JPH07324160A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition being small in an increase in specific gravity and improved in strengths, rigidity and toughness by using a specified thermoplastic resin composition and an intercalation compound in which the host is a layered silicate having a cation exchange capacity, and the guest is an organic onium ion. CONSTITUTION:An intercalation compound in which the host is a layered silicate having as cation exchange capacity of 30meq/100g or above, and the guest is 0.8-2.0, in relation to the cation exchange capacity, of organic onium ions and used in an amount to give an inorganic ash content of 0.1-10wt.% is dispersed in a thermoplastic resin composition comprising 100-40wt.% polyphenylene ether having an intrinsic viscosity of 0.2-0.6dl/g as measured in chloroform in a concentration of 0.6g/dl at 25 deg.C and 0-60wt.% thermoplastic resin composition comprising a thermoplastic resin other than the polyphenylene ether and/or thermoplastic elastomer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyphenylene ether resin composition comprising a polyphenylene ether, or a thermoplastic resin composition containing polyphenylene ether as a main component, in which a specific intercalation compound is extremely uniformly dispersed. The present invention relates to a polyphenylene ether-polyamide resin composition composed of a polyphenylene ether resin composition and a polyamide resin.

[0002]

2. Description of the Related Art Conventionally, various fillers have been used for the purpose of increasing strength and rigidity of thermoplastic resin materials and increasing dimensional accuracy.
For example, glass fibers, carbon fibers, inorganic fibers such as potassium titanate whiskers, and glass flakes, glass beads, talc, mica, kaolin, wollastonite, and other inorganic powders have been compounded. However, although these methods increase strength and rigidity, they have drawbacks of impairing toughness, increasing specific gravity, and decreasing surface appearance. It is generally considered that one of the drawbacks in mixing fillers is poor dispersion of the fillers or the size of the dispersions being too large. Attempts have been made to improve dispersion by devising the shape.

As an attempt to reduce the dispersion size, a method has been proposed in which an intercalation compound in which an organic onium ion is intercalated in a layered silicate having a cation exchange ability is uniformly dispersed in a thermoplastic resin matrix,
For example, regarding a polyamide resin, JP-A-48-10
3653, JP-A-51-109998, JP-A-58-35542, JP-A-62-74957.
JP-A-3-
It is disclosed in Japanese Patent No. 62846.

However, although the use of various inorganic fillers has been proposed for the purpose of improving the strength and rigidity of the thermoplastic resin, a relatively hydrophobic and low polar resin such as polyphenylene ether resin. Improving the dispersibility in the matrix is not always satisfactory, and high strength /
It has been difficult to obtain a polyphenylene ether resin composition that satisfies both high rigidity and high toughness.

[0005]

The object of the present invention is to provide a polyphenylene ether resin composition having excellent strength and rigidity as well as toughness, and a small increase in specific gravity and an excellent appearance of the molding surface, and heat resistance, strength and rigidity. Another object of the present invention is to provide a polyphenylene ether-polyamide resin composition having excellent toughness and melt fluidity.

[0006]

The present invention has been made to solve the above-mentioned problems, and its gist is to provide a polyphenylene ether, or a thermoplastic resin and / or a thermoplastic elastomer other than polyphenylene ether and polyphenylene ether. And a thermoplastic resin composition containing a cation-exchangeable layered silicate as a host and an organic onium ion as a guest, and an inorganic ash content of 0.1 to 10% by weight. And a polyphenylene ether-polyamide resin composition comprising the polyphenylene ether-based resin composition and a polyamide resin.

The present invention will be described in more detail below. The polyphenylene ether in the present invention is a polymer in which benzene ring residues are linked via an ether bond and can be heated and melted. These are produced by a known method, for example, oxidative coupling polymerization with oxygen or an oxygen-containing gas using an oxidative coupling catalyst, using a phenol or a reactive derivative thereof as a raw material. Specific examples of the phenols and the polymerization catalyst are described in detail, for example, in JP-A-4-239029, and typical phenols are phenol, o-cresol, 2,6-xylenol, 2,5. Examples include methylphenols such as -xylenol and 2,3,6-trimethylphenol. These phenols may be used alone or in combination of two or more kinds. The most common polyphenylene ether resin includes poly (2,6-dimethyl-1,4-phenylene) ether or a copolymer having a main structure thereof, but a mixture containing two or more polyphenylene ether resins. Can also be used. Although the molecular weight of the polyphenylene ether resin used in the present invention is not particularly limited, the intrinsic viscosity [η] of a chloroform solution having a concentration of 0.6 g / dl at 25 ° C. is usually 0.2 to 0.6 dl / g. From the viewpoint of toughness and formability, 0.35 is preferable.
It is 0.55 dl / g.

