JP3080752B2 - Thermoplastic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly to a maleic anhydride-modified polyphenylene ether-modified polyphenylene ether modified with maleic anhydride or a derivative thereof (hereinafter referred to as maleic anhydride-modified PPO or modified PPO). The present invention relates to a thermoplastic resin composition containing, as a main component, a styrene-based polymer having a high syndiotactic structure, which has improved long-term heat stability by incorporating the compound.

[0002]

2. Description of the Related Art Conventionally, various thermoplastic resins are mixed with glass fibers and other inorganic fillers to improve the mechanical properties, particularly rigidity and heat resistance. Was taken. For example, JP-A-62-257948 and JP-A-1-1823
No. 44 discloses a resin composition having excellent heat resistance and mechanical properties, in which an inorganic filler is compounded in syndiotactic polystyrene and a thermoplastic resin and / or rubber is mixed in syndiotactic polystyrene. Things have been suggested. However, in these resin compositions, the adhesion between the syndiotactic polystyrene and the inorganic filler was insufficient, and a satisfactory resin composition was not obtained.

For this reason, these improved techniques are disclosed in
-126743. That is, it is proposed that a resin composition having excellent impact resistance, heat resistance and mechanical properties can be obtained by adding maleic anhydride-modified PPO. However, in the case of this improved technique, since the modification ratio of the maleic anhydride-modified PPO is low,
In order to exert a sufficient effect, it was necessary to add the syndiotactic polystyrene in an amount of 5 parts by weight or more. However, when a long-term heat resistance test was performed on the resin composition to which the maleic anhydride-modified PPO was added, the decrease in the molecular weight of syndiotactic polystyrene increased with an increase in the amount of the addition, and the mechanical properties decreased. It has been found that the tendency becomes remarkable when the amount is 5 parts by weight or more. Also, in the case of alloys with polyamides, it is necessary to add a large amount of maleic anhydride-modified PPO in order to exhibit a sufficient compatibilizing effect, and as a result, the crystallinity of syndiotactic polystyrene decreases. However, when a long-term heat test is performed, a decrease in molecular weight cannot be avoided.

In view of the above situation, the present inventors have found that, when a glass fiber or other inorganic filler is mixed with a styrenic polymer having a high syndiotactic structure, its mechanical properties, particularly rigidity, long-term heat resistance, etc. Intensive research was conducted to develop a thermoplastic resin composition excellent in the above. As a result, they have found that the above object can be achieved only by blending a small amount of maleic anhydride-modified PPO, particularly a maleic anhydride-modified PPO with an increased modification rate. The present invention has been completed based on such findings.

[0005]

That is, the present invention provides:
(A) 100 parts by weight of a styrenic polymer having a high syndiotactic structure, (B) 1 to 350 parts by weight of an inorganic filler, and (C) 0.1 to 3.5 parts by weight of maleic anhydride-modified polyphenylene ether. The present invention provides a thermoplastic resin composition comprising: Further, the present invention provides (A) 100 parts by weight of a styrene-based polymer having a high syndiotactic structure, (B) 1 to 350 parts by weight of an inorganic filler, (D) 5 to 100 parts by weight of a rubbery elastic material, (C) A thermoplastic resin composition comprising 0.1 to 3.5 parts by weight of maleic anhydride-modified polyphenylene ether is also provided.

