JPH0673268A - Flame retardant composition and flame retardant styrene resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Halogenated bisphenol A type epoxy resin and halogenated epoxy resin type flame retardant (A) such as its terminal epoxy group blocked product, and polyhalogenated diphenylalkane (B) such as decabromodiphenylethane (B). And a flame retardant styrene resin composition containing the flame retardant (A), the flame retardant (B) and a styrene resin (C). [Effect] It is possible to provide a flame-retardant styrene-based resin composition having excellent impact resistance, heat resistance, light resistance, molding fluidity, and excellent surface gloss.

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, light resistance, molding fluidity and surface gloss, and a flame retardant composition used therefor.

[0002]

2. Description of the Related Art Conventionally, as a method for obtaining a flame-retardant styrene resin composition, a halogenated epoxy resin is used as a flame retardant for a styrene resin, and some or all of terminal epoxy groups of the halogenated epoxy resin are halogenated phenol. A method obtained by adding a halogenated epoxy resin-based flame retardant such as a compound having a blocked structure (Japanese Patent Laid-Open No. 50-27).
843, JP-A-50-158697, JP-A-57-38624, JP-A-61-241343.
JP-A-61-211354), or a method obtained by adding a polyhalogenated diphenylalkane such as decabromodiphenylethane as a flame retardant (JP-A-2-42031). There is.

[0003]

However, a flame-retardant styrenic resin composition obtained by adding a halogenated epoxy resin-based flame retardant as a flame retardant to the above-mentioned conventional styrene-based resin has light resistance, molding flow Although it was excellent in heat resistance and surface gloss, it was not always excellent in heat resistance.

On the other hand, a flame-retardant styrene resin composition obtained by adding a polyhalogenated diphenylalkane as a flame retardant has excellent heat resistance, but light resistance,
Molding fluidity and surface gloss were not good.

The problem to be solved by the present invention is to provide a flame-retardant styrene resin composition which is excellent in heat resistance, light resistance, molding fluidity and surface gloss, and a flame retardant composition used therefor. To do.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a halogenated epoxy resin flame retardant and a polyhalogenated diphenylalkane are used as flame retardants in a styrene resin. By adding the flame retardant composition contained, surprisingly, the above problems of both flame retardants are improved, and the flame-retardant styrene-based resin has excellent heat resistance, light resistance, molding fluidity, and excellent surface gloss. It was found that a resin composition was obtained, and the present invention was completed.

That is, the present invention is a flame retardant composition containing a halogenated epoxy resin flame retardant (A) and a polyhalogenated diphenylalkane (B), and a halogenated epoxy resin flame retardant. It relates to a flame-retardant styrene resin composition containing (A), a polyhalogenated diphenylalkane (B) and a styrene resin (C).

The halogenated epoxy resin-based flame retardant (A) used in the present invention has, for example, a structure in which a part or all of terminal epoxy groups of a halogenated epoxy resin or a halogenated epoxy resin is blocked with a halogenated phenol. A compound etc. are mentioned.

Specific examples of these are halogenated bisphenol type epoxy resin, halogenated phenol novolac type epoxy resin, halogenated cresol novolac type epoxy resin, halogenated resorcinol type epoxy resin, halogenated hydroquinone type epoxy resin, halogenated bisphenol. A novolac type epoxy resin, halogenated methylresorcinol type epoxy resin, halogenated resorcinol novolak type epoxy resin and other halogenated epoxy resins, and a part or all of terminal epoxy groups of these halogenated epoxy resins are blocked with halogenated phenol. There are compounds having a structure.

As the halogenated epoxy resin (A), the following general formula (I) is used.

[0011]

A halogenated bisphenol type epoxy resin-based flame retardant represented by the formula: is preferable, and a halogenated bisphenol type epoxy resin having an average polymerization degree n in the general formula (I) of 0 to 3, particularly 0 to 1.5. The flame retardants are particularly preferable in that they have excellent molding fluidity and a large effect of improving the heat resistance when used in combination with the polyhalogenated diphenylalkane (B).