Examples of the thermoplastic elastomer in the thermoplastic resin composition of the polyphenylene ether and the thermoplastic resin and / or the thermoplastic elastomer other than the polyphenylene ether include polystyrene-polybutadiene as a thermoplastic elastomer excellent in compatibility with the polyphenylene ether. Block copolymer (SBS), polystyrene-hydrogenated polybutadiene block copolymer (S
Styrene-based thermoplastic elastomers such as EBS) and polystyrene-poly (ethylene-propylene) block copolymers (SEP) can be blended. As the thermoplastic resin, for example, styrene-based resins such as polystyrene resin and ABS resin can be blended. In addition, crystalline resins such as polypropylene resin and polyarylene sulfide resin, styrene-maleic anhydride copolymer, polystyrene resin modified with a compound having an epoxy group, aromatic polycarbonate-polyphenylene ether copolymer, and the like. Also, these can be used in combination of two or more kinds. Among these, polystyrene-polybutadiene block copolymer (SBS), polystyrene-hydrogenated polybutadiene block copolymer (SEBS), polystyrene-poly (ethylene-propylene) block copolymer (SEP)
Preferred are styrene-based thermoplastic elastomers and the like. The ratio of the thermoplastic resin other than polyphenylene ether and / or the thermoplastic elastomer in the thermoplastic resin composition of the polyphenylene ether and the thermoplastic resin other than the polyphenylene ether and / or the thermoplastic elastomer is usually 60% by weight to 0% by weight, preferably Is 40% by weight to 0
% By weight.

The intercalation compound in the present invention uses a layered silicate having a cation exchange ability as a host and an organic onium ion as a guest. Here, the intercalation compound is
A compound produced by an ion-exchange reaction between an organic onium ion and a layered silicate containing a negative layer lattice and an exchangeable cation, wherein the onium ion is intercalated between layers (intercalation) To do.
The ion exchange reaction can be carried out in accordance with a known method described in, for example, Japanese Patent Publication No. 61-5492 and Japanese Patent Application Laid-Open No. 60-42451, and preferable reaction conditions are, for example, Japanese Patent Application No. No. 245199, Japanese Patent Application No. 5-
The reaction and purification method in the case of inserting a quaternary ammonium ion described in Japanese Patent No. 245200 can be applied.

As the layered silicate having a cation exchange ability, a 2: 1 type in which an octahedral sheet structure containing Al, Mg, Li and the like is sandwiched by two SiO ₄ tetrahedral sheet structures is preferable. The thickness of one layer, which is the unit structure, is usually 9.5.
It is about Angstrom. Specifically, smectite clay minerals such as montmorillonite, hectorite, fluorohectorite, saponite, beidellite, and stevensite, Li-type fluoroteniolite, Na-type fluoroteniolite, Na-type tetrasilicon-fluorine mica, Li-type tetrasilicon-fluorine mica, etc. Examples of the swelling synthetic mica, vermiculite, fluorine vermiculite, halloysite, etc. may be natural or synthetic. The cation exchange capacity (CEC) of these layered silicates is typically 30 meq /
100 g or more, preferably 50 meq / 10
It is 0 g or more, more preferably 70 meq / 100 g or more. The cation exchange capacity is measured by determining the amount of methylene blue adsorbed. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of organic onium ions between layers becomes insufficient and the dispersibility in the thermoplastic resin deteriorates, so that the strength and rigidity of the thermoplastic resin composition increase. Is not sufficient and the appearance of the molded surface is also poor. Among these layered silicates due to their cation exchange capacity and availability, smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite,
Swelling synthetic mica such as Na-type fluoro-teniolite and Na-type tetrasilicon-fluorine mica is preferably used. Particularly, montmorillonite obtained by refining bentonite is easy to obtain, and Li-type fluorine-teniolite (the following formula: Swellable fluoromica such as a), Na type fluoroteniolite (the following formula b), Na type tetrasilicon fluoromica (the following formula c) and the like is most suitable for the first invention. It should be noted that the expressions a, b, and c represent the ideal composition of c and do not need to be exactly the same.

[0011]

Embedded image LiMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (a) NaMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (b) NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ (c)

As the organic onium ion, ammonium ion, phosphonium ion, sulfonium ion,
Examples include onium ions derived from a heteroaromatic ring. These onium ions introduce an organic compound between the layers of the negatively charged silicate layer, and the ionic species thereof are not essentially limited. However, among these, from the viewpoint of availability and stability, ammonium ion, phosphonium ion,
Onium ions derived from heteroaromatic rings are preferred. Ammonium ions include dodecyl ammonium, hexadecyl ammonium, octadecyl ammonium, [PE
G] ammonium (hereinafter [PEG] represents a polyethylene glycol chain) and the like, methyl dodecyl ammonium, butyl dodecyl ammonium, methyl octadecyl ammonium, methyl [PEG] ammonium, dodecyl [PEG] ammonium, hexadecyl [PEG] ammonium Secondary ammonium such as dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, dimethyl [PEG] ammonium, methyl dodecyl [PEG] ammonium, methyl octadecyl [PEG] ammonium, methyl bis [PEG ]

