JP2000290491A - Polyphenylene ether resin composition and preparation of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene ether resin composition suppressing anisotropy and bending without damaging surface appearance, having improved mechanical properties. SOLUTION: This polyphenylene ether resin composition includes the polyphenylene ether resin and a silane clay-complex in which the silane clay- complex is prepared by introducing a silane based compound expressed by a general formula: YnSiX4-n (n is an integer of 0-3, Y is a 1-25C hydrocarbon group and an organic functional group comprising a 1-25C hydrocarbon and a substituting group, X is a hydrolysable group and/or OH, X and Y may be same or different.) to a swellable silicate, and the average thickness of the silane-clay complex in the resin composition is <=500 Å.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polyphenylene ether resin composition containing a polyphenylene ether resin and a silane clay composite, and a method for producing the resin composition.

[0002]

2. Description of the Related Art Polyphenylene ether resins have a glass transition temperature of about 220 ° C. or higher and have excellent heat resistance.
It is known as a resin having excellent acid / alkali resistance and hydrolysis resistance. Among them, polyphenylene ether resin modified with styrene resin, as modified polyphenylene ether resin, heat resistance, mechanical properties, moldability, impact resistance,
As a material having an excellent balance of dimensional accuracy and the like, it is widely used in various fields such as the OA equipment field, the automobile field, and the electric / electronic field. Particularly in the field of materials for OA equipment such as copiers and facsimile machines, high rigidity and low anisotropy are required. Therefore, a fibrous reinforcing material such as glass fiber and a plate-like filler such as talc and glass flake are used in combination. Have been.

[0003] The appearance of the surface of a molded article is likely to deteriorate due to the floating of the fibrous reinforcing material, but the appearance has been improved by reducing the fiber diameter or the like. The anisotropy tends to increase when the fibrous reinforcing material is oriented in the flow direction during injection molding, but the anisotropy is reduced by adding a large amount of plate-like filler. However, their effects were insufficient and problematic. It is generally considered that such a defect in the blending of the inorganic filler is caused by poor dispersion of the inorganic filler or an excessively large size of the dispersed particles.

As a technique for finely dispersing inorganic fillers,
(1) An organic metal compound such as a silane-based compound is bonded, and the average layer thickness is about 50 ° or less and the maximum layer thickness is about 100 °.
Invention relating to a resin composite material containing the following layered particles and a resin matrix (WO 95/06090)
Pamphlet (1995), US Patent 5,514,734
No., WO 93/04118 pamphlet (199
3), WO 93/11190 pamphlet (19)
93)), (2) The thermoplastic resin has an average layer thickness of 25 to 1
Invention relating to a resin composition in which a layered silicate having an aspect ratio of 20 to 300 at 000 ° is dispersed (Japanese Unexamined Patent Application Publication No.
No. 124836).

In the invention of the above (1), the tensile modulus of the nylon 6-based composite material composed of montmorillonite and nylon 6 bonded with isocyanatopropyltriethoxysilane and the like in which caprolactam is copolymerized is improved as compared with nylon 6 alone. It has been done, but it is not enough. Further, although a nylon 6-based composite material is disclosed, it is difficult to obtain a polyphenylene ether resin composite material in which layered particles are finely dispersed by directly applying the nylon 6-based method to a polyphenylene ether resin. Was.

In the technique (2), swelling mica is used as a layered silicate, and swelling mica swelled with water or alkylammonium-treated swelling mica swelled with xylene is extruded with a resin. The technology of the resin composition obtained by this is disclosed. However, according to the above technique, the layered silicate is incomplete and inhomogeneous even though it is partially finely dispersed, so that a polyphenylene ether resin composition having desired physical properties cannot be obtained.

[0007]

Accordingly, the layered silicate layer is cleaved to be uniformly dispersed in the polyphenylene ether resin in the form of a small thin plate. At present, a technique for obtaining a polyphenylene ether resin composition having sufficiently improved mechanical properties has not yet been provided, and an object of the present invention is to solve such conventional problems.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have separated and cleaved unit layers of swellable silicate,
The above-mentioned object is achieved by containing a thin silane clay composite prepared by subdividing one swellable silicate agglomerated particle into a very large number of very fine thin particles in a polyphenylene ether resin. That you can achieve
The present invention has been completed.

That is, a first aspect of the present invention is a polyphenylene ether resin composition containing a polyphenylene ether resin and a silane clay composite, wherein the silane clay composite is converted into a swellable silicate by the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3, and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. The present invention relates to a polyphenylene ether resin composition prepared by introducing a silane compound represented by the formula (1), wherein the average thickness of the silane clay composite in the resin composition is 500 ° or less.

In a preferred embodiment, the present invention relates to the above polyphenylene ether resin composition, wherein the maximum thickness of the silane clay composite is 2000 ° or less.

In a further preferred embodiment, the [N] value is 30 or more, wherein the [N] value is present in an area of 100 μm ² of the resin composition and the particles per unit ratio of the silane clay composite. A polyphenylene ether resin composition as described above, defined as being a number.

In a further preferred embodiment, the average aspect ratio of the silane clay composite in the resin composition (layer length / length)
(The ratio of layer thickness) is 10 to 300.

A second aspect of the present invention is a polyphenylene ether resin composition containing a polyphenylene ether resin and a silane clay composite, wherein the silane clay composite has the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is prepared by introducing a silane compound represented by the formula (1), and the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300, and [ N] value is 30 or more, wherein the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition. Composition.

The third aspect of the present invention is (A) a step of preparing a silane clay composite, (B) a silane clay composite and the following general formula (2):

[0015]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a halogen atom, an alkyl group optionally substituted with a functional group, an aralkyl group optionally substituted with a functional group, The phenolic compound represented by the formula (I) is an aryl group which may be substituted or an alkoxy group which may be substituted by a functional group), and (C) a step of polymerizing the phenolic compound. And a method for producing a polyphenylene ether resin composition.

In a preferred embodiment, the step (B)
The present invention relates to a method for producing a polyphenylene ether resin composition, wherein the bottom spacing of the silane clay composite after mixing with the phenolic compound is at least three times the bottom spacing of the swellable silicate.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The polyphenylene ether resin used in the present invention is represented by the following general formula (2):

[0018]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a halogen atom, an alkyl group optionally substituted with a functional group, an aralkyl group optionally substituted with a functional group, An aryl group which may be substituted, or an alkoxy group which may be substituted with a functional group).

Specific examples of the polyphenylene ether homopolymer include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,
4-phenylene) ether, poly (2,6-diethyl-)
1,4-phenylene) ether, poly (2-ethyl-6)
-N-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-ethyl-6-n-butyl-1,4-)
Phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloro-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl) -1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like.

The above-mentioned polyphenylene ether resins can be used alone or in combination of two or more having different compositions or components and / or different molecular weights.

