JPH10265668A - Production of reinforced polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having high strengths, high modulus, high heat resistance, high toughness and high elongation by mixing monomers forming a polyamide resin with a layered silicate having a cation exchange capacity in a specified range and an aqueous solution of an amine or lactam salt of an aminocarboxylic acid having the specified or larger number of carbon atoms in a specified ratio and polymerizing the mixture. SOLUTION: Monomers in amounts to give 100 pts.wt. polyamide resin (nylon 6 or a copolymer thereof) are mixed with 0.01-20 pts.wt. layered silicate having a cation exchange capacity of 50-200 milliequivalents/100 g and an aqueous solution of an amine or lactam salt of a 10C or higher aminocarboxylic acid in an amount 0.01-5 times by mole the cation exchange capacity of the layered silicate, and the mixture is polymerized. The aqueous solution of the amine or lactam salt of the aminocarboxylic acid is obtained by reacting equimolar amounts of an aminocarboxylic acid or a lactam and an acid having a pKa (25 deg.C in water) in the range of 0-4 or negative values in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyamide resin and a layered silicate which are uniformly dispersed at a molecular level, and have a high strength,
The present invention relates to a method for producing a reinforced polyamide resin composition having high elastic modulus, high heat resistance, high toughness and high elongation.

[0002]

2. Description of the Related Art Hitherto, resin compositions in which polyamide is reinforced with a fibrous material such as glass fiber or carbon fiber or an inorganic filler such as calcium carbonate have been widely known. However, these reinforcing materials have poor affinity with polyamide, and although the mechanical strength and heat resistance of the reinforced polyamide are improved, the toughness is reduced, and the resin composition reinforced with fibrous material causes warpage of the molded product. There was a problem of becoming larger. In addition, the resin composition reinforced with the above-mentioned inorganic filler has a problem that the mechanical strength and heat resistance are not improved unless a large amount of the filler is blended.

As an attempt to improve the disadvantages of the reinforced polyamide, a resin composition comprising a polyamide and a clay mineral represented by montmorillonite has been proposed (JP-A-62-74957, JP-A-63-95757). No. 230766,
JP-A-2-102261, JP-A-3-7729). However, this resin composition has high rigidity and high heat resistance, but has a drawback of low toughness.

As an attempt to improve the low toughness, which is a drawback of the above resin composition, a polyamide resin composition in which an impact resistance improving material is blended with the above resin composition has been proposed (JP-A-2-29457). No.). However, when a molded article is formed using this resin composition, there is a problem that the strength, elastic modulus, and the like are reduced as compared with a molded article using an unreinforced polyamide.

[0005]

The object of the present invention is to provide a polyamide resin and a layered silicate which are uniformly dispersed at a molecular level, and have a high strength, a high elastic modulus, a high heat resistance, a high toughness and a high elongation. It is intended to provide a method for producing a reinforced polyamide resin composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the gist of the present invention is as follows. Polyamide resin (nylon 6 or its copolymer) 10
0 to 20 parts by weight of the phyllosilicate having a cation exchange capacity of 50 to 200 meq / 100 g, and 0.01 to 20 parts by weight of the phyllosilicate, based on the total cation exchange capacity of the phyllosilicate.
A method for producing a reinforced polyamide resin composition, comprising mixing an aqueous solution of an amine salt of an aminocarboxylic acid having 10 or more carbon atoms and an aqueous solution of a lactam salt in an amount of 0.01 to 5 moles and polymerizing the monomer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The polyamide (nylon 6 or a copolymer thereof) used in the method of the present invention comprises ε-caprolactam and / or 6-aminocarboxylic acid as a main raw material monomer and, if necessary, a copolymerized monomer. It is manufactured by melt polymerization. The relative viscosity is preferably in the range of 1.5 to 5.0 as determined by using 96% by weight concentrated sulfuric acid as a solvent at a temperature of 25 ° C. and a concentration of 1 g / dl. If the relative viscosity is less than 1.5, the mechanical strength of a molded product is undesirably reduced. On the other hand, if the relative viscosity exceeds 5.0, the moldability of the resin composition rapidly decreases, which is not preferable.

