JPH11310643A - Production of resin composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for the subject material capable of dispersing a nonorganic clay into a thermoplastic resin low in affinity for water by contacting a solvent containing water, clay and thermoplastic resin with one another at a temperature no less than the melting temperature of the resin. SOLUTION: This method comprises contacting (A) a solvent containing water or a proton donor (e.g. ethylene glycol), (B) a clay and (C) a thermoplastic resin (pref. e.g. polyethylene) with one another at a temperature no less than the melting temperature of the component C. A non-organized clay of the component B is exemplified by montmorillonite and pref. used in the proportion of 0.1 to 30 pts.wt. based on 100 pts.wt. of the component C. The component A is pref. added in the proportion of 1 to 200 pts.wt. based on 1 pts.wt. of the component C and in the proportion of <=200 pts.wt. based on 100 pts.wt. of the component C. The objective material is obtained by squeezing the component B swollen in the component A into the component C molten and fluidized for kneading it through a twin screw kneader.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lightweight, high-rigidity resin composite material.

[0002]

2. Description of the Related Art Clay is mixed with a resin to improve the properties of the resin. However, since the compatibility between the resin and the clay is low, various improvements have been conventionally taken in mixing the two.

[0003] As a specific example, there is a method of obtaining a composite material by organizing clay to form an organized clay, adding it to a polyamide together with a swelling agent and a dispersion medium and mixing the same with polyamide (Japanese Patent Publication No. 7-47644). . In this composite material, a monomer such as caprolactam is used as a swelling agent, and nylon 6 is used as a polyamide. In addition, there is a method of kneading an organically modified clay that has been organized with a secondary ammonium and a resin or rubber (Japanese Patent No. 2674720). In addition, there is a method of kneading an organically modified clay and a thermoplastic resin under high shear (Japanese Patent Application Laid-Open No. Hei 9-217012).

[0004] Further, a method is disclosed in which non-organized clay is used instead of organized clay. Use of a non-organized clay is advantageous in terms of cost and simplicity. As a method of dispersing the non-organized clay in the resin, there is a conventional method of mixing a solution in which a polyamic acid is dissolved in a basic solvent and an aqueous dispersion of the non-organized clay (Japanese Patent Laid-Open No. 9-208822). ). This method utilizes the fact that a polyamide which is a precursor of polyimide is dissolved in a basic aqueous solution. Further, a method has been proposed in which steam is introduced into a mixture of a non-organized clay and a resin and kneaded (Japanese Patent Application No. 8-331520).

[0005]

However, in the above-mentioned conventional method, the non-organized clay can be dispersed only in a resin having a high affinity for water, for example, polyvinyl alcohol, polyamic acid, polyacrylic acid and the like. For this reason, the non-organized clay cannot be dispersed in the thermoplastic resin having low affinity for water.

The present invention has been made in view of such conventional problems, and provides a method for producing a resin composite material in which non-organized clay can be dispersed in a thermoplastic resin having low affinity for water. What you want to do.

[0007]

The present invention relates to a resin composite material comprising contacting a solvent containing water or a proton donor, a clay, and a thermoplastic resin at a temperature not lower than the melting temperature of the thermoplastic resin. It is a manufacturing method of.

Next, the operation of the present invention will be described. Since the surface of the clay is slightly negatively charged by replacing a trivalent ion such as Al ³⁺ in the silicate layer with a divalent ion such as Fe ²⁺ , the clay dissolves water or a proton donor. Easy to disperse in containing solvents. In addition, non-organized clay which is not organized among clays has high hydrophilicity, and is easily dispersed in a solvent. Therefore, when clay is mixed with water or a solvent containing a proton donor, the solvent containing water or a proton donor intervenes between the silicate layers of the clay, and the clay layers are enlarged and become uniform in the solvent. Will be dispersed. Also, the chemical bonding of the clay silicate layer is weakened.

[0009] The solvent containing water or the proton donor is heated to become a vapor, thereby creating a high-pressure atmosphere. A high-pressure atmosphere is a thermoplastic that breaks weak chemical bonds in the silicate layer and allows water or a solvent vapor containing a proton donor to escape from the silicate layer and instead melts by heating to obtain fluidity. The resin is introduced between the silicate layers. In addition, since the interlayer of the clay is expanded by the intervention of the solvent, the introduction of the thermoplastic resin is performed smoothly.

