JP2000290506A - Polysulfone resin composition and preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition with improved mechanical properties without loss of heat stability during retention, dimensional accuracy and the like by blending a polysulfone resin and a clay intercalation compound prepared by mixing an amino compound and a swelling silicate in a dispersion medium. SOLUTION: An amino compound is preferably a 1-25C hydrocarbon compound which has one or more amino groups selected from one or more kinds of primary, secondary or tertiary amino groups and/or a compound which has one or more substituents selected from an OH group, SH group, ether group, CO group and Cl. A clay intercalation compound in the polysulfone composition preferably has an average layer thickness of 500 Å or less; a maximum layer thickness of 2,000 Å or less; and an average aspect ratio (the ratio of layer length to layer thickness) of 10-300. The composition preferably has an [N] value of 30 or more, the [N] value being the number of particles per unit proportion of the clay intercalation compound present in 100 μm2 of the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polysulfone resin composition containing a polysulfone resin and a clay interlayer compound, 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 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 and to improve the affinity with the polysulfone resin. The melt 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, and injection speed are required especially when injection molding small parts having complicated shapes or parts having thin parts. In some cases, heat generated during injection or melting and staying in a cylinder causes a crosslinking reaction by a sizing agent, resulting in thickening and gelling. 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, particulate inorganic substances have been used. Since a sizing agent is not required for the particulate inorganic material, the melt heat stability is not impaired, and since there is no orientation at the time of injection molding, there is no concern that anisotropy will occur. However, simply melting and kneading the particulate inorganic material with the resin has not been sufficient in improving the mechanical strength and the elastic modulus. It is generally considered that such a defect in the compounding of the particulate inorganic substance is caused by an excessively large size of the dispersed particles of the particulate inorganic substance, and various attempts have been made to improve the physical properties by uniformly and finely dispersing the particles.

A layered silicate is used as a particulate inorganic substance,
As a technique for facilitating cleavage of the layer for the purpose of forming the layered silicate into fine particles, (1) a low molecular compound (intercalant monomer) such as hexamethylenediamine is intercalated between the layers of the layered silicate to form an interlayer. Techniques for preparing compounds (JP-A-9-175816, European Patent 0780340)
No.) is disclosed.

[0005] Another technique is disclosed in (2) a resin composition in which a layered silicate having an average layer thickness of 25 to 1000 ° and an aspect ratio of 20 to 300 is dispersed in a thermoplastic resin. Japanese Unexamined Patent Publication No. 9-124836) is disclosed.

[0006] However, in the invention of the above (1), although an interlayer compound is disclosed, there is no disclosure about a technique for cleaving the interlayer compound and uniformly finely dispersing it in a polysulfone resin to improve physical properties. It is difficult to finely disperse layered particles in a polysulfone resin to obtain a polysulfone resin composition having improved physical properties.

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.

[0008]

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.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have separated and cleaved unit layers of swellable silicate,
The swellable silicate agglomerated particles are finely divided into a very large number of extremely small lamella-like particles, and the lamella-like clay intercalation compound is uniformly dispersed in the polysulfone resin. The inventors have found that the object can be achieved, and have completed the present invention.

That is, the first of the present invention is prepared by mixing (a) a polysulfone resin, and (b) an amino compound having at least one amino group with a swellable silicate in a dispersion medium. The present invention relates to a polysulfone resin composition containing a clay interlayer compound.

In a preferred embodiment, the amino compound has 1 to 25 carbon atoms and has at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups. And a polysulfone resin composition as described above.

In a further preferred embodiment, the amino compound has at least one substituent selected from the group consisting of a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom. And a polysulfone resin composition.

In a further preferred embodiment, the average thickness of the clay interlayer compound in the polysulfone resin composition is 500.
<4> The present invention relates to the following polysulfone resin composition:

In a further preferred embodiment, the maximum thickness of the clay intercalation compound in the polysulfone resin composition is 200.
The present invention relates to the polysulfone resin composition according to any one of the above, wherein 0 ° or less.