In this case, as the copolymerized monomer, there are various aminocarboxylic acids or lactams and nylon salts.
Specifically, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, ω-laurolactam, nylon 46 salt, nylon 66 salt, nylon 610 salt, nylon 6T salt, nylon 6I salt, meta-xylylenediamine And salts of adipic acid, which are copolymerized at a ratio of 20 mol% or less.

The layered silicate used in the method of the present invention has a structure comprising a negatively charged layer mainly composed of silicate and a positive charge (ion) interposed between the layers. It is necessary that the obtained cation exchange capacity is in the range of 50 to 200 meq / 100 g. When the cation exchange capacity is less than 50 meq / 100 g, cleavage of the layered silicate does not proceed sufficiently, and a resin composition having excellent mechanical strength and heat resistance cannot be obtained. On the other hand, the cation exchange capacity
If the amount exceeds 200 meq / 100 g, a resin composition satisfying the characteristics of the present invention cannot be obtained at the same time because the bonding strength between layers is strong.

Preferred examples of such a layered silicate include:
Smectite group (for example, montmorillonite, beidellite, saponite, hectorite, sauconite), vermiculite group (for example, vermiculite), mica group (for example, fluoromica, muscovite, paragonite phlogopite, biotite, lepidolite), brittle mica ( For example, there are margarite, clintite, anandite), chlorite (for example, dombasite, sudoite, coucheite, clinochlore, chamosite, nimmite) and the like.

These layered silicates may be naturally occurring, artificially synthesized or modified, or treated with an organic substance such as an onium salt. Is also good.

Among the above-mentioned layered silicates, swellable fluoromica-based minerals are most preferable in terms of whiteness, which is represented by the following formula and can be easily synthesized. α (MF) · β (aMgF ₂ · bMgO) · γSiO ₂ (where M represents sodium or lithium, α, β,
γ, a and b each represent a coefficient, and 0.1 ≦ α ≦ 2, 2 ≦ β
≦ 3.5, 3 ≦ γ ≦ 4, 0 ≦ a ≦ 1, 0 ≦ b ≦ 1, a + b
= 1. )

As a method for producing such a swellable fluoromica-based mineral, for example, silicon oxide, magnesium oxide, and various fluorides are mixed, and the mixture is heated at a temperature of 1400 to 1500 ° C. in an electric furnace or a gas furnace. There is a so-called melting method in which the mica is completely melted in the range and the fluorine mica-based mineral grows in the reaction vessel during the cooling process.

There is also a method of using talc as a starting material and intercalating an alkali metal ion with the starting material to obtain a swellable fluoromica-based mineral (Japanese Patent Laid-Open No. 2-1494).
No. 15). In this method, talc is mixed with an alkali silicate or an alkali fluoride, and is mixed in a magnetic crucible for about 7 minutes.
By performing a short heat treatment at 00 to 1200 ° C., a swellable fluoromica-based mineral can be obtained.

At this time, the amount of alkali silicate or alkali fluoride mixed with talc is 10 to 35% of the whole mixture.
It is preferable to be within the range of weight%, and if it is out of this range, the production yield of the swellable fluoromica-based mineral is undesirably reduced.

In order to obtain the above-mentioned swellable fluoromica-based mineral, the alkali metal of alkali silicate or alkali fluoride must be sodium or lithium. These alkali metals may be used alone or in combination. In addition, in the case of potassium among alkali metals, a swellable fluoromica-based mineral cannot be obtained, but it can be used in combination with sodium or lithium, and in a limited amount, for the purpose of adjusting the swellability. It is.

Further, in the step of producing the swellable fluoromica-based mineral, it is possible to adjust the swellability of the resulting swellable fluoromica-based mineral by adding a small amount of alumina.