Ammonium, tertiary ammonium such as dodecylbis [PEG] ammonium, hexadecylbis [PEG] ammonium, quaternary ammonium having the same alkyl group such as tetraethylammonium, tetrabutylammoniumtetraoctylammonium, trimethyloctylammonium and trimethyl. Decyl ammonium, trimethyl dodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium and other trimethyl alkyl ammonium, triethyl dodecyl ammonium, Triethyltetradecylammonium Ethyl hexadecyl ammonium,
Triethyl alkyl ammonium such as triethyl octadecyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, tributyl alkyl ammonium such as tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexa Dimethyldialkylammonium such as decylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldioctadecylammonium Dibutyldialkylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, etc., methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzyldihexadecyl Tribenzylmethylammonium such as dibenzyldialkylammonium such as ammonium, trioctylmethylammonium, tridodecylmethylammonium, tritetradecylmethylammonium, trioctylethylammonium,
Derived from aromatic amines such as trialkylethylammonium such as tridodecylethylammonium, trioctylbutylammonium, trialkylbutylammonium such as tridodecylbutylammonium, quaternary ammonium having an aromatic ring such as trimethylbenzylammonium, and trimethylphenylammonium Quaternary ammonium,
[PEG] -containing quaternary ammonium represented by the following formula d (in the formulas d and e, R ₁ and R ₂ independently represent an alkyl group having 20 or less carbon atoms, and m and n are integers of 1 and 2 <
m + n <60, preferably 10 ≦ m + n <30. ), Specifically, dimethylbis [PEG] ammonium, diethylbis [PEG] ammonium, dibutylbis [PEG] ammonium, methylethylbis [PE]
Ions such as dialkylbis [PEG] ammonium such as G] ammonium, methyldodecylbis [PEG] ammonium, and methyloctadecylbis [PEG] ammonium are tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, and trimethyl as phosphonium ions. Alkyl quaternary phosphonium such as dodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, and tributyloctadecylphosphonium, [PEG] -containing quaternary phosphonium represented by the above formula e, specifically Is dimethylbis [PEG] phosphonium, diethylbis [PEG] phosphonium, dibutylbis [PEG] phos Chloride, methyl ethyl bis [PE
G] phosphonium, methyl dodecyl bis [PEG] phosphonium, methyl octadecyl bis [PEG] phosphonium and other dialkyl bis [PEG] phosphonium ions, the heteroaromatic ring-derived onium ion, pyridinium, methyl pyridinium, dimethyl pyridinium, Examples include ions such as quinolinium and isoquinolinium.

[0014]

[Chemical 2]

Of these organic onium ions, a quaternary ammonium ion and / or a quaternary phosphonium ion are preferable from the viewpoint of the effectiveness of the hydrocarbon structure that contributes to the hydrophobicity between silicate layers, and examples thereof include trimethyldodecyl ammonium and trimethyl tetra Quaternary ammonium having one alkyl group having 12 or more carbon atoms in one molecule such as decyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, and triethyl octadecyl ammonium, Dimethyldidodecylammonium, dimethylditetradecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, die Distearate dodecyl ammonium, diethyl ditetradecyl ammonium,

Quaternary ammonium having two alkyl groups having 12 or more carbon atoms in one molecule such as diethyldihexadecylammonium and diethyldioctadecylammonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium. Having an alkyl group having 12 or more carbon atoms such as tributylhexadecylphosphonium and tributyloctadecylphosphonium 4
Ions such as primary phosphonium are preferably used. Among them, carbons such as quaternary ammonium having one alkyl group having 16 or more carbon atoms in one molecule such as trimethylhexadecyl ammonium, trimethyl octadecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium, etc. Quaternary ammonium having two or more alkyl groups having 14 or more carbon atoms in one molecule, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributylhexadecylphosphonium, tributyloctadecylphosphonium, etc. quaternary phosphonium having an alkyl group having 14 or more carbon atoms, etc. Is more preferable from the viewpoints of maintaining the toughness and availability of the resin composition of the present invention, most preferably trimethyloctadecyl ammonium ion,

Examples are dimethyldihexadecylammonium ion, dimethyldioctadecylammonium ion, tributylhexadecylphosphonium ion and tributyloctadecylphosphonium ion. These organic onium ions can be used alone or as a mixture of plural kinds.

The amount of organic onium ion in the intercalation compound is 0.8 with respect to the cation exchange capacity of the layered silicate as a raw material.
There is no particular limitation as long as it is in the range of 2.0 to 2.0 equivalents, but it is about 1.0 to 1.3 equivalents under normal reaction conditions. When this amount is less than 0.8 equivalent, dispersibility in the matrix resin is lowered, and when it is more than 2.0 equivalent, the free compound derived from the onium ion becomes prominent and the thermal stability at the time of molding is lowered,
May cause smoke, mold contamination, odor, etc.

In the polyphenylene ether resin composition of the present invention, the intercalation compound is 0.1 to 10% by weight as the amount of inorganic ash, preferably 0.3 to 8% by weight from the viewpoint of maintaining toughness and reinforcing effect. Preferably 0.3
~ 5 wt%, most preferably 0.3-4 wt%.
It is also possible to mix the composition as a so-called masterbatch and dilute and mix it to a predetermined amount of inorganic ash,
In this case, the preferred inorganic ash content of the composition is 6 to 10% by weight, and more preferably 8 to 10% by weight from the viewpoint of economical efficiency of using the masterbatch. Here, the amount of inorganic ash means the organic component of the polyphenylene ether resin composition at 650 ° C.
It is the weight fraction of the residue that is completely burned in the electric furnace. When the amount of the inorganic ash is less than 0.1% by weight, the mechanical strength and elastic modulus are not significantly improved, while when it exceeds 20% by weight, the toughness and the stability of the molten strand are significantly deteriorated. This is also not preferable. Also in use as a masterbatch, if the amount of the inorganic ash exceeds 20% by weight, the dispersibility of the intercalation compound during diluting and mixing may deteriorate, which is not preferable. When adding the intercalation compound, they may be used alone or in combination.

