressed in eq / g. (3) HLC-8020 manufactured by Tosoh Corp. was used as an apparatus for measuring the amount of a polymer having a weight average molecular weight and a degree of polymerization of 1 by GPC.
The column is TSKgel G400 manufactured by Tosoh Corporation.
0HXL, G3000HXL, G2000HXL, G2
Each 7.8 mm ID × 300 mm of 000 HXL was connected and used. THF is used as a solvent, and the column temperature is 40
℃, the pressure is 78kg / cm ^2, The flow rate is zero.
The measurement was performed at a setting of 7 ml / min. The calibration curve has a molecular weight of 1
6,700, 6,200, 2,800, 800, 580
The one prepared with the polystyrene standard substance of was used.
The molecular weight calculated from the calibration curve is represented by rounding off the tens place. (4) Heat distortion temperature test (load 18.6 kg / cm ² ) It was measured according to ASTM D-648. (5) Drop Weight Impact Strength Test (With Notch) Twenty square test pieces having a length of 80, a width of 80 and a thickness of 3 mm were prepared, and the drop weight impact strength was measured according to JIS K7211.

The weight used in the test was a steel spherical shape and had a HI
PS resin has a weight of 0.5 kg and a diameter of 50 mm (sphere 1 shape), ABS resin has a weight of 1 kg,
It has a diameter of 50 mm (sphere 2).

The impact strength is represented by the height (unit: cm) when 50% of the number of test pieces is broken, and the vertical distance between the test pieces is 10 cm. (6) Light resistance test 10 with a sunshine weatherometer (manufactured by Suga Test Instruments)
A 0-hour test was performed, and the change in appearance of the test piece before and after the test was measured using a color difference meter. (7) Flammability test (UL-94) Subject 9 of Underwriters Laboratories
Based on method No. 4, length 5 inches x width 1/2 inches x
The measurement was performed using five test pieces having a thickness of 1/8 inch.

Synthesis Example 1 Tetrabromobisphenol A (hereinafter abbreviated as TBA) 272 g (0.50 mol) and 10% aqueous sodium hydroxide solution 393 g were placed in a 2 liter flask equipped with a thermometer and a stirrer, and the inside was filled with nitrogen. After purging with gas, the contents are heated to 50 ° C. Next, 83.3 g of epichlorohydrin (hereinafter abbreviated as ECH) with stirring
After adding (0.90 mol), the mixture was reacted at 90 ° C. for 3 hours. Then, 300 g of methyl isobutyl ketone is added to dissolve the reaction product. After the dissolution, the mixture is allowed to stand and the organic layer and the saline layer are separated. Then, the alkali contained in the organic layer is neutralized with phosphoric acid and separated. The organic layer is distilled under reduced pressure to completely remove methyl isobutyl ketone. The contents were poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant A. In addition, Table 1 shows the property value of the flame retardant, the weight average molecular weight, and the amount of the polymer having a polymerization degree of 1.

Synthesis Example 2 272 g (0.50 mol) of TBA and ECH 68.5
g (0.79 mol), 10% aqueous sodium hydroxide solution
Flame retardant powder was obtained in the same manner as in Example 1 except that 356 g was used. This is designated as flame retardant B.
In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Synthesis Example 3 272 g (0.50 mol) of TBA and ECH 64.8
g (0.70 mol), 10% aqueous sodium hydroxide solution
Flame retardant powder was obtained in the same manner as in Example 1 except that 314 g was used. This is designated as flame retardant C.
In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Synthesis Example 4 272 g (0.50 mol) of TBA and ECH 56.4
g (0.61 mol) was placed in a 2 liter flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, and then the content was heated to 50 ° C. Then, while stirring, 10
90% after adding 278 g of aqueous sodium hydroxide solution
The reaction was carried out at 0 ° C for 3 hours. Then, 300 g of methyl isobutyl ketone is added to dissolve the reaction product. After dissolution, leave still,
Separate the organic and saline layers. Then, the alkali contained in the organic layer is neutralized with phosphoric acid and separated. The organic layer is distilled under reduced pressure to completely remove methyl isobutyl ketone.
The contents were poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant D.
In addition, Table 1 shows the property value of the flame retardant, the weight average molecular weight, and the amount of the polymer having a polymerization degree of 1.

