JPH0450228A - Production of smectite-containing nylon composition and the same composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in transparency, tensile and flexural elastic modulus and heat resistance and useful as automotive parts by heating a gelatinous aqueous dispersion containing water-swellable smectite under dehydrating conditions in an inert atmosphere. CONSTITUTION:A homogenous gelatinous aqueous dispersion containing (A) water-swellable smectite and (B) nylon monomer is prepared and then heated under dehydrating conditions in an inert atmosphere to polymerize the component (B). Thereby, the objective composition is obtained. Furthermore, the aforementioned composition preferably contains 0.1-5.0wt.% component (A). The amount of the component (A) is preferably 0.01-80 pts.wt. based on 100 pts.wt. component (B). The component (A) is preferably synthetic stevensite having 20-160mequiv./100g ion exchange capacity and 16-26Angstrom spacing in a state treated with ethylene glycol.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a smectite clay mineral-containing nylon composition and a method for producing the same, and more specifically to a method for producing a nylon monomer through a gel-like aqueous dispersion of water-swellable smectite. The present invention relates to a smectite-containing nylon composition with excellent mechanical strength and heat resistance obtained by polymerizing the same, and a method for producing the same.

(Prior art) Nylon such as nylon 6 is a typical engineering material because its molded products have excellent mechanical properties.
Plastics (hereinafter referred to as engineering plastics) are widely used as injection molding materials for parts such as automobiles and electrical products.

However, the above-mentioned nylons are not necessarily fully satisfied in terms of rigidity, impact resistance, and heat resistance. Therefore, in order to reinforce and improve the mechanical strength and heat resistance of organic polymer materials, The addition of inorganic fillers or reinforcing agents such as calcium, finely divided silicic acid, silica, and clay minerals has been considered.

Recently, even so-called engineering plastics are required to have more advanced properties, and simply mixing inorganic materials mechanically or mechanically does not provide sufficient reinforcing effect or property improvement. Even if the surface is treated with a camping agent to improve the affinity with the organic polymer of the base material, the compatibility between the two will be slightly improved, and the inorganic material will be uniformly and evenly dispersed in the base material. The purpose of improving the reinforcing effect and heat resistance by integrating the two as closely as possible has not yet been fully satisfied.

In addition, in order not to impair the toughness of the base material, there is a limit to the amount of inorganic materials that can be blended, and it is important to find a way to disperse the minimum amount of additives finely and uniformly into the base material. This seems to be the point.

In order to solve these problems and improve the integrity of the compounding agent and the base material, organic montmorillonite, which is made by intercalating organic substances such as amines, carboxylic acids, and alcohols between the eyebrows of layered clay minerals, is used as a compounding agent. It has been proposed to use nylon and mix it with nylon (Japanese Patent Application Laid-Open No. 62
-74957, JP-A-62-252426, JP-A-62-252425, and JP-A-2-29457).

(Problems to be Solved by the Invention) The montmorillonite-containing nylon composition proposed above uses organic montmorillonite, which is intercalated with an organic substance to widen the glabella of montmorillonite, in order to uniformly disperse montmorillonite in the nylon monomer. However, this aims to improve the dispersibility of montmorillonite in the base material and improve its properties as an engineering plastic.

It is true that in the mixed system of organic montmorillonite and nylon monomer proposed above, the interlayers are expanded and it is true that nylon
It is thought that the monomer easily penetrates between the layers, and as a result, the montmorillonite particles are stabilized in the base material, and the compatibility between the two becomes better, and the degree of monodispersion reaches a high level.

However, even if the montmorillonite particles are swollen with an organic substance in advance to improve their compatibility with the base material, if the montmorillonite particles themselves are not finely divided, the dispersion of the two cannot be said to be at the molecular level.

As a result of intensive studies to solve the above problems, the present inventors found that the water-swellable smectite clay mineral becomes a transparent gel-like aqueous dispersion in an aqueous medium, and that the layered clay mineral in this system is Noting that it is dispersed at least at the basic crystallite level (hereinafter referred to as the heavy molecule level),
It has been found that when a nylon monomer is polymerized in an aqueous system using this dispersion, a smectite clay-containing nylon composition having an extremely uniform and finely dispersed state can be obtained.

An object of the present invention is to provide a smectite clay-containing nylon composition in which smectite clay, which is a layered mineral, is dispersed at the basic crystallite level in a nylon matrix and has excellent mechanical strength and heat resistance, and a method for producing the same. be.

Another object of the present invention is that smectite clay minerals, particularly synthetic stevensite and specific magnesium and potassium phyllosilicates, form an aqueous dispersion with excellent transparency and water swelling properties, and that nylon monomer is added to this aqueous dispersion. The object of the present invention is to provide a method for producing a smectite clay-containing nylon composition having the above characteristics by utilizing dissolution.