First, the thermoplastic resin composition of the present invention comprises:
As the component (A), a styrene polymer having a high syndiotactic structure is used. Here, the high syndiotactic structure in the styrene-based polymer is a syndiotactic structure having a high stereochemical structure, i.e., a phenyl group or a side chain that is a side chain with respect to a main chain formed from carbon-carbon bonds. It means that the phenyl group has a steric structure alternately located in the opposite direction, and its tacticity is determined by nuclear magnetic resonance ( ¹³ C-NMR) using isotope carbon.
Quantified by ^The tacticity measured by the ¹³ C-NMR method can be represented by the proportion of a plurality of continuous constituent units, for example, a dyad for two, a triad for three, and a pentad for five. . The “styrene polymer having a high degree of syndiotactic structure” referred to in the present invention is usually 75% or more, preferably 85% or more in racemic diad, or 30% or more, preferably 50% in racemic pentad. Polystyrene, poly (alkylstyrene), poly (halogenated styrene), which have the above syndiotacticity,
Poly (halogenated alkyl styrene), poly (alkoxy styrene), poly (vinyl benzoate), hydrogenated polymers thereof and mixtures thereof, or copolymers containing these as main components. Here, poly (alkylstyrene) includes poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary butylstyrene), poly (phenylstyrene), poly (vinylstyrene), Poly (vinyl naphthalene) and the like, and poly (halogenated styrene) include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene) and the like. Examples of poly (halogenated alkylstyrene) include poly (chloromethylstyrene), and examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, particularly preferred styrene polymers include polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene),
Copolymers containing these structural units, such as poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), hydrogenated polystyrene and copolymers of styrene and p-methylstyrene Polymers.

The molecular weight of the styrenic polymer having a high syndiotactic structure is not particularly limited, but is generally 10,000 or more, preferably 50,000 or more. Further, the molecular weight distribution is not limited to a wide or narrow range, and various types can be applied. Here, if the weight average molecular weight is less than 10,000, the thermal and mechanical properties of the obtained composition or molded product are undesirably reduced. Styrene-based polymer having such a high syndiotactic structure, for example,
It can be manufactured with reference to the technology disclosed in Japanese Patent Application Laid-Open No. 62-187708. That is, in an inert hydrocarbon solvent or in the absence of a solvent, a styrene-based monomer (a monomer corresponding to the above-mentioned styrene-based weight body) is used as a catalyst with a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst. Can be produced by polymerizing For poly (halogenated alkylstyrene), refer to JP-A-1-46912, and for these hydrogenated polymers, refer to JP-A-1-17850.
No. 5 can be produced by the methods described in each of the publications.

Next, the inorganic filler as the component (B) constituting the thermoplastic resin composition of the present invention may be of various types or forms such as fibrous, granular or powdery. it can. Among them, examples of the fibrous filler include glass fiber, carbon fiber, and whisker. Examples of the shape include a cloth, a mat, a cut bundle, a short fiber, a filament, and a whisker. In the case of a bundle cut shape, one having a length of 0.05 to 50 mm and a fiber diameter of 5 to 20 μm is preferably used. On the other hand, examples of the granular or powdery filler include talc, carbon black, graphite, titanium dioxide, silica, mica, calcium carbonate, calcium sulfate, barium carbonate, magnesium carbonate, magnesium sulfate, magnesium sulfate, barium sulfate, and oxy. Examples include sulfate, tin oxide, alumina, kaolin, silicon carbide, metal powder, glass powder, glass flake, and glass beads. These inorganic fillers can be used alone or in combination of two or more.

[0009] Among the various inorganic fillers as described above, glass fillers, for example, glass powder, glass flakes, glass beads, glass filaments, glass fibers, glass lobing, and glass mats are preferably used. Further, these inorganic fillers are effective when subjected to a surface treatment in order to increase the affinity with the resin. The coupling agent used for the assertion treatment is arbitrarily selected from conventionally known ones such as silane coupling agents such as aminosilane, epoxysilane, vinylsilane and methacrylsilane, and titanium coupling agents. Can be used. Among these, γ
-Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, β-
Aminosilanes such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, epoxysilane, isopropyltri (N-amidoethyl, aminoethyl) titanate and the like are preferably used. In addition, what is necessary is just to process using a well-known method as a surface treatment method of an inorganic filler,
There is no particular limitation.

