JP2000290505A - Polysulfone resin composition and production method - Google Patents

Abstract

(57) [Problem] To provide a polysulfone resin composition in which anisotropy and warpage are suppressed without impairing surface smoothness and retention heat stability and mechanical properties are improved. A polysulfone resin composition containing a polysulfone 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 polysulfone 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 polysulfone resin composition is 500 ° or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polysulfone resin composition containing a polysulfone resin and a silane clay composite, and a method for producing the resin composition.

[0002]

2. Description of the Related Art Polysulfone resins are widely used in various fields such as electric / electronics, precision machinery, food / medicine, etc. due to their excellent heat resistance, transparency, impact resistance, dimensional accuracy and creep resistance. ing. By adding a fibrous reinforcing agent such as glass fiber to the polysulfone resin, the molding shrinkage becomes smaller, and the mechanical strength and the elastic modulus are improved. It is applied to switches, connectors, sockets, coil bobbins, etc. The glass fiber is surface-treated with a sizing agent such as epoxy resin to give the convergence of the glass fiber itself to facilitate the compoundability with the resin or to improve the affinity with the resin. In such a case, the melting heat stability of the polysulfone resin may be impaired. In other words, because the melt viscosity of polysulfone resin is relatively high, high molding temperature / injection pressure / injection speed is required especially when injection molding small parts having complicated shapes or parts having thin parts. In some cases, decomposition gas is generated due to heat at the time of injection or melting and staying in a cylinder, or a cross-linking reaction is caused to cause thickening and gelation. Another problem is that the glass fibers are oriented during the injection molding to cause anisotropy, resulting in a decrease in dimensional accuracy, and the floating of the glass fibers impairing the surface smoothness of the molded product.

As another means for improving mechanical strength and elastic modulus, inorganic fillers have been used. Since the inorganic filler does not require a sizing agent, it does not impair the melt heat stability, and does not undergo orientation during injection molding, so there is no fear of anisotropy. However, the effect of improving the mechanical strength and the elastic modulus was not sufficient with the addition of the inorganic filler. It is generally considered that such a defect in the blending of the inorganic filler is caused by an excessively large size of the dispersed particles of the inorganic filler.

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).

However, in the above invention (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 higher than that of nylon 6 alone. It has been improved, but it is not enough. Further, although a nylon 6-based composite material is disclosed, it has been difficult to obtain a polysulfone resin composite material in which layered particles are finely dispersed by directly applying the nylon 6-based method to a polysulfone resin.

In the technique (2), swellable mica is used as a layered silicate, and swellable mica swelled with water or alkylammonium-treated swellable mica swelled with xylene is mixed with a polypropylene resin or the like. A technique of a resin composition obtained by screw extrusion is disclosed. However, even if the above technique is directly applied to the polysulfone resin, the layered silicate is incomplete and non-uniform even though it is partially finely dispersed, so that a polysulfone resin composition having desired physical properties is obtained. Can not do.

[0007]

Accordingly, there is still provided a technique for obtaining a polysulfone resin composition having sufficiently improved mechanical strength and elastic modulus without impairing the retention heat stability, dimensional accuracy and surface smoothness. At present, there is no such object, and an object of the present invention is to solve such a conventional problem.

[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 sheet-like silane clay composite prepared by subdividing one swellable silicate aggregated particle into a very large number of extremely fine sheet-like particles is uniformly dispersed in a polysulfone resin. The inventors have found that the object can be achieved, and have completed the present invention.

That is, a first aspect of the present invention is a polysulfone resin composition containing a polysulfone 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 polysulfone 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.

[0010] In a preferred embodiment, the present invention relates to the polysulfone resin composition described above, wherein the maximum thickness of the silane clay composite is 2000 ° or less.

In a further preferred embodiment, the [N] value defined as the number of particles per unit ratio of the silane clay composite in an area of 100 μm ² of the resin composition is 30 or more. And a polysulfone resin composition.

