JPH10310420A - Swelling mica intercalation compound and thermoplastic resin composition containing the compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart a desired rheological characteristic to an aq. solvent forming a matrix even by the addition in a small amt. by interposing a dispersion stabilizer between the layers of swelling mica having a specified thickness. SOLUTION: A swelling mica having 0.1-6.0 mm diameter and <=500 Åaverage thickness is swollen by <=30 wt.% in >=1 kind of dispersion medium selected from water, a polar solvent compatible with water in an optional ratio and a mixture of the water and the polar solvent to obtain a dispersion. A soln. of >=1 kind of dispersion stabilizer selected from a compd. having a polysiloxane chain as the principal chain and a compd. with a polyether chain as the principal chain is added to the dispersion and sufficiently mixed, then the dispersion medium is removed, and a swelling mica intercalation compd. with 0.1-60 pts.wt., preferably 0.2-50 pts.wt. or more preferably 0.3-40 pts.wt., of the dispersion stabilizer soluble in aq. solvent interposed between the layers of 100 pts.wt. of the swelling mica is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a swellable mica intercalation compound and a thermoplastic resin composition containing the swellable mica intercalation compound.

[0002]

2. Description of the Related Art Swellable mica having the property of swelling by taking in specific solvent molecules between layers is characterized by being dispersed in various compounds serving as a matrix to adjust or improve rheological properties. For example, it is used as a viscosity modifier for fluid fine chemical products such as paints, printing inks, and cosmetics. Layered silicates are also used as fillers or reinforcing agents for the purpose of improving physical properties such as rigidity, mechanical properties, and heat deformation resistance of polymer materials such as rubber and plastic.

[0003] Specific solvents entering between the layers of the swelling mica include water and ethylene glycol.
The number of molecules that can enter is only a few molecules, and shows only so-called limited swelling, so that it still has a laminated structure. Therefore, there is a problem that a rheology modifying effect and a thickening effect cannot be sufficiently obtained with a small amount of the compounding ratio.

[0004] A similar problem occurs when the above-mentioned swellable mica is used as a filler or reinforcing agent for a resin. That is, conventionally, since the swellable mica is merely dispersed in the resin in a layered structure of the order of μm, a small amount of addition does not provide a reinforcing effect such as improvement of mechanical properties.

The following is an example of an attempt to improve the physical properties by uniformly dispersing swellable mica in a resin to solve the above problem.

That is, (1) 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),
(2) 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 Unexamined Patent Publication No. 268
188, JP-A-8-73710), (3)
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. (4) swelling with respect to a monomer forming a reinforced polyamide resin composition obtained by polymerizing a monomer (JP-A-8-59822), and (4) 100 parts (parts by weight, hereinafter the same) of nylon 6 or a copolymer thereof. 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).

[0007] In order to study the techniques described in (1) and (2) in detail, the present inventors disclosed in Japanese Patent Application Laid-Open No. 8-737.
According to the method described in Japanese Patent Publication No.
Then, according to the examples described in JP-A-7-26123, a thermoplastic polyester resin composition comprising a polyester resin and a swellable fluoromica was obtained, and a layer charge of 0 was obtained. .2 to 1.
Although a composition using the swellable fluorine mica as a layered inorganic filler having a value of 0 was produced as a trial, it was not possible to obtain a composition having desired dispersibility, layer thickness and physical properties. 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 dispersion state of the swellable fluoromica in the thermoplastic polyester resin composition remain the same as the swellable fluoromica before blending. Determined by line diffraction measurements.

Further, the present inventors have conducted a detailed study on the technique described in (3).
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 (1) and (2), as observed by transmission electron microscope observation and small-angle X-ray diffraction measurement. Turned out by.

Further, in the case of the technique described in (4), 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, there is a need for a specially-processed reaction equipment that can withstand corrosion by high temperature, high pressure, and acid, which causes 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 yet been proposed. Is the current situation.

