JP2001302900A - Polyphenylene ether resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition excellent in balance between fluidity and heat resistance, slightly causing a change in quality due to molding processing temperature and further excellent in color tone and mechanical characteristics. SOLUTION: This polyphenylene ether resin composition is characterized as comprising specific ratios of (A) a polyphenylene ether resin containing a functionalized polyphenylene ether produced by reaction at a reactional temperature of not higher than the melting point of the polyphenylene ether, (B) a polyetyrene and/or a rubber-modified polystyrene and (C) a styrene-acrylonitrile copolymer containing >=7 and <11 wt.% of an acrylonitrile component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to fluidity, heat resistance,
The present invention relates to a polyphenylene ether resin composition having excellent mechanical properties and color tone.

[0002]

2. Description of the Related Art Generally, thermoplastic resins have fluidity, heat resistance,
What has a good balance of mechanical properties is demanded for industrial use. For example, polyphenylene ether-based resins have properties such as excellent mechanical properties, electrical properties, acid resistance, alkali resistance, and heat resistance, as well as low water absorption and good dimensional stability. Are widely used as materials for housing chassis of OA equipment. In addition, these materials often require flame retardancy due to fire problems. However, with the remarkable progress of recent OA equipment, the equipment has been advanced and downsized and lightened, and as a result, these materials are often formed in a thin wall, and further fluidity (moldability).
Improvement is desired.

Polyphenylene ether has poor fluidity, and is generally used as a polymer blend composition with polystyrene as shown in JP-B-43-17812 and US Pat. No. 3,383,435. Polyphenylene ether and polystyrene are completely compatible at an arbitrary ratio, and the fluidity increases in proportion to the polystyrene ratio, but the heat resistance decreases inversely. In addition, Shoko 4
No. 8-40046 discloses a mixture of a polyphenylene ether and a styrene-acrylonitrile copolymer containing 3 to 18% by weight of an acrylonitrile component.
The balance between heat resistance and fluidity mechanical properties was not always satisfactory.

Further, Japanese Patent Application Laid-Open No. 6-306254 discloses a technique for improving the balance between heat resistance and fluidity by using an AS resin having a specific AN content. However, there was a problem that the practical strength was low. JP-A-9-33121 discloses a melt flow rate containing 7 to 11% by weight of a polyphenylene ether, polystyrene and / or rubber-modified polystyrene, and an acrylonitrile component of 5 to 100 g / 10.
Styrene-acrylonitrile copolymer in a specific ratio to improve the fluidity of the resin composition obtained by mixing, the flowability is improved, the lower the molding temperature, the lower the impact, A decrease in strength and heat deformation temperature was observed.

Further, in order to improve this drawback, JP-A-11-106642 discloses a resin composition using a modified polyphenylene ether partially or entirely modified with an unsaturated carboxylic acid or a functional derivative thereof. Is disclosed. It has been desired that the resin composition is difficult to use a large amount of the modified polyphenylene ether because of the deterioration of the color tone that amplifies the brownish color, which is considered to be caused by the modified polyphenylene ether, and further improves the mechanical properties.

Hitherto, as a means for obtaining a modified polyphenylene ether by modifying polyphenylene ether, a method of chemically modifying a compound having a polar group and polyphenylene ether in a solution state or a molten state has been studied. For example, as a related technology, Japanese Patent Publication No. 52-1986
No. 4, JP-B-52-30991 discloses that polyphenylene ether is mixed with styrene and maleic anhydride or another polymerizable modifying compound in a solution state in the presence of a radical generator. A method for obtaining a functionalized polyphenylene ether by polymerizing for a long time has been proposed. However, these methods require a dissolution, a polymerization step, and a solvent removal step, and the cost is high in terms of equipment and energy.

Also, Japanese Patent Publication No. 3-52486, Japanese Patent Application Laid-Open No. Sho 62-132924, and Japanese Patent Publication No. Sho 63-50080
No. 3 and JP-A-63-54425 disclose polyphenylene ether in the presence of a radical generator, or
A method has been proposed in which a radical generator is mixed with maleic anhydride or another reactable modifying compound in the absence of the radical generator and modified in a molten state such as melt kneading to obtain a functionalized polyphenylene ether. However, in these methods, since the temperature at which the polyphenylene ether can be melt-kneaded is very high, and the melt viscosity of the polyphenylene ether is very high, the reaction temperature becomes extremely high, causing various problems. ing.