The intercalation compound in which the organic onium ion is intercalated in the layered silicate having a cation exchange ability in the present invention is a polyphenylene ether or a thermoplastic resin and / or a thermoplastic elastomer other than polyphenylene ether and polyphenylene ether. It has excellent cleavage dispersibility for the plastic resin composition and therefore has excellent smoothness of the molding surface of the polyphenylene ether resin composition, which improves strength and rigidity extremely efficiently, and further selects an appropriate compounding amount. Can improve the toughness.

In the polyphenylene ether resin composition of the present invention, it is preferable that the contained intercalation compound is uniformly dispersed in the matrix of the polyphenylene ether resin composition, and the uniform dispersion means dispersion. The average particle size of the particles is usually 5000 angstroms or less,
It means a dispersed state of preferably 3000 angstroms or less, and most preferably 1500 angstroms or less. The average particle size is, for example, an amount determined by light scattering measurement of a good solvent solution (for example, chloroform) of the polyphenylene ether resin composition or an image obtained by observation with a transmission electron microscope. If the average particle size exceeds 5000 Å, the surface smoothness of the molded product may be impaired and the effect of improving strength and rigidity may be reduced, which is not preferable.

The method of dispersing the intercalation compound is not particularly limited, but it is usually carried out by melt mixing with a polyphenylene ether resin or a thermoplastic resin containing the same, and it is preferable that a strong shearing force is involved. For example, it is preferable to use a kneading machine such as an extruder from the viewpoint of productivity, simplicity, and versatility. Among them, it is preferable to use a twin-screw extruder having high shearing efficiency, and a vented twin-screw extruder capable of efficiently removing volatile components. Is best used.

In order to promote the dispersion due to such shearing force, it is extremely effective to use an intercalation compound having a layered silicate as a host and an organic onium ion as a guest, rather than using the layered silicate alone. Can be said. That is,
In the phenomenon of exchange of cations and organic onium ions between layers of layered silicate having cation exchange ability (intercalation of organic onium ions), the hydrophobicity between the layers is changed by controlling the structure of the organic onium ions. By the synergistic effect of decreasing the interlayer attraction force and increasing the interlayer distance by controlling the intercalation of organic onium ions, even by a simple means such as mechanical shearing force in a thermoplastic resin containing molten polyphenylene ether. It is considered that the cleavage dispersion of the interphase compound is achieved.

In the polyphenylene ether resin composition of the present invention, various conventional additives may be added, if necessary, as long as the object of the present invention is not impaired, for example, glass fibers, inorganic fibers such as carbon fibers, glass flakes and glass. Inorganic powder such as beads and mica, various plasticizers, stabilizers, colorants, flame retardants and the like can be added. The polyphenylene ether-polyamide resin composition of the present invention comprises the polyphenylene ether resin composition and a polyamide resin. A polyphenylene ether-polyamide resin composition comprising a polyphenylene ether-based composition and a polyamide resin is obtained by blending a polyamide resin as a component of the polymer alloy in the polyphenylene ether-based resin composition, and its phase structure is not particularly limited. However, from the viewpoints of moldability and toughness, it is desirable that the polyamide resin phase that does not substantially contain an intercalation compound forms a matrix as a continuous phase and the polyphenylene ether resin composition phase forms a dispersed phase. In this case, the polyphenylene ether-based resin composition serving as the dispersed phase may include a third component such as an elastomer component for the purpose of improving the properties of the polyphenylene ether-polyamide-based resin composition such as impact resistance. As such an elastomer component, an elastomer having excellent compatibility with the polyphenylene ether resin, for example, polystyrene-polybutadiene block copolymer (SBS), polystyrene-hydrogenated polybutadiene block copolymer (SEBS), polystyrene-poly (ethylene- Suitable examples include styrene-based thermoplastic elastomers such as propylene) block copolymer (SEP). Furthermore, the polyamide resin phase which does not substantially contain the interphase compound to be the continuous phase may contain components such as an elastomer component for the purpose of improving the properties of the polyphenylene ether-polyamide resin composition such as impact resistance. Often,
As such an elastomer component, one having excellent compatibility with a polyamide resin is preferable, and for example, an acid anhydride group, a carboxyl group, an ethylene-propylene copolymer modified with a compound having any of an epoxy group, ethylene- Modified ethylene-α-olefin copolymer such as butene copolymer, similarly modified polystyrene-polybutadiene block copolymer (SBS), polystyrene-hydrogenated polybutadiene block copolymer (SEBS), polystyrene-poly (ethylene- Modified styrene thermoplastic elastomer such as propylene) block copolymer (SEP), similarly modified acrylic rubber, modified acrylic rubber such as core-shell type acrylic rubber, MBS rubber, polyamide elastomer, polyester elastomer and the like. .