Specific examples of the halogenated bisphenol constituting the halogenated bisphenol type epoxy resin type flame retardant include dibromobisphenol A, tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F and tetrabromobisphenol. F, dichlorobisphenol F, tetrachlorobisphenol F, dibromobisphenol S, tetrabromobisphenol S, dichlorobisphenol S, tetrachlorobisphenol S
Etc. Among them, among others, tetrabromobisphenol A
Is preferred.

The halogenated phenols used as a compound for blocking a part or all of the terminal epoxy groups of the halogenated epoxy resin include, for example, dibromophenol, dibromocresol, tribromophenol,
Pentabromophenol, dichlorophenol, dichlorocresol, trichlorophenol, pentachlorophenol, dibromobutylphenol, dibromoethylphenol, dibromopropylphenol and the like can be mentioned, and among them, tribromophenol is preferable.

Next, the method for producing the halogenated epoxy resin flame retardant (A) used in the present invention will be specifically described by taking a halogenated bisphenol type epoxy resin as an example.
That is, a method in which a halogenated bisphenol and epichlorohydrin are subjected to a condensation reaction, and then a halogenated phenol is optionally heated at 100 to 230 ° C. in the presence of a catalyst to produce a product, and a halogenated bisphenol and epichlorohydrin are subjected to a condensation reaction. The diglycidyl ether of halogenated bisphenol thus obtained and halogenated bisphenol were added in the presence of a catalyst to 100 to
A method of producing by heating at 230 ° C. and then heating a halogenated phenol under the same conditions, if necessary, a halogenated bisphenol diglycidyl ether obtained by condensation reaction of halogenated bisphenol and epichlorohydrin, and a halogen. Bisphenol and halogenated phenol in the presence of a catalyst for 10
A method of producing by heating reaction at 0 to 230 ° C., a condensation reaction of halogenated bisphenol and epichlorohydrin, and then optionally heating halogenated phenol at 100 to 230 ° C. in the presence of a catalyst. A method etc. can be mentioned.

Examples of the catalyst used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as dimethylbenzylamine, and 2-
Examples thereof include imidazoles such as ethyl-4methylimidazole, quaternary ammonium salts such as tetramethylammonium chloride, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine.

As the polyhalogenated diphenylalkane (B) used in the present invention, diphenylalkanes such as diphenylmethane, 1,2-diphenylethane, 1
-Methyl-1,2-diphenylethane, 1,4-diphenylbutane, 1,6-diphenylhexane, 2,3-dimethyl-1,4-diphenylbutane, 2-methyl-1,
Examples include those in which 4-1 and 7-diphenylhexane are substituted with two or more halogens, preferably 4 to 5 bromines. Among them, decabromodiphenylethane is excellent in impact resistance and heat resistance. It is preferable in terms.

Next, a method for producing the polyhalogenated diphenylalkane (B) will be described by taking decabromodiphenylethane as an example. That is, a method of producing diphenylethane by bromination with bromine in a solvent in the presence of a bromination catalyst by a conventional method, or JP-A-2-42.
Specific method as disclosed in 031, that is, a method of producing by adding a halogenated hydrocarbon solution of diphenylethane to a mixture of bromine and a bromination catalyst in a dropwise manner to cause a reaction, and the like.

The styrene resin (C) used in the present invention is not particularly limited, and examples thereof include polystyrene, rubber-modified polystyrene (HIPS resin), acrylonitrile-
Butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), methylmethacrylate-butadiene-styrene copolymer (MB
Resin), styrene-maleic anhydride copolymer resin, styrene-methacrylic acid copolymer resin; or a polymer alloy containing an ABS resin such as an alloy of ABS resin and polycarbonate resin, an alloy of ABS resin and polyester resin as one component. A polymer alloy of polystyrene and polyphenylene oxide (PPO) resin, and the like,
Among them, HIPS resin and ABS resin are preferable because the effect of improving impact resistance, heat resistance, and molding fluidity becomes remarkable.