Also, when a solvent containing water or a proton donor is injected under coexistence of clay and a molten thermoplastic resin, the solvent similarly becomes vapor to create a high-pressure atmosphere. In a high-pressure atmosphere, a thermoplastic resin, which melts by heating and obtains fluidity by breaking a weak chemical bond of the silicate layer, is pressed into the silicate layer of the clay. Further, since the silicate layer is covered with the solvent vapor, the thermoplastic resin is smoothly introduced between the silicate layers. The above-mentioned action is achieved regardless of whether the clay is organized or non-organized.

Therefore, according to the production method of the present invention, a non-organized clay can be dispersed in a thermoplastic resin having low affinity for water. It can also be dispersed at the nanometer level.

Further, according to the present invention, since clay can be finely dispersed in a thermoplastic resin, a small amount of clay exhibits a reinforcing effect that cannot be achieved with other fillers. In particular, mechanical properties such as strength and elastic modulus, heat resistance, thermal properties such as heat deformation temperature and low-temperature embrittlement temperature, and properties such as gas barrier properties can be improved.

Therefore, the obtained resin composite material has a light weight and a high rigidity, and is highly useful for automobiles, aircrafts and the like. In addition, the application is not limited to these, and any field can be used as long as the above excellent properties can be utilized.

When the clay is made of a non-organic material, the following effects are obtained. In the silicate layer of the non-organized clay, alkali metal ions are bonded and dispersed uniformly while maintaining a neutral state. Therefore, when used for a material requiring electrical insulation, local dielectric breakdown does not occur and the material strength does not decrease. Moreover, in the thermoplastic resin, the alkali metal coordinated between the layers of the non-organized clay is strongly bonded to the silicate layer, and is not discharged to the outside from the resin composite material. Therefore, when a molded body of the resin composite material is produced, the alkali metal does not dissolve in water or oil and can be used for electric parts, food films and the like.

Next, the details of the present invention will be described. (Clay) The clay used in the present invention may be an organized clay or a non-organized non-organized clay. Non-organized clay refers to clay (clay mineral) that has not been organized. Non-organized clay is
It is mainly composed of silicate layers and L
i, Na, K and the like are ionized and bound, and have a property of swelling with a polar solvent such as water, ethylene glycol and cellosolve.

The non-organized clay is negatively charged. The characteristics of the non-organized clay differ depending on the density and distribution of the negative charges, but in the present invention, it is preferable that the non-organized clay is a layered clay having an area occupied by 25 to ²⁰⁰ square meters per layer of the negative charge.

As the non-organized clay, a layered clay is mainly used. Examples of the layered clay include a layered phyllosilicate mineral formed of a magnesium silicate layer or an aluminum silicate layer having a thickness of 7 to 12 °. Layered clay refers to a so-called layered phyllosilicate. Examples thereof include smectite-based layered clays such as montmorillonite, saponite, hectorite, beidellite, stevensite, and nontronite, vermiculite, halloysite, and swollen mica. These can be used either naturally or synthetically.

The non-organized clay is preferably contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the thermoplastic resin. If the amount is less than 0.1 parts by weight, the rigidity and gas barrier properties of the resin composite material may be reduced. If the amount exceeds 30 parts by weight, the impact resistance of the resin composite material may be reduced. Further, as the organized clay, a clay to which an organic polymer is bonded can be used, and the kind thereof is not limited.

(Thermoplastic resin) The thermoplastic resin is not particularly limited as long as it is a thermoplastic polymer. In particular, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polybutylene terephthalate, polystyrene, ABS resin (Acrylonitrile-butadiene-styrene copolymer resin), AS resin (acrylonitrile-styrene copolymer resin), polymethyl methacrylate, polyamide, polyacetal, polycarbonate, polyphenylene sulfide, polyphenylene ether, polyether ether ketone, polysulfone, polyether sulfone, Polyamide imide,
Polyetherimide, thermoplastic polyimide, natural rubber,
It is preferable to use isoprene rubber, chloroprene rubber, styrene rubber, nitrile rubber, ethylene-propylene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, urethane rubber, fluorine rubber, silicone rubber, and the like. Thereby, the clay can be uniformly dispersed.

(Solvent Containing Water or a Proton Donor) The solvent containing water or a proton donor is not particularly limited. For example, water, diethylene glycol, ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, ethylene glycol diethyl ether ,
Examples include ethylene glycol monoacetylate, ethylene glycol diacetylate, polyethylene glycol, and polypropylene glycol. Note that the solvent containing water or the proton donor may contain a solvent other than water or the proton donor.