The polyamide resin is a polymer containing an amide bond (-NHCO-) in the main chain and capable of being heated and melted. Suitable polyamide resins include polytetramethylene adipamide (nylon 46), polycaprolactam (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 61).
0), polyhexamethylene dodecamide (nylon 61
2), polyundecanolactam (nylon 11), polydodecanolactam (nylon 12), polyamide obtained from terephthalic acid and / or isophthalic acid and hexamethylenediamine, polyamide obtained from adipic acid and metaxylylenediamine , A polyamide obtained from terephthalic acid, adipic acid, and hexamethylenediamine, a copolymerized polyamide containing a dimerized fatty acid as a copolymerization component, and a polyamide copolymer containing at least two different polyamide forming components And mixtures thereof. Of these, nylon 6 and nylon 66 are particularly suitable because they have excellent balance between toughness and rigidity. The raw material of such polyamide is
Diamine and dicarboxylic acid, lactams, or polymerizable ω-amino acids, salts of diamine and dicarboxylic acid,
And oligomers of these raw materials. Specific examples of such polyamide raw materials are as described in detail in Japanese Patent Application No. 5-245199, and the diamines include tetramethylenediamine, aliphatic diamines such as hexamethylenediamine, and xylylenediamines. Examples of dicarboxylic acids include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and dimerized fatty acids, and examples of lactams include caprolactam, undecanolactam and dodecanoic acid. Typical examples of polymerizable ω-amino acids such as lactam are 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. These various polyamide resins or polyamide raw materials may be used in combination. The molecular weight of these polyamide resins is not particularly limited, but the relative viscosity ηrel of a concentrated sulfuric acid solution having a concentration of 1 g / dl at 25 ° C. is usually 0.9 to 6.0.
In terms of toughness and formability, preferably 1.0 to
It is in the range of 5.0.

In the polyphenylene ether-polyamide resin composition of the present invention, the content of the polyamide resin is usually 20 to 90% by weight, preferably 3 from the viewpoint of toughness.
5 to 90% by weight, more preferably 35 to 75% by weight, and most preferably 40 to 6 in terms of rigidity, strength and heat resistance.
It is 5% by weight. For the purpose of stabilizing the phase structure in the polyphenylene ether-polyamide resin composition of the present invention, it is preferable to use a so-called compatibilizer. Here, the stabilization of the phase structure means that coarsening of the dispersed particle size does not substantially occur even when retained in the molten state. The average particle size of the stabilized dispersed phase is usually 5 μm or less, preferably 2 μm or less, and most preferably 1 μm or less in terms of toughness. The average particle diameter is, for example, a scanning electron by extracting a fracture surface obtained by brittle fracture after sufficiently cooling the thermoplastic resin composition in liquid nitrogen with a good solvent of polyphenylene ether such as chloroform and vapor-depositing gold or platinum. It is obtained from the image obtained by observing under a microscope. As the compatibilizing agent, a known compatibilizing agent of a polyphenylene ether resin and a polyamide resin is suitable, but among them, maleic anhydride, maleic acid, a carboxylic acid compound having a carbon-carbon unsaturated bond such as fumaric acid or the like. Acid anhydride or malic acid,
Citric acid and the like are preferable, and these may be used alone or in combination. The amount of the compatibilizing agent to be used is not particularly limited, but is usually 0. 0 with respect to a thermoplastic resin composition of polyphenylene ether or a thermoplastic resin other than polyphenylene ether and / or a thermoplastic elastomer. 01-5% by weight, preferably 0.1-3% by weight, particularly preferably 0.5-2
% By weight.

In the polyphenylene ether-polyamide resin composition, the interphase compound is 0.01 to 8% by weight as the amount of inorganic ash, and 0.1 to 6% by weight, preferably 0 from the viewpoint of maintaining toughness and reinforcing effect. 0.5 to 5% by weight, most preferably 1 to 4% by weight. The polyphenylene ether-polyamide resin composition is produced by melting and mixing the compounding ingredients, but the production method is not particularly limited. Specifically, a melt-kneader such as a twin-screw extruder, a single-screw extruder, a roll, a Banbury mixer, and a Brabender can be used, but the twin-screw extruder is most suitable in terms of kneading efficiency.

In the polyphenylene ether-polyamide resin composition of the present invention, if necessary, various commonly used additive components such as glass fibers, inorganic fibers such as carbon fibers, glass flakes and glass can be used as long as the object of the present invention is not impaired. Inorganic powder such as beads and mica, various plasticizers, stabilizers, colorants, flame retardants and the like may be added.

[0029]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the description of the following Examples unless it exceeds the gist. Evaluation item and measuring method-Tensile test: According to ASTM D-638. The yield strength (abbreviated as YS, unit kg / cm ² ), elastic modulus (abbreviated as TM, unit kg / cm ² ) and elongation at break (abbreviated as UE, unit%) were measured. The measurement was performed in an absolutely dry state. Bending test: The flexural modulus (abbreviated as FM, unit: kg / cm ² ) was measured by ASTM D-790. The measurement was performed in an absolutely dry state. -Surface appearance observation: The surface smoothness of injection-molded articles was compared by visual evaluation.・ Heat resistance: 18.5 kg / cm ^{2 according} to ASTM D-648
The deflection temperature under load (DTUL) was measured.

