JPH0892445A - Flame-retardant styrenic resin composition - Google Patents

Abstract

PURPOSE: To obtain a flame-retardant styrenic resin compsn. excellent in flame retardance and the balance among heat resistance, impact resistance, and flowability by compounding a styrenic resin with two specific halogenous flame retardants, an auxiliary flame retardant, and a small amt. of polytetrafluoroethylene. CONSTITUTION: This resin compsn. comprises 100 pts.wt. styrenic resin (A), 2-18 pts.wt. halogenated arom. -diol-based ether deriv. (B) having a wt.-average mol.wt. of 500-10,000 [a compd. of formula I (wherein R is H, a group of formula II, etc.; X is Br or Cl; (i), (j), (k), and (m) are each 1-4; and (n) is 0-30)], 2-16 pts.wt. polyhalogenated diphenylalkane (C) of formula III [wherein X is Br or Cl; (l) and (m) are each 0-5 excluding the case where they are both 0; and R is Cn H2n (wherein (n) is 1-10)], 1-10 pts.wt. Sb2 O3 (D), and 0.01-0.5 pt.wt. polytetrafluoroethylene (E), the sum of components B and C being 12-21 pts.wt. Thus, a compsn. excellent in flame retardance and the balance among heat resistance, impact resistance, and flowability is obtd. with a reduced amt. of halogenous flame retardants.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a styrene resin composition, and more particularly to a styrene resin composition which is excellent in flame retardancy and in which heat resistance, impact resistance and fluidity are well balanced.

[0002]

2. Description of the Related Art Styrenic resins are used in many fields because of their excellent moldability, mechanical properties and electrical properties. However, since it is easily flammable, it is necessary to make the resin flame-retardant when it is used for OA equipment, housings of home electric appliances and parts related to electricity and electronics. This flame retardancy is regulated by UL standards and the like, and various flame retardant means have been studied in recent years. Among them, in the housing field of home appliances, the above flame retardancy regulation and heat resistance,
Impact resistance and fluidity are required, and a well-balanced styrene-based resin satisfying all the required performances is required.

Generally, JP-A-58-187450 discloses that a flame-retardant styrene resin is used in combination with a high melting point halogen-containing flame retardant such as decabromodiphenyl oxide and antimony trioxide. ing. However, the drawbacks of this flame retardant are the problems of reduced fluidity and deterioration of the light resistance of the molded product. Further, in recent years, the toxicity of gas generated under certain conditions of this flame retardant has been taken up as an environmental problem.

Further, the combined use of a brominated bisphenol A type epoxy resin and antimony trioxide is disclosed in JP-A-63-72749. However, since this flame retardant has a low halogen content, a considerable amount of the flame retardant is required to obtain the desired flame retardancy, and thus impact resistance and heat resistance are significantly reduced, and
There was also a cost problem.

Further, if the polyhalogenated diphenylalkane is used as a styrene resin to make it flame-retardant, a large amount of non-melting solid is added to the resin in order to obtain the desired flame-retardant performance. There was a problem that strength and fluidity were lowered. Further, JP-A-6-73268 discloses that a polyhalogenated diphenylalkane and a brominated bisphenol A type epoxy resin are used in combination. However, it is possible to improve the fluidity by adding the polyhalogenated diphenylalkane. However, there is a problem that the impact resistance is lowered due to the decrease in the amount and the addition of the brominated bisphenol A type epoxy resin.

On the other hand, many studies have been conducted on the addition of halogen-containing substances and polytetrafluoroethylene to resins. For example, Japanese Patent Publication No. 59-36657,
JP-A-60-13844, JP-B-62-5862
No. 9, JP-B-64-3900, JP-A 2-3
2154 and JP-A-5-27531, the basic resin is a combination of a polycarbonate oligomer type and an acrylonitrile-butadiene-styrene type or a modified polyphenylene ether type.
Moreover, the addition of polytetrafluoroethylene is for the purpose of reducing the melt-dripping property of those resins. Further, regarding the polystyrene type, although it is described in JP-A No. 50-44241, depending on the kind of halide to be added,
There was a problem that the effect was very different.