Comparative Synthesis Example 1 Tetrabromobisphenol A diglycidyl ether (EPICLON15 manufactured by Dainippon Ink and Chemicals, Inc.)
2, epoxy equivalent 360, bromine content 48%, below, E
(Abbreviated as PICLON152) 720 g (1 mol) and TBA 51 g (0.093 mol) were placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, and the contents were heated and melted. After adding 0.39 g of a 10% aqueous solution of sodium hydroxide at 100 ° C., the mixture was reacted at 160 ° C. for 5 hours. After the reaction, the reaction product was poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant E. Also,
Table 1 shows the property value of the flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Comparative Synthesis Example 2 720 g (1 mol) of EPICLON 152 and TBA
126 g (0.23 mol) and 10% of sodium hydroxide
Flame retardant powder was obtained in the same manner as Comparative Example 1 except that 0.43 g of the aqueous solution was used and the reaction was performed at 180 ° C. for 10 hours. This is designated as flame retardant F. In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Comparative Synthesis Example 3 720 g (1 mol) of EPICLON 152 and TBA
238 g (0.44 mol) and 10% of sodium hydroxide
Flame retardant powder was obtained in the same manner as in Comparative Example 1 except that 0.48 g of an aqueous solution was used and the reaction was performed at 180 ° C. for 10 hours. This is designated as flame retardant G. In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Comparative Synthesis Example 4 720 g (1 mol) of EPICLON 152 and TBA
Flame retardant powder was obtained in the same manner as in Comparative Example 1 except that 318 g (0.58) and 0.52 g of a 10% aqueous solution of sodium hydroxide were used and the reaction was performed at 180 ° C. for 10 hours. Let this thing be the flame retardant H. In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

Comparative Synthesis Example 5 272 g (0.50 mol) of tetrabromobisphenol A (hereinafter abbreviated as TBA) and 433 g of 10% sodium hydroxide aqueous solution were placed in a 2 liter flask equipped with a thermometer and a stirrer, and the inside was charged. After purging with nitrogen gas, the contents are heated to 50 ° C. Next, EC while stirring
After adding H83.5g (0.90mol), it was made to react at 90 degreeC for 3 hours. Then methyl isobutyl ketone
Add 300 g to dissolve reaction product. After the dissolution, the mixture is allowed to stand and the organic layer and the saline layer are separated. Then, the alkali contained in the organic layer is neutralized with phosphoric acid and separated. The organic layer is distilled under reduced pressure to completely remove methyl isobutyl ketone. The contents were poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow flame retardant powder. This is designated as flame retardant I. Also, the property value, weight average molecular weight and degree of polymerization of this flame retardant 1
The amount of the polymer is shown in Table 1. Comparative Synthesis Example 6 272 g (0.50 mol) of TBA and ECH 54.3
g (0.59 mol) 10% sodium hydroxide aqueous solution 2
Flame retardant powder was obtained in the same manner as in Example 1 except that 82 g was used. This is designated as flame retardant J. In addition, Table 1 shows the property values of this flame retardant, the weight average molecular weight, and the amount of the polymer having a degree of polymerization of 1.

[0032]

[Table 1]

[0033]

[Table 2]

[0034]

[Table 3] (In Table 1, EP152 represents EPICLON 152.) Examples 1 to 8 Flame retardants A to D were blended in the composition shown in Table 2, premixed with a tumbler mixer, and then pelletized with a 30 mmφ twin-screw extruder. To obtain a flame-retardant styrene resin composition. A test piece was then made with a 5 ounce injection molding machine.

The cylinder set temperatures of the extruder and the injection molding machine were 230 ° C. for ABS resin and 230 ° C. for HIPS resin. The test pieces were used for measurement of heat distortion temperature, falling weight impact strength, light resistance and flammability, and the results are shown in Table 3. Comparative Examples 1 to 12 Flame retardants E to J were blended in the compositions shown in Table 2, pre-mixed in a tumbler mixer, and pelletized by a 30 mmφ twin-screw extruder to obtain flame-retardant styrene resin compositions. . A test piece was then made with a 5 ounce injection molding machine.

The cylinder set temperatures of the extruder and the injection molding machine were 230 ° C. for ABS resin and 230 ° C. for HIPS resin. The test pieces were used to measure the heat distortion temperature, falling weight impact strength, light resistance and flammability. The results are shown in Table 3.

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7] (In Table 2, ABS resin is "Cevian V" manufactured by Daicel Chemical Co., Ltd., HIPS resin is "GH-7000" manufactured by Dainippon Ink and Chemicals, and antimony trioxide is "ATOX-F" manufactured by Nippon Mining Co., Ltd. Represent each.)

[0041]

[Table 8]

[0042]

[Table 9]

[0043]

The flame-retardant styrene resin composition of the present invention is excellent in heat resistance and light resistance and has good impact resistance. It is useful as a material.

Claims (5)

[Claims] 1. A halogenated bisphenol type epoxy resin (B) containing 15 to 30% by weight of a styrene resin (A) and a polymerization degree of 1 and having a weight average molecular weight of 1,000 to 3,000. ) And a flame-retardant styrenic resin composition. 2. The resin composition according to claim 1, wherein the halogenated bisphenol type epoxy resin (B) is a tetrabromobisphenol A type epoxy resin. 3. The resin composition according to claim 1, further comprising antimony trioxide (C). 4. A halogenated bisphenol type epoxy resin (B) with respect to 100 parts by weight of the styrene resin (A).
The resin composition according to claim 2 or 3, which contains 5 to 35 parts by weight. 5. The styrene resin (A) is a rubber-modified polystyrene resin or an acrylonitrile-butadiene-styrene resin, which is characterized in that
The flame-retardant styrene resin composition described.