(Means for Solving the Problem) The present inventors have discovered that water-swellable smectite is extremely well dispersed in an aqueous medium, and that in the dispersion system, layered molecules of smectite particles with a low stacking degree form a house of cards. By utilizing the fact that nylon monomer is dispersed at a quasi-molecular level as a gel, and the nylon monomer is dissolved homogeneously in this aqueous dispersion system at a high concentration, both of them form a stable dispersion system at a quasi-molecular level. It has been found that when nylon is polymerized in a dispersion system, a smectite clay-containing nylon composition having an extremely uniform and finely dispersed state can be obtained.

That is, according to the present invention, a homogeneous gel-like aqueous dispersion containing water-swellable smectite and a nylon monomer is prepared, and the gel-like aqueous dispersion is heated under dehydration conditions in an inert atmosphere to remove the nylon monomer. A method of polymerizing a smectite clay-containing nylon composition is provided.

The present invention also provides a smectite-containing nylon composition comprising a nylon matrix and smectite dispersed therein, wherein the smectite is a water-swellable magnesium phyllosilicate salt, and the water-swellable magnesium phyllosilicate salt is a nylon 100 smectite-containing nylon composition. 0.0 per part by weight
There is provided a nylon composition, characterized in that it is dispersed at the molecular level in nylon in an amount of 1 to 80 parts by weight. In the present invention, the water-swellable smectite clay mineral is prepared by preparing a homogeneous gel-like aqueous dispersion containing the water-swellable smectite clay mineral, and then heating the gel-like aqueous dispersion under dehydrating conditions in an inert atmosphere to polymerize the nylon monomer. The selection of inorganic fillers is based on the fact that they are uniformly, finely and stably dispersed in an aqueous medium to form a transparent gel-like aqueous dispersion, and that nylon monomers are added to this system. When incorporated, the nylon monomer dissolves in the system without destroying the stable dispersion state of the smectite clay mineral, and this state is stably maintained throughout the polymerization process of the nylon monomer. Thus, according to the present invention, by using this dispersion to polymerize nylon monomer in an aqueous system, a smectite clay-containing nylon composition having an extremely uniform and fine dispersion state, that is, smectite clay, which is a layered mineral, is the basis. A smectite clay-containing nylon composition is obtained which is dispersed in a nylon matrix at the crystallite level and has excellent mechanical strength and heat resistance.

Smectite clay minerals are typical layered minerals, generally three layers in which two 5in4 tetrahedral layers are sandwiched between an octahedral layer of metal oxide, such as an MgO6 octahedral layer or an AlO2 octahedral layer. This basic structure forms a multilayer crystal structure in which layers are stacked in the C-axis direction.

This space between the eyebrows of crystallites, that is, the space between the basic three-layer structures of adjacent crystallites, is easy to incorporate other molecules, and in water-swellable smectite clay minerals, the degree of stacking of this basic three-layer structure is small, and the size of the crystallites is small. is small, and a large amount of water molecules are incorporated between the layers of the basic three-layer structure, and flaky crystallites are dispersed in the aqueous medium, and these crystallites rearrange in water to form a so-called house-of-card gel. form. This is the reason why the dispersion state of water-swellable smectite clay minerals in aqueous media is based on crystallites, which can be called quasi-molecular size, and is fine and stable. In particular, synthetic smectite and microcrystalline smectite have a small thickness in the C-axis direction, weak interaction between laminated layers, and low regularity, so that an ideal dispersion state can be obtained.

In the present invention, a good dispersion state is obtained by finely dispersing smectite in an aqueous medium and well dissolving the nylon monomer in this aqueous medium. It is believed that there is a special interaction between the nylon monomer and the nylon monomer in the aqueous medium. In other words, smectite basically has the three-layer structure described above, but there are isomorphic substitutions in the tetrahedral and octahedral layers.
In order to compensate for the lack of valence due to this isomorphic substitution, -valent or divalent cations are coordinated. On the other hand, nylon has an amide group in its molecule, and the carbonyl in this amide group is negatively polarized. It is thought that physical bonding or ionic coordination occurs. This is the reason why the aqueous dispersion used in the present invention has excellent stability and maintains a finely dispersed state throughout the polymerization process.The smectite clay-containing nylon composition of the present invention has excellent mechanical strength and heat resistance. In particular, the bending strength under heating is significantly improved.

This is thought to be because the aforementioned dispersed structure of smectite and nylon monomer in the aqueous dispersion is brought into the nylon composition after polymerization almost unchanged. That is, it seems that the dispersion of smectite in crystallite size and the ionic interaction between smectite and nylon are maintained in the nylon composition.

In the present invention, it is preferable to use the smectite clay mineral in an amount of 0.01 to 80 parts by weight, preferably 0.0!5 to 80 parts by weight, based on 100 parts by weight of the nylon monomer. If it is less than .01 part by weight, the improvement in mold releasability, rigidity, and heat resistance will not be significant;
If the amount exceeds 0 parts by weight, a homogeneous gel-like aqueous dispersion containing the nylon monomer cannot be obtained, and smectite clay particles as an inorganic filler are not added to the nylon polymer as an inorganic filler on the order of the molecular level. It is difficult to disperse the

(Preferred III of the Invention) Water-swellable smectite clay mineral The water-swellable smectite clay mineral used in the present invention is such that it is dispersed in the basic crystallite size particles of smectite clay in an aqueous dispersion system; When mixed, a gel-like aqueous dispersion with excellent transparency and thickening properties is formed, so that suitability can be determined. Natural minerals or synthetic minerals may be used as long as they pass this criterion, but synthetic minerals are more preferable because they are less likely to be contaminated with impurities.

