JPH09183910A - Crystalline thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crystalline thermoplastic resin composition improved in a melting point, crystallizability, etc., and therefore improved in mechanical properties and thermal properties by mixing a crystalline thermoplastic resin with a specified layered silicate. SOLUTION: A layered silicate is swollen by immersion in a solvent in a weight ratio of the silicate to the solvent of 1:0.5 to 1:100 to obtain a layered silicate having an interlayer distance of 30Åor above and an aspect ratio (a ratio of the major diameter to the minor diameter) of 20 or above. One hundred (100) pts.wt. crystalline resin having a melt flow rate (as measured at 230 deg.C under a load of 2.16kg) of 0.01-250g/10min is mixed with 0.01-11 pts.wt. above obtained layered silicate, and the obtained mixture is melt-kneaded for 3-10min at a temperature higher than the melting point of the thermoplastic resin by 2-30 deg.C to disperse the silicate on a molecular level as a nucleator in the resin.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a crystalline thermoplastic resin composition comprising a crystalline thermoplastic resin and a layered silicate dispersed at a molecular level and having improved mechanical and thermal properties.

[0002]

2. Description of the Related Art Conventionally, in order to improve various properties of crystalline thermoplastic resins, particularly mechanical properties and thermal properties, an inorganic filler is mixed. At this time,
It is known that some inorganic fillers have a nucleating effect on crystalline resins. For example, talc is known to act as a nucleating agent for various crystalline resins, improve the melting point and crystallization of the crystalline resin, and improve the mechanical and thermal properties. However, the effect is not sufficient,
There has been a demand for an inorganic filler having a greater effect.
On the other hand, clay minerals, which are a type of inorganic layered compound, have long been attempted to be used as fillers, but with ordinary mixing and kneading, secondary agglomeration occurs and it is difficult to uniformly disperse them in the resin. Met. Therefore, the nucleating effect of the clay mineral was almost nonexistent. Therefore, JP-A-63-
In Japanese Patent No. 215775, a polymer is polymerized between layers of clay minerals, and in Japanese Patent Laid-Open Nos. 6-93133 and 6-41346, clay minerals are dispersed in a solvent while a thermoplastic resin is used. Is disclosed to be dissolved in a solvent and both are mixed in solution, but it is still difficult to uniformly disperse the resin and the clay mineral, and
Clay minerals have not been able to significantly improve the crystallinity of crystalline resins.

[0003]

Therefore, it serves as a nucleating agent for the crystalline thermoplastic resin and significantly improves the melting point, crystallization and the like of the crystalline thermoplastic resin, and the mechanical and mechanical properties of the crystalline thermoplastic resin are improved.
There has been a desire for inorganic fillers that can significantly improve thermal properties.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a resin composition comprising a crystalline thermoplastic resin and a layered silicate, A resin molded product having a crystal nucleus with a high aspect ratio in which a salt is dispersed at the molecular level exhibits a very high nucleating agent effect, and the mechanical and thermal properties of the crystalline thermoplastic resin composition are significantly improved. The inventors have found that and reached the present invention.

That is, according to the present invention, (a) 100 parts by weight of the crystalline thermoplastic resin, (b) 0.02 layered silicate is used.
A resin composition containing 1 to 11 parts by weight, which is a crystal nucleus in which the layered silicate is dispersed at a molecular level, and has an aspect ratio represented by a ratio of major axis to minor axis of the crystal nucleus of 20 or more. Is a crystalline thermoplastic resin composition. In particular, the above-mentioned crystalline thermoplastic resin composition is characterized in that the crystalline thermoplastic resin is a polyolefin resin.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. <Crystalline thermoplastic resin (component) (a)> The crystalline thermoplastic resin used in the present invention has a non-glass-like property that can be melted by heating and has a clear crystal structure or molecular structure. And has a definite melting point with a measurable heat of fusion. The melting point and the heat of fusion are measured by a differential scanning calorimeter (DSC: eg PERKIN-).
It can be measured using an ELMER DSC-II).

