JPH0288669A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-retardant composition containing a polyphenylene ether, a polyamide, a thermoplastic rubbery substance, a specific modified block copolymer and red phosphorus, keeping the resin components dispersed in specific state and having excellent molding fluidity, impact resistance, etc. CONSTITUTION:The objective composition is composed of (A) 25-70wt.% of a polyphenylene ether, (B) 25-70wt.% of a polyamide, (C) 2-25wt.% of a thermoplastic rubbery substance (preferably a styrene-butadiene block copolymer containing 25-60wt.% of styrene), (D) 0.5-15 pts.wt. (based on 100 pts.wt. of A+B+C) of (D1) a vinyl aromatic/conjugated diene block copolymer containing 60-97wt.% of the vinyl aromatic compound unit and modified with (D2) an unsaturated dicarboxylic acid (derivative) to give a modified product containing 0.05-5wt.% of the dicarboxylic acid residue and (E) 0.3-5 pts.wt. of red phosphorus. The component B forms a continuous phase containing the component A dispersed in the continuous phase in the form of a dispersed phase having an average particle diameter of 0.1-8mum and containing the component C dispersed in microscopic state in the dispersed phase.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a flame-retardant resin composition that has excellent molding fluidity, mechanical properties, heat resistance, and oil resistance and is suitable for parts materials related to electrical and electronic equipment. Regarding.

<Prior art> Resin compositions containing polyphenylene ether and polyamide as basic components are disclosed in JP-A-56-49753, JP-A-59-33614, and JP-A-63-161053. In addition, it compensates for the shortcomings of each component and has an excellent balance of dimensional properties, oil resistance, moldability, heat resistance, mechanical properties, etc. Therefore, although development has been actively progressing in recent years, flame retardance has not been sufficient.

For this reason, techniques for imparting flame retardancy have been developed. For example, JP-A-57-165448 and JP-A-63
JP-A-61047 proposes a composition whose basic components are polyphenylene ether and polyamide, which contain red phosphorus as a flame retardant.

<Problems to be solved by the invention> Polyphenylene ether and polyamide are the basic components,
Further, flame-retardant resin compositions containing red phosphorus are optimal for use in the electrical and electronic fields due to their characteristics.

Among them, electrically connected precision parts such as connectors and switches are
The fluidity and impact resistance of thin-wall molding and the strength of the welds that occur in molded products are very important.

However, conventional compositions do not have a sufficient balance between thin-wall molding fluidity and impact resistance, and when fluidity is improved, the impact resistance decreases significantly and the strength of the weld part is inferior, making it difficult to use them for these applications. It was a problem to do so.

Under these circumstances, the object of the present invention is to improve molding fluidity in a resin composition containing polyphenylene ether and polyamide as basic components without impairing heat resistance, oil resistance, dimensional properties, and electrical properties. It is an object of the present invention to provide a flame-retardant resin composition that has excellent balance in impact resistance and extremely excellent strength in weld portions.

<Means for solving the problem> In order to develop a flame-retardant resin composition having the above-mentioned well-balanced physical properties, the present inventors have conducted intensive research and found that polyphenylene ether, polyamide, thermoplastic It is believed that this objective can be achieved by a composition containing a rubber-like substance, a modified block copolymer having a specific composition, and red phosphorus in a specific proportion, and in which the dispersion form of the resin component is adjusted to a specific state. Based on this finding, we have completed the present invention.

That is, the present invention (A) Polyphenylene ether.

(B) Polyamide, (Cl) Thermoplastic rubbery substance (l) Consisting of a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of conjugated diene compound units, Using a block copolymer having a content of 60 to 97% by weight, at least one selected from unsaturated dicarboxylic acids and derivatives thereof, the content of residues thereof is O, OS to 5% by weight. A modified block copolymer modified so that ~70% by weight, (B)
The content of component (D) is within the range of 25 to 7% by weight of component and 2 to 25% by weight of component (C), per 100X parts of the total amount of components (A), (B) and (C). amount is 0.5
~15 parts by weight and (the content of the El component is in the range of 0.3 to 5 parts by weight, and the (B) component forms a continuous phase, and in this continuous phase, the (A) component has an average particle size of 0. This is a flame-retardant resin composition characterized in that the flame-retardant resin composition exists as a dispersed phase with a diameter of 1 to 8 μm, and that substantially all component (C) is present in a microdispersed state in the dispersed phase.