To the flame retardant composition and flame-retardant styrene resin composition of the present invention, it is preferable to add an inorganic flame retardant aid (D) in order to further enhance the flame retardant effect. Examples of the inorganic flame retardant aid (D) include antimony oxides such as antimony trioxide, antimony tetraoxide and antimony pentoxide, tin compounds such as tin oxide and tin hydroxide, molybdenum oxide and molybdenum ammonium molybdate. Examples thereof include zirconium-based compounds, zirconium-based compounds such as zirconium oxide and zirconium hydroxide, and boron-based compounds such as zinc borate and barium metaborate. Among them, antimony oxide is preferable because the flame retardancy improving effect is remarkably excellent.

As a method for obtaining the flame-retardant styrene resin composition of the present invention, a halogenated epoxy resin flame retardant (A), a polyhalogenated diphenylalkane (B), and a styrene resin (C) are further required. By blending the inorganic flame retardant aid (D) with a halogenated epoxy resin flame retardant (A) and a polyhalogenated diphenylalkane (B) in advance, and if necessary, the inorganic flame retardant aid (D). To prepare a flame retardant composition, which is a styrene resin (C)
And the like.

The mixing ratio of these is 1 to 30 parts by weight of the halogenated epoxy resin-based flame retardant (A) and 1 to 10 parts by weight of the polyhalogenated diphenylalkane (B) with respect to 100 parts by weight of the styrene resin (C). 20 parts by weight, and the inorganic flame retardant aid (D) can be varied over a wide range from 0 to 7 parts by weight. A particularly preferable blending ratio is styrene resin (C)
6 to 15 parts by weight of halogenated epoxy resin flame retardant (A), 5 to 12 parts by weight of polyhalogenated diphenylalkane (B), and 3 parts of inorganic flame retardant aid (D) per 100 parts by weight. The range is from 6 to 6 parts by weight.

As a method of blending the above-mentioned respective components, for example, there is a method of preliminarily mixing 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.

The flame retardant composition and the flame-retardant styrene resin composition of the present invention may further contain other flame retardants such as chlorine flame retardants, bromine flame retardants, phosphorus flame retardants, and ultraviolet rays, if necessary. Add additives such as absorbers, light stabilizers, release agents, lubricants, colorants, plasticizers, fillers, foaming agents, heat stabilizers, and reinforcing materials such as glass fibers, carbon fibers, and aramid fibers. You can

[0024]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples, 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 (however, gloss values are excluded), and various tests are evaluated by the following measuring methods.

(1) Softening point test (ring-and-ball type) It was measured according to JIS K-7234. (2) Heat distortion temperature (HDT) test (load 18.6 kg /
cm ² ) Measured according to ASTM D-648. (3) Molding fluidity (MI: melt index) test It was measured according to ASTM D-1238.

When a HIPS resin was used as the styrene resin, the measurement was carried out at a temperature of 200 ° C. and a load of 5 kg. When ABS resin is used as styrene resin,
The measurement was performed at a temperature of 230 ° C. under a load of 5 kg.

(4) 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. (5) 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. (6) Gloss measurement test According to ASTM D-523, the measurement was performed at an incident angle of 60 °.

Synthesis Example 1 (Synthesis of Halogenated Epoxy Resin Flame Retardant) Tetrabromobisphenol A diglycidyl ether [EPICLON 15 manufactured by Dainippon Ink and Chemicals, Inc.]
2, epoxy equivalent 360g / eq, bromine content 48%]
545 g and 2,4,6-tribromophenol (hereinafter T
455 g) is placed in a 1-liter separable flask equipped with a thermometer and a stirrer, the inside is replaced with nitrogen gas, the contents are heated and melted, and a 10% aqueous solution of sodium hydroxide at 100 ° C. 1 After adding 0.0 g, 160-1
The reaction was carried out at 70 ° C for 7 hours. After the reaction, the reaction product was poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow halogenated epoxy resin flame retardant powder. This flame retardant had a softening point of 100 ° C., a bromine content of 59%, and an average degree of polymerization of 0.1. This is designated as a flame retardant (A-1)).