(Dispersion of Clay in Solvent) In dispersing clay in a solvent containing water or a proton donor, the clay is mixed with a solvent. As a result, the solvent enters between the clay layers in a liquid or gas state, and the clay layers swell. Therefore, the clay is uniformly dispersed in the solvent at the molecular level.

Specifically, the amount of the solvent to be added is preferably 0.01 to 1000 parts by weight based on 1 part by weight of the clay. Thereby, the clay can be uniformly dispersed. Further, since the added solvent evaporates while the thermoplastic resin cools, no solvent remains in the obtained resin composite material. If the amount is less than 0.01 parts by weight, the degree of swelling of the clay is insufficient, and the clay may not be uniformly dispersed in the thermoplastic resin. On the other hand, when the amount exceeds 1,000 parts by weight, the swelling state of the clay is not different from that when the amount is 1000 parts by weight or less, but water may remain in the obtained resin composite material.

The amount of the solvent added is more preferably 0.1 to 500 parts by weight based on 1 part by weight of the clay.
If the amount is less than 0.1 part by weight, the pressure generated by the solvent vapor is low, and a high kneading force may be required for uniform dispersion. Therefore, it is necessary to devise a manufacturing process. May be expensive. 500
If the amount exceeds the weight part, the temperature of the thermoplastic resin may drop below the melting temperature and solidify due to latent heat of evaporation due to evaporation of the solvent. This may make kneading impossible.

Most preferably, the amount of the solvent is 1 to 200 parts by weight per 1 part by weight of the clay. When the amount is less than 1 part by weight, the pressure produced by the solvent vapor is low, and the dispersion can be carried out with ordinary kneading force, but a long kneading time may be required. For this reason, productivity may deteriorate. If the amount exceeds 200 parts by weight, a large amount of heat is required to supplement the latent heat of evaporation by the solvent, which may increase the cost.

The amount of the solvent to be added depends on the amount of the thermoplastic resin 10.
It is preferable that the amount is 1000 parts by weight or less based on 0 parts by weight. As a result, the clay can be uniformly dispersed, and no solvent remains in the obtained resin composite material. On the other hand, even if the solvent is added in an amount exceeding 1000 parts by weight, the swelling state of the clay is not different from the case of adding the solvent in an amount of 1000 parts by weight or less. If the amount exceeds 1,000 parts by weight, the solvent may remain in the obtained resin composite material.

More preferably, the amount of the solvent is 500 parts by weight or less based on 100 parts by weight of the thermoplastic resin. If it exceeds 500 parts by weight, the temperature of the thermoplastic resin may drop below the melting temperature and solidify due to latent heat of evaporation due to evaporation of the solvent. This may make kneading impossible.

Further, the amount of the solvent to be added depends on the amount of the thermoplastic resin 10.
The most preferable is 200 parts by weight or less based on 0 parts by weight. 2
If the amount exceeds 00 parts by weight, a large amount of heat is required to supplement latent heat of evaporation by the solvent, which may increase costs.

(Contact between Clay and Thermoplastic Resin) In the present invention, the melt of the thermoplastic resin may be brought into contact with the clay swollen by the solvent. Therefore, in this case, the timing of the addition of the solvent needs to be when the thermoplastic resin in the molten state and the clay coexist or before.

In the present invention, the solvent may be added after mixing the thermoplastic resin and the clay and heating. In this case, it is preferable to add the solvent after the melt of the thermoplastic resin and the clay are sufficiently kneaded.

Therefore, the solvent may be present together with the clay before the thermoplastic resin is melted, or may be added to the melt after the thermoplastic resin is melted.
The solvent may be added when the clay and the thermoplastic resin are heated to a melting temperature or higher, or when the melt is kneaded after the heating. Alternatively, the clay may be swollen with a solvent and heated after being mixed with a thermoplastic resin. Alternatively, clay that has been swollen with a solvent after the thermoplastic resin has been melted may be injected.

A specific example will be described. 1) Thermoplastic resin pellets and clay are mixed in a dry state, and heated to a temperature higher than the melting temperature of the thermoplastic resin. The solvent is injected during the process of melting and flowing the thermoplastic resin.
The solvent is volatilized in a subsequent step.

2) Clay swelled with a solvent and thermoplastic resin pellets are mixed and heated to a temperature higher than the melting temperature of the thermoplastic resin. Then, the solvent evaporates in the process of melting and flowing the thermoplastic resin. 3) Heat the thermoplastic resin above the melting temperature. While the thermoplastic resin is molten and flowing, press the clay swollen in the solvent.