Using this device, for example, 10 per minute
The heat of fusion can be measured at a temperature rising rate of ° C. Heating the sample to a temperature above the expected melting point, then cooling the sample at a rate of 10 ° C per minute to 20 ° C, leaving it for about 1 minute and then heating at a rate of 10 ° C per minute. Can be measured by. For the heat of fusion, the value measured in the cycle of temperature increase and temperature decrease shall be constant within the experimental error range. The crystalline thermoplastic resin in the present invention is defined as having a heat of fusion of more than 1 calorie / gram as measured by this method.

Examples of the crystalline thermoplastic resin used in the present invention include resins such as polyolefins, polyamides, polyesters, polyacetals, halogen-containing thermoplastic resins and polysulfones. One or more selected from these groups. Is a crystalline thermoplastic resin. Among these, the most preferable crystalline thermoplastic resin is a polyolefin resin. For polyolefin resin, α
-Olefin homopolymers or copolymers of these α-olefins, or these α-olefins (may be plural types) as main components, and optionally other unsaturated monomers (may be plural types) as subcomponents. Copolymers and the like. Here, the copolymer may be any type of copolymer such as block, random, graft or composite thereof. Further, these olefin polymers include those modified by chlorination, sulfonation, carbonylation and the like.

The above-mentioned α-olefins are, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and the like, having 2 to 8 carbon atoms because of their easy availability. Is preferred. Examples of the unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid ester, unsaturated organic acids such as maleic acid, and the like, and anhydrides thereof. Specific examples of these polyolefin resins include low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polybutene, ethylene / propylene block or random copolymer. These may be used in combination.

Among them, the polyolefin resin is a crystalline olefin polymer, for example, a crystalline homopolymer of ethylene or propylene, a copolymer having ethylene or propylene as a main constituent, ethylene or propylene and other ethylene. A crystalline copolymer with a polyunsaturated monomer is preferable. Among these, particularly preferable examples are low, medium or high density polyethylene, polypropylene, and propylene / ethylene block copolymer,
Among them, high density polyethylene, polypropylene, and propylene / ethylene block copolymer are most preferable.

These melt flow rates (MFR;
230 ° C, load 2.16 kg) is 0.01 to 250 g /
The range of 10 minutes is preferable, the range of 0.05 to 200 g / 10 minutes is more preferable, and the range of 0.1 to 100 g / 1 is especially preferable.
A range of 0 minutes is preferred. When the MFR value is lower than this range, molding workability is difficult, and when it is higher than this range, the mechanical strength level is not preferable.

Further, in the present invention, a sensitive derivative of the polyolefin resin can be used as a part (up to 20 mol%) of the polyolefin resin. The term "sensitive derivative" used herein means that a polyolefin resin is an unsaturated organic acid or anhydride (for example, acrylic acid, maleic acid, itaconic acid or its anhydride) or an unsaturated organic silane compound (for example,
(Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, propenyltrimethoxysilane) or the like, or a polyolefin graft-modified with an organic acid or an anhydride thereof. Examples thereof include ionomers in which a part of the carboxyl groups attached to the resin graft chain is metal-ionized. Further, as the sensitive derivative of polyolefin, in addition to the specific examples given here, those in which a hydrophilic group is introduced by a grafting, block, random copolymerization method, a substitution reaction, an oxidation reaction or the like may be used. it can.

<Layered Silicate (Component (b))> The layered silicate used in the present invention can be exemplified by a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate. Specifically, montmorillonite,
Examples include smectite clay minerals such as savonite, beidellite, nontronite, hectorite, and stevensite, as well as mica, talc, vermiculite, and virosite. It may be one. Among these, synthetic mica, montmorillonite and vermiculite are preferable.