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

A second aspect of the present invention is a polysulfone resin composition containing a polysulfone resin and a silane clay composite, wherein the silane clay composite is added to 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 resin composition 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 a resin. The present invention relates to a polysulfone resin composition having an [N] value of 30 or more, which 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} composition.

A third aspect of the present invention is a step (A) of preparing a clay dispersion containing a silane clay composite and a dispersion medium, and (B) a step of mixing the polymerizable monomer of the polysulfone resin with the above clay dispersion. And (C) a method for producing a polysulfone resin composition according to any one of the above, comprising a step of polymerizing a polymerizable monomer.

In a preferred embodiment, the distance between the bottom surfaces of the silane clay complex in the clay dispersion obtained in the step (A) is at least three times the distance between the bottom surfaces of the swellable silicate. The present invention relates to a method for producing the polysulfone resin composition described above.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The polysulfone resin used in the present invention is a constitutional unit in which an arylene unit, an ether bond and a sulfone bond are essential, and the arylene unit is located randomly or orderly together with the ether bond and the sulfone bond. Defined as polyarylene compound. As typical examples, the following general formulas (2), (3),
Examples include those having a repeating unit as in (4), but are not limited thereto. General formula (2):

[0017]

Embedded image (Wherein, R ¹ is an alkyl group having 1 to 6 carbon atoms, 3 to
Represents 10 alkenyl groups, phenyl groups or halogen atoms, and p is an integer of 0-4. m and n indicate the average number of repeating units, and m and n are positive numbers of 0.1 to 100. Each R ¹ may be the same or different. Each p may be the same or different. General formula (3):

[0018]

Embedded image (Wherein R ² is an alkyl group having 1 to 6 carbon atoms, 3 to
Represents 10 alkenyl groups, phenyl groups or halogen atoms, and p is an integer of 0-4. m and n indicate the average number of repeating units, and m and n are positive numbers of 0.1 to 100. Each R ² may be the same or different. Each p may be the same or different.
The compound of (3) includes a random copolymer.) General formula (4):

[0019]

Embedded image (Wherein, R ³ is an alkyl group having 1 to 6 carbon atoms,
Represents 10 alkenyl groups, phenyl groups or halogen atoms, and p is an integer of 0-4. q, m, and n each represent an average number of repeating units, q is an integer of 1 to 3, and m and n are each 0.
It is a positive number from 1 to 100. Each R ³ may be the same or different. Each q may be the same or different. This compound includes a random copolymer. As the polysulfone resin used in the present invention, (m / m + n) in the repeating unit represented by the general formula (3) or (4) is preferably 0.8 or more. Further, q in the structural unit of the general formula (4) is preferably 1.

Accordingly, specific examples of the polysulfone resin used in the present invention include the following formulas (5) to (20):

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

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[0029]

Embedded image

[0030]

Embedded image

[0031]

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[0032]

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[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image And those represented by the following structural formula. Above all, those having structures of formulas (5) to (10) are preferable. The above-mentioned polysulfone 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 refers to a swellable silicate represented by 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 using a smectite group clay and swellable mica as the swellable silicate, the dispersibility of the swellable silicate in the polysulfone resin composition of the present invention, the availability and improvement of the physical properties of the resin composition. Preferred from the point.

The smectite group clay is represented by the following general formula (21): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (21) (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 (2)
2): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (22) (where X is selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr) Y is M
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 vermiculites, and such vermiculite equivalents and the like can also be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (23): (Mg, Fe , Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 (M ⁺ , M ²⁺ _1/2 ) _x · nH ₂ O (23) (where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0) .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 viewpoints of dispersibility in the polysulfone 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 preferably 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 one 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 represents 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 compared to 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 introduction of the silane compound 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 complex 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-based compound is removed from the silane-clay composite by washing with an organic solvent, and after drying, the small-angle X-ray diffraction method (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.

After washing with an organic solvent as described above,
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 polysulfone resin composition of the present invention, the compounding amount of the silane clay composite per 100 parts by weight of the polysulfone resin is typically 0.1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, Preferably 0.3-4
It is prepared so as to be 0 parts by weight, more preferably 0.4 to 35 parts by weight, particularly preferably 0.5 to 30 parts by weight.
If the amount of the silane clay composite is less than 0.1 part by weight, the effect of improving mechanical properties and dimensional accuracy may be insufficient, and if it exceeds 50 parts by weight, surface smoothness tends to be impaired. .

