JPH06306225A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in impact resistance, tensile strength, etc., and useful for automotive part items, etc., by including a specific group-modified olefinic resin, an alcoholic hydroxy group-modified polyphenylene ether and an organosilane compound in a specific ratio. CONSTITUTION:The objective composition contains (A) a carboxyl group or an acid anhydride group-modified olefinic resin, (B) an alcoholic hydroxy group- modified polyphenylene ether, (C) 0.05-30 pts.wt., especially preferably 0.1-5 pts.wt. organosilane compound of the formula [R<1> is direct bond or 1-50C aliphatic or aromatic polyvalent hydrocarbon; R<2> and R<3> are H, 1-20C alkyl or aryl; Y is hydrocarbon having polar functional group (e.g. amino or mercapto); (m), (n) and (r) are 1-3] (preferably 3-aminopropyl trimethoxysilane) based on 100 pts.wt. total amount of the component A and the component B. Furthermore, the composition ratio of the component A and the component B is preferably (10:90) to (90:10), especially preferably (30:70) to (70:30).

Description

Detailed Description of the Invention

[0001]

The present invention relates to impact resistance, tensile strength,
The present invention relates to a polyphenylene ether-based thermoplastic resin composition having excellent mechanical properties such as flexural modulus.

[0002]

2. Description of the Related Art Polyphenylene ether (hereinafter referred to as "PP
"E") has excellent heat resistance and is excellent in mechanical strength, electrical characteristics, water resistance, flame retardancy, and the like, and is useful as an industrial material, but it has drawbacks in impact resistance and solvent resistance. Therefore, the range of use of these is limited.

Therefore, attempts have been made to improve this drawback by blending PPE with polyolefin.
Since both of them have poor compatibility, improvement in impact strength and solvent resistance is insufficient. Therefore, by using a modified product having a reactive polar group, the polar groups are reacted with each other,
Attempts have been made to improve the compatibility of the two.

Japanese Patent Laid-Open No. 80252/1992 discloses improvement of impact resistance and solvent resistance by using polyolefin having a carboxyl group and PPE having a hydroxyl group.
However, the balance of mechanical properties needs further improvement.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems and provide a thermoplastic resin composition having an excellent balance of mechanical properties such as impact strength, tensile strength and elastic modulus. And

[0006]

As a result of intensive investigations, the inventors of the present invention have found that the compatibility of the composition of a carboxyl group- or acid anhydride group-modified olefin resin with a hydroxyl group-modified PPE is improved. Therefore, the above object can be achieved by adding a bifunctional organic silane compound having an alkoxysilyl group highly reactive with a hydroxyl group and a reactive functional group to a carboxyl group or an acid anhydride group. And completed the present invention.

That is, the present invention provides the following component (A),
It is a thermoplastic resin composition characterized by containing (B) and (C). (A) carboxyl group or acid anhydride group-modified olefinic resin (B) alcoholic hydroxyl-modified polyphenylene ether (C) the general formula (I) Y _m -R ¹ - _{^{[Si (R 2) 3-n}} (OR 3) _n ] _r (I) (in the formula, R ¹ represents a direct bond or an aliphatic or aromatic polyvalent hydrocarbon group having 1 to 50 carbon atoms, which is interrupted by an oxygen, nitrogen or sulfur atom. R ² and R ³ each represent a hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms, Y represents a hydrocarbon group having a polar functional group, and m, n and r each represent 1 to 1 It is an integer of 3.)
0.05 to 30 parts by weight based on 100 parts by weight of the components (A) and (B) in total.