In a further preferred embodiment, the [N] value defined as the number of particles per unit ratio of the clay intercalation compound present in an area of 100 μm ² of the resin composition is 30 or more. Or a polysulfone resin composition as described above.

According to a further preferred embodiment, the polysulfone resin composition according to any one of the above, wherein the average aspect ratio (ratio of layer length / layer thickness) of the clay intercalation compound in the polysulfone resin composition is from 10 to 300. .

In the second aspect of the present invention, (A) a step of preparing a clay dispersion containing a clay interlayer compound and a dispersion medium, (B) a step of mixing the polymerizable monomer of the polysulfone resin with the above clay dispersion, (C) The 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 clay intercalation compounds in the clay dispersion obtained in the step (A) is as follows:
The present invention relates to the method for producing a polysulfone resin composition as described above, wherein the distance between the bottom surfaces of the swellable silicate is three times or more.

[0019]

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 (1), (2),
Examples include those having a repeating unit as in (3), but are not limited thereto.

[0020]

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.
Further, the compound (2) includes a random copolymer),

[0021]

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.
Further, the compound (3) includes a random copolymer),

[0022]

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 p 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 (2) or (3) is preferably 0.8 or more. Further, q in the structural unit of (3) is preferably 1.

Accordingly, specific examples of the polysulfone resin used in the present invention include the following (4) to (19):

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

Embedded image And those represented by the following structural formula. Above all, those having the structures of (4) to (9) 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 clay intercalation compound used in the present invention is:
It is prepared by mixing a swellable silicate and an amino compound having at least one amino group in a dispersion medium.

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 smectite clay and swellable mica are used as the swellable silicate, the dispersibility of the swellable silicate in the polysulfone resin composition of the present invention, the availability of the swellable silicate and the improvement of the physical properties of the resin composition are improved. Is preferred.

The smectite group clay is represented by the following general formula (20): X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (20) (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)
1): X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (21) (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 swelling mica have a structure similar to that of vermiculite, and such a vermiculite equivalent can be used. The said vermiculite such equivalent has three octahedral type and dioctahedral the following general formula (22): (Mg, Fe , Al) 2 ~ 3 (Si 4-x Al x) O 10 (OH) 2 _{^{· (M +, M 2+ 1/2}} ) x · nH 2 O (22) ( although, M is an alkali or alkaline earth metal exchangeable cations such as Na and Mg, x = 0.6~0. 9, n =
3.5 to 5). In the initial state of aggregation of the vermiculite-equivalent product, the distance between the bottom surfaces is approximately 10 to 17 °, and the average particle size in the aggregated state is approximately 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 desirably high in purity, which is regularly stacked in the c-axis direction. However, 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.

The amino compound used in the present invention is 1
Having at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups, and selected from the group consisting of hydroxyl, ether, mercapto, carbonyl, nitro and chlorine. It is preferably a hydrocarbon compound having 1 to 25 carbon atoms, which may have one or more substituents selected.

In the present specification, the hydrocarbon group in the hydrocarbon compound means a linear or branched (ie, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, aromatic group, or the like. It means a hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group. 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.

