JPH08302068A - Composite material containing dispersed inorganic filler - Google Patents

Abstract

PURPOSE: To obtain a composite material having excellent rigidity and durability by preparing a disperse phase composed of a laminar compound consisting of an inorganic filler having a fibrous form and specific thickness and length and a resin intruded between the layers and dispersing the obtained disperse phase into a matrix resin. CONSTITUTION: An organic cation expressed by formula (R<1> to R<4> are each an alkyl and one of the groups is a 4-30C alkyl; X is a halogen) is inserted into a swelling laminar compound composed of an inorganic filler (e.g. tetrasilic mica) having a fibrous form, a thickness S of 10-40Å and a length L of >=300Å to impart affinity to organic compound to the laminar compound. The laminar compound is infinitely swollen by the use of a mixing resin such as an electron- donative organic compound (e.g. glycerol) and/or an aromatic compound (e.g. o-dichlorobenzene) to obtain a disperse phase 1, which is mixed and disperse in a matrix resin 2 (e.g. propylene homopolymer resin) to obtain the objective composite material containing dispersed inorganic filler and useful e.g. for a molded article having excellent rigidity, heat-resistance and impact resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to various molded products, particularly molded products required to have rigidity, heat resistance and impact resistance, for example, resin moldings used for automobiles, home electric appliances parts, building materials and industrial materials. It is about things.

[0002]

2. Description of the Related Art Conventionally, in order to improve various properties of resins such as polyolefins, particularly mechanical properties and heat resistance, an inorganic filler having high rigidity is mixed and kneaded. The polyolefin resin composition added with an inorganic filler has excellent rigidity and heat resistance as compared with a polyolefin resin composition not added,
In particular, it is widely used as a molding material in the fields of automobiles, home appliances, construction and industrial materials.

An example of such a device is Japanese Patent Laid-Open No. 2-102.
261 and JP-A-2-105856 disclose energy released when a layered clay mineral is doped with amines as a guest to widen the interlayer distance, and then a resin monomer is placed between the layers to polymerize it. Discloses an inorganic filler dispersion composite in which a layered clay mineral is self-disintegrated and dispersed at an angstrom level.

[0004]

However, although these can efficiently disperse the filler, they require special polymerization equipment and bear a high fixed cost for the product price, and are not economical. Further, the reaction is limited to condensation polymerization, or suspension and emulsion polymerization among radical polymerization systems. In addition, it is necessary to sequentially add the monomer having the monomer inserted between the layers as the reaction progresses, so that it is difficult to control the apparatus and it is difficult to obtain a material having a uniform concentration. Therefore, it is difficult to obtain a complex with a particularly high concentration. Further, in order to make the monomers such as ethylene, propylene, butene, and isoprene, etc., which are doped between the layers, stably exist between the layers, it is necessary to raise the monomer concentration. Must be present, which is practically difficult. Therefore, it is conceivable to prolong the residence time in the reactor, but this is not economical.

Therefore, the intercalation compound in which the monomer is inserted is kept under high pressure when it is injected into the polymerization system, but there is a restriction on the apparatus to use it as a monomer even in the case of homopolymerization or copolymerization. Liquid form is desirable.
In addition, if the above method is applied to an anionic coordination polymerization system used for polyolefins, a large amount of active hydrogen such as amino acids existing between layers is present and acts as a catalyst poison in the atmosphere, which is not suitable. . Therefore, in order to obtain an inorganic filler-dispersed composite having an angstrom level filler dispersed therein, only a filler having a low concentration and a low resin material has been obtained. In the polymerization system, even if the inorganic layered viscosity mineral is dispersed in units close to one layer of the mineral, that is, in smectite, mica compound, etc., dispersed at about 10 angstroms, the composite will reach the level of binding the molecule with the inorganic filler. However, since the swelling layered mineral is inferior in crystal rigidity to conventional fillers, the aspect of the filler has not been effectively utilized.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an inorganic filler-dispersed composite in which an inorganic filler is finely dispersed in a resin and which is excellent in high rigidity and heat resistance. .

[0007]

The inorganic filler-dispersed composite of the present invention is a fibrous layered compound composed of an inorganic filler having a thickness of 10 to 40 Å and a length of 300 Å or more, and the layered compound. The dispersed phase composed of the resin mixed between the layers is dispersed in the matrix resin.