The silane clay composite used in the present invention is a swellable silicate having the following general formula (1): Y _n SiX _4-n (1) (where n is an integer of 0 to 3, Y has 1 to 1 carbon atoms
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is introduced.

The above-mentioned swellable silicate is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide, and examples thereof include smectite group clay and swellable mica. Can be When the smectite group clay and the swellable mica are used as the swellable silicate, the dispersibility of the swellable silicate in the polyphenylene ether resin composition of the present invention, the availability and the improvement of the physical properties of the resin composition are improved. Preferred from the point.

The above smectite group clay is represented by the following general formula (3): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (3) (where X is K, Na, 1 / 2Ca and 1 / 2Mg
At least one member selected from the group consisting of
e, Mn, Ni, Zn, Li, Al, and at least one member selected from the group consisting of Cr, and Z is at least one member selected from the group consisting of Si and Al. Note that H ₂ O represents a water molecule bonded to an interlayer ion, and n varies remarkably depending on the interlayer ion and the relative humidity. Specific examples of the smectite group clay include, for example, montmorillonite,
Examples include beidellite, nontronite, saponite, iron saponite, hectorite, sauconite, stevensite, bentonite, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the smectite group clay in the initial aggregation state is about 10 to 1
7 °, and the average particle size of the smectite group clay in the agglomerated state is approximately 1000-1,000,000 °.

The swellable mica is represented by the following general formula (4): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (4) (where X is Li, Na, At least one member selected from the group consisting of K, Rb, Ca, Ba, and Sr;
g, one or more selected from the group consisting of Fe, Ni, Mn, Al, and Li, and Z is Si, Ge, Al, F
at least one selected from the group consisting of e and B. )
And natural or synthetic. These are substances having the property of swelling in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type Examples thereof include silicon mica, sodium tetrasilicic mica, and the like, and substituted substances, derivatives, and mixtures thereof. The distance between the bottom surfaces of the swellable mica in the initial aggregation state is approximately 10 to 17
Å, and the average particle size of the swellable mica in the aggregated state is about 10
It is 00 to 1,000,000 °.

Some of the above-mentioned swellable mica have a structure similar to that of vermiculite, and such an equivalent of vermiculite can also be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (5): (Mg, Fe , Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (5) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.6) 9, n =
3.5 to 5). The distance between the bottom surfaces of the vermiculite in the initial aggregation state is about 10 to 17 °, and the average particle size of the vermiculite in the aggregation state is about 1000 to 5,000,000 °.

The swellable silicate may be used alone.
It may be used in combination of more than one kind. Of these,
Montmorillonite, bentonite, hectorite and swellable mica having sodium ions between layers are preferred from the viewpoint of dispersibility in the polyphenylene ether resin composition of the present invention, availability, and the effect of improving the physical properties of the resin composition.

The crystal structure of the swellable silicate is desirably high in purity, which is regularly stacked in the c-axis direction, but a so-called mixed layer mineral in which the crystal cycle is disordered and a plurality of types of crystal structures are mixed is also used. Can be done.

As the silane compound to be introduced into the swellable silicate, any compound generally used can be used, and is represented by the following general formula (1): Y _n SiX _4-n (1) Things. N in the general formula (1) is an integer of 0 to 3, and Y is a group having 1 carbon atom which may have a substituent.
~ 25 hydrocarbon groups. When the hydrocarbon group having 1 to 25 carbon atoms has a substituent, examples of the substituent include a group bonded by an ester bond, a group bonded by an ether bond, an epoxy group, an amino group, and a carboxyl group. , A group having a carbonyl group at the terminal, an amide group, a mercapto group, a group bonded by a sulfonyl bond, a group bonded by a sulfinyl bond, a nitro group, a nitroso group, a nitrile group, a halogen atom and a hydroxyl group. . One of these may be substituted, or two or more may be substituted. X is a hydrolyzable group and / or
A hydroxyl group, and examples of the hydrolyzable group include at least one selected from the group consisting of an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen atom. . In the general formula (1), when n or 4-n is 2 or more, n Y or 4-n X may be the same or different.

As used herein, the term "hydrocarbon group" means a linear or branched (ie, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, and an aromatic hydrocarbon group. An alicyclic hydrocarbon group means an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, a cycloalkyl group and the like. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group include alkenylene group, alkynylene group, phenylene group, naphthylene group, cycloalkylene group, and the like, respectively.

In the above general formula (1), Y has 1 carbon atom.
Examples of the hydrocarbon group having from 25 to 25 include those having a linear long-chain alkyl group such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, and 2-hexenyltrimethoxy. Those having an unsaturated hydrocarbon group such as silane, those having an alkyl group having a side chain such as 2-ethylhexyltrimethoxysilane, those having a phenyl group such as phenyltriethoxysilane, and 3-β-naphthyl Examples include those having a naphthyl group such as propyltrimethoxysilane, and those having an aralkyl group such as p-vinylbenzyltrimethoxysilane. Examples of the case where Y is a group having a vinyl group among hydrocarbon groups having 1 to 25 carbon atoms include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. Y
Is a group having a group substituted with a group bonded by an ester group, and examples thereof include γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. Examples of a case where Y is a group substituted with an epoxy group include γ-glycidoxypropyltrimethoxysilane. Examples of the case where Y is a group substituted with an amino group include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. No. Examples of the case where Y is a group substituted with a group having a carbonyl group at the terminal include γ-ureidopropyltriethoxysilane. Examples of the case where Y is a group substituted with a mercapto group include γ-mercaptopropyltrimethoxysilane. Examples of a case where Y is a group substituted with a halogen atom include γ-chloropropyltriethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by a sulfonyl group include γ-phenylsulfonylpropyltrimethoxysilane. Examples of the case where Y is a group having a group substituted with a group bonded by a sulfinyl group include γ-phenylsulfinylpropyltrimethoxysilane. Examples of a case where Y is a group substituted with a nitro group include γ-nitropropyltriethoxysilane. Examples of the case where Y is a group substituted by a nitroso group include γ-
Nitrosopropyltriethoxysilane may be mentioned. Y
Is a group substituted with a nitrile group, examples thereof include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane. Examples of the case where Y is a group substituted with a carboxyl group include γ- (4-carboxyphenyl) propyltrimethoxysilane. In addition to the above, silane compounds in which Y is a group having a hydroxyl group can also be used. Such an example includes N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane. Hydroxyl groups can also be in the form of silanol groups (SiOH).

Substitutes or derivatives of the above silane compounds can also be used. These silane compounds can be used alone or in combination of two or more.