The compounding amount of the layered silicate is as follows.
It is necessary that the amount be 0.01 to 20 parts by weight based on the amount of the monomer forming 00 parts by weight. If the amount is less than 0.01 part by weight, the effect of improving mechanical strength and heat resistance is small. on the other hand,
If the amount is more than 20 parts by weight, the toughness and elongation are undesirably increased.

The aqueous solution of an amine salt of an aminocarboxylic acid having 10 or more carbon atoms or an aqueous solution of a lactam salt (hereinafter referred to as “aqueous organic salt solution”) used in the method of the present invention is an aminocarboxylic acid or a lactam having 10 or more carbon atoms. And a pKa (value in water at 25 ° C.) of 0 to 4 or a negative acid, respectively, obtained by reacting in an equimolar amount in water. Here, as the aminocarboxylic acid or lactam having 10 or more carbon atoms, one having 10 to 30 carbon atoms is preferable, and one having 10 to 20 carbon atoms is more preferable.

Examples of the above aminocarboxylic acids include, for example,
Examples include 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 18-aminostearic acid, and the lactam includes ω-laurolactam.

The above-mentioned acid may be an inorganic acid or an organic acid, such as benzoic acid, sebacic acid, formic acid, acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, nitrous acid, and the like. Nitric acid, phosphoric acid, phosphorous acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, perchloric acid, fluorosulfonic acid-pentafluoroantimony (1: 1) [Aldrich “Magic Acid” (product Name)] and fluoroantimonic acid.

The organic salt aqueous solution is usually reacted with the above-mentioned aminocarboxylic acid or lactam and the above-mentioned acid in water to form a uniform aqueous solution. At this time, the concentration of the organic salt aqueous solution is preferably in the range of 2 to 10% by weight. If the concentration is less than 2% by weight, it becomes necessary to remove a large amount of water during the polymerization of the polyamide monomer, and the production efficiency of the reinforced polyamide resin composition tends to decrease. On the other hand, if the concentration exceeds 10% by weight, it tends to be difficult to obtain a uniform aqueous solution depending on the type of organic salt to be produced.

The amount of the aqueous solution of the organic salt is 0.01 to 5 times the total cation exchange capacity of the layered silicate used.
It is necessary to make the molar amount twice, preferably
The molar amount is 0.5 to 2 times, more preferably 0.9 to 1.1 times. If the amount is less than 0.01 mole, a molded product with high elongation cannot be obtained. On the other hand, if the amount exceeds 5 times the molar amount, a molded article having good mechanical strength and heat resistance cannot be obtained.

In the method of the present invention, the monomers forming the above-mentioned polyamide resin (nylon 6 or a copolymer thereof), a layered silicate and an aqueous solution of an organic salt are mixed within the scope of the present invention, and then the monomers are polymerized. I do. In this case, the polymerization is preferably carried out at a temperature of 240 to 300 ° C. and a pressure of ² to 30 kg / cm ² for 1 to 5 hours. If necessary, after the polymerization is completed, the temperature is maintained at 240 to 300 ° C., the pressure is once returned to normal pressure, and then degassing is performed at a nitrogen pressure of ² to 30 kg / cm ² for 5 minutes to 3 hours. If it does, pellets will not float during hot water scouring, which will be described later.

During the mixing, the pKa (25
When the acid having a value of 0 to 4 or a negative acid in water at 2 ° C. is added in a proportion of 2 mol or less, preferably 1 mol or less with respect to the total cation exchange capacity of the layered silicate used, the toughness and elongation can be improved. A molded product having higher rigidity and higher heat resistance can be obtained without lowering the degree.

Then, the resin composition obtained through the above polymerization and degassing steps is discharged into a strand, cooled, solidified, and cut to obtain a diameter of 2 to 5 mm and a length of 2 to 6 mm.
It is practically necessary to perform scouring in hot water at 90 to 100 ° C. for 5 to 10 hours after making the pellets into mm.

