JP3142885B2 - Polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene ether resin composition. Specifically, in a flame-retardant polyphenylene ether-based resin composition in which a polyphosphate compound is blended with a polyphenylene ether-based resin composition,
A flame-retardant polyphenylene ether-based resin composition containing a metal oxide as a stabilizer for preventing gelation during extrusion.

[0002]

2. Description of the Related Art Polyphenylene ether resins have excellent properties such as excellent mechanical properties, electrical properties, acid resistance, alkali resistance, and heat resistance, and have low water absorption and good dimensional stability. Resin. Polyphenylene ether resin has excellent flame retardancy, but is generally used as an alloy with a styrene resin because of poor processability, but the flame retardancy is impaired.

Various phosphate esters have been proposed for the purpose of improving the flame retardancy. For example, Japanese Patent Publication No. 48-38
No. 768 discloses an aromatic phosphate compound, and Japanese Patent Publication No. 53-418 discloses a triorganophosphate, a tris (halogenated organic) phosphate, and JP-A-55-1.
No. 18957 discloses bisphenol-A bisphosphate, bisphenol-A polyphosphate and hydroquinone bisphosphate, Japanese Patent Publication No. 1-15033.
In the publication, a combination of polyphosphates and triphenyl phosphate is disclosed. However, there has not yet been proposed any proposal for preventing gelation during extrusion as shown in the present invention.

[0004]

Generally, resin extrusion is generally performed in an inert gas atmosphere in order to prevent oxidative deterioration due to oxygen. Extrusion processing of polyphenylene ether resin is not an exception. However, when a polyphosphate compound is added to a polyphenylene ether-based resin and extrusion processing is performed in an inert gas atmosphere, generation of a gel is recognized, and there is a problem that quality is significantly impaired.

[0005] It is an object of the present invention to prevent a gel from being generated when a polyphosphate compound is added to a polyphenylene ether-based resin and extruded in an inert gas atmosphere.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have studied various stabilizers to prevent gels from being generated when a polyphosphate compound is added to a polyphenylene ether-based resin and extruded. The inventors have found that gelation can be prevented by adding a small amount of metal oxide, and completed the present invention.

That is , the present invention relates to : (a) 99 to 70 parts by weight of a polyphenylene ether-based resin; (b) a resin 100 comprising 1 to 30 parts by weight of a polyphosphate compound represented by the following general formula (I) or (II): Parts by weight and (c)
Polyphenylene ether-based resin composition comprising the zinc oxide or magnesium oxide from 0.5 to 5 parts by weight, or.

[0008]

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[0009]

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(B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ ,
B _8, B ₉ are individually alkyl group, a phenyl group, an alkylphenyl group, B ₇ is 1 to phenyl or carbon atoms
6 represents a lower alkyl group or an SO ₂ group. n and p are 1 to
It is an integer of 30. Hereinafter, the present invention will be described in detail. As the polyphenylene ether resin used in the present invention, polyphenylene ether resin itself (hereinafter referred to as PPE),
It may be a composition of PPE and a polystyrene resin or a composition of PPE and a polyamide resin.

The PPE in the present invention is represented by the following general formula (II)
I),

[0012]

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(Wherein Q ₁ and Q ₂ each have 1 carbon atom)
Represents an alkyl group or a halogen atom. q is an integer indicating the degree of polymerization. ) Is used. Specific examples of the compound represented by the general formula (III) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether. (2,6-diethyl-1,4-
Phenylene) ether, poly (2-ethyl-6-npropyl-1,4-phenylene) ether, poly (2,6-
Di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-nbutyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4)
-Phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6- Homopolymers such as chloroethyl-1,4-phenylene) ether are exemplified.

Among them, preferred are poly (2,6)
-Dimethyl-1,4-phenylene) ether. Further, a polyphenylene ether copolymer mainly composed of the chemical structure represented by the above general formula is also included. Specific examples thereof include 2,6-dimethylphenol and 2,3,6-
Copolymers of trimethylphenol are exemplified.

