JP2935161B2 - Flame retardant and flame retardant resin composition containing the flame retardant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant for styrenic resins, and a flame-retardant styrenic resin composition containing the flame retardant. The present invention relates to a flame-retardant styrenic resin composition that has excellent heat resistance and fluidity and that reduces adhesion to metal.

[0002]

2. Description of the Related Art High impact polystyrene (HIP)
S), styrene-based resins such as ABS have good mechanical properties, and excellent electrical insulation properties and moldability, and thus are widely used in recent years, such as OA equipment, housings of home electric appliances, and automobile parts. However, since styrene resins are flammable, flame retardancy is required for safety. In particular, in the fields of OA equipment, home electric appliances, etc., they are used indoors, but are exposed to fluorescent light and light coming from outside, so that light resistance is emphasized. Conventionally, various halogenated organic compounds have been proposed for imparting flame retardancy to styrene resins. Typically, tetrabromobisphenol A (TBA), decabromodiphenyl ether (DBDPE), brominated epoxy resin, and the epoxy group of this brominated epoxy resin are blocked with tribromophenol (TBP). Are known. Particularly, the above two are widely used because they are inexpensive. However, when TBA is blended with a styrene-based resin, there is a drawback that heat resistance and light resistance are significantly reduced, and an epoxy resin blocked with DBDPE and TBP has a drawback of reducing light resistance. In addition, the brominated epoxy resin has high adhesion to metal parts such as an extruder at the time of melt-kneading and a molding machine at the time of molding, so that the attached matter is exposed to a high temperature for a long time, causing discoloration and deterioration. As a result, it is mixed as a foreign substance into a compound or a molded product.

[0003]

The present inventors have found 0005] made extensive research results in order to improve the drawbacks of this like, short chain part or all of the epoxy groups of the brominated epoxy resin monoalcohols - Le <br / > The blocked halogen-containing compound imparts flame retardancy to the polystyrene resin without deteriorating light resistance,
Furthermore, by using a flame retardant aid and optionally other additives together with the flame retardant, it is excellent in weather resistance, heat resistance and fluidity with high flame retardancy, and adheres to metal. It has been found that a flame-retardant styrenic resin composition having reduced flame retardancy can be obtained, and the present invention has been completed. An object of the present invention is to provide a flame retardant and a flame-retardant resin containing the flame retardant. It is to provide a composition.

[0004]

SUMMARY OF THE INVENTION The means for solving the problem], a part of the epoxy groups of the halogenated epoxy resin or entirely short Kusarimo Noaruko below 8 carbon atoms - have a blocked structure Le <br / > styrene resin for flame retardant agent characterized by consisting end sequestered halogen-end you, and flame retardancy, characterized by comprising the following (a) (B) (C ) It is a styrene resin composition. (A) Styrene resin. At least one flame halogen-containing compounds end sealed end that having a blocked structure Le - (B) a portion of the epoxy groups of the halogenated epoxy resin or entirely short Kusarimo Noaruko eight carbon atoms Flame retardant. (C) a flame retardant aid.

Hereinafter, the flame retardant of the present invention will be described. The flame retardant (B) used in the present invention is a halogenated epoxy resin.
Part or all of the epoxy group of the xy resin has 8 or less carbon atoms
Having a structure blocked with a short-chain monoalcohol
It is a chained halogen compound. The blocking ratio of the epoxy group of the halogenated epoxy resin in this compound is 20%.
-100% is preferable, and 50% or more is more preferable.
If the epoxy group blocking rate is 20% or less, the effect of reducing the adhesion to metal cannot be expected. Moreover, short-chain monoalcohols that used to blockade of the epoxy groups of the halogenated epoxy resin -
When a compound having 10 or more carbon atoms is used, the halogen content of the flame retardant is remarkably reduced, the effect of imparting flame retardancy is reduced, and the flame retardant composition is used. Heat resistance, heat distortion temperature, mechanical properties, etc. are reduced.