The ash content of the polysulfone 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 to 25% by weight, still more preferably 0.4 to 23% by weight, particularly preferably 0.5 to 20% by weight. Is done. If the ash content is less than 0.1% by weight, the effect of improving mechanical properties and dimensional accuracy may be insufficient, and 3
If it exceeds 0% by weight, the surface smoothness tends to be impaired.

The structure of the silane clay composite dispersed in the polysulfone resin composition of the present invention has an aggregated structure of μm size in which a large number of layers are laminated, such as the swellable silicate before compounding. Completely different. 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 polysulfone resin composition in a very fine and independent lamellar form, 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 composite in the polysulfone resin composition of the present invention is defined. Average body aspect ratio is 10-300
And 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 and dimensional accuracy of the polysulfone resin composition of the present invention may not be sufficiently obtained. Further, even if it is larger than 300, the effect does not change any more, so that it is not necessary to make the average aspect ratio larger than 300.

Further, the [N] value is calculated based on the polysulfone resin composition.
Object area 100μm^TwoSwellable silicate units in
If defined as the number of dispersed particles per weight ratio,
Silane clay complex in Ming polysulfone resin composition
Has an [N] value of 30 or more, preferably 45 or more.
And more preferably 60 or more. No upper limit
However, when the [N] value exceeds about 1000, it becomes more effective.
The fruit will not change, so it needs to be larger than 1000
There is no. The [N] value is obtained, for example, as follows.
obtain. That is, the polysulfone resin composition is about 50 μm
１００100 μm-thick ultrathin section, and the section
Area is 100μm on the image taken ^TwoAny area of
The number of particles of the silane clay complex present in
It can be determined by dividing by the weight ratio of the silicate.
Alternatively, on the TEM image, there are 100 or more particles.
Select an arbitrary area (area is measured)
The number of particles present is determined by the weight ratio of the swellable silicate used.
100 μm^TwoIs converted to [N] value
Is also good. Therefore, the [N] value of the polysulfone resin composition
It can be quantified by using a TEM 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 polysulfone resin composition of the present invention is 500 ° or less, preferably 450 ° or less, more preferably 400 ° or less. If the average layer thickness is larger than 500 °, the effect of improving the mechanical properties and dimensional accuracy of the polysulfone 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. Further, 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 polysulfone resin composition of the present invention, the upper limit of the maximum layer thickness of the silane clay composite is 2000 ° or less, preferably 1
It is 800 ° or less, and more preferably 1500 ° or less. If the maximum layer thickness is more than 2000 °, the balance of mechanical properties, dimensional accuracy and surface smoothness of the polysulfone 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 polysulfone resin composition of the present invention and then hot press molding or stretch molding, and a thin molded product obtained by injection molding the molten resin. Can be determined from an image captured 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 polysulfone resin composition of the present invention is not particularly limited. For example, (A) a step of preparing a clay dispersion containing a silane clay composite and a dispersion medium; (B)
A method including a step of mixing the polymerizable monomer of the polysulfone resin with the above clay dispersion and a step of (C) polymerizing the polymerizable monomer are preferred.

First, the step (A) will be described in detail. In the step (A), the silane clay composite is obtained, for example, by adding a silane-based compound after expanding a bottom surface interval of a swellable silicate in a dispersion medium.