As the layered silicate, it is preferable to use a layered silicate that has been swollen in advance with a solvent. The solvent used for swelling the layered silicate is not particularly limited as long as it is a liquid at room temperature. For example, aromatic hydrocarbons such as benzene, toluene and xylene; chain and cyclic aliphatic hydrocarbons such as heptane and cyclohexane;
Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene and dichloromethane; ethers such as dioxane and diethyl ether; ketones such as acetone, cyclohexanone, methyl ethyl ketone and acetophenone; esters such as ethyl acetate and propiolactone; acetonitrile; Nitriles such as benzonitrile; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol and diethylene glycol; and other organic solvents such as water, nitrobenzene, sulfolane, dimethylformamide and dimethylsulfoxide. These may be used alone or as a mixture. Aromatic hydrocarbons, halogenated hydrocarbons, alcohols and water are preferable, and xylene, toluene, and particularly preferable ones.
Dichlorobenzene, trichlorobenzene, methanol,
Solvents such as ethanol and water are mentioned, and water is particularly preferable.

Here, the amount of the solvent used for swelling the layered silicate is 1: 0.5 by weight of layered silicate: solvent.
˜1: 100, more preferably 1: 2 to 1:80, and even more preferably 1: 4 to 1:60.
It is. If it is less than 1: 0.5, the swelling is insufficient and the nucleating agent effect is small, and if it exceeds 1: 100, melt-kneading is difficult. In the present invention, the interlayer distance of the swollen layered silicate is preferably 30 angstroms or more, more preferably 50 angstroms or more, further preferably 70 angstroms or more, and particularly preferably 90 angstroms or more. The distance between layers is 3
When it is less than 0 angstrom, the layered silicate is not uniformly dispersed in the resin, and the nucleating agent effect is small.

The layered silicate is preferably treated with a swelling agent because it easily swells in a solvent. Examples of the swelling agent include ammonium salts, pyridinium salts and sulfonium salts, which are onium salts having an onium ion group in the molecule. More specifically, those having octadecyl ammonium ion, monomethyl octadecyl ammonium ion, dimethyl octacyl ammonium ion, dodecyl ammonium ion, 6-amino-n-caproate ion, 12-aminododecanoate ion can be exemplified. However, when swelling with water, untreated layered silicate is more likely to swell, and therefore it is preferable not to treat with a swelling agent.

In the present invention, the swelling means a phenomenon in which the layered silicate absorbs the solvent to increase its volume, and the preferable combination for the swelling has a swelling degree of 1 cc / cc.
g or more, preferably 10 to 100 cc / g of a layered silicate and a solvent. There are various methods for measuring the degree of swelling, but the sedimentation volume method (Clay Handbook 51
It may also be determined by the ratio of the volume obtained by page 3) to the dry weight of the layered silicate. If the swelling properties of the layered silicate and the solvent are very good, the layered silicate will be super-dispersed in the solvent and will not sediment due to gravity, making measurement impossible. Of course, also in this case, the combination of the layered silicate and the solvent which swells very well.

<Composition Ratio of Constituent Components> The amount of the layered silicate (component (b)) is 0.01 to 11 parts by weight, preferably 100 parts by weight of the crystalline thermoplastic resin (component (a)). Is 0.02 to 9 parts by weight, particularly preferably 0.03 to 7
Parts by weight. Crystalline thermoplastic resin (component (a)) 10
0 parts by weight of the layered silicate (component (b)) was 0.
If it is less than 01 parts by weight, the effect of the nucleating agent is unsatisfactory, and if it exceeds 11 parts by weight, moldability and appearance are difficult.

