JPH0781070B2 - Flame-retardant polyphenylene ether resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a polyphenylene ether resin and a polyamide resin. More specifically, the present invention relates to a flame-retardant polyphenylene ether resin composition in which red phosphorus is mixed in a resin mixture system containing a modified polyphenylene ether resin and a polyamide resin.

[Conventional technology]

The polyphenylene ether resin is excellent in various properties such as thermal properties, mechanical properties, and electrical properties, but has a drawback that it is inferior in moldability because it has a high melt processing temperature and low fluidity. Further, it has strong resistance to inorganic chemicals such as acids and alkalis, but it dissolves and swells in certain organic solvents, and improvement in solvent resistance and oil resistance is strongly demanded. ing.

Several attempts have been made to improve both the moldability and oil resistance. For example, a method of blending polyamide with polyphenylene ether in an amount of 20% or less (Japanese Patent Publication No. 45-997).
No.), polyphenylene ether with 30-95% polyamide
There is a method of blending within the range (Japanese Patent Publication No. 59-41663).
When a small amount of polyamide is added, the molding processability is improved to some extent, while it is difficult to say that it is a sufficient improvement in terms of oil resistance, while when a relatively large amount is added, the solvent resistance is improved, and toughness is improved. No brittle material. This is essentially due to the poor compatibility between the polyphenylene ether resin and the polyamide resin.

Several methods have been proposed for increasing the compatibility between the polyphenylene ether resin (hereinafter referred to as PPE) and the polyamide resin. For example, a method in which a compound having a carbon-carbon double bond and a functional group such as a carboxylic acid group, an acid anhydride group, an acid amide group, or an imide group in the molecule of maleic acid or maleimide is blended as a third component (special feature (Kaisho 56-26913) and a method of blending a copolymer of a styrene compound and an α, β-unsaturated dicarboxylic acid (Japanese Patent Publication No. 59-33614). Even if maleic anhydride or maleimide is blended as the third component, it is not possible to sufficiently improve the compatibility, and in high temperature and high speed molding such as injection molding, the molded product exhibits delamination and poor appearance, and It is difficult to obtain a material having sufficient toughness.
Further, when a copolymer of maleic anhydride and styrene is blended, heat resistance is lowered.

[Problems to be solved by the invention]

The present inventors thermally grafted a 1,2-substituted olefin compound having an acid anhydride structure on a side chain methyl group of PPE as a tough resin composition having improved compatibility between PPE and a polyamide resin. We have completed the invention of a resin composition consisting of a modified PPE that has been converted to a polyamide resin, and have previously filed a patent application (Japanese Patent Application Nos. 61-154235 and 61-154236).

This resin composition has a smaller water absorption rate and a smaller change in physical properties when absorbing water than a polyamide resin alone. However, since it contains a polyamide resin, the change in physical properties during absorption of water is unavoidable.
In addition, it was revealed that this composition does not exhibit satisfactory performance in terms of flame retardancy which is an original feature of PPE.

An object of the present invention is to impart flame retardancy to a resin composition of PPE and a polyamide resin without impairing the original physical properties.

[Means for solving problems]

The present inventors have conducted extensive studies in order to impart flame retardancy to a resin composition composed of a modified PPE and a polyamide resin (hereinafter sometimes abbreviated as PA), and as a result, the resin composition It has been found that the addition of red phosphorus to the composition imparts excellent flame retardancy to the present invention.

By the way, when well-known phosphoric acid esters and organic halides are used as flame retardants for PPE resin compositions, it is well known that exudation of flame retardants, deterioration of physical properties, and other inconveniences are unavoidable. However, the composition of the present invention does not have such inconvenience.

The present invention includes (a) a general formula (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and
R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms) and a polyphenylene ether resin having a structural unit represented by the main chain and a 1,2-substituted olefin compound having an acid anhydride structure. A flame-retardant polyphenylene ether-based resin composition containing a modified polyphenylene ether resin obtained by reacting in a molten state in the absence of a catalyst, (b) a polyamide resin, and (c) red phosphorus.

The polyphenylene ether resin (PP
E) has a structural unit represented by the above general formula in its main chain and may be a homopolymer, a copolymer or a graft polymer. Specifically, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4) -Phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether and the like, but especially poly (2 , 6-Dimethyl-1,4-phenylene) ether, 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, and a graft copolymer obtained by graft-polymerizing styrene to these are used in the present invention. Preferred as polyphenylene ether resin.