The halogenated epoxy resin used herein is a reaction product of a halogenated bisphenol with an epihalohydrin, a reaction product of a halogenated phenol-novolak or a halogenated cresol-novolak with an epihalohydrin, or a reaction product of the reaction. Reaction product of a halogenated epoxy resin with a halogenated bisphenol. The degree of polymerization is preferably about 0 to 30. When the degree of polymerization is higher than 30, the flowability and impact resistance of the flame-retardant resin composition tend to decrease.

Specific examples of the halogenated epoxy resin include diglycidyl ether of tetrachlorobisphenol A and diglycidyl ether of tetrabromobisphenol A.
And diglycidyl ether of tetrabromobisphenol S, diglycidyl ether of tetrachlorobisphenol S, and diglycidyl ether of dibromophenol novolak. Halogenated epoxy short carbon number you block the epoxy groups of 8 or fewer resin monoalcohols - Le can be, for example, methanol -, ethanol - le,
Examples thereof include propanol, butanol, amyl alcohol, hexanole, heptanol, benzyl alcohol, and isomers thereof.

[0008] As manufacturing <br/> method for producing compounds which are flame retardant used in the present invention include the following methods. i. Short Kusarimo Noaruko - and the presence DEHA halogenated epoxy resin catalyst sequestering agent for the epoxy groups reacting with an epoxy group such as Le, optionally halogenated bisphenol - heating reaction and Le acids to 80 ° C. to 220 ° C. How to let. ii. Halogenated bisphenol - le compound with epihalohydrin and upper Kitan chain monoalkoxy - How an epoxy group blocking agent consisting of Le in the presence of an alkali metal and a non-reactive solvent hydroxide, obtained by reacting. iii. As Le hydroxyl, upper Kitan chain monoalcohols - - terminus of the halogenated epoxy resin is phenol Le of glycidyl - method of heating react and ether in the presence of a catalyst. Catalysts used in these reactions include alkali metal hydroxides,
Tertiary amines, imitazoles, quaternary amonium salts,
Phosphines and phosphonium salts are known.
The method for producing the flame retardant is not particularly limited, and can be easily produced by a known method.

Next, the flame-retardant resin composition according to the present invention will be described. The styrene resin as the component (A) used in the present invention is a homopolymer or a copolymer of a styrene compound such as styrene, α-methylstyrene, vinyltoluene and o-chlorostyrene, and if necessary, these monomers. And acrylate copolymers such as acrylonitrile and polybutadiene rubber; and maleimide copolymers such as maleimide and N-phenylmaleimide. Typically, polystyrene, HIPS, AS resin, ABS resin, AES resin, MBS resin and the like can be mentioned.

The styrenic resin (A) is blended with the above-mentioned flame retardant (B) of the present invention and a flame retardant aid. As the flame retardant aid, for example, antimony trioxide, antimony pentoxide, molybdenum oxide and the like are used, and when these are used in combination, the flame retardant effect is further enhanced. Further, the composition of the present invention, if necessary, commonly used ultraviolet absorbers, antioxidants, lubricants, coloring agents, release agents, fillers,
Dyes and pigments can be added. Hereinafter, the effects of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the method for producing a flame retardant and the method for producing a flame retardant composition of the present invention are not particularly limited. Absent. In the examples, all parts and percentages are based on weight.

The test methods in the examples are as follows. (1) Epoxy equivalent: JIS K-7234. (2) Softening point: JIS K-7236. (3) Heat deformation temperature: JIS K-7207. (4) Light resistance ΔE: An exposure test (no rain) was conducted at 63 ° C. for 48 hours using a sunshine weather meter.
The color difference of the test piece before and after the exposure was measured with a color difference meter (manufactured by Tokyo Denshoku Co., Ltd.). (5) Flammability test: Based on UL-94 test method. (6) Tensile strength: JIS K-7113. (7) Low adhesion test: In a metal heat roll, the first roll was set at 200 ° C. and the second roll was set at 60 ° C., and the test piece was placed on the first roll. After gently pressing for 3 minutes and then operating for 3 minutes, the test piece was peeled off and the state of adhesion to the roll was observed. ：: Does not adhere to the roll. Δ: easily peeled off from the roll. ×: Adhered to the roll and not peeled off.

