JPH11217482A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant resin compsn. which gives molded items exhibiting no unevenness in gloss by compounding a rubber-modified vinylarom. resin with a polyhalogenated diphenylalkane, an ether deriv. of a halogenated diol, a halogenated bisimide flame retardant, a flame retardant aid, and a white mineral oil, each in a specified amt. SOLUTION: This compsn. comprises (A) 100 pts.wt. rubber-modified vinylarom. resin (e.g. a rubber-modified styrene resin), (B) 3-13 pts.wt. polyhalogeneated diphenylalkane of the formula (e.g. decabromodiphenylethane), (C) 0-20 pts.wt. ether deriv. of a halogenated arom. diol (e.g. a tetrabromobisphenol A epoxy resin), (D) 0-15 pts.wt. halogenated bisimide flame retardant, 0-10 pts.wt. flame retardant aid (e.g. Sb2 O3 ), and 0.1-3 pts.wt. white mineral oil having an inital boiling point (at 10 mmHg) of 229 deg.C or higher and a naphthene content of 28% or higher, the sum of ingredients B, C and D being 13-25 pts.wt. In the formula, X is Br or Cl; j and k are each 1-5 provided j+k>=2; and R is Cn H2n (wherein n is 1-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention provides a molded article having good flow moldability, heat resistance and thermal stability, excellent impact strength, surface gloss, light resistance, good appearance without gloss unevenness, and The present invention relates to a flame-retardant resin composition that can be molded without mold contamination.

[0002]

2. Description of the Related Art Styrene-based resins are widely used as OA equipment and home electric appliances. In addition to heat resistance, impact resistance, flow moldability, surface gloss, appearance, and light resistance, resin properties that are well-balanced with heat stability, which can withstand special molding systems such as hot runners, are required. I have. As a method for obtaining the above-mentioned flame-retardant styrenic resin, a method in which a halogenated diphenylalkane is added to a resin (JP-A-2-42031), a method in which a halogenated diphenylalkane and another flame retardant such as brominated bisphenol A are used. (JP-A-6-17)
No. 2607) and a combination use with a brominated bisphenol A epoxy resin (JP-A-6-73268).

[0003] However, when the halogenated diphenylalkane is used, its characteristics are excellent in heat resistance, heat stability and light resistance, but on the other hand, it has disadvantages as follows.
It was mentioned that the fluid formability and the surface gloss were not good, and that poor gloss unevenness, which was undesirable in appearance, was likely to occur. In addition, in a combined system of a halogenated diphenylalkane and a brominated bisphenol A, or a mixed system of a halogenated diphenylalkane and a brominated bisphenol A type epoxy resin, the flow moldability and the surface gloss can be improved to some extent.
Poor gloss unevenness is still likely to occur, and there is a drawback that the commercial value of appearance in molded products and the like is significantly impaired.
On the other hand, a method for improving poor gloss unevenness by blending a small amount of fatty acid polyhydric alcohol esters (Japanese Patent Laid-Open No. 8-283)
No. 525) is also disclosed, but the effect of improvement is still insufficient for a molded product having a complicatedly complicated shape including ribs and bosses.

[0004]

The problems to be solved by the present invention are heat resistance, impact resistance, flow moldability, surface gloss,
An object of the present invention is to obtain a flame-retardant resin composition that maintains a balance between light resistance and thermal stability, has no uneven gloss even in a complicated molded product, and can be molded without mold contamination.

[0005]

Means for Solving the Problems In order to solve the above problems, the present inventors have intensively studied and obtained a flame-retardant resin composition having a good balance of physical properties as described in detail below. It was completed.

That is, the present invention relates to (A) a polyhalogenated diphenylalkane 3 to (B) represented by the following general formula (I) per 100 parts by weight of a rubber-modified vinyl aromatic resin.
13 parts by weight, (C) 0 to 20 parts by weight of an ether derivative of a halogen-containing aromatic diol, (D) 0 to 15 parts by weight of a halogenated bisimide flame retardant, (E) 0 to 10 parts by weight of a flame retardant auxiliary, (F) ) 0.1 to 3 parts by weight of a white mineral oil whose initial storage temperature at 10 mmHg is 229 ° C. or higher, and whose naphthene component is at least 28% by ndM ring analysis, and It is a flame-retardant resin composition in which the total of B), (C) and (D) is 13 to 25 parts by weight.