The present invention will be explained in detail below.

In the composition of the present invention, the polyphenylene ether used as the optical component has the general formula A homopolymer consisting of a repeating unit represented by an alkyl group, an aryl group, a hydrogen atom, the remainder of which is a hydrogen atom, which may be the same or different from each other, and the general formula shown above. The repeating unit represented by (I) and the general formula (R in the formula,
, R4, R, and R6 are each a linear, secondary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a hydrogen atom, etc. may be the same or different from each other, but R3 and R4 cannot be hydrogen atoms at the same time); homopolymers and copolymers thereof; These include graft copolymers in which styrene is graft-polymerized.

A typical example of a homopolymer of polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene) ether, yt! (2-methyl-6-ethyl 1,4-phenylene) ether, poly(2,6-dinityl-1,4-
) unicine ether, poly(2ethyl-6-n-propyl-1,4-phenylene)ether, poly(2,6-
di-n-propyl-1,4-phenylene)ether, poly(2-methyl-6n-butyl-1,4-)unisine)
Ether, poly(2-ethyl-6-improvir-1,
4-phenylene)ether, po')C2-methyl-6-
chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl-1,4)
-phenylene) ether and the like.

The polyphenylene ether copolymer is composed of an alkyl substituted phenol such as 2,3,6- It includes polyphenylene ether copolymers mainly having a polyphenylene ether structure obtained by copolymerization.

The polyamide used as component (B) in the composition of the present invention can be any polyamide as long as it has a -C-NH- bond in the polymer main chain and can be melted by heating.

Typical examples include 4-nylon, 6-nylon, 6.6-f ylon, 12-f ylon, 6.10-nylon, polyamide obtained from terephthalic acid and trimethylhexamethylene diamine, and polyamide obtained from adipic acid and methane. Polyamide obtained from xylylene diamine, polyamide obtained from adipic acid, azelaic acid, and 2,2-bis(p-aminonechlorohexyl) to fluorane, and polyamide obtained from terephthalic acid and 4,4'-diaminodicyclohexylmethane. Examples include polyamides and copolyamides consisting of a combination of two or more of these.

Among these, 6-nylon, 6.6-nylon, 6
．． 10-nylon and copolymers of nylon 6 and 6,6 are preferred.

The thermoplastic rubber-like substance used as component (C) in the composition of the present invention must be substantially entirely microdispersed in the polyphenylene ether phase present as a dispersed phase in the composition. This requires a rubber-like material that has a strong affinity for polyphenylene ether rather than polyamide. Therefore, the thermoplastic rubbery substance that can be used in the composition of the present invention is composed of a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of conjugated diene compound units.
Each block has at least one block, and the content of vinyl aromatic compound units is 25 to 60% by weight. The preferable range of the content of the vinyl aromatic compound unit is 30 to 50% by weight. This content is 25
Below 60% by weight, the block copolymer cannot be present in microdispersion in the polyphenylene ether phase, which is present as a dispersed phase, under any mixing conditions, whereas above 60% by weight, a rubbery substance is formed. The reinforcing effect is significantly reduced, and sufficient impact strength cannot be obtained.

Examples of the vinyl aromatic compound units constituting the block copolymer include styrene units, α-methylstyrene units, vinyltoluene units, etc., and these units may be contained in one quantity or two in quantity. Styrene units may be used, but styrene units are particularly preferred. Further, examples of the conjugated diene compound unit include butadiene unit, isoprene unit, 1,3-pentadiene unit, etc.
These units may be combined in units of about 1 or 2 units, but a butadiene unit is particularly preferred. Moreover, those in which part or all of the butadiene units are hydrogenated can also be used.