The present invention will be described in detail below. <Carboxyl Group or Acid Anhydride Group Modified Olefin Resin (A)> (1) Olefin Resin The olefin resin used in the present invention is ethylene or α.
-Formed from olefins, specific examples of the α-olefin include propylene, 1-butene, 1-hexene,
3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-
1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclo Examples thereof include propane, vinylcyclohexane and 2-vinylbicyclo [2.2.1] heptane.
Of these, preferred are ethylene propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene. And the like, and ethylene, propylene, 1-butene, 3-methyl-1-butene or 4-methyl-1-pentene are particularly preferable. These ethylene or α-olefins may be used alone or in combination of two or more, and may be copolymerized with a diene compound.

Specific examples of the diene compound include 4-
Methyl-1,4-hexadiene, 5-methyl-1,4-
Hexadiene, 7-methyl-1,6-octadiene,
1,8-nonadiene, 1,9-decadiene or 1,12
-Tridecadiene or divinylbenzene etc.

These diene compounds may be used alone or in combination of two or more, and the preferable example of the latter is 4-
Methyl-1,4-hexadiene and 5-methyl-1,4-
A combination with hexadiene (weight ratio 95: 5 to 5:95) can be mentioned.

The olefin resin can be polymerized or copolymerized by using a Ziegler-Natta catalyst, and the diene compound may be distributed randomly or as a block in the olefin copolymer resin.

(2) Introduction of Carboxyl Group or Acid Anhydride Group The method for introducing the carboxyl group or acid anhydride group into the olefin resin is not particularly limited, and all known methods described in literatures and the like can be applied. . For example, the following (i) to (iii)
The method of is mentioned.

(I) An olefin resin is a compound having an ethylenic double bond and a carboxyl group or an acid anhydride group, specifically acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, There is a method of modifying with citraconic acid, crotonic acid, isocrotonic acid, itaconic acid, hymic acid and the like or their anhydrides in the presence of a radical generator such as an organic peroxide. Of these, a particularly preferred method is modification with maleic anhydride.

(Ii) A method of using the above unsaturated carboxylic acid derivative, for example, an acid halide, amide, imide, or ester, and modifying the olefin resin in the presence of a radical generator, followed by hydrolysis. (Iii) A method of oxidizing the hydroxyl group introduced into the olefin resin by various methods with permanganate, dichromic acid, or the like.

When the above-mentioned functional group is introduced by these methods, a monomer other than the unsaturated monomer having the above-mentioned functional group, for example, styrene, acrylic acid methyl ester, methacrylic acid methyl ester, vinyl acetate or the like is used as a majority of the above-mentioned compound. It is also possible to copolymerize within a range not exceeding the amount.

The radical reaction conditions include a method of irradiating with radiation such as γ-ray and electron beam in the coexistence of the above-mentioned olefin resin and the above-mentioned polymerizable monomer, and irradiation of the olefin resin with a polymerizable monomer. Any method such as a method of coexistence, a method of coexistence of an olefin resin and a polymerizable monomer and heating in the presence or absence of a radical generator may be used.

Radical generators include benzoyl peroxide, t-butyl peroxybenzoate, t-butyl hydroperoxide, t-butyl peroxyacetate, diisopropyl peroxydicarbonate, 2,
Used are organic and inorganic peroxides such as 2-bis (t-butylperoxy) octane, methyl ethyl ketone peroxide, potassium peroxide and hydrogen peroxide, and azo compounds such as α, α′-azobisisobutyronitrile. To be The peroxide can be used as a redox system in combination with a reducing agent. For example, a combination of hydrogen peroxide and a ferrous salt and the like. These radical generators can be appropriately selected in relation to the modifier and the reaction form. Moreover, two or more types can be used together.

The amount of the radical generator used is 0 to 100 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the olefin resin. The temperature at the time of graft copolymerization is usually 30 to 350 ° C., preferably 50 to 3
The temperature is 00 ° C., and the modification reaction time is 50 hours or less, preferably 1 minute to 24 hours.

