JP2007297489A - Intercalation compound and composite material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intercalation compound which improves the properties of a composite material to be obtained by compounding with a polymeric material and a composite material which can exhibit improved properties based on compounding of the intercalation compound. <P>SOLUTION: The intercalation compound is obtained by inserting an organic compound between layers of an inorganic layered substance. This intercalation compound is constituted by inserting an organic compound in a non-ionized state between layers of an ion-exchangeable inorganic substance where an exchangeable ion is present. The composite material is obtained by compounding the intercalation compound with a polymeric material. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an intercalation compound in which an organic compound is inserted between layers of an inorganic layered substance and a composite material obtained by compositing the intercalation compound and a polymer material.

As an interlayer compound, a compound in which a cationic organic compound is inserted between layers of an inorganic layered substance is known (see, for example, Patent Document 1). This type of intercalation compound is obtained by ion exchange between a metal cation present between layers of an inorganic layered substance and a cationic organic compound. Such insertion of chemical species between layers of an inorganic layered substance is generally called intercalation. For example, the triazine salt silicate complex of Patent Document 1 has a triazine compound derivative inserted between layers of a swellable layered silicate. This triazine-based compound derivative is a triazine-based compound having at least one group having a positive charge, and is obtained by an acid / base reaction of a Lewis acid compound with the triazine-based compound. The silicic acid triazine salt composite is obtained by ion exchange between a metal cation existing between layers of the swellable layered silicate and a triazine compound derivative. The resin composite obtained by mixing the silicate triazine salt composite and the thermoplastic resin is said to be excellent in mechanical properties and heat resistance.
JP-A-10-81510

  In a composite material obtained by combining a polymer material and an intercalation compound, further improvement in physical properties is desired. The present invention has been made by finding a novel intercalation compound capable of enhancing the physical properties of a composite material as a result of intensive studies by the present inventors.

  A first object of the present invention is to provide an intercalation compound capable of enhancing the physical properties of a composite material obtained by compounding with a polymer material. A second object is to provide a composite material capable of exhibiting enhanced physical properties based on the compounding with an intercalation compound.

  In order to achieve the above object, the intercalation compound of the invention according to claim 1 is an intercalation compound in which an organic compound is inserted between layers of an inorganic layered substance, and exchangeable ions are present between the interlaminar layers. The gist is that the organic compound is inserted in a non-ionized state between layers of the exchangeable inorganic substance.

  The gist of the invention according to claim 2 is that the exchangeable ion content of the ion-exchangeable inorganic substance is retained in the inorganic layered substance in the intercalation compound according to claim 1.

  According to a third aspect of the present invention, in the intercalation compound according to the second aspect, the difference between the ion exchange capacity of the ion-exchangeable inorganic substance and the ion exchange capacity of the inorganic layered substance is 10 milligram equivalent / 100 g. It is a summary to be less than.

  According to a fourth aspect of the present invention, in the intercalation compound according to any one of the first to third aspects, the ion exchange capacity of the ion-exchangeable inorganic substance is 25 to 195 milligram equivalent / 100 g. This is the gist.

  The gist of the composite material of the invention according to claim 5 is that the intercalation compound according to any one of claims 1 to 4 is combined with the polymer material.

  According to the intercalation compound of the present invention, the physical properties of a composite material obtained by compounding with a polymer material can be enhanced. Moreover, according to the composite material of this invention, the physical property raised based on the composite_body | complex by an interlayer compound can be exhibited.

DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments embodying the present invention will be described in detail.
The intercalation compound in this embodiment is one in which an organic compound is inserted between layers of an inorganic layered substance. This intercalation compound is constituted by inserting an organic compound in a non-ionized state between layers of an ion exchangeable inorganic substance having ion exchange capability. Such an intercalation compound can be combined with a polymer material to obtain a composite material with improved physical properties.

<Ion-exchangeable inorganic substance>
The ion exchangeable inorganic substance is an inorganic substance that can be combined with a polymer material, and is at least one selected from a cation exchangeable inorganic substance and an anion exchangeable inorganic substance.

  A cation exchange compound is an inorganic substance in which exchangeable cations exist between layers. For example, swellable mica (swellable mica), smectite group clay mineral, vermiculite group clay mineral, zeolite, sepiolite, etc. Can be mentioned.

  Examples of the swellable mica include Na-type tetrasilicic fluorine mica, Li-type tetrasilicic fluorine mica, Na-type fluorine teniolite, Li-type fluorine teniolite, and the like. Examples of the smectite group clay mineral include montmorillonite, beidellite, nontronite, saponite, hectorite, and stevensite. Examples of the vermiculite group clay mineral include trioctahedral vermiculite, dioctahedral vermiculite, and the like.