That is, since the functionalized polyphenylene ether obtained by the conventional melt-kneading method has a processing temperature close to the decomposition temperature, discoloration occurs due to thermal deterioration, and this functionalized polyphenylene ether causes problems in color tone and appearance. In order to solve the problems of color tone and appearance, a method has been proposed in which additives such as a heat stabilizer and an antioxidant are added to polyphenylene ether and melt-extruded. The appearance does not improve sufficiently. Therefore, the functionalized polyphenylene ether obtained by the conventional technology has a problem in terms of equipment and energy, or has an insufficient balance of color tone / appearance and heat resistance / mechanical properties, so that it sufficiently meets the demands of the industry. Not something.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyphenylene ether composition which is excellent in fluidity, heat resistance, quality change due to molding temperature and excellent in color tone and mechanical properties.

[0010]

Means for Solving the Problems The present inventors diligently studied techniques for achieving the above-mentioned objects, and as a result, they found that it becomes possible by containing a functionalized polyphenylene ether obtained by a novel method. Completed the invention.

That is, the present invention comprises (A) 30 to 95% by weight of a polyphenylene ether resin, (B) 2 to 60% by weight of polystyrene and / or rubber-modified polystyrene, and (C) 7 to 11% by weight of an acrylonitrile component. (A) a polyphenylene ether resin comprising 3 to 40% by weight of a styrene-acrylonitrile copolymer represented by the following formula (1): At least one functionalized compound (b) having at least one carbon-carbon double or triple bond and at least one carboxyl group, acyl oxide group or imide group.
A part or all of the functionalized polyphenylene ether (a-2) produced by reacting the mixture added with 01 to 10.0 parts by weight at a reaction temperature from room temperature to the melting point of the polyphenylene ether (a-1). This has been achieved by developing a polyphenylene ether resin composition characterized in that it is used.

As the polyphenylene ether resin (A) used in the present invention, all may be functionalized polyphenylene ether (a-2), but unfunctionalized polyphenylene ether and functionalized polyphenylene ether (a-2) Can also be used in combination. Unfunctionalized polyphenylene ether and functionalized polyphenylene ether (a
When -2) is used in combination, the functionalized polyphenylene ether (a-2) is preferably used in an amount of 1% by weight or more, preferably 2% by weight or more of the entire polyphenylene ether resin (A).

The polyphenylene ether of the present invention (a-
1) is composed of the structural unit represented by (Formula 1),

Embedded image

(R1 and R4 each independently represent hydrogen, halogen, primary or secondary lower alkyl,
Represents phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms separate a halogen atom and an oxygen atom), and R2 and R3 each independently represent hydrogen , Halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate the halogen atom from the oxygen atom. ) Reduced viscosity (0.5 g / dl, chloroform solution, 30 ° C)
(Measurement) is in the range of 0.15 to 1.0 dl / g, more preferably in the range of 0.20 to 0.70 dl / g.

Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2-methyl-6-ethyl-1,4-
Phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like.
2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-
And polyphenylene ether copolymers such as copolymers with (6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether),
Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, and poly (2,6-dimethylphenol) is more preferred.
6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing the polyphenylene ether (a-1) used in the present invention is not particularly limited. As an example of the method for producing the polyphenylene ether (a-1) used in the present invention, a complex of a cuprous salt and an amine described in US Pat. No. 3,308,874 is used as a catalyst,
There is a method of oxidative polymerization of 2,6-xylenol. U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, Japanese Patent Publication No. 52-1788.
No. 0, JP-A-50-51197 and JP-A-63-1
The methods described in JP-A-52628 and the like are also preferable as the method for producing polyphenylene ether (a-1).

The polyphenylene ether of the present invention (a-
The terminal structure of 1) is preferably a structure of the following (formula 2).

Embedded image [Wherein, R1, R2, R3, and R4 are each defined in the same manner as R1, R2, R3, and R4 in Formula 1 above. ]

The polyphenylene ether of the present invention (a-
More preferably, the terminal structure of 1) has a structure of the following (formula 2 ′).