The present invention has been made to solve the above-mentioned problems of the prior art, and provides a swellable mica-based material which can give desired rheological properties to an aqueous solvent system serving as a matrix even with a small amount of addition. It is another object of the present invention to provide a thermoplastic resin composition excellent in various properties such as mechanical properties and heat deformation resistance by compounding the swellable mica-based material with a thermoplastic resin.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, completed the present invention.

That is, according to the present invention, the average layer thickness is 500 °
It contains the following swellable mica (A) and dispersion stabilizer (B), wherein dispersion stabilizer (B) is interposed between layers of swellable mica (A), and dispersion stabilization is carried out. A swelling mica intercalation compound (C) (claim 1), wherein the agent (B) is soluble in an aqueous solvent; a compound in which the dispersion stabilizer (B) has a polysiloxane chain as a main chain; The swellable mica intercalation compound according to claim 1, which is at least one selected from the group consisting of compounds having an ether chain as a main chain (claim 2).
The swellable mica interlayer compound according to claim 1 or 2, wherein the bottom surface interval is at least 1.5 times the initial value (claim 3), the swellable mica interlayer compound according to claim 1, 2 or 3, and a thermoplastic resin ( D) The thermoplastic resin composition (Claim 4), wherein the inorganic ash content derived from the swellable mica intercalation compound is 0.1 to 60% (% by weight, the same applies hereinafter). (5) The composition according to (4) or (5), wherein the dispersed swellable mica intercalation compound has an average layer thickness of 500 ° or less.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The swellable mica intercalation compound (C) of the present invention has a mean layer thickness of 500 ° or less.
And a dispersion stabilizer (B), which is a nonionic compound that facilitates fine dispersion of the swellable mica (A). The ratio of the dispersion stabilizer (B) sandwiched between layers of the swelling mica (A) is 0.1 to 35%, preferably 0.2 to 30%, more preferably 0.3 to 25%. It is. If it is less than 0.1%, the effect of fine dispersion is reduced, and if it is more than 35%, the handleability of the swelling mica interlayer compound (C) tends to be reduced.

The ratio of the dispersion stabilizer (B) sandwiched between the layers of the swelling mica (A) can be determined by measuring the ash content of the obtained swelling mica intercalation compound (C) and using the following formula.

(Ratio (average value) of dispersion stabilizer (B) sandwiched between layers of swellable mica (A)) (%) = 100
× ｛(weight (g) of swelling mica intercalation compound (C)) −
(Ash content (g) of swelling mica intercalation compound (C))} /
(Weight (g) of Sinterable Mica Intercalation Compound (C)) The layer thickness was measured by embedding the swelling mica intercalation compound (C) of the present invention in an epoxy resin or the like so as not to aggregate with each other, and using a transmission electron microscope. By measuring the layer thickness of the individual swellable mica (A) at any site.

The swellable mica (A), which is a raw material of the swellable mica intercalation compound (C), is selected from water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. It has the property of swelling with one or more kinds (hereinafter also referred to as an aqueous solvent), and is a natural or synthetic swelling mica such as lithium-type teniolite, sodium-type teniolite, lithium-type tetrasilicic mica, and sodium-type tetrasilicic mica. A swelling mica having lithium ions or sodium ions between layers, a substituted product thereof,
Derivatives. Vermiculite equivalents can also be used. These may be used alone or in combination of two or more.

The crystal structure of the swellable mica (A) 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 used.

The dispersion stabilizer (B) is a nonionic compound that is soluble in an aqueous solvent, has no adverse effect such as decomposition on the matrix compound to be used, and has a low temperature even at the processing temperature of the matrix compound. It is a compound that exists stably.

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, and polyvinylpyrrolidone. , 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 at least one of water, a polar solvent compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent. In addition to the above-mentioned compounds, natural polymer compounds such as starches, mannan, seaweeds, plant mucilage, microbial mucilage, protein and the like can also be used as dispersion stabilizers (B).
Can be suitably used.