The distance between the bottom surfaces of the silane clay composite used in the present invention can be increased as compared with the initial distance between the bottom surfaces of the swellable silicate due to the presence of the introduced silane compound. For example, a swellable silicate dispersed in a dispersion medium and having an increased bottom surface interval, when the silane-based compound is not introduced, when the dispersion medium is removed, the layers return to a state in which the layers are aggregated again. For example, by introducing the silane compound after expanding the bottom surface interval, even after removing the dispersion medium, the obtained silane clay composite can exist in a state where the bottom surface interval is expanded without the layers being aggregated. . The distance between the bottom surfaces of the silane clay complex is at least 1.3 times, preferably at least 1.5 times, more preferably at least 1.7 times, particularly preferably at least 2 times, the initial distance of the swellable silicate. It is expanding. As described above, the affinity between the silane clay composite and the resin can be increased by introducing the silane-based compound and by increasing the distance between the bottom surfaces.

Here, the fact that the silane compound has been introduced into the swellable silicate can be confirmed by various methods. As a method for confirmation, for example, the following method can be mentioned.

First, by simply washing the silane clay complex with an organic solvent such as tetrahydrofuran or chloroform, the adsorbed silane compound is simply washed and removed. The washed silane clay composite is powdered in a mortar or the like and then dried sufficiently. Subsequently, the silane clay composite is sufficiently mixed with a window material such as powdered potassium bromide (KBr) at a predetermined ratio to form a tablet under pressure, and the Fourier transform (FT) -IR is used to perform a transmission method or the like. , The absorption band derived from the silane compound is measured. When more accurate measurement is desired, or when the amount of the introduced silane compound is small, it is possible to measure a sufficiently dried powdery silane clay complex by a diffuse reflection method (DRIFT) as it is. desirable.

The fact that the distance between the bottom surfaces of the silane clay composite is larger than that of the swellable silicate can be confirmed by various methods. For example, the following method can be used.

That is, in the same manner as described above, the adsorbed silane compound is removed from the silane clay composite by washing with an organic solvent, dried, and then subjected to small-angle X-ray diffraction (SAX
S) or the like. In this method, the X-ray diffraction peak angle value derived from the (001) plane of the powdery silane clay composite is measured by SAXS, and the angle is applied to Bragg's formula to calculate the bottom surface interval. Similarly, the base spacing of the initial swellable silicate is measured, and by comparing the two, the expansion of the base spacing can be confirmed.

As mentioned above, after washing with an organic solvent,
The absorption band derived from the added silane compound is FT-IR
By measuring with SAXS or the like that the bottom surface interval is larger than that of the raw material swellable silicate, it can be seen that a silane clay complex has been formed.

In the polyphenylene ether resin composition of the present invention, the compounding amount of the silane clay composite per 100 parts by weight of the polyphenylene ether resin is typically 0.1.
1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, more preferably 0.3 to 40 parts by weight, still more preferably 0.4 to 40 parts by weight.
It is prepared to be 35 parts by weight, particularly preferably 0.5 to 30 parts by weight. The compounding amount of the silane clay composite is 0.1
If the amount is less than 10 parts by weight, the effect of improving mechanical properties, anisotropy, and warpage may be insufficient.

The ash content of the polyphenylene ether resin composition derived from the silane clay composite is typically 0.1 to 30% by weight, preferably 0.2 to 28% by weight, more preferably 0.3. ~ 25% by weight, more preferably 0.4%
To 23% by weight, particularly preferably 0.5 to 20% by weight. If the ash content is less than 0.1% by weight, the effect of improving mechanical properties, anisotropy and warpage may be insufficient, and if it exceeds 30% by weight, the surface appearance tends to be impaired.

The structure of the silane clay composite dispersed in the polyphenylene ether resin composition of the present invention has a structure in which a large number of layers are stacked, such as a swellable silicate before being compounded, having a size of μm. Completely different from the structure. That is, by using a silane clay composite in which a silane-based compound having an affinity for the matrix resin is introduced and the bottom surface interval is increased compared to the initial swellable silicate, the layers are cleaved and become independent from each other. And subdivide it. As a result, the silane clay composite is dispersed in the polyphenylene ether resin composition in a very fine and independent thin plate shape, and the number thereof is significantly increased as compared with the swellable silicate as the raw material. The dispersion state of such a thin silane clay composite can be represented by the aspect ratio (ratio of layer length / layer thickness), the number of dispersed particles, the maximum layer thickness, and the average layer thickness described below.

First, when the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the silane clay composite dispersed in the resin, the silane clay in the polyphenylene ether resin composition of the present invention is defined. The composite has an average aspect ratio of 1
0 to 300, preferably 15 to 300. More preferably, it is 20 to 300. If the average aspect ratio of the silane clay composite is less than 10, the effect of improving the mechanical properties, anisotropy, and warpage of the polyphenylene ether resin composition of the present invention may not be sufficiently obtained. Also,
Since the effect does not change anymore even if it is larger than 300,
The average aspect ratio need not be greater than 300.

When the [N] value is defined as the number of dispersed particles per unit weight ratio of the swellable silicate in the area of 100 μm 2 of the polyphenylene ether resin composition, the value of [N] in the polyphenylene ether resin composition of the present invention is obtained. The [N] value of the silane clay composite is 30 or more,
Preferably it is 45 or more, more preferably 60 or more. There is no particular upper limit, but if the [N] value exceeds about 1000, the effect will not change any more.
It need not be greater than zero. The [N] value can be obtained, for example, as follows. That is, the polyphenylene ether resin composition is cut into an ultrathin section having a thickness of about 50 μm to 100 μm, and the section is imaged by TEM or the like.
It can be determined by dividing the number of particles of the silane clay complex present in an arbitrary area having an area of 100 μm ² by the weight ratio of the swellable silicate used. Alternatively, on a TEM image, an arbitrary region (area is measured) in which 100 or more particles are present is selected, and the number of particles present in the region is divided by the weight ratio of the swellable silicate used. And the area is 100 μm
^The value converted into ² may be used as the [N] value. Therefore,
[N] value is a TEM of the polyphenylene ether resin composition.
It can be quantified by using a photograph or the like.

When the average layer thickness is defined as the number average value of the layer thickness of the silane clay composite dispersed in a thin plate shape,
The upper limit of the average layer thickness of the silane clay composite in the polyphenylene ether resin composition of the present invention is 500 ° or less,
Preferably not more than 450 °, more preferably 400 °
Å It is below. If the average layer thickness is more than 500 °, the effect of improving the mechanical properties, anisotropy and warpage of the polyphenylene ether resin composition of the present invention may not be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is preferably larger than 50 °, more preferably 60 ° or more, and further preferably 70 ° or more. When the maximum layer thickness is defined as the maximum value of the layer thickness of the silane clay composite dispersed in a thin plate shape in the polyphenylene ether resin composition of the present invention, the upper limit of the maximum layer thickness of the silane clay composite is , 2000 ° or less, preferably 1800 ° or less, more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance of mechanical properties, anisotropy, warpage and surface appearance of the polyphenylene ether resin composition of the present invention may be impaired. The lower limit of the maximum layer thickness of the silane clay composite is not particularly limited, but is preferably larger than 100 °, more preferably 150 ° or more, and further preferably 200 ° or more.