At this time, it is preferable that the dispersed phase has a mean square diameter of 10 μm or less and an average aspect ratio of 4 or more.

Further, it is preferable that the content of the inorganic filler in the dispersed phase in the whole composite is 0.1 to 40 vol% and the content of the resin in the dispersed phase is 40 vol% or less.

[0010]

The present invention will be described in detail below. As shown in FIG. 1, the inorganic filler-dispersed composite of the present invention is in a state where the dispersed phase 1 is dispersed in the matrix resin 2. Further, the dispersed phase 1 is composed of an inorganic layered compound composed of an inorganic filler and a resin mixed between the layers of the layered compound. Further, the inorganic filler is fibrous and has a thickness of 10 to 40 Å and a length of 30.
More than 0 angstrom. The thickness of the fibrous inorganic filler does not become less than 10 angstroms, and when it is thicker than 40 angstroms, the amount of resin entering between the layers becomes small, the dispersibility is poor, and the interfacial adhesion with the matrix resin is deteriorated. Not preferable. Further, if the length of the inorganic filler is less than 300 angstroms, the distance of the lamella of the resin that has penetrated into the layered compound or the length of the tie molecule is approximately 200 angstroms, so sufficient molecular restraint of the resin cannot be performed, which is preferable. Absent. The layered compounds are mainly clay minerals,
Swelling clay compounds, zirconium phosphate and the like are suitable. Swelling clay minerals include smectite, vermiculite, mica, chlorite and the like. Examples of these naturally occurring crystalline layered clay minerals include the following compounds. The smectite structure includes saponite, hectorite, montmorillonite, and sauconite. Similar to vermiculite are trioctohedral-vermiculite and geotokhedral-vermiculite. For mica, muscovite, phyllogopite, biotite, lepidolite, paragonite, tetrasilicic mica, etc. Further, talc may be subjected to fluorine treatment to synthesize swelling mica, or talc may be obtained by hydrothermal synthesis to obtain the above structure. Furthermore,
Various compounds can be applied to the cation inserted between the layers by substituting different ions of the same kind such as sodium, potassium and lithium.

The content of this layered compound in the dispersed phase is preferably 0.1 to 40 vol% with respect to the entire composite. If the layered compound content is less than 0.1 vol%, sufficient resin penetration and substitution will not occur between the layers of the inorganic layered compound, the adhesive strength with the matrix resin will be reduced, and the rigidity and heat resistance of the composite will be excellent. Is reduced, which is not preferable. If it is more than 40 vol%, the amount of organic cations added to the layered compound is large, so that thermal molecular mobility cannot sufficiently restrain the molecule to become an inorganic layered compound, resulting in lower heat resistance. It is not preferable.

Furthermore, the dispersed phase in the present invention is in a state in which a resin is mixed between the layers of the layered compound. As the resin in the dispersed phase (hereinafter referred to as "mixed resin"), an aromatic compound or an electron donating organic compound, particularly an aliphatic alcohol having an electron donor structure and / or an ether thereof is preferable. Further, it may be an electron donor of a high dielectric constant solvent. For example, aromatic compounds include benzene, toluene, xylene, decahydronaphthalene, orthodichlorobenzene, and homologues such as alkylbenzene, pyridine, and quinoline. Examples of the aliphatic alcohols include methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, hexanol, cycloquexanol, octanol, diethylene glycol and glycerin. Examples of the aliphatic ethers include diethylene glycol monomethyl ether, tetrahydrofuran and butyl ethyl ether. Examples of the electron donor of the high dielectric constant solvent include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and dimethylsulfamide.

The resin content in this dispersed phase is 40 vol%
The following is desirable. More preferably 0.5-3
It is 0 vol%, more preferably 1.5 to 20 vol%. Four
This is because if it is more than 0 vol%, the action as an inorganic filler decreases, and the improvement in rigidity and heat resistance is small.
Further, it is preferably at least 0.5 vol% or more, and the resin is not sufficiently invaded and replaced with respect to the inorganic layered compound, the adhesive strength with the matrix resin is lowered, and the rigidity is lowered.