The content of the carboxyl group or acid anhydride group introduced by the method (i), (ii) or (iii) is the content of the compound containing the functional group in the modified olefin resin. Is preferably 0.01 to 30% by weight, more preferably 0.1 to 10% by weight. 0.0
If it is less than 1% by weight, there is almost no effect of improving the compatibility of the composition, and if it exceeds 30% by weight, the mechanical properties of the composition are difficult to be exhibited.

For these reactions, an olefinic resin in a dissolved, molten, suspended or swollen state may be used. As the solvent used, aliphatic, alicyclic,
It is preferable to be selected from aromatic hydrocarbons or halides thereof, esters having 6 or more carbon atoms, ethers, ketones, and carbon disulfide, and it is also possible to use a mixed solvent of two or more kinds. The reaction rate does not necessarily have to be 100%, and if the carboxyl group or the acid anhydride group is substantially introduced, the product of the side reaction may be mixed.

10 to 90% by weight of the olefin resin modified with a carboxyl group or an acid anhydride group may be replaced with the above-mentioned olefin resin having no functional group. Such an olefin resin is a homopolymer such as ethylene, propylene, butene-1, 3-methyl-butene-1, 4-methyl-pentene-1, or a copolymer thereof, or a majority amount of these olefins, Examples thereof include copolymers with vinyl acetate, acrylic acid alkyl ester, and methacrylic acid alkyl ester. Among them, a crystalline propylene polymer, that is, a crystalline propylene homopolymer, a crystalline propylene-ethylene copolymer, a crystalline propylene-butene-1 random copolymer or a block copolymer is preferable.

<Alcoholic hydroxyl group-modified PPE (B)> (1) PPE The PPE used in the present invention has the general formula (I)

[0023]

[Chemical 1]

(Wherein Q ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and Q ² represents a hydrogen atom. , A halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group, and p represents a number of 10 or more). It is a polymer or a copolymer. Preferred examples of the primary alkyl group for Q ¹ and Q ² include methyl, ethyl, n-propyl, n-
Butyl, n-amyl, isoamyl, 2-methylbutyl,
It is n-hexyl, 2,3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, Q ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q ² is a hydrogen atom.

Suitable homopolymers of PPE are, for example, those composed of 2,6-dimethyl-1,4-phenylene ether units. A preferred copolymer is a random copolymer composed of a combination of the above units and 2,3,6-trimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers are described in the patents and literature. Also suitable are PPE containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and / or impact strength.

The molecular weight of PPE is such that the intrinsic viscosity at 30 ° C. usually measured in chloroform is about 0.2 to 0.8 dl / g.

PPE is usually produced by oxidative coupling polymerization of the above-mentioned monomers. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE.
There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, or cobalt, usually in combination with various other substances, and the like.

(2) Introduction of alcoholic hydroxyl group The method for introducing an alcoholic hydroxyl group into PPE is not particularly limited, and all known methods described in literatures and the like can be applied. For example, the following methods (i) to (vii) can be mentioned.

(I) PPE is a compound having both an ethylenic double bond and a hydroxyl group, specifically 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc., and an organic peroxide. A method of denaturing in the presence of a radical generator such as.

(Ii) Hydroxyl group-containing polymerizable monomers such as 2- (3-hydroxypropyl) -6-methylphenol and 2- {3- (2-hydroxyethylthio) propyl} -6-methylphenol. Method for obtaining hydroxyl group-modified PPE by copolymerizing monomers (Japanese Patent Application No. 3-325)
045 specification and Japanese Patent Laid-Open No. 4-202223).

(Iii) A method of oxidizing PPE reacted with a borane compound having a boron-hydrogen bond in the presence of an alkali (JP-A-3-292325).

(Iv) A method of reacting a terminal phenolic hydroxyl group of PPE with a compound having an alcoholic hydroxyl group in the presence of a basic catalyst, (v) a method of reacting a compound which produces a hydroxyl group by the reaction, (vi) hydrolysis A method of reacting a compound that produces a hydroxyl group by decomposition.