The molecular structure of the block copolymer is not particularly limited, and may be linear, branched, radial, or any combination thereof. Furthermore, two or more types of block copolymers having different contents of vinyl aromatic compound units may be used, as long as the average value of the content of vinyl aromatic compound units can be kept within the above range.

Further, the block copolymer may be modified with an unsaturated carboxylic acid or a glycidyl compound.

The modified block copolymer used as component (D) in the composition of the present invention has a base composed of a polymer block mainly composed of vinyl aromatic compound units and a polymer block mainly composed of conjugated diene compound units. A block copolymer modified with at least one selected from unsaturated dicarboxylic acids and derivatives thereof so that the content of the residue is 0.05 to 5% by weight. .

The block copolymer serving as the base contains one or more, preferably two or more, polymer blocks mainly composed of vinyl aromatic compound units and one or more polymer blocks mainly composed of conjugated diene compound units. It is something. The content of vinyl aromatic compound units in this block copolymer is 6
It is necessary that the content be within the range of 0 to 97% by weight.

Examples of the vinyl aromatic compound units constituting the block copolymer include styrene units, α-methylstyrene units, vinyltoluene units, etc., and these units may be combined in groups of about 1 or 2 units. The styrene unit is particularly preferred, although it may also be a styrene unit. In addition, examples of the conjugated diene compound unit include butadiene units, isoprene units, 1,3-pentadiene units, etc., and these units may be combined by about 1, or may be contained in an amount of 2N or more. , particularly butadiene units are preferred.

The molecular structure of the block copolymer is not particularly limited, and may be linear, branched, radial, or any combination thereof. Furthermore, two or more types of block copolymers having different contents of vinyl aromatic compound units may be used, as long as the average value of the content of vinyl aromatic compound units can be kept within the above range.

The modified block copolymer used in the present invention is preferably one modified by adding an unsaturated dicarboxylic acid or a derivative thereof to the conjugated diene compound unit of the block copolymer serving as the base.

Examples of the unsaturated dicarboxylic acids and their derivatives include maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and their acid anhydrides, esters, semi-alkyl esters,
Examples include amides and imides, and α,β-unsaturated dicarboxylic acids and derivatives thereof, specifically maleic acid and maleic anhydride, are particularly suitable.

These unsaturated dicarboxylic acids and their derivatives may be used alone or in combination of two or more.

The red phosphorus used in the composition of the present invention may of course be commercially available red phosphorus;
It is also possible to use the red phosphorus particles disclosed in JP-A No. 105996 and JP-A-52-125489 in which the surfaces of the red phosphorus particles are coated with a thermosetting resin or the like to stabilize them.

The role of the modified block copolymer (component) in the composition of the present invention is to microdisperse the thermoplastic rubber-like material (component (C)) in the polyphenylene ether, and to transport the polyphenylene ether phase into the polyamide constituting the continuous phase. The purpose is to finely disperse it. It is known from the following fact that the modified block copolymer has a unique dispersion shape controlling effect. In other words, in a system without the addition of component (D) (if the thermoplastic rubber-like material of component C1 is not dispersed in the polyphenylene ether phase and exists in a phase-separated state in the polyamide phase, a small amount of component (D) is added to the system). A desired dispersion form can be obtained by adding .In addition, although the location of the modified block copolymer of component CD) is not necessarily clear, it can be inferred from the above effects that it is added to the polysunilene ether phase. It is thought that it exists.

In the composition of the present invention (Al polyphenylene ether,
(B) polyamide, (C) thermoplastic rubbery material, (D)
Regarding the blending ratio of the modified block copolymer and (Gain Red Phosphorus), based on the total weight of the components (A), (Bl and (C)), polyphenylene ether is 25 to roMi.
%, preferably from 30 to 60% by weight, polyamide from 25 to
70% by weight, preferably 30-60% by weight, and thermoplastic rubber-like material should be selected in the range of 2-2% SyIL, preferably 5-20% by weight.