<Form of Resin Composition> In the present invention,
The layered silicate in the resin composition is dispersed at the molecular level and present as crystal nuclei in the resin composition, and the aspect ratio represented by the ratio of the major axis to the minor axis of the crystal nuclei is 20 or more, preferably 30. Or more, more preferably 40 or more,
The maximum aspect ratio may be about 80 or about 200. The existence and size of the crystal nucleus as referred to herein can be confirmed by observing the molded product with an electron microscope. That is, after dyeing with ruthenium tetroxide or osmium tetroxide to clarify the crystal structure in the molded product, when an ultrathin section was prepared and observed with a transmission electron microscope, the layered silicate in the molded body was agglomerated. In addition to those dispersed in, it is possible to observe streaky crystal nuclei dispersed in a molecular form. The aspect ratio of crystal nuclei can be obtained by image processing of electron micrographs and statistical processing. When the aspect ratio is less than 20, the nucleating agent effect is small. Further, in the present invention, it is preferable that a crystalline lamella grows from the crystal nuclei in the vertical direction, and the thickness of the lamella is 1.1 times or more as compared with that without the addition of the layered silicate. It is preferably 1.2 times or more, more preferably 1.3 times or more. The shape of the layered silicate in the final composition of the present invention has a side length of preferably 0.002 to 5 μm, more preferably 0.05 to 1 μm.
m, particularly preferably 0.4 to 0.8 μm, and the thickness of the layered silicate is preferably 30 to 1,000 angstroms, more preferably 50 to 500 angstroms, and particularly preferably 100 to 200 angstroms. The interlayer distance of the layered silicate is preferably 20 angstroms or more.

<Additional component> Other additional components may be added to the resin composition according to the present invention. For example,
Amorphous thermoplastics, well-known antioxidants, weather resistance modifiers, other nucleating agents, flame retardants, impact modifiers, plasticizers, flow modifiers; and organic and inorganic materials other than layered silicates filler,
Addition of a reinforcing agent, particularly glass fiber, potassium titanate, calcium carbonate, silica or the like is effective in improving rigidity, heat resistance, dimensional accuracy and the like. For practical use, various colorants and their dispersants can be used well-known ones.

<Production Method of Resin Composition> In the present invention,
In order to obtain a resin composition containing a crystalline thermoplastic resin of component (a) and a layered silicate of component (b), a method of swelling a monomer in the layered silicate to carry out polymerization, a crystalline thermoplastic A method of melting and kneading a resin and a layered silicate, a method of mixing a crystalline thermoplastic resin and a layered silicate in a solution, and the like can be used, but use a kneading machine to melt the crystalline thermoplastic resin and the layered silicate. It is preferable to knead.

Melt Kneading As the melt kneading machine used in the present invention, a kneading machine generally used for thermoplastic resins can be applied. For example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, or the like may be used. In the present invention, it is preferable that the kneading machine is provided with a vent port and the vent port is kept at a reduced pressure during the melt kneading. At least a part of the resin in the kneader should be melted in the front part of the ventro so that it can be vacuum-sealed. Further, if the resin in the kneader is held in a molten state for a long time before reaching the vent port, the impact resistance decreases, so it is preferable to melt the resin within a possible range immediately before reaching the ventro. The vacuum device directly connected to the vent port may have this capability selected according to the degree of pressure reduction at the vent port, and its type and the like are arbitrary.

The pressure at the vent port is preferably 200 Torr or less, more preferably 100 Torr or less, and particularly preferably 50 Torr or less. If the vent port pressure is higher than 200 Torr, the heat resistance and the molding appearance will be unsatisfactory. The kneading conditions in the present invention are preferably such that the resin temperature at the time of melt kneading is 2 to 30 ° C. higher than the melting point measured using the differential scanning calorimeter described above, and more preferably 5
-25 ° C higher temperature, particularly preferably 10-20 ° C higher temperature. The average residence time during melt-kneading is preferably 3 to 10 minutes, more preferably 3 to 7 minutes, and particularly preferably 4 to 6 minutes. The solvent in the final composition is preferably 1% by weight or less, more preferably 0.9% by weight.
It is not more than 0.5% by weight, particularly preferably not more than 0.5% by weight. If the solvent in the final composition exceeds 1% by weight, heat resistance and appearance are unsatisfactory. The order of kneading may be to knead all the components at the same time, or to knead using a preliminarily kneaded blend, or to feed and knead each component sequentially from the middle of the extruder. In particular, when the property of the layered silicate / solvent mixture is liquid, it is preferable to feed it from the middle of the extruder using a liquid addition pump.