In the dispersed phase, the fibrous filler swelled to a nano level as described later, if the mixed resin is crystalline, restrains the molecules that connect the crystalline lamella.
At that time, if the volume content of the inorganic filler is higher than that of the mixed resin, the behavior is almost similar to that of the inorganic filler. For this reason, the dispersed phase in which the resin is mixed with the inorganic layered compound behaves as if it were one inorganic filler. Furthermore, as one of the factors that determine the rigidity of the inorganic filler-dispersed composite, when the dispersed phase is considered to have an elliptical shape, the aspect ratio that is the ratio of the major axis L to the minor axis S of the dispersed phase 1 as shown in FIG. There is a ratio (L / S). It is known that the longer the aspect ratio, the higher the rigidity and heat resistance (Halpin Tasai; "Primer on Composit
e Materials: Analysis "(Technomic, Stamford, Con
n., 1969) Ch. 5.HLCox, Brit.J.Appl.Phys. 3 (195
2) 72.).

In the present invention, the major axis L and the minor axis S of each dispersed phase are measured, and the number% of the aspect ratio values is calculated with respect to the root mean square (Dp = (L / S) / 2). An aspect ratio (Asp) was calculated when the total was 50% and the total average was 50%. The aspect ratio of the dispersed phase of the present invention is 4 or more, preferably 8 or more, more preferably 10 or more. This is because if the aspect ratio is less than 4, the improvement in rigidity and heat resistance is small. further,
In the present invention, since the interface between the dispersed phase and the matrix resin is in a state close to perfect adhesion, the size of the dispersed phase affects rigidity and heat resistance. That is, in the present invention,
It is desired that the size of the dispersed phase is 10 μm or less in terms of the root mean square diameter. If it is larger than 10 μm, it is difficult to improve the rigidity and heat resistance.

In the present invention, a crystalline polymer or an amorphous polymer is applied as the matrix resin in which the dispersed phase is dispersed. Examples of the crystalline polymer include polypropylene, polyethylene, low-density polyethylene, linear low-density polyethylene, polyamide 6, polyamide 6,6, polyamide 11, polyamide 12 and other polyamide resins and / or copolymers thereof, aliphatic polyesters, aromatics. Polybutylene terephthalate, polyether ketone, etc. are mentioned as a group polyester and / or its copolymer, and its similar compound. Further, the amorphous polymer has a glass transition temperature (Tg) of room temperature (23 ° C.) or higher, for example, polyvinylidene chloride, polystyrene, polycarbonate, amorphous polyamide, polyphenylene ether,
There are polyacetal, polysulfone, ABS resin and the like.
These may be a single or a combination of a plurality of crystalline / amorphous materials or a combination of amorphous / amorphous materials as long as they are compatible with each other and form a stable matrix to form a polymer alloy. For example, there are combinations of polypropylene / polyamide, polycarbonate / polybutylene terephthalate, polycarbonate / ABS and the like.

In the inorganic filler dispersed composite of the present invention comprising such a matrix resin and a dispersed phase, the interface between the dispersed phase and the matrix resin of the resin alone is almost completely adhered. In the conventional case, even if it had a high aspect ratio like whiskers, complete adhesion with the resin could not be achieved, so that a high concentration was forced to be added. However, according to the present invention, since the interfacial strength close to perfect adhesion is obtained, the dispersed phase acts almost as an inorganic filler, and the mechanical properties and thermal properties are improved even if the dispersed phase is in a small amount.

In the inorganic filler-dispersed composite of the present invention, an organic cation is inserted into the swellable layered compound so as to have an organic affinity, and then a mixed resin, preferably an electron-donating organic compound and / or an aromatic compound is used. Infinite swelling using
It can be obtained by kneading it with a matrix resin composition of a crystalline resin and / or an amorphous resin, preferably mechanical kneading, and melt-dispersing.

The organic cation used in the production process is preferably a positively charged organic compound such as trialkylammonium salt or amino acid. The tetraalkylammonium salt is represented by the following chemical formula.