[0007]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a styrene resin composition which is excellent in flame retardancy and also has a good balance of heat resistance, impact resistance and fluidity.

[0008]

Therefore, as a result of intensive studies to solve the above problems, the inventors of the present invention have found that two types of halogen-based flame retardants, a flame-retardant aid, and a small amount of styrene-based resins, which are specific to styrene-based resins, are used. It has been found that the addition amount of a specific halogen-based flame retardant is reduced and the object is achieved by combining and blending polytetrafluoroethylene, and the present invention has been completed.

That is, the present invention comprises (A) 100 parts by weight of a styrene resin and (B) a weight average molecular weight of 500 to 100.
Halogen-containing aromatic diol ether derivative of 00 2
.About.18 parts by weight, (C) 2 to 16 parts by weight of a polyhalogenated diphenylalkane represented by the following formula (1), (D) 1 to 10 parts by weight of antimony trioxide, and (E) polytetrafluoroethylene of 0.1. Consisting of 01-0.5 parts, (B)
The present invention provides a flame-retardant styrene resin composition, characterized in that + (C) is 12 to 21 parts by weight.

[0010]

[Chemical 2]

[In the formula, X represents a bromine atom or a chlorine atom, and l and m are integers of 0 to 5 (provided that both l and m are 0.
Never be. ), And R is C _n H _2n (n = 1 to 1
10) is shown. The present invention will be described in detail below. The styrene-based resin (A) used in the present invention is a polymer in which a rubber-like polymer is dispersed in particles in a matrix made of a vinyl aromatic polymer. Generally, the rubber-like polymer is a vinyl polymer. It is obtained by dissolving in an aromatic monomer (and a liquid containing an inert solvent), carrying out bulk polymerization, bulk suspension polymerization or solution polymerization under stirring, and depositing a rubber-like polymer to form particles. However, it is not limited to the polymerization method.

Examples of the vinyl aromatic monomer include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene,
Nuclear alkyl-substituted styrenes such as ethyl styrene and p-tertiary-butyl styrene, α-alkyl substituted styrenes such as α-methyl styrene and α-methyl-p-methyl styrene, and the like can be mentioned. Typical examples are styrene. Is. These may be used in combination of two or more thereof.

Examples of the rubber-like polymer include polybutadiene, styrene / butadiene copolymer, polyisoprene, butadiene / isoprene copolymer, natural rubber and ethylene / propylene copolymer.
Generally, polybutadiene and styrene-butadiene copolymer are preferred. The weight average molecular weight of the matrix portion of the rubber-modified vinyl aromatic resin that constitutes the resin composition of the present invention is usually adjusted to a range of 15 × 10 ⁴ or more in view of the strength. Drops sharply.

The rubber-like polymer content of the rubber-modified vinyl aromatic resin is not particularly limited, but generally 4 to 1
It is 5% by weight, more preferably 6 to 12% by weight. Further, the average particle size of the rubber particles in the rubber-modified vinyl aromatic resin is controlled in the range of 0.5 to 6.0 μm. Also,
The gel content (toluene-insoluble matter) of the styrene resin is
The amount is adjusted to 15 to 40% by weight, which is a conventional method, and more preferably 20 to 35% by weight. Next, the ether derivative of the halogen-containing aromatic diol used in the present invention is generally represented by the following formula (2).

[0015]

[Chemical 3]

[Wherein R is a hydrogen atom, represented by the following formula (3) or the following formula (4), X is a bromine or chlorine atom,
i, j, k, and m are integers of 1 to 4, and n is an integer of 0 to 30. ]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[R 'represents a phenyl group (which may be substituted with a lower alkyl group, bromine and / or chlorine atom). ] As a specific example, halogen-containing bisphenol A
The reaction product of halogen-containing bisphenol A epoxy resin, halogen-containing bisphenol A and epichlorohydrin were obtained by reacting them in a conventional manner, and the reaction ratio of halogen-containing bisphenol A and halogen-containing bisphenol A epoxy resin was It is possible to change the terminal to an OH group, to change to an epoxy group, or to change one to an OH group and the other to an epoxy group by changing it, and the reaction products thus obtained are all suitable. Flame retardant resin composition. Further, an ether derivative obtained by reacting the terminal epoxy group with tribromophenol, pentabromophenol or trichlorophenol is also a flame retardant suitable for the purpose of the present invention.

