JPH073107A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in heat resistance, impact resistance and flame retardancy and having a high flowability. CONSTITUTION:The composition consists of 100 pts.wt. rubber toughened styrene resin (A), 5-35 pts.wt. total of a tetrabromobisphenol A epoxy resin (B) of a weight-average molecular weight of 10,000 to 100,000 and a tetrabromobisphenol A epoxy oligomer (C) of a weight-average molecular weight of 500 to 3,000, 2-15 pts.wt. antimony trioxide (D), 1-15 pts.wt. chlorinated polyethylene (E), at most 8 pts.wt. condensed phosphoric ester (F) and at most 2 pts.wt. silicon compound (G), wherein the total of components B, C, D, E, F and G is 10-50 pts.wt. and the weight ratio of component B to component C is (20:80) to (80:20).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a rubber-reinforced styrene resin composition having excellent heat resistance, impact resistance and flame retardancy.

[0002]

2. Description of the Related Art In recent years, in order to clear various legal rules for fire prevention, flame-retardant acrylonitrile-butadiene-styrene copolymers (hereinafter abbreviated as ABS resins) are used. Rubber-reinforced styrene resins are widely used in the fields of home appliances, office automation equipment and the like. As a flame-retardant method of rubber-reinforced styrene resin, a method of using a brominated flame retardant and antimony trioxide in combination is generally used, depending on the required flame retardancy and mechanical properties, the type of brominated flame retardant, Although the method of setting the amount and the amount of antimony trioxide has been adopted, there is a problem that mechanical properties are deteriorated when flame retardancy is improved. In order to improve flame retardancy, a method in which two carbonate oligomers of tetrabromobisphenol A and tetrabromobisphenol A are combined as a brominated flame retardant (JP-A-60-
192761), or a method of combining three kinds of a carbonate oligomer of tetrabromobisphenol A, tetrabromobisphenol A and polydibromophenylene oxide (JP-A-58-38746). However, these methods have a drawback that the flame resistance is improved but the impact resistance is decreased.

[0003]

DISCLOSURE OF THE INVENTION In the present invention, as a result of extensive studies to solve the above-mentioned drawbacks, surprisingly, an epoxy resin of tetrabromobisphenol A (hereinafter sometimes abbreviated as TBA) and tetra. Using an epoxy oligomer of brombisphenol A as a brominated flame retardant,
The inventors have found that when antimony trioxide, chlorinated polyethylene, condensed phosphoric acid ester, and a silicon compound are combined, the flame retardancy is improved without lowering the impact resistance and heat resistance, and the present invention has been completed.

That is, the present invention comprises the following components (A) to (G):
The total amount of (B) and (C) is 5 to 35 parts by weight, and (B), (C), (D), (E), (F),
Difficulty characterized by being added such that the total amount of (G) is 10 to 50 parts by weight and the weight ratio of (B) / (C) is 20/80 to 80/20. The content is a flammable resin composition. (A) 100 parts by weight of rubber-reinforced styrene resin, (B) epoxy resin of tetrabromobisphenol A having a weight average molecular weight of 10,000 to 100,000, (C) tetrabromobisphenol A having a weight average molecular weight of 500 to 3,000 Epoxy oligomer of (D) antimony trioxide 2
˜15 parts by weight, (E) 1 to 15 parts by weight of chlorinated polyethylene, (F) 8 parts by weight or less of condensed phosphate ester, and (G) 2 parts by weight or less of a silicon compound.

The rubber-reinforced styrenic resin used in the present invention is at least one selected from aromatic vinyl compounds, vinyl cyanide compounds, acrylic acid esters and methacrylic acid esters in the presence of a rubber-like polymer. Examples thereof include a resin obtained by graft-polymerizing a compound, or a resin obtained by mixing a polymer obtained by polymerizing one or more compounds selected from the above compound group with the graft polymer.