[0020]

Embedded image In the chemical formula, R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups having 1 or more carbon atoms, and at least one of the alkyl groups
One has a main chain length and has 4 carbon atoms (referred to as C4. The same applies hereinafter).
Therefore, C30 or less is preferable. More desirably C12 to C2
The range of 5 is preferable, and the range of C15 to C22 is more preferable. When the carbon number is less than C4, the interlayer distance is not sufficiently opened, and a large amount of solvent is required for the subsequent swelling with the solvent.
When the number of carbon atoms is larger than C30, the molecular size is large and it is difficult to enter the layers, and the absolute amount inserted between the layers is small. As a result, even if a large amount of solvent is used, the layer is infinitely swollen to one unit. It is not preferable because it does not reach the conversion region. In the formula, X is various halogens, but chlorine is particularly preferable. When the ω-amino acid is used, it is preferable that it is an aliphatic straight-chain amino acid, contains a carboxylic acid, and has a main chain carbon number of C4 or more and C30 or less. The range of C10 to C25 is more preferable, and the range of C12 to C22 is further preferable. Further, when the amino group is not at the end of the main chain, it may be after the position (δ) at the 4-position from the position of the carboxylic acid. Further, it may be a diaminomonocarboxylic acid having at least one amino group at the position 4 or later from the position of the carboxylic acid as described above. For example, lysine, arginine, γ-aminocyclohexylcarboxylic acid and the like can be mentioned. Similarly, examples of monoaminodicarboxylic acid include glutamic acid. As those having an aromatic ring, p
-Aminohydrocinnamic acid and the like are also preferable. Further, it may be an amino acid having a heterocyclic structure, histidine, tryptophan or the like.

By adding this organic cation to the above-mentioned layered compound, ion exchange is carried out and swelling and organic affinity treatment are carried out. Specifically, as the swelling treatment, after the powder of the layered compound is sufficiently solvated with water, alcohol or the like, an organic cation is added and stirred to replace the metal ion between the layers of the layered compound with the organic ion. Then, the unsubstituted organic cation is thoroughly washed, filtered and dried. The amount of the organic cation added is, for example, the column permeation method (see "Clay Handbook", pages 576-577, published by Gidoudou).
Alternatively, the cation exchange capacity (CEC) of the layered compound is measured and determined by a method such as methylene blue adsorption amount measurement method (Japan Bentonite Industry Association standard test method, JBAS-107-91). The addition amount of the organic cation is preferably in the range of 1 equivalent to 10 equivalents with respect to CEC.

Next, a mixed resin is added to the obtained lipophilic compound and brought into contact with the lipophilic compound for nano-level dispersion. At that time, the lipophilic compound is infinitely swelled by heat of an extruder or the like, and melted. The resin in the state enters between the layers. In addition, the non-polar resin may not easily penetrate between the layers of the lipophilic compound. In that case, an organic solvent may be added to the lipophilic compound in advance and infinitely swollen, and then mixed into the resin, or the mixed resin may be brought into contact with the organic solvent and then brought into contact with the lipophilic compound. At this time, the degree of freedom of the molecule of the organic cation is increased by the solvation of the organic cation, and the longest main chain of the alkylammonium salt is the most stable conformation. As a result, the main chain of the molecule is in the most stable state, that is, the main chain is fully extended in the solvent. At that time, the ionically coordinated organic cations are conformed like pillars, and the interlayer distance is widened. Then, the layers are released from the mutual electric ionic bonding force between the layers, are separated to the level of a single unit of the layers, and are dispersed in the solvent.
Therefore, when the longest main chain length of the organic cation is less than C4, the infinite swelling hardly occurs even if the mixed resin is added. Even if the main chain of the organic cation is sufficiently long, if the amount of substitution is extremely small, the solvation with the organic cation occurs due to the intrusion of the mixed resin, but the effect is extremely small, and the addition amount of the theoretical substitution ion amount is A range of 1 equivalent or more to 10 equivalents is required.

The layered compound infinitely swollen as a single unit does not precipitate as a colloid because the organic cation in each is ionically coordinated.

The infinitely swollen lipophilic compound is kneaded with the matrix resin and dispersed.