Specifically, as disclosed in JP-A-3-292326, a method of reacting a halogenated alkyl alcohol such as 2-chloroethanol or 3-chloro-1-propanol; and JP-A-3-250025. As disclosed in Japanese Patent Laid-Open Publication No. Hei 3 (1999) -163, a method of reacting an epoxy-containing alcohol such as glycidol; a method of reacting an epihalohydrin such as epichlorohydrin and then hydrolyzing it;
As disclosed in JP-A-250027, a method of reacting an alkylene carbonate such as ethylene carbonate or propylene carbonate; JP-A-63-128021.
As disclosed in the publication, a method of reacting an alkylene oxide such as ethylene oxide or propylene oxide can be mentioned. (Vii) Japanese Patent Laid-Open No. 2-107634 and Japanese Patent Laid-Open No. 3-5
As disclosed in Japanese Patent No. 2926, a method of reacting PPE metallized with an alkali metal with ethylene oxide.

The content of the hydroxyl group introduced by these methods is preferably 0.01 to 30% by weight, more preferably 0.1 to 30% by weight as the content of the compound in the modified PPE.
10 to 10% by weight. If it is less than 0.01% by weight, there is almost no compatibilizing effect according to the present invention, and if it exceeds 30% by weight, the mechanical properties of the composition are difficult to exert.

In the present invention, the alcoholic hydroxyl group-modified PPE may be used alone or in a mixture with the unmodified PPE. Usually alcoholic hydroxyl group modified PPE
And the mixing ratio of unmodified PPE is 100: 0 to 10: 9.
A range of 0% by weight is preferred. If the proportion of the modified resin is less than 10% by weight, the effect of improving the compatibility becomes low, which is not preferable.

<Organosilane Compound (C)> The organosilane compound used in the present invention is represented by the general formula (I). Y _m -R ¹ - _{^{[Si (R 2) 3-n}} (OR 3) n ] _r (I)

In the formula, m, n and r each represent an integer of 1 to 3, R ¹ represents a direct bond or a polyvalent group of an aliphatic or aromatic hydrocarbon having 1 to 50 carbon atoms, and these are oxygen. , Optionally interrupted by nitrogen or sulfur atoms. R ² and R ³
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group, and Y represents a polar functional group such as an acrylate group, a methacrylate group, an ester group, an amide group, an amino group, a halogen atom, an epoxy group, a hydroxyl group and a mercapto group. It is a hydrocarbon group having a group. Preferred is aminoalkoxysilane, epoxyalkoxysilane or mercaptoalkoxysilane in which R ³ has 1 to ³ carbon atoms and Y has a polar functional group which is an amino group, an epoxy group or a mercapto group.

Specific examples thereof include 2- (3,4-
Epoxycyclohexylethyl) trimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-phenylaminopropyl Examples thereof include trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like. Particularly preferred is
3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

<Composition Ratio of Constituents> The composition ratio of the component (A) carboxyl group- or acid anhydride group-modified olefin resin and the component (B) alcoholic hydroxyl group-modified PPE in the thermoplastic resin composition of the present invention. May be any values, but in view of the balance between mechanical strength and organic solvent resistance, both the composition ratios of component (A) and component (B) are preferably in the range of 10:90 to 90:10. , More preferably 20:80 to 80:20, particularly preferably 30:70.
˜70: 30.

The amount of the essential component (C) organosilane compound added to the composition of the present invention is 0.05 to 30 parts by weight, preferably 0 to 100 parts by weight of the total of the components (A) and (B). 0.05 to 20 parts by weight, more preferably 0.1 to 5
Parts by weight. If it is less than 0.05 parts by weight, the effect of improving the compatibility, which is the object of the present invention, is small, and if it exceeds 30 parts by weight, the adverse effect due to the decomposition of the organic silane becomes significant, which is not preferable.