The PPE used in the present invention has an intrinsic viscosity of 0.35 to 0.5 when measured at 30 ° C. in chloroform.
Those having a range of 75 dl / g are preferred. More preferably, it is 0.40 to 0.70 dl / g. This PPE
In addition, a low molecular weight amine or polystyrene may be bonded to Q ₁ and Q ₂ , and a compound in which diphenoquinone or the like is bonded to a part of the PPE main chain is also a target.

In the present invention, the styrene-based polymer which can be used as a mixture with PPE includes polystyrene, a copolymer of styrene with at least one other vinyl compound, and a rubber-modified polymer thereof. . Specific examples of the copolymer of styrene and at least one other vinyl compound include styrene-acrylonitrile copolymer, styrene-methyl methacrylate copolymer, styrene-α-
Examples include a methylstyrene copolymer and a styrene-maleic anhydride copolymer.

Examples of the rubber-modified polymer include rubber-modified polystyrene (HIPS), rubber-modified styrene-acrylonitrile copolymer (ABS), and rubber-modified styrene-maleic anhydride copolymer. Among them, particularly preferred polymers are polystyrene (PS) and rubber-modified polystyrene (HIPS).

The blend ratio of PPE and styrene polymer is not particularly limited, but is preferably in the range of 95 to 10 parts by weight of PPE and 5 to 90 parts by weight of styrene polymer. In the present invention, as the polyamide resin that can be used by mixing with PPE,

[0019]

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[0020] Nylon-4, nylon-6, nylon-
6,6, nylon-4,6, nylon-12, nylon-6,10 and the like. Of these, nylon-6,6 and nylon-6 are preferred. The blending ratio of PPE and polyamide resin is not particularly limited.
The range is preferably 95 to 10 parts by weight of PE and 5 to 90 parts by weight of the polyamide resin.

The polyphosphate compound used in the present invention is a compound represented by the following general formula.

[0022]

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[0023]

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(B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₆ ,
B _8, B ₉ are individually alkyl group, a phenyl group, an alkylphenyl group, B ₇ is 1 to phenyl or carbon atoms
6 represents a lower alkyl group or an SO ₂ group. n and p are 1 to
It is an integer of 30. ) Specifically, phenyl resorcinol polyphosphate, phenyl cresyl resorcinol polyphosphate, cresyl resorcinol polyphosphate, phenyl hydroquinone polyphosphate, phenyl bisphenol-A polyphosphate, phenyl Bisphenol-S polyphosphate and the like can be mentioned.

The amount of the polyphosphate compound used in the present invention is 1 to 3 with respect to 99 to 70 parts by weight of PPE.
0 parts by weight, preferably 5 to 25 parts by weight. If it is less than 1 part by weight, it does not reach the practical level as a flame retardant, and if it exceeds 30 parts by weight, extrusion becomes difficult due to the plasticizing effect. The present invention further includes zinc oxide or mug oxide.
Nesium is used . Zinc oxide or
Magnesium oxide is used in an amount of 99 to 70 parts by weight of polyphenylene ether resin and polyphosphate compounds 1 to 3.
0.5 to 5 with respect to 100 parts by weight of resin consisting of 0 parts by weight
Is a heavy amount. If the amount is less than 0.5 part by weight, the effect of preventing gelation at the time of extrusion processing is insufficient. If the amount exceeds 5 parts by weight, the effect of preventing gelation does not change, but physical properties such as a decrease in impact resistance and a change in rigidity are obtained. The above problem is not preferable.

The composition of the present invention may contain other additives, for example,
Plasticizers, ultraviolet absorbers, antioxidants, coloring materials, release agents,
Reinforcing agents, fillers and the like can be added.

[0027]

The present invention will be described below with reference to examples.
This does not limit the invention.