Molding Process In the present invention, the shear rate in the extruder is 200.
It is preferably SEC ^-1 or more, more preferably 3
It is 00 SEC ^-1 or more, more preferably 400 SEC ^-1 or more, and particularly preferably 500 SEC ^-1 or more. The crystalline thermoplastic resin composition of the present invention is obtained by molding the resin composition obtained in the above step. The molding method used here is not particularly limited, and molding methods generally used for thermoplastic resins, that is, injection molding, hollow molding, extrusion molding, sheet molding, thermoforming, rotational molding, lamination molding, press molding A molding method such as molding can be applied. Among these, injection molding, hollow molding, extrusion molding, and sheet molding are preferable, and injection molding is particularly preferable. Further, in the present invention, the resin composition in which the layered silicate is dispersed and the usual crystalline thermoplastic resin may be dry blended at the time of molding to obtain a molded body.

[0025]

The present invention will now be described by way of Examples and Comparative Examples.
This will be specifically described. [I] Raw materials The components used are as follows. Crystalline thermoplastic resin (component (a)) (a-1): Polyamide 6 (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Novamid 1020) (a-2): Polypropylene (Mitsubishi Chemical Co., Ltd. trade name: Noblene TA8) (a -3): Polybutylene terephthalate (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: Novadur 5010) Amorphous thermoplastic resin PPE: Polyphenylene ether (Nippon Polyether Co., Ltd., intrinsic viscosity: 0.40 dl / dg) PC: Polycarbonate (Mitsubishi Engineering Co., Ltd.) Made
(Product name: Novarex 7025A)

Layered silicate (component (b)) (b-1): Synthetic mica (trade name: ME100, swelling agent untreated) (b-2): synthetic mica (trade name: corp chemical) MAE swelling agent (using dimethyl distearyl ammonium salt))

Other MAH: Commercially available maleic anhydride (reagent grade) SEPS: Hydrogenated product of styrene-isoprene block copolymer (Kuraray Co., Ltd., trade name: 2104) MMPP: Maleic anhydride modified polypropylene (Mitsubishi Chemical Co., Ltd.) Talc (Fuji Talc product name: KT300) PEP36: Bis (2,6-di-tert-butyl-4)
-Methylphenyl) pentaerythritol diphosphite (manufactured by Asahi Denka Co., Ltd.) Swelling solvent xylene: commercially available xylene (reagent grade) water: pure water

[II] Measuring Method In addition, for evaluation, each physical property value and various characteristics were measured by the following methods, and the results are shown in Table 1. (1) Dispersion form A part was cut out from a molded product, an ultrathin section was prepared using an ultramicrotome, and observed with a transmission electron microscope (JEM2010) manufactured by JEOL Ltd. The morphology of crystal nuclei in which silicate was dispersed at the molecular level was confirmed. From the observed photograph, the size of the crystal nucleus existing in the resin in the thickness direction and the size in the direction perpendicular to it are calculated by an image analyzer (Spica 2 manufactured by Nippon Avionisque), and the aspect ratio is calculated from the ratio. It was These values were measured for 100 or more crystal nuclei dispersed in the resin, and a number average value was obtained for each.

(2) Flexural Modulus ISO R178-1974 Procedure 1
According to 2 (JIS K7203), it measured using the Instron tester. (3) Heat distortion temperature Using an HDT tester manufactured by Toyo Seiki Seisakusho, JIS
It was measured according to K7207 under a load of 18.6 kg. (4) Melting end temperature A molded body was cut out and used as a sample, and PERKIN-ELMER
Using a DSC-II manufactured by the company, the melting end temperature was measured when the temperature was raised at a temperature rising rate of 10 ° C. per minute.

[Example 1] The components (b) and the solvent were thoroughly mixed and stirred in a supermixer at the ratios shown in Table-1,
The component (b) was swollen in the solvent. Next, the layered silicate swollen in the above step was thoroughly mixed and stirred with the crystalline thermoplastic resin in a supermixer at the compounding ratio shown in Table-1. Then, using a TEX44 twin-screw extruder manufactured by Japan Steel Works, this was set at a temperature of 230 ° C. and the screw rotation speed was 35.
After melt-kneading under a kneading condition of 0 rpm, and melt-kneading under a reduced pressure condition (vent pressure: 10 torr) at a vent port installed downstream from the kneading part to obtain a resin composition,
Pelletized.