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 as a main chain. The compound having a polysiloxane chain as a main chain refers to a linear polysiloxane, in addition to an alkyl group,
Amino group, acetyl group, hydroxyl group, ether group and mercapto group are bonded to the side chain and copolymerized to the main chain in order to have water solubility.

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

[0023]

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[0024]

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[0025]

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

[0027]

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

The aqueous solvent is a polar solvent compatible with water at an arbitrary ratio, a mixed solvent of the polar solvent and water or water.

Examples of the polar solvent include methanol,
Alcohols such as 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 dimethyl sulfoxide, methyl cellosolve, 2-pyrrolidone, and the like.

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

In the swelling mica intercalation compound (C), the amount of the dispersion stabilizer (B) is preferably from 0.1 to 60 parts, more preferably from 0.1 part to 100 parts of the swelling mica (A). It is 2 to 50 parts, particularly preferably 0.3 to 40 parts. When the amount of the dispersion stabilizer (B) is less than 0.1 part, the effect of finely dispersing the swellable mica intercalation compound (C) tends to be insufficient. There is a tendency that the handleability as the fumic mica intercalation compound (C) is reduced, and that the rheological properties of the matrix compound and the properties inherent to the matrix compound are impaired.

As a method for producing the swellable mica intercalation compound (C) of the present invention, for example, water, a polar solvent compatible with water at any ratio, and water and a polar solvent A step of obtaining a dispersion by swelling in one or more dispersion media of the mixed solution (a swelling process), adding a dispersion stabilizer (B) to the dispersion, and thoroughly mixing the dispersion; A method including a step of removing (intercalation compounding step) is exemplified.

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

First, the swellable mica (A) is dispersed in an aqueous solvent and swelled. The solid dispersion concentration of the swellable mica (A) finely dispersed in the dispersion medium can be freely set within a concentration range in which the swellable mica can be sufficiently dispersed.
Further, it is preferably 25% or less, particularly preferably 20%.

When it is desired to promote fine dispersion of the swellable mica (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 finely pulverizing a filler,
For example, there is a method using hard particles. In this method, the hard particles, the swellable mica (A), and the dispersion medium are mixed and stirred at high speed, and the hard particles and the swellable mica (A) are subjected to physical collision to convert the swellable mica (A) into units. Separate into layers. Hard particles commonly used are filler grinding beads, such as glass beads and zirconia beads, but are not limited thereto.
These crushing beads are selected in consideration of the hardness of the swelling mica (A) or the material of the stirrer, and the particle size is determined in consideration of the swelling mica (A), so that it is generally limited to a numerical value. Although not performed, those having a diameter in the range of 0.1 to 6.0 mm are preferable.

The interlayer compounding step (second step) can be performed, 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, swellable mica (A) is mixed with water, a polar solvent compatible with water at an arbitrary ratio, and water and the polar solvent. A dispersion comprising one or more dispersion media of a mixed solvent of solvents is prepared, and a dispersion stabilizer solution comprising a dispersion stabilizer (B) and another solvent is separately prepared. This can be achieved by thoroughly stirring and mixing the agent solution. The mixing ratio can be arbitrarily set as long as the dispersibility of the swellable mica (A) and the solubility of the dispersion stabilizer (B) are maintained. For example, a dispersion in which swellable mica (A) is dispersed in water and tetrahydrofuran (THF) having a molecular weight of 5,000 to 600
When mixed with a solution of dimethylpolysiloxane in which epoxy groups and carbinol groups are grafted at 0,
When the proportion of water is 30% or more, the dispersibility of the swellable mica (A) is maintained, and when the THF is 30% or more, the solubility of the polysiloxane is maintained. Therefore, in the above mixed system, water / T
HF 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 swellable mica interlayer compound (C) of the present invention.

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

The formation of the swellable mica intercalation compound (C) of the present invention can be easily confirmed from the measurement of the spacing between the (001) planes by small angle X-ray diffraction (SAXS).