Embedded image [Wherein R5 and R6 represent hydrogen or an alkyl group. ]

The polyphenylene ether of the present invention (a-
In 1), a desired additive may be added according to the purpose. Additives that can be used include heat stabilizers, antioxidants, UV absorbers,
Surfactant, lubricant, filler, polymer additive, dialkyl peroxide, diacyl peroxide, peroxy, peroxycarbonate, hydroperoxide,
And peroxyketal.

The functionalized compound (b) used in the present invention has at least one carbon-carbon double bond or triple bond and at least one carboxyl group, acyl oxide group or imide group in the molecular structure. One type of organic compound. Specific examples thereof include maleic anhydride, maleic acid, fumaric acid, phenylmaleimide, and itaconic acid, with maleic anhydride being preferred. Further, an organic compound which can be isomerized at a reaction temperature for obtaining the functionalized polyphenylene ether to become the above-mentioned functionalized compound (b) is also used. Examples include compounds that can thermally decompose themselves at the reaction temperature during the production of the functionalized polyphenylene ether and become functional derivatives used in the present invention, specifically malic acid, citric acid, and the like.

The amount of the functionalized compound (b) of the present invention is
It is 0.01 to 10.0 parts by weight based on 100 parts by weight of the polyphenylene ether (a-1). Preferably 0.
The amount is 1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight. When the amount of the functionalized compound (b) is less than 0.01 part by weight, the amount of the functional group is insufficient, and when it exceeds 10.0 parts by weight, the unreacted functionalized compound (b) in the functionalized polyphenylene ether Remains in a large amount and causes silver streaks at the time of molding.

In the present invention, the reaction temperature for reacting the polyphenylene ether (a-1) with the functionalized compound (b) is a temperature not lower than room temperature and not higher than the melting point of (a-1). When the reaction temperature is lower than room temperature, the polyphenylene ether (a-1) does not sufficiently react with the functionalized compound (b).
Here, room temperature is 27 ° C. In the present invention, crystalline polyphenylene ether having a melting point is used as the raw material polyphenylene ether (a-1).

References showing the relationship between crystalline polyphenylene ether and its melting point include, for example, Journal.
of Polymer Science, Part
A-2 (6) 1141-1148 (1968), E
european Polymer Journal
(9) pp. 293-300 (1973), Polyme
r (19) 81-84 (1978). In the present invention, the melting point of the polyphenylene ether (a-1) is determined by using a differential scanning calorimeter (DSC) for (a-1).
Is defined as the peak-top temperature of the peak observed in the temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min, and when there are a plurality of peak-top temperatures, the peak temperature is the highest temperature. Defined.

The polyphenylene ether of the present invention (a-
1) is a powdery substance obtained by precipitation from a solution, and is preferably a polyphenylene ether having a melting point of 240 ° C to 260 ° C. Further, this powder has a heat of fusion (ΔH) obtained from a peak in DSC measurement of 2 J /
g or more. In the present invention, when the reaction temperature exceeds the melting point of the polyphenylene ether (a-1), the polyphenylene ether (a-1) melts and the viscosity increases, so that mixing with the functionalized compound (b) is inhibited, Does not accelerate the reaction. At this time, if the polyphenylene ether (a-1) and the functionalized compound (b) are strongly kneaded to promote the reaction, the color tone and appearance of the polyphenylene ether (a-1) deteriorate due to heat generation during kneading.

In the present invention, the reaction temperature is 100 to 23.
0 ° C., and the reaction temperature is 15 ° C.
It is very preferable that the temperature is in the range of 0 to 220 ° C. The reaction of the polyphenylene ether (a-1) of the present invention with the functionalized compound (b) is preferably produced using a paddle dryer as a reactor. By using a paddle dryer in which the jacket temperature is set to a desired temperature, efficient production can be achieved.

The polyphenylene ether of the present invention (a-
More preferably, the reaction between 1) and the functionalized compound (b) is produced using a Henschel mixer as a reactor.
When a Henschel mixer is used, the polyphenylene ether (a-1) and the functionalized compound (b) can be efficiently mixed and heated by shear heat generation, and the functionalized polyphenylene ether (a-2) of the present invention can be efficiently used. Can be manufactured. However, the reaction method of the polyphenylene ether (a-1) of the present invention with the functionalized compound (b) is not particularly limited.