Next, maleic anhydride-modified PPO as a component (C) which constitutes the thermoplastic resin composition of the present invention and is effective for improving long-term heat resistance is polyphenylene ether (hereinafter referred to as PPO). Is modified with maleic anhydride or a derivative thereof to obtain a modified polyphenylene ether having a desired modification ratio. The PPO used in the maleic anhydride-modified PPO is a known compound, and for this purpose, US Pat.
No. 6,874, No. 3,306,875, No. 3,257,35
7 and 3,257,358 can be referred to. PPO is usually in the presence of one or more of a copper amine complex, one to three substituted phenols,
It is prepared by an oxidative coupling reaction that produces a homopolymer or copolymer. Here, as the copper amine complex, a copper amine complex derived from primary, secondary and / or tertiary amines can be used. Also, PPO
Specifically, for example, poly (2,3-dimethyl-6-ethyl-1,4-phenylene ether), poly (2
-Methyl-6-chloromethyl-1,4-phenylene ether), poly (2-methyl-6-hydroxyethyl-1,4)
-Phenylene ether), poly (2-methyl-6-n-)
Butyl-1,4-phenylene ether), poly (2-ethyl-6-isopropyl-1,4-phenylene ether),
Poly (2-ethyl-6-n-propyl-1,4-phenylene ether), poly (2,3,6-trimethyl-1,4-phenylene ether), poly [2- (4'-methylphenyl)- 1,4-phenylene ether], poly (2-phenyl-1,4-phenylene ether), poly (2-chloro-
1,4-phenylene ether), poly (2-methyl-1,4
-Phenylene ether), poly (2-chloro-6-ethyl-1,4-phenylene ether), poly (2-chloro-
6-bromo-1,4-phenylene ether), poly (2,
6-di-n-propyl-1,4-phenylene ether),
Poly (2-methyl-6-isopropyl-1,4-phenylene ether), poly (2-chloro-6-methyl-1,4-
Phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2,6-dibromo-1,4-phenylene ether), poly (2,6-dichloro-1,4- Phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), poly (2,6-
Dimethyl-1,4-phenylene ether). Also suitable are copolymers, such as, for example, copolymers derived from two or more of the phenolic compounds used in the preparation of the homopolymers. Further, for example, a graft copolymer and a block copolymer of a vinyl aromatic compound such as polystyrene and the above-mentioned polyphenylene ether can be mentioned. Among them, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferably used. The degree of polymerization of these PPOs is not particularly limited, and may be appropriately selected according to the purpose of use. Usually, it is selected from the range of 60 to 400. If the degree of polymerization is less than 60, the compatibilizing agent,
The effect as an adhesive is small. Conversely, if it exceeds 400, the viscosity becomes high and handling becomes inconvenient.

From these PPO, maleic anhydride-modified P
In order to obtain PO, it may be modified by reacting PPO with maleic anhydride or a derivative thereof in the presence or absence of a solvent or another resin in the presence or absence of a radical generator. That is, the denaturation is known to be solution denaturation or melt denaturation. As a modifying agent used to modify maleic anhydride-modified PPO from PPO, maleic anhydride or a derivative thereof is used. Here, the maleic anhydride derivative is a compound having an ethylenic double bond and a polar group such as a carboxyl group or an acid anhydride group in the same molecule. Specifically, for example, maleic acid, maleic acid monoester, maleic diester, maleimide and N-substituted products thereof (for example, N-substituted maleimide, maleic monoamide, maleic diamide, etc.), ammonium salt of maleic acid, and maleic acid Metal salts, acrylic acid, methacrylic acid, methacrylic acid esters, glycidyl methacrylate and the like can be mentioned. Among these, maleic anhydride is particularly preferably used.