<Additional Components> The thermoplastic resin composition of the present invention may contain additional components other than the above components (A), (B) and (C). For example, well-known antioxidants, weather resistance improvers, nucleating agents, flame retardants, and other additives for olefin resins; well-known antioxidants, weather resistance improvers, plasticizers, fluidity improvers, etc. for PPE. It can be used as an additional ingredient. Further, addition of organic / inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica and the like is effective in improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various colorants or dispersants thereof may be known ones.

Further, in the thermoplastic resin composition of the present invention,
In order to exhibit the characteristics of the composition more effectively, an auxiliary agent such as trimethylamine, triethylamine, tri-n-butylamine or pyridine can be added.
Further, an organic solvent such as benzene, xylene, toluene, chlorobenzene, dichlorobenzene or trichlorobenzene may be used in combination.

Further, addition of a styrene-butadiene copolymer rubber or its hydride, or an ethylene-propylene- (diene) copolymer rubber as an impact resistance improver is effective for improving the impact resistance of the composition. Is. The above impact strength improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the target physical property value. For example, in the case of improving the balance between the rigidity and the impact strength of the composition, 5 to 30 parts by weight per 100 parts by weight of the resin component of the composition is used. Is.

<Manufacturing Method and Molding Method of Thermoplastic Resin Composition> As a melt-kneading method for obtaining the thermoplastic resin composition of the present invention, a kneading method generally used for thermoplastic resins can be applied. For example, the powdery or granular components are uniformly mixed together with the additives described in the section of additional components, if necessary, by a Henschel mixer, ribbon blender, V-type blender, etc., and then uniaxial or multiaxial kneading extrusion. It can be kneaded with a machine, a roll, a Banbury mixer or the like.

Further, the order of mixing the respective components may be any order of possible combinations, but in the case of mixing by the melt-kneading method, a method of sequentially mixing from the one having high viscosity is a preferable method.

The molding method of the thermoplastic resin composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, sheet molding, and heat molding are used. Various molding methods such as molding, rotational molding, laminated molding and press molding can be applied.

[0047]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following, parts and percentages are based on weight.

Reference Example 1: Production of maleic anhydride-modified polypropylene Propylene homopolymer powder (230 ° C. melt flow rate (MFR): 1 g / 10 minutes, melting point: about 164 ° C.) 2
50 g of maleic anhydride and 50 g of maleic anhydride were put into a 10-liter glass flask equipped with a stirrer, which had been sufficiently purged with nitrogen, 5 liters of chlorobenzene were added, and 110 ° C.
It was heated and stirred to dissolve. Chlorbenzene 5 in this solution
25 g of benzoyl peroxide dissolved in 00 ml was added dropwise over 2 hours, and after completion of the addition, the reaction was further continued at 110 ° C. for 3 hours. The obtained reaction product was poured into 15 liters of acetone, the product was precipitated, and filtration and washing were performed twice. Then, the product was dried under reduced pressure to obtain maleic anhydride-modified polypropylene (maleic anhydride-modified PP. Will be written as)
Got

The modified polypropylene thus obtained had a maleic anhydride content of 1.23% as determined by infrared spectroscopy.
The MFR was 5.1 g / 10 minutes.

Reference Example 2: Production of hydroxyl group-modified PPE Poly (2,6-dimethyl-1,4-phenylene ether) (Nippon Polyether Co., Ltd., intrinsic viscosity measured in chloroform at 30 ° C .: 0.3 dl / g ) To 500 g, 5 liters of toluene were added and completely dissolved by stirring at 100 ° C. under a nitrogen atmosphere. After adding 75 g of sodium ethoxide as a catalyst and 500 ml of methanol to this solution, 250 g of glycidol was added dropwise over 30 minutes. 1 more
Stirring was continued at 00 ° C. for 7 hours. The reaction mixture was poured into 25 liters of methanol to precipitate the product hydroxyalkylated PPE. The product was separated by filtration, washed twice with methanol, and dried under reduced pressure at 80 ° C.

