JPH0859999A - Flame-resistant thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain a thermoplastic resin composition giving molded products free from the bleeding of additives on the surfaces of the molded products, having high flame retardancy and not generating a corrosive gas and an injurious gas on their processing and combustion, maintaining the characteristics of the thermoplastic resin, and extremely improved in the flame retardancy. CONSTITUTION: This flame-resistant thermoplastic resin composition is obtained by melt-kneading (A) 100 pts.wt. of a thermoplastic resin with 5-80 pts.wt. of the mixture or melt-kneaded product of (B) one or more kinds of random copolymers selected from a random copolymer and its hydrogenated products with (C) one or more kinds of non-halogen flame retardant compounds selected from a phenolic resin and phosphorus, nitrogen, boron compounds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition having good cold resistance and flame retardancy, which is useful for various molded articles obtained by injection molding or the like or for applications obtained by extrusion molding. is there.

[0002]

2. Description of the Related Art Generally, thermoplastic resins have excellent properties in terms of mechanical properties, heat resistance, electrical properties and moldability, and are generally used in electrical parts, automobile parts, precision machine parts, etc. Widely used in the industrial field. However, these thermoplastic resins have a drawback that they are relatively easy to burn, and their application is limited to applications such as electronic devices such as televisions, electric parts, and automobile engine room parts that require flame retardancy. There is a problem that Therefore, it is strongly required to impart excellent flame retardancy to the thermoplastic resin. For this reason, many methods of adding various halogen compounds and phosphorus compounds have been proposed. Although conventional flame retardants impart excellent flame retardancy, they have excellent mechanical properties and electrical properties inherent to thermoplastic resins. Unsatisfactory in terms of reducing properties and processability. Further, halogen compounds also have the problems of generating harmful gases and destroying the environment when they burn.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a non-halogen thermoplastic resin having improved flame retardancy with almost no deterioration in properties.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the non-halogen flame retardation of a thermoplastic resin, and as a result, a method of simply blending a thermoplastic resin and a phenol resin improves the flame retardancy, but improves the cold resistance. It has been found that there is a drawback in that the properties such as resistance and impact resistance are deteriorated. In addition, the method of simply blending phosphorus, nitrogen, and boron-based compounds has a drawback that the effect of improving flame retardancy is insufficient, and further bleeding occurs, which causes deterioration of properties such as cold resistance and heat resistance. It turned out to occur. Therefore, as a result of further intensive study, the brittleness of the phosphorus, nitrogen, and boron compounds was covered by melting and kneading the random copolymer (B) and the halogen-free flame-retardant compound (C) to cover the brittleness of the phenol resin. Therefore, the inventors have found that the conventional drawbacks, such as cold resistance and deterioration of mechanical properties, are improved, and have completed the present invention. That is, the present invention relates to the thermoplastic resin (A)
5 to 80 parts by weight of a mixture of the random copolymer (B) and the non-halogen flame-retardant compound (C) is added to 100 parts by weight, and if necessary, an inorganic hydrate (D) 30 to 1 is added.
The present invention relates to a thermoplastic resin composition comprising 60 parts by weight and melt-kneaded, preferably a random copolymer (B) and a non-halogen flame-retardant compound (C) are melt-kneaded in advance. Then, the present invention relates to a thermoplastic resin composition characterized by being blended with a thermoplastic resin and melt-kneaded.

The thermoplastic resin used as the component (A) of the present invention is not particularly limited and is commercially available. Among these, polyolefin resins, polystyrene resins, and polyphenylene ether resins are preferable. The polyolefin resin is not particularly limited and is commercially available. Among these, polyethylene resin and polypropylene resin are preferable. The modified polyethylene resin used in the present invention is not particularly limited and is commercially available.
Examples thereof include a (meth) acrylic acid copolymer, an ethylene- (meth) acrylic acid ester copolymer, an ethylene- (meth) acrylic acid methyl copolymer, an ethylene- (meth) acrylic acid ethyl copolymer. The modified polypropylene resin used in the present invention is not particularly limited and is commercially available. The polystyrene resin is not particularly limited and is commercially available. For example, a polystyrene resin is a polymer of styrene and an α-substituted styrene such as α-methylstyrene, a polymer of a styrene derivative such as vinyltoluene, or a monomer mainly containing these monomers and a monomer copolymerizable therewith, For example, a copolymer of one or more kinds of acrylonitrile, butadiene, isoprene and the like can be mentioned. The polyphenylene ether resin is not particularly limited and is commercially available. For example, poly (2,6-dimethylphenylene-1,4-ether),
Poly (2,6-diethylphenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,
4-ether) resins and the like, for example, modified polyphenylene ether-based resins having different styrene ratios.