The distance between the bottom surfaces can be calculated by applying the diffraction peak angle value in SAXS to Bragg's equation. When the dispersion stabilizer (B) is sandwiched between the layers of the swelling mica (A) to form the swelling mica intercalation compound (C), the distance between the bottom surfaces increases. The distance between the bottom surfaces of the swelling mica intercalation compound (C) of the present invention is 1.5 times or more as compared with the initial value (the distance between the bottom surfaces of the swelling mica (A)).
The magnification is preferably at least 2 times, more preferably at least 2.5 times.

The upper limit of the distance between the bottom surfaces of the swelling mica intercalation compound (C) of the present invention is not particularly present, but if it exceeds 10 times, the excess amount of the dispersion stabilizer (B) between the layers of the swelling mica (A) is excessive. Since it is present, the handleability of the swellable mica intercalation compound (C) of the present invention tends to decrease, or the rheological properties of the system and the properties inherent to the matrix compound tend to be impaired.

The swellable mica intercalation compound (C) of the present invention thus obtained is a good solvent for the dispersion stabilizer (B),
That is, since it has an affinity for various aqueous solvents, it can be well dispersed in the aqueous solvents. Therefore, the swellable mica intercalation compound (C) of the present invention is uniformly dispersed without aggregation even in an aqueous solvent, and has an excellent thickening effect on an aqueous solvent and a denaturing / modifying effect such as rheological properties even with a small amount of addition. Have.

The swellable mica intercalation compound (C) is used in various applications as a thickener or a gelling agent by adding it to various aqueous solvent compositions and dispersing it by stirring or the like in a usual manner. . At this time, the thickening effect is higher as the amount (dispersion concentration) used is higher as long as the concentration can be dispersed in the aqueous solvent composition. Since the specific dispersion concentration differs depending on the solvent, it cannot be determined unconditionally, but is generally 0.01%.
-50%, preferably 0.05-35%, more preferably 0.1-20%.

The swelling mica intercalation compound (C) may be added to various aqueous solvents to prepare a swelling mica intercalation compound (C) dispersion.

The dispersion of the swelling mica intercalation compound (C) is prepared by adding the swelling mica intercalation compound (C) to an arbitrary aqueous solvent,
By stirring or after mixing the swellable mica (A) and the dispersion stabilizer (B) in the intercalation compounding step in the method for producing the swellable mica interlayer compound (C), the dispersion medium and the like are removed to swell. Such a swellable mica intercalation compound (C) dispersion may be directly produced without isolating the swelling mica intercalation compound (C). In this case, after mixing the swellable mica (A) and the dispersion stabilizer (B) in the dispersion medium, a desired aqueous solvent is newly added, and the dispersion medium is removed by a usual fractionation operation. A swellable mica intercalation compound (C) dispersion comprising the swelling mica intercalation compound (C) and a newly added aqueous solvent can be obtained.

It is considered that a layer space is formed in the swellable mica interlayer compound (C). By utilizing this layer space, the swellable mica intercalation compound (C) can be used as an organic substance storage agent, sustained release agent, catalyst, adsorbent, carrier, filler and the like.

The thermoplastic resin composition (E) of the present invention is a composition containing the swellable mica interlayer compound (C) obtained as described above and the thermoplastic resin (D). Since the composition contains the swellable mica intercalation compound (C), the composition has excellent properties such as mechanical properties and heat deformation resistance without impairing the appearance of the molded article.

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 molecular weight of the thermoplastic resin (D) may be selected in consideration of the 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, an appropriate molecular weight may be set 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 swellable mica intercalation compound (C) and the thermoplastic resin (D) in the thermoplastic resin composition (E) is based on 100 parts of the thermoplastic resin (D).
0.1 to 400 parts, preferably 0.2 to 200 parts, more preferably 0.6 to 8 parts of the swellable mica intercalation compound (C).
0 parts. If the amount of the swelling mica intercalation compound (C) is less than 0.1 part, the effect of improving mechanical properties tends not to be obtained. Tends to be impaired.