[0012] Among the denaturation of PPO with maleic anhydride or a derivative thereof, the solution denaturation is carried out in the presence or absence of an aromatic hydrocarbon solvent or another resin by combining PPO with maleic anhydride or a derivative thereof as a radical generator. By reacting in the presence or absence of the compound, a maleic anhydride-modified PPO can be obtained. Here, the aromatic hydrocarbon solvent is not particularly limited as long as it dissolves the above-mentioned PPO, maleic anhydride or a derivative thereof and a radical generator and is inert to generated radicals. . Specifically, for example, benzene, toluene, ethylbenzene, xylene, chlorobenzene, t-butylbenzene and the like can be mentioned as preferable ones. Among them, benzene, toluene, chlorobenzene, and t-butylbenzene having particularly small chain transfer constants are particularly preferable. These may be used alone or in combination. Then, the usage ratio of these aromatic hydrocarbon solvents is not particularly limited, and may be appropriately selected depending on various situations.
Generally 1 to 20 times (weight ratio) of PPO used
It may be determined within the range. If it is too small, it will not function sufficiently as a solvent, and if it is too large, the efficiency of the radical generator will decrease, which is not preferable. The proportion of maleic anhydride or a derivative thereof used as a modifier is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the PPO. If the amount is less than 1 part by weight, the modification rate is insufficiently improved, and if it exceeds 20 parts by weight, sufficient purification is required to remove excess maleic anhydride, which makes the operation complicated and economically disadvantageous. It is.

The radical generator used for the solution denaturation of PPO with maleic anhydride or a derivative thereof includes:
Although the type is not particularly limited, a material having a large hydrogen extraction ability is preferable because it has a decomposition temperature suitable for the reaction temperature and effectively grafts maleic anhydride or a derivative thereof to PPO. Specifically, for example, di-t-butyl peroxide; dicumyl peroxide; 1,1-bis (t-butylperoxy) cyclohexane; 1,1-bis (t-butylperoxy) 3,3,3 Examples include, but are not limited to, 5-trimethylcyclohexane; benzoyl peroxide; decanoyl peroxide. And the usage ratio of this radical generator is
It should not exceed 15 parts by weight per 100 parts by weight of PPO. If the amount of the radical generator exceeds 15 parts by weight, insoluble components may be generated, which is not preferable. If the above modification is performed in the absence of a radical generator, only a modified PPO having a low modification rate (for example, 0.3 to 0.5% by weight) can be obtained.

There are various procedures for modifying PPO. Specifically, in the solution denaturation, for example, when PPO and maleic anhydride or a derivative thereof are dissolved in an aromatic hydrocarbon solvent to be uniform, and when a radical generator is used, the radical generator is reduced by half. The radical generator is added at an arbitrary temperature at which the period becomes 1 hour or less, and the reaction is carried out at that temperature. A temperature at which the half-life of the radical generator used exceeds 1 hour is not preferred because a long reaction time is required. The reaction time is appropriately selected, but in order to make the radical generator act effectively, it is preferable to carry out a time denaturing reaction at a predetermined reaction temperature for a time equal to or more than three times the half-life of the radical generator. After completion of the reaction, the reaction solution is added to a poor solvent for PPO such as methanol, and the precipitated modified PPO is recovered and dried to obtain the desired modified PPO. Here, ordinary means may be used for drying.

On the other hand, for the melt modification, the types of PPO and maleic anhydride or derivatives thereof are the same as described above, and PPO and maleic anhydride or derivatives thereof are converted in the presence or absence of a radical generator. It can be produced by melt-kneading using an extruder. Here, the usage ratio of maleic anhydride or a derivative thereof is 1 to 5 parts by weight, preferably 2 to 4 parts by weight based on 100 parts by weight of PPO. If the amount is less than 1 part by weight, the modification rate is insufficiently improved. If the amount exceeds 5 parts by weight, the efficiency of maleic anhydride or a derivative thereof is poor, and the amount of maleic anhydride or the like remaining in the pellets is undesirably increased. .
Further, the radical generator used in the melt modification,
It has a half-life of 1 minute and a temperature of 300 ° C. or higher.
When the temperature showing a half-life of 1 minute is less than 300 ° C., such as a peroxide or an azo compound, the modifying effect of PPO is not sufficient. There are various types of such radical generators. Specifically, for example, 2,3-dimethyl-2,3-diphenylbutane; 2,3-diethyl-2,
3-diphenylbutane; 2,3-diethyl-2,3-diphenylhexane; 2,3-dimethyl-2,3-di (p
-Methylphenyl) butane and the like. Among these, 2,3- at which the temperature showing a half-life of 1 minute is 330 ° C.
Dimethyl-2,3-diphenylbutane is most preferably used. The usage ratio of this radical generator is P
0.1 to 3 parts by weight, preferably 100 parts by weight of PO
It is selected in the range of 0.5 to 2 parts by weight. If the amount is less than 0.1 part by weight, the modifying effect is small, and if it exceeds 3 parts by weight, the efficiency of the radical generator for modification is poor, and insoluble components may be generated, which is not preferable.