Water-swellable smectite clay minerals include, but are not limited to, synthetic stevensite, synthetic hectorite, synthetic savonite, and magnesium potassium phyllosilicate as stevensite-like minerals, as 3-octahedral smectites.

Examples of 2-octahedral smectites include activated bentonite purified montmorillonite, which all have large water-swelling ability, gel-forming ability, and the ability to clathrate organic and inorganic compounds.

Among the above-mentioned water-swellable synthetic smectites, there are synthetic stevensite (Japanese Patent Application Laid-Open No. 190705) whose nine compositions were previously proposed by the present inventor and are composed of simple metal elements of silicon, magnesium, and sodium; Synthetic magnesium/potassium phyllosilicate using potassium component instead of sodium (Unexamined Japanese Patent Publication No. 01-908
No. 18) is preferably used.

(a) Synthetic stevensite This stevensite type magnesium sodium phyllosilicate has the formula % formula % (2) where X and y are z + y (under the condition of 3, X is a number of 2 or more.

y is a number from 0 to 0.1.

2 is a number greater than O and up to 1.0.

This synthetic stibsite is MgO6 from the above formula (2).
A portion of the Mg atoms in the octahedral layer are replaced with Na, and the remaining portion is vacant. To compensate for this lack of charge, 5
i04 tetrahedral layer-Mg(Na)Oa octahedral layer-5i04
Na ions are present between the laminated layers of the basic layer structure consisting of tetrahedral layers.

This synthetic stevensite is determined by the X-ray diffraction method described below, and has a diameter of 50 to 300 A, particularly 100 to 2 A, in the b-axis direction.
It has a crystallite size of 00A. In addition, this synthetic steven site has a cation exchange capacity of 20 to 160 meq/lo due to the presence of Na ions mentioned above.
in the range of ng. Furthermore, this synthetic stevensite is
The spacing is 16 when measured with ethylene glycol treatment.
It has X-ray diffraction peaks at 26A to 26A.

The above synthetic stevensite is made by combining basic magnesium carbonate represented by hydromagnesite represented by the following formula % (3) and sodium silicate or sodium hydroxide (with an atomic ratio of Si of 3). to 5:
The aqueous mixture mixed to have a concentration of 100 to 30
It is obtained by subjecting it to hydrothermal treatment at a temperature of 0°C, especially 15°C to 200°C.

(b) Synthetic magnesium/potassium phyllosilicate On the other hand, synthetic magnesium/potassium phyllosilicate generally has the formula % formula % (4) where y is a number from 0 to 0.2, and X is the formula 2 y'i: It is a number that satisfies x > y, and n is a number larger than zero.

It has the composition represented by.

These phyllosilicates generally contain 20 meq/1
00 g or more, especially 30 to 100 milliequivalents/100
The cation exchange capacity is generally 50 to 300 A, particularly 100 to 2 A, as determined by X-ray diffraction.
It has a fine axial crystallite size like 0OA, and the degree of lamination in the C-axis direction is small.

Synthetic magnesium potassium phyllosilicate (hereinafter simply referred to as PSMK), which is advantageously used in the present invention, apparently corresponds to a phyllosilicate in which sodium in stevensite is replaced with potassium, but compared to sodium, In connection with the large ionic radius of potassium, unlike stevensite, the potassium component has a chemical structural feature in that substantially all of the potassium components exist between layers. The aqueous dispersion forms a gel-like aqueous dispersion that is transparent and has excellent thickening properties, just like the synthetic stevensite described above.

Since this PSMK contains potassium ions with a large ionic radius between the basic layers, it exhibits ion exchange and ion adsorption properties for various cations, and has a relatively large cation exchange capacity, so it is suitable for nylon monomers. It is advantageous for homogeneous dispersion in aqueous media.

Furthermore, since this PSMK is a fine layered compound with a small crystallite size, it is also characterized by a large BET specific surface area of 350 to 600 2/g.

The above synthetic PMSK uses an aqueous mixture of basic magnesium carbonate and potassium silicate or potassium hydroxide so that the atomic ratio of Mg:Si is substantially 3=7 to 6:4. It can be synthesized in exactly the same manner as synthetic stevensite. The resulting PMSK powder becomes a homogeneous gel-like aqueous dispersion containing nylon monomer, similar to synthetic stevensite.

(c) Synthetic hectorite In the present invention, synthetic hectorite can also be effectively used.

