JPH10259016A - Intercalation clay compound, thermoplastic resin composition composed of intercalation clay compound and thermoplastic resin and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable the adjustment of rheological properties of solvent, etc., by using one or more lamellar silicates selected from smectite-group, vermiculite-group and kaolingroup clay minerals and having an average layer thickness thinner than a specific level in combination with a dispersion stabilizer consisting of a nonionic compound. SOLUTION: This intercalation clay compound is composed of 100 pts. wt. of one or more lamellar silicates selected from smectite-group, vermiculite-group and kaolin- group clay minerals and having an average layer thickness of <=200Å and 0.1-60 pts.wt. of a dispersion stabilizer consisting of a nonionic compound. The dispersion stabilizer is e.g. a compound soluble in one or more solvents selected from water, a polar solvent compatible with water and a mixture of water and a polar solvent and having a polysiloxane chain or a polyether chain as the main chain. The objective thermoplastic resin composition is produced by compounding 1.00 pts.wt. of a thermoplastic resin such as thermoplastic polyester resin, polyamide resin, polycarbonate resin and polyolefin resin with 0.1-400 pts.wt. of the intercalation clay compound and kneading with a kneader under melting.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a clay intercalation compound,
The present invention relates to a thermoplastic resin composition containing the clay interlayer compound and a method for producing the same.

[0002]

2. Description of the Related Art Layered silicates have the property of being dispersed in various compounds serving as a matrix to adjust or improve rheological properties, and are therefore used, for example, in paints, printing inks, cosmetics, etc. Is used as a viscosity modifier for fluid fine chemical products. Further, the layered silicate is also used as a filler or a reinforcing agent for the purpose of improving physical properties such as rigidity, mechanical properties and heat deformation resistance of a polymer material such as rubber and plastic.

[0003] The layered silicate has a laminated structure in which a number of unit layers are laminated. Although the thickness of the unit layer is about 10 °, when a large number of the unit layers are stacked, the thickness of the unit layer is generally on the order of μm on average, although it depends on the number of stacked unit layers. Since the aspect ratio and specific surface area of such a layered silicate are small, even if the layered silicate in which a large number of unit layers are laminated is blended as a viscosity modifier, the rheology modifying effect or There is a problem that the thickening effect cannot be sufficiently obtained.

As means for solving the above-mentioned problems, among layered silicates, those exhibiting the property of swelling by taking in water between layers, for example, so-called swellable layered silicates such as smectite clay minerals, swelling mica and vermiculite. The use of salt has been considered.

[0005] However, when the swellable phyllosilicate is used as a viscosity modifier in various fluid fine chemical products, various other problems arise.

For example, in the case of swelling mica, water or a specific organic solvent molecule such as ethylene glycol enters between layers of the swelling mica, but the number of molecules that can enter is 2-3.
It is only a molecular level, so-called limited swelling only.
Therefore, since the swellable mica still has a laminated structure, a sufficient rheological modification effect cannot be obtained.

On the other hand, smectite group clay minerals, especially montmorillonite, hectorite and saponite, have hydration properties, so that they infinitely swell due to the entry of water molecules, and most of them are separated into unit layers. therefore,
Smectite group clay minerals are known to have the effect of efficiently increasing the viscosity of water when added in small amounts.By changing the dispersion concentration of the smectite group clay minerals, the viscosity of fluids containing water as a main component is known. Can be adjusted.

[0008] However, the smectite group clay mineral can swell infinitely in water and exist stably, but when a solvent other than water, such as an organic solvent, is added, the layers are coherently coagulated to form a stable layer. Can no longer exist. Therefore, the smectite group clay mineral has a disadvantage that it cannot be used for improving the rheological properties and the resin properties of a solvent system other than water or a mixed solvent system containing a solvent other than water as a main component.

As described above, since the smectite group clay mineral or the swellable mica has poor dispersibility in an organic solvent, when the rheological properties of the organic solvent are adjusted using these swellable silicates, the It is necessary to increase the concentration. However, the addition of a large amount causes a high cost, and also causes problems such as impairing the color tone of the product.

In order to improve these disadvantages, a technique for promoting the dispersion of the smectite group clay mineral in a matrix other than water (a technique for treating and modifying the smectite group clay mineral) has been developed as described below. .

(1) The organic cations obtained by exchanging exchangeable cations such as alkali metals existing between the unit layers of the smectite group clay mineral with other organic cations, the organic cations are formed on the surface of the unit layer of the clay layer. A complex formed by ionic bonding. Specifically, a bentonite complex in which dodecylammonium obtained from dodecylamine and bentonite which is a kind of smectite group clay mineral is ion-bonded,
It is described in U.S. Pat. No. 2,531,427.

(2) A complex in which dimethyloctadecyl ammonium ion is introduced as a cation between the unit layers of the smectite group clay mineral. It is industrially produced by N.L.Industry (NLIndustry) or Corp Chemical, and is used as a thickener for paints.

(3) A modified bentonite that is dispersed in an organic solvent by subjecting purified bentonite to a surface treatment with an alkyl trialkoxysilane has been developed (Japanese Patent Publication No. 7-23211). This modified bentonite is extracted from the suspension of crude bentonite by natural sedimentation or centrifugation to remove the non-clay material, and then the purified bentonite is extracted. It is dried and finally dried sufficiently at 150 to 200 ° C. to produce anhydrous purified bentonite. Then, a sufficient amount of alkyl trialkoxysilane is added to the obtained anhydrous purified bentonite so as not to exhibit water repellency. Manufactured by adding and stirring in an atmosphere and pulverizing the product.

However, the solvents whose rheological properties can be adjusted by the modified smectite group clay mineral-based composites described in the prior art (1) and (2) are limited to aromatic organic solvents such as benzene and toluene. In addition, dispersibility is not good in aliphatic hydrocarbon-based organic solvents. for that reason,
In order to disperse the smectite group clay mineral complex in an aliphatic hydrocarbon solvent, an appropriate amount of a polar compound such as methanol, ethanol or acetone must be added. Such a method is complicated, and there is a problem that a polar solvent such as methanol is mixed in the dispersion composed of the smectite group clay mineral-based complex and the aliphatic hydrocarbon-based solvent.

In the case of the modified bentonite described in the prior art (3), much labor and cost are required for drying and grinding. In addition, purified bentonite can be separated only in an anhydrous atmosphere to a thickness of the order of μm in which unit layers are stacked in layers. Therefore, the alkyl trialkoxysilane only reacts with the surface of the layered silicate laminate having a size on the order of μm.
In the case where purified bentonite and an alkyl trialkoxysilane are directly reacted in an anhydrous atmosphere to obtain a silane-modified purified bentonite efficiently, usually,
Although a catalyst such as an amine compound is required, in the method described in JP-B-7-23211 described in (3), a silane-modified purified bentonite can be efficiently obtained because no catalyst is used. Is difficult and industrially difficult to use. Furthermore, since the functional group of the alkyl trialkoxysilane used in the method (3) is a saturated alkyl group having 1 to 22 carbon atoms, the surface of the bentonite is made hydrophobic. The affinity between the bentonite thus hydrophobized and a highly polar solvent such as alcohols, ethers and amine compounds is low, and sufficient fine dispersion becomes difficult. Therefore, the use of the modified bentonite obtained by the method (3) in a highly polar solvent is limited.

As described above, a modified layered silicate which is well dispersed uniformly in various solvents and can adjust the rheological properties of the solvent even with a small amount of addition has not yet been provided. is there.