In this melt modification, there are various procedures for modifying the PPO. Specifically, for example, the aforementioned P
PO, maleic anhydride or its derivative and a radical generator are uniformly dry-blended at room temperature, and substantially PP
The melting reaction is performed in the range of 300 to 350 ° C., which is the kneading temperature of O. If it is less than 300 ° C., the melt viscosity is high, and if it exceeds 350 ° C., PPO is decomposed, which is not preferable. In the case of melt modification, a modification reaction can be generally performed by melt kneading using an extruder. However, the method is not limited to this method, and a known method can be used as long as the method can be performed in a temperature range of 300 to 350 ° C.

Thus, a maleic anhydride-modified PPO can be obtained. In the present invention, the content of maleic anhydride in the maleic anhydride-modified PPO anhydride 1. 3 or wt% or more, particularly 1.3 to 5.0 wt% is optimum. When the modification ratio of the maleic anhydride-modified PPO is less than 1.3% by weight, it is necessary to increase the addition ratio of the maleic anhydride-modified PPO in order to develop sufficient mechanical properties and heat resistance, and to obtain long-term heat resistance. It is not preferable from the viewpoint of improvement and economy. When the modification ratio of the maleic anhydride-modified PPO is 1.3% by weight or more,
The long-term heat stability can be improved only by adding a small amount of the maleic anhydride-modified PPO.

The thermoplastic resin composition of the present invention comprises the above-mentioned components (A) to (C), and the compounding ratio thereof is (A) a styrenic polymer having a high syndiotactic structure. (B) 1 to 350 parts by weight, preferably 5 to 200 parts by weight, and (C) 0.1 to 3.5 parts by weight of maleic anhydride-modified PPO, preferably 0.5 to 100 parts by weight, based on 100 parts by weight. 3.0 parts by weight. Here, if the compounding amount of the inorganic filler is less than 1 part by weight, a sufficient compounding effect as the filler is not recognized. On the other hand, if it exceeds 350 parts by weight, the dispersibility becomes poor and molding becomes difficult, which is not preferable. And maleic anhydride-modified P
If the amount of PO is less than 0.1 part by weight, the effect of improving the mechanical properties and heat resistance is small, and if it exceeds 3.5 parts by weight, the long-term heat stability is unfavorably impaired.

The thermoplastic resin composition of the present invention can be obtained by blending a rubber-like elastic material as a component (D), if necessary, in addition to the components (A), (B) and (C). Further, impact resistance can be imparted. In the present invention, examples of the rubber-like elastic body capable of imparting impact resistance include natural rubber, polybutadiene rubber, polyisoprene, polyisobutylene rubber, neoprene rubber,
Holisulphide rubber, Thiokol rubber, Acrylic rubber,
Urethane rubber, silicone rubber, epichlorohydrin rubber, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, styrene-isoprene block copolymer, ethylene Examples include propylene rubber, ethylene propylene diene rubber, and rubber modified from these. Among them, hydrogenated styrene-butadiene-styrene block copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer and the like are particularly preferably used. The mixing ratio of these rubber-like elastic bodies is
(A) 5 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of the styrene-based polymer having a high syndiotactic structure. Here, if the amount of the rubber-like elastic material is less than 5 parts by weight, the effect of improving the impact resistance is small, and if it exceeds 100 parts by weight, the heat resistance and rigidity are greatly reduced, which is not preferable.

[0020] Incidentally, the thermoplastic resin composition of the present invention, unless impair the object, other thermoplastic resins, more can contain various additives and the like. Here, the mixing ratio of the other thermoplastic resin may be appropriately selected according to the situation, but is preferably 150 parts by weight or less based on 100 parts by weight of PPO. As other thermoplastic resins, for example,
Styrene-based resins, polyolefins, polyamides and the like are listed. Further, as other additives, an antioxidant, a nucleating agent and the like can be blended.