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 expansion of the distance between the bottom surfaces of the swellable silicate in the dispersion medium can be achieved 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 bottom surface interval of the swellable silicate refers to a particulate swellable silicate in which unit layers are stacked and aggregated before addition to a 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 effectively increase the distance between the bottom surfaces of the swellable silicate, stirring may be performed at a speed of several thousand 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, and the layers in the aggregated state are cleaved to be separated. After the layers 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 space 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-type pulverizers, wet-type collision pulverizers that collide a sample at a high speed with a jet nozzle, and the like, and wet-type ultrasonic pulverizer using ultrasonic waves. If you want to introduce silane compounds more efficiently,
The rotation speed of the stirring is 1000 rpm or more, preferably 150 rpm.
0 rpm or more, more preferably 2000 rpm or more, or 500 (1 / s) or more, preferably 10
00 (1 / s) or more, more preferably 1500 (1 / s)
s) Apply a shear rate above. The upper limit of the number of revolutions is about 25
000 rpm, and the upper limit of the shear rate is about 50,000.
0 (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 (for example, while wet grinding).
A silane compound may be introduced.

Alternatively, a swellable silicate having an increased bottom distance due to a physical external force is added to a dispersion medium, and a silane compound is added thereto 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 distance 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 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 sufficient for the dispersibility of the silane clay composite in the clay dispersion, the affinity between the silane clay composite and the resin, and the dispersibility of the silane clay composite in the polysulfone resin composition. Can be prepared.
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,
It is 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, 2
If the amount is more than 00 parts by weight, the effect does not change, so it is not necessary to add more than 200 parts by weight.

The method for preparing the clay dispersion is not particularly limited.
For example, a method in which a system containing a dispersion medium and a silane clay composite obtained when a silane clay composite is prepared is directly used as a clay dispersion (referred to as a direct method: in this case, the silane clay composite must be prepared). Is the step (A)) or the system containing the dispersion medium and the silane clay composite obtained when the silane clay composite is prepared is mixed with another desired dispersion medium and then replaced. A method of using a system composed of a newly added desired dispersion medium and a silane clay composite as a clay dispersion (referred to as a substitution method), or a method of drying a silane clay composite obtained by removing a dispersion medium and a desired silane clay composite. A method of sufficiently mixing a dispersion medium (referred to as a mixing method) is exemplified.

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 dispersion obtained in the step (A), the initial lamination / agglomeration structure, which the swellable silicate had, had almost completely disappeared, and the silane clay composite became a thin plate. Either it is subdivided or the interval between the layers is 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 dispersion is preferably at least three times, preferably at least four times, the initial distance between the bottom surfaces of the swellable silicate in order for the silane clay complex to be finely divided and formed into a thin plate. Is more preferable, and more preferably 5 times or more.

Next, the step (B), that is, the step of mixing the clay dispersion and the polymerizable monomer of the polysulfone resin is performed. The polymerizable monomer of the polysulfone resin includes, for example, 2,2-bis (4-hydroxyphenyl) propane (“bisphenol A”), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (“Bisphenol TMC”), bis (4-hydroxyphenyl) cyclohexylmethane,
2,2-bis (4′-hydroxy-3,5′-dibromophenyl) propane, 2,2-bis (4′-hydroxy-3 ′, 5′-dimethylphenyl) propane, 1,1-
Bis (4'-hydroxyphenyl) -1-phenylethane, 4,4'-dihydroxydiphenyl ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, 4,4'-dihydroxybenzophenone, and bis (4- The following general formula (24) such as (hydroxyphenyl) sulfide:

[0081]

Embedded image (Wherein -A- is -O-, -S-, -SO-, -CO
-, An alkylene group having 1 to 20 carbon atoms or 6 to 2 carbon atoms
0 alkylidene group, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are all a hydrogen atom, a halogen atom or a monovalent hydrocarbon group having 1 to 5 carbon atoms. And they may be the same or different. ), Methylsulfonic acid, chlorosulfonic acid, dichlorosulfone, bis (4-chloro-3,5-dimethylphenyl) sulfone, 4,4′-dichlorodiphenylsulfone, diphenylsulfone, etc. (25): R ¹² —SO ₂ —R ¹³ (25) (wherein, R ¹² and R ¹³ are a hydrocarbon group having 1 to 15 carbon atoms which may have a substituent, a hydroxyl group, and a halogen atom. ,
They may each be different. )).