[0028]

Example 1 Intrinsic viscosity 0.52 (30 ° C. in chloroform)
64 parts by weight of poly-2,6-dimethyl-1,4-phenylene ether (hereinafter abbreviated as PPE) and an impact-resistant polystyrene resin (hereinafter abbreviated as HIPS).
(Stylon 492, manufactured by Asahi Kasei Corporation) 12 parts by weight, polystyrene resin (hereinafter abbreviated as GPPS).
[Styrone 685 manufactured by Asahi Kasei Corporation] 12 parts by weight, 13 parts by weight of phenyl resorcinol polyphosphate represented by the following structural formula,

[0029]

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Octadecyl-3- (3-5-di-t-butyl-4-hydroxyphenyl) propionate 0.3
Parts by weight and 1.0 part by weight of zinc oxide were sufficiently mixed in a Henschel mixer controlled in a nitrogen atmosphere, and nitrogen replacement was performed. Then cylinder temperature 300
AS-30 twin screw extruder set to 0 ° C [Nakaya Machine Co., Ltd.
), And melt-kneaded in a nitrogen atmosphere to form pellets. The obtained pellets were kneaded in a 30C-150 Labo Plastmill (manufactured by Toyo Seiki Co., Ltd.) at 330 ° C. for 60 minutes in a nitrogen atmosphere, and the kneaded product was subjected to gel analysis. Table 1 shows the results. The gel was analyzed by the following method.

Gel analysis method: 0.5 g of the crushed sample was subjected to Soxhlet extraction for 5 hours using chloroform as a solvent, and the undissolved gel content was determined by vacuum drying at 145 ° C. for 60 minutes and expressed as a percentage of the sample weight. . The thimble used for extraction is made of Whatman cellulose (CATN).
o. 2800189) was used.

[0032]

Comparative Example 8 Examples 3 to 5 The same procedure as in Example 1 was carried out except that the amount of zinc oxide shown in Table 1 was used. Table 1 shows the results.

[0033]

Comparative Example 1 The procedure of Example 1 was repeated, except that zinc oxide was not added. Table 1 shows the results.

[0034]

Comparative Example 2 The procedure was the same as in Example 1 except that the amount of zinc oxide was changed to 0.1 part by weight. Table 1 shows the results.

[0035]

Comparative Example 9 Intrinsic viscosity 0.52 (in chloroform at 30 ° C.)
75 parts by weight of PPE, 10 parts by weight of HIPS (Stylon 492 manufactured by Asahi Kasei Corporation), GPPS
[Styrone 685, manufactured by Asahi Kasei Kogyo Co., Ltd.] 10 parts by weight, 5 parts by weight of phenyl resorcinol polyphosphate used in Example 1, 2-t-butyl-6- (3-t)
-Butyl-5-methyl-2-hydroxybenzyl) -4-
0.5 parts by weight of methylphenyl acrylate and 0.2 parts by weight of magnesium oxide were sufficiently mixed in a Henschel mixer controlled in a nitrogen atmosphere, and the atmosphere was replaced with nitrogen.

Next, the mixture was melt-kneaded in a nitrogen atmosphere with an AS-30 twin-screw extruder (manufactured by Nakatani Machinery Co., Ltd.) set at a cylinder temperature of 300 ° C. to form pellets. The obtained pellets were kneaded in a 30C-150 Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 330 ° C. for 60 minutes in a nitrogen atmosphere, and the kneaded product was subjected to gel analysis. Table 1 shows the results.

[0037]

Example 7 Intrinsic viscosity 0.52 (30 ° C. in chloroform)
64 parts by weight of PPE, 12 parts by weight of HIPS [Stylon 492, manufactured by Asahi Kasei Corporation], GPPS
[Styrone 685, manufactured by Asahi Kasei Corporation] 12 parts by weight, 12 parts by weight of phenyl resorcinol polyphosphate used in Example 1, 2-t-butyl-6- (3-t
-Butyl-5-methyl-2-hydroxybenzyl) -4-
0.5 parts by weight of methylphenyl acrylate and 0.5 parts by weight of magnesium oxide were sufficiently mixed in a Henschel mixer controlled in a nitrogen atmosphere, and the atmosphere was replaced with nitrogen.