Incidentally, the layered silicate is blended with a polymer compound and is used for imparting an effect of adjusting and improving rheological properties or an effect of improving mechanical properties and heat resistance (for example, Japanese Patent Application Laid-Open No. Sho 53-53). No. 77245, JP-A-53-125479, JP-B-63-28464, etc.). However, when the layered silicate is used as a filler and a reinforcing agent for a polymer compound,
There are various problems as described below.

That is, even if a resin and a layered silicate are melt-mixed using a kneader such as an extruder, the layered silicate is merely dispersed as a layered product having an order of μm. In the laminated structure of the layered silicate, the interlayer distance between the unit layers is very close to several Å, but the distance between the laminated structures is on the order of μm. In other words, the concentration of the layered silicate is high in the portion where the laminated structure exists, but the concentration of the layered silicate is zero in the portion of the resin only where the laminated structure does not exist. Is very non-uniform. For the above reasons, even if the layered silicate in which a large number of unit layers are laminated is blended with the polymer compound, a small blending ratio does not provide sufficient reinforcing effects such as improvement of mechanical properties. Therefore, it is necessary to increase the mixing ratio.

However, in many cases, these layered silicates have a low affinity for the polymer compound forming the matrix, and when the compounding ratio is increased, the impact characteristics and mechanical properties are reduced.
The surface appearance of the molded article is reduced, the specific gravity is increased, and the color tone of the product is deteriorated. In addition, problems such as clogging of a filter and tearing of a film in a process of forming a film or the like occur. In addition, problems such as fish eye appearance and dropout of magnetic tape occur.

For the purpose of improving the adhesiveness of the interface between the layered silicate and the polymer compound to improve the impact characteristics, a treatment with a surface treating agent such as a silane coupling agent is generally used. A composite of a surface-treated filler obtained by treating a silicate with a silane coupling agent and a polyester resin has been disclosed (for example, Japanese Patent Application Laid-Open No. SHO 51-51).
24653, JP-A-51-24654, etc.).

However, although the impact characteristics are certainly improved to some extent by the surface treatment agent, they are not satisfactory. In the conventional surface treatment method, since the layered silicate has a laminated structure, the problems caused by the small aspect ratio, the small specific surface area, and the non-uniform dispersion still occur.

In order to solve the above-mentioned problem, the interlayer distance between the unit layers of the layered silicate in the composition is made larger than the interlayer distance in the raw material stage, whereby the layer is uniformly dispersed, and as a result, the aspect ratio is reduced by reducing the layer thickness. The following techniques for increasing the ratio and specific surface area and improving the physical properties of the composition have been disclosed.

That is, (4) the layer charge is from 0.2 to 1.
0, which is obtained by swelling the layered inorganic filler with glycols and then polymerizing the polyester resin between the layers of the layered inorganic filler, the heat comprising the finely dispersed layered inorganic filler and a polyester resin. A plastic polyester resin composition (JP-A-7-26123),
(5) A thermoplastic polyester resin composition in which an inorganic compound obtained by heat-treating a mixture of talc and alkali silicofluoride, for example, swellable fluoromica, is dispersed in a thermoplastic polyester resin (Japanese Patent Laid-Open No. 7-1995). 268
188, JP-A-8-73710), (6)
A slurry prepared using a medium having a swelling action with a swellable fluoromica obtained by heat-treating a mixture of talc and an alkali silicofluoride at a specific ratio is mixed with a polymerizable monomer of a polyamide to polymerize the polyamide. (7) swelling with respect to a monomer forming a reinforced polyamide resin composition obtained by polymerizing a monomer (JP-A-8-59822), and (7) nylon 6 or 100 parts thereof (parts by weight, hereinafter the same). Fluorinated mica based mineral 0.01-1
A method for producing a reinforced polyamide resin composition by polymerizing the monomer in the presence of 00 parts and 0.001 to 5 mol% of an acid having a pKa of 0 to 6 with respect to the monomer (Japanese Patent Laid-Open No. No. 8-3310).

The present inventors obtained a swellable fluorine mica having a layer charge of about 0.6 in order to study the techniques described in (4) and (5) in detail.
According to the examples described in JP-A-26123, a thermoplastic polyester resin composition comprising a polyester resin and swellable fluoromica was prepared, having a layer charge of 0.2 to 1.0.
The composition using the swellable fluoromica as a layered inorganic filler was produced as a trial, but the desired dispersibility, layer thickness and physical properties could not be obtained. That is, after the swellable fluoromica was swelled with ethylene glycol, polyethylene terephthalate was polymerized in the presence of the swellable swellable fluoromica. Was not improved at all. Further, the layer thickness and the dispersed state of the swellable fluoromica in the thermoplastic polyester resin composition may remain the same as the swellable fluoromica before blending,
It was revealed by transmission electron microscope observation and small angle X-ray diffraction measurement.

Further, the present inventors have conducted a detailed study on the technique described in (6).
No. 22, the composition was prepared according to the examples of
It has been found that the heat distortion temperature, mechanical properties after moisture absorption, and the like of the obtained composition are not different from those of a composition produced by simply melt-kneading a polyamide resin and swellable fluoromica. Furthermore, the swellable fluorine mica in the composition remains in a laminated structure as in the case of the techniques described in (4) and (5), as observed by transmission electron microscopy and small-angle X-ray diffraction measurement. Turned out by.

Further, in the case of the technique described in (7), when the polyamide-based polymer is polymerized in the presence of a swellable fluoromica-based mineral and an acid having a pKa of 0 to 6, the reaction system is reduced to 26.
It is necessary to maintain the temperature at 0 ° C., increase the pressure to at least 5 kg / cm ^2, and continue the polymerization for 3 hours or more in that state. Therefore, a specially-processed polymerization facility that can withstand high-temperature, high-pressure, and acid corrosion is required, resulting in a problem that the production cost is increased.

As described above, a resin composition having excellent physical properties by uniformly and finely dispersing a layered silicate in a resin and a technique for producing the resin composition with high productivity have not been proposed yet. Is the current situation.

The present invention has been made to solve the above-mentioned problems of the prior art, and a layered silicate-based material capable of giving a desired rheological property to an aqueous solvent system serving as a matrix even with a small amount of addition, and a layered silicate material thereof. Provided is a thermoplastic resin composition excellent in various properties such as mechanical properties and heat deformation resistance, and a method for producing the same by providing a production method and by compounding the layered silicate material and a thermoplastic resin. The purpose is to do.

[0029]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, completed the present invention.

That is, the present invention relates to a layered silicate (A) having an average layer thickness of 200 ° or less selected from the group consisting of a smectite group, a vermiculite group and a kaolin group clay mineral, and a dispersion stabilizer (A). B), wherein the dispersion stabilizer (B) is sandwiched between the layered silicates (A) and the dispersion stabilizer (B) is compatible with water and water at an arbitrary ratio. A clay intercalation compound (C) (claim 1) and a dispersion stabilizer (B), which are nonionic compounds soluble in at least one of a solvent and a mixed solvent of water and the polar solvent. 2. The clay intercalation compound (C) according to claim 1, which is at least one selected from the group consisting of a compound having a polysiloxane chain as a main chain and a compound having a polyether chain as a main chain. The interval is at least twice the initial value. Clay intercalation compound other 2 wherein (C)
(Claim 3) The method for producing the clay intercalation compound (C) according to claim 1, 2 or 3, wherein the layered silicate (A) and the dispersion stabilizer (B) are mixed with water or water. A method for producing a clay intercalation compound, comprising mixing in a mixed solvent comprising a polar solvent and water which are compatible at an arbitrary ratio, and then removing the water or the mixed solvent (claim 4), claim 1, 2 or The thermoplastic resin composition (E) comprising the clay intercalation compound (C) and the thermoplastic resin (D) according to (3), wherein the inorganic ash content derived from the clay intercalation compound (C) is 0.1 to 60. % (% By weight, hereinafter the same), wherein the thermoplastic resin composition (E) according to claim 5 (claim 6) and the clay interlayer compound (C) in a dispersed state have an average layer thickness of 200 ° or less. The thermoplastic resin composition (E) according to the fifth or sixth aspect (claim 7), the fifth or sixth aspect. Or a method for producing the thermoplastic resin composition (E) according to claim 7, wherein a step of preparing a mixture of the clay interlayer compound (C) according to claim 1, 2 or 3 and a polymerizable monomer; A method for producing a thermoplastic resin composition comprising a step of polymerizing the polymerizable monomer in a mixture (claim 8), and a method for producing the thermoplastic resin composition (E) according to claim 5, 6, or 7. In addition, the present invention relates to a method for producing a thermoplastic resin composition in which the clay interlayer compound (C) and the thermoplastic resin (D) are melt-mixed using a kneader (claim 9).