[0007]

Embedded image

(Where X is Br and / or Cl,
j and k are integers of 1 to 5, j + k ≧ 2, and R is C _n H _2n
(N is an integer of 1 to 10). )

The rubber-modified vinyl aromatic resin (A) used in the present invention is, for example, a method in which a rubber-like polymer is dissolved in a mixed solution of an aromatic vinyl monomer and an inert solvent, and the mixture is stirred to perform bulk polymerization, suspension, and the like. A polymer in which a rubbery polymer is dispersed in a matrix in an aromatic vinyl polymer matrix obtained by performing polymerization, solution polymerization, or the like. The weight average molecular weight of the matrix portion is 150,000 or more, preferably 150,000 to 230,000. If it is less than 150,000, the strength is reduced. The rubber content is not particularly limited, but is preferably 5 to 10% by weight generally used for rubber-modified vinyl aromatic resins. The average particle diameter of the rubbery polymer is suitably from 0.4 to 6.0 μm, preferably from 1.0 to 3.0 μm. If the particle size of the rubber is too small, the impact strength is low, and if the particle size is too large, the appearance such as the surface gloss of the molded product deteriorates.

The above aromatic vinyl monomers include styrene, o-methylstyrene, m-methylstyrene and p-methylstyrene.
Methyl styrene, 2,4-dimethyl styrene and the like and a combination thereof can be mentioned, but styrene is most preferably used.

Examples of the rubbery polymer include polybutadiene, styrene / butadiene copolymer, polyisoprene, etc. Among them, polybutadiene and styrene / butadiene copolymer are preferable.

The polyhalogenated diphenylalkane (B) used in the present invention is a diphenylalkane such as diphenylmethane, 1,2-diphenylethane, 1-methyl-1,2-diphenylethane, 1,4-diphenylbutane, , 6-diphenylhexane, etc., in which one or more halogen atoms, preferably 4 to 5 bromine atoms, are substituted for a hydrogen atom attached to one phenyl group by nucleus. Among them, decabromodiphenylethane is preferred for its heat resistance. Excellent and preferred. The addition amount of (B) is suitably 3 to 13 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of the rubber-modified vinyl aromatic resin (A). And reduces surface gloss and flow.

The halogen-containing aromatic diol ether derivative (C) used in the present invention is, for example, a reaction product of halogen-containing bisphenol A and a halogen-containing bisphenol A epoxy resin, or halogen-containing bisphenol A and epichlorohydrin. The terminal of which is an ether derivative having an epoxy group or a structure obtained by reacting an epoxy group with tribromophenol, pentabromophenol, trichlorophenol, or the like.

As the halogen-containing bisphenol A,
Tetrabromobisphenol A, dibromobisphenol A and the like are listed. The halogen-containing bisphenol A epoxy resin is represented by the following general formula (II), and preferred are diglycidyl ether of tetrabromobisphenol A and dibromobisphenol A. Diglycidyl ether.

[0015]

Embedded image

(Where R is a hydrogen atom, the following (III)
Formula or the following formula (IV), X is a bromine or chlorine atom, i
Represents an integer of 1 to 4, and n represents an integer of 0 to 30. )

[0017]

Embedded image

[0018]

Embedded image

(Where R ′ is a lower alkyl group and / or
Or a phenyl group which may be substituted with a bromine or chlorine atom. )

The ether derivative (C) is preferably a reaction product of tetrabromobisphenol A with a diglycidyl ether of tetrabromobisphenol A and a reaction product of tetrabromobisphenol A with epichlorohydrin. The terminal is an ether derivative having a structure obtained by reacting an epoxy group or tribromophenol.

The weight average molecular weight of the above ether derivative (C) is suitably from 500 to 10,000. If it is lower than 500, the heat resistance is inferior, and if it is higher than 10,000, the impact strength decreases. The amount of the ether derivative (C) to be added is suitably 20 parts by weight or less, preferably 15 parts by weight or less based on 100 parts by weight of the rubber-modified vinyl aromatic resin (A). Decreases heat resistance and thermal stability.

The halogenated bisimide flame retardant (D) used in the present invention includes alkylene bisphthalimides such as methylene bisphthalimide, ethylene bisphthalimide, propylene bisphthalimide and the like, when two or more halogens, preferably four bromines are used. In particular, ethylene bistetrabromophthalimide is preferable in view of heat resistance. The addition amount of (D) is suitably 15 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the rubber-modified vinyl aromatic resin (A).
When the amount is more than the weight part, uneven gloss is produced, and the surface gloss and the flow are reduced.

The flame retardant aid (E) used in the present invention is
It acts to further enhance the flame retardant effect of the flame retardants of (B), (C) and (D), for example, as a boron-based compound such as antimony oxide, such as antimony trioxide, antimony tetroxide, and antimony pentoxide. Zinc borate, barium metaborate, zinc borate anhydride, boric anhydride, etc .; tin stannate, zinc hydroxy stannate, etc. as tin compounds; molybdenum oxide, ammonium molybdate, etc. as molybdenum compounds; zirconium oxide as zirconium compounds. , Zirconium hydroxide and the like, and zinc-based compounds such as zinc sulfide are preferable, and it is preferable to add antimony oxide, and it is particularly preferable to use antimony trioxide. The amount of (E) added is from 0 to 100 parts by weight of the rubber-modified vinyl aromatic resin (A).
10 parts by weight, preferably 1 to 5 parts by weight, is suitable.
If the amount is more than 0 parts by weight, glowing combustibility is increased, which is not preferable.