In the reinforced polyamide resin composition obtained by the method of the present invention, the layered silicate is uniformly dispersed at the molecular level in the polyamide resin. here,
Uniformly dispersed at the molecular level means that when the layered silicate is dispersed in the polyamide resin matrix, each is maintained at an average interlayer distance of 20 ° or more. Furthermore, the interlayer distance refers to the distance between the centers of gravity of the phyllosilicate slabs, and the "uniformly dispersed" means that the phyllosilicates are layered in parallel with each other or with an average overlap of 5 layers or less. Alternatively, it refers to a state where 50% or more, preferably 70% or more thereof is dispersed without forming a lump in a state where random and parallel and random are mixed. Specifically, wide-angle X-ray diffraction measurement described later is performed on the chip of the polyamide resin composition, which can be confirmed by the disappearance of the peak due to the thickness direction of the layered silicate.

The reinforced polyamide resin composition obtained by the method of the present invention contains pigments, heat stabilizers, antioxidants, weathering agents, flame retardants, plasticizers, as long as the properties thereof are not significantly impaired.
A release agent and a reinforcing agent other than the layered silicate may be added.

As the heat stabilizer and antioxidant, for example, hindered phenols, phosphides, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and mixtures thereof can be used.

Examples of the reinforcing agent include clay, talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, and the like.
Sodium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate whisker, boron nitride, graphite, glass Fiber, carbon fiber and the like.

These additives are added at the time of polymerization or at the time of melt-kneading or melt-molding the obtained resin composition.

Further, another thermoplastic polymer may be mixed in the reinforced polyamide resin composition obtained by the method of the present invention. Examples of such a thermoplastic polymer include polyamides other than nylon 6 or a copolymer thereof, specifically, polytetramethylene adipamide (nylon 46) and polyhexamethylene adipamide (nylon 6
6), polyhexamethylene sebacamide (nylon 61
0), polyhexamethylene dodecamide (nylon 61
2) Polyundecamethylene adipamide (nylon 11
6), polyundecamide (nylon 11), polydodecamide (nylon 12), polytrimethylhexamethylene terephthalamide (nylon TMHT), polyhexamethylene isophthalamide (nylon 6I), polyhexamethylene terephthal / isophthalamide (nylon 6T / 6I), Polybis (4-aminocyclohexyl) methane dodecamide (nylon PACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (nylon dimethyl PACM12), polymetaxylylene adipamide (nylon
MXD6), polyundecamethylene terephthalamide (nylon 11T), polyundecamethylene hexahydroterephthalamide (nylon 11T (H)), etc.
Elastomers such as butadiene / styrene copolymer, acrylic rubber, ethylene / propylene copolymer, ethylene / propylene / diene copolymer, natural rubber, chlorinated butyl rubber, chlorinated polyethylene, and acid-modified products of these with maleic anhydride and the like Styrene / maleic anhydride copolymer, styrene / phenylmaleimide copolymer, polyethylene, polypropylene, butadiene / acrylonitrile copolymer, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyvinylidene fluoride, polysulfone, polyphenylene sulfide , Polyether sulfone, phenoxy resin,
Polyphenylene ether, polymethyl methacrylate,
Examples include polyether ketone, polycarbonate, polytetrafluoroethylene, and polyarylate.

The pellets obtained by the method of the present invention are:
The desired molded product can be obtained by a normal molding method. For example, injection molding, extrusion molding, blow molding, hot-melt molding methods such as sintering and casting from organic solvent solutions,
A method of forming a thin film can be adopted.

Further, the molded article obtained by using the pellets obtained by the method of the present invention has remarkably improved mechanical strength, heat resistance and dimensional stability as compared with the case of using the polyamide resin alone, Little change in mechanical properties and dimensions. Due to their excellent performance, these molded products are mechanical parts and housings such as switches and connectors in the field of electric and electronic equipment, underbonnet parts and exterior parts in the automotive field, optical parts such as outer panel parts and reflectors, etc. Alternatively, it is used as a gear or a bearing retainer in the mechanical field.