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The clay interlayer compound (C) of the present invention
Is a layered silicate (A) having an average layer thickness of 200 ° or less selected from the group consisting of a smectite group clay mineral, a vermiculite group clay mineral and a kaolin group clay mineral, and the layered silicate (A). )), In which a dispersion stabilizer (B), which is a nonionic compound that facilitates fine dispersion, is sandwiched. Layered silicate (A)
The ratio of the dispersion stabilizer (B) sandwiched between the layers is 0.1
To 35%, preferably 0.2 to 30%, more preferably 0.3 to 25%. If it is less than 0.1%, the effect of fine dispersion tends to decrease, and if it exceeds 35%, the handleability of the clay interlayer compound (C) tends to decrease.

The ratio of the dispersion stabilizer (B) sandwiched between the layers of the layered silicate (A) can be determined from the following formula by measuring the amount of the inorganic ash of the obtained clay intercalation compound (C).

(Ratio (average value) of dispersion stabilizer (B) sandwiched between layers of layered silicate (A)) (%) = 10
0 × {(weight (g) of clay interlayer compound (C)) − (amount of inorganic ash (g) of clay interlayer compound (C)} / (weight (g) of clay interlayer compound (C))

The thickness of the layer is measured by embedding the clay intercalation compound (C) of the present invention in an epoxy resin or the like so as not to agglomerate each other, and using a transmission electron microscope to obtain individual layered silicates at an arbitrary site. It can be carried out by measuring the layer thickness of (A).

The layered silicate (A), which is a raw material of the clay intercalation compound (C), has a property of swelling in a dispersion medium (water or a solvent containing water as a main component). Swellable layered silicates such as smectite group clay minerals and vermiculite group clay minerals and kaolin group clay minerals, which are composed of tetrahedral sheets and octahedral sheets mainly composed of metal hydroxide.

Examples of the smectite group clay mineral include natural or synthetic hectorite, saponite, montmorillonite, stevensite, beidellite, nontronite, bentonite and the like, and their substituted products and derivatives. These may be used alone or in combination of two or more.

The vermiculite-group clay minerals include a trioctahedral type and a dioctahedral type. The general formula (I): (Mg, Fe, Al) _2-3 (Si _4-x Al _x ) O ₁₀ (OH) ₂ · (M ₁ ⁺ , M _{2 2} ⁺ _1/2 ) _x · nH ₂ O (I) (where M ₁ is an alkali metal such as Na, and M ₂ is an alkaline earth metal such as Mg) , M ₁ and M ₂ are exchangeable cations,
x is 0.6 to 0.9 and n is 3.5 to 5). These may be used alone or in combination of two or more.

Examples of the kaolin group clay mineral include natural or synthetic kaolinite, dickalite, halloysite, and their substituted products and derivatives. These may be used alone or in combination of two or more.

The layered silicate (A) may be used alone or in combination of two or more.

The crystal structure of the layered silicate (A) is desirably a high-purity one that is regularly stacked in the c-axis direction. However, a so-called mixed layer mineral having a disordered crystal cycle and a mixture of a plurality of types of crystal structures is preferred. One can also be used.

Among the layered silicates (A), the smectite group clay minerals and the kaolin group clay minerals are preferably used from the viewpoint of easy swelling, and the smectite group clay minerals are more preferable.

The dispersion stabilizer (B) is a nonionic compound which is soluble in water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. It is a compound that does not have an adverse effect such as decomposition on the matrix compound to be used and that can be stably present even at the processing temperature of the matrix compound.

Specific examples of the dispersion stabilizer (B) include compounds having a polysiloxane chain as a main chain such as silicone compounds, compounds having a polyether chain as a main chain, polyvinyl alcohol, sodium polyacrylate, polyvinyl pyrrolidone, and the like. Polyacrylic acid ester, polyacrylamide, cellulose-based processed natural polymer, polymer compound such as starch-based processed natural polymer, a compound having a polysiloxane chain as a main chain, a compound having a polyether chain as a main chain,
Polyvinyl alcohol, sodium polyacrylate, polyvinylpyrrolidone, polyacrylic acid ester, oligomers such as compounds having 2 to 20 repeating units in the main chain of polyacrylamide, water-soluble surfactants, water-soluble amino acids, monosaccharides, etc. Examples include, but are not limited to, molecular compounds. These may have a substituent as long as they are soluble in an aqueous solvent. In addition to the compounds, starchy, mannan, seaweed, plant mucilage,
Natural polymer compounds such as mucous substances and proteins by microorganisms can also be suitably used as the dispersion stabilizer (B).

Among the above specific examples of the dispersion stabilizer (B), preferred are a compound having a polysiloxane chain as a main chain and a compound having a polyether chain as a main chain. The compound having a polysiloxane chain as a main chain means, in addition to a linear polysiloxane and an alkyl group, an amino group, an acetyl group, a hydroxyl group, and an ether group bonded to a side chain in order to have water solubility. It is copolymerized inside.

Preferred examples of the compound having a polysiloxane chain as a main chain include the following compounds.

[0046]

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[0047]

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[0048]

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Preferred examples of the compound having a polyether chain as a main chain include the following compounds.

[0050]

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The dispersion stabilizer (B) may be used alone or in combination of two or more.

Examples of polar solvents compatible with water at an arbitrary ratio include alcohols such as methanol, ethanol and isopropanol, glycols such as ethylene glycol, propylene glycol and 1,4-butanediol, acetone and methyl ethyl ketone. Ketones, such as
Examples thereof include ethers such as diethyl ether and tetrahydrofuran, amide compounds such as dimethylformamide, and other solvents such as dimethyl sulfoxide, methyl cellosolve, and 2-pyrrolidone.

The polar solvents may be used alone or in combination of two or more.

In the clay intercalation compound (C), the amount of the dispersion stabilizer (B) is preferably 0.1 to 60 parts, more preferably 0.1 to 100 parts with respect to 100 parts of the layered silicate (A).
It is 2 to 50 parts, particularly preferably 0.3 to 40 parts.
The effect of finely dispersing the clay intercalation compound (C), in which the amount of the dispersion stabilizer (B) is less than 0.1 part, tends to be insufficient, which is not preferable. On the other hand, if the addition amount exceeds 60 parts, the handleability as a clay interlayer compound (C) decreases,
Further, the rheological properties of the matrix compound and the properties inherent to the matrix compound tend to be impaired, which is not preferable.