The method of mixing the clay dispersion and the polymerizable monomer is not particularly limited. For example, a method of directly mixing the polymerizable monomer of polysulfone into the clay dispersion, or a method of mixing a solvent such as dimethyl sulfoxide (DMSO). After dissolving the polymerizable monomer, mixing with the clay dispersion, mixing the clay dispersion with the polymerizable monomer in the molten state or in solution during the polymerization, or adding / mixing continuously / sequentially Method. In the case of continuous addition, the rate of addition of the clay dispersion is not particularly limited.
0.01 to 10.0 parts by weight / minute, preferably 0.03 to 8.0 parts by weight / minute, more preferably 0.05 to 6.0 parts by weight, per 100 parts by weight of the clay dispersion. Add continuously or sequentially in minutes.

Then, step (C), that is, a step of polymerizing a polymerizable monomer can be performed. The polymerization method is not particularly limited, and can be carried out by a generally-used polymerization method of polysulfone resin, but desalting polycondensation in a solution is preferably employed.

In the desalting polycondensation, for example, a bisphenol compound such as bisphenol A dissolved in an aqueous alkali solution such as an aqueous sodium hydroxide solution and 4,4′-dichlorodiphenyl sulfone dissolved in an aprotic polar solvent such as DMSO are used. Is reacted at room temperature in the presence of a catalyst, and one or both of the aqueous alkali solution and the aprotic polar solvent is a clay dispersion in which a silane clay complex is dispersed. Alternatively, a method in which a separately prepared clay dispersion is added and mixed at an arbitrary stage of the reaction between the bisphenol compound dissolved in the alkaline aqueous solution and the sulfone compound dissolved in the aprotic polar solvent can be preferably performed.

[0085] The polysulfone resin composition of the present invention can also be produced by the following method.

First, a good solvent for a polysulfone resin such as DMSO is thoroughly mixed with a silane clay complex prepared in advance. The number of agitation during mixing and the like are the same as those described above, and the bottom spacing of the silane clay composite after mixing is preferably at least three times, more preferably at least four times the initial bottom spacing of the swellable silicate. More preferably 5 times or more. Next, the polysulfone resin composition is obtained by adding and dissolving the polysulfone resin, thoroughly mixing and removing the solvent.

The reason why the polysulfone resin composition of the present invention has excellent mechanical strength and elastic modulus without impairing dimensional accuracy and surface smoothness is that the polysulfone resin contains a large number of fine sheet-like silane clay composites. This is because the average layer thickness, the maximum layer thickness, the number of dispersed particles, and the average aspect ratio of the silane clay composite, which are dispersed as particles and serve as indicators of the dispersion state, are in the above-described 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 polysulfone resin composition.

That is, for example, in the direct method in the step (A), if the stirring force and the shearing force at the time of dispersing the swellable silicate are constant, the kind of the dispersion medium and plural kinds of dispersion medium are used. In this case, the state of swelling / cleavage of the swellable silicate changes according to the mixing ratio and the order of mixing. 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 and tetrahydrofuran (TH
F), methyl ethyl ketone (MEK), pyridine, N,
When a mixed solvent of water and a polar solvent such as N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP) is used as a dispersion medium, or montmorillonite is dispersed in the polar solvent. In the case where water is added and then water is added, about several to several hundreds of unit layers are cleaved and subdivided into a laminated state. 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 polysulfone resin composition so as to maintain those states.

In the substitution method (method of replacing the dispersion medium used for preparing the silane clay composite with another desired dispersion medium) in the step (A), the kind of the dispersion medium to be newly added and a plurality of kinds of dispersion mediums are used. When used, the dispersion state of the silane clay composite in the clay dispersion varies depending on the mixing ratio and the order of mixing. For example, when a polar solvent having a low affinity for the functional group of the silane-based compound is added to a water matrix dispersion containing the silane clay complex in a unit layer state and replaced with water, the silane clay complex in the unit layer state is obtained. About several to about several tens of bodies agglomerate and can be laminated. The dispersion state of the silane clay composite can be controlled by performing steps (B) and (C) in the method for producing a polysulfone resin composition so as to maintain those states.