[Layered silicate used] Table 2 shows the names, mineral names, types, cation exchange capacities (abbreviated as CEC) measured by the methylene blue adsorption method, and manufacturers of the commercially available layered silicates used.

[0031]

[Table 1] Table-1 1) Unit: Milliequivalent / 100g ──────────────────────────────────── ─ Name Mineral name Type CEC ¹⁾ Manufacturer ───────────────────────────────────── Kunipia F Montmorillonite Natural 120 Kunimine Industrial Co., Ltd. ME100 Swellable Fluorine Mica Synthetic 80 Corp Chemical Co. ─────────────────────────────────────

[Preparation of Intercalation Compound] About 100 g of a layered silicate or a layered silicate reacted with a functionalizing agent was precisely weighed and then dispersed by stirring in 10 liters of water at room temperature to obtain a homogeneous suspension. 1.2 times equivalent of onium ion hydrochloride of CEC of layered silicate was added thereto and stirred for 2 hours. The purified precipitated solid was filtered off, then washed with stirring in 25 liters of demineralized water, and then filtered off again. This washing and filtering operation was performed at least three times, and it was confirmed by the silver nitrate test of the washing liquid that chloride ions could not be detected. The solid obtained is 3-7.
After air drying in the day, crush in a mortar and dry with warm air at 50 ° C for 3 ~
After 10 hours, it was crushed again in a mortar. Drying conditions vary depending on the type of guest onium ion, but the maximum particle size is 1
The amount of residual water evaluated by the thermogravimetric reduction when it was kept at 120 ° C for 1 hour under a nitrogen stream was 2
The index was set to be ~ 3 wt%. As onium ions, dimethyldioctadecyl ammonium (Me in the table
₂ (C ₁₈ ) ₂ N ⁺ ), tributylhexadecylphosphonium ion (abbreviated as Bu ₃ C ₁₆ P ^{+ in the} table), and ammonium 12-aminododecanoate (abbreviated as 12ADA + in the table) were used.

[The thermoplastic resin used] Polyphenylene ether (abbreviated as PPE)
EM Polymer Co., Ltd. PPE (intrinsic viscosity [η] = 0.47 of a 0.6 g / dl concentration chloroform solution at 25 ° C.)
(Dl / g), but the Huggins constant was 0.30. ) Nylon 6 ... Novamid 1020J (manufactured by Mitsubishi Kasei Co., Ltd., relative viscosity ηrel = 3.5 at 25 ° C. of a concentrated sulfuric acid solution having a concentration of 1 g / dl) Nylon 66 ... Zitel FE3421 (manufactured by DuPont) Relative viscosity of concentrated sulfuric acid solution of 1 g / dl concentration at 25 ° C. ηrel = 3.0) Amorphous amorphous nylon (abbreviated as APA) ... Novamid X21 (Mitsubishi Kasei Co., Ltd., concentrated concentration of 1 g / dl) Polyamide resin consisting of isophthalic acid, terephthalic acid, and hexamethylenediamine having a relative viscosity ηrel = 2.0 at 25 ° C of a sulfuric acid solution)

[Examples 1 to 4] Table 2 in which dimethyldioctadecyl ammonium ion was intercalated
Is the twin screw extruder T manufactured by Toshiba Machine Co., Ltd.
PPE while using a vent under the conditions of barrel temperature setting 320 ° C and screw rotation speed 150 rpm by EM35B.
This was melt-kneaded with (powder) and made into chips to obtain a polyphenylene ether-based resin composition. The obtained chips were vacuum dried at 120 ° C (for one day and night), and then injection molding machine J manufactured by Japan Steel Works Ltd.
With 28 SA, molding was performed under the conditions of a barrel temperature of 310 ° C., a mold surface actual measurement temperature of 95 ° C., injection / cooling = 15/15 seconds, and maximum injection speed to obtain a tensile test piece. The amount of the inorganic ash was obtained by precisely weighing about 1.5 g of the molded piece and calculating the weight fraction of the residue in which the organic matter was completely burned out in an electric furnace at 650 ° C. The ash content is shown in Table 2.

Example 5 The procedure of Example 2 was repeated, except that the interphase compound shown in Table 2 in which tributylhexadecylphosphonium ion was intercalated was used as the interphase compound.

Comparative Example 1 The procedure of Example 1 was repeated except that the intercalation compound was not added. Comparative Example 2 The procedure of Example 2 was repeated except that Kunipia F was used instead of the intercalation compound.

Comparative Example 3 The procedure of Example 2 was repeated except that 0.5% by weight of dimethyldioctadecyl ammonium chloride was added instead of the intercalation compound. Comparative Example 4 The procedure of Example 1 was repeated except that the amount of the intercalation compound was reduced. [Comparative Example 5] The same procedure as in Example 4 was carried out except that the amount of the interlayer compound was increased.

