JPH07330998A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition which can give a molding that does not suffer from bleeding to the surface and generates neither corrosive nor noxious gases during processing or in burning and which is markedly improved in flame retardancy without detriment to the features of the thermoplastic resin. CONSTITUTION:This resin composition is prepared by mixing 100 pts.wt. thermoplastic resin with 5-80 pts.wt. product of melt kneading of at least one acid- modified resin selected from among an acid-modified polystyrene, a graft compound thereof, an acid-modified acrylic resin and a graft compound thereof an at least one nonhalogenous flame-retarding compound selected from among a phenolic resin and phosphorus, nitrogen and boron compounds, and melt- kneading the resultant mixture.

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 articles obtained by injection molding or the like or 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. 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 studying the non-halogen flame retardation of a thermoplastic resin, the present inventors have found that flame retardancy is not improved by a method of simply blending a thermoplastic resin and a phenol resin having good flame retardancy. Although it is improved, it has been found that there is a drawback that characteristics such as impact 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, resulting in deterioration of properties such as impact resistance and heat resistance. It turned out that Then, as a result of further diligent study, by melt-kneading the acid-modified resin (B) and the non-halogen flame-retardant compound (C), the brittleness of the phenol resin is covered and the bleeding of phosphorus, nitrogen and boron compounds is covered. Improved, impact resistance, which was a conventional drawback
The inventors have found that the deterioration of mechanical properties and the like is improved and have completed the present invention. That is, in the present invention, 5 to 80 parts by weight of a melt-kneaded product of an acid-modified resin (B) and a non-halogen flame-retardant compound (C) is mixed with 100 parts by weight of a thermoplastic resin (A) and melt-kneaded. It relates to a thermoplastic resin composition characterized in that it is preferably melt-kneaded with an acid-modified resin (B) and a non-halogen flame-retardant compound (C) in advance, and then blended into the thermoplastic resin, The present invention relates to a thermoplastic resin composition characterized by being melt-kneaded. Further, with respect to 100 parts by weight of the thermoplastic resin (A), 20-80% by weight of the acid-modified resin (B) and 80-20
5 to 80 parts by weight of a melt-kneaded product with a non-halogen flame-retardant compound (C) in an amount of wt% and an inorganic hydrate (D) 30 to 160
The present invention relates to a thermoplastic resin composition which is prepared by blending parts by weight and melt-kneading.

The thermoplastic resin used as the component (A) of the present invention is not particularly limited and is commercially available. Of these, polystyrene resins, polyphenylene ether resins, and acrylic resins are preferable.
The polystyrene resin is not particularly limited and is commercially available. For example, polystyrene resins include styrene and α-substituted styrenes such as α-methylstyrene,
A polymer of a styrene derivative such as vinyltoluene, or a monomer mainly containing these monomers and copolymerizable with one or more of them, such as acrylonitrile, butadiene, isoprene, and the hydrogenation thereof. Things 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),
Examples thereof include poly (2-methyl-6-ethylphenylene-1,4-ether) resins and the like, for example, modified polyphenylene ether-based resins having different styrene ratios. The acrylic resin is a well-known polymer mainly composed of methyl methacrylate, and as a copolymer component, (meth) acrylic acid ester, (meth) acrylic acid and the like can be mentioned. Examples include terpolymers and the like.

The acid-modified resin which is the component (B) of the present invention has a function of improving impact 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. And bleeding that occurs when phosphorus, nitrogen, or a boron compound is further added to the thermoplastic resin,
It is a very important component that also has the function of improving the reduction of impact resistance and heat resistance. The acid-modified resin used in the present invention is not particularly limited and is commercially available,
Terminal carboxylic acid group-containing polystyrene, maleic anhydride modified polystyrene, maleic anhydride modified acrylic resin-
Examples thereof include polymethylmethacrylate graft copolymers and maleic anhydride-modified acrylic resin-polystyrene graft copolymers.

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 thereof include phosphoric compounds such as phosphoric acid esters and aromatic phosphoric acid esters, and carboxylic acid anhydrides. Phosphorus having a functional group that reacts with a group, nitrogen compounds are not particularly limited and are generally commercially available, and as the functional group, for example, those having an amino group, an isocyanate group, an oxazoline group are suitable. used. Specific examples of the compound include polyphosphoric acid, ammonium polyphosphate, phosphorus compounds such as amino group- or hydroxyl group-containing phosphate ester, melamine or melamine cyanurate compound, melamine phosphate, melamine derivative such as melamine borate, guanidine or Examples thereof include guanidine-based derivatives such as guanidine sulfamate and guanidine phosphate. These non-halogen flame retardant compounds may be used alone or in combination of two or more.

