JPH07316415A - Flame-retardant polyphenylene ether resin composition and production thereof - Google Patents

Abstract

PURPOSE:To improve the flame-retardancy of the title composition by compounding a polyphenylene ether resin with a mixture of melamine phosphate, a phenolic novolak resin, and a hydrogenated block copolymer and/or its modification with epoxy. CONSTITUTION:100 pts.wt. polyphenylene ether resin (A) comprising, e.g. poly(2,6- dimethylphenylene-1,4-ether) and 5-50 pts.wt. mixture of melamine phosphate (B), a phenolid novolak resin (C), and component (D) comprising a hydrogenated block copolymer, such as a hydrogenated styrene-ethylene butylene-styrene block copolymer, and/or its modification with epoxy at a weight ratio of (90:10) to (50:50), with a weight ratio of component C to component D of (80:20) to (20:80) are weighed. The components B, C and D are melt kneaded by, e.g. a pressure kneader at about 100-250 deg.C for about 10-30min, and the compound is then melt kneaded with component A at about 200-300 deg.C to give the title composition.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyphenylene ether resin composition having good flame retardancy, and is used in many industrial applications requiring heat resistance, including films, fibers and molded articles. It is useful.

[0002]

2. Description of the Related Art Polyphenylene ether resin, which is one of the typical polyphenylene ether resins, has heat resistance,
It has excellent properties such as rigidity and electrical properties and is widely used as a useful engineering plastic. However, the polyphenylene ether resin is inferior in moldability and impact resistance, and the flame retardancy is not sufficient by itself. A technique of compounding a styrene resin or an elastomer-reinforced styrene resin is exemplified for the purpose of improving moldability and impact resistance, but the flame retardancy of polyphenylene ether resin is greatly impaired by compounding a styrene resin. Is well known. Therefore, it is well known that the blending of a flame retardant is indispensable in order to use the polyphenylene ether-based resin in applications where flame retardancy is required. The flame retardants are phosphorus-containing compounds and halogen-containing compounds. However, in the case of a phosphorus-containing compound, although it exhibits an excellent flame-retardant effect, it is unavoidable that the heat distortion temperature, heat resistance, and mechanical properties such as tensile strength are significantly lowered. A further serious problem is that these phosphorus-containing compounds are volatilized from the resin phase during the molding process, contaminating the mold, and thus impairing the appearance of the molded product. On the other hand, a halogen-containing compound does not have a plasticizing effect on the polyphenylene ether-based resin, and it is a characteristic not seen in the phosphorus-containing compound that the heat resistance of the polyphenylene ether-based resin is hardly impaired. However, the fact that the moldability is not improved is a drawback. Further, it is well known that bleeding occurs due to migration of the halogen-containing compound to the molding surface, and problems such as corrosion of a molding machine or a mold due to a thermal decomposition product of the halogen-containing compound occur. In order to improve these drawbacks, a method relating to a composition obtained by blending a polyphenylene ether resin with a flame retardant biphenylyl phosphate compound is exemplified in JP-A-61-197653, but the polyphenylene ether resin of the present invention is used. Although the resin composition has an effect of improving flame retardancy, heat resistance and mechanical properties are deteriorated by this method, and a resin composition having a practical level has not been obtained.

[0003]

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

[0004]

The present inventors have investigated a method of simply blending various non-halogen flame retardants for flame retarding a polyphenylene ether resin, but this method has an effect of improving flame retardancy. However, it was found that there is a drawback that bleeding occurs and mechanical properties and heat resistance are deteriorated. Then, as a result of further diligent study, it was found that when melamine phosphate was used as a specific non-halogen flame retardant for the polyphenylene ether resin, flame retardancy was improved with almost no bleeding. When this melamine phosphate is used in combination with a phenol novolac resin, the flame retardancy is further improved without lowering the properties such as mechanical properties and heat resistance, and melamine phosphate and a hydrogenated block copolymer and / or an epoxy modified product thereof. It was found that when used together with, flame retardancy was improved without bleeding at all. Further, when melamine phosphate, a phenol novolac resin and a hydrogenated block copolymer and / or an epoxy modified product thereof are used in combination, bleeding does not occur at all,
The inventors have found that the flame retardancy is remarkably improved and have completed the present invention. That is, the present invention is characterized in that (B) 5 to 50 parts by weight of melamine phosphate is blended with 100 parts by weight of (A) polyphenylene ether resin, and melt-kneaded to obtain a flame-retardant polyphenylene ether resin composition. Preferably, (B) melamine phosphate and (C) phenol novolac resin or (D) hydrogenated block copolymer and / or its epoxy modification relative to 100 parts by weight of (A) polyphenylene ether resin. Things are 80: 2
The present invention relates to a flame-retardant polyphenylene ether resin composition and a method for producing the same, which comprises mixing 5 to 50 parts by weight of a mixture in a ratio of 0 to 20:80 and melt-kneading the mixture, and more preferably (A ) 9 parts of (B) melamine phosphate, (C) phenol novolac resin and (D) hydrogenated block copolymer and / or epoxy modified product thereof are added to 100 parts by weight of the polyphenylene ether resin composition.
5 to 50 parts by weight of a mixture of (C) phenol novolac resin and (D) hydrogenated block copolymer and / or epoxy modified product thereof in a ratio of 0:10 to 50:50, 80:20 to 20:80. The present invention relates to a flame-retardant polyphenylene ether-based resin composition comprising:

The polyphenylene ether resin used as the component (A) of the present invention 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 resin having a different styrene ratio.

Melamine phosphate, which is the component (B) of the present invention, has an excellent compatibility with the polyphenylene ether resin and is an important component which imparts a high degree of flame retardancy to the polyphenylene ether resin. The melamine phosphate which is the component (B) of the present invention is not particularly limited, and a commercially available product may be used as it is. For example, MPP-A [Sanwa Chemical]
Co., Ltd.], P-7202 [Sanwa Chemical Co., Ltd.] and the like.

The phenol novolac resin used as the component (C) of the present invention is not particularly limited and is commercially available. For example, the phenol / formalin and formaldehyde / phenol molar ratios are:
The mixture was charged into a reaction kettle at a compounding ratio of 0.5 to 1.0, and a catalyst such as oxalic acid, hydrochloric acid, sulfuric acid, and toluenesulfonic acid was further added, and the mixture was heated and refluxed for an appropriate time. It can be obtained by a method such as vacuum dehydration or static dehydration for removing separated water, 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 hydrogenated block copolymer which is the component (D) of the present invention has a function of microdispersing melamine phosphate in a polyphenylene ether resin. Further, the epoxy modified product of the hydrogenated block copolymer has an epoxy group that reacts with melamine phosphate, and the resulting compound has a component having an affinity for each of the polyphenylene ether resin and the melamine phosphate. Acts as a compatibilizer for ether resins and melamine phosphate,
It is preferable because it has a function of preventing bleeding of melamine phosphate and further microdispersing melamine phosphate in the polyphenylene ether 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, styrene / ethylene / propylene / styrene block copolymer. Is mentioned. 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, epoxidized styrene-ethylene.・
Examples include propylene-styrene block copolymers.

The polyphenylene ether resin composition of the present invention comprises a polyolefin resin as component (A), melamine phosphate as component (B), a phenol novolac resin as component (C) and / or hydrogenated component (D). The block copolymer and / or its epoxy modified product are put in at one time, and the pressure kneader, Banbury mixer, etc. are used at 200 to 300 ° C., 10 to 3
The method of melt-kneading for 0 minutes, or the melamine phosphate as the component (B) and the phenol novolac resin as the component (C) and / or the hydrogenated block copolymer as the component (D) and / or the epoxy modified product thereof are mixed in advance with 100 parts. After melt-kneading at ˜250 ° C. for 10-30 minutes, a polyphenylene ether resin as the component (A) is added and further melt-kneaded. The latter is more suitable than the melamine phosphate as the component (B) and (C). Component) and / or the hydrogenated block copolymer of component (D) and / or its epoxy-modified product are uniformly mixed, which is preferable. In the polyphenylene ether-based resin composition of the present invention, melamine phosphate as the component (B) or melamine phosphate as the component (B) and (C) the phenol novolac resin per 100 parts by weight of the polyphenylene ether-based resin as the component (A) and / Alternatively, the mixture of the hydrogenated block copolymer of the component (D) and / or its epoxy modified product must be blended in the range of 5 to 50 parts by weight. Further, the melamine phosphate as the component (B) and the phenol novolac resin as the component (C) or the hydrogenated block copolymer and / or the epoxy modified product thereof as the component (D) are 80:
A ratio of 20 to 20:80 is more preferably used.
(B) component melamine phosphate or (B) component melamine phosphate and (C) component phenol novolac resin and / or
Alternatively, when the mixture of the hydrogenated block copolymer of component (D) and / or its epoxy modified product is 5 parts by weight or less, the flame retardancy improving effect is insufficient, and when it is 50 parts by weight or more, polyphenylene is used. Various advantages of the ether resin are reduced. The proportion of melamine phosphate in the mixture of the melamine phosphate as the component (B) and the phenol novolac resin as the component (C) or the hydrogenated block copolymer as the component (D) and / or its epoxy modified product is 80 wt%. If it exceeds, the effect of the addition of the phenol novolac resin of the component (C) or the hydrogenated block copolymer of the component (D) and / or its epoxy modified product tends to disappear, and if it is less than 20 wt%, the flame retardancy tends to decrease. become.