As specific examples of the above amino compounds, 1
1 selected from the group consisting of primary, secondary and tertiary amino groups
Examples of the case where at least one kind of amino group and a hydrocarbon group having 1 to 25 carbon atoms are constituents include butylamine, N, N-
Dimethylbutylamine, 1,2-dimethylpropylamine, dodecylamine, hexylamine, N-methylhexylamine, 3-pentylamine, dimethylaminoethylamine, 2-octylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1, 2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, tetramethyl-1,3-diaminopropane,
1,2-diaminobutane, 1,4-diaminobutane, N
-(3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine, N, N'-bis (aminopropyl) -1,3-propylenediamine,
N, N'-bis (aminopropyl) -1,4-butylenediamine, diallylamine, isoamylamine, N-ethylisoamylamine, 2-hexenylamine, N, N
-Diisopropylaminoethylamine, N, N-diisopropylethylamine, 2-ethylhexylamine, N
-Ethyl-1,2-dimethylpropylamine, diisobutylamine, 2-ethylhexylamine, aniline, β
-Naphthylamine, o-phenylenediamine, p-phenylenediamine, toluene-2,4-diamine, N,
N'-dimethyl-p-phenylenediamine, divinylpropylamine and the like can be mentioned. Examples of the amino compound having a hydroxyl group include 2- (hydroxymethylamino) ethanol, N-isomethyldiethanolamine, 2-aminopropanol, 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, and 4-aminobutanol.
Methylaminobutanol, 2-hydroxyethylaminopropylamine, diethanolaminopropylamine,
1-amino-3-phenoxy-2-propanol and the like. Examples of the amino compound having an ether group include bis (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, and 1,3-bis (3-aminopropoxy) -2,2-dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether, α, ω-bis (3-aminopropyl) diethylene glycol ether, 3-methoxypropylamine, 3-
Ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2
-Ethylhexyloxypropylamine, 3-decyloxypropylamine and the like. Examples of the amino compound having a mercapto group include 2-mercaptoethylamine, N- (2-mercaptoethyl) acetamide,
And mercaptopyridine. Examples of amino compounds having a carbonyl group include formanilide, acetanilide, acetoacetanilide, dodecylamide,
Examples include tetradecylamide, hexadecylamide and the like. Examples of amino compounds having a nitro group include 2-
Examples include nitroaniline, 3-nitroaniline, 2,4-dinitroaniline, and 2,4,6-trinitroaniline. Examples of amino compounds having a chlorine atom include 2
-Chloroaniline, 3-chloroaniline, 2,5-dichloroaniline and the like.

Among the above-mentioned amino compounds, dimethylaminoethylamine, ethylaminoethylamine, diethylaminoethylamine, tetramethylethylenediamine, 1,2-diaminopropane, methylaminopropylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropyl Amines, tetramethyl-1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, N- (3-aminopropyl) -1,3-propanediamine, pentamethyldiethylenetriamine and N, N ' -Bis (aminopropyl) -1,3-propylenediamine, etc.
An amino compound having two or more amino groups in one molecule,
2- (hydroxymethylamino) ethanol, N-isomethyldiethanolamine, 2-aminopropanol,
Amino having a hydroxyl group such as 3-aminopropanol, 3-dimethylaminopropanol, 4-aminobutanol, 4-methylaminobutanol, 2-hydroxyethylaminopropylamine and 1-amino-3-phenoxy-2-propanol; Compound, bis (3-aminopropyl) ether, dimethylaminoethoxypropylamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-bis (3-aminopropoxy) -2,2-
Amino compounds having an ether group such as dimethylpropane, α, ω-bis (3-aminopropyl) polyethylene glycol ether and α, ω-bis (3-aminopropyl) diethylene glycol ether can be preferably used.

Substitutes or derivatives of the above amino compounds can also be used. These amino compounds are used alone,
Alternatively, two or more kinds may be used in combination.

The bottom spacing of the clay intercalation compound used in the present invention can be enlarged compared to the initial bottom spacing of the swellable silicate due to the presence of the introduced amino compound. For example, the swellable silicate dispersed in the dispersion medium and the bottom surface interval is enlarged, when the amino compound is not introduced, when the dispersion medium is removed, the layers return to a state where the layers are aggregated again. After the dispersion medium is removed by introducing the amino compound after increasing the bottom surface interval, the obtained clay interlayer compound can exist in a state in which the bottom surface interval is enlarged without agglomeration of the layers. The distance between the bottom surfaces of the clay intercalation compound is 1.1 times or more, preferably 1.2 times or more, more preferably 1.3 times or more, and particularly preferably 1.5 times or more as compared with the initial distance between the bottom surfaces of the swellable silicate. More than doubled. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like.
According to this method, the X-ray diffraction peak angle value derived from the (001) plane of a dried and powdered clay intercalation compound is determined by SAXS
, And by substituting into Bragg's formula for calculation, the bottom surface interval can be obtained. 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. By confirming that the bottom surface interval has expanded in this way, it can be confirmed that a clay interlayer compound has been generated.