In addition, the modified block copolymer and red phosphorus are
, (per 100 parts by weight of the total amount of Bl and (C) components, the modified block copolymer is in the range of 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, and the red phosphorus is in the range of 0.3 to 5 parts by weight) , preferably in the range of 1 to 4 parts by weight.

Furthermore, regarding the dispersion form of each component, polyamide forms a continuous phase, polyphenylene ether is dispersed in the continuous phase, and the average particle size is 0.1 to 8 μm, preferably 0.2 μm.
It is necessary that substantially all of the thermoplastic rubber-like material be microdispersed in the dispersed phase (10 Bo!J phenylene ether) to form a dispersed phase of ~5 μm.

In addition, if the polyamide is less than 25% by weight or the polyphenylene ether is more than 70% by weight with respect to the total amount of the components (A), (n, (c'la), the polyamide is a continuous phase under any mixing conditions. The polyphenylene ether cannot form a dispersed phase, and on the other hand, if the polyamide exceeds 70% by weight or the polyphenylene ether exceeds 25% by weight, the heat deformation resistance of the composition under high loads is poor, so it is preferable. Furthermore, the block copolymer of component (C) is necessary to improve impact resistance, and if its content is less than 2% by weight, there is no impact resistance improvement effect, while if it exceeds 25% by weight, Heat-resistant,
Rigidity decreases.

Q) The blending ratio of the modified block copolymer as the l component is (4)
.

(0.5% by weight based on the total weight of (Bl and (C1 components)
If it is less than 15, there is almost no effect of improving impact resistance.
If it exceeds % by weight, the heat distortion temperature will decrease.

If the content of vinyl aromatic compound units in the base block copolymer in the modified block copolymer is less than 60% by weight, the dispersion shape adjustment effect will hardly be exhibited;
When it exceeds 7% by weight, the content of the modified group is 0.05% by weight.
This is not the case, and it shows almost no dispersion shape adjustment effect.

Furthermore, if the content of residues of unsaturated dicarboxylic acids or derivatives thereof in the modified block copolymer is less than 0.05% by weight, the effect of controlling the dispersion morphology is hardly exhibited;
If it exceeds % by weight, the effect will hardly be improved and it will be economically disadvantageous.

The blending ratio of red phosphorus may be appropriately selected depending on the resin composition and the desired degree of flame retardancy, but it is 0.3! If the amount is less than 5 parts by weight, the S flame effect will be small, and if the amount is more than 5 parts by weight, it is no longer necessary from the viewpoint of flame retardancy, and mechanical properties such as impact resistance will deteriorate, making it meaningless.

In addition, the dispersion form of each resin component is set as described above.
If the polyamide forms the dispersed phase, or if both the polyamide and the polyphenylene ether form the continuous phase, the oil resistance, heat resistance, and stiffness of the composition decrease, and the dispersed phase of the polyphenylene ether decreases in average particle size. If it is less than 8 μm, the impact resistance and molding fluidity will decrease;
If it exceeds μm, it becomes difficult to form a dispersed phase in a stable state even under severe molding conditions, and furthermore, if a large amount of thermoplastic rubber-like substance exists independently in the polyamide phase, the heat distortion temperature and stiffness will decrease significantly. Due to reasons such as.

Next, a general manufacturing method for the composition of the present invention will be described, but of course other manufacturing methods can be used as long as the above conditions are satisfied.

That is, the composition of the present invention is obtained by melt-kneading polyamide, polyphenylene ether, thermoplastic rubber-like material, modified block copolymer, and red phosphorus. In the mixing method, five components may be kneaded at once. Furthermore, the remaining components may be kneaded into a blend obtained by pre-kneading two or more components.

Furthermore, when producing a modified block copolymer, that is, when mixing and reacting the base block copolymer with an unsaturated dicarboxylic acid or its derivative in an extruder, polyphenylene ether, polyamide (C1 component thermoplastic rubber It is preferable from the viewpoint of process simplification to supply the substance and red phosphorus and form the composition at once.