The thermoplastic resin composition (E) is produced by melt-mixing the swellable mica intercalation compound (C) and the thermoplastic resin (D) using various general methods, for example, using a kneader. Can be done by

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 production of the thermoplastic resin composition (E), the dispersion medium and the aqueous solvent are usually removed before the production of the thermoplastic resin composition. However, the dispersion medium and the aqueous solvent may deteriorate the thermoplastic resin. If you do not mimic
If the removal of the dispersion medium and the aqueous solvent is omitted and the swellable mica intercalation compound (C) containing the dispersion medium and the aqueous solvent is used, the uniformity with respect to the resin is improved. May be manufactured.

The average layer thickness of the swellable mica interlayer compound (C) in the obtained thermoplastic resin composition (E) is at most 500 °, preferably at most 400 °, more preferably at most 300 °. If the average layer thickness is more than 500 °, it will be difficult to obtain the effect of improving the mechanical properties and rheological properties of the resin composition of the present invention. The lower limit of the average layer thickness is not particularly limited, but is preferably about 10 °.

The average layer thickness was measured by a transmission electron microscope (TEM).
The layer thickness of each swellable mica intercalation compound (C) at an arbitrary site of the thermoplastic resin composition (E) is measured using, for example, a method, and the average is obtained.

The inorganic ash content of the thermoplastic resin composition (E) derived from the swellable mica interlayer compound (C) is 0.1 to 60.
%, More preferably 0.2 to 50%, especially 0.5 to 35%
Is preferred. If the inorganic ash content is less than 0.1%, the effect of improving mechanical 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.

The thermoplastic resin composition (E) may be produced by mixing the swellable mica intercalation compound (C) and the thermoplastic resin (D) as described above. After preparing a mixture of the separated swellable mica 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, swellable mica (A) in a dispersion medium
To give a dispersion. Further, one or more dispersion stabilizers (B) are dissolved in an aqueous solvent to separately prepare a solution. The dispersion and the solution are sufficiently stirred to produce a swellable mica intercalation compound (C), and the swellable mica intercalation compound (C) containing a dispersion medium and an aqueous solvent is mixed with a polymerizable monomer. It is manufactured by mixing and polymerizing the polymerizable monomer in the mixture. Here, the dispersion medium, the aqueous solvent, and the polymerizable monomer may be the same or different.

Examples of the polymerizable monomer 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 containing an aromatic dicarboxylic acid or an ester-forming derivative thereof as a main component, and a diol compound or an ester-forming derivative thereof as a main component. 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, adipic acid, azelaic acid, dodecanedioic acid,
One or more aliphatic dicarboxylic acids such as sebacic acid may be used as a mixture.

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 (III): H ₂ N—X—NH ₂ (III) (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 of this 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 (I)
V): HOOC-Y-COOH (IV) (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-trimethylsiloxane ("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, when the thermoplastic resin composition (E) is produced by polymerizing the swellable mica interlayer compound (C) and the polymerizable monomer constituting the thermoplastic resin (D), It is preferable because the fumic mica intercalation compound (C) is easily finely dispersed.

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 swellable mica intercalation compound (C) and the thermoplastic resin (D) in the obtained thermoplastic resin composition (E), the average layer thickness of the swellable mica intercalation compound (C), the inorganic ash content, etc. This is the same as the case where the swellable mica intercalation compound (C) and the thermoplastic resin (D) are melt-mixed using a mixer, and therefore 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 has excellent appearance, excellent mechanical properties and heat resistance.
It is suitably used for household daily necessities, packaging materials, and other general industrial materials.

[0085]

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.

Swellable mica (A): JP-A-2-14941
No. 5 was synthesized according to the method described therein. That is, 16.9 g of talc and 3.1 sodium fluoride
g) and heat-treated at 800 ° C. to obtain 18.8 g of swellable mica having a base spacing of 12 °.