Specific examples of the halogen-containing bisphenol A include tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A and dibromobisphenol A. Specific examples of the halogen-containing bisphenol A epoxy resin include tetrabromobisphenol A diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, dichlorobisphenol A diglycidyl ether, and dibromobisphenol A diglycidyl ether. .

Particularly preferred are a reaction product of tetrabromobisphenol A and a diglycidyl ether of tetrabromobisphenol A, and an ether derivative obtained by reacting tetrabromobisphenol A with epichlorohydrin. The flame retardant (B) represented by the formula (2) in the present invention has a weight average molecular weight of 50.
It is necessary to be 0 to 10000. When the weight average molecular weight is lower than 500, the heat resistance of the molded product and the thermal stability at the time of molding are deteriorated, and sufficient flame retardancy cannot be imparted. On the other hand, when the weight average molecular weight is higher than 10,000, the compatibility with the resin is lowered and the impact resistance is remarkably lowered.

Next, the polyhalogenated diphenylalkane (C) in the present invention is represented by the above formula (1). Specific examples of the halogen-substituted phenyl group include dibromophenyl, tribromophenyl, tetrabromophenyl, pentabromophenyl, dichlorophenyl, trichlorophenyl, tetrachlorophenyl and pentachlorophenyl. The method for producing the flame retardant (C) is not particularly limited, but those produced by the method described in, for example, JP-A-2-42031 or JP-A-6-73268 may be used. As the polyhalogenated diphenylalkane (C) used in the present invention, a commercially available product may be used. For example, brominated diphenylethane (trade name Sayt manufactured by Albemarle Corporation in the United States) may be used.
ex8010).

Furthermore, the antimony trioxide which is the component (D) of the present invention is a substance which acts as a flame retardant aid. With respect to 100 parts by weight of the styrene-based resin (A), the compounding ratio thereof is 2 to 18 parts by weight of the ether derivative (B) of the halogen-containing aromatic diol, 2 to 16 parts by weight of the polyhalogenated diphenylalkane (C), and 1-10 parts by weight of antimony trioxide (D), 0.01-0.5 parts by weight of polytetrafluoroethylene (E), and (B)
+ (C) is 12 to 21 parts by weight. Preferably, the ether derivative of a halogen-containing aromatic diol is 2 to 13 parts by weight, polyhalogenated diphenylalkane is 5 to 13 parts by weight, antimony trioxide is 3 to 7 parts by weight, and polytetrafluoroethylene is 0.05 to 0. 1 part by weight, (B) +
(C) is 15 to 19 parts by weight.

In the method for producing the flame-retardant resin composition of the present invention, there is no particular limitation on the blending method by blending these components in predetermined amounts, and a Henschel mixer, a tumbler mixer, a super mixer, a Banbury mixer, a kneader, There are methods such as roll, single-screw extruder, and twin-screw extruder. In the composition of the present invention, other additives within a range that does not impair the object of the present invention, for example, chlorine compounds, bromine compounds, plasticizers, lubricants, stabilizers, ultraviolet absorbers, fillers, colorants,
A reinforcing agent or the like can be added.

[0025]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples. In the following examples and comparative examples, various properties of various flame-retarded styrene resins were measured and evaluated by the following methods. (1) Izod impact strength: Measured by ASTM-D256 at 23 ° C. using a notched test piece. (2) Vicat softening point: measured by ASTM-D1525. (3) Fluidity: Melt flow rate is ASTM-D12
38. (4) Flammability: Underwriters Laboratory, Inc. (Underwriters)
Laboratories Inc. , U. S. 94V described in 7-10 items of "UL94 Safety Standard: Combustion test of plastic materials for parts of equipment" published by A).
-2, 94V-1, 94V-0 (hereinafter "V-2", "V
Abbreviated as "-1" and "V-0". ).