As a method for producing the clay intercalation compound (C) of the present invention, for example, the layered silicate (A) is mixed with water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. A step of swelling in one or more kinds of dispersion medium to obtain a dispersion (swelling step), a step of adding the dispersion stabilizer (B) to the dispersion and mixing them sufficiently, and then removing the dispersion medium ( A method including an interlayer compound step) is exemplified.

The swelling step (first step) can be performed, for example, by the following method.

First, the layered silicate (A) is dispersed and swelled in water, a polar solvent compatible with water at an arbitrary ratio, or a mixed solvent of water and the polar solvent. The solid dispersion concentration of the layered silicate (A) finely dispersed in the dispersion medium can be freely set within a concentration range in which the layered silicate can be sufficiently dispersed. % Or less, particularly preferably 20% or less.

In order to promote the fine dispersion of the layered silicate (A), a physical external force such as a shearing force or a pressure can be used. The physical external force can be applied, for example, by using a commonly used method of pulverizing a filler.

As a general method of pulverizing the filler,
For example, there is a method using hard particles. In this method, the hard particles, the layered silicate (A) and the dispersion medium are mixed and stirred at high speed, and the hard particles and the layered silicate (A) are caused to physically collide with each other to form the layered silicate (A). ) Is cleaved. The hard particles usually used are filler grinding beads, for example, glass beads and zirconia beads, but are not limited thereto. These pulverizing beads are selected in consideration of the hardness of the layered silicate (A) or the material of the stirrer, and the particle size thereof is also selected.
Is not taken into account, and is not necessarily limited to a numerical value, but is preferably in the range of 0.1 to 6.0 mm in diameter.

Layered silicate (A) and dispersion stabilizer (B)
Can be mixed, for example, by the following method.

That is, it can be carried out by adding and dissolving a dispersion stabilizer (B) soluble in the dispersion to the dispersion prepared in the swelling step, and sufficiently stirring the dispersion. Alternatively, when the dispersion stabilizer (B) is difficult to dissolve in the dispersion, first, the layered silicate (A) is mixed with water, a polar solvent compatible with water at an arbitrary ratio, and water. A dispersion comprising one or more dispersion media of the mixed solvent of the polar solvent is prepared, and a dispersion stabilizer solution comprising the dispersion stabilizer (B) and another solvent is separately prepared. This can be achieved by thoroughly stirring and mixing the stabilizer solution. The mixing ratio can be arbitrarily set as long as the dispersibility of the layered silicate (A) and the solubility of the dispersion stabilizer (B) are maintained.
For example, a dispersion obtained by dispersing the layered silicate (A) in water and tetrahydrofuran (THF) having a molecular weight of 5000
When mixing with a solution of dimethylpolysiloxane grafted with epoxy groups or carbinol groups at 6000 to 6000, the layered silicate (A) maintains dispersibility if the water ratio is 30% or more, and THF is added. Is 30% or more, the polysiloxane maintains solubility. Therefore, in the mixed system, water / THF can be arbitrarily set between 30/70 and 70/30 (weight ratio).

The dispersion medium can be removed by drying or reprecipitation. After removing the dispersion medium, the mixture is pulverized, if necessary, to obtain the clay interlayer compound (C) of the present invention.

Although the room temperature at the time of production is sufficient, it may be heated if necessary. The maximum temperature during heating can be set arbitrarily as long as it is lower than the decomposition temperature of the dispersion stabilizer (B) and the boiling point of the dispersion medium.

The formation of the clay intercalation compound (C) of the present invention can be confirmed by the small-angle X-ray diffraction method (SAXS).
01) It can be easily confirmed from the measurement of the interval between the bottom surfaces.

The distance between the bottom surfaces can be calculated by applying the diffraction peak angle value in SAXS to the Bragg equation. When the dispersion stabilizer (B) is sandwiched between the layered silicates (A) and becomes a clay interlayer compound, the distance between the bottom surfaces increases. Clay intercalation compound (C) of the present invention
Is the initial value (bottom distance of layered silicate (A))
As compared with, the magnification is at least 2 times, preferably at least 2.5 times, and more preferably at least 3 times. The upper limit is ten times,
If it exceeds this, the dispersion stabilizer (B) between the layers of the layered silicate (A) will be present in an excessive amount, so that the handleability of the clay intercalation compound (C) of the present invention will decrease or Tends to impair the rheological properties of the matrix and the properties originally possessed by the matrix compound. For example, layered silicate (A)
The bottom spacing of the unit layer of natural montmorillonite which is preferably used as the material is 12 to 16 at ordinary temperature and humidity.
Å. On the other hand, the bottom spacing of the clay intercalation compound (C) of the present invention depends on the type of the dispersion stabilizer (B), but is larger than 32 ° in any case.

The clay intercalation compound (C) of the present invention thus obtained is a good solvent for the dispersion stabilizer (B), that is, various kinds of water, a polar solvent compatible with water at an arbitrary ratio, and Since it has an affinity for a mixed solvent of water and the polar solvent, it can be well dispersed in the solvent. Therefore,
The clay intercalation compound (C) of the present invention is uniformly dispersed without aggregation even in the above-mentioned solvent, and has an excellent thickening effect and a modifying / modifying effect such as rheological properties even when added in a small amount.

The clay intercalation compound (C) is added to a solvent composition containing water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent as a main component. It is used for various uses as a thickener or a gelling agent by being dispersed by stirring or the like. At this time, the thickening effect is higher as the use amount (dispersion concentration) is higher as long as the concentration can be dispersed in the solvent composition. The specific dispersion concentration varies depending on the solvent and cannot be determined unconditionally, but is generally 0.01 to 50%, preferably 0.05 to 35%.
%, More preferably 0.1 to 20%.

The clay intercalation compound (C) is added to one or more of water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent to form a clay intercalation compound (C) dispersion. May be used.

The clay intercalation compound (C) dispersion can be prepared by adding the clay intercalation compound (C) to the solvent and stirring the mixture or by mixing the clay intercalation compound in the above-mentioned method for producing the clay intercalation compound (C). After mixing the acid salt (A) and the dispersion stabilizer (B), the dispersion of the clay intercalation compound (C) is directly produced without removing the dispersion medium or the like and isolating the clay intercalation compound (C). It may be manufactured. In this case, after mixing the layered silicate (A) and the dispersion stabilizer (B) in the dispersion medium, a desired solvent is newly added, and the dispersion medium is removed by a normal fractionation operation. And a dispersion of the clay intercalation compound (C) comprising the clay intercalation compound (C) and a newly added solvent.

It is considered that a layer space is formed in the clay interlayer compound (C). Utilizing this layer space, the clay intercalation compound (C) can be used as an organic substance storage agent, sustained release agent, catalyst, adsorbent, carrier,
It can also be used as a filler or the like.

The thermoplastic resin composition (E) of the present invention is a composition containing the clay interlayer compound (C) obtained as described above and the thermoplastic resin (D). Since the composition contains the clay intercalation compound (C), the composition does not impair the appearance of the molded product and has excellent properties such as mechanical properties and heat deformation resistance.

As the thermoplastic resin (D) used in the thermoplastic resin composition (E), any thermoplastic resin can be used. Examples of the thermoplastic resin (D) include, for example,
In addition to thermoplastic polyester resin, polyamide resin, polycarbonate resin, elastomer, and polyolefin resin, vinyl polymer compound, polyimide resin, polyphenylene sulfide, polyphenylene oxide, polyacetal, polysulfone, polyether sulfone, fluororesin, polyolefin copolymer , Rubber and the like. These thermoplastic resins (D) may be used alone or in combination of two or more.