The layer thickness and the layer length are determined by heating and melting the polyphenylene ether resin composition of the present invention, and then performing hot press molding or stretching molding, and thin molding obtained by injection molding the molten resin. An article or the like can be obtained from an image photographed using a microscope or the like.

That is, the thickness of the film prepared by the above-described method on the XY plane is about 0.5 to 0.5.
It is assumed that a thin flat injection-molded test piece of about 2 mm is placed. Approximately 50 μm to 100 μm of the above film or test piece in a plane parallel to the XZ plane or the YZ plane
The thickness can be determined by cutting out an ultrathin section and observing the section with a transmission electron microscope or the like at a high magnification of about 4 to 100,000 or more. The measurement is performed by placing an arbitrary area containing 100 or more silane clay composites on an elephant of the transmission electron microscope obtained by the above method, forming an image with an image processing device or the like, and performing computer processing. And the like. Alternatively, it can also be obtained by measuring using a ruler or the like.

The method for producing the polyphenylene ether resin composition of the present invention is not particularly limited. For example, (A) a step of preparing a silane clay composite, (B) a silane clay composite and the following general formula (2) :

[0047]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a halogen atom, an alkyl group optionally substituted with a functional group, an aralkyl group optionally substituted with a functional group, A phenolic compound represented by the formula (C): polymerizing a phenolic compound.

First, the step (A) will be described in detail. The silane clay composite is obtained, for example, by adding a silane-based compound after expanding the swellable silicate in a dispersion medium to increase the distance between the bottom surfaces.

The above-mentioned dispersion medium means water, a polar solvent compatible with water, and a mixed solvent of water and the polar solvent. Examples of the polar solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol and 1,4-butanediol; ketones such as acetone and methyl ethyl ketone; ethers such as diethyl ether and tetrahydrofuran. And amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and other solvents such as pyridine, dimethylsulfoxide and N-methylpyrrolidone. Also, carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can be used. These polar solvents may be used alone or in combination of two or more.

The distance between the bottom surfaces of the swellable silicate can be increased in the dispersion medium by sufficiently stirring and dispersing the swellable silicate in the dispersion medium. The spacing between the bottom surfaces after the enlargement is preferably at least 3 times, more preferably at least 4 times, particularly preferably at least 5 times, as compared to the initial spacing of the swellable silicate. There is no particular upper limit. However, when the distance between the bottom surfaces is increased by about 10 times or more, the measurement of the distance between the bottom surfaces becomes difficult. In this case, the swellable silicate substantially exists in a unit layer.

Here, in the present specification, the initial distance between the bottom surfaces of the swellable silicate refers to a particulate swellable silicate in which unit layers are stacked and aggregated before addition to the dispersion medium. It is intended to be the bottom spacing.

The distance between the bottom surfaces can be determined by small angle X-ray diffraction (SAXS) or the like. That is, the X-ray diffraction peak angle value of the dispersion containing the dispersion medium and the swellable silicate is determined by SA
XS is measured, and the peak angle value is applied to Bragg's formula to calculate the bottom surface interval.

In order to efficiently increase the distance between the bottom surfaces of the swellable silicate, stirring may be performed at a speed of several thousands rpm or more, or a method of applying a physical external force as described below. Physical external forces can be applied by using commonly performed wet milling of fillers. As a general wet-milling method of a filler, for example, a method using hard particles can be mentioned. In this method, the hard particles, the swellable silicate, and an optional solvent are mixed and stirred, and the swellable silicate is separated by physical collision between the hard particles and the swellable silicate. Hard particles generally used are filler grinding beads, for example, glass beads or zirconia beads. These grinding beads are selected in consideration of the hardness of the swellable silicate or the material of the stirrer, and are not limited to the above-mentioned glass or zirconia. The particle size is also not specifically limited by a numerical value because it is determined in consideration of the size of the swellable silicate and the like, but a particle having a diameter of 0.1 to 6.0 mm is preferable. . Although the solvent used here is not particularly limited, for example, the above-described dispersion medium is preferable.

As described above, the interval between the bottom surfaces of the swellable silicate is enlarged, the cohesive layers are cleaved and separated, and after the swellable silicates are independently present, the silane compound is added and stirred. . In this way, a silane clay composite is obtained by introducing the silane compound to the surface of the cleaved swellable silicate layer.

In the case of using a dispersion medium, the silane-based compound is introduced by adding the silane-based compound to a dispersion containing the swellable silicate having an enlarged bottom surface interval and the dispersion medium, followed by stirring. Can be done. The method of stirring is not particularly limited, and for example, is performed using a conventionally known wet stirrer.
Examples of the wet stirrer include a high-speed stirrer in which a stirring blade rotates at a high speed and stirs, a wet mill for wet-milling a sample in a gap between a rotor and a stator at a high shear rate, and a mechanical method using a hard medium. Examples include wet crushers and wet crushers that collide a sample at a high speed with a jet nozzle or the like. When it is desired to introduce the silane compound more efficiently, the rotation speed of the stirring should be 1000 rpm or more,
Preferably 1500 rpm or more, more preferably 200 rpm
The shear rate is set to 0 rpm or more, or 500 (1 / s) or more, preferably 1000 (1 / s) or more, and more preferably 1500 (1 / s) or more. The upper limit of the number of revolutions is about 25,000 rpm, and the upper limit of the shear rate is about 500,000 (1 / s). It is not necessary to stir at a value larger than the upper limit since stirring does not tend to change the effect even if the stirring is performed at a value larger than the upper limit or shearing is applied.

In the case of a method using a physical external force, a silane compound is added to the swellable silicate while applying a physical external force thereto (for example, while wet milling).
A silane compound may be introduced.

Alternatively, by adding a swellable silicate having an increased bottom distance by a physical external force to a dispersion medium and adding a silane compound to the dispersion medium in the same manner as in the above-described method using a dispersion medium. Alternatively, a silane compound can be introduced into the swellable silicate.

The introduction of the silane compound into the swellable silicic acid is carried out by reacting a hydroxyl group present on the surface of the swellable silicate having an increased bottom spacing with a hydrolyzable group and / or a hydroxyl group of the silane compound. By doing so, a silane compound can be introduced into the swellable silicate.

When the silane compound introduced into the swellable silicate further has a reactive functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or a vinyl group, such a silane compound may be used. It is also possible to further add a compound capable of reacting with a reactive group and react the compound with the reactive group. Thus, the chain length of the functional group chain of the silane compound introduced into the swellable silicate and the polarity can be changed. In this case, as the compound to be added, the above-mentioned silane-based compound itself can be used, but the compound is not limited thereto, and any compound can be used according to the purpose. For example, an epoxy group-containing compound, an amino group Examples of the compound include a compound containing a carboxyl group, a compound containing an acid anhydride group, and a compound containing a hydroxyl group.