In the polysulfone resin composition of the present invention, the amount of the clay intercalation compound is typically 0.1 to 50 parts by weight, preferably 0.2 to 45 parts by weight, more preferably 100 parts by weight of the polysulfone resin. Is 0.3 to 40
The amount is adjusted to be 0.5 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 clay interlayer compound 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, the surface smoothness tends to be impaired.

The ash content of the polysulfone resin composition derived from the clay intercalation compound is typically 0.1 to 30% by weight, preferably 0.2 to 28% by weight, more preferably 0.3 to 25%. % By weight, more preferably from 0.4 to 23% by weight, particularly preferably from 0.5 to 20% by weight. 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 clay intercalation compound dispersed in the polysulfone resin composition of the present invention has a coherent structure of a μm size in which a number of layers are laminated, such as the swellable silicate before compounding. Is completely different. That is, by using a clay intercalation compound in which an amino compound having an affinity for the matrix resin is introduced and the interval between the bottom surfaces is enlarged compared to the initial swellable silicate, the layers are cleaved and independently of each other. Subdivide. As a result, the clay intercalation compound 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 a raw material. The dispersion state of such a lamellar clay intercalation compound is determined by the aspect ratio (layer length / layer length) described below.
(Layer thickness ratio), the number of dispersed particles, the maximum layer thickness, and the average layer thickness.

First, when the average aspect ratio is defined as the number average value of the ratio of the layer length / layer thickness of the clay intercalation compound dispersed in the resin, the clay intercalation compound in the polysulfone resin composition of the present invention is defined as follows. The average aspect ratio is 10 to 300, preferably 15 to 300, and more preferably 2 to 300.
0 to 300. If the average aspect ratio of the clay interlayer compound 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.

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 polysulfone resin composition, the clay in the polysulfone resin composition of the present invention is defined as: The [N] value of the intercalation compound is 30 or more, preferably 45 or more, and more preferably 60 or more. There is no particular upper limit, but when the [N] value exceeds about 1000, the effect does not change any more. The [N] value can be obtained, for example, as follows. That is, the polysulfone resin composition is about 50 μm
100 [mu] m cut into an ultrathin section having a thickness, The sections on the image taken by TEM or the like, the number of particles of the clay intercalation compounds area is present in any area of 100 [mu] m ^2, the weight ratio of the swellable silicate using Divided by 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. The value converted to the area of 100 μm ² may be used as the [N] value. Therefore, the [N] value is the T of the polysulfone resin composition.
It can be quantified by using an EM photograph or the like.

When the average layer thickness is defined as the number average value of the layer thickness of the clay interlayer compound dispersed in the form of a thin plate, the upper limit of the average layer thickness of the clay interlayer compound in the polysulfone resin composition of the present invention is defined. Is less than 500 °, preferably 45
0 ° 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.

When the maximum layer thickness is defined as the maximum value of the layer thickness of the clay intercalation compound dispersed in the form of a sheet in the polysulfone resin composition of the present invention, the upper limit of the maximum layer thickness of the clay intercalation compound is as follows. , 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 clay interlayer compound 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, 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 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 region containing 100 or more clay intercalation compounds on an elephant of the transmission electron microscope obtained by the above method, forming an image with an image processing device, and performing computer processing. Can be quantified by 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 clay interlayer compound and a dispersion medium, (B) a polymerizability of the polysulfone resin A method including a step of mixing a monomer and the above clay dispersion and a step of (C) polymerizing a polymerizable monomer are preferred.

