JPH07331085A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having improved flame- retardancy and useful for various products molded by injection molding, extrusion molding, etc., by melt-kneading a specific blocked copolymer and a halogen- free flame-retarding compound and melt-kneading the product to a thermoplastic resin. CONSTITUTION:This thermoplastic resin composition is produced by kneading 100 pts.wt. of a thermoplastic resin (A) with 5-80 pts.wt. of a melt-kneaded mixture produced by kneading a hydrogenated block copolymer (B) produced by hydrogenating a block copolymer of a polymer block composed mainly of a vinylaromatic compound and a polymer block composed mainly of a conjugated diene compound and an arbitrary halogen-free flame-retarding compound (C) selected from phenolic resin, phosphorus compound, nitrogen compound and boron compound.

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. In addition, halogen compounds also have the problems of generating harmful gases when burned and environmental damage.

[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 As a result of investigations on a thermoplastic resin and a halogen-free flame-retardant compound, the present inventors have found that flame retardancy is improved by a method of simply blending a thermoplastic resin and a phenol resin. However, it has been found that there is a drawback that properties such as cold resistance and heat 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. Then, as a result of further diligent study, by melt-kneading the hydrogenated block copolymer (B) and the non-halogen flame-retardant compound (C), the brittleness of the phenol resin was covered, and the phosphorus, nitrogen and boron compounds were compounded. It was found that the bleeding was improved and the conventional drawbacks such as cold resistance and mechanical properties were lowered, and the present invention was completed. That is, the present invention blends 5 to 80 parts by weight of a melt-kneaded product of the hydrogenated block copolymer (B) and the halogen-free flame-retardant compound (C) with respect to 100 parts by weight of the thermoplastic resin (A), It relates to a thermoplastic resin composition characterized by being melt-kneaded,
Preferably, the hydrogenated block copolymer (B) and the non-halogen flame-retardant compound (C) are melt-kneaded in advance, then blended in a thermoplastic resin, and melt-kneaded to form a thermoplastic resin composition. It is about things.

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, and examples thereof include ethylene-propylene copolymers and ethylene-propylene-diene copolymers. These resins may be used alone or in combination of two or more. 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 hydrogenated block copolymer which is the component (B) of the present invention has a cold resistance which decreases when a phenol resin which is a relatively low molecular weight and brittle resin is blended with a thermoplastic resin,
It has the function of improving mechanical properties, and also phosphorus, nitrogen,
It is a very important component that also has the function of improving bleeding, cold resistance and heat resistance deterioration that occur when a boron compound is mixed with a thermoplastic resin. The hydrogenated block copolymer used in the present invention is not particularly limited and is commercially available, such as styrene-ethylene / butylene-styrene block copolymer and styrene-ethylene / propylene-styrene block copolymer. Is mentioned.

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-based compound is not particularly limited and is generally commercially available. The phosphorus, nitrogen and boron compounds used as the component (C) of the present invention are not particularly limited and are generally commercially available, and specific examples thereof include polyphosphoric acid, ammonium polyphosphate, phosphoric acid ester and the like. , Phosphorus 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 phosphates such as guanidine Examples include derivatives.

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.

In the thermoplastic resin composition of the present invention, the thermoplastic resin (A), the hydrogenated block copolymer (B) and the non-halogen flame retardant compound (C) are added all at once. 150-30 with a pressure kneader or Banbury mixer
A method of melt-kneading at 0 ° C. for 10 to 30 minutes, or a hydrogenated block copolymer of the component (B) and a non-halogen flame-retardant compound of the component (C) are melt-kneaded at 100 to 300 ° C. for 10 to 30 minutes in advance. After that, it is obtained by a method of adding a thermoplastic resin of the component (A) and further melt-kneading. The latter is a hydrogenated block copolymer of the component (B) and a halogen-free flame-retardant compound of the component (C). Are more preferable because they are selectively mixed. In the thermoplastic resin composition of the present invention, a melt-kneaded product of the hydrogenated block copolymer of the component (B) and the 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. When the melt-kneaded product of the hydrogenated block 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 parts by weight is added. When it exceeds the above range, the properties of each thermoplastic resin deteriorate. 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 hydrogenated block copolymer as the component) has an affinity for both the thermoplastic resin as the component (A) and the non-halogen flame-retardant compound as the component (C). It is considered that the good non-halogen flame-retardant compound as the component (C) became microdispersed.

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 a usual thermoplastic resin molded product, such as injection molding or extrusion molding.

[0011]

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. (Examples 1 to 12 and Comparative Examples 1 to 21) Specimens were prepared by kneading and mixing the compounds shown in Tables 1 to 9 by a conventional method, and the following evaluations were performed. 1 to Table 9 are shown. 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 JI.
SK6301, oxygen index is ASTM-D2863, combustion test is Underwriters Laboratories safety standard UL9
4 (○: Burning time is within 10 seconds △: Burning for 10 seconds or more ×:
It is the result of measurement by burning. As the polyolefin-based resin as the component (A), polyethylene [PE; Ultzex 2022L manufactured by Mitsui Petrochemical Co., Ltd.] and polypropylene [PP; Sumitomo Noblen H501 manufactured by Sumitomo Chemical Co., Ltd.] are used. Polystyrene [PS: Showa Denko Co., Ltd. S-Bright 500A] and ABS resin [ABS: Mitsubishi Rayon Co., Ltd. Diapet ABS RSE-7] are used. As polyphenylene ether resin, Zylon X0061 [PPE Asahi Kasei Kogyo Co., Ltd.] or Iupiace AV40 [PPE; Mitsubishi Gas Chemical Co., Ltd.] was used. As the component (B), a styrene-butadiene-styrene block copolymer hydrogenated product Tuftec
H1041 [SEBS; manufactured by Asahi Chemical Industry Co., Ltd.] and a hydrogenated product of a styrene-isoprene-styrene block copolymer [SEPS; manufactured by Kuraray Co., Ltd.] were used. As the component (C), straight phenol novolac resin [P
N: Sumilite resin PR- manufactured by Sumitomo Dures Co., Ltd.
51470], condensed phosphoric acid ester [PX-201 Daihachi Chemical Co., Ltd.], hydroxyl group-containing phosphoric acid ester [CR-
757 Daihachi Chemical Co., Ltd.], melamine phosphate [MPP-
A manufactured by Sanwa Chemical Co., Ltd.] was used. As the component (D), magnesium hydroxide and aluminum hydroxide were used.

