JPH02132153A - Fire retardant polyphenylene ether composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition suitable for electronic or electric device, etc., having excellent balance of resistance to impact and stiffness, etc., without losing fire retardance and heat resistance, etc., by blending specific amounts of polyamide and styrene-containing thermoplastic rubber, etc., and making resin component to specific dispersing state. CONSTITUTION:100 pts.wt. resin comprising (A) 20-60wt.% polyphenylene ether, (B) 35-70wt.% polyamide (e.g., 6-nylon) and (C) 2-25-wt.% styrene-containing thermoplastic rubber such as styrene-butadiene block copolymer containing 25-60wt.% styrene is blended with (D) 3.40 pts.wt. halogenated polystyrene polymerized with monomer expressed by the formula (R is H, etc.; X1-X5 are vinyl or halogen, etc.) and (E) 0.5-20 pts.wt. antimony-containing compound (e.g., antimony trioxide). The component A exists in continuous phase composed of the component B as dispersion phase of 0.1-4mum particle diameter and further the component C is dispersed in the dispersion phase.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a flame-retardant polyphenylene ether composition having excellent mechanical properties, heat resistance, oil resistance, and thermal stability.

[Conventional technology]

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, respectively. It compensates for the drawbacks of the above components and has an excellent balance of dimensional properties, oil resistance, moldability, heat resistance, and ibx-like properties. 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-60-155259 and JP-A-63-61,047 disclose compositions whose basic components are polyphenylene ether and polyamide, which contain halogenated polystyrene as a flame retardant.

[Problem that the invention seeks to solve]

The basic ingredients are polyphenylene ether and polyamide,
Furthermore, a resin composition imparted with flame retardance is optimal for use in the electrical and electronic fields due to its characteristics.

However, it has the following problems.

Molded products obtained by injection molding usually have one or several welded parts, and mechanical strength such as impact resistance is generally weakest in the welded parts, so the practical strength of the molded product is is substantially controlled by the strength of the weld portion.

Furthermore, during molding, the resin that remains in the molding machine undergoes thermal deterioration, resulting in a decrease in physical properties, particularly a decrease in impact resistance.

Resin compositions consisting of polyphenylene ether, polyamide, rubber components and flame retardants particularly have the above-mentioned drawbacks, namely poor weld strength and poor thermal stability.

Under these circumstances, the object of the present invention is to improve rigidity and heat resistance, oil resistance, dimensional properties, and electrical properties in a resin composition containing polyphenylene ether and polyamide as basic components. Excellent balance of impact resistance, thermal stability and
It is an object of the present invention to provide a flame-retardant resin composition that has excellent weld part strength.

[Means to solve 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, a specific thermoplastic rubber-like substance, halogen It was discovered that the object could be achieved by a composition containing polystyrene and antimony-containing compounds in a specific proportion and in which the dispersion form of the resin component was adjusted to a specific state, and based on this knowledge, the present invention was completed. I ended up doing it.

That is, the present invention provides (A) polyphenylene ether 20 to 60fflffi
%, (B) 35 to 70% by weight of polyamide, (C) 2 to 25% by weight of styrene-containing thermoplastic rubber, and (D) a monomer of the following general formula is polymerized. 3 to 40 parts by weight of halogenated polystyrene having the structure, either halogenated alkyl or lower alkyl, and at least one of X1 to X is a halogen. ) (E) Contains 0.5 to 20 parts by weight of atimone-containing compound, and component (B) forms a continuous phase, in which (
A flame retardant characterized in that component A) is present as a dispersed phase with an average particle diameter of 0.1 to 4 μm, and substantially all of component (C) is present in a microdispersed state in the dispersed phase. It is a synthetic resin composition.

The present invention will be explained in detail below.

The polyphenylene ether used as component (A) in the composition of the present invention has the general formula R (where R is hydrogen, lower alkyl, halogen, or halogenated lower alkyl, and X+-Xs is vinyl, /SI cogen, hydrogen, lower haR2 (In the formula, at least one of R1 and R2 is a linear, primary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, The remaining halogen atoms are hydrogen atoms, which may be the same or different from each other); a repeating unit represented by the general formula (1) above; and the general formula (R3 in the formula
, Ra, Rs and R. are each a linear or primary or secondary branched alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen atom, a hydrogen atom, etc.
These may be the same or different from each other, but R and R4 cannot be hydrogen atoms at the same time), and homopolymers thereof. and a graft copolymer obtained by grafting styrene onto a copolymer.

