JPH0841351A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition markedly improved in flame retardancy without detriment to the constituent thermoplastic resin by mixing the thermoplastic resin with a product of melt kneading of an epoxy- modified resin and a flame-retardant compound and melt-kneading the resultant mixture. CONSTITUTION:This composition is obtained by mixing 100 pts.wt. thermoplastic resin with 5-80 pts.wt. product of melt kneading of an epoxy-modified resin selected from among an epoxy-modified polyolefin, an epoxy-modified product of hydrogenated block copolymer obtained by hydrogenating a vinylaromatic compound/conjugated diene compound block copolymer, an epoxy-modified product of a block terpolymer comprising a block based on an acrylic resin, a block of a polymer based on a conjugated diene compound and a block of a polymer based on a vinylaromatic compound and an epoxy-modified product of an acrylic resin and a flame-retardant compound comprising a phenolic resin or a halogen-containing flame retardant, and melt-kneading the resulting mixture. This composition can give a molding not suffering from bleeding and having both flame retardancy and impact resistance.

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 impact resistance and flame retardancy, which is useful for various molded products obtained by injection molding or the like or for applications obtained by extrusion molding. Is.

[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.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a thermoplastic resin composition 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 flame retardant compound, the present inventors have found that flame retardancy is improved by a method of simply blending a thermoplastic resin and a flame retardant compound. However, it has been found that there is a drawback that characteristics such as bleeding, impact resistance and heat resistance are deteriorated.
Therefore, as a result of further diligent study, epoxy-modified resin (B)
By melt-kneading and the flame-retardant compound (C), the bleeding of the flame-retardant compound was improved, and it was found that the conventional drawbacks such as impact resistance and heat resistance were reduced. The invention was completed. That is, in the present invention, 5 to 80 parts by weight of a melt-kneaded product of an epoxy-modified resin (B) and a flame-retardant compound (C) is mixed with 100 parts by weight of a thermoplastic resin (A) and melt-kneaded. The present invention relates to a thermoplastic resin composition, which is preferably melt-kneaded with an epoxy-modified resin (B) and a flame-retardant compound (C) in advance, then blended with the thermoplastic resin and melt-kneaded. And a thermoplastic resin composition.

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, Examples thereof include copolymers of one or more kinds of acrylonitrile, butadiene, isoprene, and hydrogenated products thereof. 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) resin, and the like, for example, modified polyphenylene ether-based resins having different styrene ratios.

The epoxy-modified resin which is the component (B) of the present invention has a function of improving cold resistance and mechanical properties which are deteriorated when a phenol resin which is a resin having a relatively low molecular weight and is brittle is blended with a thermoplastic resin. However, it is also a very important component which also has a function of improving bleeding, impact resistance and heat resistance deterioration which occur when a halogen-based flame retardant compound is blended with a thermoplastic resin. Modified polyolefin containing an epoxy group in the molecule used in the present invention is not particularly limited and is commercially available, a copolymer of ethylene and glycidyl methacrylate or an ethylene-acrylic acid copolymer, Ethylene / methacrylic acid copolymer,
Examples thereof include ethylene / acrylate copolymers, terpolymers of ethylene / methacrylate copolymers and glycidyl methacrylate, and propylene grafted with glycidyl methacrylate. The hydrogenated block copolymer containing an epoxy group used in the present invention is not particularly limited and is commercially available, epoxidized styrene-ethylene / butylene-styrene block copolymer,
Examples include epoxidized styrene-ethylene / propylene-styrene block copolymers. A ternary material comprising a polymer block mainly composed of an acrylic resin used in the present invention, a polymer block mainly composed of at least one conjugated diene compound and a polymer block mainly composed of at least one vinyl aromatic compound. Epoxy modified products of block copolymers, epoxy modified products of acrylic resins are commercially available without any particular limitation, and epoxidized methacrylate-butadiene-styrene copolymers, epoxidized methyl acrylate and the like are available. Can be 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. The halogen-based flame retardant used as the component (C) of the present invention is not particularly limited and is commercially available, and examples of the bromine-based flame retardant compound include hexabromobenzene, tribromophenol, decabromodiphenyl ether and tetra. Bromobisphenol A etc. are mentioned.
Examples of chlorine-based flame retardants include chlorinated paraffin and chlorinated polyethylene.