In the step (B), the dispersion state of the silane clay composite changes depending on the type and molecular weight of the polymerizable monomer mixed with the clay dispersion. The dispersion state of the silane clay composite can be controlled by performing the step (C) in the method for producing a polysulfone resin composition so as to maintain those states.

In the polysulfone resin composition of the present invention, if necessary, 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 (including any copolymer such as random, block and graft, and 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. Thermoplastic resins such as reinforced styrene resins, polyamide resins, polyphenylene sulfide resins, polyphenylene ether resins, polyacetal resins, polyarylate resins, polyimides, polyetherimide resins, and unsaturated polyester resins, epoxy resins, and phenol novolak resins The thermosetting resins may be used alone or in combination of two or more.

Further, according to the purpose, the polysulfone resin composition of the present invention may contain a pigment or a dye, a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a lubricant, a plasticizer, a flame retardant,
And an additive such as an antistatic agent. The polysulfone resin composition of the present invention may be molded by injection molding, extrusion molding, hot press molding, or can be used for blow molding. Such molded products are excellent in appearance, mechanical properties, etc., for example, automotive parts, household electrical parts, precision machinery parts, household daily necessities, packaging / container materials, electro-magnetic base materials, and other general industrial materials. It is preferably used.

In the polysulfone resin composition of the present invention, the silane clay composite is very fine and thin and plate-like, and is uniformly dispersed, so that the mechanical properties can be improved without impairing the dimensional stability and surface smoothness. Can be improved.

[0095]

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 Examples and Comparative Examples are shown below. Unless otherwise specified, the raw materials were not purified. (Raw materials) 4,4'-dichlorodiphenylsulfone: 4,4'-dichlorodiphenylsulfone (Wako first grade) from Wako Pure Chemical Industries, Ltd. (hereinafter referred to as DCDPS) was used. Bisphenol A: 2,2'-bis (4-hydroxyphenyl) -propane (Wako first grade) from Wako Pure Chemical Industries, Ltd.
(Hereinafter referred to as bisphenol A). -Dimethyl sulfoxide: Wako Pure Chemical Industries, Ltd.'s dimethyl sulfoxide (special grade reagent) (hereinafter referred to as DMSO)
Was used.・ Swellable silicate: Kunimine F Co., Ltd.
(Hereinafter, referred to as Kunipia F, bottom spacing = 13 °), and Wenger HVP of Toyshun Yoko Co., Ltd. (hereinafter, referred to as Wenger HVP, bottom spacing = 13 °). -Γ- (2-aminoethyl) aminopropyltrimethoxysilane: manufactured by Nippon Unicar Co., Ltd., A-1120 (hereinafter A
1120)-γ-aminopropyltrimethoxysilane: A-1110 of Nippon Unicar Co., Ltd. (hereinafter referred to as A1110) was used. -Polyethylene glycol diglycidyl ether: Polyethylene glycol diglycidyl ether of Nagase Kasei Co., Ltd. (hereinafter referred to as PEGDG) 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 value 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 inappropriate, 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 280 to 320 ° 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 not dispersed in the form of a plate was defined as the 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 the 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 °. (Residence heat stability) Using a capillagraph of Toyo Seiki Seisakusho, using an orifice with a diameter of 1 mm and a length of 10 mm,
The apparent melt viscosity at a set temperature of 380 ° C. and a shear rate of 1000 (1 / S) was measured. (Bending characteristics) The polysulfone resin composition was dried (120
C. for 5 hours). Using an injection molding machine with a mold clamping pressure of 75 t (IS-75E, manufactured by Toshiba Machine Co., Ltd.), resin temperature of 320
Injection molding was performed at a temperature of 10 ° C., a gauge pressure of about 10 MPa, and an injection speed of about 50% 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. (Dimensional Accuracy; Anisotropy) Anisotropy was evaluated based on the ratio of the coefficient of linear expansion in the MD direction and the TD direction of a JIS No. 1 dumbbell-shaped test piece having a thickness of about 3 mm and manufactured under the same conditions as described above. 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 measured as follows.