In the kneading or dispersion of the lipophilic compound and the matrix resin composition, which have been infinitely swollen in advance, the organic solvent is vaporized in the kneading machine due to the high viscosity of the matrix resin composition, and the infinitely swollen structure collapses and separates. Mixing is carried out before that, followed by dispersion by shearing, and the infinitely swollen layered compound is dispersed at the nano level through a step of degassing the organic solvent remaining in the melt polymer. Examples of the kneader used for this purpose include a Banbury mixer, a continuous mixer with a rotor, and a twin-screw extruder (screw rotating directions are different directions, same direction).

An example of the dispersion device is shown in FIG. This disperser uses the extruder 10 with two axes in the same direction, and for example, has a screw diameter of 40 mm and a screw length / screw ratio of 51. In the one shown in FIG.
The barrel portion of the screw is divided and has a structure in which barrels of three pitches are added, and is composed of 17 blocks (first block to 17th block) in total. The vent port is composed of four vent ports of the fifth block, the tenth block, the thirteenth block, and the fifteenth block, counting from the hopper 12. All of those vent ports are connected to the vacuum pump 14.

The infinitely swelled slurry of the lipophilic compound is supplied from the slurry tank 16 to the third block via the supply pump. For the supply pump, an optimum one is selected according to the viscosity of the slurry of the organic solvent in order to perform stable supply. For example, when the viscosity of the organic solvent slurry is 10 × 10 ⁴ cps or more, it is desirable to use the gear pump 18 as a supply pump, and when the viscosity is less than that, a plunger pump 20 connected in a cascade is used. Then, when the matrix resin composition is supplied from the hopper 12, the matrix resin composition is transferred by the screw and comes into contact with the slurry side-fed between the second block and the fifth block centering on the third block. The zone in between must be set below the boiling point of the organic solvent used in the slurry. Primary venting of excess organic solvent is performed at the vent port of the fifth block ahead. Then, between the sixth block and the tenth block, the temperature is set to be temporarily higher from the vent port of the fifth block so as to reach the temperature at which the matrix resin composition is plasticized.

If a gas that deteriorates the appearance due to volatile components is generated during molding, the volatile components may not be sufficiently removed. In that case, the volatile component (water + solvent) in the resin can be reduced to 300 PPM or less by injecting water from the twelfth block with a plunger pump or the like to cause azeotropic distillation. In addition, when the slurry is poured into a molten resin and dispersed, the infinitely swollen slurry has a viscosity equal to or higher than that of the molten resin, and when the injection work is extremely difficult, or a large amount of solvent is used for infinite swelling. Since it was used, in order to degas the organic solvent after kneading with the molten resin,
If the screw of the extruder is lengthened and the residence time in the extruder is lengthened, the amount of extrusion may be 1/10 or less of the original amount, resulting in lack of economy. In this case, the layered compound and the matrix resin composition are previously dispersed with a disperser such as a Henschel mixer, and in the step of kneading the mixture with an extruder, only the mixed resin is press-fitted from the side surface of the extruder by a measuring pump. Then, it is preferable that the slurry of the layered compound swollen by the mixed resin / matrix resin composition / organic cation is formed in the extruder to infinitely swell and physically mix with the elastomer.

[0029]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. [Example 1] Fluorine-type tetrasilicic mica
A layered compound (NaDP _2.5 (Si ₄ O ₁₀ ) F ₂ ] (“DP-DM” manufactured by Topy Industries, Ltd.) was immersed in distilled water in a beaker and stirred to give a suspension. While stirring the suspension at about 60 ° C., an aqueous solution of an organic cation, a main chain C4 to C22 n-alkylammonium salt chloride ("NOSSAN cation" manufactured by NOF CORPORATION, and synthesis from reagents) was added. And stirred well to prepare a homogeneous suspension. CE of tetrasilicic mica by column immersion method
Since C was approximately 170 meq / 100 g, the mixing ratio was 3.4 × 10 ² mmol of organic cations per 100 g of fluorine-type tetrasilicic mica.