Dispersion stabilizer (B): Nippon Unicar Co., Ltd.
Silicone compounds L7002, FZ2123 (methylpolysiloxane grafted with polyalkylene oxide chains, respectively), FZ3707 (methylpolysiloxane grafted with amino groups) Adecapluronic L-64 (polyoxygen, manufactured by Asahi Denka Kogyo KK) Ethylene-polyoxypropylene condensate, L-
64) Thermoplastic resin (D): The following resin was used without purification.

PBK2 (polyethylene terephthalate (PET) resin, logarithmic viscosity 0.63 dl /
g) Amilan CM1026 (nylon 6, relative viscosity 2.9) manufactured by Toray Industries, Ltd. Novarex 7025PJ (bisphenol A type polycarbonate (PC) resin, weight average molecular weight (Mw) 45000) manufactured by Mitsubishi Chemical Corporation Sumitomo Chemical H501 (polypropylene (P
(P) Resin, MI 3.0 g / 10 min) Further, evaluations in Examples, Comparative Examples and Reference Examples were performed by the following methods.

(Layer spacing by small-angle X-ray diffraction (SAXS)) X-ray generator (RU-200B manufactured by Rigaku Corporation)
Using a target CuKα ray, a Ni filter, a voltage of 40 kV, a current of 200 mA, and a scanning angle 2θ of 0.2 to 1.
Under the measurement conditions of 6.0 ° and a step angle of 0.02 °, the bottom distance between the swellable mica (A), the swellable mica intercalation compound (C) and the swellable mica intercalation compound (C) in the dispersion is measured. did.

The pelletized thermoplastic resin composition was dried at 120 ° C. for 4 hours and then heated at 270 ° C. (PET), 240 ° C. (Nylon 6), 280 ° C. (PC), respectively. 180 ° C (PP), pressure 85
A 10 × 100 × 6 mm test piece was prepared under the condition of 0 kg / cm ² , and the obtained test piece was subjected to SAXS measurement. From the diffraction peak angle, (001) of the dispersed swelling mica intercalation compound (C) was obtained. ) The bottom spacing of the faces was calculated.

(Apparent Viscosity) The apparent viscosity at 25 ° C. of an aqueous dispersion of the swellable mica intercalation compound (C) obtained by dispersing the swellable mica intercalation compound (C) in various aqueous solvents was measured using a B-type viscometer. did.

The swellable mica interlayer compound (C) was added to 400 ml of the aqueous solvent shown in Table 2 so that the dispersion concentration became 6.5%, and the mixture was stirred at a high speed (5000 rpm) for 15 minutes. A compound (C) aqueous dispersion was prepared.
The obtained aqueous dispersion was transferred to a 500 ml mayonnaise bottle, allowed to stand for 3 hours, and then the rotor was directly inserted. The apparent viscosity at a rotor rotation speed of 6 rpm (shear speed: 1.68 sec ^-1 ) was measured using a B-type viscometer. It was measured. The rotor used No1, No2, No3 or BL adapter depending on the viscosity of the dispersion.

(Inorganic Ash Content of Swellable Mica Intercalation Compound (C)) The inorganic ash content of the thermoplastic resin composition (E) derived from the swelling mica intercalation compound (C) is JIS K 7052.
It measured according to.

(Measurement of Layer Thickness by Transmission Electron Microscope (TEM))
It was cut out into a flake having a thickness of nm. Using a transmission electron microscope (JEOL JEM-1200EX), acceleration voltage 80 kV
Was measured.

The average value of the layer thickness is the layer thickness of each swelling mica intercalation compound at an arbitrary site where 100 or more swelling mica intercalation compounds are present in the TME image of the thermoplastic resin composition of the present invention. Was measured, and the number was averaged.