The random copolymer which is the component (B) of the present invention is melt-kneaded with the non-halogen flame-retardant compound to significantly reduce the resistance when the non-halogen flame-retardant compound is simply added to the thermoplastic resin. Improves impact resistance and cold resistance, and
It has an effect of preventing bleeding, and is an important component having a compatibilizing action between the thermoplastic resin and the non-halogen flame-retardant compound and a stress relaxation action at the interface thereof. The random copolymer which is the component (B) of the present invention is not particularly limited and is commercially available. To improve cold resistance and impact resistance, the molecular weight at a glass transition temperature of -30 ° C or lower is used. Those of 50,000 to 1,000,000 are preferable. For example, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene random copolymer and hydrogenated products thereof are preferably used. Elastomers include random copolymers and block copolymers, but the block copolymers are harder at low temperatures than the random copolymers, and the effect of improving impact resistance at low temperatures is insufficient. Therefore, a random copolymer is preferably used.

The phenol resin used as the component (C) of the present invention is not particularly limited and is commercially available. For example, a phenol / formalin / formaldehyde / phenol molar ratio is 0.5. ~
The mixture was charged into a reaction kettle at a compounding ratio of 1.0, and a catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid was added, and the mixture was heated and refluxed for an appropriate time. For removal, it can be obtained by vacuum dehydration or static dehydration, and further removing remaining water and unreacted phenols. The co-condensed phenol resin obtained by using these resins or a plurality of raw material components may be used alone or in combination of two or more kinds. Phosphorus, nitrogen used as the component (C) of the present invention,
The boron compound is not particularly limited and is generally commercially available, and specific examples include polyphosphoric acid,
Phosphorus compounds such as ammonium polyphosphate and phosphoric acid esters, boron compounds such as boric acid and zinc borate, melamine or melamine cyanurate compounds, melamine phosphates, melamine derivatives such as melamine borate, guanidine or guanidine sulfamate. , Guanidine-based derivatives such as guanidine phosphate and the like.

The inorganic hydrate used as the component (D) of the present invention is not particularly limited and is commercially available. For example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like can be mentioned.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin as the component (A), a random copolymer as the component (B) and a non-halogen flame-retardant compound as the component (C), which are collectively added to a pressure kneader. 150-300 with a Banbury mixer, etc.
C., melt-kneading for 10 to 30 minutes, or after the random copolymer of the component (B) and the non-halogen flame-retardant compound of the component (C) are melt-kneaded at 100 to 300.degree. C. for 10 to 30 minutes in advance. It is obtained by a method of adding a thermoplastic resin of component A) and further melt-kneading. In the latter, the random copolymer of component (B) and the halogen-free flame-retardant compound of component (C) are selectively mixed. It is more preferable because it fits. In the thermoplastic resin composition of the present invention, a mixture or melt-kneaded product of a random copolymer of the component (B) and a halogen-free flame-retardant compound of the component (C) with respect to 100 parts by weight of the thermoplastic resin of the component (A). Must be compounded in the range of 5 to 80 parts by weight.

If the mixture or melt-kneaded product of the random copolymer of the component (B) and the non-halogen flame-retardant compound of the component (C) is less than 5 parts by weight, the effect of improving the flame retardancy becomes insufficient, and 80 When the amount is more than parts by weight, the properties of each thermoplastic resin are deteriorated. As described above, the thermoplastic resin composition of the present invention has an effect of improving flame retardancy with almost no deterioration of the characteristics of the thermoplastic resin as the component (A). The melt-kneaded product of the random copolymer as the component) and the non-halogen flame-retardant compound as the component (C) has affinity for both the thermoplastic resin as the component (A) and the non-halogen flame-retardant compound as the component (C). Since it has, it becomes possible to microdisperse the non-halogen flame-retardant compound of the component (C) having good flame retardancy in the thermoplastic resin.
Good flame retardancy is exhibited, bleeding of non-halogen flame retardant compounds can be prevented, and further, random copolymer components are dispersed at the interface to cause stress relaxation action, and thus impact resistance and cold resistance can be reduced. it is conceivable that.

The thermoplastic resin composition of the present invention may further contain other compounding agents such as talc, mica, depending on the use and purpose.
Impact resistance of inorganic fillers such as calcium carbonate and wollastonite, coupling agents or reinforcing agents such as glass fibers and carbon fibers, flame retardant aids, antistatic agents, stabilizers, pigments, release agents, elastomers, etc. An improver and the like can be added. The thermoplastic resin composition of the present invention can be easily processed into a molded product by a processing method used for usual thermoplastic resin molded products, such as injection molding or extrusion molding.