[0012]

EXAMPLES AND COMPARATIVE EXAMPLES Example 1 640 g of YDB-400, 725 g of TBA and Epoxy
Butyl glycidyl ether 1 having a siquivalent weight of 135 g / eq.
And 63 g of triphenylphosphine as a catalyst.
Add 0.44g, attach thermometer, stirrer, condenser
Into a 1 liter separable flask,
After gas replacement, heat and melt.
After adding 0.6 ml of min, at 120-160 ° C,
The reaction was performed for 5 hours. After the reaction, remove the reactant
Put, cooled, and pulverized to obtain a flame retardant b _1. That sex
The conditions are shown in Table 1.

[0013] Example 2 (hereinafter referred to as ECH) epichlorohydrin 250g and T
BA1014g, methanol 57g and methyl isobutyl
136 g of ketone (hereinafter abbreviated as MIBK) with a thermometer,
1 liter with stirrer, dripping device and condenser
Charge into a separable flask and raise the temperature while purging with nitrogen
Dissolve and add 47 g of 48% NaOH aqueous solution at 75 ° C.
After reacting for 2 hours, 170 g of MIBK and N
240 g of an aOH aqueous solution was added and reacted for 5 hours. Anti
After the reaction, dilute the resin liquid with MIBK and ion exchange water
After washing and removing the salt, MIBK is evaporated off,
To obtain a flame retardant b ₂ a pale yellow. The properties are shown in Table 1.

[0014] Comparative Example 1 YDB-400 800 g and TBA136g and tribromo phenol - charged and Le 445g in the same manner as in Example 1, triphenylphosphine 0.35g was added as a catalyst, 1
The reaction was performed at 70 to 180 ° C. for 5 hours. The resulting flame retardant F ₁ having properties shown in Table 1.

[0015] charged with Comparative Example 2 YDB-400 800 g and TBA200g as in Example 1, triphenyl phosphine 0.1
2 g was added and reacted at 170-180 ° C. The resulting properties of the flame retardant F ₂ shown in Table 1.

[0016]

[Table 1]

[0017] Examples 3-4 and Comparative Examples 3-5 Examples 1-2 and Comparative Examples 1 and 2 from the resulting flame-retardant and decabromodiphenyl et - blended ether with compositions each shown in Table 2 After mixing with a Henschel mixer, the mixture was melt-mixed with a twin screw extruder (Ikegai PCM-30) to obtain a compound. A test piece was further prepared from the obtained compound by injection molding. Using this test piece, the flammability, release property, light resistance, heat deformation temperature, and tensile strength were measured. Table 2 shows the results.

[0018]

[Table 2]

[0019]

Flame retardant of the present invention exhibits that sequester epoxy groups of the halogenated epoxy resin with short-chain monoalcohol, or a short chain alkyl the end of halogenated epoxy resin
By using a compound having an ether bond together with antimony trioxide as a flame retardant aid, it is possible to provide a flame retardant styrene resin. Furthermore, in the flame retardant composition of a styrene resin using the flame retardant of the present invention, it is possible to obtain excellent light resistance and excellent mold releasability on a metal part of an extruder or an injection molding machine, and at the same time, molding. It is useful for improving productivity such as processing.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-238194 (JP, A) JP-A-7-216162 (JP, A) JP-A 5-125238 (JP, A) JP-A 5- 117463 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 59/14-59/16 C08L 25/00-25/18 C08L 63/00-63/10 C09K 21/14

Claims (2)

(57) [Claims] Be made of halogen-containing compounds end sealed end that having a blocked structure Le - 1. A part of the epoxy groups of the halogenated epoxy resin or entirely short Kusarimo Noaruko below 8 carbon atoms A flame retardant for a styrenic resin characterized by the following. 2. A flame-retardant styrenic resin composition containing the following (A), (B) and (C). (A) Styrene resin. At least one flame halogen-containing compounds end sealed end that having a blocked structure Le - (B) a portion of the epoxy groups of the halogenated epoxy resin or entirely short Kusarimo Noaruko eight carbon atoms Flame retardant. (C) a flame retardant aid.