Among the thermoplastic resins (D), thermoplastic polyester resins, polyamide resins, polycarbonate resins and polyolefin resins are preferred.

The thermoplastic polyester resin includes:
Any known polyester resin obtained by polymerizing a dicarboxylic acid compound and / or an ester-forming derivative of a dicarboxylic acid and a diol compound and / or an ester-forming derivative of a diol compound can be used. Specific examples thereof include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, and polyhexene. Examples thereof include methylene naphthalate and the like, and copolymerized polyesters thereof. These may be used alone or in combination of two or more.

The polyamide resin is not particularly limited, and a known polyamide resin can be used. Specific examples thereof include polycaproamide (nylon 6),
Polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecamethylene adipamide (Nylon 116), polyundecamide (nylon 11), polydodecamide (nylon 1
2), polytrimethylhexamethylene terephthalamide (TMHT), polyhexamethylene terephthalamide (nylon 6T), polyhexamethylene isophthalamide (nylon 6I), polybis (4-aminocyclohexyl)
Methanedodecamide (nylon dimethyl PACM12),
Polymethaxylylene adipamide (nylon MXD6),
Polyundecamethylene terephthalamide (nylon 11
T), polyundecamethylene hexahydroterephthalamide (nylon 11TH), and copolymers thereof. These may be used alone or in combination of two or more.

Examples of the polycarbonate resin include any conventionally known polycarbonate resins obtained by reacting a dihydric phenol compound with phosgene or a dihydric phenol with a carbonic acid diester. Specific examples thereof include 2,2-bis (4-hydroxyphenyl) propane-type polycarbonate resin, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane-type polycarbonate resin, and 1,1-bis (4 -Hydroxyphenyl) cyclohexane type polycarbonate, 4,4'-dihydroxyphenyl ether type polycarbonate, 4,4'-dihydroxydiphenyl sulfide type polycarbonate,
4,4'-dihydroxydiphenylsulfone type polycarbonate, bis (4-hydroxyphenyl) ketone type polycarbonate, 1,4-bis (4-hydroxyphenylsulfonyl) benzene and the like can be mentioned. These may be used alone or in combination of two or more.

The polyolefin resin is not particularly limited, and a known polyolefin resin can be used. Specific examples thereof include homopolymers of α-olefins containing ethylene, and copolymers of two or more α-olefins (including any copolymers such as random, block, and graft, and mixtures thereof. And olefin-based elastomers. As the ethylene homopolymer, low density polyethylene (LDPE), high density polyethylene (HDPE), linear low density polyethylene (LLDPE), and the like can be used. The propylene polymer is not limited to a propylene homopolymer,
Copolymers of propylene and ethylene are also included. The olefin-based elastomer means a copolymer of ethylene and one or more α-olefins other than ethylene (for example, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene). Specific examples include ethylene-propylene copolymer (EPR), ethylene-butene copolymer (EBR), ethylene-propylene-diene copolymer (EPDM), and the like. These may be used alone or in combination of two or more.

The molecular weight of the thermoplastic resin (D) is selected in consideration of molding fluidity in the molding step and various physical properties of the final product, and it is not preferable that the molecular weight is too low or too high. Since the optimum molecular weight is determined mainly by the primary structure of each thermoplastic resin, it is necessary to set a suitable molecular weight for each thermoplastic resin.

For example, the molecular weight of the thermoplastic polyester resin suitably used for the thermoplastic resin composition (E) is as follows:
The logarithmic viscosity measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent is 0.3 to
2.0 dl / g is desirable. Logarithmic viscosity 0.3d
When it is less than 1 / g, the mechanical properties and impact resistance of the obtained molded article of the thermoplastic polyester resin composition tend to be low, and when it is more than 2.0 dl / g, the fluidity during molding, etc. There is a tendency that a problem is apt to occur in the workability of the steel.

Further, for example, the thermoplastic resin composition (E)
The molecular weight of the polyamide resin preferably used is 98%
It is desirable that the relative viscosity measured at 25 ° C. at a concentration of 1.0% using concentrated sulfuric acid is 1.5 to 5.0. When the relative viscosity is less than 1.5, the mechanical properties and impact resistance of the obtained molded article of the polyamide resin composition tend to be low, and when the relative viscosity is more than 5.0, the flowability during molding is poor. There is a tendency for problems in workability to occur.

Further, for example, the thermoplastic resin composition (E)
The molecular weight of the polycarbonate resin preferably used for,
In gel permeation chromatography (GPC) measurement using tetrahydrofuran (THF) solvent,
The weight average molecular weight (Mw) measured at 40 ° C. is 15,000 to 80,000, preferably 30,000 to 65,000 in terms of monomolecular weight dispersed polystyrene. Mw is 150
When it is less than 00, the mechanical properties and impact resistance of the obtained molded article from the polycarbonate resin composition tend to be low, and when it is more than 80,000, there is a problem in processability such as fluidity during molding. Tends to be easy.

Further, for example, the thermoplastic resin composition (E)
The molecular weight of polypropylene among the polyolefin-based resins suitably used for the resin has an MI (melt index) of 0.3 to 30 g measured at 230 ° C. under a load of 2.16 kg.
/ 10 min, more preferably 0.5 to 15 g / 10 min. If the MI is greater than 30 g / 10 minutes, the mechanical properties and impact resistance of the molded article tend to be low.
If it is less than 0.3 g / 10 minutes, a problem tends to easily occur in processability such as fluidity during molding.

The mixing ratio of the clay interlayer compound (C) and the thermoplastic resin (D) in the thermoplastic resin composition (E) is such that the clay interlayer compound (C) is based on 100 parts of the thermoplastic resin (D). 0.1-400 parts, preferably 0.2
To 200 parts, more preferably 0.6 to 80 parts.
If the amount of the clay intercalation compound (C) is less than 0.1 part, the effect of improving mechanical properties tends not to be obtained, and if it is more than 400 parts, the surface appearance of the molded article and the fluidity during molding are impaired. There is a tendency.

The production of the thermoplastic resin composition (E) is carried out by melt-mixing the clay intercalation compound (C) and the thermoplastic resin (D) using various general methods, for example, using a kneader. be able to.

Examples of the kneading machine include a single screw extruder,
A kneader capable of giving a high shearing force to the system, such as a screw extruder, a Banbury mixer, and a roll, may be used. Particularly, a meshing twin-screw extruder having a kneading disk portion is preferable.

In the process for producing the thermoplastic resin composition (E), usually, water, a polar solvent that is compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent are removed beforehand. When the dispersion medium and the aqueous solvent do not cause deterioration of the thermoplastic resin, the removal of the dispersion medium and the aqueous solvent is omitted, and the clay intercalation compound (C When (1) is used, the thermoplastic resin composition may be produced without removing the dispersion medium and the aqueous solvent, since the uniformity with respect to the resin is good.

The average layer thickness of the clay interlayer compound (C) in the obtained thermoplastic resin composition (E) is 200 ° or less, preferably 180 ° or less, more preferably 150 ° or less. If the average layer thickness is larger than 200 °, it is difficult to obtain the effect of improving the mechanical properties and rheological properties of the resin composition of the present invention. The average layer thickness is obtained by measuring the layer thickness of each clay interlayer compound (C) in an arbitrary portion of the thermoplastic resin composition (E) using a transmission electron microscope or the like, and averaging them.