From the pellets of the above resin composition, an in-line screw type injection molding machine (J100 manufactured by Japan Steel Works, Ltd.) was used.
Mold) with a cylinder temperature of 260 ° C. and a mold cooling temperature of 6
Injection molding was performed at 0 ° C to prepare a test piece. During injection molding, use a vacuum dryer until immediately before,
It was dried for 48 hours under the conditions of 0.1 mmHg and 80 ° C. The injection-molded test pieces were placed in a desiccator immediately after molding, allowed to stand at 23 ° C. for 4 to 6 days, and then evaluated, and the results are shown in Table 1.

[Example 2] Using polypropylene as a crystalline resin, the set temperature of the twin-screw extruder is 180 ° C, the cylinder temperature of the injection molding machine is 220 ° C, and the mold cooling temperature is 40 ° C.
The same operation as in Example 1 was performed except that the temperature was changed to ° C. Table 1 shows the results. [Example 3] The same operation as in Example 2 was performed except that water was used instead of xylene. Table 1 shows the results. In addition, as a result of observing the obtained crystalline thermoplastic resin composition with an electron microscope at a magnification of 80,000, it was found that several parallel, substantially straight, elongated white line portions (crystal nucleus: aspect ratio of about 40) were used. ) And its parallel straight elongated white line portions, a large number of streak white line portions (crystalline lamellas) were observed in the direction perpendicular to the elongated white lines. Can be observed growing. The thickness of the crystalline lamella was about twice as large as the electron microscope of the resin composition obtained in Comparative Example 1 described later.

Example 4 Component (b) and water were mixed and stirred in a supermixer at the mixing ratios shown in Table-1,
The component (b) was swollen in the solvent. Next, using a TEX44 twin-screw extruder manufactured by Japan Steel Works, Ltd., the set temperature is 180.
℃, while melt-kneading the resin components under the kneading conditions of the screw rotation speed 350 rpm, the layered silicate that has been adjusted and swollen in the above step is added directly to the kneading part by using a pump, and is introduced downstream from the kneading part. The composition was melt-kneaded under the condition of the installed vent port pressure of 10 Torr to prepare a composition and then pelletized.

Example 5 First, pelletization was carried out under the same conditions as in Example 4 except that the components were mixed in the proportions shown in Table 1. Then, the obtained composition and polypropylene (trade name: Noblene MA8 manufactured by Mitsubishi Chemical Co., Ltd.) were dry blended in a weight ratio of 50:50, and molded and evaluated in the same manner as in Example 4. Table 1 shows the results. [Example 6] The same procedure as in Example 1 was carried out except that polyphenylene ether was used as the amorphous resin and maleic anhydride was further added. The results are shown in Table-2. [Example 7] The same procedure as in Example 4 was carried out except that polyphenylene ether was used as the amorphous resin and SEPS of the styrene copolymer was further added. The results are shown in Table-2. Example 8 The procedure of Example 2 was repeated except that polybutylene terephthalate was used as the crystalline resin and polycarbonate was used as the amorphous resin. The results are shown in Table-2.

Example 9 Polybutylene terephthalate was used as the crystalline resin, polyphenylene ether was used as the amorphous resin, and a phosphite ester (trade name of Asahi Denka Co., Ltd .:
Example 2 was repeated except that PEP36) was further added. The results are shown in Table-2. [Example 10] The same procedure as in Example 2 was carried out except that polyamide 6 and polypropylene were used as the crystalline resin, and maleic anhydride-modified polypropylene was further added. The results are shown in Table-2. [Example 11] The same procedure as in Example 3 was performed except that polyamide 6 and polypropylene were used as the crystalline resin and maleic anhydride-modified polypropylene was further added. The results are shown in Table-2.