Representative examples of polyphenylene ether homopolymers include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl 1,4-phenylene) ether, and poly(2-methyl-6-ethyl 1,4-phenylene) ether. .6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) Ether, poly(2-methyl-6-n-7'thyl-1,4-phenylene)ether, poly(2-ethyl-6-isopropyl-1,4-phenylene)ether, poly(2-methyl-6- Homopolymers such as chloro-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly(2-methyl-6-chloroethyl/L/1+4-phenylene) ether can be mentioned.

Polyphenylene ether copolymers are 0-cresol or alkyl-substituted 2,3,6-trimethylphenol represented by the general formula (wherein Ri, Ra, Rs, and R have the same meanings as above). It includes polyphenylene ether copolymers mainly having a polyphenylene ether structure obtained by copolymerizing with phenol.

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

Typical examples include 4-nylon, 6-nylon, 6.6-nylon, 12-nylon, 6.10-nylon, polyamide obtained from terephthalic acid and trimethylhexamethylene diamine, and adivic acid and metaxylylene diamine. Polyamides obtained from adivic acid and azelaic acid and 2,2-bis(p-aminocyclohexyl)-propane; Polyamides 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 styrene-containing thermoplastic rubber used as component (C) in the composition of the present invention is substantially entirely micro-decomposed 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. The styrene-containing thermoplastic rubber-like material that can be used in the composition of the present invention has at least one polymer block mainly composed of styrene units and at least one polymer block mainly composed of conjugated diene compound units, and The content of styrene units is 25 to 60% by weight. The preferred range of the content of styrene units is 30 to 50% by weight. If this content is less than 25% by weight, the block copolymer cannot exist in a microdispersed state in the polyphenylene ether phase which exists as a substantially splitting phase under any mixing conditions; If it exceeds the weight percentage, the reinforcing effect as a rubber-like material will be significantly reduced, and sufficient impact strength will not be obtained.

Examples of the conjugated diene compound units include butadiene units, isoprene units, 1,3-pentadiene units, etc., and one type of these units may be included, or two types of these units may be included.
Although more than one type of unit may be included, butadiene units are 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, for example, linear, branched, radial, or any combination thereof. Furthermore, two or more types of block copolymers having different styrene unit contents may be used as long as the average value of the styrene unit content can be kept within the above range. Further, the block copolymer may be modified with an unsaturated carboxylic acid or a glycidyl compound.

The halogenated polystyrene used as component (D) in the composition of the present invention can be widely used, ranging from low molecular weight ones called oligomers to infinite molecular weight ones with a three-dimensional structure, and can be obtained from monomers of the following general formula. A styrene monomer that has been halogenated in advance may be polymerized, or a styrene monomer may be polymerized and then halogenated, and it can be used alone or in combination of two or more. .

Ri, X. -X, is vinyl, halogen, hydrogen, lower alkyl, or lower halogenated alkyl;
At least one of X is a halogen. ) Specific examples of monomers constituting halogenated polystyrene include chlorostyrene, promostyrene, 2.6-dichlorostyrene, 2.6-dibromostyrene, 2.4.6
- }Libromostyrene, 2,4.6 - }Libromostyrene, α-methylene styrene, α-methyl-bromostyrene, 2,6-dichloro4-methylstyrene, 2,6-dibromo-4-methyl Examples include styrene, pentachlorostyrene, pentabromostyrene, 2,6-bromo-1,4-divinylbenzene, and the like. A particularly preferred halogen is bromine.

The antimony-containing compound used as the component ([) in the composition of the present invention can be either an inorganic compound or an organic compound. For example, antimony oxide, antimony chloride, antimony phosphate, KSb(Off)6, NII. SbF,
, sbsyu, K (Sb) tartrate, Sb cabronate, Sb (OCII zclI 3) 3, sb polymethylene glycolate, triphenyl antimony, and the like. A particularly preferred antimony compound is antimony oxide.

(A) polyphenylene ether in the composition of the present invention,
(B) polyamide, (C) styrene-containing thermoplastic rubber 1,
, (D) halogenated polystyrene and (E) antimony-containing compound, as described in (A) above.
Based on the total weight of components (+3) and (C), polyphenylene ether is present in an amount of 20 to 60% by amount, preferably 2%.
The range is from 5 to 50 weight percent, polyamide from 35 to 70 weight percent, preferably 40 to 60 weight percent, and styrene-containing thermoplastic rubber from 2 to 25 weight percent, preferably 5 to 20 weight percent.