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. 5 to 80 parts by weight of a melt-kneaded product of 20 to 80% by weight of an acid-modified resin (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). And 30 to 160 parts by weight of the inorganic hydrate (D) are preferably blended. If the amount added is less than 30 parts by weight, there is no flame retardant effect and 1
If it exceeds 60 parts by weight, the moldability becomes poor.

The thermoplastic resin composition of the present invention comprises a thermoplastic resin as the component (A), an acid-modified resin as the component (B), and a halogen-free flame-retardant compound as the component (C), which are added in a pressure kneader or a kneader. 150-300 ℃ with a Banbury mixer, 10
~ 30 minutes by melt-kneading, or (B) component epoxy-modified resin and (C) component non-halogen flame-retardant compound is melt-kneaded at 100 ~ 300 ° C. for 10 to 30 minutes in advance, followed by (A) component It can be obtained by a method of adding a thermoplastic resin and further melt-kneading. The latter is more preferable because the acid-modified resin as the component (B) and the non-halogen flame-retardant compound as the component (C) are selectively mixed. In the thermoplastic resin composition of the present invention, 5 parts of a melt-kneaded product of the acid-modified resin of the component (B) and the halogen-free flame-retardant compound of the component (C) is added to 100 parts by weight of the thermoplastic resin of the component (A). It must be compounded in the range of 80 parts by weight. If the melt-kneaded product of the acid-modified resin as the component (B) and the non-halogen flame-retardant compound as the component (C) is less than 5 parts by weight, the flame retardancy-improving effect becomes insufficient, and if it exceeds 80 parts by weight, each of The properties of the 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 product obtained by melt-kneading the acid-modified resin as the component) and the halogen-free flame-retardant compound as the component (C) is a thermoplastic resin as the component (A) and a halogen-free flame-retardant compound as the component (C). It is considered that it is possible to microdisperse the non-halogen flame-retardant compound of the component (C), which has good flame retardancy, in the thermoplastic resin because it has an affinity for both.

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 ordinary thermoplastic resin molded products, 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. A test piece was prepared from a composition prepared by kneading and mixing the compounds shown in Tables 1 to 9 by a conventional method, and the following evaluation was performed. The results are shown in Tables 1 to 9. Tensile test is AS
TM-D638, heat distortion temperature is ASTM-D648
(4.6 kgf / cm2), Izod impact test is JI
SK6871, oxygen index is ASTM-D2863, combustion test is underwriter UL Laboratories safety standard UL
94 (○: Burning time within 10 seconds △: Burning over 10 seconds
X: The result of measurement by total burning). (Examples and Comparative Examples) As the polystyrene resin of the component (A), polystyrene [PS: S-Bright 500A manufactured by Showa Denko KK], ABS resin [ABS: Diapet ABS RSE-7 manufactured by Mitsubishi Rayon Co., Ltd.] ], As the polyphenylene ether resin, [PPE
: Asahi Kasei Corporation Zylon X0061] or Iupiace AV40 [PPE: Mitsubishi Gas Chemical Co., Ltd.
Iupiace AV40] was used, and polymethylmethacrylate [PMMA: Delpet 560F manufactured by Asahi Kasei Kogyo Co., Ltd.] was used as the acrylic resin. As the component (B), maleic anhydride-modified polystyrene [MAH-
PS: Sanyo Kasei Co., Ltd.], maleic anhydride modified acrylic-styrene graft copolymer [GP-400: Reseda G
P-400 manufactured by Toagosei Kagaku Co., Ltd.] was used. (C)
As a component, straight phenol novolac resin [PN; Sumilite resin PR manufactured by Sumitomo Dures Co., Ltd.]
-51470], condensed phosphoric acid ester [PX-201
Daihachi Chemical Co., Ltd.], boric acid, 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) PS 100 100 ABS 100 100 PN 21 20 10 MAH-PS 9 10 GP-400 10 20 PX-201 15 15 Boric acid 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 (Kg · cm / cm) 8.6 30 8.6 29 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Molten droplets None None None None

Table 2 Example 5 6 7 8 Compounding (parts by weight) PPE 100 100 PPE 100 100 PN 21 20 10 MAH-PS 9 10 GP-400 10 20 PX-201 15 15 Boric acid 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 ○ ○ ○ ○ Melted droplets No No No No

Table 3 Example 9 10 11 12 Compounding (parts by weight) PMMA 100 100 100 100 100 PN 21 20 10 GP-400 9 10 20 20 PX-201 15 Boric acid 20 MPP-A 20 Magnesium hydroxide 100 Aluminum hydroxide 100 Properties Tensile strength ( Kg / cm ² ) 690 655 650 680 UL94 1st ignition ○ ○ ○ ○ 2nd ignition ○ ○ ○ ○ Molten droplet No No No No