First, the step (A) will be described in detail. In the step (A), the clay intercalation compound is obtained, for example, by expanding the bottom surface interval of the swellable silicate in a dispersion medium, and then adding and mixing an amino compound.

The above-mentioned dispersion medium is intended to include water, a polar solvent compatible with water at an arbitrary ratio, 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. , Amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide and
-Pyrrolidone and the like. These polar solvents may be used alone or in combination of two or more.

The expansion of the spacing 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 distance between the bottom surfaces after the enlargement is preferably 3 times or more, more preferably 4 times or more, and still more preferably 5 times or more, compared to the initial distance between the bottom surfaces 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 the unit layers are stacked and aggregated before being added to the dispersion medium. It is intended to be the bottom spacing. The distance between the bottom surfaces can be confirmed by small angle X-ray diffraction (SAXS) or the like. That is, an X-ray diffraction peak angle value of a mixture comprising a dispersion medium and a swellable silicate is measured by SAXS, and the peak angle value is determined by Bragg.
By substituting into the formula of g and calculating, the bottom surface interval can be obtained.

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, the cohesive layers are cleaved to be separated, and the amino compounds are added independently after they are independently present, and then sufficiently stirred. Then, a clay intercalation compound is obtained by mixing.

When the swellable silicate is treated with an amino compound, in the case of a method using a dispersion medium, the amino compound is added to a dispersion containing the swellable silicate having an enlarged bottom surface interval and the dispersion medium. This can be done by stirring. 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. Wet grinding machines,
Examples include wet-type collision pulverizers that collide a sample at a high speed with a jet nozzle or the like, and ultrasonic pulverizers using ultrasonic waves. When it is desired to efficiently generate the clay intercalation compound, the rotation speed of the stirring is set to 1000 rpm or more, preferably 1500 rpm or more, more preferably 2000 rpm.
pm or more, or 500 (1 / s) or more, preferably 1000 (1 / s) or more, and more preferably 15 or more.
Apply a shear rate of 00 (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 clay intercalation compound is obtained by adding an amino compound thereto while applying a physical external force to the swellable silicate (for example, while wet milling).

Alternatively, a swellable silicate whose bottom surface interval is enlarged by a physical external force may be added to a dispersion medium, and an amino compound may be added thereto as in the case of the above-mentioned method using a dispersion medium. .

Although the treatment of the swellable silicate with the amino compound can be carried out sufficiently at room temperature, the system may be heated if necessary. The maximum temperature at the time of heating can be arbitrarily set as long as it is lower than the decomposition temperature of the amino compound to be used and lower than the boiling point of the dispersion medium.

The amount of the amino compound to be used can be adjusted so that the dispersibility in the obtained clay intercalation compound and polysulfone resin or clay dispersion is sufficiently enhanced. If necessary, a plurality of amino compounds having different structures can be used in combination. Accordingly, the amount of the amino compound to be added is not necessarily limited by numerical values, 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 0.3 to 160 parts by weight, even more preferably 0.4 to 14 parts by weight.
0 parts by weight, particularly preferably 0.5 to 120 parts by weight. When the amount of the amino compound is less than 0.1 part by weight, the effect of finely dispersing the obtained clay interlayer compound tends to be insufficient. If the amount exceeds 200 parts by weight, the effect does not change at the above, 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 clay intercalation compound obtained when a clay intercalation compound is prepared is directly used as a clay dispersion (referred to as a direct method: in this case, the process of preparing the clay intercalation compound is a process). (A)), or
By adding another desired dispersion medium to the system containing the dispersion medium and the clay intercalation compound obtained when the clay intercalation compound is prepared and mixing and then replacing the mixture, the newly added desired dispersion medium and clay are added. A method of using a system comprising an intercalation compound as a clay dispersion (referred to as a substitution method), or a method of thoroughly mixing a clay intercalation compound obtained by drying and removing a dispersion medium with a desired dispersion medium (referred to as a mixing method) And the like.