[0037]

Next, the present invention will be described more specifically with reference to examples. In addition, the measuring method of the raw material and physical property test used in the Examples and Comparative Examples is as follows. 1. Raw materials (1) Swellable fluoromica mineral Mineral talc ground by a ball mill to have an average particle diameter of 4 μm was mixed with sodium silicate having the same average particle diameter of 4 μm so that the total amount would be 15% by weight. This was put in a magnetic crucible and reacted in an electric furnace at 850 ° C. for 1 hour to synthesize. The powder was subjected to wide-angle X-ray diffraction measurement. As a result, the thickness of the raw material talc in the c-axis direction was 9.2.
The peak corresponding to Å disappeared, and a peak corresponding to 12 to 16 示 す indicating the formation of a swellable fluoromica-based mineral was observed. The cation exchange capacity was 70 meq / 100 g. (2) Montmorillonite Natural montmorillonite (Na-layer ion type) from Yamagata Prefecture, manufactured by Kunimine Industries, Inc. Cation exchange capacity: 115 meq / 100g (3) Hectorite Synthetic hectorite (Li interlayer ion type), Topy Industries Cation exchange capacity: 80 meq / 100 g (4) Vermiculite Synthetic vermiculite (Li interlayer ion type), manufactured by Topy Industries, Inc. Cation exchange capacity: 160 meq / 100 g

2. Measurement method (a) Dispersibility of swellable fluoromica-based mineral Using a pellet of a reinforced polyamide resin composition, measurement was performed with a wide-angle X-ray diffractometer (Rigaku, RAD-rB type). (b) Cation exchange capacity (milliequivalent / 100 g) Determined by the method of Frank O. Jones Jr. [Clay Handbook (2nd edition), page 587, Gihodo Shuppan Co., Ltd., 1987]. That is, an aqueous solution of a 2% by weight layered silicate 50 m
1, 15 ml of 3% by weight aqueous hydrogen peroxide and 0.5 m of 5N dilute sulfuric acid
Boil gently in a 250 ml flask for 10 minutes.
After cooling the solution, 0.5 ml of a 1 / 100N methylene blue solution is added at a time, and shaken well for 30 seconds. Then, a drop of the sample is taken from the flask with a glass rod and placed on the filter paper to check whether a bright blue ring appears around the dark blue spot. At this time, if a bright blue ring appears, shake for 2 minutes. This operation is repeated, and finally, a stage where no bright blue ring appears even after shaking for 2 minutes is determined as an end point. The cation exchange capacity was determined by the following equation. Cation exchange capacity (milli-equivalent / 100 g) = addition amount of methylene blue (milli-equivalent) × 100 / laminar silicate used (g) Further, the swellable fluoromica-based mineral and montmorillonite are each of the Na interlayer ion type, Since hectorite and vermiculite are each of the ionic type between the Li layers, the cation exchange capacity is 1 meq / 100 g =
This corresponds to 1 mmol / 100 g. (c) Tensile strength, tensile modulus and elongation at break Measured based on ASTM D-638. (d) Flexural strength and flexural modulus Measured based on ASTM D-790. (e) Izod impact strength Based on ASTM D-256, a 3.2 mm thick test piece was measured with a notch of a predetermined depth. (f) Heat deformation temperature Measured under a load of 1.86 MPa based on ASTM D-648.