The center of the above dumbbell-shaped test piece was set to about 7
mm × 7mm, S manufactured by Seiko Electronics Co., Ltd.
It was measured using SC-5200 and TMA-120C. (Warp) Dry the polysulfone resin composition (120 ° C., 5
Time), and using an injection molding machine (IS-75E, manufactured by Toshiba Machine Co., Ltd.) with a mold clamping pressure of 75t, a mold temperature of 80 ° C, a resin temperature of 320 ° C, a gauge pressure of about 10 MPa, and an injection speed of about 5
Injection molding under 0% condition, dimension about 120 × 120 × 1
mm plate-shaped test pieces were prepared. The flat test piece was placed on a flat surface, and the degree of warpage was checked. (Surface Smoothness) The center line average roughness of a JIS No. 1 dumbbell-shaped test piece having a thickness of about 3 mm and manufactured under the same conditions as in the case of the dimensional accuracy 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 polysulfone resin composition derived from the silane clay composite was measured according to JIS K7052. (Example 1) Step (A) 160 g of montmorillonite was added to 3500 g of ion-exchanged water, and the resulting mixture was mixed with a wet mill manufactured by Nippon Seiki Co., Ltd. for 500 days.
The mixture was stirred at 0 rpm for 5 minutes and mixed. Thereafter, 16 g of A1120 was added, and the mixture was further stirred under the conditions shown in Table 1 to prepare a silane clay composite. (Confirmation of the silane clay complex was conducted by separating, drying, and pulverizing the solid content, measuring the bottom surface interval with SAXS, and washing the product with THF to determine the absorption band of the functional group derived from the silane compound by FT-IR. The results are shown in Table 1.)

[0104]

[Table 1] Then, 4000 mL of DMSO was added and mixed well, followed by heating to remove water, that is, a clay dispersion containing the silane clay composite and DMSO was prepared by a substitution method. The bottom spacing of the silane clay composite in the clay dispersion was> 100 °.

Step (B) In a nitrogen atmosphere, add 10,000 mL to the above clay dispersion.
Of DMSO was added and mixed well. Then, inside, 15
50 g of DCDPS was dissolved and stirred and mixed.

Step (C) In a nitrogen atmosphere, 13
90 g of bisphenol A, 44 g of pt-butylphenol, and 3120 mL of a 5N aqueous sodium hydroxide solution were charged and mixed well to prepare an alkaline aqueous solution of bisphenol A.

Next, under a nitrogen atmosphere, 4000 ml of ion-exchanged water and a polymerization catalyst were charged into a separately prepared reaction vessel.

The aqueous solution containing the above polymerization catalyst is mixed with 500 to 8
While stirring at 00 rpm, the previously prepared alkaline aqueous solution of bisphenol A, the mixture containing the clay dispersion prepared in step (B) and DCDPS are mixed and simultaneously continuously over about 30 minutes. The mixture was added and stirred for 3 hours. Thereafter, neutralization, washing, desalting, and drying were performed to obtain and evaluate a polysulfone resin composition. The results are shown in Table 2.

[0109]

[Table 2] (Example 2) Step (A) A clay dispersion was prepared in the same manner as in Example 1 except that the amount of A1120 was changed to 8 g. The results are shown in Table 1. The distance between the bottom surfaces of the silane clay composite in the clay dispersion was 80 °. Steps (B) and (C) Performed in the same manner as in Example 1 to obtain a polysulfone resin composition.
evaluated. The results are shown in Table 2. (Example 3) Step (A) A clay dispersion was prepared in the same manner as in Example 1 except that 180 g of Wengel HVP was used instead of Kunipia F and the amount of A1120 was changed to 18 g. The results are shown in Table 1. The bottom spacing of the silane clay composite in the clay dispersion was> 100 °. Steps (B) and (C) Performed in the same manner as in Example 1 to obtain a polysulfone resin composition,
evaluated. The results are shown in Table 2. (Example 4) Step (A) Example 1 was repeated except that 15 g of A1110 was used instead of A1120 to prepare a silane clay complex, and then 15 g of PEGDG was added and stirring was further continued for 30 minutes. Performed similarly. The results are shown in Table 1. Steps (B) and (C) Performed in the same manner as in Example 1 to obtain a polysulfone resin composition,
evaluated. The results are shown in Table 2. (Example 5) A polysulfone resin was polymerized in the same manner as in steps (B) and (C) of Example 1 except that only DMSO was used instead of the clay dispersion.