As the aromatic vinyl compound, styrene,
α-methylstyrene, o-methylstyrene, p-methylstyrene, chlorostyrene, bromostyrene, dibromostyrene, tribromostyrene, etc., and the vinyl cyanide compound, acrylonitrile, methacrylonitrile, etc., acrylic acid ester. As, methyl acrylate, ethyl acrylate, butyl acrylate, 2-
Ethylhexyl acrylate, stearyl acrylate, and the like, and methacrylic acid esters include methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, and the like, all of which are used alone or in combination of two or more.

Examples of the rubber-like polymer include dibutadiene rubber-like polymers such as polybutadiene rubber and butadiene-styrene rubber (SBR), ethylene-propylene copolymer, ethylene-propylene-diene copolymer, acrylic acid. Examples thereof include acrylic rubber mainly containing an ester, and these may be used alone or in combination of two or more kinds.

As the rubber-reinforced styrenic resin (A) used in the present invention, ABS resin or acrylonitrile-ethylene-propylene-styrene copolymer (hereinafter abbreviated as AES resin) is workability and impact resistance. sex,
When it is suitable from the viewpoint of heat resistance and further requires heat resistance, the ABS resin or AES resin is copolymerized with α-methylstyrene or phenylmaleimide, or α-methylstyrene or phenylmaleimide is copolymerized. Mixing the polymers is suitable. Further, it is necessary to use a resin in which the residual amount of the sulfur-based chain transfer agent in the rubber-reinforced styrene-based resin is preferably 0.25% by weight or less, more preferably 0.15% by weight or less in terms of thermal stability. Is preferred. As the polymerization method, any of emulsion polymerization, suspension polymerization, solution polymerization and bulk polymerization may be used. When synthesizing the rubber-reinforced styrene resin (A) by emulsion polymerization or suspension polymerization, a sulfonic acid emulsifier is used as a surfactant to be used at the time of polymerization from the viewpoint of mold stain resistance. The resin is preferably 80% by weight or more, more preferably 90% by weight or more.

The tetrabromobisphenol A (TBA) epoxy resin (B) and tetrabromobisphenol A (TBA) epoxy oligomer (C) used in the present invention are compounds represented by the general formula (I).

[0010]

[Chemical 1]

However, in the general formula (I), Y1 and Y2 are either the general formula (II) or the general formula (III). n is an integer that can be determined according to the weight average molecular weight.

[0012]

[Chemical 2]

[0013]

[Chemical 3]

Here, X is a bromine atom or chlorine atom, R is a lower alkyl group, i is 0 or an integer of 1 to 4, j is an integer of 0 or 1 to 5, and i + j is 5 or less. From the viewpoint of impact resistance, the epoxy oligomer (C) of TBA is either one of Y1 and Y2 in the general formula (I) (abbreviated as one end cap), or both Y1 and Y2 (both ends capped). (Abbreviation) is preferably general formula (II). The epoxy resin (B) of TBA has a weight average molecular weight of 10,000 to
100,000, preferably 20,000-80,000
The range is 0. When the molecular weight is less than 10,000, impact resistance is lowered, and when it exceeds 100,000, fluidity is significantly lowered. The epoxy oligomer (C) of TBA has a weight average molecular weight of 500 to 3,000, preferably 700 to 3,000.
The range is 2,500. If the molecular weight is less than 500 or exceeds 3,000, the impact resistance decreases.

The amount of the TBA epoxy resin (B) and the TBA epoxy oligomer (C) used is 5 to 35 parts by weight in total of (B) and (C) per 100 parts by weight of the rubber-reinforced styrene resin. Yes, and preferably 10 to 30.
In order to increase the flame retardancy, the larger the amounts of the TBA epoxy oligomer (C) and the TBA epoxy resin (B), the better, but from the viewpoint of impact resistance, it is 35 parts by weight or less. TBA
From the viewpoint of fluidity and impact resistance, the use ratio of the epoxy resin (B) and the epoxy oligomer (C) of TBA is
The weight ratio of (B) / (C) is 20/80 to 80/20, preferably 25/75 to 75/25. When (B) is less than this weight ratio, impact resistance is lowered, and when it is more than this weight ratio, fluidity is lowered.