Example 1 10 kg of ε-caprolactam and a swellable fluoromica-based mineral 200
g (total cation exchange capacity corresponds to 0.14 mol) at 80 ° C. in an autoclave. To this mixture, an aqueous solution of amine hydrochloride of 12-aminododecanoic acid [30 g of 12-aminododecanoic acid (0.14
Mol) and 14 g (0.14 mol) of 36% by weight hydrochloric acid in 1 kg of water.
Aqueous solution made homogeneous by reaction at 80 ° C., concentration of amine hydrochloride of 12-aminododecanoic acid: 3.3% by weight] was added. Next, the mixture was heated to 260 ° C. while stirring, and the pressure was increased to 10 kg / cm ² . Then, while gradually releasing the water vapor, polymerization was carried out for 2 hours while maintaining the pressure at 10 kg / cm ² and the temperature at 260 ° C., and then the pressure was released to normal pressure over 1 hour, and then 30 minutes.
After polymerization for 1 minute, the mixture was degassed at 260 ° C. under a nitrogen pressure of 7 kg / cm ² for 1 hour. When the polymerization and degassing were completed, the reaction product was discharged in a strand, cooled, solidified, and cut to obtain a chip made of a reinforced nylon 6 resin composition. Next, this chip was scoured with hot water of 95 ° C. for 8 hours, and then dried under vacuum to obtain a chip for molding. Next, using a twin-screw extruder (PCM-45 type, manufactured by Ikegai Iron Works Co., Ltd.), the chip temperature was 260 ° C, the mold temperature was 70 ° C, and the injection time was 6 hours.
Injection molding was performed in seconds and a cooling time of 6 seconds to produce a 3.2 mm thick test piece, which was subjected to a physical property test.

Examples 2 to 4 Chips of a reinforced nylon 6 resin composition were obtained in the same manner as in Example 1 except that the acids shown in Table 1 were used instead of the 36% by weight hydrochloric acid. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests.

The results in Examples 1 to 4 are summarized in Table 1.

[0042]

[Table 1]

Examples 5 to 8 A chip of a reinforced nylon 6 resin composition was obtained in the same manner as in Example 1 except that the aminocarboxylic acid or lactam shown in Table 2 was used instead of 12-aminododecanoic acid. Was. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests.

The results in Examples 5 to 8 are summarized in Table 2.

[0045]

[Table 2]

Example 9 Example 1 was repeated except that 21 g (0.21 mol) of 36% by weight hydrochloric acid was used.
In the same manner as in the above, a chip of a reinforced nylon 6 resin composition was obtained. Using these chips, the thickness was determined in the same manner as in Example 1.
A 3.2 mm test piece was prepared and subjected to a physical property test.

Comparative Example 1 A chip of a reinforced nylon 6 resin composition was obtained in the same manner as in Example 1 except that 12-aminododecanoic acid was not used. Using these chips, a thickness of 3.2 mm was obtained in the same manner as in Example 1.
Was prepared and subjected to a physical property test. The elongation at break was lower than that of Example 1.

Comparative Example 2 A reinforced nylon 6 resin composition chip was obtained in the same manner as in Example 1 except that 36% by weight of hydrochloric acid was not used. Using these chips, a test piece having a thickness of 3.2 mm was prepared in the same manner as in Example 1 and subjected to a physical property test. The elongation at break was lower than that of Example 1.

Comparative Example 3 10 kg of ε-caprolactam, swellable fluoromica-based mineral 200
g (total cation exchange capacity corresponds to 0.14 mol), 12
30 g (0.14 mol) of aminododecanoic acid and 36% by weight hydrochloric acid
14 g (0.14 mol) were simultaneously charged into an autoclave, and the other conditions were the same as in Example 1 to obtain chips of a reinforced nylon 6 resin composition. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests. The elongation at break was lower than that of Example 1.

Table 3 summarizes the results of Example 9 and Comparative Examples 1 to 3.