The contact between the thermoplastic resin and the clay is carried out by kneading the two. This kneading is performed by stirring the thermoplastic resin and the clay which are heated to a melting temperature or higher and are in a molten state. For example, a twin-screw kneader that stirs by rotating two screws (rotating shaft) can be used.

The ratio (L / D) of the shaft length (L) to the screw diameter (D) is preferably 10 to 50. If it is less than 10, the stirring power is small, and it may be difficult to stir efficiently. On the other hand, L / D
The larger the value, the greater the stirring power is obtained. However, if it exceeds 50, the silicate layer of the clay itself is finely broken, and the gas barrier property may not be improved. The rotation speed of the screw is preferably 100 to 2500 rpm. If the ratio is outside this range, it may be difficult to stir efficiently.

When the clay dispersed in the solvent is added to the thermoplastic resin, it is preferable to positively apply pressure to the clay and press the clay into the thermoplastic resin.
The reason is that the solvent interposed between the layers of the clay evaporates due to the heat of the thermoplastic resin, and if no pressure is applied, the solvent between the layers evaporates before the thermoplastic resin intervenes between the layers of the clay. This is because the interlayer swelling effect of the solvent may be lost and the thermoplastic resin may not be introduced between the layers. As a method of press-fitting the clay, for example, there is a method of press-fitting the thermoplastic resin with a liquid feed pump.

The contact between the clay dispersed in the solvent and the thermoplastic resin (above the melting temperature of the thermoplastic resin) is performed in an environment at a temperature higher than the melting temperature of the thermoplastic resin. As a result, the thermoplastic resin is melted to obtain fluidity, and the clay is dispersed. On the other hand, when the contact is made at a temperature lower than the melting temperature of the thermoplastic resin, the dispersibility of the clay becomes low. Note that “above the melting temperature of the thermoplastic resin” differs depending on the type of the thermoplastic resin. The upper limit of the “temperature equal to or higher than the melting temperature of the thermoplastic resin” is preferably a temperature at which the thermoplastic resin does not deteriorate.

(Heating Environment) When the clay and the thermoplastic resin are brought into contact under the above temperature environment, they may be heated. When heating, it is desirable to use a closed state because high pressure steam can be obtained. The closed state is a state in which the solvent is converted into a vapor by heating to create a high-pressure atmosphere, for example, an internal state of a twin-screw kneader or the like.

[0038]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1 A method for producing a clay composite material according to an embodiment of the present invention will be described with reference to FIG. To explain the outline of the production method of this example, first, a non-organized clay was added to a thermoplastic resin in a dry state. Next, the mixture was heated at a temperature equal to or higher than the melting temperature while being kneaded to melt the thermoplastic resin, and water was added to the mixture for molding.

Next, details of the manufacturing method of this embodiment will be described. First, as a thermoplastic resin, polyphenylene sulfide (hereinafter, polyplastic FORTRON 022) is used.
OA-9, called PPS. ) Was prepared. Examples of the non-organized clay include particulate sodium montmorillonite (manufactured by Kunimine Industries, trade name: Kunipia F, hereinafter, Na-M).
It is called t. ) Was prepared.

Further, as shown in FIG.
A twin-screw kneader 1 having the screws 6 and 7 was prepared. The twin-screw kneader 1 includes hoppers 91 and 92 for feeding a thermoplastic resin (PPS) 910 and a non-organized clay (Na-Mt) 920 into the cylinder 9, a heater 93 for heating the thermoplastic resin, and water 950. And a tank 95 for storing
And a molding port 96 provided at the rear of the cylinder 9. The water 950 in the tank 95 was injected from a pressure inlet 952 by a liquid feed pump 951.

The amount of PPS and Na-Mt charged into the cylinder was 70 g / min. , 3.5 g / min. And N
The amount of a-Mt was 5 parts by weight with respect to 100 parts by weight of PPS. The water 950 is 70 k
g / cm ² and 7.0 g / min. Was press-fitted into the cylinder 9. The amount of water added is PPS10
10 parts by weight with respect to 0 parts by weight.

The diameter of the screws 6 and 7 was 3.0 cm, the diameter of the cylinder 9 was 9.0 cm, and their length was 135 cm. The rotation speed of the screws 6 and 7 was 100 rpm. The temperature of the heater 93 was 300 ° C. The molding port 96 was opened in a square shape having a size of 0.5 mm × 2 mm.