As described above, the polyphenylene ether resin composition of the present invention has the effect of improving the flame retardancy without causing the deterioration of the characteristics of the polyphenylene ether resin as the component (A). As a reason, having phosphorus and nitrogen elements in the molecule, melamine phosphate excellent in flame retardance has good compatibility with polyphenylene ether resin, and by using melamine phosphate and phenol novolac resin in combination, phosphorus It is considered that this is because a synergistic effect of two kinds of flame-retardant effects can be obtained by forming a film with melamine acid and forming a shell with a phenol novolac resin during combustion.
When melamine phosphate is used in combination with hydrogenated block copolymer and / or epoxy modified product thereof, melamine phosphate can be micro-dispersed in polyphenylene ether resin. Further, the epoxy modified product of the hydrogenated block copolymer has a compound whose epoxy group reacts with melamine phosphate has a component having an affinity for both melamine phosphate and polyphenylene ether resin in the molecule, It is more preferable because it acts as a compatibilizer, prevents bleeding of melamine phosphate, and enables melamine phosphate to be microdispersed in the polyphenylene ether-based resin. Furthermore, by using melamine phosphate, a phenol novolac resin and a hydrogenated block copolymer and / or an epoxy modified product thereof in combination, there is a synergistic effect of flame retardancy, and melamine phosphate is microdispersed in a polyphenylene ether resin. It is thought that it is possible to do. The polyphenylene ether resin composition of the present invention further comprises other compounding agents depending on the use and purpose, for example, talc, mica, calcium carbonate, inorganic fillers such as wollastonite, coupling agents or glass fibers, carbon fibers, etc. Reinforcing agents, antistatic agents, stabilizers, pigments, mold release agents, impact modifiers such as elastomers, etc. can be added. The polyphenylene ether-based 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.

[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. The tensile test is ASTM-D638, the heat distortion temperature is ASTM-D648 (4.6 kgf / cm ² ), and the combustion test is Underwriters Laboratories safety standard UL9.
4 (○: burning time within 10 seconds, △: burning for 10 seconds or more,
X: burnt out), molding appearance (*: no bleed at all ◯: almost no ∆: little, x: yes, visually determined). (Example) As component (A), polyphenylene ether [PPE; Zylon X0061 Asahi Kasei
Co., Ltd.] or [PPE; Iupiace AV40 Mitsubishi Gas Chemical Co., Ltd.], (B) component melamine phosphate [MPP-A: Sanwa Chemical Co., Ltd.], (D) component Is phenol novolac resin [PN: Sumitomo Dures
PR-51470] manufactured by Asahi Kasei Corporation as an (E) component and epoxy-modified SEBS [Ep-SEBS: manufactured by Asahi Kasei Corporation]
Tuftec Z-514] was used. The blending and evaluation results are shown in Table 1. (Comparative Example) As the component (A), polyphenylene ether [PPE; Zylon X0061 Asahi Kasei Corporation
Co., Ltd.] or [PPE; Iupiace AV40 Mitsubishi Gas Chemical Co., Ltd.], (B) component melamine phosphate [MPP-A: Sanwa Chemical Co., Ltd.], (D) component Is phenol novolac resin [PN: Sumitomo Dures
PR-51470] manufactured by Asahi Kasei Corporation as an (E) component and epoxy-modified SEBS [Ep-SEBS: manufactured by Asahi Kasei Corporation]
Tuftec Z-514] was used. The blending and evaluation results are shown in Tables 2 and 3.