The reaction proceeds sufficiently at room temperature, but may be heated if necessary. The maximum temperature during heating can be arbitrarily set as long as it is lower than the decomposition temperature of the silane compound used and lower than the boiling point of the dispersion medium.

The amount of the silane compound used is determined by the affinity between the obtained silane clay composite and the polyphenylene ether resin, or the mixed system containing the silane clay composite and the phenolic compound (hereinafter referred to as a clay-phenol dispersion, ) Can be adjusted to sufficiently increase the dispersibility in the above. If necessary, a plurality of silane compounds having different functional groups may be used in combination. Therefore, the amount of the silane compound to be added is not limited to a numerical value, but is 0.1 to 200 parts by weight, preferably 0.2 to 180 parts by weight, based on 100 parts by weight of the swellable silicate. Parts by weight, more preferably from 0.3 to 160 parts by weight, even more preferably from 0.4 to 140 parts by weight, particularly preferably from 0.5 to 120 parts by weight. When the amount of the silane compound is less than 0.1 part by weight, the effect of finely dispersing the obtained silane clay composite tends to be insufficient. Also, 20
If the amount is more than 0 parts by weight, the effect does not change, so it is not necessary to add more than 200 parts by weight.

Next, in the step (B), the silane clay composite and the following general formula (2):

[0063]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a halogen atom, an alkyl group optionally substituted with a functional group, an aralkyl group optionally substituted with a functional group, A phenolic compound represented by an aryl group which may be substituted or an alkoxy group which may be substituted by a functional group).

Here, examples of the phenolic compound include 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, and 2-ethyl-phenol. 6-n
-Propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-
Propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-
Di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol,
2,6-diphenylphenol, 2,6-bis- (4-
Fluorophenyl) phenol, 2-methyl-6-tolylphenol, 2,6-ditolylphenol and the like. These phenolic compounds may be used alone or in combination of two or more. Also, a small amount of phenol, o-cresol, m-cresol, p
-Cresol, 2,4-dimethylphenol, 2-ethylphenol and the like may be contained. Among these phenolic compounds, 2,6-dimethylphenol and 2,6-diethylphenol are important.

The method for preparing the clay-phenol dispersion by mixing the silane clay complex and the phenolic compound is not particularly limited, and may be carried out using a conventionally known wet stirrer. A method in which a silane clay complex and a phenolic compound are mixed therein.

The organic solvent used here is not particularly limited as long as it is hardly oxidized as compared with the phenolic compound and has little reactivity to various radicals considered to be generated in the course of the polymerization reaction. However, it is preferable to dissolve the phenolic compound and dissolve a part or all of the catalyst used in the reaction. Specific examples of such an organic solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, chloroform, methylene chloride, 1,2-dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. And nitro compounds such as nitrobenzene, and these can be used as good solvents for the polymer. One or more of these good solvents can be used.

Also, poor solvents for the polymer can be used.
Specific examples of the poor solvent include methanol, ethanol, propanol, butanol, benzyl alcohol, alcohols such as cyclohexanol, pentane, hexane,
Aliphatic hydrocarbons such as heptane, cyclohexane and cyclopentane, ketones such as acetone and methyl ethyl ketone, ester compounds such as ethyl acetate and ethyl formate, ether compounds such as tetrahydrofuran and diethyl ether, amide compounds such as dimethylformamide, dimethyl sulfoxide and the like And water. One or more of these poor solvents can be used by mixing with the above-mentioned good solvent, if necessary. It is preferable to contain alcohols such as methanol and ethanol from the viewpoint of activity.

Other mixing methods include, for example, a method of adding a phenolic compound to a dispersion medium and a mixture containing a silane clay complex obtained when a silane clay composite is prepared, or a method of mixing silane clay. When the complex is prepared, the dispersion medium and the silane clay complex are added to the one containing the silane clay complex. Or a method of adding and mixing a phenolic compound, or mixing the silane clay complex obtained by drying and removing the dispersion medium and a desired good solvent, and then adding the phenolic compound. And mixing.

For efficient mixing, the rotation speed of the stirring should be 500 rpm or more, or 300 (1 / s).
Apply the above shear rate. The maximum number of revolutions is 25000
rpm, and the upper limit of the shear rate is 500000 (1 /
s). There is a tendency that the effect does not change even if the stirring is performed at a value larger than the upper limit, so that it is not necessary to perform the stirring at a value larger than the upper limit.

In the silane clay composite contained in the clay-phenol dispersion obtained in the step (B), the initial lamination / agglomeration structure, which the swellable silicate had, had disappeared almost completely, and The layers are subdivided into shapes, or the intervals between the layers are enlarged, so that a so-called swollen state is obtained. The bottom surface interval can be used as an index indicating the swelling state. The distance between the bottom surfaces of the silane clay composite in the clay-phenol dispersion is preferably at least three times the initial distance between the bottom surfaces of the swellable silicate in order for the silane clay composite to be finely divided and formed into a thin plate. It is more preferably at least five times, more preferably at least five times.

Step (C), that is, step (B)
A step of polymerizing the phenolic compound in the clay-phenol dispersion obtained in the above. The polymerization method is not particularly limited, and the polymerization can be performed according to a generally-used polymerization method of a polyphenylene ether resin, for example, a method of oxidatively polymerizing a phenolic compound in the presence of a catalyst such as a nitrogen-containing compound or a copper compound.

Examples of the nitrogen-containing compound include, for example,
One or more compounds selected from the group consisting of aliphatic or aromatic primary, secondary, or tertiary monoamines, diamines, triamine compounds, and cyclic compounds containing a nitrogen atom as a hetero atom are used. For example,
Monoalkylamine, dialkylamine, trialkylamine, alkanolamines, aniline, N-hydrocarbon-substituted anilines, diphenylamines, cyclic amines, pyridines, ethylenediamine and their hydrocarbons, propanediamine and these hydrocarbons, Examples thereof include imidazoles, diethylenetriamine and substituted hydrocarbons thereof, dipropanetriamine and substituted hydrocarbons thereof.

Further, as the above-mentioned copper compound, for example,
Cuprous chloride, cuprous bromide, cuprous sulfate, cuprous nitrate, cuprous acetate, cuprous azide, cuprous compounds such as cuprous toluate, cupric chloride, odor One or more selected from the group consisting of cupric compounds such as cupric chloride, cupric sulfate, cupric nitrate, cupric acetate, cupric azide and cupric toluate can be used. .

A solution polymerization method or a precipitation polymerization method can be carried out depending on the ratio of a good solvent and a poor solvent to polyphenylene ether obtained by oxidative polymerization of a phenolic compound. For example, according to the solution polymerization method, the silane clay composite is dispersed in toluene, which is a good solvent, and then, 2,6-dimethylphenol, which is a phenolic compound, is dissolved. Next, the above catalyst was added and the temperature was controlled.
Oxidative polymerization is carried out while introducing oxygen.