Comparative Example 1 The procedure of Example 1 was repeated except that talc was used instead of the layered silicate. Table-
3 is shown. Further, as a result of observing the obtained crystalline thermoplastic resin composition with an electron microscope at a magnification of 80,000 times as in Example 3, some streak-like crystalline lamellae can be observed in some places. It was not possible to observe the crystal nuclei with a high aspect ratio as in Example 3. The thickness of the crystalline lamella was about half that of the crystalline thermoplastic resin composition obtained in Example 3. [Comparative Example 2] The procedure of Example 2 was repeated except that the layered silicate and the solvent were not added. Table 3 shows the results. Comparative Example 3 The procedure of Example 3 was repeated except that no solvent was used. Table 3 shows the results. [Comparative Example 4] The same procedure as in Example 3 was carried out except that the amount of solvent was changed to that shown in Table 3. Table 3 shows the results. [Comparative Example 5] The same operation as in Example 4 was carried out except that the amount of solvent was changed to that shown in Table 3. It was impossible to carry out melt-kneading. [Comparative Example 6] The same operation as in Example 7 was carried out except that talc was used instead of the layered silicate and water. Table-
It is shown in FIG. [Comparative Example 7] The same procedure as in Comparative Example 6 was performed except that talc was not used. Table 4 shows the results.

[Comparative Example 8] The same procedure as in Example 7 was carried out except that a synthetic mica treated with a swelling agent (ME100) was used as the layered silicate instead of the synthetic mica not treated with the swelling agent, and no solvent was used. I did. Table 4 shows the results. [Comparative Example 9] The procedure of Comparative Example 7 was repeated except that no solvent was used. Table 4 shows the results. [Comparative Example 10] Except that kneading was carried out under the conditions that the resin temperature in the kneader was higher by 105 ° C than the melting point of polypropylene which is a crystalline thermoplastic resin, and kneading was carried out at such a production amount that the average residence time was 1 minute. The same procedure as in Example 3 was performed. Table 4 shows the results. [Comparative Example 11] Except that kneading was carried out under conditions that the resin temperature in the kneading machine was 35 ° C higher than the melting point of polypropylene, which is a crystalline thermoplastic resin, and kneading was carried out at such a production amount that the average residence time was 10 minutes. The same procedure as in Example 3 was performed. Table 4 shows the results.

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

[0042]

From the results of the above-described evaluation test, the molded article of the present invention obtained by molding a resin composition comprising a crystalline thermoplastic resin and a layered silicate has a high molecular weight distribution of the layered silicate. It can be seen that it has crystal nuclei with an aspect ratio and the mechanical and thermal properties are greatly improved. Therefore, according to the present invention, a highly heat-resistant crystalline thermoplastic resin molded article can be produced, has a wide range of uses, and can be an industrially useful material.

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[Procedure amendment]

[Submission date] December 11, 1996

[Procedure amendment 1]

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<Layered Silicate (Component (b))> The layered silicate used in the present invention can be exemplified by a layered phyllosilicate mineral composed of a layer of magnesium silicate or aluminum silicate. Specifically, montmorillonite,
Examples include smectite clay minerals such as saponite, beidellite, nontronite, hectorite, and stevensite, as well as mica, talc, vermiculite, halloysite, etc. May be Among these, synthetic mica, montmorillonite and vermiculite are preferable.

[Procedure 3]

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Layered silicate (component (b)) (b-1): Synthetic mica (trade name: ME100, swelling agent untreated) (b-2): synthetic mica (trade name: corp chemical) MAE swelling agent (using dimethyl distearyl ammonium salt)) Talc (Fuji Talc Co., Ltd. product name: KT300)

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Other MAH: Commercially available maleic anhydride (reagent grade) SEPS: Hydrogenated product of styrene-isoprene block copolymer (Kuraray Co., Ltd., trade name: 2104) MMPP: Maleic anhydride modified polypropylene (Mitsubishi Chemical Co., Ltd.) PEP36: Bis (2,6-di-tert-butyl-4)
-Methylphenyl) pentaerythritol diphosphite (manufactured by Asahi Denka Co., Ltd.) Swelling solvent xylene: commercially available xylene (reagent grade) water: pure water