The antimony trioxide (D) used in the present invention is an essential component for efficiently obtaining flame retardancy. The amount of antimony trioxide (D) used is 2 to 15 parts by weight with respect to 100 parts by weight of the rubber-reinforced styrene resin,
It is preferably 5 to 12 parts by weight. Antimony trioxide (D) has a synergistic effect of brominated flame retardant and flame retardant, and preferably 1/8 to 1 / of the above brominated flame retardants (B) and (C).
Amounts of 2 and more preferably 1/6 to 1 / 2.5 are effective. The antimony trioxide (D) used has an average particle size of preferably 2 μm or less, more preferably 1.5 μm or less, from the viewpoint of flame retardancy and impact resistance. Further, from the viewpoint of thermal stability, the sulfur content of antimony trioxide (D) is preferably 0.02% by weight or less, more preferably 0.01% by weight or less.

The chlorinated polyethylene (E) of the present invention is an essential component for obtaining a high degree of flame retardancy and impact resistance. The amount of chlorinated polyethylene (E) used is 1 to 15 parts by weight, preferably 2 to 12 parts by weight. The flame retardancy and impact resistance are improved as the amount used is increased, but the heat resistance is remarkably lowered when the amount exceeds 15 parts by weight. The chlorine content of the chlorinated polyethylene (E) is preferably 40 from the viewpoint of thermal stability.
% Or less, more preferably 30% or less, and preferably 15% or more from the viewpoint of flame retardancy.

The condensed phosphoric acid ester (F) of the present invention is a necessary component for obtaining high flame retardancy, impact resistance and fluidity. The amount of the condensed phosphoric acid ester (F) used is 8 parts by weight or less, preferably 0.1 to 5 from the viewpoint of impact resistance.
Parts by weight. The condensed phosphoric acid ester (F) is preferably a compound having a melting point of 100 ° C. or higher from the viewpoint of mold contamination.
The condensed phosphoric acid ester has the general formula (IV)

[0019]

[Chemical 4]

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are aryl groups, alkaryl groups and X is an arylene group,
m ₁ , m ₂ , m ₃ , and m ₄ are 0 or 1, and n is 1 to 5
Or an average value of 1 to 5 for blends. And an oligomeric phosphoric acid ester having a) or a blend of oligomeric phosphoric acid esters.

The silicon compound (G) of the present invention is a necessary component for obtaining high flame retardancy and impact resistance. The amount of the silicon compound (G) used is 2 parts by weight or less from the viewpoint of flame retardancy and impact resistance, and preferably 0.01-1.
5 parts by weight. Examples of the silicon-based compound (G) include dimethylpolysiloxane, methylphenylpolysiloxane, silicic acid esters and terminal modified derivatives thereof, and these may be used alone or in combination of two or more.

In the flame-retardant resin composition of the present invention, T is added to 100 parts by weight of the rubber-reinforced styrene resin (A).
BA epoxy resin (B), TBA epoxy oligomer (C), antimony trioxide (D), chlorinated polyethylene (E), condensed phosphoric acid ester (F) and silicon compound (G) are 10 to 10 in total. High flame retardancy can be obtained by using 50 parts by weight and setting the weight ratio of (B) / (C) within the range of 20/80 to 80/20. (B),
The total amount of (C), (D), (E), (F), and (G) is 1
If it is less than 0 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 50 parts by weight, the impact resistance is significantly lowered. Ingredient (B) T
Epoxy resin of BA, TPO epoxy oligomer of component (C), antimony trioxide of component (D) and component (E)
Unless a complex system of the chlorinated polyethylene of No. 1, the condensed phosphoric ester of component (F) and the silicon compound of component (G) is not used, high flame resistance is maintained and high impact resistance and high heat resistance are obtained. Neither can it be obtained or the amount of flame retardant used cannot be reduced.