Example 6 Using a twin-screw extruder TEM35B manufactured by Toshiba Machine Co., Ltd., the barrel temperature was set to 320 ° C., the screw rotation speed was set to 150 rpm, and maleic anhydride pulverized in a mortar was set to 1.6. PPE mixed with weight% (powder)
PPE mixed with Kunipia F intercalated with dimethyldioctadecyl ammonium ion from the first feed port so that the theoretical inorganic ash content was 12% by weight.
(Powder) was charged from each of the second feed ports, melted and kneaded into chips (hereinafter, the product obtained here is referred to as the PPE resin composition of Example 6). The raw material supply rate ratio from each feed port is 1 / second = 62.5 / 37.5
(% By weight). The inorganic ash content of this chip is 4.55
Since the content was 6% by weight, the same weight as nylon 6 chips was mixed, and the barrel temperature was set to 290 ° C and the screw rotation speed was set to 200 rpm using the TEM35B twin-screw extruder. Kneaded into chips. The PPE resin composition thus obtained and nylon 6
Chips of a polyphenylene ether-polyamide resin composition containing and are vacuum dried at 120 ° C. (one day and night), and a barrel temperature of 280 ° C. and a mold surface measured temperature of 93 ° C. are measured by an injection molding machine J28SA manufactured by Japan Steel Works Ltd. Injection / cooling = 1
Molding was carried out under conditions of maximum injection speed for 5/15 seconds to obtain tensile test pieces and bending test pieces. The amount of the inorganic ash was obtained by precisely weighing about 1.5 g of the molded piece and calculating the weight fraction of the residue in which the organic matter was completely burned out in an electric furnace at 650 ° C. The ash content is shown in Table 3. Further, the chips of the polyphenylene ether-polyamide resin composition are crushed at a liquid nitrogen temperature,
The PPE phase alone was extracted by Soxhlet extraction with chloroform, and the residue obtained by concentrating the PPE phase was quantified by the electric furnace method described above. The results are also shown in Table 3. However, since pure PPE also gives a charcoal residue by the electric furnace method, the amount of charcoal residue given by a unit weight of PPE was obtained in advance and calculated by adding a correction accordingly.

Example 7 The PPE resin composition chip of Example 6 and nylon 66 chip were mixed in the same weight, and melt-kneaded under the same conditions as in Example 6 to form chips into a polyphenylene ether-polyamide resin composition. I got a thing.
Molding was carried out by changing the barrel temperature of the injection molding machine to 2 in Example 6.
The same procedure as in Example 6 was performed except that the temperature was set to 90 ° C. [Example 8] The same experiment as in Example 7 was conducted except that APA was used in place of nylon 66 in Example 7.
However, the barrel temperature setting for melt kneading and injection molding is 280 ° C.
And

[Comparative Example 6] Under the condition that the PPE resin composition of Example 6 was prepared, P containing 1% by weight of maleic anhydride pulverized from the first feed was used without using the second feed.
PE (powder) was added and melt-kneaded into chips (hereinafter,
The one obtained here is referred to as the PPE resin composition of Comparative Example 6). The same weight mixture of this chip and nylon 6 chip was mixed with the interphase compound used in Example 6 so that the theoretical inorganic ash content was 2.3% by weight, and PP in Example 6 was used.
Melt kneading was carried out in the same manner under the conditions for producing a resin composition containing E and nylon 6. The molding conditions were the same as in Example 6.

[Comparative Example 7] Nylon 6 in Comparative Example 6
Comparative Example 6 was repeated except that nylon 66 was used instead of. The molding conditions were the same as in Example 7. [Comparative Example 8] The same operation as in Comparative Example 7 was carried out except that APA was used in place of Nylon 66 in Comparative Example 7. However, the barrel temperature setting for melt kneading and injection molding is 28
It was set to 0 ° C.

Comparative Example 9 Kunipia F intercalated with 12ADA + was prepared as ε-caprolactam / 6-
Aminocaproic acid was mixed with a mixture of 9/1 (weight ratio). Then, the reaction mixture was charged into a reactor, and after nitrogen substitution, the temperature was raised to 100 ° C., melting was performed, and stirring was performed for 30 minutes to disperse the intercalation compound.
After that, the temperature was raised to 250 ° C. and the reaction was carried out at atmospheric pressure for 2 hours, then 50 T
Polymerization was completed by reducing the pressure to orr. Total decompression time is 2
It was time. The composition thus produced had a very high melt viscosity in a state where the shear rate was low, and it was difficult to carry out the usual operation of extracting from the reactor. The pulverized product of the composition thus obtained is extracted with hot water to remove water-soluble components, and then vacuum dried (120 ° C, 1
6 hours). The amount of inorganic ash of this product is 4.58% by weight
And gel permeation chromatography at 40 ° C. using a mixed solvent of m-cresol / chloroform = 3/7 (weight ratio) as a developing solution (column: PL manufactured by Tosoh Corp.).
-Gel 10 μm MIXED) according to nylon 6
The number average degree of polymerization of the components was 180, which corresponded to the relative viscosity ηrel = 2.9 at 25 ° C. of a concentrated sulfuric acid solution having a concentration of 1 g / dl. The nylon 6 resin composition and the PPE resin composition of Comparative Example 6 were mixed in the same weight, and melt kneading and molding were performed in the same manner as in Comparative Example 6.