The modified polyphenylene ether resin (modified PPE) used in the present invention is obtained by melt-kneading PPE and a 1,2-substituted olefin compound having an acid anhydride structure under heating. The melt kneading method is not particularly limited, such as a kneader, a Banbury mixer, and an extruder, but it is preferable to use an extruder from the viewpoint of operability and the like.

The 1,2-substituted olefin compound having an acid anhydride structure is
Examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and maleic anhydride is particularly preferable.

The amount of acid anhydride required for the modification of PPE is 0.01 to 10% by weight, preferably 0.1 to 3% by weight, particularly preferably 0.1 to 1% by weight, based on 100 parts by weight of PPE. If it is used less than this, the effect of improving the compatibility of PPE and PA is small, it is difficult to obtain a tough composition, and if it is used more than this range, there is a problem such as excess acid anhydride being thermally decomposed. In addition, undesired phenomena such as deterioration of heat resistance and poor appearance appear.

Polyamide resin (PA) used in the present invention has a main chain Those having a bond, for example, 4-nylon, 4,
Examples thereof include 6-nylon, 6-nylon, 6,6-nylon, 12-nylon, 11-nylon, 6,10-nylon and aromatic nylon. Here, the aromatic nylon is a polyamide polymer containing an amide bond having an aromatic nucleus represented by the following formula (I) or (II) in the main chain as a repeating structural unit, and will be described more specifically. , A polymer obtained by reacting an aromatic diamine component and a dicarboxylic acid component by a conventional method and a polymer obtained by reacting an ω'-carboxyl compound having an aromatic nucleus by a conventional method are appropriately selected. Used.

[In the formula, R ₄ represents an alkylenephenylene group or a dialkylenephenylene group, and R ₅ represents a phenylene group, a dialkylenephenylene group, a biphenylene group or a formula. A bridging bond represented by (where X is an alkylene group having 1 to 5 carbon atoms, an oxygen atom, a sulfur atom, a carbonyl bond or a sulfone bond), and R ₆ is an alkylene group having 3 to 10 carbon atoms, a phenylene group or naphthalene. Means each group. When the above-mentioned aromatic nylon is blended, it is particularly useful because it is excellent in water resistance, and a polyamide derived from xylylenediamine and adipic acid is preferable.

The blending ratio of the modified polyphenylene ether resin and the polyamide resin can be selected within a wide range, but preferably PPE / PA = 0.1 to 5 by weight ratio, particularly preferably PPE / PA = 0.3 to 3
Is the range. Outside this range, the water resistance, dimensional stability, oil resistance, etc., which are the characteristics of the PPE / PA composition, are impaired.

The red phosphorus used in the present invention is a stabilized red phosphorus surface-treated with fibrous hydrated alumina (fibrous boehmite gel), which is available from Nippon Kagaku Kogyo Co., Ltd. in “Hishigad CP”,
It is commercially available under the trade name of "Hishiguard RP" and can be easily obtained.

The blending amount of red phosphorus can be arbitrarily selected to the amount required to make the PPE / PA composition flame-retardant, but it is generally 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the resin component. .
If it is used in a larger amount than necessary, ductility and impact resistance are impaired, which is not preferable.

The method for producing the composition of the present invention is not particularly limited, but those capable of being melted are preferable. Generally, a kneader, a Banbury mixer, an extruder and the like are used, but it is particularly preferable to use the extruder.

There is no particular limitation on the order of mixing the composition components, and red phosphorus can be allowed to coexist when acid-modifying PPE, or a small amount of PPE powder and red phosphorus can be powder-blended to obtain modified PPE and PA.
It is also possible to combine them during the mixing.