Further, the functionalized polyphenylene ether of the present invention can be produced by adding a reaction aid.
The functionalized polyphenylene ether of the present invention is preferably a radical initiator as a reaction assistant. The non-functional polyphenylene ether used together with the functionalized polyphenylene ether (a-2) as the polyphenylene ether resin (A) of the present invention may be either crystalline or non-crystalline polyphenylene ether. For example, any of polyphenylene ether alone or melt-kneaded with polysterene, and those obtained by grafting an unsaturated compound can be used.

The polystyrene as the component (B) is a homopolymer of styrene, and the rubber-modified polystyrene is a graft copolymer of a rubbery polymer and styrene. Further, as the rubber used for the rubber-modified polystyrene, polybutadiene, styrene-butadiene copolymer, polyisoprene,
Butadiene-isoprene copolymer, natural rubber, ethylene-propylene copolymer and the like can be mentioned. Particularly, polybutadiene and styrene-butadiene copolymer are preferable.

The styrene-acrylonitrile copolymer of the component (C) used in the present invention is acrylonitrile (AN)
It is preferable that the composition contains 7 to 11% by weight, preferably 8 to 10% by weight, more preferably 8.5 to 9.5% by weight, and a melt flow rate of 5 to 100 g / 10 minutes. Further, the composition distribution of the copolymer is preferably narrow,
The styrene-acrylonitrile copolymer having an N content of 7% by weight or more and less than 11% by weight is preferably 60% by weight or more, more preferably 70% by weight or more. The composition distribution of the copolymer can be measured by liquid chromatography.

A three-component melt mixture of the copolymer containing 7 to 11% by weight of an acrylonitrile component, a modified polyphenylene ether resin and polystyrene shows two glass transition points according to dynamic viscoelasticity measurement, Observation of the morphology with a scanning electron microscope confirms the phase separation structure.

The reason why the copolymer preferably has a narrow composition distribution is that when the content of the acrylonitrile component is 7% by weight or less, when it is mixed with polyphenylene ether resin and polystyrene, it is the same as the mixture of polyphenylene ether resin and polystyrene. It exhibits the same viscoelastic behavior and balance between fluidity and heat resistance. If the content of the acrylonitrile component is 11% by weight or more, the compatibility is poor, so the glass transition temperature close to that of the styrene-acrylonitrile copolymer alone and the glass transition temperature of the mixture of polyphenylene ether resin and polystyrene are shown. This is because delamination is likely to occur and the practical value tends to decrease, and mechanical properties also tend to decrease.

The styrene-acrylonitrile copolymer preferably has a melt flow rate of 5 to 100 g / 10 minutes, more preferably 30 to 80 g / 1.
0 minutes, and a more preferred range is 40 to 60 g / 10 minutes. The higher the melt flow rate of the styrene-acrylonitrile copolymer, the better the fluidity of the composition.
If it is 0 g / 10 min or more, the mechanical strength of the composition is inferior, which is not preferable.

The mixing ratio of each of the components (A), (B) and (C) is as follows: (A) 30 to 95% by weight of polyphenylene ether resin, (B) 2 to 60% by weight of polystyrene and / or rubber-modified polystyrene, Component (C) is preferably in the range of 3 to 40% by weight of the styrene-acrylonitrile copolymer. More preferably, 40 to 80% by weight of the component (A),
The range is from 3 to 50% by weight of the component (B) and from 10 to 35% by weight of the component (C).

In this case, if the content of the polyphenylene ether resin is 30% by weight or less, the heat resistance is low and the characteristics of the composition of the present invention are not exhibited. When the polystyrene or rubber-modified polystyrene content is 60% by weight or more, the heat resistance is similarly low and the characteristics of the composition of the present invention are not exhibited. The styrene-acrylonitrile copolymer may be blended within a range to obtain a desired fluidity, but if it is 40% by weight or more, the heat resistance is greatly reduced, and if it is less than 3% by weight, the effect of improving the fluidity and heat resistance is reduced. Is not preferred.

The component (D) phosphate compound used in the present invention refers to all phosphate ester flame retardants. For example, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, toxhexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, Phosphoric acid esters such as dimethylethyl phosphate, methyldibutylphosphate, ethyldipropylphosphate, hydroxyphenyldiphenylphosphate, compounds modified with these various substituents, and various condensed type phosphoric acid ester compounds. Ester compounds are preferred.

Of these, phosphate compounds represented by the following (formula 3) are particularly preferred.