Next, a thermoplastic resin (PPS) 910 was placed in the hopper 91 on the upstream side, and a non-organized clay (Na-Mt) 920 was placed in the hopper 92 on the downstream side. Next, a valve 9 provided at the outlet pipe of the hoppers 91 and 92 is used.
11, 921 was opened, and the thermoplastic resin 910 and the non-organized clay 920 were charged into the cylinder 9.

Then, the PPS was extruded downstream of the cylinder 9 while being kneaded with Na-Mt in a dry state by the rotation of the screws 6 and 7. These kneaded materials were heated to 300 ° C. by the heater 93 to melt the PPS.

When the melt composed of the melted PPS and Na-Mt is pushed further downstream by the screw,
The melt was kneaded with water 950 injected from an inlet 95. Since the temperature of the melt was 300 ° C., water gasified upon contact with the melt and was uniformly dispersed in the melt at the molecular level.

The melt was extruded from the forming opening 96 of the cylinder 9 and formed into a sheet having a thickness of 0.5 mm.
The compact 4 is taken up by a take-up roller 97 by a conveyor 97.
1 and wound up in a roll by a winding roller 971. The molded body 4 gradually dissipated heat while being transported to the winding roller 971. In addition, most of the water contained in the compact evaporated during transportation by the conveyor 97. Thus, a molded body 4 made of the resin composite material was obtained.

Observation of the obtained molded body with a transmission electron microscope revealed that 1 to 5 montmorillonite silicate layers (1 nm in thickness) were uniformly dispersed in PPS.

Embodiment 2 The manufacturing method of this embodiment is the same as that of Embodiment 1 except that swellable fluorine mica (ME110 manufactured by Corp Chemical Co., Ltd.) is used as the non-organized clay. The addition amount of the swellable fluorine mica was 5 parts by weight based on 100 parts by weight of PPS.

Embodiment 3 In the manufacturing method of this embodiment, the amount of Na-Mt
It is the same as the first embodiment except that 10 parts by weight is used for 0 part by weight.

Embodiment 4 In the manufacturing method of this embodiment, the amount of Na-Mt
It is the same as the first embodiment except that 30 parts by weight is used for 0 part by weight.

Comparative Example 1 In this example, a molded article was obtained without adding any of the non-organized clay and water to the PPS. PPS was kneaded and melted by heating to obtain a molded body. Other configurations are the same as those of the first embodiment.

Comparative Example 2 In this example, a compact was obtained without adding water to PPS and Na-Mt. That is, 5 parts by weight of Na-Mt was added to 100 parts by weight of PPS, and these were kneaded, heated and melted. Other configurations are the same as those of the first embodiment. Observation of the obtained molded body with a transmission electron microscope revealed that montmorillonite had a diameter of 1 to 3 in PPS.
An aggregate of 100 μm was formed. This aggregate was visually observed as particles.

(Experimental Example 1) In this example, the gas barrier properties of a molded body made of a clay composite material were evaluated. The molded bodies subjected to the evaluation are the molded bodies obtained in the above-described Embodiments 1 to 4 and Comparative Examples 1 and 2. The evaluation was performed by measuring the nitrogen gas transmission coefficient of a sheet-shaped molded body (thickness: 0.1 mm). Table 1 shows the measurement results. From Table 1, the gas permeability coefficients of the first to fourth embodiments are comparative examples 1 and 2.
It was lower than. From this, the first to fourth embodiment examples
It can be seen that the resin composite material of the present invention is excellent in gas barrier properties.

[0054]

[Table 1]

Embodiment 5 A method for producing a clay composite material according to an embodiment of the present invention will be described with reference to FIG. To explain the outline of the production method of this example, first, a thermoplastic resin was kneaded while being heated at a temperature equal to or higher than a melting temperature and melted. To this was added an aqueous dispersion of a non-organized clay.

Next, details of the manufacturing method of this embodiment will be described. First, as shown in FIG. 2, a twin-screw kneader 1 having two screws 6 and 7 in a cylinder 9 was prepared. The cylinder 9 includes a hopper 91 for charging a thermoplastic resin 913 into the cylinder 9, a tank 954 for storing an aqueous dispersion 953 of a non-organized clay, and a heater 93 for heating the thermoplastic resin.
And an opening 92 for discharging water evaporated in the cylinder 9 and a molding port 96 provided at the rear of the cylinder 9. The tank 954 has a liquid sending pump 951 and a pressure inlet 952 for press-fitting the aqueous dispersion 953 of the non-organized clay therein into the cylinder 9.