This hydroxyalkylated PPE showed absorption derived from a hydroxyl group at around 3,380 cm ^{-1 in} its infrared absorption spectrum. Further, when the amount of the phenolic hydroxyl group of the terminal group was quantified, it was found that 88% was reacted.

Examples 1 to 5 and Comparative Examples 1 to 4 Using the modified resins obtained in Reference Examples 1 and 2 and the polypropylene, PPE and organosilane compounds shown below,
A resin composition having the composition shown in Table 1 was produced.

The production was carried out by using a Labo Plastomill kneading machine (manufactured by Toyo Seiki Seisakusho Co., Ltd.) having an internal volume of 60 ml to melt and knead each of the components in a predetermined dry amount for 5 minutes at 230.degree. To obtain a granular resin composition.

Polypropylene (PP): Propylene resin (manufactured by Mitsubishi Petrochemical Co., Ltd., trade name: Mitsubishi Polypro MA3) PPE: Poly (2,6-dimethyl-1,4-phenylene ether) (manufactured by Nippon Polyether Co., 30 ° C.) Intrinsic viscosity measured in chloroform at 0.3 dl / g) Organosilane compounds: 3-aminopropyltrimethoxysilane (LS-1420, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltrimethoxysilane (the same, LS -2
940)

[0055]

[Table 1]

The resin composition obtained was measured and evaluated by the following methods, and the results are shown in Table 1. (1) Impact strength Injection molding machine (Custom Scientific (Custom
(CS-183MMX Minimax manufactured by Scientific) is used to injection-mold a test piece having a length of 31.5 mm, a width of 6.2 mm and a thickness of 3.2 mm under the condition of a temperature of 280 ° C., and an Izod impact tester ( The Izod impact strength without notch at 23 ° C. was measured using a custom scientific Minimax CS-138TI type).

(2) Tensile Strength Using the above injection molding machine, a tensile test piece having a parallel part length of 7.0 mm and a parallel part diameter of 1.5 mm was injection molded at a temperature of 280 ° C. A tensile test was performed under the conditions of 23 ° C. and a tensile speed of 1 cm / min using CS-183TE manufactured by Fick Co., Ltd., and the strength at break and the elongation at break were measured.

(3) Bending elastic modulus A test piece having a length of 47 mm, a width of 5 mm and a thickness of 2 mm was injection-molded,
Using a solid viscoelasticity measuring device (RSAII manufactured by Rheometrics Far East Co., Ltd.), the temperature dependence of the storage elastic modulus (E ′) was measured under the condition of a frequency of 1 Hertz, and the bending elastic modulus at 30 ° C. was obtained.

[0059]

INDUSTRIAL APPLICABILITY The thermoplastic composition of the present invention improves the compatibility between olefin resin and PPE by adding an organic silane compound, and is excellent in mechanical strength balance such as impact strength, tensile strength and elastic modulus. Therefore, it can be used as a useful industrial material in a wide range of fields such as automobile parts and electric parts.

Claims (1)

[Claims] 1. A thermoplastic resin composition comprising the following components (A), (B) and (C). (A) carboxyl group or acid anhydride group-modified olefinic resin (B) alcoholic hydroxyl-modified polyphenylene ether (C) the general formula (I) Y _m -R ¹ - _{^{[Si (R 2) 3-n}} (OR 3) _n ] _r (I) (in the formula, R ¹ represents a direct bond or an aliphatic or aromatic polyvalent hydrocarbon group having 1 to 50 carbon atoms, which is interrupted by an oxygen, nitrogen or sulfur atom. R ² and R ³ each represent a hydrogen atom, an alkyl group or an aryl group having 1 to 20 carbon atoms, Y represents a hydrocarbon group having a polar functional group, and m, n and r each represent 1 to 1 It is an integer of 3.)
0.05 to 30 parts by weight based on 100 parts by weight of the components (A) and (B) in total.