[0012]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited thereto. The tensile test is ASTM-D638, the heat distortion temperature is ASTM-D648 (4.6 kgf / cm ² ), the Izod impact test is JIS K6871, and the cold resistance is JIS K630.
1, oxygen index is ASTM-D2863, combustion test is Und
erwriters Laboratories safety standard UL94 (○: burning time within 10 seconds Δ: burning for 10 seconds or more ×: burnt out). (Examples and Comparative Examples) Polyolefin resin as the component (A) includes polyethylene [PE: Ultzex 2022L manufactured by Mitsui Petrochemical Co., Ltd.] and polypropylene [P
P: Sumitomo Chemical Co., Ltd. Sumitomo Noblen H501]
As the polystyrene resin, polystyrene [PS: S-Bright 500A manufactured by Showa Denko KK], A
BS resin [ABS: Diapet ABS RSE-7 manufactured by Mitsubishi Rayon Co., Ltd.] is used, and as the polyphenylene ether resin, [PPE: Zylon X0061 manufactured by Asahi Kasei Kogyo Co., Ltd.] or [PPE: Mitsubishi Gas Chemical Co., Ltd.
The product of Jupiace AV40 manufactured by Co., Ltd. was used. As the component (B), hydrogenated styrene-butadiene random copolymer [HSBR: Dynaron 13 manufactured by Nippon Synthetic Rubber Co., Ltd.]
20P], ethylene-propylene random copolymer [E
P: EP02P manufactured by Japan Synthetic Rubber Co., Ltd., and styrene-butadiene block copolymer [SBS: Tuffprene A manufactured by Asahi Kasei Kogyo Co., Ltd.] were used. As the component (C), straight phenol novolac resin [PN: Sumirite Resin PR-51470 manufactured by Sumitomo Durez Co., Ltd.], condensed phosphoric acid ester [PX-201 manufactured by Daihachi Chemical Co., Ltd.],
Hydroxyl group-containing phosphate ester [CR-757 Daihachi Chemical
KK] and melamine phosphate [MPP-A (manufactured by Sanwa Chemical Co., Ltd.)] were used. Magnesium hydroxide and aluminum hydroxide were used as the component (D). In Examples and Comparative Examples of the present invention, the random copolymer of the component (B) and the non-halogen flame-retardant compound of the component (C) were kneaded in advance with a pressure kneader, and then the thermoplastic resin of the component (A) was used. The inorganic flame retardant as the component (D) was added and kneaded.

Table 1 Example 1 2 3 4 Compounding (parts by weight) PE 100 100 PP 100 100 PN 21 20 10 HSBR 9 10 EP 10 20 PX-201 15 CR-757 20 MPP-A 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristics oxygen Index 31.2 33.5 33.7 33.4 Cold resistance (° C) -60 -58 -60 -58 Tensile strength (Kg / cm ² ) 155 285 140 265 Tensile elongation (%) 540 530 485 515 UL94 1st ignition ○ ○ ○ ○ 2nd time Ignition ○ ○ ○ ○ Molten droplets No No No No

Table 2 Example 5 6 7 8 compounding (parts by weight) PS 100 100 ABS 100 100 PN 21 20 10 HSBR 9 10 10 20 PX-201 15 CR-757 20 MPP-A 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristics tensile strength (Kg / cm ² ) 255 405 245 395 Tensile elongation (%) 42 54 40 52 Izod impact test (Kg · cm / cm) 9.0 32 8.6 31 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Melting No droplet None None None

Table 3 Example 9 10 11 12 Blend (parts by weight) PPE 100 100 PPE 100 100 PN 21 20 10 HSBR 9 10 10 20 PX-201 15 CR-757 20 MPP-A 20 Magnesium hydroxide 100 Aluminum hydroxide 100 Characteristic heat deformation Temperature (℃) 105 100 100 95 Tensile strength (Kg / cm ² ) 455 450 460 450 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Molten droplets None None None

Table 4 Comparative Example 1 2 3 4 Compounding (parts by weight) PE 100 100 PP 100 100 PN 30 PX-201 30 Magnesium hydroxide 100 100 Aluminum hydroxide 100 100 Properties Oxygen index 29.8 30.0 30.1 33.2 Cold resistance (° C) -62 -60 -15 -36 Tensile strength (Kg / cm ² ) 155 285 80 180 Tensile elongation (%) 600 520 310 320 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

Table 5 Comparative Example 5 6 7 8 Formulation (parts by weight) PE 100 100 PP 100 100 PN 27 30 1 21 HSBR 3 2 EP 30 SBS 9 CR-757 30 MPP-A 1 magnesium hydroxide 100 100 aluminum hydroxide 100 100 characteristics oxygen Index 30.4 34.6 28.9 31.2 Cold resistance (℃) -34 -18 -60 -38 Tensile strength (Kg / cm ² ) 110 110 140 130 Tensile elongation (%) 350 260 550 400 UL94 1st ignition ○ ○ × ○ 2nd time Ignition ○ ○ × ○ Melt droplet No No Yes Yes No