[Procedure Amendment 5]

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Comparative Example 1 The procedure of Example 1 was repeated except that swelling talc was used instead of the layered silicate. Table 3 shows the results. Further, the obtained crystalline thermoplastic resin composition was examined with an electron microscope in the same manner as in Example 3 to obtain 80,0.
As a result of observing with a magnifying power of 00, it was possible to observe some streaky crystal lamellas in some places, but it was not possible to observe crystal nuclei with a high aspect ratio as in Example 3. The thickness of the crystalline lamella was about half that of the crystalline thermoplastic resin composition obtained in Example 3. [Comparative Example 2] The procedure of Example 2 was repeated except that the layered silicate and the solvent were not added. Table 3 shows the results. Comparative Example 3 The procedure of Example 3 was repeated except that no solvent was used. Table 3 shows the results. [Comparative Example 4] The same procedure as in Example 3 was carried out except that the amount of solvent was changed to that shown in Table 3. Table 3 shows the results. [Comparative Example 5] The same operation as in Example 4 was carried out except that the amount of solvent was changed to that shown in Table 3. It was impossible to carry out melt-kneading. [Comparative Example 6] The same operation as in Example 7 was carried out except that talc was used instead of the layered silicate and water. Table-
It is shown in FIG. [Comparative Example 7] The same procedure as in Comparative Example 6 was performed except that talc was not used. Table 4 shows the results.

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[Comparative Example 8] The same procedure as in Example 7 was conducted except that a swelling agent-treated synthetic mica (MAE) was used as the layered silicate instead of the swelling agent-untreated synthetic mica (MAE), and no solvent was used. I did. Table 4 shows the results. [Comparative Example 9] The same operation as in Example 7 was carried out except that no solvent was used. Table 4 shows the results. [Comparative Example 10] Except that kneading was carried out under the conditions that the resin temperature in the kneader was higher by 105 ° C than the melting point of polypropylene which is a crystalline thermoplastic resin, and kneading was carried out at such a production amount that the average residence time was 1 minute. The same procedure as in Example 3 was performed. Table 4 shows the results. [Comparative Example 11] Except that kneading was carried out under conditions that the resin temperature in the kneading machine was 35 ° C higher than the melting point of polypropylene, which is a crystalline thermoplastic resin, and kneading was carried out at such a production amount that the average residence time was 10 minutes. The same procedure as in Example 3 was performed. Table 4 shows the results.

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction contents]

[0039]

[Table 2]

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

[0040]

[Table 3]

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

[0041]

[Table 4]

Front page continued (72) Inventor Hironari Sano 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Chemical Co., Ltd. Yokkaichi Research Institute

Claims (8)

[Claims] 1. A resin composition containing 0.01 to 11 parts by weight of a layered silicate (b) per 100 parts by weight of a crystalline thermoplastic resin (a), wherein the layered silicate is at a molecular level. 2. The crystalline thermoplastic resin composition, wherein the crystalline nuclei are dispersed in 1. and the aspect ratio represented by the ratio of the major axis to the minor axis of the crystalline nuclei is 20 or more. 2. The crystalline thermoplastic resin composition according to claim 1, wherein the crystalline thermoplastic resin as the component (a) is a polyolefin resin. 3. The crystalline thermoplastic resin composition according to claim 1, wherein the layered silicate is swollen. 4. The crystalline thermoplastic resin composition according to claim 1, wherein the layered silicate is swollen with a solvent. 5. The crystalline thermoplastic resin composition according to claim 4, wherein the solvent is water and / or an organic solvent. 6. The crystalline thermoplastic resin composition according to claim 1, wherein the layered silicate is treated with a swelling agent. 7. The crystalline thermoplastic resin composition according to claim 6, wherein the swelling agent is an onium salt having an onium ion group in the molecule. 8. The crystalline thermoplastic resin composition according to claim 1, wherein the dispersion is melt-kneaded at a resin temperature 2 to 30 ° C. higher than the melting point and a residence time of 3 to 10 minutes.