In this embodiment, nylon 6 (grade 1015B manufactured by Ube Industries, hereinafter referred to as “PA”) is used as the thermoplastic resin.
6 ". ) Was used. As the non-organized clay, sodium-type montmorillonite (manufactured by Kunimine Kogyo Co., Ltd., trade name Kunipia F, hereinafter referred to as Na-Mt) similar to that of Embodiment 1 was used.

A thermoplastic resin (PA6 in this example) 913 was placed in the hopper 91. The amount of PA6 charged into the cylinder 9 was 60 g / min. Na-Mt was dispersed in ion-exchanged water to obtain a 2% by weight dispersion. The injection pressure of the aqueous dispersion 953 of Na-Mt was 60 g / min. That is, Na- in the resin composite material obtained by melt-kneading.
The amount of Mt was Na-M with respect to PA6 (100 parts by weight).
t2 parts by weight.

The diameter of the screws 6 and 7 was 3.0 cm, the diameter of the cylinder 9 was 9.0 cm, and their length was 135 cm. The rotation speed of the screws 6 and 7 was 300 rpm. The temperature of the heater 93 is 250
° C. The molding port 96 was opened in a circular shape having a diameter of 5 mm, and two of them were provided.

Next, the procedure for producing the resin composite material of the present invention will be described in detail. The thermoplastic resin (PA6) 913 was put in the hopper 91. Also, an aqueous dispersion 953 of Na-Mt was put in the tank 95. The temperature in the cylinder 9 is 250
After confirming that the temperature reached ° C, the screws 6 and 7 were rotated.

Next, the valve 911 was opened, and the thermoplastic resin 913 was charged into the cylinder 9. Then, by heating at 250 ° C., the thermoplastic resin 913 melted and was extruded downstream of the cylinder 9. Next, the valve 952 was opened and the pump 951 was moved to press the aqueous dispersion 953 of Na-Mt into the cylinder 9.

The aqueous dispersion 953 was kneaded with the molten thermoplastic resin 913 by the rotation of the screws 6 and 7. Since the molten thermoplastic resin has a temperature of 250 ° C., the water of the aqueous dispersion 953 is gasified and released into the atmosphere through the opening 92, but the Na-Mt of the aqueous dispersion 953 is contained in the thermoplastic resin (PA6). And remained dispersed.

Then, the molten and kneaded material of Na-Mt and PA6 was extruded from the forming port 96 of the cylinder 9 and formed into a string having a diameter of 5 mm. The molded body 4 was cooled in a water tank 98 and cut by a winding cutter 99 to obtain pellets 40 of a resin composite material.

Observation of the obtained pellets with a transmission electron microscope revealed that 1 to 5 layers of montmorillonite silicate layers (1 mm thick) were uniformly dispersed in PA6.

Embodiment 6 In this embodiment, an aqueous dispersion in which Na-Mt was dispersed at a ratio of 10% by weight was prepared. 20 parts by weight of the prepared aqueous dispersion of Na-Mt was mixed with PA6 (100 parts by weight). That is, N to PA6 (100 parts by weight)
The ratio of a-Mt is 2 parts by weight. This mixture was formed into pellets using the same twin-screw kneader 1 as in Embodiment 5 shown in FIG. That is, the mixture was put into the hopper 91, the valve 911 was opened, and the mixture was put into the cylinder 9. However, the injection of the aqueous dispersion of Na-Mt from the tank 954 was not performed. Except for these, it is the same as the fifth embodiment.

Observation of the obtained molded body with a transmission electron microscope showed that 1 to 5 montmorillonite silicate layers (1 nm in thickness) were uniformly dispersed in PA6.

Comparative Example 3 In this example, a compact was obtained without adding an aqueous dispersion of Na-Mt to PA6. Others are the fifth embodiment.
Is the same as

Comparative Example 4 In this example, Na-Mt was added to PA6 (100 parts by weight).
5 parts by weight were mixed, and this mixture was put into a hopper 91 of a twin-screw kneader 1 shown in FIG. Next, the valve 910 was opened and charged into the cylinder 9. However, Na
The injection of the aqueous dispersion of -Mt was not performed. Other than these, the configuration is the same as that of the fifth embodiment.

When the obtained molded product was observed with a transmission electron microscope, montmorillonite formed an aggregate having a diameter of 1 to 100 μm in PA6. This aggregate was partially observed visually.