Table 1 Example 1 2 3 4 Compounding (parts by weight) PPE 100 100 PPE 100 100 MPP-A 15 10 10 20 PN 10 5 Ep-SEBS 10 5 Characteristic tensile strength (Kg / cm ² ) 500 480 510 460 Heat deformation temperature (℃) 120 110 115 110 UL94 1st ignition ○ ○ ○ ○ 2nd ignition △ ○ △ ○ Molten droplets No No No No Molded appearance ○ ○ ※ ※

Table 2 Comparative Example 1 2 3 4 Compounding (parts by weight) PPE 100 100 PPE 100 100 MPP-A 60 3 Characteristics Tensile strength (Kg / cm ² ) 500 480 300 480 Heat distortion temperature (° C) 120 110 80 110 UL94 1st time Ignition × × ○ × Second ignition × × ○ × Molten droplets Yes Yes No Yes Molding appearance * * △ ○

Table 3 Comparative Example 5 6 7 8 Compounding (parts by weight) PPE 100 100 PPE 100 100 MPP-A 30 5 30 PN 30 30 30 15 Ep-SEBS 35 15 15 Tensile strength (Kg / cm ² ) 380 290 390 340 Thermal deformation temperature (℃) 80 85 70 80 UL94 1st ignition ○ ○ × ○ 2nd ignition △ ○ × ○ Melted droplets Yes No Yes No Molding appearance * △ * *

[0015]

As is apparent from the table, the polyphenylene ether resin composition of the present invention is a novel material in which the flame retardancy is remarkably improved while maintaining the characteristics of the polyphenylene ether resin. A product which is easily processed into a molded product by a processing method used for a thermoplastic molding material, such as injection molding or extrusion molding, and which has an excellent balance of physical properties such as mechanical strength and moldability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C08L 63/00 NJY

Claims (9)

[Claims] 1. (A) Polyphenylene ether-based resin 1
A flame-retardant polyphenylene ether resin composition comprising (B) 5 to 50 parts by weight of melamine phosphate mixed with 100 parts by weight. 2. A (A) polyphenylene ether resin 1
5 parts by weight of a mixture of (B) melamine phosphate and (C) phenol novolac resin in an amount of 80:20 to 20:80 with respect to 00 parts by weight. Polyphenylene ether resin composition. 3. The flame-retardant polyphenylene ether resin composition according to claim 2, which is a mixture of (B) melamine phosphate and (C) phenol novolac resin in a ratio of 70:30 to 30:70. 4. A polyphenylene ether-based resin (A) 1
A block composed of (B) a melamine phosphate and (D) a polymer block containing at least one vinyl aromatic compound as a main component and at least one polymer block containing at least one conjugated diene compound, based on 100 parts by weight. The hydrogenated block copolymer obtained by hydrogenating the copolymer and / or the epoxy modified product thereof is mixed in an amount of 5 to 50 parts by weight of a mixture in a ratio of 80:20 to 20:80. Flame-retardant polyphenylene ether resin composition. 5. A block copolymer comprising (B) a melamine phosphate, (D) a polymer block mainly containing at least one vinyl aromatic compound and at least one polymer block mainly containing a conjugated diene compound. The flame-retardant polyphenylene ether resin composition according to claim 4, wherein the hydrogenated block copolymer obtained by hydrogenating the polymer and / or the epoxy modified product thereof is a mixture in a ratio of 70:30 to 30:70. . 6. A (A) polyphenylene ether resin 1
(B) melamine phosphate, (C) phenol novolac resin, and (D) at least one vinyl aromatic compound-based polymer block and at least one conjugated diene compound The hydrogenated block copolymer obtained by hydrogenating the block copolymer consisting of the polymer block and / or (C) phenol novolac resin having a ratio of 90:10 to 50:50 with the epoxy modified product. D) A flame-retardant polyphenylene ether system characterized by comprising 5 to 50 parts by weight of a mixture of the hydrogenated block copolymer and / or the epoxy modified product thereof in a ratio of 80:20 to 20:80. Resin composition. 7. The melamine phosphate (B) and the phenol novolac resin (C) are melt-kneaded in advance, then mixed with the polyphenylene ether resin, and further melt-kneaded. A method for producing a flame-retardant polyphenylene ether resin composition. 8. A method in which (B) melamine phosphate and (D) hydrogenated block copolymer and / or epoxy modified product thereof are melt-kneaded in advance, then blended with a polyphenylene ether resin, and further melt-kneaded. Claim 4 or 5 characterized
A method for producing the flame-retardant polyphenylene ether resin composition described. 9. (B) Melamine phosphate, (C) phenol novolac resin and (D) hydrogenated block copolymer and / or epoxy modified product thereof are melt-kneaded in advance and then blended with a polyphenylene ether resin. The method for producing a flame-retardant polyphenylene ether resin composition according to claim 6, further comprising melt-kneading.