Furthermore, during melt mixing, a maleic acid compound, a copolymer of a styrene compound and an α,β-unsaturated dicarboxylic acid derivative, a silane compound, etc. may be used as a dispersion particle size control agent for polyphenylene ether. good. Examples of maleic acid compounds include maleic acid, maleic anhydride, half-alkyl esters of maleic acid, maleic acid amide, maleic acid imide, and among these, maleic acid and maleic anhydride are preferred. Copolymers of styrene compounds and α,β-unsaturated dicarboxylic acid derivatives include, for example, copolymers of styrene and maleic anhydride, copolymers of styrene and semi-alkyl esters of maleic acid, and copolymers of styrene and maleic acid semi-alkyl esters. Among them, a copolymer of styrene and maleic anhydride is preferred. Furthermore, the silane compound is a compound having at the same time (a) a carbon-silicon bond, (b) a halogen or alkoxy group, and (C) an alkyl group, a vinyl group, an amine group, an epoxy group, or a mercapto group; For example, vinylmethoxysilane, γ-aminopropylmethoxysilane, etc. are preferably used.

The amount of these dispersed particle size regulators added is 0.05 to 10% by weight, preferably 0.05 to 10% by weight, based on the total amount of the three components.
It is desirable to select it in the range of 1 to 5% by weight. If the amount added is less than 0.05% by weight, it will be difficult to reduce the average dispersed particle size of the polyphenylene ether to 8 μm or less, and if the amount added exceeds 10% by weight, it is economically unnecessary.

At the time of melt mixing, it is preferable to further add a small amount of a fluidity improver as necessary to adjust the melt viscosity of the composition.

That is, the melt viscosity is 500 to 20,000 poise, preferably L000 when using a capillary viscometer and applying a shear rate of 100 seconds at a temperature of 280°C.
~12,000 poise, more preferably 2,000~
s, ooo poise range. As fluidity improvers, saturated carboxylic acids, trans-type dicarboxylic acids, and metal salts thereof are effective, and citric acid, succinic acid, fumaric acid, stearic acid, calcium stearate, zinc stearate, etc. are preferable. Two or more types may be used.

The temperature and time for melt-kneading vary depending on the strain of polyamide used and the composition ratio of polyamide and polyphenylene ether, but usually the temperature is in the range of 240 to 350°C, preferably 260 to 320°C, or 0. 2-10
A crosstalk time of about 0.5 to 5 minutes is used, preferably about 0.5 to 5 minutes. As the melt mixing device, an extruder, a kneader roll, etc. can be used, but an extruder is particularly suitable.

The composition of the present invention may contain other polymer plasticizers, other flame retardants, or fillers such as glass fibers, carbon fibers, carbon blanks, silica, clay, etc., as desired, without impairing the purpose of the present invention. It can be added within this range. The other polymer is preferably a polymer that is substantially compatible with the polyphenylene ether phase, such as polystyrene, rubber-modified polystyrene, and the like.

In addition, the dispersion form and the dispersed particle diameter in the present invention can be determined by electron microphotography, and the dispersed particle diameter can be calculated as follows.

That is, a transmission electron micrograph (photo magnification: 4.000x) of an ultrathin section cut from the molded product is adjusted, the dispersed particle diameter di and the number of particles ni are determined, and the average diameter of the dispersed phase is calculated using the following formula. .

In this case, if the particle shape cannot be regarded as spherical, the short axis and long axis were measured, and the particle diameter was determined as a percentage of the sum of both.

Furthermore, to calculate the average particle diameter, the diameters of at least 2,000 particles are measured.

<Effects of the Invention> The flame-retardant resin composition of the present invention contains polyphenylene ether, polyamide, a thermoplastic rubber-like substance, a modified block copolymer with a specific composition, and red phosphorus as main components. , the above five components have a specific composition,
Furthermore, since the resin component has a specific dispersion form, it has flame retardancy,
It exhibits a better balance of molding fluidity, impact resistance, and weld strength than conventional products without compromising heat resistance, oil resistance, etc.