Table 6 Comparative Example 9 10 11 12 Blend (parts by weight) PS 100 100 ABS 100 100 PN 30 PX-201 30 Magnesium hydroxide 100 100 Aluminum hydroxide 100 100 Properties Tensile strength (Kg / cm ² ) 255 410 130 220 Tensile elongation (%) 45 55 10 30 Izod impact test (Kg · cm / cm) 9.0 35 4.3 15 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

Table 7 Comparative Example 13 14 15 16 Compounding (parts by weight) PS 100 100 ABS 100 100 PN 27 30 1 21 HSBR 3 30 2 SBS 9 CR-757 30 MPP-A 1 magnesium hydroxide 100 100 aluminum hydroxide 100 100 characteristics tensile strength (Kg / cm ² ) 120 290 250 215 Tensile elongation (%) 18 25 40 26 Izod impact test (Kg · cm / cm) 4.5 14 8.2 6.8 UL94 First ignition ○ ○ × ○ Second ignition ○ ○ × ○ Melting Drop No No Yes Yes No

Table 8 Comparative Example 17 18 19 20 Compounding (parts by weight) PPE 100 100 PPE 100 100 PN 30 PX-201 30 Magnesium hydroxide 100 100 Aluminum hydroxide 100 100 Properties Tensile strength (Kg / cm ² ) 465 445 310 320 Thermal deformation temperature (℃) 110 105 85 70 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

Table 9 Comparative Example 21 22 23 24 Formulation (parts by weight) PPE 100 100 PPE 100 100 PN 27 30 1 21 HSBR 3 30 2 SBS 9 CR-757 30 MPP-A 1 magnesium hydroxide 100 100 aluminum hydroxide 100 100 characteristics tensile strength (Kg / cm ² ) 295 245 410 380 Heat distortion temperature (℃) 80 63 95 80 UL94 1st ignition ○ ○ × ○ 2nd ignition ○ ○ × ○ Molten droplet No No Yes Yes No

[0022]

As is apparent from the table, the thermoplastic resin composition of the present invention is a novel material in which flame retardancy is remarkably improved while maintaining the characteristics of the thermoplastic resin. That is, there is no bleeding on the surface of the molded product, a flame-retardant thermoplastic resin composition that can be obtained a molded product that does not generate corrosive gas or harmful gas at the time of processing or burning, and among them, high flame retardancy. A flame-retardant polyolefin resin composition having, a flame-retardant polystyrene resin composition having both flame resistance and impact resistance, and a flame-retardant polyphenylene ether resin composition having both flame resistance and heat resistance. It is a thing.

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Claims (7)

[Claims] 1. One or more random copolymers (B) selected from a random copolymer rubber or a hydrogenated product thereof, a phenol resin, and phosphorus per 100 parts by weight of a thermoplastic resin (A). It is obtained by blending 5 to 80 parts by weight of a mixture or melt-kneaded product with one or more non-halogen flame-retardant compound (C) selected from nitrogen and boron-based compounds, and melt-kneading. A flame-retardant thermoplastic resin composition. 2. One or more random copolymers (B) selected from a random copolymer rubber or a hydrogenated product thereof, a phenol resin and phosphorus, relative to 100 parts by weight of the thermoplastic resin (A). 5-80 parts by weight of a mixture or melt-kneaded product with one or more non-halogen flame-retardant compound (C) selected from nitrogen and boron compounds and 30-160 parts by weight of inorganic hydrate (D). A flame-retardant thermoplastic resin composition obtained by melt-kneading. 3. The thermoplastic resin (A) is polyethylene,
The flame-retardant thermoplastic resin composition according to claim 1 or 2, which is a modified polyethylene, polypropylene, modified polypropylene, polystyrene resin or polyphenylene ether resin. 4. The random copolymer (B) has a glass transition temperature of −30 ° C. or lower and a molecular weight of 50,000 to 1,000.
A random copolymer having a molecular weight of 10,000.
Or the flame-retardant thermoplastic resin composition described in 3. 5. The random copolymer (B) is ethylene-
α-olefin random copolymer, ethylene-α-olefin-non-conjugated diene random copolymer, at least 1
The flame-retardant heat according to claim 1, 2, 3 or 4, which is a random copolymer of one conjugated diene and a vinyl aromatic compound or one or more random copolymers selected from hydrogenated products thereof. Plastic resin composition. 6. The halogen-free flame-retardant compound (C) is
Phenol novolac resin, phosphoric acid ester or polyphosphate having a functional group selected from amino group, hydroxyl group and carboxyl group, boric acid or zinc borate, or melamine, melamine phosphate, melamine derivative, guanidine A compound of at least one kind selected from guanidine derivatives.
The flame-retardant thermoplastic resin composition according to 3, 4, or 5. 7. The flame-retardant thermoplastic resin composition according to claim 2, wherein the inorganic hydrate (D) is magnesium hydroxide, aluminum hydroxide or calcium hydroxide.