As such synthetic hectorite, for example, JP-A-81-
Although it is possible to use hectorite that does not contain fluorine ions, it is preferable to use hectorite that does not contain fluorine ions, that is, as disclosed in JP-A-02-48410, the metal component is substantially magnesium, silica, etc. , consisting of sodium and lithium, substantially of the following formula, aNa20(bMgocLi20) [8SiO2]
nH2O...a, b, c and n in formula (5)
is the formula 0 < a < 2, 4 < b < 6,
It is preferable to use a 3-octahedral smectite clay mineral with excellent water swelling properties, which is a number satisfying O<c<1 and n≧2.

This synthetic hectorite has a cation exchange capacity of 20 milliequivalents/100 g or more, has fine crystal particles, a crystallite size in the b-axis direction of 200 A or less, and is a gel-like aqueous dispersion with excellent transparency and thickening properties. It can be used to form homogeneous gel-like aqueous dispersions with nylon monomers.

(d) Synthetic sabonite In the present invention, synthetic sabonite can also be effectively used.

The synthetic sabonite that can be effectively used in the present invention is
2-48411, in which the metal component substantially consists of magnesium, aluminum, silicon and sodium components, and has the following formula, aNa20(6MgO)
(bsio2cA1203) nH,0...(9)
a, b, c and n in the formula are the formula 0<a<2゜6
< b < 8, c = (b −6) /
2 and n≧2.

It is a 3-octahedral water-swellable smectite clay mineral having the composition shown below. Although the octahedral layer in this saponite does not contain a lithium component like the synthetic stevensite described above, it is characterized in that a portion of the silicic acid in the tetrahedral layer is isomorphically substituted with alumina.

This synthetic sabonite also has excellent water-swelling properties and becomes a transparent gel-like aqueous dispersion with strong thickening properties.

Also, you win 20 millimeters! It has a cation exchange capacity of /100 g or more, a crystallite size of 200 A or less in the b-axis direction, and forms a homogeneous gel-like aqueous dispersion with nylon monomers like other smectites.

Smectite-containing nylon composition and method for producing the same According to the present invention, an aqueous dispersion containing a water-swellable smectite and a nylon monomer is prepared.

The order of preparation of the aqueous dispersion is not particularly limited, but it is generally preferable to disperse the water-swellable smectite clay in water and dissolve the nylon monomer in this aqueous dispersion.The ratio of the two is also not particularly limited, but The smectite clay was dispersed at a concentration of 0.1 to 5.0% by weight, and a gel-like aqueous dispersion was prepared by mW&S.
．． It is preferable to mix in a range of 0.01 to 50 parts by weight.

The aqueous dispersion of smectite clay is a fairly viscous gel, but since this gel has thixotropic properties, the nylon monomer can be well dispersed by mixing by stirring.

Although the preparation of aqueous dispersions is generally carried out at room temperature.

If desired, heating is performed to increase solubility,
Alternatively, it can also be carried out under cooling.

In order to reliably maintain the fine and finely dispersed state of nylon and smectite clay from the monomer stage to the polymerization completion stage, alkali ions in this gel-like dispersion form an ionic bond or ionic interaction between the two. The concentration should be maintained such that . For this, the amount of alkali ions in the dispersion is adjusted to M 20 / 51
02 molar ratio (M represents an alkali metal) is preferably in the range of 0.56 to 0.097; if it is less than the above range, the dispersion stability may be impaired in the polymerization stage. If the amount exceeds the above range, the final nylon composition will have poor chemical stability, weather resistance, etc. If there are sufficient alkali ions in the raw material smectite clay, of course you can use them, but if they are insufficient, you can use them with alkali metal hydroxides such as KOH, NaOH, etc.
Alternatively, carbonate may be added in the form of monocarbonate. Furthermore, if the amount is in excess, the generated @ may be removed by washing with water after neutralization with an acid if necessary.

Any nylon monomer that is water-soluble and polymerizable can be used. The nylon monomer may be any of lactams, ω-aminocarboxylic acids, or nylon salts, and these may be used alone or in combination of two or more.

Generally, caprolactam is used alone or in combination with other monomers or in combination with oligomers.

According to the invention, a homogeneous aqueous mixture containing smectite and nylon monomer is heated under dehydrating conditions in an inert atmosphere to polymerize the nylon monomer. By maintaining the inside of the container containing the aqueous mixture under reduced pressure or vacuum, the polymerization atmosphere can be made inert and in which water can easily evaporate. In order to promote the evaporation of water, an inert gas such as nitrogen can be passed as a carrier gas.6 The mixture may be polymerized while it is left standing in the polymerization container, or it may be polymerized while being stirred. Polymerization conditions are not particularly limited to I11, but generally 200 to 26
The reaction is preferably carried out at a temperature of 0° C. for 15 to 20 hours.

Of course, the polymerization can also be carried out in two stages, such as ordinary melt polymerization and solid phase polymerization.

A purified smectite-containing nylon composition is obtained by crushing or pulverizing the obtained polymer, then removing unreacted nylon monomers and contaminating alkali ions with hot water, and drying under reduced pressure or N2 atmosphere. .