Since the composition of the present invention has the above-mentioned performance, it is suitable for use in electronic and electrical precision parts such as connector switches, gas appliances, lighter parts, and the like.

<Examples> Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, the physical property values in the examples were measured by molding a test piece at 280° C. using a 5-ounce injection molding machine and according to the following test method.

Melt viscosity: The melt viscosity was determined using a cavilograph manufactured by Toyo Seiki Co., Ltd., with an orifice diameter of 1 mφ, a temperature of 280° C., and a shear rate of 100 sec.

Flow: Thickness 1.6B + Length 1271K + Width 12.
Short shot pressure (hereinafter abbreviated as ssp) when molded pieces in the order 7 are injection molded at 280°C Izont impact strength: ASTM D-256 (notched, !4 inch thickness) Weld piece tensile elongation: Thickness 1.6 jig * length" 27111 s width 12
．． A tensile test was conducted under the following conditions using a test piece with seven balls and a weld in the center.

A tensile test was carried out with a distance between specimen attachments of 50 ut and a tensile speed of 50 mx layer, and the elongation at break is shown in %.

A test piece with a thickness of 1.6 m was used in accordance with UL-94 for flammability.

Oil resistance: 1,1.1-) 1 to the vapor of chlorethane
The appearance of the molded product after 0 minute exposure was visually determined.

Heat distortion temperature: ASTM D-648 (load 264 psi) Examples 1 to 2 and Comparative Examples 1 to 5 Intrinsic viscosity is o, s 6 (aoC, in phosphorous roform)
Poly(2,6-dimethylphenylene-1,4 ether) (hereinafter referred to as PPE) nylon-6,6 [manufactured by Asahi Kasei Corporation (Button, trade name: Leona 1300S), as a thermoplastic rubber-like material Styrene-butadiene block copolymers shown in Table 1, modified block copolymers obtained by modifying styrene-butadiene block copolymers containing 80% by weight of styrene units with maleic anhydride, maleic anhydride and red phosphorus as The mixture was blended in the proportions shown in the table and fed to a 53 mm diameter twin-screw extruder at a temperature of 290'C120Orpm (
However, in Comparative Example 3, extrusion kneading was carried out using 50 ryn) to form pellets.

The modified block copolymer was prepared by adding 21 parts by weight of maleic anhydride to 100 parts by weight of the styrene-butadiene block copolymer.
It was produced by blending i part by weight and 0.5 part by weight of fetchazine as a stabilizer, and performing melt extrusion at 290°C using a twin screw extruder. When this modified block copolymer was dissolved in toluene and subjected to neutralization titration, the content of maleic acid residues was found to be about 1% by weight.

Comparative Example 1 used a styrene-butadiene random copolymer instead of the styrene-butadiene block copolymer, and Comparative Example 2 used polybutadiene.

Comparative Example 4 is Example 1, but instead of the modified block copolymer, a styrene-maleic anhydride copolymer (manufactured by ARCO Polymer Co., Ltd., trade name: Dylark 232) was used, and maleic anhydride was not blended. Furthermore, Comparative Example 5 is a case in which the modified block copolymer in Example 1 was not used.

Table 1 shows the composition, dispersion form, and measured physical properties of these compositions.

From the above results, the compositions of Examples 1 and 2, in which the modified block copolymer was blended and the dispersion form of the composition was adjusted using a thermoplastic rubber-like substance, were different from those of Comparative Examples 1 to 5. In comparison, it can be seen that it has an excellent balance of flow, Izot impact strength, weld piece tensile elongation, and other physical properties.

2? - Examples 3 to 5 and Comparative Examples 6 to 7 In Example 1, a modified block copolymer with a maleic acid content of 0.5% was used, and 0.5 part of fumaric acid was blended as a fluidity improver. The same operation as in Example 1 was carried out by changing the ratio of PPE and nylon. The results are shown in Table 2.

From Table 2, the compositions of Examples 3 to 5, which are within the composition range of the present invention, are superior to the compositions of Comparative Examples 6 and 7 in terms of Izont impact strength and weld piece tensile elongation, and furthermore, It can be seen that it has an excellent balance of heat resistance and heat resistance.