Synthesis Example 2 (Same as above) 545 g of EPICLON 152, 135 g of tetrabromobisphenol A (hereinafter abbreviated as TBA) and TBP32.
0 g was placed in a 1 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, the contents were heated and melted, and 1.0 g of a 10% aqueous solution of sodium hydroxide was added at 100 ° C. Then, the mixture was reacted at 170 to 180 ° C. for 7 hours. After the reaction, the reaction product was poured into a stainless pan,
After cooling, it was pulverized to obtain a pale yellow halogenated epoxy resin flame retardant powder. This flame retardant had a softening point of 115 ° C., a bromine content of 56%, and an average degree of polymerization of 1.1. Let this be a flame retardant (A-2).

Synthesis Example 3 (same as above) EPICLON 152 553 g, TBA 235 g and T
A light yellow halogenated epoxy resin flame retardant powder was obtained in the same manner as in Synthesis Example 2 except that 212 g of BP was used. This flame retardant has a softening point of 140 ° C. and a bromine content of 55.
%, And the average degree of polymerization was 2.8. Let this be a flame retardant (A-3).

Synthesis Example 4 (same as above) 808 g of EPICLON152 and 192 g of TBA 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 at 100 ° C. 10% aqueous solution of sodium hydroxide O.C.
After adding 7g, it was made to react at 160-170 degreeC for 7 hours. After the reaction, the reaction product was poured into a stainless pan, cooled, and then pulverized to obtain a pale yellow halogenated epoxy resin flame retardant powder. This flame retardant had a softening point of 100 ° C., a bromine content of 50%, and an average degree of polymerization of 1.1. Let this be a flame retardant (A-4).

Synthesis Example 5 (same as above) A pale yellow halogenated epoxy resin flame retardant powder was obtained in exactly the same manner as in Synthesis Example 4 except that 725 g of EPICLON 152 and 275 g of TBA were used. This flame retardant had a softening point of 125 ° C., a bromine content of 50%, and an average degree of polymerization of 2.2. This is designated as a flame retardant (A-5).

Synthesis Example 6 (Same as above) A pale yellow halogenated epoxy resin flame retardant powder was obtained in the same manner as in Synthesis Example 1 except that 685 g of EPICLON152 and 315 g of TBP were used. This flame retardant is
It had a softening point of 95 ° C., a bromine content of 54%, and an average degree of polymerization of 0.1. This is designated as a flame retardant (A-6).

Synthesis Example 7 (same as above) 1197 g of TBA and 20% NaOH aqueous solution were placed in a 5 liter separable flask equipped with a thermometer and a stirrer, the inside was replaced with nitrogen gas, and the contents were heated to 60 ° C. . After that, 292 g of epichlorohydrin was added to 70-
The reaction was carried out at 80 ° C for 5 hours. After the reaction, 1800 g of methyl isobutyl ketone was added to dissolve the product. The saline layer and the methyl isobutyl ketone solution layer were separated, and the methyl isobutyl ketone solution layer was neutralized with phosphoric acid. Then, the methyl isobutyl ketone solution layer was distilled and dehydrated by decantation. The obtained methyl isobutyl ketone solution was filtered and heated, and then methyl isobutyl ketone was distilled to be completely removed. Then, the reaction product was poured into a stainless steel pan, cooled, and then pulverized to obtain a pale yellow halogenated epoxy resin-based flame retardant powder. This flame retardant has a softening point of 100 ° C,
It had a bromine content of 50% and an average degree of polymerization of 1.1. This is designated as a flame retardant (A-7).