Table 4 Comparative Example 1 2 3 4 Compounding (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 ) 255 410 120 220 Tensile elongation (%) 45 55 10 29 Izod impact test (Kg · cm / cm) 9.0 32 4.2 14 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Melted droplet Yes Yes No Yes

[0016]

Table 6 Comparative Example 8 9 10 11 Blend (parts by weight) PPE 100 100 PPE 100 100 PN 30 PX-201 30 Magnesium hydroxide 100 100 Aluminum hydroxide 100 100 Characteristic heat distortion temperature (° C) 110 98 82 66 Tensile strength (Kg / Kg / cm ² ) 455 435 310 305 UL94 1st ignition × × ○ ○ 2nd ignition × × ○ × Molten droplet Yes Yes No Yes

[0018]

Table 8 Comparative Example 15 16 17 18 Composition (parts by weight) PMMA 100 100 100 100 100 PN 30 27 GP-400 3 PX-201 30 Magnesium hydroxide 100 100 100 Aluminum hydroxide 100 100 Properties Tensile strength (Kg / cm ² ) 680 355 450 380 UL94 1st ignition × ○ ○ ○ 2nd ignition × ○ × ○ Molten droplets Yes No Yes No No

[0020]

As is clear from the table, the thermoplastic resin composition of the present invention gives a molded product which does not bleed to the surface of the molded product and does not generate corrosive gas or harmful gas during processing or combustion, It is a novel material in which the flame retardancy is remarkably improved while maintaining the characteristics of the thermoplastic resin. That is, it is a flame-retardant polystyrene resin composition having both flame resistance and impact resistance, a flame-retardant polyphenylene ether resin composition having both flame resistance and heat resistance, excellent in flame retardance. It is a polymethylmethacrylate resin composition.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C08L 33/04 LJA 61/06 LMY 71/12 LQP

Claims (10)

[Claims] 1. One or more kinds selected from an acid-modified polystyrene, a graft compound of an acid-modified polystyrene, an acid-modified acrylic resin, and a graft compound of an acid-modified acrylic resin with respect to 100 parts by weight of a thermoplastic resin (A). 5 to 80 parts by weight of a melt-kneaded product of an acid-modified resin (B) and a phenol resin and one or more non-halogen flame-retardant compound (C) selected from phosphorus, nitrogen and boron compounds, A thermoplastic resin composition characterized by being melt-kneaded. 2. 20 to 80% by weight of an acid-modified resin (B) and 80 to 20 relative to 100 parts by weight of a thermoplastic resin (A).
5 to 80 parts by weight of a melt-kneaded product with a non-halogen flame-retardant compound (C) in an amount of wt% and an inorganic hydrate (D) 30 to 160
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition is blended by weight and melt-kneaded. 3. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin (A) is a polystyrene resin, a polyphenylene ether resin, or an acrylic resin. 4. The acid-modified resin (B) is maleic anhydride-modified polystyrene, maleic anhydride-modified acrylonitrile-
Butadiene-styrene copolymer, maleic anhydride modified polystyrene graft compound, maleic anhydride modified acrylonitrile-butadiene-styrene copolymer graft compound, maleic anhydride modified acrylic resin, maleic anhydride modified acrylic resin graft compound The thermoplastic resin composition according to claim 1, 2, or 3. 5. 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). 6. Use of at least one compound selected from phosphorus and nitrogen compounds having a functional group capable of reacting with a carboxylic acid anhydride group as an essential component of the halogen-free flame-retardant compound (C). The thermoplastic resin composition according to claim 1, 2, 3, or 4. 7. Use of a phosphoric acid ester and / or a polyphosphoric acid salt having a functional group selected from an amino group, an isocyanate group, an oxazoline group and a hydroxyl group as an essential component of the halogen-free flame-retardant compound (C). The thermoplastic resin composition according to claim 1, 2, 3, or 4. 8. At least one selected from melamine, melamine derivatives, guanidine, and guanidine derivatives as an essential component of the halogen-free flame-retardant compound (C).
2. Use of one or more compounds,
The thermoplastic resin composition according to 2, 3, or 4. 9. The thermoplastic resin composition according to claim 1, wherein melamine phosphate is used as an essential component of the halogen-free flame-retardant compound (C). 10. The thermoplastic according to claim 1, 2, 3, 4, 5, 6, 7, 8 or 9, wherein the inorganic hydrate (D) is magnesium hydroxide, aluminum hydroxide or calcium hydroxide. Resin composition.