The thermoplastic resin composition (E) containing the clay intercalation compound (C) has an inorganic ash content derived from the clay intercalation compound (C) of 0.1 to 60%, more preferably 0.2 to 50%.
In particular, 0.5 to 35% is preferable. If the inorganic ash content is less than 0.1%, the effect of improving the inorganic properties and heat resistance cannot be sufficiently obtained, and if it exceeds 60%, the surface appearance and workability of the molded article tend to be poor. .

As the clay intercalation compound (C), those which have not been subjected to a surface treatment as described above can be used.
Various surface treatment agents such as silane-based coupling agents, titanate-based coupling agents, alumina-based coupling agents, etc., in order to improve the affinity with the thermoplastic resin (D) and not reduce the mechanical properties. The clay intercalation compound (C) surface-treated with is also preferably used.
As the surface treatment method of the clay interlayer compound (C), a method generally performed generally, for example, a dry method, a slurry method,
Spray method, integral blend method and the like can be mentioned. The surface treatment agents may be used alone or in combination of two or more.

The production of the thermoplastic resin composition (E) may be carried out by melt-mixing the clay intercalation compound (C) and the thermoplastic resin (D) using a kneader as described above. After preparing a mixture of the produced clay interlayer compound (C) and the polymerizable monomer constituting the thermoplastic resin (D), the mixture may be produced by polymerizing the polymerizable monomer in the mixture.

Specifically, the layered silicate (at least one solvent selected from the group consisting of water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent) is used. A)
To give a dispersion. One or more dispersion stabilizers (B) are dissolved in the dispersion and mixed well to produce a clay intercalation compound (C). The clay intercalation compound (C) containing the solvent is mixed with the clay intercalation compound (C). It is manufactured by mixing a polymerizable monomer and polymerizing the polymerizable monomer in the mixture. Here, the solvent and the polymerizable monomer may be the same or different.

The polymerizable monomers constituting the thermoplastic resin (D) include the following monomers.

Examples of the polymerizable monomer constituting the thermoplastic polyester resin include, for example, an acid component mainly containing an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a diol compound or an ester-forming derivative thereof mainly. And a diol component.

Examples of the acid component include terephthalic acid, isophthalic acid, orthophthalic acid, 2,5-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid,
Examples thereof include 4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, and 4,4'-diphenylisopropylidenedicarboxylic acid, and substituted and derivatives thereof are also preferably used. These may be used alone or in combination of two or more.

If the amount is small enough not to impair the properties of the thermoplastic polyester resin, one kind of aliphatic dicarboxylic acid such as adipic acid, azelaic acid, dodecane diacid, sebacic acid and the like is used together with these aromatic dicarboxylic acids. These may be used in combination.

Examples of the diol component include aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and neopentyl glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and bis ( 4,4'-
Aromatic diols such as dihydroxyphenyl) ethane are exemplified, and their substituted products and derivatives can also be preferably used. These may be used alone or in combination of two or more. Furthermore, if the amount is small enough not to significantly lower the elastic modulus of the polyester resin, alkylene oxides of bisphenols represented by long-chain diols, for example, polyethylene glycol, polytetramethylene glycol, ethylene oxide addition polymer of bisphenol A, etc. One or more kinds of addition polymers may be mixed.

The monomers of the polyamide resin include:
Examples thereof include diamines and dicarboxylic acids, lactams, polymerizable ω-amino acids, and salts composed of diamines and dicarboxylic acids.

The diamine is represented by the following general formula (II): H ₂ N—X—NH ₂ (II) (wherein X is a divalent aliphatic group, a divalent alicyclic group or a divalent alicyclic group)
Which are valent aromatic groups, and these groups may have a substituent). Examples thereof include trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, phenylenediamines, xylylenediamines, 2,2,4-trimethylhexamethylenediamine, 2,4,4 4-trimethylhexamethylenediamine, bis (4-aminocyclohexyl)
Examples include, but are not limited to, methane and bis (4-amino-3-methylcyclohexyl) methane. These may be used alone or in combination of two or more.

The dicarboxylic acid has a general formula (II)
I): HOOOC-Y-COOH (III) (wherein, Y is a divalent aliphatic group, a divalent alicyclic group, or a divalent aromatic group, and these groups have a substituent May be used). Examples thereof include aliphatic dicarboxylic acids such as sebacic acid, octadecandioic acid, suberic acid, glutaric acid, pimelic acid and adipic acid, aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid, and cyclohexane-1,4-dicarboxylic acid. Acids and alicyclic dicarboxylic acids such as cyclohexane-1,3-dicarboxylic acid. These may be used alone or in combination of two or more.

Examples of the lactams include butyl lactam, pivalolactam, caprolactam, caprylactam, enantholactam, undecanolactam, dodecanolactam and the like. These may be used alone or in combination of two or more.

Examples of the polymerizable ω-amino acids include, for example, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. These may be used alone or in combination of two or more.

The monomers for the polycarbonate resin include a dihydric phenol compound and phosgene or a carbonic acid diester.

As the dihydric phenol compound constituting the polycarbonate resin, for example, 2,2-bis (4
-Hydroxyphenyl) propane ("bisphenol A"), bis (4-hydroxyphenyl) methane, 1,
1-bis (4'-hydroxyphenyl) ethane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (“bisphenol TMC”),
Bis (4-hydroxyphenyl) cyclohexylmethane, 2,2-bis (4'-hydroxy-3,5'-dibromophenyl) propane, bis (4-hydroxy-3,
5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 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, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dimethyl) Phenyl) sulfone, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide and the like. Further, a dihydric phenol having a benzotriazole group may be copolymerized to enhance the flame retardancy. Substitutes or derivatives of these dihydric phenol compounds may also be used. These may be used alone or in combination of two or more.

The polyolefin resin monomers include, for example, ethylene, propylene, butene,
Olefin compounds such as isoprene and pentene are mentioned. These may be used alone or in combination of two or more. Furthermore, to the extent that the properties of the polyolefin resin are not significantly impaired, butadiene, vinyl chloride, vinylidene chloride, styrene, acrylic acid, methacrylic acid, t-butylacrylamide, acrylonitrile,
Norbornadiene, N-vinylcarbazole, vinylpyridine, vinylpyrrolidone, 1-butene, isobutene,
Vinylidene cyanide, 4-methylpentene, vinyl acetate, vinyl isobutyl ether, methyl vinyl ketone,
One or more vinyl compounds such as phenyl vinyl ketone, phenyl vinyl sulfide, and acrolein may be mixed.

As described above, the thermoplastic resin composition (E) of the present invention is obtained by polymerizing the polymerizable monomer in the mixture of the clay interlayer compound (C) and the polymerizable monomer constituting the thermoplastic resin (D). ) Is preferred because the clay interlayer compound (C) is easily finely dispersed in the thermoplastic resin (E).

The conditions for producing the thermoplastic resin composition (E) by the above method may be the same as those for producing each of the thermoplastic resins (D). The ratio of the clay interlayer compound (C) and the thermoplastic resin (D) in the obtained thermoplastic resin composition (E), the average layer thickness of the clay interlayer compound (C), the inorganic ash content, etc. This is the same as the case where (C) and the thermoplastic resin (D) are melt-mixed using a kneading machine, and the description is omitted.

The thermoplastic resin composition (E) of the present invention comprises:
Depending on the purpose, additives such as pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents can be added.

The thermoplastic resin composition (E) of the present invention can be used for injection molding, hot press molding, blow molding and the like, and may be obtained by reaction molding in a mold.

The molded article from the thermoplastic resin composition (E) of the present invention is excellent in appearance, mechanical properties, heat resistance, etc., and therefore, for example, automobile parts, household electric parts,
It is suitably used for household daily necessities, packaging materials, and other general industrial materials.