If the temperature of the polymerization reaction is too low, the reaction hardly proceeds, and if it is too high, the catalyst may be deactivated. Therefore, the polymerization is carried out at a temperature of 0 to 80 ° C., preferably 10 to 70 ° C. Is preferred. As the oxygen in the oxidative polymerization, in addition to pure oxygen, those mixed with an inert gas such as nitrogen at an arbitrary ratio, air, and the like can be used. The pressure in the system during the reaction is usually at normal pressure, but may be reduced or increased as necessary.

There is no particular limitation on the post-treatment after the polymerization reaction. Usually, an acid such as hydrochloric acid or acetic acid, or ethylenediaminetetraacetic acid (EDTA) and its salt, nitrilopolyacetic acid and its salt, etc. are added to the system to deactivate the catalyst. Wash and dry.

The reason why the polyphenylene ether resin composition of the present invention has a small warpage or anisotropy without deteriorating the surface appearance and has excellent mechanical properties is that the silane clay composite in the polyphenylene ether resin contains many fine particles. This is because the silane clay composite is dispersed in the form of thin plate-like particles, and the average layer thickness, maximum layer thickness, number of dispersed particles, and average aspect ratio of the silane clay composite are in the above-mentioned ranges.

The dispersion state of the silane clay composite can be controlled by one or more steps selected from the steps (A) and (B) in the above-mentioned method for producing a polyphenylene ether resin composition.

For example, in the step (A), the dispersion state of the silane clay composite can be controlled by the organic functional group of the silane compound to be introduced, the amount of the silane compound used, the type of the dispersion medium to be used, and the like. Assuming that the stirring force and shearing force when dispersing the swellable silicate are constant, the type of the dispersion medium, and when using a plurality of types of dispersion medium, the swelling is performed according to the mixing ratio and the order of mixing. The state of swelling and cleavage of the silicate changes. For example, when montmorillonite is used as the swellable silicate, if the dispersion medium is only water, montmorillonite swells and cleaves to a state close to the unit layer, and in that state, an amino group, a mercapto group, a nitrile group, etc. By reacting a silane compound having a highly polar group, a dispersion in which a silane clay composite having a unit layer thickness of approximately approximately is dispersed is prepared. On the other hand, ethanol, tetrahydrofuran (THF), methyl ethyl ketone (MEK), pyridine, N, N-dimethylformamide (DMF),
When a mixed solvent of a polar solvent such as N, N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP) and water is used as a dispersion medium, or when montmorillonite is dispersed in the polar solvent and then water is added. Is cleaved and subdivided into a state in which about several to several hundreds of unit layers are stacked. By reacting the silane compound in this state, a dispersion in which the silane clay composite having a thickness of about several to about one hundred and several tens of sheets is dispersed is prepared. The dispersion state of the silane clay composite can be controlled by performing steps (B) and (C) in the method for producing a polyphenylene ether resin composition so as to maintain those states.

In the step (B), the silane-clay composite in the clay-phenol dispersion is adjusted under the mixing conditions of the silane-clay composite and the phenolic compound, for example, the number of stirring, the shearing force during stirring, and the stirring time. Is controlled. The dispersion state of the silane clay composite can be controlled by performing the step (C) in the method for producing a polyphenylene ether resin composition so as to maintain those states.

The polyphenylene ether resin composition of the present invention may contain polybutadiene, butadiene-
Styrene copolymer, acrylic rubber, ionomer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, natural rubber, chlorinated butyl rubber, homopolymer of α-olefin, copolymer of two or more α-olefins Polymer (including any copolymer such as random, block, and graft, and may be a mixture thereof),
Alternatively, an impact modifier such as a thermoplastic elastomer such as an olefin-based elastomer can be added. These may be modified with an acid compound such as maleic anhydride or an epoxy compound such as glycidyl methacrylate. In addition, other arbitrary resins, for example, a polyester resin, a polycarbonate resin, a polyester carbonate resin, a liquid crystal polyester resin, a polyolefin resin, a styrene resin, and a rubbery polymer, as long as the properties such as mechanical properties and moldability are not impaired. Thermoplastics such as reinforced styrenic resins, polyamide resins, polyphenylene sulfide resins, polyarylate resins, polyacetal resins, polysulfone resins, polyimides, polyetherimide resins, and the heat of unsaturated polyester resins, epoxy resins, and phenol novolak resins The curable resins may be used alone or in combination of two or more.

Further, the polyphenylene ether resin composition of the present invention may contain a pigment, a dye, a heat stabilizer,
Antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers,
Additives such as a flame retardant and an antistatic agent can be added. The polyphenylene ether resin composition of the present invention,
It may be formed by injection molding, extrusion molding, hot press molding,
Can also be used for blow molding.

Such molded articles have dimensional accuracy, appearance,
Because of its excellent mechanical properties, it is suitably used for, for example, automobile parts, household electric parts, precision mechanical parts, household daily necessities, packaging / container materials, electro-magnetic base materials, and other general industrial materials.

In the polyphenylene ether resin composition of the present invention, since the silane clay composite is very fine and uniformly dispersed in a thin plate shape, the specific gravity is significantly increased without impairing the surface appearance. In addition, mechanical properties can be improved, and anisotropy and warpage can be reduced.

[0085]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

The main raw materials used in the examples and comparative examples are summarized below. Unless otherwise specified, the raw materials were not purified.

(Raw materials) 2,6-Dimethylphenol: 2,6-dimethylphenol (Wako-specified product) manufactured by Wako Pure Chemical Industries, Ltd. (hereinafter referred to as 26D)
P) was used.・ Swellable silicate: Kunimine F Co., Ltd.
(Hereinafter, referred to as Kunipia, bottom spacing = 13 °), and Wenger HVP of Toyshun Yoko Co., Ltd. (hereinafter, referred to as Wenger, bottom spacing = 13 °) were used. -Γ-aminopropyltrimethoxysilane: A-1110 from Nippon Unicar Co., Ltd. (hereinafter referred to as A1110) was used. Phenyl glycidyl ether: Phenyl glycidyl ether of Nagase Kasei Co., Ltd. (hereinafter referred to as PGE) was used. -Higher alcohol glycidyl ether: Higher alcohol glycidyl ether of Sakamoto Yakuhin Kogyo Co., Ltd.
GE).・ Polystyrene resin: Sumibright of Sumitomo Chemical Co., Ltd.
GPPS-M140 (hereinafter, referred to as M140) was used. Glass fiber: T-195H of Nippon Electric Glass Co., Ltd. (hereinafter referred to as T195H) was used. The evaluation methods in Examples and Comparative Examples are summarized below. (FT-IR) 1.0 g of the silane clay complex was added to 50 ml of tetrahydrofuran (THF), and the mixture was stirred for 24 hours to wash and remove the adsorbed silane compound, and then centrifuged to separate the supernatant. This washing operation was repeated three times. After washing, a well dried silane clay complex about 1
mg and about 200 mg of KBr powder were sufficiently mixed in a mortar, and a KBr disk for measurement was prepared using a tabletop press. Next, an infrared spectrometer (Shimadzu Corporation, 810
0M) by the transmission method. The detector used was an MCT detector cooled with liquid nitrogen, the resolution was 4 cm ⁻¹ , and the number of scans was 100. (Measurement of dispersion state) Regarding the silane clay composite, TE
The following procedure was performed using M.