This suspension was washed, centrifuged, freeze-dried and then pulverized to give a layered compound. In order to confirm the intercalation, the interlayer distance when the length of the main chain of n-alkylammonium chloride was changed was measured by a powder X-ray diffraction method using an X-ray analyzer (RINT2000) manufactured by Rigaku Corporation. . This powder X-ray diffraction measurement confirmed that the interlayer distance increased from 1.4 nm to 3.8 nm as the length of the main chain changed from C4 to C22.
Further, in order to confirm the packing density of the quaternary ammonium salt between the layers, Rigaku Corporation's suggested heat / thermobalance measurement (TG-DT
A) Thermogravimetric measurement was performed using an apparatus (TAS200). As a result, the organic cation content of this lipophilic compound was about 21 wt% of the layered compound. Next, this lipophilic compound was added to xylene so that the layer compound component was 10 wt% with respect to xylene, and stirred for about 1 hour to prepare a homogeneous infinitely swollen slurry.

The viscosity of the slurry was measured at 23 ° C. using a B-type viscometer (“B8L” manufactured by Tokyo Keiki Co., Ltd.). The viscosity was 3 × 10 ⁴ cps. This slurry was kneaded with the matrix resin composition using the disperser shown in FIG. As the matrix resin composition, homopolypropylene having a melt flow rate of 60 g / 10 min was used. The matrix resin composition is put into the extruder from the hopper 12 and melted, and the slurry is injected into the melted resin from the vent port in the middle of the extruder using the gear pump 18, and kneaded and degassed of the organic solvent to form an organic cation. An inorganic filler-dispersed composite containing 8.5 wt% of an inorganic component was obtained except for the amount and the amount of the solvent. Observation of the morphology of this inorganic filler-dispersed composite revealed that the volume fraction of the dispersed phase was 3.0 vol% with respect to the composite, and the specific gravity conversion (specific gravity 2.7) was 6.8 w.
The average particle size was 0.01% and the aspect ratio was 8.0.

The content of the resin in the dispersed phase was 20 vol% as measured by a transmission microscope. The inorganic layered compound in the dispersed phase had a thickness of 10 to 40 Å and a length of 1000 Å or more. It was fibrous. The bending elastic modulus (kg / cm ² ) and the heat distortion temperature (HDT (° C)) of the obtained inorganic filler-dispersed composite were measured. Table 1 shows the measurement results. In Table 1, the type of matrix resin, wt% of the filler in the total composite, volume fraction of the dispersed phase in the total composite, volume fraction of the inorganic filler in the dispersed phase, and in the dispersed phase Resin content of (vol
%), The average particle size of the dispersed phase and the average aspect ratio are also shown.

The volume fraction of the dispersed phase was determined as follows. Assume a volume V of a dispersed phase in a sample piece having a volume L ³ as shown in FIG. Letting A (X) be the sum of the areas observed at the cuts of the dispersed phase on the sample cross section, the relational expression of the volume fraction V ₀ of this dispersed phase is established by the following mathematical formula.

[0034]

[Equation 1]

Therefore, the volume fraction V ₀ can be estimated from the area fraction. It is also understood that the sample cross sections may be randomly extracted. Therefore, the volume fraction of the dispersed phase can be obtained by the observation method. The area fraction of the dispersed phase is obtained by cutting a sample into thin pieces with a microtome and observing the sliced pieces with a transmission electron microscope. When the dispersion phase and the matrix resin have the same electron beam transmission coefficient and the boundary is not clear, for example, when the sample is polypropylene and ethylene propylene copolymer (EPR), RuO ₄ staining and EPR are used.
It is used because it is dyed. Further, in order to obtain the particle size of the dispersed phase dispersed in the matrix resin, the particle size of 50% in total was calculated as the average particle size from the number particle size distribution formula.
That is, if the particle size is measured with a microscope, the following equation holds.

[0036]

[Equation 2] However, Dp is 2 of each dispersed phase observed with a transmission electron microscope.
It is the root-mean-square diameter, Da is the total mean of the root-mean-square diameters of the dispersed phase observed by a transmission electron microscope, and n is the total number of the dispersed phases.

The flexural modulus is ASTM 790.
(Dry state, 23 ° C.). The heat distortion temperature was measured according to ASTM D648,
The load was applied to the center of the test piece for 5 minutes so that the fiber stress of 0.0464 kg / mm ² (66 psi) acted, and the temperature was raised at a rate of 2 ± 0.2 ° C./min for measurement.
The measurement sample is the FANAC injection molding machine "model".
"100 type" was molded at a cylinder temperature of 210 ° C., an injection pressure of 750 kg / cm ² , and a mold clamping pressure of 100 tons.