If desired, the composition of the present invention may contain a rubber-like elastic body (elastomer) which is an impact modifier. Such a rubber-like elastic material is described in "Properties and S of Polymers" written by AV Tobolsky.
tructures of Polymers) "[John Wiley & Sons, Inc.] (1960) 71
The definition adopted on page 78 can be quoted, and the Young's modulus at room temperature of elastomers is 10 ⁵ to 10 ⁹ dynes / cm ² (0.1 to 1020
kg / cm ² ) means a polymer. Specific examples of the elastomer include A-B-A 'type elastomeric block copolymers and A in which the double bond of the polybutadiene portion is hydrogenated.
-BA 'type elastomeric block copolymer, polybutadiene, polyisoprene, copolymer of diene compound and vinyl aromatic compound, nitrile rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer ( EPDM), thiocol rubber, polysulfide rubber, acrylate rubber, polyurethane rubber, grafted product of butyl rubber and polyethylene, polyester elastomer and the like. Above all, an AB-A 'type elastomeric block copolymer is preferable. The terminal blocks A and A'of this block copolymer are polymerized vinyl aromatic hydrocarbon blocks, B is a polymerized conjugated diene block, and the molecular weight of B block is the combination of A and A'blocks. It is desirable that the molecular weight is larger than the molecular weight. The end blocks A and A'may be the same or different, and the blocks are thermoplastic homopolymers or copolymers derived from vinylaromatic compounds whose aromatic moieties may be monocyclic or polycyclic. Examples of such vinyl aromatic compounds include styrene, α-methylstyrene, vinyltoluene, vinylxylene, ethylvinylxylene, vinylnaphthalene and mixtures thereof. Central block B is an elastomeric polymer derived from conjugated diene hydrocarbons such as 1,3-butadiene, 2,3-dimethylbutadiene, isoprene and 1,3-pentadiene and mixtures thereof. The molecular weight of each end block A and A'is preferably in the range of about 2,000 to about 100,000, while the molecular weight of the central block B is preferably in the range of about 25,000 to about 1,000,000.

The composition of the present invention may be blended with a fiber-reinforced material such as glass fiber or carbon fiber, and if desired,
Various additives generally used for polymer materials, for example, stabilizers, facial dyes, mold release agents, lubricants, fillers, etc. can be appropriately added.

[Examples] Hereinafter, the polyphenylene ether-based resin composition of the present invention will be specifically described with reference to Examples. The number of parts in Examples is based on weight.

Example 1 and Comparative Examples 1-3 PP with an intrinsic viscosity of 0.46 dl / g measured in chloroform at 25 ° C
To 5 kg of E, 25 g of maleic anhydride was added, mixed for 3 minutes with a super mixer, and then kneaded under heating and melting with a twin-screw extruder to obtain a maleic anhydride-modified PPE.

3 kg of the modified PPE thus obtained was mixed with 3 kg of 6-nylon and 180 gr of stabilized red phosphorus (manufactured by Nippon Kagaku Kogyo Co., Ltd., trade name "Hishigad CP-15") surface-treated with fibrous hydrated alumina, and melted. Then, the mixture was kneaded to obtain the resin composition of the present invention.

For comparison, in Example 1, a composition containing no red phosphorus (Comparative Example 1), a composition containing triphenylphosphonate in place of red phosphorus (Comparative Example 2) and bromine in place of red phosphorus was used. A composition (Comparative Example 3) using a modified organic compound-based flame retardant (trade name "Pyrotierc 68PB" manufactured by Fuero Co., Ltd.) was prepared.

For each of the obtained compositions, various test pieces were molded by a conventional method, and various physical properties were measured. The results are shown in Table 1.

Examples 2 to 4 and Comparative Examples 4 to 6 Using the modified PPE obtained in Example 1, the polyamide resin, the rubber-like elastic body and the flame retardant shown in Table 2 were blended in the amounts shown in Table 2, respectively. Various resin compositions were obtained in the same manner as in Example 1.

The physical property values of each composition are shown in Tables 2 and 3.

[Effect] As is clear from the results of Examples and Comparative Examples, when a conventionally known brominated organic compound or a phosphate compound is used as a flame retardant, a decrease in physical properties or a lack of flame retardance cannot be avoided. On the other hand, it can be seen that the resin composition of the present invention using red phosphorus has high flame retardancy and a high level of physical properties.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-59-66452 (JP, A) JP-A-63-68663 (JP, A) JP-A-59-11332 (JP, A) JP-A-57- 165448 (JP, A) JP 58-196259 (JP, A) JP 63-48356 (JP, A) JP 61-111342 (JP, A)

Claims (3)

[Claims] 1. (a) General formula (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and
R ₃ is a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms) A polyphenylene ether resin having a structural unit represented by the main chain and a 1,2-substituted olefin compound having an acid anhydride structure, A composition comprising a modified polyphenylene ether resin obtained by reacting in a molten state in the absence of a catalyst, (b) a polyamide resin, and (c) a stabilized red phosphorus surface-treated with fibrous hydrated alumina. And a modified polyphenylene ether resin / polyamide resin weight ratio of 0.1 to 5, and a blending amount of red phosphorus of 10 parts by weight or less based on 100 parts by weight of the resin component. . 2. The resin composition according to claim 1, further comprising (d) a rubber-like elastic material as a resin component. 3. The resin composition according to claim 1, wherein the polyamide resin is an aromatic polyamide resin.