(Experimental Example 2) In this example, the mechanical properties of the resin composite material were evaluated. The materials used for the evaluation are the materials obtained in the above-mentioned Examples 5 and 6 and Comparative Examples 3 and 4.
These materials are used for injection molding machine PS40E2 manufactured by Nissei Plastic Industry.
Dumbbell-type tensile test pieces were injection molded using ASE and FS75. This molded product is made of ASTM D638M
Tensile tests were performed in accordance with and the tensile strength, elongation, and elastic modulus were evaluated. Table 2 shows the measurement results.

From Table 2, it can be seen that Examples 5 and 6 are equal to or higher than Comparative Examples 3 and 4 in tensile strength, elongation and elastic modulus, and are excellent in mechanical strength.

[0072]

[Table 2]

(Experimental Example 3) In this example, the gas barrier properties of the resin composite material were evaluated. The materials used for the evaluation are the materials obtained in the above-mentioned Examples 5 and 6 and Comparative Examples 3 and 4. These materials are melted by heating to 250 ° C,
A sheet-shaped molded body (100 μm in thickness) was obtained with a press molding machine. For the obtained sheet-like molded body, the nitrogen gas permeability coefficient was determined according to ASTM D1434. The measurement temperature was 60 ° C. Table 3 shows the results.

As shown in Table 3, Embodiments 5 and 6
Compared with Comparative Examples 3 and 4, the nitrogen gas permeation coefficient was smaller.
This indicates that the resin composite materials of Embodiments 5 and 6 have excellent gas barrier properties.

[0075]

[Table 3]

Embodiment 7 A resin composite material was manufactured in the same manner as in Embodiment 5 except that nylon 66 (grade 2020B manufactured by Ube Industries, hereinafter abbreviated as PA66) was used as the thermoplastic resin and the heater temperature was set to 265 ° C. Was prepared to obtain pellets of the resin composite material. Observation of the obtained pellets with a transmission electron microscope revealed that a silicate layer of montmorillonite (thickness: 1 n
m) in which 1 to 5 layers were laminated, were uniformly dispersed in PA66.

Comparative Example 5 In this example, a molded product was obtained without adding an aqueous dispersion of Na-Mt to PA66. Others are the same as the seventh embodiment.

Comparative Example 6 In this example, Na-M was added to PA66 (100 parts by weight).
t2 parts by weight were mixed, and this mixture was put into the hopper 91 of the twin-screw kneader 1 shown in FIG. Next, the valve 910 was opened and charged into the cylinder 9. However, the injection of the aqueous dispersion of Na-Mt from the tank 954 was not performed. Other points are the same as in the seventh embodiment. Observation of the obtained molded body with a transmission electron microscope revealed that montmorillonite had formed an aggregate having a diameter of 1 to 100 μm in PA66. This aggregate had a size that was partially observable visually.

(Experimental Example 4) In this example, the mechanical properties of the resin composite material were evaluated. The materials used for the evaluation were the materials obtained in Example 7 and Comparative Examples 5 and 6. These materials were molded in the same manner as in Experimental Example 2, and ASTM D63
A tensile test was performed according to 8M to evaluate tensile strength, elongation and elastic modulus. Table 4 shows the measurement results. From Table 4, it can be seen that the embodiment 7 has the same or higher tensile strength, elongation and elastic modulus than the comparative examples 5 and 6, and is excellent in mechanical strength.

[0080]

[Table 4]

(Experimental Example 5) In this example, the gas barrier properties of the resin composite material were evaluated. The materials used for the evaluation were the materials obtained in Example 7 and Comparative Examples 5 and 6. These materials were melted by heating to 280 ° C., and a sheet-like molded body (thickness: 100 μm) was obtained with a press molding machine. For the obtained sheet-like molded body, the nitrogen gas transmission coefficient was determined according to ASTM D1434. The measurement temperature was 60 ° C. Table 5 shows the results. As shown in Table 5, Example 7 had a smaller nitrogen gas permeability coefficient than Comparative Examples 5 and 6. This indicates that the resin composite material of Embodiment 7 has excellent gas barrier properties.

[0082]

[Table 5]

Embodiment 8 Nylon 12 (grade 3024B manufactured by Ube Industries, hereinafter abbreviated as PA12) was used as the thermoplastic resin, the heater temperature was 210 ° C., and the concentration of the aqueous dispersion of Na-Mt was 2.5. % By weight. Otherwise, the procedure of Example 5 was repeated to prepare a resin composite material, and pellets were obtained.
Observation of the obtained pellets with a transmission electron microscope revealed that a montmorillonite silicate layer (1 nm thick) was used.
Were stacked in PA12 uniformly in PA12.