Example 2 In Example 1, a lipophilic compound was produced using synthetic smectite as the layered compound. That is, the synthetic smectite [ratio Na _0.33 (M
g _2.67 Li _0.33 ) Si ₄ O ₁₀ (OH) ₂ ], and a layered compound (“SWN” manufactured by Corp. Chemical Co., Ltd.) was used.
The same process was performed. However, CE of synthetic smectite
Since C was approximately 100 meq / 100 g, the mixing ratio was 2.0 g of organic cation with respect to 100 g of synthetic smectite.
It was set to × 10 ² mmol. In the powder X-ray diffraction measurement, the interlayer distance was changed from 1.4 nm to 2.2 as C4 changed to C22.
It was confirmed to increase to 5 nm. Also suggest fever /
In the thermobalance measurement (TG-DTA), the organic cation content was about 23 wt% of the layered compound.

Also in Example 2, this lipophilic compound was prepared in an organic solvent of xylene to a solution concentration of 10 wt%. The viscosity at that time was 3.4 × 10 ⁴ cps.
It was injected into a molten resin using a plunger pump and kneaded in the same manner as in Example 1 to obtain an inorganic filler-dispersed composite containing 8.5 wt% of inorganic filler except for the amount of organic cation and the amount of solvent. Observation of the morphology of the obtained inorganic filler-dispersed composite showed that its volume fraction was 3.0 vol% with respect to the composite, and 6.8 wt% in terms of specific gravity.
become. The average particle size was 0.3 μm. The amount of resin in the dispersed phase was 20 vol% with respect to the dispersed phase. The inorganic layered compound was a fibrous substance having a thickness of 10 to 30 Å and a length of 380 Å or more. The flexural modulus (kg / cm ² ) and heat distortion temperature (HDT) of this inorganic filler dispersed composite
(° C.)) was measured. Table 1 shows the measurement results.

Example 3 In Example 1, the layered compound was homopolypropylene except for the amount of organic cations.
Blend it so that it will be 5 wt%, in the same way with a Henschel mixer, side inject with a gear pump and melt knead,
It was dry blended. This blended product was fed from the hopper of the extruder, melt-kneaded, and then side-injected from the vent port in the middle of the extruder with a gear pump to melt-knead to obtain an inorganic filler-dispersed composite. The amount of xylene added at that time was adjusted to 40 wt% with respect to the blended product. Observation of the morphology of this inorganic filler-dispersed composite revealed that the volume fraction of the dispersed phase in the composite was 3.0 vol%, the average particle size of the dispersed phase was 5 μm, and the aspect ratio thereof was 14. The amount of resin in the dispersed phase is 20
The inorganic layered compound had a vol%, a thickness of 10 to 20 angstroms, and a length of 1300 angstroms or more. Flexural modulus (kg / cm ² ) and heat distortion temperature (HDT (° C)) of this inorganic filler-dispersed composite.
Was measured. Table 1 shows the measurement results.

Example 4 An inorganic filler-dispersed composite was produced in the same manner as in Example 1 except that the content of the inorganic layered compound was 19.6 wt% in the entire composite. The volume fraction of the dispersed phase at that time was 7.5 vol%. The elastic modulus and heat distortion temperature of the inorganic filler dispersion composite were measured.
Table 1 shows the measurement results.

[Example 5] The content of the inorganic layered compound was 6
An inorganic filler-dispersed composite was produced in the same manner as in Example 1 except that the content was 2.8 wt%. The volume fraction of the dispersed phase at that time was 36 vol%. The elastic modulus and heat distortion temperature of the inorganic filler dispersion composite were measured. Table 1 shows the measurement results
Shown in

[Example 6] The inorganic filler-dispersed composite obtained in Example 1 was further diluted with homopolypropylene so that the total content of the inorganic layered compound was 8.5 wt%. Then, the elastic modulus and the heat distortion temperature of the inorganic filler dispersed composite were measured. Table 1 shows the measurement results.