Next, the mixture was melt-kneaded in a nitrogen atmosphere with an AS-30 twin-screw extruder (manufactured by Nakatani Machinery Co., Ltd.) set at a cylinder temperature of 300 ° C. to form pellets. The obtained pellets were kneaded in a 30C-150 Labo Plastmill (manufactured by Toyo Seiki Co., Ltd.) at 330 ° C. for 60 minutes in a nitrogen atmosphere, and the kneaded product was subjected to gel analysis. Table 1 shows the results.

[0039]

Examples 8 and 9 The magnesium oxide of Example 7 was prepared as shown in Table 1.
Example 7 was carried out in the same manner as in Example 7, except that the amount was changed to Table 1 shows the results.

[0040]

Comparative Example 4 The same operation as in Example 7 was carried out except that magnesium oxide was not added. The results are shown in Table 1.

[0041]

Comparative Example 5 The same procedure as in Example 7 was carried out except that the addition amount of magnesium oxide was changed to 0.1 part by weight. Table 1 shows the results.

[0042]

Example 10 Extreme viscosity 0.48 (30 in chloroform)
C.), 64 parts by weight of PPE, 12 parts by weight of HIPS [Stylon 492, manufactured by Asahi Kasei Corporation], GPPS
[Styrone 685, manufactured by Asahi Kasei Corporation] 12 parts by weight, cresyl resorcinol polyphosphate 13 parts by weight, 2-t-butyl-6- (3-t-butyl-5-methyl-2-hydroxybenzyl) -4 0.5 parts by weight of methylphenyl acrylate and 0.5 parts by weight of zinc oxide were sufficiently mixed in a Henschel mixer controlled in a nitrogen atmosphere, and the atmosphere was replaced with nitrogen.

Next, the mixture was melt-kneaded in a nitrogen atmosphere using an AS-30 twin-screw extruder (manufactured by Nakatani Machinery Co., Ltd.) set at a cylinder temperature of 300 ° C. to form pellets. The obtained pellets were kneaded in a 30C-150 Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.) at 330 ° C. for 60 minutes in a nitrogen atmosphere, and the kneaded product was subjected to gel analysis. Table 1 shows the results.

[0044]

Example 11 Phenyl bisphenol was used in place of the cresyl resorcinol polyphosphite of Example 10.
A, except that polyphosphite was used. Table 1 shows the results.

[0045]

Comparative Example 6 The same procedure as in Example 10 was carried out except that zinc oxide was not added. Table 1 shows the results.

[0046]

Comparative Example 7 The same procedure as in Example 11 was carried out except that zinc oxide was not added. Table 1 shows the results.

[0047]

[Table 1]

[0048]

According to the present invention, it is possible to stably produce a high-quality resin by adding a polyphosphate compound to a polyphenylene ether-based resin and preventing gels generated during extrusion processing in an inert gas atmosphere. became.

Claims (1)

(57) [Claims] (A) polyphenylene ether-based resin 9
9 to 70 parts by weight (b) the following general formula (I) or (II)
In represented polyphosphate compounds 1 to 30 parts by weight a 100 parts by weight of the resin from the (c) zinc oxide or Ma
A polyphenylene ether-based resin composition comprising 0.5 to 5 parts by weight of gnesium . Embedded image Embedded image (B ₁ , B ₂ , B ₃ , B ₄ , B ₅ , B ₈ , and B ₉ each independently represent an alkyl group, a phenyl group, or an alkylphenyl group, and B ₇ represents a phenyl group or a lower alkyl having 1 to 6 carbon atoms. .n showing a group or a SO ₂ group, p is an integer from 1 to 30.)