The white mineral oil (F) used in the present invention is characterized in that its initial reservoir temperature at 10 mmHg is 2 mm.
When the temperature is 29 ° C. or more and the naphthene component (Cn) is at least 28% or more, preferably 30 to 40%, according to the ndM ring analysis method, the flow of the obtained flame-retardant resin composition Good moldability and uneven gloss improvement effect. If the above-mentioned initial storage temperature is lower than 229 ° C., a part of the white mineral oil will be in a vaporized state during the molding process, and when it is injected together with the resin into the cooled mold, it is separated as an oily substance while being separated from the resin. Causes oil stains. The ndM ring analysis is a method for testing the composition of a high-boiling petroleum fraction, and determines the carbon distribution of each hydrocarbon. The carbon distribution is the content of carbon atoms in the aromatic ring (% Ca), the content of carbon atoms in the naphthene ring (% Cn), and the content of carbon atoms in the paraffin chain structure (% Cp). These calculations are based on JIS
Refractive index (n) according to K-2421, JIS K-224
It is called the ndM ring analysis method because it can be obtained from the density (d) according to No. 9 and the molecular weight (M) known from the molecular weight measurement. The amount of (F) added is 0.1 to 3 parts by weight, preferably 0.5 to 2 parts by weight, per 100 parts by weight of the rubber-modified vinyl aromatic resin (A). If the amount is too large, the heat resistance decreases.

The compounding ratio of the composition in the present invention is such that the polyhalogenated diphenylalkane (B) is 3 to 13 parts by weight, and the halogen-containing aromatic diol ether derivative is 100 parts by weight of the rubber-modified vinyl aromatic (A). (C) is 0
~ 20 parts by weight, 0% halogenated bisimide flame retardant (D)
１５15 parts by weight, the flame retardant aid (E) is 0-10 parts by weight, the initial storage temperature (under a reduced pressure of 10 mmHg) is 229 ° C. or more, and n
The naphthene component is at least 28 by dM ring analysis
% Or more of white mineral oil is 0.1 to 3 parts by weight,
The total of (B), (C) and (D) is 13 to 25 parts by weight.

The method for producing the flame-retardant resin composition of the present invention comprises:
It is based on mixing the above components in predetermined amounts. The compounding method is not particularly limited, and examples thereof include a mixer such as Henschel, tumbler and Banbury, a kneader, a roll, a single screw extruder, and a twin screw extruder.

The flame-retardant resin composition of the present invention may contain other additives such as a plasticizer, a lubricant, a stabilizer, an ultraviolet absorber, a filler, a coloring agent, and a reinforcing agent within a range not to impair the object of the present invention. Agents and the like can be added.

[0028]

The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, various properties of the flame-retardant resin composition were measured and evaluated by the following methods. (1) Vicat softening point: Measured according to JIS K-6871. (2) Izod impact strength: Measured at 23 ° C. using a notched specimen in accordance with ASTM-D256. (3) Melt flow rate: Measured according to ASTM-D1238. (4) Light fastness: The degree of discoloration of a test piece after irradiation with a xenon weatherometer (Atlas Ci65A, manufactured by Toyo Seiki Seisaku-sho, Ltd.) for 300 hours was determined by comparing the color difference with a non-irradiated sample (△).
E) was measured and evaluated with a color difference meter (Nippon Denshoku Industries Co., Ltd., # 80). (5) Thermal stability: A plate is formed by retaining at 250 ° C. for 10 minutes with an in-line screw injection molding machine (manufactured by Toshiba Machine Co., Ltd., IS-50EP), and the color difference from the plate during non-retention molding (ΔE) Was measured with a color difference meter (Nippon Denshoku Industries Co., Ltd., # 80). (6) Uneven gloss test: A pin gate box-shaped molded product (width 120 mm × length 190 mm × height 25 mm) of FIG. 1 is molded by an injection molding machine (Nestal 515/150, manufactured by Sumitomo Heavy Industries, Ltd.), and a gate and a weld are formed. The gloss unevenness observed in the part was visually observed. The evaluation results were represented by ○: no gloss unevenness, Δ: thin and spread gloss unevenness, ×: white cloud-like gloss unevenness. (7) Surface gloss: measured in accordance with JIS Z-8741. (8) Flammability: based on the method (UL-94) of Subject No. 94 of Underwriters Laboratories
Judgment was made by a vertical burning test of an 8-inch thick test piece. (9) Mold stain: Plates were continuously molded for 5 hours at a mold temperature of 40 ° C and a molding temperature of 250 ° C using an inline screw-type injection molding machine (IS-50EP, manufactured by Toshiba Machine Co., Ltd.), and the number of defective oil stains Was evaluated.