Comparative Example 1 The homopolypropylene used in Example 1 and tetrasilicic mica as a layered compound were crushed by a jet mill and blended so that the content of the inorganic filler was 8.5 wt%, Only the blended product dry-blended with the Henschel mixer was continuously fed from the hopper of the extruder at 30 kg / hr to obtain an inorganic filler dispersed composite. The average particle diameter of the dispersed phase in the inorganic filler-dispersed composite was 15 μm, and the aspect ratio was 8.0. Further, no mixing and dispersion of the resin in the dispersed phase was observed, and the dispersed phase was composed only of the inorganic layered compound.
Table 1 shows the elastic modulus and heat distortion temperature of the obtained inorganic filler dispersed composite.

Comparative Example 2 The homopolypropylene used in Example 2 and synthetic smectite as a layered compound were pulverized by a jet mill, and the content of the inorganic filler was 8.
Only the blended product which was blended so as to be 5 wt% and dry-blended with a Henschel mixer was continuously fed from the hopper of the extruder at 30 kg / hr to obtain an inorganic filler-dispersed composite. The average particle size of the dispersed phase in the inorganic filler-dispersed composite was 0.01 μm, and the aspect ratio was 3.8. Further, no mixing and dispersion of the resin in the dispersed phase was observed, and the dispersed phase was composed only of the inorganic layered compound.
Table 1 shows the elastic modulus and heat distortion temperature of the obtained inorganic filler dispersed composite.

[Comparative Example 3] In the same manner as in Example 1, tetrasilicic mica was infinitely swollen with xylene. Then, this was mixed with a mixed solution of polypropylene and a large amount of xylene that had been heated and mixed in advance, and the xylene solvent was removed by evaporation to obtain a composite.

[Comparative Example 4] A composite was prepared in the same manner as in Example 1 except that the content of the inorganic layered compound was 73.5 wt% with respect to the entire composite. In addition, H at the press
When a DT sample was prepared, the average value was 120 ° C., but the variation was large.

[0048]

[Table 1]

It can be seen from Table 1 that the inorganic filler-dispersed composites (1-6) of this example have excellent rigidity and heat resistance which cannot be obtained by the conventional method. On the other hand, in Comparative Examples 1 to 4 in which the resin is not contained in the dispersed phase, the bending elastic modulus is small and the rigidity is low. Moreover, when the average particle size of the dispersed phase is larger than 10 μm in Comparative Example 1, the heat resistance is poor. Also, the heat resistance of Comparative Example 2 in which the aspect ratio of the dispersed phase is less than 4 is inferior. In Comparative Example 3, the dispersed phase was not formed, and the filler thickness was 10 to 40 Å,
A continuous phase of fibrous filler having a length of 800 Å or more was formed. In Comparative Example 4, poor dispersion occurred.

[0050]

EFFECT OF THE INVENTION In the inorganic filler dispersion composite of the present invention, the fine inorganic filler having an angstrom level is dispersed in an amorphous resin having a crystallinity and / or a glass transition temperature of room temperature or higher, and the conventional inorganic filler is used. It has higher rigidity and heat resistance than the filled resin composition. In particular, the matrix resin composition has almost no restrictions and can be used for many purposes and has high versatility. Further, the manufacturing process is simple and easy, and no special equipment is required, so that the manufacturing cost is low.

[Brief description of drawings]

FIG. 1 is a schematic view of an inorganic filler dispersion composite of the present invention.

FIG. 2 is a configuration diagram illustrating an example of a dispersion device.

FIG. 3 is a model diagram for explaining how to obtain a volume fraction of a dispersed phase.

[Explanation of symbols]

 1 Dispersed Phase 2 Matrix Resin 10 Extruder

Claims (3)

[Claims] 1. A dispersed phase comprising a fibrous layered compound composed of an inorganic filler having a thickness of 10 to 40 angstroms and a length of 300 angstroms or more, and a resin mixed between the layers of the layered compound is a matrix. An inorganic filler dispersion composite characterized by being dispersed in a resin. 2. The size of the disperse phase is 1 as the root mean square diameter.
The inorganic filler-dispersed composite according to claim 1, wherein the composite has an average aspect ratio of 0 μm or less and 4 or more. 3. The content of the inorganic filler in the dispersed phase and the content of the resin in the dispersed phase are 40 vol% or less in all the composites, respectively. Alternatively, the inorganic filler-dispersed composite described in 2.