An ultra-thin section having a thickness of 50 to 100 μm was used. Transmission electron microscope (JEOL JEM-1200E
Using X), the dispersion state of the silane clay composite was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. TEM
In the photograph, a region where 100 or more dispersed particles are present is selected, and the number of particles ([N] value), layer thickness and layer length are manually measured using a ruler with a scale, or interquest as required. The measurement was performed by processing using an image analysis device PIASIII of the company. The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each silane clay composite.
[N] value was measured as follows. First, TE
On the M image, the number of particles of the silane clay composite present in the selected area is determined. Separately, the ash content of the resin composition derived from the silane clay composite is measured. The value obtained by dividing the number of particles by the ash content and converting the result to an area of 100 μm ² was defined as the [N] value.

The average layer thickness was the number average of the individual silane clay composite layer thicknesses, and the maximum layer thickness was the maximum value among the individual silane clay composite layer thicknesses.

If the dispersed particles are large and observation with a TEM is unsuitable, the [N] value can be determined using an optical microscope (optical microscope BH-2 manufactured by Olympus Optical Co., Ltd.) in the same manner as described above. I asked. However, if necessary, the sample was melted at 250 to 280 ° C. using a hot stage THM600 manufactured by LINKAM, and the state of the dispersed particles was measured in the molten state.

The aspect ratio of the dispersed particles that are not dispersed in a plate shape was a value of major axis / minor axis. Here, the long diameter is intended to be the long side of the rectangle assuming a rectangle having the smallest area among rectangles circumscribing the target particle in a microscope image or the like. Further, the minor axis is intended to mean the short side of the minimum rectangle. (Measurement of bottom spacing by small angle X-ray diffraction (SAXS))
Using an X-ray generator (RU-200B, manufactured by Rigaku Corporation), target CuKα ray, Ni filter, voltage 4
0 kV, current 200 mA, scanning angle 2θ = 0.2 to 16.0
°, the step angle = 0.02 ° under the measurement conditions, the bottom spacing was measured.

The distance between the bottom surfaces is represented by a small angle X-ray diffraction peak angle value of B
It was calculated by substituting into the formula of ragg. However, when it is difficult to confirm the small-angle X-ray peak angle value, it is confirmed that the layer has been sufficiently cleaved and the crystallinity has substantially disappeared, or the peak angle value is approximately 0.8 ° or less. Was considered difficult, and the evaluation result of the bottom surface spacing was set to> 100 °. (Warp) Dry the polyphenylene ether resin composition (1
(20 ° C, 5 hours), and then, using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75t, a mold temperature of 50 ° C, a resin temperature of 200 ° C, a gauge pressure of about 10 MPa, and an injection speed of about 10 MPa. Injection molding under the condition of 50%, size about 120 ×
A 120 × 1 mm flat test piece was prepared. The flat test piece was placed on a flat surface, and the degree of warpage was checked. (Surface appearance) The polyphenylene ether resin composition was dried (120 ° C., 5 hours). Using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t, a JIS No. 1 dumbbell-shaped test having a thickness of about 3 mm at a resin temperature of 200 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50%. The pieces were injection molded and evaluated by center line average roughness. The center line surface roughness is a surface roughness meter manufactured by Tokyo Seimitsu Co., Ltd .;
It measured using 500A. (Bending Characteristics) The polyphenylene ether resin composition was dried (120 ° C., 5 hours). Using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75 t, a resin temperature of about 260 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50%
Injection molding was performed under the conditions described above to produce a test piece having a size of about 10 × 100 × 6 mm. The bending strength and the flexural modulus of the obtained test piece were measured according to ASTM D-790. (Anisotropic; linear expansion coefficient) produced under the same conditions as above,
The anisotropy was measured by the ratio of the linear expansion coefficient between the MD direction and the TD direction of a JIS No. 1 dumbbell-shaped test piece having a thickness of about 3 mm. The closer the ratio is to 1, the smaller the anisotropy and the more isotropic, ie, the better the dimensional accuracy. The coefficient of linear expansion was determined by measuring the center of the above dumbbell-shaped test piece by about 7
mm × 7mm, S manufactured by Seiko Electronics Co., Ltd.
It was measured using SC-5200 and TMA-120C. (Surface appearance) Manufactured under the same conditions as for dimensional accuracy.
The center line average roughness of a JIS No. 1 dumbbell-shaped specimen having a thickness of about 3 mm was evaluated.

The center line surface roughness was measured using a surface roughness meter; Surfcom 1500A manufactured by Tokyo Seimitsu Co., Ltd. (Ash content) The ash content of the polyphenylene ether resin composition derived from the silane clay composite was measured according to JIS K7052. (Example 1) Step (A) 180 g of Kunipia F was added to 4000 g of ion-exchanged water, and the mixture was cooled to 5000 rpm using a wet mill manufactured by Nippon Seiki Co., Ltd.
m, and mixed by stirring for 5 minutes. Then, 36 g of A11
After adding 10 and stirring further under the conditions shown in Table 1, a silane clay composite was prepared. (Confirmation of the silane clay complex is as follows:
The measurement was performed by measuring the bottom surface interval by AXS and measuring the absorption band of the functional group derived from the silane compound by FT-IR after washing with THF. Table 1 shows the results
Shown in ). Then, 18 g of PGE and 18 g of S
GE was added and stirring was continued for another 30 minutes, followed by dry powdering.

[0094]

[Table 1] Step (B) The above silane clay complex and 2700 g of toluene were sufficiently mixed by a wet mill (5000 rpm × 30 minutes), and then 900 g of methanol and 700 g of n-butanol were added and mixed well. Then, under nitrogen atmosphere, 800 g
Is dissolved and stirred to obtain a clay containing the silane clay complex and the phenolic compound 26DP.
A phenol dispersion was obtained. The bottom spacing of the silane clay composite in the clay-phenol dispersion was> 100 °. Step (C) 0.58 g of cupric chloride, 4.5 g of p-toluenesulfonic acid monohydrate, 360 g of methanol, 40 g of N, N,
N, 'N,'-Tetramethyl-1,3-diaminopropane, 8 g of di-n-butylamine, 1070 g of toluene and 360 g of n-butanol were sufficiently mixed to prepare a catalyst solution. Separately, the above clay-phenol dispersion was charged into a reaction vessel. The reaction tank was replaced with oxygen while stirring, and an oxygen stream was allowed to flow as it was. Next, the catalyst solution described above was added while vigorously stirring the clay-phenol dispersion, and polymerization was carried out at 40 ° C. for 3 hours. Next, a polymer was precipitated with methanol and washed to polymerize a polyphenylene ether resin containing a silane clay composite.