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 clay intercalation compound 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 it was subdivided into a thin plate. Or the distance between the layers is increased, resulting in a so-called swelling state. The bottom surface interval can be used as an index indicating the swelling state. In order for the clay intercalation compound to be finely divided in the resin to form a thin plate, the bottom spacing of the clay intercalation compound in the clay dispersion is preferably at least three times the initial bottom spacing of the swellable silicate, and is preferably four times. The above 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 is
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 ′
-The following general formula (23) such as dihydroxybenzophenone and bis (4-hydroxyphenyl) sulfide:

[0080]

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. Yes, and they may be different. ), Methylsulfonic acid, chlorosulfonic acid, dichlorosulfone, bis (4-chloro-3,5-dimethylphenyl) sulfone, 4,4′-dichlorodiphenylsulfone, diphenylsulfone, etc. (24): R ¹² —SO ₂ —R ¹³ (24) (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 be the same or different. )), But is not limited thereto.

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 with 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 desalination 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 are clay dispersions in which a clay interlayer compound 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.

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 sufficiently mixed with a previously prepared clay interlayer compound. The number of agitation at the time of mixing and the like are the same as those described above, and the bottom spacing of the clay interlayer compound after mixing is preferably 3 times or more, more preferably 4 times or more 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 is excellent in mechanical strength and elastic modulus without impairing the dimensional accuracy and surface smoothness is that the clay intercalation compound in the polysulfone resin contains a large number of fine thin particles. This is because the average layer thickness, the maximum layer thickness, the number of dispersed particles, and the average aspect ratio of the clay interlayer compound, which are indicators of the dispersion state, are in the above-described ranges.

The dispersion state of the clay intercalation compound 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 water alone, the montmorillonite swells and cleaves to a state close to the unit layer, and in that state, a polar group such as a hydroxyl group, a mercapto group, or a nitro group is formed. Is reacted with an amino compound having a group having a high content of a compound to prepare a dispersion in which a clay intercalation compound having a unit thickness of about 1 is dispersed. on the other hand,
Mixing of a polar solvent such as ethanol, tetrahydrofuran (THF), methyl ethyl ketone (MEK), pyridine, N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) with water When a solvent is used as a dispersion medium or when montmorillonite is dispersed in the polar solvent and then water is added, about several to about one hundred and several tens of unit layers are cleaved and subdivided. If an amino compound is mixed in that state, a dispersion in which a clay interlayer compound having a thickness of about several to about several hundreds is dispersed is prepared. The dispersion state of the clay intercalation compound 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 clay interlayer compound with another desired dispersion medium) in the step (A), the kind of the dispersion medium to be newly added and plural kinds of dispersion mediums are used. In this case, the dispersion state of the clay intercalation compound 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 amino compound is added to a dispersion of an aqueous matrix containing a clay interlayer compound in a unit layer state and replaced with water, the clay interlayer compound in the unit layer state becomes about Several to about several tens of sheets can aggregate and be laminated. The dispersion state of the clay intercalation compound 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 clay intercalation compound changes depending on the type and molecular weight of the polymerizable monomer mixed with the clay dispersion. The dispersion state of the clay intercalation compound can be controlled by performing 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, the polysulfone resin composition of the present invention may contain a pigment, 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 mechanical properties are improved without impairing the dimensional accuracy and the surface smoothness, since the clay intercalation compound is very fine and thinly dispersed in a plate shape. be able to.

[0094]

EXAMPLES The main raw materials used in Examples and Comparative Examples are summarized 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, base spacing = 13 °) and Wenger HVP of Toyshun Yoko Co., Ltd. (hereinafter Wenger HV)
P, the bottom surface interval = 13 °) was used. Α, ω-bis (3-aminopropyl) polyethylene glycol ether; an amino compound of Koei Chemical Co., Ltd. was used (hereinafter referred to as αωAPEG). 1,2-bis- (3-aminopropoxy) ethane: an amino compound manufactured by Koei Chemical Co., Ltd. was used (hereinafter referred to as BAPE
). The evaluation methods in Examples and Comparative Examples are summarized below. (Measurement of dispersion state) Regarding clay intercalation compounds, TEM
Was carried out as follows.

