JP2687431B2 - Flame-retardant polyphenylene ether resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition containing a modified polyphenylene ether resin and a polyamide resin. More specifically, it relates to an improvement of a flame-retardant polyphenylene ether resin composition in which red phosphorus is blended in a resin mixture system containing a polyphenylene ether resin and a polyamide resin, and is a material suitable for the field of OA equipment, the field of home appliances and miscellaneous goods Is provided.

(Prior art and its problems) Polyphenylene ether resin is excellent in various properties such as thermal properties, mechanical properties, and electrical properties, but has a high melt processing temperature and low fluidity, and therefore has poor moldability. It has inferior drawbacks. Further, although it has strong resistance to inorganic chemicals such as acids and alkalis, it is strongly required to improve solvent resistance and oil resistance because it dissolves and swells in certain organic solvents. 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).
Gazette), polyphenylene ether with polyamide
Method of blending in the range of 95% (Japanese Patent Publication No. 59-41663)
There is. When a small amount of polyamide is blended, the molding processability is improved to some extent, but it is difficult to say that it is a sufficient improvement in terms of oil resistance, and although the solvent resistance is improved when the blending amount is relatively large, Only a brittle material without toughness. 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 this polyphenylene ether (hereinafter referred to as PPE) and polyamide (hereinafter referred to as PA).

For example, carbon atoms in the molecule such as maleic acid and maleimide
A method in which a compound having a 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 is blended as a third component (JP-A-56-26913), a styrene compound and There is a method of blending a copolymer with α, β-unsaturated dicarboxylic acid (Japanese Patent Publication No. 59-33614).
Furthermore, the PPE was thermally grafted with a 1,2-substituted olefin compound having an acid anhydride structure to PPE in the absence of a catalyst to give a modified polyphenylene ether resin (hereinafter, abbreviated as modified PPE).
And the like (JP-A-62-132924).

As described above, the resin composition comprising the polyphenylene ether resin and the polyamide resin has significantly improved solvent resistance, chemical resistance, and fluidity as compared with the polyphenylene ether resin, and also has excellent moldability. Is.

(Problems to be solved by the invention) A resin composition comprising a polyphenylene ether resin and a polyamide resin is a resin composition having both excellent heat resistance and excellent oil resistance and fluidity of the polyamide resin, Unfortunately, the flame retardant properties of polyphenylene ether resins are impaired, thus narrowing the field of application.

Therefore, various flame-retardant methods for compositions comprising polyphenylene ether resin and polyamide resin have been proposed. For example, there is a method in which an organic halide and antimony trioxide are used in combination, but there are drawbacks such that impact resistance and heat resistance are impaired. On the other hand, when flame-retarded with red phosphorus, the physical properties of the composition comprising the polyphenylene ether resin and the polyamide resin are hardly impaired, but toning is limited because it is colored reddish brown and is substantially black except It was difficult.

(Means for Solving Problems) The inventors of the present invention have earnestly studied about a method without coloring in a method of flame retarding a resin composition composed of a polyphenylene ether resin and a polyamide resin with red phosphorus. As a result, it was found that by blending red phosphorus coated with titanium oxide, a flame-retardant resin composition having almost no coloring can be obtained without impairing the original flame retardancy of red phosphorus, and the present invention I arrived.

Incidentally, titanium oxide is widely known as a white pigment for various resins, and titanium oxide is added to a composition obtained by flame retarding a resin composition composed of a polyphenylene ether resin and a polyamide resin with red phosphorus. However, it is impossible to prevent reddish brown coloring. However, it was surprisingly found that a composition obtained by flame retarding a resin composition composed of a polyphenylene ether resin and a polyamide resin with red phosphorus previously coated with titanium oxide has almost no coloring.

That is, the present invention provides: (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, R ₂ and R ₃ are hydrogen atoms or a lower alkyl group having 1 to 3 carbon atoms.) In the main chain Polyphenylene ether resin (b) A polyamide resin, and (c) a flame-retardant polyphenylene ether resin composition containing titanium oxide-coated red phosphorus.

The polyphenylene ether resin (PPE) used in the resin composition of the present invention has the general formula (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ are hydrogen atoms or a lower alkyl group having 1 to 3 carbon atoms.) In the main chain The polymer may be a homopolymer or a copolymer, and specifically, for example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-ether) 1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl, 6-ethyl-1,4-
Examples thereof include phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, and particularly, poly (2,6-dimethyl-1,4-phenylene) ether and 2,6-dimethyl. Phenol / 2,3,6-trimethylphenol copolymer is preferred.

Further, the polyphenylene ether resin preferably used in the present invention is obtained by previously melt-kneading the polyphenylene ether resin and the 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.

Here, examples of the 1,2-substituted olefin compound having an acid anhydride structure include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and maleic anhydride is particularly preferable.