[0021]

Next, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples. Production Example 1 1 kg of PPO and 30 g of maleic anhydride were dry-blended, and the screw rotation speed was 200 using a 30 mm twin screw extruder.
The mixture was melt-kneaded at 300 rpm at a set temperature of rpm. The resin temperature at this time was about 330 ° C. The strand was cooled and pelletized to obtain a maleic anhydride-modified PPO. For the measurement of the denaturation rate, 1 g of the obtained modified PPO was dissolved in chloroform, reprecipitated in methanol, the recovered polymer was subjected to Soxhlet extraction with methanol, dried and dried, and the intensity of carbonyl absorption in infrared (IR) absorption spectrum was measured. And the denaturation rate was determined by titration. Table 1 shows the results.

[0022]

[Table 1]

Production Example 2 As a radical generator, 2,3-dimethyl-2,3-diphenylbutane [NOFMER BC, manufactured by NOF Corporation] was used.
The same procedure as in Production Example 1 was carried out except that 0 g was dry-blended. Table 1 shows the results. Production Example 3 The same operation as in Production Example 2 was carried out except that 20 g of 2,3-dimethyl-2,3-diphenylbutane was dry-blended as a radical generator. Table 1 shows the results.

Comparative Example 1 Syndiotactic polystyrene (SPS, weight average molecular weight 348,000, weight average molecular weight / number average molecular weight 2.6)
4) With respect to 100 parts by weight, 0.5 parts by weight of the maleic anhydride-modified PPO obtained in Production Example 1 and pt-butyl aluminum benzoate as nucleic acid [PTBBA-Al, manufactured by Dainippon Ink and Chemicals, Incorporated. ) 1 part by weight, as antioxidant (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (PE, manufactured by Adeka Argus Co., Ltd.)
P-36] 0.1 part by weight and tetrakis (methylene-3-
(3′5′-t-butyl-4′-hydroxyphenyl)
Propionate [MARK A060 by Adeka Argus]
After adding 0.1 part by weight and dry blending with a Henschel mixer, 43 parts by weight of aminosilane-treated glass fiber (13 μm / 3 mm) as a filler was pelletized by a twin-screw extruder while side-feeding. Using the obtained pellet, injection molding was performed to obtain a tensile test piece.
The tensile strength before and after the long-term heat test was performed using the obtained test piece. Table 2 shows the results. The measurement of the tensile strength was based on the following. Tensile strength: JIS K 7113

[0025] except for changing the addition amount of Comparative Example 2-6 maleic anhydride-modified PPO, the ratio
It carried out similarly to the comparative example 1 . Table 2 shows the results.

[0026]

[Table 2]

According to Table 2, the maleic anhydride-modified PPO was
By compounding in a range of 0.1 to 3.5 parts by weight, the case of no additive <br/> pressure and can improve the mechanical properties as compared, and significantly as compared with the case of adding 5 parts by weight or more It can be seen that the long-term heat resistance has been improved.

Examples 1 to 6 and Comparative Examples 7 and 8 The same procedure as in Comparative Example 1 was carried out except that the maleic anhydride-modified PPO shown in Table 3 was used. Table 3 shows the results.

[0029]

[Table 3]

From Table 3, it can be seen that the use of maleic anhydride-modified PPO having a modification ratio of 1.3% by weight or more is more economical in improving the mechanical properties and is economical. Further, it can be seen that the long-term heat resistance is significantly improved as compared with the case where 5 parts by weight or more is added.