Comparative Example 7 In this example, a compact was obtained without adding an aqueous dispersion of Na-Mt to PA12. Others are the same as the eighth embodiment.

Comparative Example 8 In this example, Na-M was added to PA12 (100 parts by weight).
Then, 2.5 parts by weight of t were mixed, and this mixture was put into the hopper 91 of the twin-screw kneader 1 shown in FIG. Next, the valve 91
0 was opened and charged into the cylinder 9. However, tank 954
No injection of an aqueous dispersion of Na-Mt was performed. Except for these, it is the same as the eighth embodiment. Observation of the obtained molded body with a transmission electron microscope showed that montmorillonite had formed an aggregate having a diameter of 1 to 100 μm in PA12. This aggregate was partially observed visually.

(Experimental Example 6) In this example, the mechanical properties of the resin composite material were evaluated. The materials used for the evaluation are the materials obtained in the above-mentioned Embodiment 8 and Comparative Examples 7 and 8. A bending test piece was injection-molded from these materials in the same manner as in Experimental Example 2, and a bending test was performed according to ASTM D790 to evaluate bending strength and flexural modulus. Table 6 shows the measurement results.
From Table 6, it can be seen that Embodiment Example 8 is equal to or higher in flexural strength and flexural modulus than Comparative Examples 7 and 8, and is superior in mechanical strength.

[0087]

[Table 6]

Embodiment 9 Copolymer nylon (grade 5033B manufactured by Ube Industries, hereinafter abbreviated as copolymer PA) was used as the thermoplastic resin, the heater temperature was set to 220 ° C., and the concentration of the aqueous dispersion of Na—Mt was 2%. 0.0% by weight. Otherwise, a resin composite material was produced in the same manner as in Embodiment 5 to obtain pellets thereof.
Observation of the obtained resin composite material with a transmission electron microscope revealed that a montmorillonite silicate layer (1 n thick) was used.
In the case where m) was laminated in 1 to 5 layers, they were uniformly dispersed in the copolymerized PA.

Comparative Example 9 In this example, a molded product was obtained without adding an aqueous dispersion of Na-Mt to copolymerized PA. Others are the same as the ninth embodiment.

(Experimental Example 7) In this example, the gas barrier properties of the resin composite material were evaluated. The materials used for the evaluation were the materials obtained in Example 9 and Comparative Example 9. These materials were melted by heating to 250 ° C., and a sheet-like molded body (thickness: 100 μm) was obtained by a press molding machine. Regarding the obtained sheet-like molded body, the nitrogen gas permeability coefficient was A
It was determined according to STMD1434. The measurement temperature was 60 ° C. Table 7 shows the results. As shown in Table 7, Example 9 had a smaller nitrogen gas permeability coefficient than Comparative Example 9. This indicates that the resin composite material of Embodiment 9 is excellent in gas barrier properties.

[0091]

[Table 7]

[0092]

According to the present invention, it is possible to provide a method for producing a resin composite material in which a non-organized clay can be dispersed in a thermoplastic resin having low affinity for water.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram illustrating a method for manufacturing a resin composite material according to a first embodiment.

FIG. 2 is an explanatory view showing a method for manufacturing a resin composite material according to a fifth embodiment.

[Explanation of Codes] . . 3. twin-screw kneader, . . Molded article, 40. . . Pellets, 6,7. . . Screw, 9. . . Cylinder, 910, 913. . . Thermoplastic resin, 920. . . Non-organized clay, 950. . . Water, 953. . . Aqueous dispersion,

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Naoki Hasegawa 41-cho, Yokomichi, Nagakute-cho, Aichi-gun, Aichi Prefecture Inside Toyota Central Research Laboratory Co., Ltd. No. 41, Chochu-Yokomichi, Toyota Central Research Laboratory Co., Ltd. (72) Inventor Norio Sato No. 41, Toyota Chuo Research Institute, Nagakute-cho, Aichi-gun, Aichi, Japan

Claims (1)

[Claims] 1. A method for producing a resin composite material, comprising: bringing a solvent containing water or a proton donor into contact with a clay and a thermoplastic resin at a temperature equal to or higher than the melting temperature of the thermoplastic resin.