The amount of the 1,2-substituted olefin compound having an acid anhydride structure required for the modification of PPE is 0.01-10 with respect to 100 parts by weight of PPE.
% By weight, preferably 0.1-3% by weight, particularly preferably 0.1
~ 2 wt% range. For smaller amounts, PPE
The effect of improving the compatibility of PA and PA is small, it is difficult to obtain a tough composition, and if it is used in excess of this range, there are problems such as an increase in the dispersed diameter of PPE particles, and further deterioration of heat resistance and poor appearance. An undesired phenomenon occurs.

The polyamide resin used in the resin composition of the present invention (P
A) is a polymer having a --CO--NH-- bond in the main chain, and is, for example, 4-nylon, 4,6-nylon, 6-nylon, 6,6-nylon, 12-nylon, 11-nylon. ,
Examples include 6,10-nylon and MXD-nylon.

The blending ratio of the modified PPE and PA can be selected in a wide range, but is preferably in the range of PPE / PA = 0.1 to 5, particularly preferably in the range of 0.3 to 3. A composition smaller than this range impairs the excellent water resistance and dimensional stability of PPE, and a composition larger than this range does not sufficiently improve the oil resistance and moldability.

Next, the red phosphorus coated with titanium oxide used in the resin composition of the present invention is obtained by coating the surface of red phosphorus with titanium oxide, and for example, titanium oxide is coated on the surface of red phosphorus particles in water. After being electrically coagulated and deposited, it is dried separately. Furthermore, fibrous hydrated alumina, or red phosphorus stabilized with a phenol resin or the like and having a surface coated with titanium oxide can also be used.

In the present invention, the amount of titanium oxide coating red phosphorus is
The amount should be enough to hide the red phosphorus color. The amount required to hide is generally 50 for 100 parts by weight of red phosphorus.
Is selected from the range of up to 300 parts by weight. If it is 50 parts by weight or less, the hiding effect will not be sufficiently exerted. If it is more than 300 parts by weight, impact resistance is lowered, which is not preferable.

The amount of red phosphorus coated with titanium oxide used in the present invention needs to be 1 to 20 parts by weight based on 100 parts by weight of a resin composition composed of modified PPE and a polyamide resin as red phosphorus. . If it is 1 part by weight or less, the flame retardant effect is not sufficiently exhibited. Further, if it is 20 parts by weight or more, the original properties of the resin composition are lost, which is not preferable. As the red phosphorus coated with titanium oxide, a commercially available product can be used.

The method for producing the resin composition of the present invention is not particularly limited, but a method that can be performed under melting is preferable. Generally, a kneader, a Banbury mixer, an extruder, etc. are used,
It is particularly preferable to use an extruder. There is no particular limitation on the mixing order of the components of the resin composition of the present invention, and red phosphorus coated with titanium oxide can be allowed to coexist when the PPE is modified, or red phosphorus coated with titanium oxide can be mixed with PPE. And PA
It is also possible to add it at the time of mixing.

If desired, a rubber-like elastic body (elastomer), which is an impact modifier, can be added to the resin composition of the present invention. An example of such a rubber-like elastic material is “Properties and Structures of Polymers” by AV Tobolsky.
nd Structures of Polymers) "[John Wiley
The definition adopted on pages 71-78 of John Wiley & Sons, Inc. (published in 1960) can be quoted. An elastomer has a Young's modulus of 10 ⁵ to 10 ⁹ dynes / cm at room temperature.
² (0.1-1020 Kg / cm ² ) means a polymer. Specific examples of the elastomer include an ABA 'type elastomeric block copolymer, an ABA' type elastomeric block copolymer in which a double bond in a polybutadiene portion is hydrogenated, polybutadiene, and polyisoprene. , A copolymer of a diene compound and a vinyl aromatic compound, a nitrile rubber, an ethylene-propylene copolymer, an ethylene-propylene-diene copolymer (EPDM), a thiochol rubber, a polysulfide rubber, an acrylic rubber, a polyurethane rubber,
Examples include graft products of butyl rubber and polyethylene, polyester elastomers, and the like. Above all, AB-
The A'type elastomeric block copolymer or its hydrogenated elastomer is desirable. 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. The central block B is a conjugated diene hydrocarbon, such as
Elastomeric polymers derived from 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 from about 2,000 to about 10.
The molecular weight of central block B is
It is preferably in the range of about 25,000 to about 1,000,000.

Fiber reinforced materials such as glass fibers and carbon fibers can be added to the resin composition of the present invention as desired. Furthermore, various additives generally used for polymer materials, such as stabilizers, facial dyes, mold release agents, lubricants, and fillers, can be appropriately mixed.

(Examples) Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the number of parts in Examples is expressed on a weight basis. The physical property values shown in Examples and Comparative Examples are measured by the following methods for test pieces obtained by pelletizing the composition and injection molding.