Examples 6 to 8 and Comparative Examples 8 to 9 In Example 1, the styrene content of the modified block copolymer was changed, and 0.5 parts of fumaric acid was blended as a fluidity improver with the composition shown in Table 3. , the same operation as in Example 1 was performed. The results are shown in Table 3. From Table 3, it can be seen that Comparative Example 8, which used a modified block copolymer with a lower styrene content, had better flow and resistance than Examples 6 to 8, which were within the composition range of the present invention. Poor impact resistance and oil resistance, etc.
Furthermore, Comparative Example 9 in which polystyrene was blended also had significantly poor impact resistance.

Example 9 and Comparative Example 10 In Example 1, nylon-6,6 was replaced with nylon-6 [
Manufactured by Asahi Kasei Kogyo Co., Ltd., trade name: Semi-Prite]
The same procedure as in Example 1 was carried out using the same composition except that maleic anhydride was replaced with vinylmethoxysilane, and the results of Example 9 shown in Table 4 were obtained.

For comparison, Table 4 shows Comparative Example 10 using an unmodified block copolymer. As is clear from Table 4, Comparative Example 10 had significantly poor impact resistance.

Examples 10 to 11 and Comparative Example 10 In Example 1, as the thermoplastic rubbery material, block SBH
The same procedure as in Example 1 was carried out, except that part or all of was changed to a hydrogenated styrene-butadiene block copolymer (manufactured by Asahi Kasei Industries, Ltd., trade name: Toughtic UI 041, hereinafter abbreviated as HT'R). performed the operation. The result is the fifth
Shown in the table.

Comparative Example 10 is the same as Example 11 except that the modified block copolymer was not used.

Procedural amendment (voluntary) October 2, 1986 Yoshi, Commissioner of the Patent Office 1) Takeshi Moon 1. The display of the incident is 3-no3decino36. .

Patent filed on September 27, 1986 (3) 2, Name of the invention: Flame-retardant resin composition 3, Relationship with the person making the amendment Patent applicant: 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture No. 4, No number of claims increased by amendment 5, "Detailed description of the invention" column 6 of the specification subject to amendment, Contents of the amendment (1) "Table 1" on page 28 of the specification, Please make a correction to the attached “Table 1”.

(2) "Table 2" on page 30 of the same page is corrected to the attached "Table 2."

(3) "Table 3" on page 32 of the same page is corrected to the attached "Table 3."

(4) "Table 4" on page 34 of the same page is corrected to the attached "Table 4."

(5) "Table 5" on page 36 of the same page is corrected to the attached "Table 5."

Below Up No. table Unmodified block copolymer No. table

Claims (1)

[Claims] 1. (A) polyphenylene ether, (B) polyamide, (C) thermoplastic rubber-like material, (D) polymer block mainly consisting of vinyl aromatic compound units and conjugated diene compound units A block copolymer consisting of a polymer block having a vinyl aromatic compound unit content of 60 to 97% by weight is combined with at least one type selected from unsaturated dicarboxylic acids and derivatives thereof. a modified block copolymer obtained by modifying the same so that the content of its residues is 0.05 to 5% by weight, and (E) containing red phosphorus, (A), (B) and ( C) The content based on the total amount of components is within the range of 25 to 70% by weight of component (A), 25 to 70% by weight of component (B), and 2 to 25% by weight of component (C), , total amount of components (B) and (C) 1
The content of component (D) is in the range of 0.5 to 15 parts by weight and the content of component (E) is in the range of 0.3 to 5 parts by weight per 00 parts by weight, and component (B) forms a continuous phase. Component (A) is present in this continuous phase as a dispersed phase with an average particle size of 0.1 to 8 μm, and substantially all of component (C) is present in a microdispersed state in the dispersed phase. Flame retardant resin composition 2, characterized in that (C) the thermoplastic rubbery substance contains 25 to 6 styrene;
The composition according to claim 1, which is a styrene-butadiene block copolymer containing 0% by weight.