The flame-retardant resin composition of the present invention comprises a rubber-reinforced styrene resin (A) in powder or pellet form,
Tetrabrom bisphenol A epoxy resin (B),
It is obtained by blending an epoxy oligomer of tetrabromobisphenol A (C), antimony trioxide (D), chlorinated polyethylene (E), condensed phosphoric acid ester (F) and silicon compound (G). Is not particularly limited. For example, it can be easily produced by a roll, Banbury mixer, or extruder.

The flame-retardant resin of the present invention includes not only antioxidants, heat stabilizers and lubricants that are generally well known, but also UV absorbers, pigments, antistatic agents, and flame retardants other than those mentioned above, if necessary. A flame retardant auxiliary can also be used together. Especially phenolic antioxidants, phosphite stabilizers, hindered amine stabilizers, benzotriazole stabilizers, tin stabilizers, lead stabilizers, and various fatty acid esters, metal soaps, waxes used in styrene resins. Internal and external lubricants such as the flame-retardant resin composition of the present invention as a molding resin,
It can be used for higher performance.

Hereinafter, the present invention will be described in more detail based on specific examples, but these examples do not limit the present invention in any way. In the following description, "part"
Indicates parts by weight, and "%" indicates% by weight.

Example 1 1. Synthesis of rubber-reinforced styrene resin (A1) (a) Synthesis of copolymer (A1-1) A reaction vessel equipped with a stirrer and a cooler was charged with the following substances in a nitrogen stream. Water 250 parts Sodium formaldehyde sulfoxylate 0.2 parts Ferrous sulfate 0.0013 parts Disodium ethylenediaminetetraacetate 0.005 parts Sodium dodecylbenzenesulfonate 1.0 parts After heating and stirring at 70 ° C. in a nitrogen stream, 70 parts of styrene, 30 parts of acrylonitrile, 0.2 part of cumene hydroperoxide as an initiator, 0.4 part of terpinolene as a polymerization degree adjuster, 0.3 part of tert-lead decyl mercaptan.
05 parts of the mixture was continuously added dropwise over 5 hours.
After the dropping was completed, stirring was further continued at 70 ° C. for 1 hour to terminate the polymerization.

(B) Synthesis of graft copolymer (A1-2) The following substances were charged in a reaction vessel equipped with a stirrer and a cooler in a nitrogen stream. Water 250 parts Sodium formaldehyde sulfoxylate 0.2 parts Ferrous sulfate 0.0025 parts Ethylenediaminetetraacetic acid disodium 0.01 parts Polybutadiene rubber * 60 parts * Polybutadiene rubber is sodium dodecylbenzenesulfonate as a surfactant. What was synthesize | combined using was used. After heating and stirring at 60 ° C. in a nitrogen stream, a mixed solution of 28 parts of styrene, 12 parts of acrylonitrile and 0.2 part of cumene hydroperoxide as an initiator was continuously added dropwise over 5 hours. 60 more after dropping
Stirring was continued for 1 hour at 0 ° C. to complete the polymerization. The copolymers (A1-1) and (A1-1) obtained in (a) and (b) above.
1-2) latex is uniformly mixed at a ratio of 2/1,
After adding a phenolic antioxidant and coagulating with an aqueous calcium chloride solution, washing with water, dehydration and drying were carried out to obtain a rubber-reinforced styrene resin (A1) powder.

2. Method for producing flame-retardant resin Rubber-reinforced styrene resin (A1) produced as described above and tetrabromobisphenol A epoxy resin (B
1), an epoxy oligomer of tetrabromobisphenol A (C1), antimony trioxide (D), a chlorine content of 20
% Chlorinated polyethylene (E), condensed phosphoric acid ester (F) CR-733S manufactured by Daihachi Chemical Co., Ltd., dimethylpolysiloxane as a silicon compound (G) and ethylenebisstearylamide (1 part) as a lubricant,
Dibutyl tin malate polymer (0.5
Parts) were blended in the ratio shown in Table 1 with a super mixer to prepare pellets with a 40 m / m extruder. A test piece was molded from the pellets with a 150TON injection molding machine under the conditions of a screw rotation speed of 60 rpm and a nozzle set temperature of 220 ° C.