Comparative Example 9 Syndiotactic polystyrene (weight average molecular weight 34
8,000, weight average molecular weight / number average molecular weight 2.64) 10
Hydrotonated styrene-butadiene-styrene block copolymer [Kraton G1 manufactured by Shell Chem. Co.
651, SEBS], 10 parts by weight, maleic anhydride-modified PPO 0.5 part by weight obtained in Production Example 1, aluminum pt-butyl benzoate (PTBBA-Al, manufactured by Dainippon Ink and Chemicals, Inc.) as a nucleic acid 1 part by weight, as antioxidant (2,
6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (PE, manufactured by Adeka Argus Co., Ltd.)
P-36] 0.1 part by weight, tetrakis (methylene-3-
(3 ', 5'-di-tbutyl-4'-hydroxyphenyl) propionate [MARK A06 manufactured by Adeka Argus Co., Ltd.]
O] 0.1 part by weight, dry-blended with a Henschel mixer, and pelletized by a twin-screw extruder while side-feeding 43 parts by weight of an aminosilane-treated glass fiber (13 µm / 3 mm) as an inorganic filler. .
The obtained pellets were subjected to injection molding to obtain tensile test pieces and Izod test pieces. The tensile strength and Izod test before and after the long-term heat test were performed using the obtained test pieces. Table 4 shows the results.

[0032] except for changing the addition amount of Comparative Example 10 to 14 maleic anhydride-modified PPO, the ratio
It carried out similarly to the comparative example 9 . Table 4 shows the results. The measurement of tensile strength and Izod impact strength was based on the following. Tensile strength: JIS K 7113 Impact strength: JIS K 7110

[0033]

[Table 4]

[0034]

[Table 5]

According to Table 4, the maleic anhydride-modified PPO was
By compounding in a range of 0.1 to 3.5 parts by weight, the case of no additive <br/> pressure and can improve the mechanical properties as compared, and significantly as compared with the case of adding 5 parts by weight or more It can be seen that the long-term heat resistance has been improved.

Examples 7 to 12 and Comparative Examples 15 and 16 The same procedure as in Comparative Example 9 was carried out except that the maleic anhydride-modified PPO shown in Table 5 was used. Table 5 shows the results.

[0037]

[Table 6]

[0038]

[Table 7]

From Table 5, it can be seen that the use of maleic anhydride-modified PPO having a modification ratio of 1.3% by weight or more has a greater effect of improving mechanical properties and is economical. Further, it can be seen that the long-term heat resistance is significantly improved as compared with the case where 5 parts by weight or more is added.

[0040]

As described above, according to the present invention, glass fibers and other inorganic fillers are blended in a thermoplastic resin composition containing a styrenic polymer having a high syndiotactic structure as a main component. In that case, its mechanical properties,
In particular, when a maleic anhydride-modified PPO, particularly a modified PPO having a modification ratio of 1.3% by weight or more, is blended to improve rigidity and heat resistance, long-term heat stability can be improved with a small blending amount. Further, by using a rubber-like elastic material together, it is possible to improve not only the long-term heat stability but also the impact resistance. Therefore, the thermoplastic resin composition of the present invention can be used for electric / electronic materials (connectors, printed circuit boards, etc.), industrial structural materials, automobile parts (vehicle-mounted connectors, wheel caps, cylinder head covers, etc.), home appliances, various mechanical parts. It can be suitably used for molding industrial materials such as.

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Claims (3)

(57) [Claims] (A) 100 parts by weight of a styrenic polymer having a high syndiotactic structure, (B) 1 to 350 parts by weight of an inorganic filler, and (C) maleic anhydride-modified polyphenylene ether of 0.1 to 3 parts by weight. Ri Do from .5 parts by weight, the inorganic water
Modification rate of maleic acid-modified polyphenylene ether is 1.3
A thermoplastic resin composition of not less than% by weight . (A) 100 parts by weight of a styrenic polymer having a high syndiotactic structure, (B) 1 to 350 parts by weight of an inorganic filler, (D) 5 to 100 parts by weight of a rubbery elastic material, C) Ri Do from absolute 0.1-3.5 parts by weight maleic acid-modified polyphenylene ether, maleic anhydride-modified
The modification rate of polyphenylene ether is 1.3% by weight or more.
The thermoplastic resin composition that. 3. The inorganic filler is a surface-treated inorganic filler.
The thermoplastic resin composition according to claim 1.