Table 1 Example 1 2 3 4 Compounding (parts by weight) PE 100 100 PP 100 100 PN 21 20 10 SEBS 9 10 SEPS 10 20 PX-201 15 CR-757 20 MPP-A 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristics oxygen Index 31.0 33.3 33.5 33.2 Cold resistance (℃) -60 -58 -60 -58 Tensile strength (Kg / cm ² ) 150 280 135 260 Tensile elongation (%) 530 520 480 510 UL94 First ignition ○ ○ ○ ○ Second time Ignition ○ ○ ○ ○ Molten droplets No No No No

Table 2 Example 5 6 7 8 Compounding (parts by weight) PS 100 100 100 ABS 100 100 PN 21 20 10 SEBS 9 10 SEPS 10 20 PX-201 15 15 CR-757 20 MPP-A 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristics tensile Strength (Kg / cm ² ) 250 400 240 390 Tensile elongation (%) 40 52 38 50 Izod impact test (Kgcm / cm) 8.8 30 8.4 29 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ No molten droplets None None None

Table 3 Example 9 10 11 12 Compounding (parts by weight) PPE 100 100 PPE 100 100 PN 21 20 10 SEBS 9 10 SEPS 10 20 PX-201 15 CR-757 20 MPP-A 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristic heat Deformation temperature (℃) 110 100 105 100 Tensile strength (Kg / cm ² ) 460 440 455 440 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

[0016]

Table 6 Comparative Example 8 9 10 11 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

[0018]

Table 8 Comparative Example 15 16 17 18 Blend (parts by weight) PPE 100 100 PPE 100 100 PN 30 PX-201 30 Magnesium hydroxide 100 100 100 Aluminum hydroxide 100 100 Characteristic heat distortion temperature (° C) 110 105 85 70 Tensile strength (Kg / Kg / cm ² ) 465 445 310 320 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

[0020]

As is apparent from the table, the thermoplastic resin composition of the present invention has no bleeding on the surface of the molded product, and a molded product is obtained which does not generate corrosive gas or harmful gas during processing or burning, It is a novel material in which the flame retardancy is remarkably improved while maintaining the characteristics of the thermoplastic resin. That is, the thermoplastic resin composition of the present invention, in addition to having the above characteristics, is a polyolefin resin composition having both flame retardancy and cold resistance, and is a polystyrene resin having both flame retardancy and impact resistance. The resin composition is a polyphenylene ether resin composition having both flame retardancy and heat resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area C08K 5/16 KAX 5/49 KBY C08L 53/02 LLX 61/06 LMU

Claims (8)

[Claims] 1. A block comprising a polymer block mainly containing at least one vinyl aromatic compound and a polymer block mainly containing at least one conjugated diene compound with respect to 100 parts by weight of a thermoplastic resin (A). Hydrogenated block copolymer (B) obtained by hydrogenating the copolymer, and one or more non-halogen flame-retardant compounds (C) selected from phenol resin and phosphorus, nitrogen and boron compounds.
The thermoplastic resin composition is characterized in that 5 to 80 parts by weight of the melt-kneaded product is mixed and melt-kneaded. 2. 20 to 80% by weight of a hydrogenated block copolymer (B) and 80 to 20% by weight of a halogen-free flame-retardant compound (C) with respect to 100 parts by weight of a thermoplastic resin (A).
5 to 80 parts by weight of a melt-kneaded product and an inorganic hydrate (D) 3
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is blended in an amount of 0 to 160 parts by weight and melt-kneaded. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is polyethylene, modified polyethylene, polypropylene, modified polypropylene, polystyrene resin or polyphenylene ether resin. 4. The thermoplastic resin composition according to claim 1, wherein a phenol novolac resin is used as an essential component of the halogen-free flame-retardant compound (C). 5. A phosphoric ester and / or polyphosphate having a functional group selected from an amino group, a hydroxyl group and a carboxyl group is used as an essential component of the halogen-free flame-retardant compound (C). The thermoplastic resin composition according to claim 1, 2 or 3. 6. The thermoplastic resin composition according to claim 1, wherein boric acid and / or zinc borate is used as an essential component of the halogen-free flame-retardant compound (C). 7. At least one selected from melamine, melamine derivatives, guanidine and guanidine derivatives as an essential component of the halogen-free flame-retardant compound (C).
3. Use of one or more compounds as claimed in claim 1.
Or the thermoplastic resin composition described in 3. 8. The thermoplastic resin composition according to claim 1, wherein the inorganic hydrate (D) is magnesium hydroxide, aluminum hydroxide or calcium hydroxide. object.