[0110]

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

The materials used in the examples and comparative examples are summarized below.

Layered silicate (A): unpurified montmorillonite from Akita (base spacing 13)
Å) Unrefined kaolinite from Georgia, United States (bottom spacing 7-10Å)

Dispersion stabilizer (B): The following compounds were used without purification. Nippon Unicar Co., Ltd. silicone compound L7002,
FZ2123 (methylpolysiloxane each having a grafted polyalkylene oxide chain), FZ3707
(Methyl polysiloxane to which amino groups are grafted),
FZ3703 (methylpolysiloxane with a carboxyl group grafted) Adecapluronic L-64 (polyoxyethylene-polyoxypropylene condensate, abbreviated as L-64) manufactured by Asahi Denka Kogyo Co., Ltd.

Thermoplastic resin (D): The following resin was used without purification. PBK2 (polyethylene terephthalate (PET) resin, logarithmic viscosity 0.63 dl / g), manufactured by Kanebo Co., Ltd. Amilan CM1026 (nylon 6, relative viscosity 3.1), manufactured by Toray Industries, Ltd. Mitsubishi Chemical Corporation, NOVAREX 7025PJ (bisphenol A type polycarbonate (PC) resin, weight average molecular weight (Mw) 45000), manufactured by Sumitomo Chemical Co., Ltd., H501 (polypropylene (P
P) Resin, MI 3.0 g / 10 min)

The evaluation in Examples, Comparative Examples and Reference Examples was performed by the following methods.

(Bottom spacing by small angle X-ray diffraction (SAXS)) X-ray generator (RU-200 manufactured by Rigaku Corporation)
B) using target CuKα ray, Ni filter,
Voltage 40 kV, current 200 mA, scan angle 2θ = 0.2 ~
Under the measurement conditions of 16.0 ° and a step angle of 0.02 °, the bottom distance between the layered silicate (A) as the raw material and the clay interlayer compound (C) isolated after the production was measured.

(Measurement of Layer Thickness by Transmission Electron Microscope (TEM)) Transmission Electron Microscope (JEOL JEM-1200)
EX), the average layer thickness of the clay interlayer compound (C) in a dispersed state at an acceleration voltage of 80 kV was measured. An ultra-thin section was cut out from the obtained molded article of the thermoplastic resin composition (E), and stained with ruthenium oxide as needed to obtain a sample.

(Apparent viscosity) 400 m of solvent shown in Table 2
1), a clay intercalation compound (C) was added so that the dispersion concentration became 6.5%, and the mixture was stirred at 5000 rpm for 15 minutes to prepare a clay intercalation compound (C) dispersion. The obtained dispersion was transferred to a 500 ml mayonnaise bottle, and allowed to stand for 3 hours.
The apparent viscosity at 25 ° C. at rpm was measured using a B-type viscometer manufactured by Tokyo Seiki Co., Ltd. The rotor is No. 3 according to the viscosity of the dispersion. One, two, three or BL adapters were used.

(Inorganic Ash Content) Thermoplastic Resin Composition (E)
Was measured according to JIS K7052. In addition, since the inorganic ash content of the thermoplastic resin (D) used in Examples and Comparative Examples is substantially 0, the obtained inorganic ash content is the inorganic ash content derived from the clay interlayer compound (C).

(HDT) The pelletized thermoplastic resin composition was vacuum-dried at 120 ° C. × 4 hours, and then heated at 270 ° C. (PET) and 240 ° C.
(Nylon 6), 280 ° C (PC), 180 ° C (P
P), 10 × 100 × under the condition of a pressure of 850 kg / cm ²
A 6 mm test piece was prepared, and the HDT of the obtained test piece was converted to A.
Measured according to STM D-648.

(Flexural Modulus) The flexural modulus of a test piece prepared in the same manner as in the case of HDT was determined according to ASTM D-790.
Was measured according to

(Surface Properties of Molded Article) The glossiness and color tone of the test piece prepared in the same manner as in the case of HDT were visually observed and evaluated according to the following criteria. ◎: glossy, no unevenness in color tone ○: devitrified or non-uniform color tone ×: devitrified and non-uniform color tone

(Logarithmic viscosity) After the pelletized thermoplastic polyester resin composition was dried at 140 ° C. for 4 hours, about 100 mg was precisely weighed and phenol / 1,1,1 was added.
20 ml of a mixed solvent of 2,2-tetrachloroethane = 5/5 (weight ratio) was added and dissolved at 120 ° C. Using an Ubbelohde viscometer, measure the solution viscosity at 25 ° C. using an automatic viscosity measurement device (Viscometer, manufactured by Lauda Co.)
Formula (I): η _inh = {ln (t / t ₀ )} / C (I) (where t is the value of the solution, t ₀ is the value of the mixed solvent, and C is the concentration (g / dl)) Logarithmic viscosity (η _inh ) was determined.

(Relative viscosity) Measured according to JIS K 6810.

The polyamide resin composition in the form of pellets was
Vacuum dried at 0 ° C. × 4 hours. Approximately 250 mg was precisely weighed, and 25 ml of 98% concentrated sulfuric acid was added and dissolved at room temperature.
Using an Ubbelohde viscometer, measure at 25 ° C. using an automatic viscosity measuring device (Viscotimer manufactured by Lauda),
The relative viscosity (η _r ) was determined from the formula (II): η _r = t / t ₀ (II) (where t is the value of the solution and t ₀ is the value of concentrated sulfuric acid only).

(Weight average molecular weight) After drying the polycarbonate resin composition in the form of pellets at 140 ° C. for 4 hours, about 5 mg was precisely weighed, and tetrahydrofuran (TH
F) 6.0 g was added and dissolved. After filtration through a 0.5 μ filter, a weight average molecular weight (Mw) in terms of monomolecular weight dispersed polystyrene was measured using a water permeation gel permeation chromatography (GPC) measuring device at a column temperature of 40 ° C. and a flow rate of 1 ml / min. Was measured.

Examples 1 to 8 (Clay interlayer compound (C)) 4 g of montmorillonite was used as a layered silicate (A) in water 1
The resulting mixture was sufficiently dispersed using a high-speed stirrer (5000 rpm, 5 minutes) to prepare a water-layered silicate dispersion.

Separately, a solution was prepared by dissolving 0.6 g of the dispersion stabilizer (B) shown in Table 1 in 300 g of water shown in Table 1 or a polar solvent compatible with water at an arbitrary ratio. did.

When the dispersion and the solution were mixed, the ratio of water to the polar solvent was 100 parts of water to 300 parts of the polar solvent, and montmorillonite and the dispersion stabilizer (B) were used. The use ratio of montmorillonite 10
The dispersion stabilizer (B) was 15 parts relative to 0 parts.

After the dispersion and the solution are mixed, the solvent is removed, dried and pulverized to obtain a clay intercalation compound (C). The bottom surface interval and the clay intercalation compound (C) are mixed with various solvents. The apparent viscosity of the resulting dispersion was measured. Table 2 shows the results.

Comparative Examples 1 to 8 The distance between the bottom surfaces of the montmorillonite used in Examples 1 to 8, and the montmorillonite and the various solvents used in Examples 1 to 8 were sufficiently stirred using a high-speed stirrer. A montmorillonite dispersion was prepared and the apparent viscosity was measured. Table 2 shows the results.