Examples 2 to 9 and Comparative Examples 1 to 7 By the same method as in Example 1 above, flame-retardant resin compositions having the compositions shown in Table 1 and test pieces thereof were prepared. The rubber-reinforced styrenic resin (A2) is a graft obtained by using the same weight parts of sodium palmitate as the surfactant instead of sodium dodecylbenzenesulfonate as a surfactant during the synthesis of the polymer of (A1-1) and the graft copolymer. Copolymer (A
1-3) was used, the phosphoric acid ester was cresyl diphenyl phosphate, and the others were similarly synthesized.

The test pieces of Examples 1 to 9 and Comparative Examples 1 to 7 were used to evaluate the impact resistance, flame retardancy, fluidity and mold stain resistance by the following methods. The results are shown in Table 1. Impact resistance is
Evaluation was made by the half-fracture energy (half-fracture height × weight load) of a flat plate (100 mm × 150 mm × thickness 3 mm). The flame retardancy was evaluated in 1/10 inch thickness based on UL-94 standard. Flowability is set temperature 220 ℃, injection pressure 110
It was evaluated by the flow length in a mosquito coil-shaped mold (thickness: 3 mm) at 0 kg / cm ² . The mold staining property was evaluated by visually evaluating the degree of haze of the mold surface after molding by molding a two-point gate flat plate at 230 ° C. using the above-mentioned molding machine. The numbers are
A larger value means less clouding.

From the results shown in Table 1, the flame-retardant resin composition of the present invention represented by Examples is particularly excellent in the balance of impact resistance and fluidity, and also excellent in flame retardancy and mold contamination. Recognize.

[0032]

[Table 1]

(Note) The polybutadiene rubber, the epoxy resins B1 to B3 of TBA, and the epoxy oligomers C1 and C2 of TBA are as follows. Polybutadiene rubber: latex having an average particle size of 2500Å, gel content 95% TBA epoxy resin (B) B1: weight average molecular weight 55,000 B2: weight average molecular weight 25,000 B3: weight average molecular weight 15,000 epoxy oligomer ( C) C1: Weight average molecular weight 1,300 C2: Weight average molecular weight 1,200 End-capped type

[0034]

The flame-retardant resin composition of the present invention has an excellent balance of impact resistance and fluidity, as well as excellent flame retardancy and mold contamination.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 55/02 LMF 63/00 NHR

Claims (4)

[Claims] 1. A composition comprising the following components (A) to (G):
The total amount of (B) and (C) is 5 to 35 parts by weight,
The total amount of (B), (C), (D), (E), (F), and (G) is 10 to 50 parts by weight, and (B) /
A flame-retardant resin composition, which is added so that the weight ratio of (C) is 20/80 to 80/20. (A) 100 parts by weight of rubber-reinforced styrene-based resin, (B) epoxy resin of tetrabromobisphenol A having a weight average molecular weight of 10,000 to 100,000, (C) tetrabromobisphenol A having a weight average molecular weight of 500 to 3,000 The epoxy oligomer of (D) 2 to 15 parts by weight of antimony trioxide, (E) 1 to 15 parts by weight of chlorinated polyethylene, (F) 8 parts by weight or less of condensed phosphate ester, and (G) 2 parts by weight of silicon compound. Less than. 2. The weight average molecular weight of the component (C) is from 500 to
The flame-retardant resin composition according to claim 1, wherein the 3,000 epoxy oligomer of tetrabromobisphenol A is an oligomer having one end or both ends blocked. 3. The flame-retardant resin composition according to claim 1, wherein the condensed phosphoric acid ester as the component (F) has a melting point of 100 ° C. or higher. 4. The rubber-reinforced styrene-based resin of component (A) is a resin obtained by using a sulfonic acid-based emulsifier as a surfactant used during polymerization in an amount of 80% or more of the total surfactant used. Item 3. The flame-retardant resin composition according to items 1 to 3.