An ultrathin section having a thickness of 50 to 100 μm was used. Transmission electron microscope (JEOL JEM-1200E
Using X), the dispersion state of the clay intercalation compound was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. In the TEM photograph, a region where 100 or more dispersed particles are present is selected, and the number of particles ([N] value), the layer thickness and the layer length are measured manually using a ruler with a scale or, if necessary, interpolated. The measurement was performed by processing using an image analyzer PIASIII manufactured by Quest.

The average aspect ratio was a number average value of the ratio between the layer length and the layer thickness of each clay interlayer compound. [N] value was measured as follows. First, on the TEM image, the number of particles of the clay intercalation compound existing in the selected region is determined. Separately, the ash content of the resin composition derived from the clay interlayer compound is measured. The number of particles was divided by the ash content to obtain an area of 10
The value converted to 0 μm ² was defined as the [N] value.

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

If the dispersed particles are large and observation with a TEM is inappropriate, the [N] value can be calculated 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 that do not disperse in a plate shape was 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.

[0100] 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 °. (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. The smaller the change in the melt viscosity, the better the retention heat stability. (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. The larger the measured value, the better the bending properties. (Anisotropic) Thickness of about 3 mm produced under the same conditions as above
The anisotropy was evaluated by the ratio of the coefficient of linear expansion in the MD and TD directions of the JIS No. 1 dumbbell-shaped test piece. The closer the ratio is to 1, the smaller the anisotropy, the more isotropic and the better. The coefficient of linear expansion was measured as follows.

The center of the above dumbbell-shaped test piece was
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 manufactured by Tokyo Seimitsu Co., Ltd .; The smaller the measured value, the smoother and better the surface. (Ash content) The ash content of the polysulfone resin composition derived from the clay interlayer compound was measured according to JIS K7052. (Example 1) Step (A) 3500 g of ion-exchanged water and 160 g of Kunipia F
5000 rpm using a wet mill manufactured by Nippon Seiki Co., Ltd.
Stir and mix for 5 minutes. Then, 25g of αω APE
After adding G, the mixture was further stirred under the conditions shown in Table 1.
(Confirmation of the clay intercalation compound was carried out by separating, drying and pulverizing the solid content and measuring the bottom interval by SAXS. The results are shown in Table 1. The results are the same in Examples 2 to 5). Then, 4000 mL of DMSO was added and mixed well, followed by heating to remove water, that is, a clay intercalation compound and a clay dispersion containing DMSO were prepared by a substitution method. The results are shown in Table 1. The spacing between the bottom surfaces of the clay interlayer compounds in the clay dispersion was> 100 °.

[0102]

[Table 1] 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.

Then, 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 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.

[0105]

[Table 2] (Example 2) Step (A) A clay dispersion was prepared in the same manner as in Example 1 except that the amount of αωAPEG was changed to 13 g. The results are shown in Table 1. The distance between the bottom surfaces of the clay interlayer compounds in the clay dispersion was 81 °. 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 30 g of BAPE was used instead of αωAPEG. The results are shown in Table 1. The distance between the bottom surfaces of the clay interlayer compounds in the clay dispersion was 75 °. 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) 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. The results are shown in Table 1. The spacing between the bottom surfaces of the clay intercalation compounds 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 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. 2500 g of the above polysulfone resin was gradually added to and mixed with the obtained clay dispersion, followed by drying to obtain a polysulfone resin composition, which was 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.

[0107]

[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.