Comparative Example 10 Comparative Example 6 was carried out in the same manner as Comparative Example 6 except that Kunipia F intercalated with dimethyldioctadecyl ammonium ion was not added. The evaluation results of Examples 1 to 4 and Comparative Examples 1 to 5 are shown in Table-2, and the evaluation results of Examples 6 to 8 and Comparative Examples 6 to 10 are shown in Table-3. For Example 6, Comparative Example 6 and Comparative Example 10, DTUL with a load of 18.5 kg / cm ² was used.
(° C) was measured and shown in Table-4.

[0044]

[Table 2] Table-2 Intercalation compound Layered onium Ash content TM YS UE surface Silicate ion (wt%) (kg / cm ² ) (kg / cm ² ) (%) Appearance ─────────── ──────────────────────── Example 1 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 0.45 24500 748 69 Gloss ant Example 2 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 1.25 25800 751 72 Gloss ant Example 3 ME100 Me ₂ (C ₁₈ ) ₂ N ⁺ 1.31 26100 763 80 Gloss ant Example 4 ME100 Me ₂ (C ₁₈ ) ₂ N ⁺ 4.02 30300 761 8 Gloss ant Example 5 Kunipore F Bu ₃ C ₁₆ P ⁺ 1.22 25800 750 68 Gloss ant Comparative example 1 ---- ----- 0.00 23400 744 46 Gloss ant Comparative example 2 Kunipore F ----- 1.20 23600 744 37 Particle ant Comparative example 3 ---- a) Me ₂ (C ₁₈ ) ₂ NCl 0.00 23400 744 50 Gloss ant Comparative example 4 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 0.08 23400 744 47 Gloss ant Comparative example 5 ME100 _{Me 2 (C 18) 2 N} + 10.2 39200 b) --- 1 Polished ───────── ──────────────────────── a) adding a salt of onium ions raw material in place of the interlayer compound. b) No surrender.

[0045]

[Table 3] Table-3 ──────────────────────────────────── Intercalation compound Polyamid Layered onium Ash content UE FM type in surface PPE phase Silicate ion (wt%) (%) (kg / cm ² ) Appearance Ash content (wt%) ─────────────────── ───────────────── Example 6 PA6 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.34 93 33 100 Gloss 4.64 Example 7 PA66 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.01 29 32400 Gloss ant 4.61 Example 8 APA Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.31 76 31100 Gloss ant 4.62 Comparative example 6 PA6 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.43 4 34700 Gloss ant 0.00 Comparative Example 7 PA66 Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.11 7 33800 Gloss Ant 0.00 Comparative Example 8 APA Kunipore F Me ₂ (C ₁₈ ) ₂ N ⁺ 2.34 9 33700 Gloss Ant 0.00 Comparative Example 9 PA6 Kunipore F 12ADA + 2.31 2 34800 Gloss ant 0.00 Comparative example 10 PA 6 --- --- 0.00 121 28400 Gloss ant --- ──────────────────────────────────── ─

[0046]

TABLE 4 TABLE -4 ───────────────────────────── 18.5kg / cm ² load DTUL (° C.) ─── ────────────────────────── Example 6 136 Comparative Example 6 141 Comparative Example 10 63 ──────────── ─────────────────

Examples 1 to 3 and 5 of Table 2 and Comparative Example 1
From the comparison with, it can be seen that the polyphenylene ether resin composition of the present invention has not only improved strength and rigidity, but also improved toughness as compared with the PPE resin. In addition, from Tables 3 and 4, the polyphenylene ether-polyamide resin compositions of the present invention (Examples 6 to 8) were compared with Comparative Examples 6 to 9 in which the layered silicate was dispersed in the continuous phase of the polyamide resin. It can be seen that the balance of rigidity, toughness and heat resistance is excellent.

[0048]

The polyphenylene ether resin composition of the present invention is excellent in strength, rigidity, toughness and surface appearance of molded articles. Further, the polyphenylene ether-polyamide resin composition of the present invention has high strength, high rigidity, and high toughness, and has an excellent surface appearance, high heat resistance, low specific gravity, excellent moldability and solvent resistance, and low water absorption. Shows sex. The resin composition of the present invention can be easily produced by a general-purpose facility such as a melt kneader, and takes advantage of characteristics such as low specific gravity, good surface appearance, high strength, high rigidity, and high toughness, It is applied to various machine parts, automobile parts, electric / electronic parts, sheets, films, packaging materials, master batches for blending, etc.

Claims (4)

[Claims] 1. A layered silicate having a cation exchange ability is used as a host in an organic onium ion in a thermoplastic resin composition of polyphenylene ether or a thermoplastic resin and / or a thermoplastic elastomer other than polyphenylene ether and polyphenylene ether. A polyphenylene ether-based resin composition comprising an intercalation compound as a guest dispersed in an amount of inorganic ash of 0.1 to 10% by weight. 2. The polyphenylene ether resin composition according to claim 1, wherein the organic onium ion is a quaternary ammonium ion and / or a quaternary phosphonium ion. 3. The organic onium ion is a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms and / or a quaternary phosphonium ion having an alkyl group having 12 or more carbon atoms. The polyphenylene ether-based resin composition. 4. A polyphenylene ether-polyamide resin composition comprising the polyphenylene ether resin composition according to any one of claims 1 to 3 and a polyamide resin.