According to the present invention, a composition in which nylon as a base material and smectite clay crystallites are stably dispersed with each other at a quasi-molecular level can be obtained. Another advantage is that even if a homogeneous gel-like aqueous dispersion is directly polymerized, a homogeneous composite composition can be easily obtained without stirring.

(Applications of smectite-containing nylon composition) The smectite-containing nylon composition according to the present invention has excellent transparency, tensile and flexural elasticity due to containing smectite clay in a uniform and finely dispersed form with crystallite size. It has excellent heat resistance, heat resistance, etc., and also has excellent anti-blocking properties. When this composition is formed into a film by a method known per se, a nylon film excellent in the various properties mentioned above can be obtained.

Further, the composition can be used to produce various molded products by injection molding, extrusion molding, compression molding, and the like. Further, this composition may be mixed in advance with other polymers such as polyamides, and other polyamide resins include b-aminocaproic acid, E-enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9 -Amylinanic acid, α
- Polymers or copolymers obtained from hyloridone, α-piperidone, etc.: hexamethylene diamine, nonamethylene diamine, undecamethylene diamine.

Diamines such as dodecamethylene diamine and metaxylylene diamine, and terephthalic acid and isophthalic acid.

Examples include polymers or copolymers obtained by polycondensation with dicarboxylic acids such as adipic acid and sebacic acid, and blends thereof.

Furthermore, other resins that can be used as a mixture include polypropylene, ABS resin, polyphenylene oxide,
Examples include polycarbonate, polyethylene terephthalate, and polybutylene terephthalate.

In addition to the smectite clay mineral used in the present invention, glass fibers and carbon fibers are used in order to improve the dimensional stability 9 mechanical properties and thermal properties of the molded body.

Gypsum whiskers Fibrous inorganic fillers such as fibrous silica salts, ceramic whiskers such as silicon nitride and potassium titanate, and carbonaceous and finely divided silicic acid.

Finely powdered aluminum silicate or the like can also be used as a filler.

In addition to the above-mentioned components, the composition of the present invention may also contain dyes, pigments, moldability improvers, plasticizers, heat resistance improvers, blowing agents, flame retardants, antistatic agents, etc., depending on the intended use. I can do it.

Furthermore, the smectite used in the present invention has a large specific surface area and, as a layered clay mineral, has properties such as ion exchange properties, inclusion properties, and adsorption properties. Antistatic agent, antifogging agent, ultraviolet absorber.

Antioxidant, insect repellent, insect repellent, antibacterial agent, 1! ! fee.

It can also be used by supporting organic components such as colorants and medicinal components.

For such uses, the content of the smectite-containing nylon composition according to the invention is preferably 70% by weight or more.

(Effects of the Invention) According to the present invention, water-swellable smectite and nylon monomer are dispersed in an aqueous medium, and the nylon monomer is polymerized in the form of this aqueous dispersion. It is possible to maintain a uniform and finely dispersed state with a heavy molecular size of .

The smectite-containing nylon composition according to the present invention has excellent transparency, tensile and flexural modulus, heat resistance, etc. because it contains smectite clay in a uniform and finely dispersed form with crystallite size. It also has excellent anti-blocking properties.

Implementation M1 Synthetic stevensite and synthetic magnesium phyllosilicate as water-swellable smectite clay minerals used in the present invention.
The production methods and properties of potassium, synthetic hectorite 2 synthetic sabonite, and activated bentonite are described below.

Synthetic stevensite Synthetic stevensite was prepared as follows in accordance with Japanese Patent Application Laid-Open No. 83-190705, which was previously proposed by the present inventors.

Commercially available basic magnesilate carbonate hydromagnesite z 9 g (12 g as MgO) and No. 3 sodium silicate 1
08 g (24 g as Sin) and 300 m÷ of water were placed in a 2181 beaker and stirred to form a homogeneous dispersed slurry.

This dispersed slurry was placed in an autoclave and stirred for 17 minutes.
Hydrothermal treatment was performed at 0°C for 5 hours. After the reaction is complete, filter
After drying, 90 g of white powder of synthetic stevensite (sample No. 5-1) was obtained.

This synthetic stevensite has a cation exchange capacity of 36 meq/100 g and a BET specific surface area of 470 2/100 g.
g, and the crystallite size in the b-axis direction was 135A.

PSMK Hiro Same 4 Patent Application Hei 01-90818 of the present inventors
It was prepared as follows according to No.

27 g of commercially available hydromagnesite (11 g as 0 in 1'l) and 125 g of potassium silicate aqueous solution (K2O
A homogeneous slurry of 5-25 gt as 5102 (24 g as 5102) and 700 *S[t, as sample No. 1
Hydrothermally treated in the same manner as in -1 to obtain a white powder of synthetic magnesium potassium phyllosilicate (sample No. S-2).
48g of the product was obtained.

This PSMK has a cation exchange capacity of 44 meq/10
0g, the BET specific surface area was 370127g, and the crystallite size in the b-axis direction was 162A.