(HDT) The pelletized thermoplastic resin composition was dried at 120 ° C. for 4 hours, and then heated to 270 ° C. (PET), 240 ° C. (Nylon 6) and 280 ° C. (PC ), A test piece of 10 × 100 × 6 mm was prepared under the conditions of 180 ° C. (PP) and a pressure of 850 kg / cm ² , and the HDT of the obtained test piece was subjected to ASTM.
It was measured according to 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 property of molded article) The gloss and the color tone 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) The pelletized thermoplastic polyester resin composition was dried at 140 ° C. for 4 hours.
About 100 mg is precisely weighed, and phenol / 1, 1, 2, 2, 2
-Tetrachloroethane = 5/5 (weight ratio) mixed solvent 20
The solution was added and dissolved at 120 ° C. Using an Ubbelohde viscometer, the solution viscosity was measured at 25 ° C. using an automatic viscosity measurement device (Viscotimer manufactured by Lauda Co.), and the 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)), and the 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 7 4 g of swellable mica (A) was added to 100 g of water and sufficiently dispersed using a high-speed stirrer (5000 rpm, 5 minutes).
A water-swellable mica dispersion was prepared.

Apart from this, the aqueous solvents 30 shown in Table 1
A solution in which 0.6 g of the dispersion stabilizer (B) shown in Table 1 was dissolved in 0 g was prepared.

After mixing the dispersion and the solution,
The solvent was removed and pulverized to obtain a swellable mica intercalation compound,
The bottom spacing was measured. The apparent viscosity of a dispersion obtained by dispersing the swellable mica intercalation compound in various solvents was measured. Table 2 shows the results.

The mixing ratio of the water and the aqueous solvent when mixing the dispersion and the solution is 100 parts of water and 300 parts of the aqueous solvent, and the swelling mica (A) and the dispersion stabilizer are used. The ratio of (B) was 100 parts of the swelling mica (A) and 15 parts of the dispersion stabilizer (B).

Comparative Examples 1 to 7 A swellable mica dispersion was prepared by sufficiently stirring the swellable mica and the various aqueous solvents used in Examples 1 to 7 using a high-speed stirrer, and the apparent viscosity was adjusted. It was measured. Table 2 shows the results.

[0109]

[Table 1]

[0110]

[Table 2]

Examples 8 to 15 In the same manner as in Examples 1 to 7, swellable mica intercalation compounds were prepared. Table 3 shows the combination of the swellable mica and the dispersion stabilizer, the inorganic ash content, and the amount of the dispersion stabilizer used per 100 parts of the swellable mica.

100 parts of PBK2 (PET) and the amount of the swellable mica intercalated compound obtained in Table 3 were mixed with a kneading disk portion in a co-rotating twin-screw extruder having a kneading disk portion at a rotation speed of 100 revolutions. 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 8 to 10 In the same manner as in Examples 8 to 15, except that only the amount of swellable mica shown in Table 3 was used instead of the swellable mica interlayer compound used in Examples 8 to 15. To prepare and evaluate the composition. Table 3 shows the results.

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

[0115]

[Table 3]

Examples 16 and 17 A swellable mica interlayer compound (C) was produced in the same manner as in Examples 1 to 7. Table 4 shows the types of the swellable mica (A) and the combination of the dispersion stabilizer (B), and the amount of the dispersion stabilizer (B) used per 100 parts of the swellable mica (A).

Amilan CM1026 (nylon 6) 10
0 parts and the swellable mica interlayer compound in the amount shown in Table 4 were melt-kneaded in the same manner as in Examples 8 to 15 (however, the temperature was 25
0 ° C.) to produce and evaluate a polyamide resin composition.
Table 4 shows the results.

Comparative Example 11 The composition was the same as in Examples 16 and 17, except that only the amount of swellable mica shown in Table 4 was used instead of the swellable mica interlayer compound used in Examples 16 and 17. Articles were manufactured and evaluated. Table 4 shows the results.