The inorganic flame retardant used as the component (D) of the present invention is not particularly limited and is commercially available. Examples thereof include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, antimony trioxide, antimony pentoxide and the like.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin as the component (A), an epoxy-modified resin as the component (B), and a flame retardant compound as the component (C), which are added all at once to a pressure kneader or a Banbury mixer. 150 ~ 300 ℃, 10 ~ 30
The method of melt-kneading for 1 minute, or 100 to 300 of the epoxy-modified resin as the component (B) and the flame-retardant compound as the component (C) in advance.
After melt-kneading at 10 ° C. for 10 to 30 minutes, a thermoplastic resin of component (A) is added and melt-kneaded, and the latter is obtained by the epoxy-modified resin of component (B) and (C).
It is more preferable because the flame retardant compounds as the components are selectively mixed. In the thermoplastic resin composition of the present invention, 5 to 80 parts by weight of a melt-kneaded product of the epoxy-modified resin as the component (B) and the flame-retardant compound as the component (C) is used with respect to 100 parts by weight of the thermoplastic resin as the component (A). Must be compounded within the range of parts.
If the amount of the melt-kneaded product of the epoxy-modified resin as the component (B) and the flame-retardant compound as the component (C) is less than 5 parts by weight, the effect of improving the flame retardancy becomes insufficient, and if it exceeds 80 parts by weight, the respective heat The properties of the plastic resin are reduced. 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 kneaded product obtained by melt-kneading the epoxy-modified resin as the component) and the flame-retardant compound as the component (C) is compatible with both the thermoplastic resin as the component (A) and the flame-retardant compound as the component (C). It is considered that the flame-retardant compound as the component (C), which has good flame-retardant property, can be micro-dispersed in the thermoplastic resin because it has the property.

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 / cm2), the Izod impact test is JIS K6871, and the oxygen index is AS.
TM-D2863, combustion test is Underwriters Laborator
ies safety standard UL94 (○: burning time within 10 seconds
Δ: Burning for 10 seconds or more ×: Total burning)

(Examples and Comparative Examples) Thermoplastic resin compositions having the compounding formulations shown in Tables 1 to 9 were prepared by a conventional method, evaluated by the above evaluation method, and the results are shown in Tables 1 to 1. 9 shows. Polyethylene [PE: Ultzex 2022L manufactured by Mitsui Petrochemical Co., Ltd.] and polypropylene [PP: Sumitomo Noblen H501 manufactured by Sumitomo Chemical Co., Ltd.] are used as the polyolefin resin of the component (A). Is polystyrene [P
S: Showa Denko KK S-Bright 500A], ABS
Resin [ABS: Mitsubishi Rayon Co., Ltd. Diapet AB
SRPSE-7], and as the polyphenylene ether-based resin, [PPE: Asahi Kasei Kogyo Co., Ltd. Zylon X0061] or [PPE: Mitsubishi Gas Chemical Co., Inc.
Iupiace AV40] was used. As the component (B), epoxy-modified polyolefin resin [Ep-PO: Bond First 20M manufactured by Sumitomo Chemical Co., Ltd.], epoxy-modified styrene-ethylene / butylene-styrene block copolymer [Ep-SEBS: Asahi Chemical Industry Co., Ltd. ) Tuftec Z-514] was used. As the component (C), a straight phenol novolac resin [PN; Sumirite resin PR-5147 manufactured by Sumitomo Dures Co., Ltd.] is used.
0], tetrabromobisphenol A (TBA), decabromobiphenyl ether (DBBE), tribromophenol (TBP) were used. As the component (D),
Magnesium hydroxide and aluminum hydroxide were used.

Table 1  Example1 2 3 4 Blend (parts by weight) PE 100 100 PP 100 100 PN 21 20 10 Ep-SEBS 9 10 Ep-PO 10 20 TBA 15 DBBE 20 TBP 20 magnesium hydroxide 100Aluminum hydroxide 100 Properties Oxygen index 32.2 34.5 34.7 34.4 Cold resistance (℃) -61 -59 -62 -59 Tensile strength (Kg / cm²) 150 280 140 265 Tensile elongation (%) 520 520 490 520 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○No molten droplets None None None