Δ Hectorite Synthetic hectorite was also developed by the present inventors in Japanese Patent Application Laid-open No. 2002-02-
48410, hydrothermal treatment was performed in the same manner as Sample No. 1-1, except that commercially available hydromagnesite, No. 3 sodium silicate, and lithium hydroxide were used as raw materials to synthesize white powder. ctolite (sample No. 5-3) was obtained.

This synthetic hectorite had a cation exchange capacity of 52 meq/100g, a BET specific surface area of 250 s2/g, and a crystallite size in the b-axis direction of 143A.

The synthetic sabonite on gold and silver is also disclosed in Japanese Unexamined Patent Application Publication No. 02-02-4 by the present inventors.
It was prepared as follows in accordance with Japanese Patent No. 8411.

111 g of commercially available No. 3 sodium silicate solution (Sin,
After cooling, add 106 g of water to make 1 (Liquid A), and then dilute 24 g of sodium aluminate (87 g as A120.) with water in the same way to make 190 ml ( Solution B) and then A under cooling.
Solution B was added to the solution to obtain a transparent solution C.

Next, 5 g of the remaining No. 3 sodium silicate was added to the hydromagtesite dispersion slurry prepared in advance (14.8 g as M and O) to make the magnesium component into a homogeneous slurry, and then poured into the above liquid C. A homogeneous slurry consisting of the three raw materials was obtained.

This slurry was then hydrothermally treated under the same conditions as the synthetic stevensite to produce a white powder of synthetic saponite (sample no.
, 5-4) was obtained.

This synthetic stevensite has a cation exchange capacity of 51 meq/100 g and a BET specific surface area of 400 m2.
/g, and the crystallite size in the b-axis direction was 158A.

Bentonite Active bentonite is 1 Patent No. 111183-5 of the present inventors.
It was prepared as follows in accordance with Publication No. 0310.

Acid clay powder was appropriately crushed and classified, impurities were removed, and the content of montmorillonite was increased. Powdered soda carbonate was added, the temperature and moisture were adjusted, and then kneaded to form bentonite. After that, it was dried and ground to obtain activated bentonite (sample No. 5-5) as a white powder.

This activated bentonite has a cation exchange capacity of 15 millimeters per 100 g, and the swelling charcoal has a cation exchange capacity of 39 mm/100 g.
Sample No. 1-1 to No. I-5 from 0 or more
When each of the water-swellable smectites was made into a 5% by weight aqueous dispersion, all were gel-like aqueous dispersions with excellent transparency and thickening properties.

The test method used in the present invention is shown below.

(1 N Cation exchange capacity (C, E, C,) Test method τ published by Japan Foundry Association, Tokai Branch, Inorganic Sand Mold Research Group
Compliant with IKS-413.

(2) BET specific surface area Measurement was performed using an automatic BET specific surface area measuring device (Sorptomatic 5eries 1800 manufactured by CARLOERBA).

(3) Crystallite size The crystallite size of the powder sample is determined by
The diffraction peak of plane index [06] was measured according to the X-ray diffraction method described in Maruzen-Publishing, page 8 (1956), and b
The crystallite size in the axial direction was determined in A units.

(4) Swelling coal (Japan Bentonite Industry Association standard test method:
JBAS-104-7) Add 2 g of the sample to a graduated cylinder with a stopper containing 100 ml of ion-exchanged water in 10 portions after the previous sample has settled at the bottom of the graduated cylinder.

Next, the apparent volume of the deposit after being stopped for 24 hours after being plugged is read, and this is taken as the swelling power (ml/2g).

Example 2 A homogeneous gel-like aqueous dispersion was prepared by incorporating a nylon monomer into the smectite clay minerals of samples No. 1-1 to 1-5 prepared in Example 1, and this was polymerized to obtain a smectite-containing nylon composition. (Sample No., N-1 to N-
The method for producing 5) and its physical properties are described below.

Nylon Composition Containing Synthetic Smectite In a glass container equipped with a stirrer, 50 g of synthetic stevensite powder (sample No. 5-1) and 950 g of nylon monomer ξ-caprolactam (Wako Pure AM) were added.

Reagent-grade) and 950 g of water were charged, and stirred while introducing N and gas. A homogeneous gel-like aqueous dispersion containing 5.26 parts of
When the condensation reaction is allowed to proceed by heating for a period of time and separating and removing the water that is desorbed during the process, the smectite-containing condensate that gradually forms is uniformly dispersed in the unreacted nylon monomer and forms a --like solid state. Nylon 6 according to the invention
polyamide composition.

Next, after crushing or crushing as necessary, stirring in warm water to elute unreacted nylon monomer and impurities, filtering, washing with warm water, and drying was used as sample N.
o, N-1.

In addition, using the smectite of Sample No. S-1, polyamide was prepared in the same manner as Sample No. S-1, except that a gel-like aqueous dispersion containing 10 parts by weight of smectite per 100 parts by weight of the nylon monomer was used. Composition (sample no.
, N-2) was obtained.