[0051]

[Table 3]

Example 10 10 kg of ε-caprolactam and 200 g of montmorillonite (total cation exchange capacity is equivalent to 0.23 mol) were placed at 80 ° C.
And mixed in an autoclave. To this mixture, an aqueous solution of amine hydrochloride of 12-aminododecanoic acid prepared in advance [49.5 g (0.23 mol) of 12-aminododecanoic acid and
Aqueous solution obtained by reacting 23 g (0.23 mol) of 36% by weight hydrochloric acid in 1 kg of water at 80 ° C., concentration of amine hydrochloride of 12-aminododecanoic acid: 6.0% by weight] 1052 g was added. Next, a chip of a reinforced nylon 6 resin composition was obtained in the same manner as in Example 1 using the above mixed solution. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests.

Example 11 10 kg of ε-caprolactam and 200 g of hectorite (total cation exchange capacity corresponds to 0.16 mol) were heated at 80 ° C.
And mixed in an autoclave. To this mixed solution, an aqueous solution of amine hydrochloride of 12-aminododecanoic acid prepared in advance [34 g (0.16 mol) of 12-aminododecanoic acid and 36
An aqueous solution made uniform by reacting 16 g (0.16 mol) of hydrochloric acid at 80 ° C. with 1 kg of water at 80 ° C., the concentration of amine hydrochloride of 12-aminododecanoic acid: 3.8 wt%] (1050 g) was added. Next, a chip of the reinforced nylon 6 resin composition was obtained in the same manner as in Example 1 for the above mixed solution. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests.

Example 12 10 kg of ε-caprolactam and 200 g of vermiculite (total cation exchange capacity corresponds to 0.32 mol) were heated at 80 ° C.
And mixed in an autoclave. To this mixture was added previously prepared aqueous solution of amine hydrochloride of 12-aminododecanoic acid [68 g (0.32 mol) of 12-aminododecanoic acid and 36
1 g of an aqueous solution obtained by reacting 32 g (0.32 mol) of hydrochloric acid at 80 ° C. with 1 kg of water at 80 ° C., the concentration of amine hydrochloride of 12-aminododecanoic acid: 7.2% by weight] was added. Next, a chip of the reinforced nylon 6 resin composition was obtained in the same manner as in Example 1 for the above mixed solution. Using these chips, test pieces having a thickness of 3.2 mm were prepared in the same manner as in Example 1 and subjected to physical property tests.

The results in Examples 10 to 12 are summarized in Table 4.

[0056]

[Table 4]

The results of wide-angle X-ray diffraction measurement of the chips in Examples 1 to 9 and Comparative Examples 1 to 3 were as follows.
In each case, the peak (12 to 16 mm) in the thickness direction of the swellable fluoromica-based mineral completely disappeared, and nylon 6
It was found that the swellable fluoromica-based mineral was uniformly dispersed at the molecular level in the resin matrix.

[0058]

According to the method of the present invention, the polyamide resin and the layered silicate are uniformly dispersed at the molecular level, and have high strength, high elastic modulus, high heat resistance, high toughness and high elongation. A reinforced polyamide resin composition can be obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Izumi Yoshida 23 Uji Kozakura, Uji-city, Kyoto Pref.

Claims (3)

[Claims] 1. A layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g based on 100 parts by weight of a polyamide resin (nylon 6 or a copolymer thereof).
0.01 to 20 parts by weight of an aqueous solution of an amine salt or a lactam salt of an aminocarboxylic acid having 10 or more carbon atoms in an amount of 0.01 to 5 moles per mole of the total cation exchange capacity of the layered silicate are mixed to form a monomer. A method for producing a reinforced polyamide resin composition, characterized by polymerizing. 2. The method according to claim 1, wherein at the time of mixing, an acid having a pKa (value in water at 25 ° C.) of 0 to 4 or a negative acid is added to the cation exchange capacity of the layered silicate twice or less. The method for producing a reinforced polyamide resin composition according to claim 1. 3. The method according to claim 1, wherein the concentration of the aqueous solution of the amine salt of the aminocarboxylic acid having 10 or more carbon atoms or the aqueous solution of the lactam salt is 2 to 10% by weight. A method for producing a polyamide resin composition.