Heat distortion temperature: ASTM D648 Molded product dimension 127 × 12.7 × 6.4 mm Weighted 4.6Kg / cm ² Izod impact strength: ASTM D256 Molded product shape Thickness 3.2mm Notched Flame resistance: UL standard 94 Molded product dimension 127 × 12.7 × 1.6 mm Color tone: Hunter whiteness Example 1 Intrinsic viscosity measured in chloroform at 25 ° C. is 0.46 dl / g
Poly (2,6-dimethyl-1,4-phenylene) ether powder (5 kg) was mixed with maleic anhydride (25 g) with a super mixer for 3 minutes, and then a twin-screw extruder (Ikegai Tekko PCM-3
0) is melt-kneaded at 290 ℃ and extruded to make modified PP.
E pellets were obtained.

50 parts of the obtained modified PPE was blended with 650 parts of nylon and 7 parts of red phosphorus coated with titanium oxide (manufactured by Rin Kagaku Kogyo Co., Ltd., trade name "Novarred 280-B" (phosphorus content 41%)). The resin composition of the present invention was obtained by melt-kneading at 270 ° C.

 The physical property test results of the composition are shown in Table 1.

Comparative Example 1 Instead of red phosphorus coated with titanium oxide, stabilized red phosphorus surface-treated with fibrous hydrated alumina (manufactured by Nippon Kagaku Kogyo Co., Ltd., trade name: HISHIGARD CP-15, phosphorus content 85
%) 3.5 parts and titanium oxide (manufactured by Titanium Industry Co., Ltd., trade name KR-380) 3.5 parts were used to obtain a resin composition in the same manner as in Example 1.

 The physical property test results of the composition are shown in Table 1.

Example 2 100 parts of PPE used in Example 1, 20 parts of SEBS elastomer (made by Shell Chemical Co., Ltd., Kraton G-1651, trade name) and 0.8 part of maleic anhydride were added and mixed with a super mixer for 3 minutes, and then twin-screw extruder Was kneaded under heating and melting to obtain a modified PPE containing an elastomer.

55 parts of the obtained modified PPE was blended with 645 parts of nylon and 8 parts of red phosphorus coated with titanium oxide (manufactured by Rin Kagaku Kogyo Co., Ltd., trade name "NOVARED 280-B" (phosphorus content 41%)). The resin composition of the present invention was obtained by melt-kneading at 270 ° C.

 The physical property test results of the composition are shown in Table 1.

Example 3 A resin composition of the present invention was obtained in the same manner as in Example 2 except that 6-nylon was replaced with 6,6-nylon.

 The physical property test results of the composition are shown in Table 1.

Comparative Example 2 Instead of the red phosphorus coated with titanium oxide used in Example 2, stabilized red phosphorus surface-treated with fibrous hydrated alumina (manufactured by Nippon Kagaku Kogyo Co., Ltd., trade name: HISHIGARD CP-
15. A resin composition was obtained in the same manner as in Example 2 except that 4 parts of phosphorus content of 85%) and 4 parts of titanium oxide (manufactured by Titanium Industry Co., Ltd., trade name KR-380) were used.

 The physical property test results of the composition are shown in Table 1.

Comparative Example 3 A resin composition was obtained in the same manner as Comparative Example 2 except that the amount of titanium oxide used in Comparative Example 2 was changed to 12 parts. The physical property test results of the composition are shown in Table 1.

(Effects of the Invention) As is clear from the examples and comparative examples, the composition of the present invention has markedly superior whiteness as compared with the composition using red phosphorus and titanium oxide in combination. In addition, the physical properties of the composition are high, and toning other than black is possible, and the range of applications is greatly expanded.

Claims (3)

(57) [Claims] (1) General formula (In the formula, R ₁ is a lower alkyl group having 1 to 3 carbon atoms, and R ₂ and R ₃ are hydrogen atoms or a lower alkyl group having 1 to 3 carbon atoms.)
Containing a polyphenylene ether resin having a structural unit represented by the main chain in the main chain, (b) a polyamide resin, and (c) red phosphorus coated with titanium oxide (titanium oxide is red 50 to 300 parts by weight to 100 parts by weight of phosphorus, red phosphorus is polyphenylene ether resin + polyamide resin 100
Flame-retardant polyphenylene resin composition containing 1 to 20 parts by weight based on parts by weight). 2. A modified polyphenylene ether obtained by reacting 100 parts by weight of a polyphenylene ether resin with 0.01 to 10 parts by weight of a 1,2-substituted olefin compound having an acid anhydride structure, in the absence of a catalyst. The resin composition according to claim 1, which is a resin. 3. The resin composition according to claim 1, further comprising (d) a rubber-like elastic material as a resin component.