After drying, 1800 g of M140 was dry blended, and a twin screw extruder (LABOTE, Nippon Steel Corporation)
X30) using a temperature of about 250 ° C. and a rotation speed of 100 rpm
Was melt-kneaded under the following conditions to obtain and evaluate a polyphenylene ether resin composition. Table 2 shows the results.

[0096]

[Table 2] (Example 2) In the step (A), the amount of A1110 was 1
A polyphenylene ether resin containing a silane clay composite was polymerized in the same manner as in Example 1 except that the amount was 8 g and the amounts of PGE and SGE were each 9 g. Incidentally, the bottom surface interval of the silane clay composite in the clay-phenol dispersion obtained in the step (B) was 84 °.

The above polyphenylene ether resin composition was melt-kneaded with M140 in the same manner as in Example 1 to obtain a polyphenylene ether resin composition, which was evaluated. The results are shown in Tables 1 and 2. (Example 3) In step (A), a polyphenylene ether resin containing a silane clay composite was polymerized in the same manner as in Example 1 except that 200 g of Wengel HVP was used instead of Kunipia F. Incidentally, the distance between the bottom surfaces of the silane clay composite in the clay-phenol dispersion obtained in the step (B) is> 1.
It was 00 $.

The above polyphenylene ether resin composition was melt-kneaded with M140 in the same manner as in Example 1 to obtain a polyphenylene ether resin composition, which was evaluated. The results are shown in Tables 1 and 2. (Example 4) 30 mm diameter twin screw extruder (Nippon Steel Corporation)
LABOTEX 30), at a temperature of about 250 ° C. and a rotation speed of 100 rpm, a polyphenylene ether resin containing a silane clay composite polymerized in the same manner as in Example 1, 1800 g of M140 and 200 g of glass fiber T195H Was melt-kneaded to obtain and evaluate a polyphenylene ether resin composition. The results are shown in Tables 1 and 2. (Comparative Example 1) A polyphenylene ether resin was polymerized in the same manner as in Example 1 without using the silane clay composite, and then melt-kneaded with M140 to obtain a polyphenylene ether resin composition and evaluated. Table 3 shows the results.

[0099]

[Table 3] (Comparative Example 2) A polyphenylene ether resin was polymerized in the same manner as in Example 1 except that 180 g of Kunipia F was used instead of the silane clay composite, and then melt-kneaded with M140 to obtain a polyphenylene ether resin composition and evaluated. did. Table 3 shows the results. (Comparative Example 3) 180 g of Kunipia F, 36 g of A111
Kunipia F was treated by mixing 0, 18 g PGE and 18 g SGE directly at room temperature and stirring for 1 hour. The distance between the bottom surfaces of the silane-treated Kunipia F was 13 °.

A polyphenylene ether resin was polymerized in the same manner as in Example 1 except that the above-mentioned silane-treated Kunipia F was used instead of the silane clay composite, and then M140
And melt-kneaded to obtain a polyphenylene ether resin composition, which was evaluated. Table 3 shows the results. (Comparative Example 4) 900 g of ion-exchanged water and 300 g of Kunipia F were mixed by applying ultrasonic waves to swell Kunipia F.

Twin screw extruder (Nippon Steel Corporation, TEX4
4), using a temperature of 190 to 200 ° C. and a rotation speed of 350 rpm
Under the conditions of m, 1320 g of polyphenylene ether resin polymerized in the same manner as in Comparative Example 1 and 3080 g of M14
0 and Kunipia F swollen with water are melt-kneaded,
A polyphenylene ether resin composition was obtained and evaluated. Table 3 shows the results. Comparative Example 5 800 g of polyphenylene ether resin polymerized in the same manner as in Comparative Example 1, 1800 g of M140 and 650 g of glass fiber T195H were melt-kneaded to obtain a polyphenylene ether resin composition, which was evaluated. Table 3 shows the results.

[0102]

In the polyphenylene ether resin, the unit layers of the swellable silicate are separated and cleaved to form one agglomerated particle of the swellable silicate into a very large number of extremely fine plate-like layers. By subdividing, the effect of reducing mechanical characteristics and warpage can be efficiently obtained without impairing the surface appearance.

Claims (7)

[Claims] 1. A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane clay composite, wherein the silane clay composite is converted into a swellable silicate by the following general formula (1): Y _n SiX _4-n ( 1) (where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. A) a polyphenylene ether resin composition prepared by introducing a silane compound represented by the formula (1), wherein the average layer thickness of the silane clay composite in the resin composition is 500 ° or less. 2. The maximum thickness of the silane clay composite is 2000.
ポ リ The polyphenylene ether resin composition according to claim 1, wherein 3. The [N] value is 30 or more, where the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition. The polyphenylene ether resin composition according to claim 1 or 2, which is used. 4. The polyphenylene ether resin composition according to claim 1, wherein the silane clay composite in the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300. 5. A polyphenylene ether resin composition containing a polyphenylene ether resin and a silane clay composite, wherein the silane clay composite is converted into a swellable silicate by the following general formula (1): Y _n SiX _4-n ( 1) (where n is an integer of 0 to 3 and Y is 1 to 3 carbon atoms)
X is a hydrolyzable group and / or a hydroxyl group, which is an organic functional group composed of 25 hydrocarbon groups and a hydrocarbon group having 1 to 25 carbon atoms and a substituent. n Y and 4-n X may be the same or different. ) Is prepared by introducing a silane compound represented by the formula (1), and the resin composition has an average aspect ratio (ratio of layer length / layer thickness) of 10 to 300, and [ N] value is 30 or more, wherein the [N] value is defined as the number of particles per unit ratio of the silane clay complex present in an area of 100 μm ² of the resin composition. Composition. (A) a step of preparing a silane clay composite, (B) a silane clay composite and the following general formula (2): (Wherein R ¹ , R ² , R ³ and R ⁴ are each hydrogen, a halogen atom, an alkyl group optionally substituted with a functional group, an aralkyl group optionally substituted with a functional group, (C) a step of polymerizing the phenolic compound.
A method for producing the polyphenylene ether resin composition according to claim 1, 2, 3, 4, or 5. 7. The method according to claim 1, wherein the distance between the bottom surfaces of the silane clay complex after mixing with the phenolic compound in the step (B) is at least three times the distance between the bottom surfaces of the swellable silicate. 7. The method for producing the polyphenylene ether resin composition according to 6.