By simply mixing Kunipia F directly with DMSO, the distance between the bottom surfaces hardly changes. Even if such a mixture is used for the polymerization of polysulfone resin, Kunipia F has a μ
Since the particles were merely dispersed with m-level coarse particles, the physical properties were not improved at all. (Comparative Example 3) 160 g of Kunipia F and 25 g of αωAP
KUNIPIA F was amino-treated by spraying EG directly with a spray and mixing for 1 hour. The distance between the bottom surfaces of the amino-treated Kunipia F was 13 °. This means that the amino-treated Kunipia F is different from the structure of the clay intercalation compound used in the present invention. A polysulfone resin was polymerized and evaluated in the same manner as in Example 1 except that the amino-treated Kunipia F was used instead of the clay dispersion. The results are shown in Table 3.

Since the amino-treated Kunipia F was only dispersed as coarse particles at the μm level, the physical properties were not improved at all.

Comparative Example 4 160 g of Kunipia was added to 3500 g of ion-exchanged water, and the mixture was stirred at 5000 rpm for 5 minutes using a wet mill (manufactured by Nippon Seiki Co., Ltd.).
Then, 25 g of n-butyraldehyde from Wako Pure Chemical Industries, Ltd.
Was added, and the mixture was further stirred at 5000 rpm for 3 hours to obtain a mixture. Then, a polysulfone resin composition was obtained by performing polymerization in the same manner as in Example 1, and evaluated. The results are shown in Table 3.

Even when Kunipia F is mixed with n-butyraldehyde, the distance between the bottom surfaces does not change much. Therefore, even when used for the polymerization of polysulfone resin, Kunipia F is merely dispersed as coarse particles of μm level. No improvement at all. (Comparative Example 5) 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. The volatile water was removed under reduced pressure from the vent.

As described above, even when Kunipia F swollen with water was melt-kneaded with a resin and a polysulfone resin, Kunipia F was not uniformly finely dispersed, so that a polysulfone resin composition having improved physical properties could not be obtained. . The results are shown in Table 3.

Comparative Example 6 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)
Is a 30 mm diameter twin screw extruder (manufactured by Nippon Steel Corporation, LAB
Using OTEX 30), the mixture was melt-kneaded at a temperature of 300 to 320 ° C. and a rotation speed of 100 rpm. The results are shown in Table 3.

[0115]

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 (9)

[Claims] 1. A polysulfone resin comprising: (a) a polysulfone resin; and (b) a clay intercalation compound prepared by mixing an amino compound having at least one amino group and a swellable silicate in a dispersion medium. Polysulfone resin composition. 2. The amino compound is a C1 to C25 hydrocarbon compound having at least one amino group selected from the group consisting of primary, secondary and tertiary amino groups. 2. The polysulfone resin composition according to 1. 3. The polysulfone resin according to claim 1, wherein the amino compound has at least one substituent selected from the group consisting of a hydroxyl group, a mercapto group, an ether group, a carbonyl group, a nitro group and a chlorine atom. Composition. 4. The polysulfone resin composition according to claim 1, wherein the average thickness of the clay interlayer compound in the polysulfone resin composition is 500 ° or less. 5. The maximum thickness of the clay intercalation compound in the polysulfone resin composition is 2000 ° or less.
The polysulfone resin composition according to the above. 6. The resin composition according to claim 1, wherein the [N] value defined as the number of particles per unit ratio of the clay intercalation compound existing in an area of 100 μm ² of the resin composition is 30 or more.
The polysulfone resin composition according to the above. 7. An average aspect ratio (ratio of layer length / layer thickness) of a clay intercalation compound in a polysulfone resin composition is 10 to 10.
The polysulfone resin composition according to claim 1, wherein the composition is 300. 8. (A) a step of preparing a clay dispersion containing a clay intercalation compound and a dispersion medium; (B) a step of mixing the polymerizable monomer of the polysulfone resin with the clay dispersion;
The method for producing a polysulfone resin composition according to any one of claims 1 to 7, further comprising (C) polymerizing a polymerizable monomer. 9. The method according to claim 8, wherein the distance between the bottom surfaces of the clay intercalation compounds in the clay dispersion obtained in the step (A) is at least three times the distance between the bottom surfaces of the swellable silicate. A method for producing a polysulfone resin composition.