[0026]

Examples 1 to 6 A brominated bisphenol A epoxy resin (trade name EC as an ether derivative of a halogen-containing aromatic diol was added to 100 parts by weight of a styrene resin.
14 Molecular weight 1400 Dainippon Ink and Chemicals, Inc.
And a brominated diphenylethane as a polyhalogenated diphenylalkane (trade name: Saytex8010).
Albemarle), antimony trioxide and polytetrafluoroethylene (trade name F104 manufactured by Daikin Industries, Ltd.) were mixed in a predetermined amount at the ratio shown in Table 1, and melt-kneaded with a twin-screw extruder (cylinder setting). Temperature 200 ℃)
After that, injection molding (cylinder temperature 200 ℃, mold temperature 60
C.) to form a molded piece. Using this test piece, Izod impact strength, Vicat softening point, fluidity, light resistance and flammability were measured. The results are shown in Table 1. However, the unit of the mixing ratio shown in the table is parts by weight. The Izod impact strength, Vicat softening point, and melt flow rate all show satisfactory values as a resin, and the flammability is V-
It has flame retardancy ranked 0 and is well balanced in total.

[0027]

[Comparative Examples 1 and 2] Test pieces were prepared in the same procedure as in Examples except that the ether derivative of the halogen-containing aromatic diol was used alone or the polyhalogenated diphenylalkane was used alone, and polytetrafluoroethylene was not used. Table 2 shows the results of measuring the physical properties by the method. The impact strength decreases when the ether derivative of the halogen-containing aromatic diol is used alone, and the fluidity decreases when the polyhalogenated diphenyl alkane is used alone.For example, the ether derivative of the halogen-containing aromatic diol alone or the polyhalogenated diphenyl alkane is used If you clear the flame retardancy with, the physical property balance will be biased.

[0028]

[Comparative Examples 3 and 4] Physical properties were measured by the same procedure as in Example except that polytetrafluoroethylene was not used. If the added amount of the polyhalogenated diphenylalkane is increased to have the desired V-0 flame retardancy, the desired Izod impact strength and fluidity cannot be obtained.

[0029]

[Comparative Examples 5 to 8] Physical properties were measured by the same procedure as in Examples and shown in Table 2. When the amount of polytetrafluoroethylene added is small, the target flame retardancy of V-0 is not achieved. Further, when the amount of polytetrafluoroethylene added is large, the glowing after the flame is extinguished does not fall within the specified time, and the definition of UL94 does not rank V-0. Further, when the total amount of the brominated bisphenol A epoxy resin and the brominated diphenylethane is less than 12 parts, even if an appropriate amount of polytetrafluoroethylene is added, the flame retardancy ranked V-0 cannot be obtained. However, if the total amount exceeds 21 parts, the physical properties of the resin cannot be maintained.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

EFFECT OF THE INVENTION It has excellent flame retardancy, and at the same time, has an excellent balance of heat resistance, impact resistance and fluidity.
Therefore, the resin composition of the present invention is expected to be effectively used in a field where flame retardancy is particularly required, specifically, home appliances, office machines, housings of information equipment, and the like.

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Claims (1)

[Claims] 1. (A) 100 parts by weight of styrene resin,
(B) 2 to 18 parts by weight of an ether derivative of a halogen-containing aromatic diol having a weight average molecular weight of 500 to 10,000,
(C) 2 to 16 parts by weight of a polyhalogenated diphenylalkane represented by the following formula (1), (D) 1 to 10 parts by weight of antimony trioxide, and (E) 0.01 to 0.5 of polytetrafluoroethylene. Consisting of parts by weight and (B) +
(C) is 12 to 21 parts by weight, which is a flame-retardant styrene resin composition. [Chemical 1] [In the formula, X represents a bromine atom or a chlorine atom, l and m represent integers of 0 to 5 (provided that both l and m do not become 0), and R represents C _n H _2n (n. = 1 to 10). ]