(Examples 1 to 5) SAYTE manufactured by Albemarle Co., Ltd. as polyhalogenated diphenylalkane (B) was used for 100 parts by weight of rubber-modified vinyl aromatic resin (A).
X8010 (decabromodiphenylethane), EC-14 manufactured by Dainippon Ink and Chemicals, Inc. as a halogen-containing aromatic diol ether derivative (C) (tetrabromobisphenol A epoxy resin flame retardant end-capped with tribromophenol) SAYTEXBT-9 manufactured by Albemarle Co., Ltd. as a halogenated bisimide flame retardant (D)
3 (ethylenebistetrabromophthalimide), antimony trioxide (E) as a flame-retardant auxiliary, white mineral oils having an initial storage temperature of 229 ° C. or higher at 10 mmHg and a naphthene component of 28% or higher by ndM ring analysis As (F), Table 1 shows an initial storage temperature of 233 ° C. at 10 mmHg, a white mineral oil with a naphthene component of 30% (F-1), and an initial storage temperature of 262 ° C. at 10 mmHg with a naphthene component of 31% (F-2). After mixing at the indicated ratio and melt-kneading with a twin-screw extruder, each test piece required for various physical properties was molded. Using these test pieces, Vicat softening point, Izod impact strength, melt flow rate, light resistance, heat stability,
The gloss unevenness test, surface gloss, flammability, and mold fouling were measured. Table 1 shows the results. The mixing ratio units in the table are parts by weight.

(Comparative Examples 1 to 7) As shown in Table 2, 10
A system not containing a white mineral oil (F) having a naphthene component of 28% or more according to an ndM ring analysis method at an initial distillation temperature of 229 ° C. or more at mmHg (Comparative Examples 2 to 4), instead of (F) 204 ° C initial temperature at 10 mmHg, nd
A system using white mineral oil (G) having a naphthene component of 25% by M-ring analysis (Comparative Example 1), polyhalogenated diphenylalkane (B), ether derivative of halogen-containing aromatic diol (C), halogenation Systems in which the amount of the bisimide flame retardant (D) is out of the claims (Comparative Examples 5 to 7)
A test was conducted in the same manner as in the example except that で あ was satisfied, and the physical properties were evaluated. The results are shown in Table 2.

[0031]

[Table 1]

[0032]

[Table 2]

In Examples 1 to 5, the thermal stability, the uneven glossiness and the surface gloss were all good, whereas in Comparative Examples 2, 3 and 4 in which (F) was not added, the uneven glossiness and surface gloss were good. The gloss was poor, and instead of (F), the initial storage temperature at 10 mmHg was 204 ° C., and the naphthene component was 2 according to the ndM ring analysis method.
In Comparative Example 1 in which 5% white mineral oil was added, the unevenness in gloss and the surface gloss were good, but the stain on the mold was remarkable. Also,
Comparative Examples 5 and 6 in which (B), (C) and (D) were not within the range of the present application even when (F) was added, had poor surface gloss or thermal stability even when glossiness was relatively good, and Example 7 resulted in poor glossiness and poor surface gloss.

[0034]

The flame-retardant resin composition of the present invention has heat resistance,
It has excellent balance of impact resistance, flow moldability, surface gloss, light resistance, and heat stability, and has good appearance without gloss unevenness, and can be molded without mold contamination. is there. Therefore, the resin composition of the present invention can be effectively used in OA equipment and home electric appliances requiring flame retardancy.

[Brief description of the drawings]

FIG. 1 is a schematic view of a pin gate box-shaped molded product molded for evaluation during a gloss unevenness test.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 51/04 63:00)

Claims (2)

[Claims] 1. A rubber-modified vinyl aromatic resin (A) 100
(B) 3 to 13 parts by weight of a polyhalogenated diphenylalkane represented by the following general formula (I),
(C) Halogen-containing aromatic diol ether derivative 0
To 20 parts by weight, (D) halogenated bisimide flame retardant 0
15 parts by weight, (E) 0 to 10 parts by weight of a flame retardant aid, (F) 1
The initial storage temperature at 0 mmHg is 229 ° C. or higher, and n
The naphthene component is at least 28 by dM ring analysis
% Or more of 0.1 to 3 parts by weight of white mineral oil, and the total of (B), (C) and (D) is 13 to
A flame-retardant resin composition characterized by being 25 parts by weight. Embedded image (Where X is Br and / or Cl, and j and k are 1
J + k ≧ 2, R is C _n H _2n (n is 1 to 1)
(An integer of 0). ) (B) is decabromodiphenylethane,
(C) is a tetrabromobisphenol A epoxy resin, (D) is ethylenebistetrabromophthalimide,
The flame-retardant resin composition according to claim 1, wherein (E) is antimony trioxide.