Embedded image

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms or hydrogen;
8, R9 and R10 represent a methyl group or hydrogen. n is an integer of 1 or more, n1 and n2 are integers of 0 to 2,
m1, m2, m3, and m4 each represent an integer of 1 to 3. )
It is represented by Q1, Q2, Q3, Q4 in (Equation 3)
Among them, hydrogen and a methyl group are particularly preferred.
In formula (3), R7 and R8 are preferably hydrogen, and R9 and R10 are preferably a methyl group. N in (Equation 3) is an integer of 1 or more, and heat resistance and workability vary depending on the number. The preferred range of n is 1 to
5 Further, the phosphoric ester may be a mixture of n-mers.

A preferred phosphoric ester compound as the component (D) has a bonding structure by "specific bifunctional phenol" and a terminal structure by "specific monofunctional phenol". Examples of the “specific bifunctional phenol” include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane, and bis (4-hydroxy Bisphenols such as phenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane;
It is not limited to this. Particularly, bisphenol A is preferable.

As the "specific monofunctional phenol", unsubstituted phenol, monoalkylphenol, dialkylphenol, and trialkylphenol can be used alone or as a mixture of two or more. Especially phenol, cresol, dimethylphenol (mixed xylenol),
2,6-dimethylphenol and trimethylphenol are preferred. These phosphorus compounds can be used alone or in combination of two or more.

The amount of component (D) is from 1 to 30 parts by weight based on 100 parts by weight of the total of components (A), (B) and (C).
Parts by weight, more preferably 2 to 20 parts by weight,
Most preferably, it is 5 to 15 parts by weight. If it is less than 1% by weight, the flame-retardant effect is insufficient, and if it is more than 30% by weight, heat resistance and mechanical properties are impaired, which is economically disadvantageous and not preferable. In addition, other flame retardants other than the phosphoric ester compound, furthermore, polytetrafluoroethylene as a dripping inhibitor, silicone resin, phenol resin, glass fiber,
It is also effective to use a combination of carbon fibers and the like.

The composition of the present invention is further blended with an inorganic filler such as glass fiber, glass flake, kaolin clay, talc and the like as the component (E) and other fibrous reinforcing agents.
A high-strength composite having excellent fluidity and heat resistance can be obtained. The amount of the component (E) is 1 to 100 with respect to 100 parts by weight of the total of the components (A), (B) and (C).
It is preferably 5 parts by weight, more preferably 5 to 80 parts by weight.

In the present invention, when all the unfunctionalized polyphenylene ether is used as the component (A) without using the functionalized polyphenylene ether (a-2), when the molding conditions are extremely changed, the heat deformation temperature ( Although physical properties such as HDT) and impact strength may fluctuate, the use of a functionalized polyphenylene ether is extremely useful because physical property fluctuations due to molding conditions can be suppressed. Furthermore, by using a functionalized polyphenylene ether produced by reacting at a reaction temperature from room temperature or higher to the melting point of polyphenylene ether or lower as a functionalized polyphenylene ether, not only the variation in physical properties due to molding conditions can be further suppressed, but also A resin composition having more excellent color tone and mechanical properties, especially impact resistance, than the above composition can be obtained. Compared with the conventional production method, that is, the resin composition of the present invention using the functionalized polyphenylene ether obtained by the novel production method of the present application, compared with the prior art resin composition using the functionalized polyphenylene ether obtained by the melt reaction extrusion method Since the object has a good color tone, coloring of the material is easy and coloring cost can be reduced.

The amount of the functionalized compound occupying in the resin composition of the present invention is usually about 10% based on the total polyphenylene ether resin.
When it is 0% by weight, it is preferably at least 0.01% by weight, preferably at least 0.03% by weight. If the amount of the unit is less than 0.01% by weight, it is not preferable because the adhesion to the inorganic filler when the inorganic filler is used becomes insufficient. 0.0
Addition of 3% by weight or more is more preferable because the effect of suppressing the variation in physical properties due to molding conditions is sufficiently exhibited. In order to stabilize the physical properties by using the functionalized polyphenylene ether, it is preferable that all components are melt-kneaded and adjusted at a temperature of 280 ° C. or more. This is because by melt-kneading at a high temperature, the effect can be exhibited with a smaller amount of the functionalized compound.