[0132]

[Table 1]

[0133]

[Table 2]

Examples 9 to 17 Clay interlayer compounds (C) were produced in the same manner as in Examples 1 to 8. The kind of the layered silicate (A) and the combination of the dispersion stabilizer (B), the inorganic ash content in the composition, and the amount of the dispersion stabilizer (B) used per 100 parts of the layered silicate (A) Is shown in Table 3.

100 parts of PBK2 (PET) and the amount shown in Table 3 of the clay intercalation compound (C) were rotated at 100 revolutions using a co-rotating twin-screw extruder having a kneading disk portion. The mixture was melt-kneaded at a melt-kneading temperature of 270 ° C. to produce a thermoplastic polyester resin composition, which was evaluated. Table 3 shows the results.

Comparative Examples 9 to 12 The same procedures as in Examples 9 to 17 were carried out except that the layered silicate (A) shown in Table 3 was used instead of the clay interlayer compound (C) used in Examples 9 to 17. Compositions were prepared and evaluated in a similar manner. Table 3 shows the results.

Reference Example 1 Evaluation was performed using only PBK2 (PET). Table 3 shows the results
Shown in

[0138]

[Table 3]

Examples 18 to 20 Clay interlayer compounds (C) were produced in the same manner as in Examples 1 to 8. The combination of the type of the layered silicate (A) and the dispersion stabilizer (B), and the layered silicate (A)
Table 4 shows the amount of the dispersion stabilizer (B) used per 100 parts.

Amilan CM 1026 (nylon 6) 1
Melt kneading was carried out in the same manner as in Examples 9 to 17 except that the amount shown in Table 4 of the clay interlayer compound (C) obtained as 00 parts was used (however,
The melt-kneading temperature was 250 ° C.) to produce and evaluate a thermoplastic polyamide resin composition. Table 4 shows the results.

Comparative Examples 13 to 14 Examples 18 to 20 were repeated except that the layered silicate (A) shown in Table 4 was used instead of the clay interlayer compound (C) used in Examples 18 to 20. Producing a composition in the same manner,
evaluated. Table 4 shows the results.

Reference Example 2 Evaluation was performed using only Amilan CM1026 (nylon 6). Table 4 shows the results.

[0143]

[Table 4]

Example 21 A clay interlayer compound (C) was produced in the same manner as in Examples 1 to 8. The combination of the type of the layered silicate (A) and the dispersion stabilizer (B), and the layered silicate (A)
Table 5 shows the amount of the dispersion stabilizer (B) used per 100 parts.

Melt kneading was carried out in the same manner as in Examples 9 to 17 except that 100 parts of NOVAREX 7025PJ (polycarbonate resin) and the amount of the clay interlayer compound (C) described in Table 5 were used (however, the melt kneading temperature was 280). ° C) to produce and evaluate a thermoplastic polycarbonate resin composition. Table 5 shows the results.

Comparative Example 15 A composition was prepared in the same manner as in Example 21 except that only the layered silicate (A) shown in Table 4 was used instead of the clay interlayer compound (C) used in Example 21. Manufactured and evaluated. Table 5 shows the results.

Reference Example 3 Evaluation was made using only NOVAREX 7025PJ (polycarbonate resin). Table 5 shows the results.

[0148]

[Table 5]

Example 22 A clay interlayer compound (C) was produced in the same manner as in Examples 1 to 8. The combination of the type of the layered silicate (A) and the dispersion stabilizer (B), and the layered silicate (A)
Table 6 shows the amount of the dispersion stabilizer (B) used per 100 parts.

Melting and kneading with 100 parts of H501 (polypropylene resin) and the amount shown in Table 6 of the clay interlayer compound (C) in the same manner as in Examples 9 to 17 (however, the melting and kneading temperature is 170 ° C.) Then, a polypropylene resin composition was manufactured and evaluated. Table 6 shows the results.

Comparative Example 16 A composition was prepared in the same manner as in Example 22 except that the layered silicate (A) shown in Table 4 was used instead of the clay interlayer compound (C) used in Example 22. Manufactured and evaluated. Table 6 shows the results.

Reference Example 4 Evaluation was made using only H501 (polypropylene resin). Table 6 shows the results.

[0153]

[Table 6]

[0154]

The clay intercalation compound (C) of the present invention is prepared by mixing a layered silicate and a dispersion stabilizing agent to increase the distance between the bottom surfaces, thereby obtaining various aqueous solvent matrices and the clay intercalation compound (C). And the affinity with the compound can be increased. Also, even with a small amount of addition, a desired rheological property can be imparted to a matrix such as water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. Therefore, the rheological properties such as the viscosity of the solvent can be adjusted by the clay interlayer compound (C) of the present invention.

Further, the clay intercalation compound (C) of the present invention is easily finely dispersed, and has an excellent rheological modification effect even when added in a small amount, so that cosmetics, pharmaceuticals,
It can be used as a composition such as a clay modifier, a dispersant, an emulsifier, and a binder in various products or industrial processes such as sanitizers, adhesives, paints, raw materials for paints, various plastic products, textile industry, etc. It is. The clay intercalation compound (C) of the present invention can be easily obtained with a commonly used compound such as a layered silicate and a silicone compound.

Further, by making the composition of the present invention containing the clay intercalation compound (C) and a thermoplastic resin,
The clay intercalation compound (C) can be finely dispersed at a nm level in a thermoplastic resin matrix, resulting in excellent mechanical properties such as elastic modulus, heat resistance such as heat distortion temperature, and properties such as molded article appearance. A thermoplastic resin composition can be manufactured.

Claims (9)

[Claims] 1. A layered silicate (A) having an average layer thickness of 200 ° or less selected from the group consisting of a smectite group, a vermiculite group, and a kaolin group clay mineral, and a dispersion stabilizer (B). The dispersion stabilizer (B) is sandwiched between the layered silicates (A), and the dispersion stabilizer (B) is water, a polar solvent compatible with water in an arbitrary ratio, and water And a non-ionic compound soluble in at least one kind of a mixed solvent of the polar solvent and the polar solvent (C). 2. The dispersion stabilizer (B) according to claim 1, which is at least one selected from the group consisting of a compound having a polysiloxane chain as a main chain and a compound having a polyether chain as a main chain. Clay interlayer compound (C). 3. The clay intercalation compound (C) according to claim 1, wherein the distance between the bottom surfaces is at least twice the initial value. 4. The method for producing a clay intercalation compound (C) according to claim 1, 2 or 3, wherein the layered silicate (A) and the dispersion stabilizer (B) are optionally mixed with water or water. A method for producing a clay intercalation compound, comprising mixing in a mixed solvent consisting of a polar solvent and water which are compatible with each other at a ratio of, and then removing water or the mixed solvent. 5. A thermoplastic resin composition (E) comprising the clay interlayer compound (C) according to claim 1, 2 or 3, and a thermoplastic resin (D). 6. The thermoplastic resin composition (E) according to claim 5, wherein the inorganic ash content derived from the clay interlayer compound (C) is 0.1 to 60% by weight. 7. The thermoplastic resin composition (E) according to claim 5, wherein the average thickness of the clay interlayer compound (C) in a dispersed state is 200 ° or less. 8. A method for producing the thermoplastic resin composition (E) according to claim 5, 6 or 7, wherein the method comprises the steps of:
Or a process for preparing a mixture of the clay intercalation compound (C) and a polymerizable monomer according to 3 and a process for polymerizing the polymerizable monomer in the mixture. 9. A method for producing the thermoplastic resin composition (E) according to claim 5, 6, or 7, wherein the method comprises the steps of:
Or a method for producing a thermoplastic resin composition, wherein the clay interlayer compound (C) and the thermoplastic resin (D) are melt-mixed using a kneader.