Separately from the polymerization of the polysulfone resin, a clay dispersion was prepared in the same manner as in Example 1. The results are shown in Table 1. The above polysulfone resin 25 was added to the obtained clay dispersion.
The polysulfone resin composition was obtained by gradually adding and mixing 00 g, followed by drying, and evaluated. The results are shown in Table 2. (Comparative Example 1) A polysulfone resin was obtained and evaluated in the same manner as in Example 5. The results are shown in Table 3.

[0111]

[Table 3] (Comparative Example 2) 160 g of Kunipia F and 14000 mL of DMSO were stirred with a high-speed stirrer at 5000 rpm for 30 minutes.
Mixed. A polysulfone resin was polymerized and evaluated in the same manner as in Example 1 except that the above mixture was used instead of the clay dispersion. The results are shown in Table 3. (Comparative Example 3) 160 g of Kunipia F, 16 g of A112
0 for 1 hour at room temperature.
Was processed. The distance between the bottoms of the silane treated Kunipia F is 13Å
Met. Silane-treated Kunipia F and 14000 mL of methylene chloride were stirred and mixed with a high-speed stirrer at 5000 rpm for 30 minutes. A polysulfone resin was polymerized and evaluated in the same manner as in Example 1 except that the above mixture was used instead of the clay dispersion. The results are shown in Table 3. (Comparative Example 4) 768 g of ion-exchanged water and 256 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 300 to 320 ° C and a rotation speed of 350 rpm
Under the conditions of m, 4000 g of the polysulfone resin polymerized in the same manner as in Example 5 and the above mixture were melt-kneaded, and volatile water was removed from the vent port under reduced pressure to obtain a polysulfone resin composition, which was evaluated. The results are shown in Table 3. (Comparative Example 5) 2500 g of polysulfone resin polymerized in the same manner as in Example 5 and 440 g of glass fiber surface-treated with an epoxy resin (0.4 parts by weight) were subjected to a twin-screw extruder (LABOTEX30, manufactured by Nippon Steel Corporation). ) And melt-kneaded under the conditions of a temperature of 300 to 320 ° C. and a rotation speed of 100 rpm to obtain and evaluate a polysulfone resin composition. The results are shown in Table 3.

[0113]

According to the present invention, in the polysulfone resin, the unit layers of the swellable silicate are separated and cleaved to subdivide the aggregated particles of the swellable silicate into a very large number of extremely small thin plate-like layers. Thus, a polysulfone resin composition can be obtained in which the effect of improving mechanical properties can be efficiently obtained without impairing the retention heat stability, surface smoothness, and dimensional stability.

Claims (7)

[Claims] 1. A polysulfone resin composition comprising a polysulfone resin and a silane clay composite, wherein the silane clay composite is formed 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 polysulfone 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 polysulfone resin composition according to claim 1, wherein 3. The method according to claim 1, wherein the [N] value 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 is 30 or more. Polysulfone resin composition. 4. The polysulfone 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 polysulfone resin composition containing a polysulfone 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 resin composition 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 a resin. A polysulfone resin composition having an [N] value of 30 or more, defined as the number of particles per unit ratio of the silane clay complex, present in an area of 100 μm ^{2 of the} composition. 6. A step of preparing a clay dispersion containing a silane clay complex and a dispersion medium, and a step of mixing a polymerizable monomer of a polysulfone resin with the clay dispersion.
The method for producing a polysulfone resin composition according to any one of claims 1, 2, 3, 4, and 5, further comprising (C) polymerizing a polymerizable monomer. 7. The silane clay composite in the clay dispersion obtained in the step (A) has a bottom surface interval of at least three times the bottom surface interval of the swellable silicate. A method for producing a polysulfone resin composition.