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

[0120]

[Table 4]

Example 18 In the same manner as in Examples 1 to 7, a swellable mica intercalation compound was produced. Table 5 shows the combination of the swellable mica and the dispersion stabilizer, and the amount of the dispersion stabilizer used relative to 100 parts of the swellable mica.

100 parts of NOVAREX 7025PJ (polycarbonate) and the swellable mica interlayer compound in the amounts shown in Table 5 were melt-kneaded (at a temperature of 280 ° C.) in the same manner as in Examples 8 to 15 to obtain a polycarbonate resin composition. Articles were manufactured and evaluated. Table 5 shows the results.

Comparative Example 12 A composition was prepared in the same manner as in Example 18 except that only the amount of swellable mica shown in Table 5 was used instead of the swellable mica intercalation compound used in Example 18. ,evaluated. Table 5 shows the results.

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

[0125]

[Table 5]

Example 19 A swellable mica intercalation compound was produced in the same manner as in Examples 1 to 7. Table 6 shows the combinations of the swellable mica and the dispersion stabilizer, and the amounts of the dispersion stabilizer used relative to 100 parts of the swellable mica.

100 parts of H501 (polypropylene),
The amount of the swellable mica intercalation compound shown in Table 6 was used in Examples 8 to
Melt-kneading in the same way as 15
Then, a polypropylene resin composition was manufactured and evaluated. Table 6 shows the results.

Comparative Example 13 A composition was prepared in the same manner as in Example 19 except that only the amount of swellable mica shown in Table 6 was used instead of the swellable mica intercalation compound used in Example 19. ,evaluated. Table 6 shows the results.

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

[0130]

[Table 6]

[0131]

The swellable mica intercalation compound (C) of the present invention
By selecting a dispersion stabilizer, the affinity between various aqueous solvent matrices and the swellable mica intercalation compound (C) can be increased. In addition, a desired rheological property can be imparted to a matrix such as various aqueous solvents even by adding a small amount. Therefore, rheological properties such as viscosity of various aqueous solvents can be adjusted by the swellable mica interlayer compound (C) of the present invention.

Further, the swellable mica intercalation compound (C) of the present invention has an affinity for various aqueous solvents, is easily finely dispersed, and has an excellent rheological modification effect even when added in a small amount. In the cosmetics, pharmaceuticals, sanitizers, adhesives, paints, paint raw materials, various plastic products, various products such as textile industry or industrial processes that require, as a composition such as a clay adjuster, dispersant, emulsifier, and binder It can be used and is very useful. The swellable mica intercalation compound (C) of the present invention can be easily obtained from commonly used compounds such as swellable mica and silicone compounds.

Further, by forming the composition of the present invention containing the swelling mica intercalation compound (C) and the thermoplastic resin, the swelling mica intercalation compound (C) is finely dispersed in the thermoplastic resin matrix at the nm level. As a result, a thermoplastic resin composition having excellent properties such as mechanical properties such as elastic modulus, heat resistance such as heat distortion temperature, and appearance of a molded product can be produced.

Claims (6)

[Claims] A swelling mica (A) having an average layer thickness of 500 ° or less and a dispersion stabilizer (B), wherein the dispersion stabilizer (B) is sandwiched between layers of the swelling mica (A). A swellable mica intercalation compound (C), which is present and wherein the dispersion stabilizer (B) is soluble in an aqueous solvent. 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. Swellable mica intercalation compound. 3. The swellable mica intercalation compound according to claim 1, wherein the distance between the bottom surfaces is at least 1.5 times the initial value. 4. A thermoplastic resin composition comprising the swellable mica intercalation compound according to claim 1, 2 or 3, and a thermoplastic resin (D). 5. The composition according to claim 4, wherein the inorganic ash content derived from the swelling mica intercalation compound is 0.1 to 60% by weight. 6. The composition according to claim 4, wherein the average thickness of the dispersed swellable mica intercalation compound is 500 ° or less.