In the resin composition of the present invention, a styrene-based thermoplastic elastomer such as a styrene-butadiene block copolymer, a styrene-isoprene block copolymer, and a hydrogenated elastomer thereof may be used as an impact modifier. it can. The resin composition of the present invention further imparts other properties, or other additives within a range that does not impair the effects of the present invention, for example, a plasticizer, an antioxidant, and a stabilizer such as an ultraviolet absorber, Antistatic agents, release agents, dyes and pigments, or other resins can be added.

The method for producing the composition of the present invention is not particularly limited, and the composition can be kneaded and manufactured using a kneader such as an extruder, a heating roll, a kneader, and a Banbury mixer. Among them, kneading with an extruder is preferable in terms of productivity. The kneading temperature is in the range of 250 to 360 ° C,
Preferably it is the range of 280-340 degreeC. The order of kneading may be to knead all the components at once, but (A)
After the components (B) and (C) are kneaded in advance, the components (D) and (E) or other components can be fed from the middle of the extruder and kneaded.

[0046]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
The physical properties of the obtained resin composition were evaluated by the following methods and conditions.

(1) Molding fluidity SSP: Minimum molding pressure required for completely filling a molded piece having a thickness of 1.6 mm, a width of 12.7 mm and a length of 127 mm in the flow direction by injection molding. (Hereafter, SSP
Abbreviated. ) Was measured and used as a measure of molding fluidity. SSP
It means that the lower the value is, the more excellent the molding fluidity is. (2) Thermal deformation temperature Measured under a load of 1.82 MPa based on ASTM D648, and used as a measure of heat resistance.

(3) Flexural strength Measured according to ASTM D790. (4) Izod impact strength Measured at a temperature of 23 ° C and a notch based on ASTM D256. (5) Flame retardancy Based on the UL-94 vertical combustion test, the flame retardancy was measured using a 1/8 inch thick injection molded test piece. (6) Drop Weight Impact Strength Using a flat molded piece of 50 mm × 90 mm × 2.5 mm in thickness, the total absorbed energy value (J: joule) was measured by a graphic impact tester manufactured by Toyo Seiki Seisaku-sho, Ltd.

The following components were used in Examples and Comparative Examples. (1) Styrene-acrylonitrile copolymer (AS-1
Production of -3) acrylonitrile 4.7 parts by weight, styrene 73.3
A mixed solution consisting of 2 parts by weight, 22 parts by weight of ethylbenzene and 0.02 part by weight of t-butyl peroxy-isopropyl carbonate as a polymerization initiator is continuously fed into a 5 liter volume complete mixing reactor at a flow rate of 2.5 liters per hour. The polymerization was carried out at 142 ° C. until the conversion reached 60%. The polymerization liquid is continuously guided to a vented extruder,
The unreacted monomer and the solvent were removed under the conditions of 260 ° C. and 40 Torr, and the polymer was continuously cooled and solidified, cut into fine particles, and a particulate styrene-acrylonitrile copolymer (AS
-1). As a result of composition analysis of this copolymer by an infrared absorption spectroscopy method, it was found that acrylonitrile unit was 9% by weight and styrene unit was 91% by weight, and the melt flow rate was 90 g / 10 minutes (ASTM D-1238).
Compliant, measured at 220 ° C. with a load of 10 kg). This copolymer is designated as AS-1.

Similarly, styrene-acrylonitrile copolymers (AS-2 and 3) having different copolymer compositions and melt flow rates were produced by changing the monomer composition and the polymerization temperature. Table 1 shows the properties of AS-1 to AS-3. The distribution of the AN content in the AS resin was measured by high performance liquid chromatography under the following conditions.

Equipment: Simazu LC-64 ser
ies column: Simpack CLC-CN (4.6 × 25
0 mm) Column temperature: 40 ° C. Flow rate: 1 ml / min Detector: UV detector (254 nm) Mobile phase: Starting with THF / n-heptane = 20/80, and set to 100/0 after 20 minutes.