Table 2 Example 5 6 7 8 Compounding (parts by weight) PS 100 100 100 ABS 100 100 PN 21 20 10 Ep-SEBS 9 10 10 20 TBA 15 DBBE 20 TBP 20 magnesium hydroxide 100 aluminum hydroxide 100 characteristics Tensile strength (Kg / cm ² ) 250 415 245 400 Tensile elongation (%) 4 56 45 55 Izod impact test (Kg · cm / cm) 8.6 29 8.8 30 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Melt droplet None None Nothing

Table 3 Example 9 10 11 12 Compounding (parts by weight) PPE 100 100 PPE 100 100 PN 21 20 10 Ep-SEBS 9 10 10 20 TBA 15 DBBE 20 TBP 20 magnesium hydroxide 100 aluminum hydroxide 100 Characteristic heat distortion temperature (° C.) 110 100 105 110 Tensile strength (Kg / cm ² ) 445 410 450 430 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Molten droplets None None None None

Table 4 Comparative Example 1 2 3 4 Compounding (parts by weight) PE 100 100 PP 100 100 PN 30 TBA 30 Magnesium hydroxide 100 100 100 Aluminum hydroxide 100 100 Properties Oxygen index 29.6 30.0 30.1 34.2 Cold resistance (° C) -60 -58 -15 -30 Tensile strength (Kg / cm ² ) 150 280 75 150 Tensile elongation (%) 595 515 310 300 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No

[0018]

Table 6 Comparative Example 8 9 10 11 Compounding (parts by weight) PS 100 100 ABS 100 100 PN 30 TBA 30 Magnesium hydroxide 100 100 100 Aluminum hydroxide 100 100 Properties Tensile strength (Kg / cm ² ) 255 410 130 210 Tensile elongation (%) ) 45 55 8 24 Izod impact test (Kg · cm / cm) 9.0 35 4.3 10 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

[0020]

Table 8 Comparative Example 15 16 17 18 Compounding (parts by weight) PPE 100 100 PPE 100 100 PN 30 TBA 30 Magnesium hydroxide 100 100 100 Aluminum hydroxide 100 100 Characteristics Heat distortion temperature (℃) 110 105 85 55 Tensile strength (Kg / cm ² ) 465 445 310 290 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

[0022]

[0023]

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, the thermoplastic resin composition of the present invention has no bleeding on the surface of the molded article, is a flame-retardant polyolefin-based resin composition having a high degree of flame retardancy, and has no bleeding on the surface of the molded article, which is difficult. It is a flame-retardant polystyrene-based resin composition having both flame resistance and impact resistance, and is a flame-retardant polyphenylene ether-based resin composition having no bleeding on the surface of a molded article and having both flame resistance and heat resistance.

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Claims (6)

[Claims] 1. An epoxy-modified polyolefin having an epoxy group in the molecule, a polymer block mainly containing at least one vinyl aromatic compound, and at least one conjugated diene, relative to 100 parts by weight of a thermoplastic resin (A). An epoxy modified product of a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block containing a compound as a main component, and a block containing an acrylic resin as a main component and at least one conjugated diene compound as a main component One or more selected from an epoxy modified product of a ternary block copolymer consisting of a polymer block containing at least one vinyl aromatic compound and an epoxy modified product of an acrylic resin. Melt-kneaded product of the epoxy-modified resin (B) and the flame-retardant compound (C) consisting of a phenol resin or a halogen-based flame retardant A thermoplastic resin composition comprising 5 to 80 parts by weight and melt-kneading. 2. 20 to 80% by weight of an epoxy-modified resin (B) and 80 parts by weight of 100 parts by weight of a thermoplastic resin (A).
~ 20 wt% melt-kneaded product with flame-retardant compound (C) 5
2. The thermoplastic resin composition according to claim 1, wherein 80 parts by weight and 5 to 160 parts by weight of the inorganic flame retardant (D) are mixed 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 halogen-based flame retardant compound having a functional group capable of reacting with an epoxy group is used as an essential component of the halogen-based flame retardant. 5. The thermoplastic resin composition according to claim 1, wherein tetrabromobisphenol A or decabromodiphenyl ether is used as an essential component of the halogen-based flame retardant. 6. The inorganic flame retardant (D) is magnesium hydroxide, aluminum hydroxide, calcium hydroxide, antimony trioxide or antimony pentoxide.
The thermoplastic resin composition according to 3, 4, or 5.