Furthermore, per 100 parts by weight of nylon monomer, sample No. S-1 was added to a 1.5 wt % aqueous dispersion of sample No. S-1.
After preparing a gel-like dispersion containing a nylon monomer so that the amount of stevensite in No. 1 is 45 parts, the dispersion was concentrated while stirring while introducing N2 gas until the whole became a viscous body, and then stirred. After stopping, sample No., N-1
A polyamide composition (sample No. N-3) was obtained in the same manner as above.

Furthermore, sample No. S-2 obtained in Example-1,
Using smectites S-3, S-4 and S-5, polyamide compositions were prepared in the same manner as samples No. and N-1. N-
It was set at 7.

The polyamide compositions of sample No. N-1 to N-7 obtained above were injection molded in a conventional manner to prepare five test pieces each, and the tensile test was conducted in accordance with JISk 7113, and one bending test was conducted in an atmosphere of 140°C. JIS K 7
203, and the average value of each
Shown in the table.

For comparison, commercially available calcium carbonate with an average particle size of 1 μm was used, and nylon monomer was contained in a 5% by weight aqueous dispersion so that calcium carbonate was 5.26 parts per 100 parts by weight of nylon monomer. Next, the sample N was concentrated in the same manner under stirring until it became viscous.
Polyamide compositions (sample No.
H-1) was treated with WJaI11.

From the above results, as is clear from Table 1, the nylon composition according to the present invention has significantly improved physical properties, and the variation in the measured values of the test pieces of the present invention during physical property tests was ±3 to 5%. On the other hand, in Comparative Example H-1, it was ±15 to 20%. This clearly indicates that the method of the present invention allows smectite particles, which are fillers, to be dispersed at a high level in the nylon matrix.

J11 Table of Procedures Amendment (Issue) September 27, 1990 Director General of the Patent Office 1, Indication of the case 1990 Patent Application No. 157746 2, Name of the invention Process for manufacturing smectite-containing nylon composition and its composition 3 Relationship with the case of the person making the amendment Patent applicant 4, agent 〒105 5 No date of amendment order 7 Contents of amendment■, Corrections are made as per the appended claims.

Il. Detailed Description of the Invention Column (1) Delete "Certainly," on page 6, line 13 of the specification.

(2) In the first and second lines of all pages 7, The phrase “as before” means Correct r to still be j.

(3) On page 8, line 6, “It is extremely well dispersed throughout the body.” There is a certain It is extremely well dispersed in one body, and 1 I am corrected.

(4) On page 9, lines 13 and 14, the phrase "In the present invention, nylon polymers are polymerized" is corrected to "Nylon polymers are polymerized. In the present invention," .

(5) Correct equation (1) on page 12 as follows.

(6) All pages 13, lines 8 to 9, rO, 05 to 80 parts by weight” There is a certain ro, os to 50 parts by weight J I am corrected.

(7) On page 14, lines 14-15, the phrase "active bentonite purified montmorillonite" is corrected to "active bentonite and purified montmorillonite."

(8) First line from the bottom of page 14 "Simple metal element components of sodium" There is a certain "Metallic element components of sodium" I am corrected.

(9) rAJ on the 2nd, 3rd, and 9th lines of all pages 16, the 10th and 11th lines of page 17, and the 6th line of page 21
Correct it to rA.

(10) On page 21, lines 14 and 15, the phrase ``It is better to dissolve it.'' is replaced by ``r.It is better to dissolve it.'' Correct it to J.

(11) In the first line from the bottom of page 21, the phrase "50 parts by weight" is corrected to 1 part by weight of rao.

(12) On page 24, lines 17 and 18 of the entire page, the statement ``Easily homogeneous without stirring even when polymerized as is'' means that even when polymerized as is, stirring is not required. It is easily corrected as homogeneous 1.

(13) On page 27, lines 10 and 11, the phrase “The content is preferably 70% by weight or more.” It is preferable that there be. Correct it as 1.

(14) In the 18th line of page 28, the statement "Take the water in the r300m diagram in the 2nd section beaker," is corrected to "J, take the water of r300mJ2 in the 2fL beaker."

(15) On page 29, lines 14 and 15, “Water 700
``Prepared with 700ml of water'' should be corrected to ``Prepared with 700ml of water.

(Eng. 6) In the 4th and 5th lines of page 31, "Hytromagnesite dispersion slurry J" is corrected to "r Hydromagnesite 8 dispersion slurry 1." 2 (17) On page 37 of the whole, Table 1 is corrected as follows.

Amended Claims (1) A homogeneous gel-like aqueous dispersion containing water-swellable smectite and nylon monomer is prepared, and the gel-like aqueous dispersion is heated under dehydrating conditions in an inert atmosphere. A method for producing a smectite-containing nylon composition, comprising polymerizing a nylon monomer.