Synthesis Example 8 (Synthesis of decabromodiphenylethane) 320 g of bromine and 1.8 g of aluminum chloride were added to a thermometer, a reflux condenser, a dropping funnel and a stirrer.
A 5 liter flask was charged. A solution prepared by dissolving 18.2 g of diphenylethane in 49.4 g of methylene bromide was added dropwise from a dropping funnel over 30 minutes. Then, it heated at 65-67 degreeC for 6 hours, and completed the reaction. The reaction was cooled to room temperature and 150 ml of water was added to deactivate the catalyst. After deactivation,
Upon heating, unreacted bromine and methylene bromide were distilled off.
The solid product was filtered and washed twice with 200 ml of water each time. By drying at 160 ° C. for 1 hour and then aging at 200 ° C. for 15 hours, 95.5 g of a white product (decabromodiphenylethane) was obtained. This product has a melting point of 34
The average bromine content was 4% to 354 ° C and the average bromine content was 82%.
Let this be a flame retardant (B-1).

Examples 1 to 9 and Comparative Examples 1 to 3 Each component was blended with the composition shown in Table 1, premixed with a tumbler mixer, and pelletized with a 30 mmφ twin-screw extruder. Then, test pieces for various tests were prepared using a 5 ounce injection molding machine, and a heat resistance test, a falling weight impact test and a molding fluidity test were performed. The results are shown in Table 1.

The cylinder set temperature of the extruder and the injection molding machine was 200 to 220 ° C. Examples 10 to 17 and Comparative Examples 4 to 7 Each component was blended with the composition shown in Table 2, premixed with a tumbler mixer, and then pelletized with a 30 mmφ twin-screw extruder. Then, test pieces for various tests were prepared using a 5 ounce extruder, and a heat resistance test, a falling weight impact test and a molding fluidity test were performed. A combustion test and a falling weight impact test were performed. The results are shown in Table 2.

The cylinder set temperature of the extruder and the injection molding machine was 220 to 240 ° C.

[0040]

[Table 1] * 1) HIPS: Rubber modified polystyrene "GH-7000" manufactured by Dainippon Ink and Chemicals, Inc. (hereinafter the same)

[0041]

[Table 2]

[0042]

[Table 3] * 2) ABS: Acrylonitrile-butadiene-styrene copolymer “Sebian V” manufactured by Daicel Chemical Industries, Ltd. (hereinafter the same)

[0043]

[Table 4]

[0044]

By using the flame retardant composition of the present invention, it is possible to provide a flame-retardant styrene resin composition which is excellent in impact resistance, heat resistance, light resistance, molding fluidity and surface gloss. Since the molded product is excellent in various physical properties, it is useful as a material for electric appliances, electronic parts, OA equipment and the like.

Claims (10)

[Claims] 1. A halogenated epoxy resin flame retardant (A).
And a polyhalogenated diphenylalkane (B). 2. A halogenated epoxy resin flame retardant (A).
Is a halogenated bisphenol type epoxy resin and /
The flame retardant composition according to claim 1, which is a compound having a structure in which a part or all of terminal epoxy groups of a halogenated bisphenol type epoxy resin is blocked with a halogenated phenol. 3. The flame retardant composition according to claim 2, wherein the halogenated bisphenol type epoxy resin has an average degree of polymerization of 0 to 1.5. 4. The flame retardant composition according to claim 1, 2 or 3, wherein the polyhalogenated diphenylalkane (B) is decabromodiphenylethane. 5. A halogenated epoxy resin flame retardant (A).
And a polyhalogenated diphenylalkane (B) and a styrene resin (C). 6. A halogenated epoxy resin flame retardant (A).
Is a halogenated bisphenol type epoxy resin and /
2. The resin composition according to claim 1, which is a compound having a structure in which a part or all of terminal epoxy groups of a halogenated bisphenol type epoxy resin is blocked with a halogenated phenol. 7. The resin composition according to claim 6, wherein the halogenated bisphenol type epoxy resin has an average degree of polymerization of 0 to 1.5. 8. The flame-retardant styrene resin composition according to claim 5, wherein the polyhalogenated diphenylalkane (B) is decabromodiphenylethane. 9. The resin composition according to claim 5, wherein the styrene resin (C) is rubber-modified polystyrene. 10. The styrene resin (C) is an acrylonitrile-butadiene-styrene copolymer.
The resin composition according to any one of items 1 to 8.