[0052]

[Table 1]

(2) Polyphenylene ether (a-1) The melting point of polyphenylene ether is measured by a differential scanning calorimeter (DSC), and a temperature-heat flow graph obtained when the temperature is increased at 20 ° C./min. Is the melting point. PPE-1: poly 2,6-dimethyl-1,4-phenylene ether having a reduced viscosity ηsp / c measured in chloroform at 30 ° C. of 0.53 dl / g. The DSC temperature-heat flow graph shows a single peak with a melting point of 250
° C. PPE-2: poly 2,6-dimethyl-1,4-phenylene ether having a reduced viscosity ηsp / c measured at 30 ° C. in chloroform of 0.43 dl / g. The DSC measurement temperature-heat flow graph shows a single peak with a melting point of 249.
° C.

(3) Functionalized polyphenylene ether (a
-2) PPE-3: polyphenylene ether (PPE-2) 1
50 kg and 2 kg of maleic anhydride as a functional compound,
The inside of a jacket-heatable FM500 type Henschel mixer manufactured by Mitsui Mining Co., Ltd. is purged with nitrogen. The stirring blade is rotated at high speed, and the contents are heated to 200 ° C by shearing heat.
Heat for 0 minutes. After the jacket temperature reaches 200 ° C., the high-speed rotation is continued for 5 minutes, and then the jacket is cooled by flowing cold water through the jacket.

Fifty grams of the contents were collected and 100 m
Wash with 1 l of acetone and filter off using a glass filter. This operation is repeated five times to obtain the washed product 1 and the filtrate 1. As a result of gas chromatogram analysis of the filtrate 1, the amount of maleic anhydride was 0.25 g. A 20 g portion of the dried product 1 from the dried product 1 was washed with 40 ml of acetone, purified, and filtered using a glass filter. This operation is repeated five times to obtain the washed product 2 and the filtrate 2. As a result of gas chromatogram analysis of the filtrate 2, maleic anhydride was not contained.

A film (film-b) was sandwiched between 1 g of the dried product-1 by placing a polytetrafluoroethylene sheet, an aluminum sheet, and an iron plate in this order from the inside, using a press molding machine set to a temperature of 280 ° C. Obtained. By the same operation, a film (film-a) was obtained from polyphenylene ether (PPE-1). Each of the obtained films was subjected to infrared spectroscopy using a FT / IR-420 type Fourier transform infrared spectrophotometer manufactured by JASCO Corporation. In the measurement for (film-b), 17 was obtained.
At 90 cm ^-1 , a peak derived from maleic anhydride added to polyphenylene ether was observed.

The functionalized polyphenylene ether was converted to PPE
-3. PPE-4: Functionalized polyphenylene ether PPE-3
In the same procedure as described above, except that the functionalized compound was changed to maleic anhydride and changed to fumaric acid, the same operation was performed to obtain a functionalized polyphenylene ether PPE-4. In the infrared spectroscopic measurement, a peak derived from fumaric acid added to polyphenylene ether was observed at 1788 cm ^-1 . PPE-4 the functionalized polyphenylene ether. PPE-5: For comparison, a functionalized polyphenylene ether was prepared by the following melt-kneading method.

100 parts by weight of PPE-2, 2 parts by weight of maleic anhydride and 0.3 parts by weight of dichlor peroxide were mixed and melt-kneaded at a set temperature of 320 ° C. using an extruder. Ether was obtained. In infrared spectroscopy, a peak derived from maleic anhydride added to polyphenylene ether was observed at 1790 cm ^-1 . Converting the functionalized polyphenylene ether to PPE
-5.

(4) Polystyrene PS-1: Asahi Kasei Kogyo Co., Ltd. homopolystyrene, Asahi Kasei Polystyrene 685. PS-2: Asahi Kasei Kogyo Co., Ltd. homopolystyrene, Asahi Kasei polystyrene 680. PS-3: rubber reinforced polystyrene manufactured by Asahi Kasei Corporation,
Asahi Kasei polystyrene 403.

(5) Phosphate ester FR-1: a mixture of n = 1 to 3 represented by (formula 4).

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FR-2: Compound represented by the formula (5)

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(6) Glass fiber GF: Chopped strand having a fiber length of 3 mm and having an aminosilane surface treatment. (7) Mica: Szolite mica 200K1 (manufactured by Kuraray) with aminosilane treatment.

[0063]

EXAMPLES AND COMPARATIVE EXAMPLES With the compounding compositions shown in Tables 2 to 6, the mixture was fed to a twin-screw extruder in which the maximum temperature of a heating cylinder was set at 320 ° C. and melt-kneaded to obtain composition pellets. Injection molding was performed using the pellets, and evaluation of molding fluidity and physical properties were performed using the obtained molded pieces. The results are shown in Tables 2 to 6.