(2) 0.1 to 5.0% by weight of the above gel-like aqueous dispersion
of water-swellable smectite, and the smectite is 0.001 to 80% per 100 parts by weight of the nylon monomer.
A method for producing a smectite-containing nylon composition according to claim 1, wherein the smectite-containing nylon composition is in the range of parts by weight.

(3) The smectite-containing material according to claim (1), wherein the water-swellable smectite is a synthetic stevensite having an ion conversion capacity of 20 to 160 meq/100g and a lattice spacing of 16 to 26 molecules when treated with ethylene glycol. A method for producing a nylon composition.

(4) When water-swellable smectite is actually purchased, the following formula % formula % In the formula, y is a number from 0 to 0.2, X is a number satisfying the formula 2y≧x>y, and n is less than zero. The method for producing a smectite-containing nylon composition according to claim 1, wherein the smectite-containing nylon composition is magnesium potassium phyllosilicate having a composition represented by the following, which is a large number, and having a cation exchange capacity of 20 meq.

(5) In a smectite-containing thyrotone composition comprising a nylon matrix and smectite dispersed therein, the smectite is a water-swellable magnesium phyllosilicate salt, and the water-swellable magnesium phyllosilicate salt is 0% per 100 parts by weight of nylon. A nylon composition characterized in that it is molecularly dispersed in nylon in an amount of .01 to 80 parts by weight.

(6) The above phyllosilicate magnesium salt has the formula % formula % where X and y are x + y x 3, X is a number of 2 or more, y is a number from 0 to 0.1, and Z is It has a composition expressed as a number from 0 to 1.0 in dogs, and has a composition of 50 to 30 in the b-axis direction as determined by X-ray diffraction method.
The smectite-containing nylon composition according to claim 5, wherein the smectite-containing nylon composition is a synthetic stevensite having a crystallite size of 0.0 and an ion exchange capacity of 20 to 160 meq/100g.

(7) The above phyllosilicate magnesium salt has the formula % formula % where y is a number from 0 to 0.2, X is a number satisfying 2y≧x>y, and n is a number larger than zero. Magnesium/potassium phyllosilicate has a composition expressed by
The smectite-containing nylon composition according to claim 5, which is a synthetic magnesium potassium phyllosilicate having a crystallite size of 0 to 300 people and an ion exchange capacity of 20 meq/100g or more.

Claims (7)

[Claims] (1) A homogeneous gel-like aqueous dispersion containing water-swellable smectite and a nylon monomer is prepared, and the gel-like aqueous dispersion is heated under dehydration conditions in an inert atmosphere to polymerize the nylon monomer. A method for producing a characteristic smectite-containing nylon composition. (2) 0.1 to 5.0% by weight of the above gel-like aqueous dispersion
of water-swellable smectite, and the amount of the smectite is 0.01 to 8 per 100 parts by weight of the nylon monomer.
A method for producing a smectite-containing nylon composition according to claim 1, wherein the smectite-containing nylon composition is in the range of 0 parts by weight. (3) The smectite-containing nylon composition according to claim 1, wherein the water-swellable smectite is a synthetic stevensite having an ion conversion capacity of 20 to 160 meq/100g and a lattice spacing of 16 to 26 A when treated with ethylene glycol. manufacturing method. (4) Water-swellable smectite substantially has the following formula K_xM
g_3_−_ySi_4O_1_0(OH)_2・nH
In the _2O formula, y is a number from 0 to 0.2, x is a number that satisfies the formula 2y≧x>y, and n is a number larger than zero. The method for producing a smectite-containing nylon composition according to claim 1, wherein the smectite-containing nylon composition is magnesium potassium phyllosilicate having a composition represented by the formula and a cation exchange capacity of 20 milliequivalents/100 g or more. (5) In a smectite-containing nylon composition comprising a nylon matrix and smectite dispersed therein, the smectite is a water-swellable magnesium phyllosilicate salt, and the water-swellable magnesium phyllosilicate is 0 per 100 parts by weight of nylon. A nylon composition characterized in that it is molecularly dispersed in nylon in an amount of .01 to 80 parts by weight. (6) The above magnesium phyllosilicate salt has the formula Mg_xN
a_ySi_4O_1_0(OH)_2・Na_z In the formula, x and y are a number of 2 or more, y is a number of 0 to 0.1, and z is larger than 0 and 1. A synthetic steven site having a composition expressed by a number up to 0, a crystallite size of 50 to 300 A in the b-axis direction as determined by X-ray diffraction, and an ion exchange capacity of 20 to 160 milliequivalents/100 g. A smectite-containing nylon composition according to claim (5). (7) The above magnesium phyllosilicate salt has the formula K_xMg
_3_-_ySi_4O_1_0(OH)_2・nH_
2O In the formula, y is a number from 0 to 0.2, x is a number satisfying the formula 2y≧x>y, and n is a number larger than zero. 100 in the b-axis direction as determined by X-ray diffraction method.
The smectite-containing nylon composition according to claim 5, which is a synthetic magnesium potassium phyllosilicate having a crystallite size of 300A to 300A and an ion exchange capacity of 20 meq/100g or more.