In addition, the blending amount of halogenated boristyrene and antimony-containing compound is 3 parts by weight of halogenated boristyrene per 100 parts by weight of the total amount of components (A), (B), and (c).
~40 parts by weight, and the antimony-containing compound ranges from 0.5 to 20 parts by weight.

Furthermore, regarding the dispersion form of each component, the polyamide forms a continuous phase, and the polyphenylene ether is dispersed in the continuous phase, with an average particle size of 0.1 to 4 μm, preferably 0.2 μm.
It is necessary to form a fractionation phase of ~3.5 μm and to have substantially all of the styrene-containing thermoplastic rubber microdispersed in the polyphenylene ether of the fractionation phase.

In addition, the above (A) and (B). (c) If the polyamide is less than 35% by weight or the polyphenylene ether is more than 60% by weight with respect to the total amount of the three components, it is difficult to achieve a particle size of 4 μm or less; More than 70% by weight or polyphenylene ether is 2%
If it is less than 0% by weight, the composition will have poor heat deformation resistance under high loads, which is not preferable. Furthermore, the styrene-containing thermoplastic rubber as component (C) is necessary for improving impact resistance, and if its content is less than 2% by weight, it will not have the effect of improving impact resistance, while if it exceeds 25% by weight, it will not improve heat resistance. The strength and rigidity decrease.

The blending amount of halogenated polystyrene is determined depending on the target level of flame retardancy, but if it is less than 3 parts by weight, it will hardly exhibit any flame retardant effect, and if it exceeds 40 parts by weight, the flame retardant effect will not increase. However, it deteriorates mechanical properties and is economically disadvantageous.

Further, the amount of the antimony-containing compound to be blended is also determined depending on the target degree of flame retardancy. If it is less than 0.5 parts by weight, the effect will be small, and if it exceeds 20 parts by weight, the effect will not further increase.

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 and molding fluidity of the composition decreases, and the polyphenylene ether dispersed phase decreases. If the average particle diameter is less than 0.1 μm, impact resistance and molding fluidity will decrease. Also, 4μ
If it exceeds m, impact resistance, weld strength and thermal stability will be poor.

Furthermore, if a large amount of styrene-containing thermoplastic rubber is independently present in the polyamide phase, the heat deformation temperature and rigidity are significantly reduced.

Next, a general method for producing the composition of the present invention will be described, but of course other production 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, styrene-containing thermoplastic comb, halogenated polystyrene, and antimony-containing compound. As for the kneading method, the five components may be kneaded all at once, or the remaining components may be kneaded into a blend obtained by pre-kneading two or more components. During melt mixing, in order to adjust the dispersed particle size of polyphenylene ether, α,β monounsaturated carboxylic acid and its mR form, a vinyl silane compound, a saturated aliphatic polycarboxylic acid and its 3L form are added as the three components. It can be added in an amount of 0.1 to 2% based on the total amount.

Typical examples of such compounds include maleic acid, maleic anhydride, maleic imide, vinylmeltoxysilane, T-
These include aminopropylmethoxysilane, citric acid, and malic acid.

Furthermore, instead of these compounds, a modified polyphenylene ether to which the compound has been added can also be blended, and a part or all of component (8) polyphenylene ether can be made into a modified polyphenylene ether. .

The temperature and time for melt-kneading vary depending on the type of polyamide used and the composition ratio of polyamide and polyphenylene ether, but the temperature is usually in the range of 240 to 350°C, preferably 260 to 320°C. Also 0.2～
A kneading time of about 10 minutes, preferably 0.5 to 5 minutes is used. As the melt-kneading device, an extruder, a mixer, a 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 fiber, carbon fiber, carbon plaque, 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: 4000 times) of an ultra-thin section cut from the molded product is adjusted 2, the dispersed particle diameter di and particle age are determined, and the average diameter of the separated phase is calculated by the following formula.

In case 2, if the particle shape cannot be regarded as spherical, the short axis and long axis were measured, and the sum of the two, 2, was taken as the particle diameter. Furthermore, to calculate the average particle diameter, the diameters of at least 2000 particles are measured.