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

[Table 4]

[0067]

[Table 5]

[0068]

[Table 6]

[0069]

The polyphenylene ether resin composition of the present invention provides a material which is excellent in balance between fluidity, heat resistance, mechanical properties, color tone and the like, and excellent in stability under molding conditions.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 25/06 C08L 25/06 25/12 25/12 51/04 51/04 F-term (Reference) 4F071 AA22 AA22X AA34X AA51 AA77 AA84 AA88 AB25 AB26 AB28 AE17 AH19 BA01 BB06 4J002 BC03Y BC04Y BC06Y BN14Y CH07W CH07X DJ037 DJ047 DL007 EW046 FA017 FA047 GC00 4J005 AA26 BD00 BD05

Claims (14)

[Claims] (A) polyphenylene ether resin 30
-95% by weight, (B) 2-60% by weight of polystyrene and / or rubber-modified polystyrene, and (C) a styrene containing from 7 to less than 11% by weight of an acrylonitrile component.
The acrylonitrile copolymer is composed of 3 to 40% by weight, and (A) the polyphenylene ether resin is represented by the following (formula 1)
(A-1) comprising a structural unit of
At least one functionalized compound (b) having at least one carbon-carbon double bond or triple bond and at least one carboxyl group, acyl oxide group, or imide group in a molecular structure with respect to 100 parts by weight. Functionalized polyphenylene ether (a) prepared by reacting a mixture containing 0.011 to 10.0 parts by weight at a reaction temperature from room temperature to the melting point of polyphenylene ether (a-1).
A polyphenylene ether resin composition characterized in that part or all of -2) is used. Embedded image [R1 and R4 are each independently hydrogen, halogen,
Represents a primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate a halogen atom from an oxygen atom; R2,
R3 is each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that
At least two carbon atoms separating a halogen atom and an oxygen atom). ] 2. The polyphenylene ether (a-1) is
The polyphenylene according to claim 1, wherein the powder contains a functionalized polyphenylene ether (a-2) obtained by using a polyphenylene ether having a melting point of 240 ° C. to 260 ° C. obtained by precipitation from a solution. Ether resin composition. 3. The reaction temperature with the functionalized compound (b) is 10
The functionalized polyphenylene ether (a-2) produced at 0 to 230 ° C is contained.
3. The polyphenylene ether resin composition according to item 1. 4. The reaction temperature with the functionalized compound (b) is 15
The polyphenylene ether resin composition according to any one of claims 1 to 3, comprising a functionalized polyphenylene ether (a-2) produced in the range of 0 to 220 ° C. 5. The polyphenylene ether resin composition according to claim 1, comprising a functionalized polyphenylene ether (a-2) produced using a paddle dryer. 6. The polyphenylene ether resin composition according to claim 1, comprising a functionalized polyphenylene ether (a-2) produced using a Henschel mixer. 7. The method according to claim 1, wherein the styrene-acrylonitrile copolymer (C) has a melt flow rate (220 ° C., under a load of 10 kg) of 5 to 100 g / 10 minutes. The polyphenylene ether resin composition according to the above. 8. The method according to claim 1, wherein (A) and (B)
A polyphenylene ether resin composition, further comprising 1 to 30 parts by weight of a phosphoric ester compound (D) based on 100 parts by weight of the total amount of (C) and (C). 9. The polyphenylene ether resin composition according to claim 8, wherein the phosphate compound (D) is a condensed phosphate ester. 10. The method according to claim 1, wherein (A)
A polyphenylene ether resin composition, further comprising 1 to 100 parts by weight of an inorganic filler (E) based on 100 parts by weight of the total amount of (B) and (C). 11. The method according to claim 1, wherein (A)
(B) and (C) in a total amount of 100 parts by weight, further comprising 1 to 30 parts by weight of a phosphate compound (D) and 1 to 100 parts by weight of an inorganic filler (E). Characteristic polyphenylene ether resin composition. 12. A molded article comprising the polyphenylene ether resin composition according to claim 8. 13. A molded article comprising the polyphenylene ether resin composition according to claim 11. 14. A large-sized chassis molded article comprising the polyphenylene ether resin composition according to claim 11.