[Effect of the invention] The flame-retardant polyphenylene ether composition of the present invention contains polyphenylene ether, polyamide,
It contains a styrene-containing thermoplastic rubber, a halogenated polystyrene, and an antimony-containing compound, and since the above five components have a specific composition and the resin component has a specific dispersion form, it has flame retardancy, heat resistance, It has an excellent balance of impact resistance and rigidity without compromising oil resistance or electrical properties, and also has excellent thermal stability during processing and strength of the weld part.

Since the composition of the present invention has the above-mentioned performance, it can be applied to a wide range of uses including those related to electrical and electronic equipment.

〔Example〕

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 test pieces at 270°C using a 5-ounce injection molding machine and according to the following test method.

(1) Izod impact strength (notched, 1/8 inch thick, measured at 23°C) Determined according to ASTM D-256.

(2) Flexural modulus It was determined in accordance with ASTM D-790.

(3) Heating deformation temperature: Determined based on ASTM D-648 with a load of 264 PSi.

(4) Thermal stability Using the same injection molding machine as above, test pieces were molded at 310°C and their Izod impact strength was measured.

The ratio to the Izod impact value of one piece of sample Hr molded at 270°C was determined.

(5) Weld strength One side of the outer circumference is 125mm, one side of the inner circumference is 100III
A U-shaped molded article was injection molded, and the strength of the weld portion was measured using a DuPont two-drop weight impact test (measured at 23°C, falling weight diameter η inches).

(6) Flame retardant IJL-94 method, thickness 3.2 mm Examples 1-2 and Comparative Examples 1-4 Intrinsic viscosity 0.56 (30°C, in chloroform)
Poly(2,6-dimethylphenylene-1.4 ether) (hereinafter referred to as PPE), nylon-6 [manufactured by Asahi Kasei Corporation, trade name: Pride] was used as the styrene-containing thermoplastic rubber component. Various rubbers with structures shown in Table 1, poly(2,4.6-}ribromustyrene) (FE
Manufactured by RRQ, product name: Baiguchi Check 68PB, hereinafter B
Abbreviated as r-PS. ) and antimony dioxide in the proportions shown in Table 1, and 0.5 parts by weight of each of maleic anhydride was added. These were processed using a 53mmφ twin-screw extruder at 280"C and 200rpm (however,
Comparative Example 4 was extruded and kneaded at 50 rpm) and pelletized.

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

Examples 3 to 4 and Comparative Examples 5 to 6 The same operations as in Example 1 were performed except that PPP and nylon-6 were changed to the proportions shown in Table 2.

The results are shown in Table 2.

Examples 5 to 7 In Example 1, a hydrogenated block copolymer (hereinafter referred to as 11TR) obtained by adding oil to half or all of the block SBR.

) and Nylon 6.6 (manufactured by Asahi Kasei Corporation, product name: Leona 1500).
The same operation as in Example 1 was carried out, and the results shown in Table 3 were obtained.

Incidentally, the oil-added IITII was obtained by the following method.

That is, HTR with a bound styrene content of 30% (SII
Manufactured by EI, 1, product name: KRATON c-165
13 70 parts by weight of paraffinic process oil [manufactured by Idemitsu Kosan Co., Ltd., trade name: Diana Process Oil p]
380) was mixed in a proportion of 30 parts by weight using a Henschel mixer.

hand Continued Supplementary Positive book (spontaneous) 5. Contents of correction 19863 February Day rK(Sb) tartrate on page 13, line E3 of the specification; ” of “K. (SbO)tartrate, ” Correct to.

Claims (1)

[Claims] (1) (A) 20 to 60% by weight of polyphenylene ether
, (B) 35 to 70% by weight of polyamide, (C) 100 parts by weight of a resin consisting of 2 to 25% by weight of styrene-containing thermoplastic rubber, and (D) a structure formed by polymerizing monomers of the following general formula. 3 to 40 parts by weight of halogenated polystyrene, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is hydrogen, lower alkyl, halogen, or halogenated lower halogenated alkyl, lower alkyl, and (At least one is a halogen.) (E) Contains 0.5 to 20 parts by weight of an antimony-containing compound, and the (B) component forms a continuous phase, and the (A) component is 0 in this continuous phase. Resin composition (2) (C
Component (3) of claim 1, wherein the component (D) is a styrene-butadiene block copolymer containing 25 to 60% by weight of styrene and a hydrogenated block copolymer thereof. is bromine. Composition (4) The composition according to claim 1, wherein the antimony-containing compound of component (E) is antimony trioxide.