Moreover, as a cation exchange inorganic substance, the swelling layered silicate shown, for example by following General formula (1) can also be mentioned.
_{[A a (X b Y c)} (Si 4-d Al d) O 10 (OH e F 2-e) ] (1)
In the general formula (1), the value of a is 0.2 ≦ a ≦ 1.0, the value of b is 0 ≦ b ≦ 3, the value of c is 0 ≦ c ≦ 2, and the value of d is 0 ≦ d ≦ 4. , And e are 0 ≦ e ≦ 2.

  A in the general formula (1) represents an exchangeable cation, and is at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions. Examples of the metal atom of the exchangeable metal ion represented by A include Li and Na.

  X and Y in the general formula (1) are cations that enter the octahedral sheet in the structure of the swellable layered silicate, and X is at least one selected from Mg, Fe, Mn, Ni, Zn, and Li. Y is a cation composed of at least one metal atom selected from Al, Fe, Mn and Cr.

  The anion-exchangeable inorganic substance is an inorganic substance in which an anion exists between layers, and examples thereof include hydrotalcite and hydrotalcite containing a hydrotalcite-like compound. Hydrotalcite is a kind of layered double hydroxide (LDH), and is represented by, for example, the following general formula (2).

^{_{[M 2+ 1-x M 3+ x}} (OH) 2 ] ^{x + _{[A n- x / n · yH 2}} O ] ^x- ··· (2)
Formula (2) ^{M 2+} is a divalent metal atom in ^{the, M 3+} is a trivalent metal ^{atom, A n-n-valent} exchangeable metal ion, x = 0.2~0.33, y is Although it is not particularly limited because it varies depending on the environmental humidity, for example, 0 <y <1. Examples of M ²⁺ include Mg ²⁺ , Mn ²⁺ , Ni ²⁺ and Zn ²⁺ . Examples of M ³⁺ include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Co ³⁺ . As A ^n-, for example ^{_{OH -, Cl -, NO 3}} -, SO 4 -, CO 3 2- and the like. Incidentally, the hydrotalcite is represented by _{Mg 6 Al 2 (OH) 16} CO 3 · 4H 2 O.

  The ion content of exchangeable ions existing between layers of an ion exchangeable inorganic substance can be measured by, for example, the column permeation method (“Clay Handbook” 2nd edition, edited by the Japan Clay Society, Sections 576-577, Technical Hall Publishing) or the methylene blue adsorption method It is shown as the ion exchange capacity of an ion-exchangeable inorganic substance by a method such as (Japan Bentonite Industry Association Standard Test Method, JBAS-107-91). This ion exchange capacity is called a cation exchange capacity (CEC) in the case of a cation exchange inorganic substance, and an anion exchange capacity (Anion) in the case of an anion exchange inorganic substance. -Exchange Capacity (AEC).

The ion exchange capacity shown in this embodiment refers to a value measured by an equilibrium method. This equilibration method is a method according to the following (Procedure 1) to (Procedure 4).
(Procedure 1) After saturating a predetermined amount of ion-exchangeable inorganic substance with a salt solution, the ion-exchangeable inorganic substance and the supernatant are separated.

(Procedure 2) The ion-exchangeable inorganic substance subjected to the saturation treatment is washed with a salt solution having the same type and low concentration as in (Procedure 1), and the ion-exchangeable inorganic substance is equilibrated at this concentration.
(Procedure 3) Next, the ion-exchangeable inorganic substance is washed with pure water, dried and pulverized.

(Procedure 4) The elements present between the layers are quantified by fluorescent X-ray analysis, and the ion exchange capacity is determined from the quantified value.
The ion exchange capacity of the ion-exchangeable inorganic substance is preferably 25 to 195 milligram equivalent / 100 g, more preferably 50 to 150 milligram equivalent / 100 g. When this ion exchange capacity is 25 to 195 milligram equivalent / 100 g, an interlayer compound obtained from such an ion-exchangeable inorganic substance is likely to cause delamination. Therefore, a composite material obtained by combining a polymer material and an interlayer compound The physical properties of can be further increased.

The charge density of the ion-exchangeable inorganic substance is preferably 70 × 10 ² to 250 × 10 ² [nm / charge], more preferably 70 × 10 ² to 200 × 10 ² [nm / charge]. When the charge density is 70 × 10 ² to 250 × 10 ² [nm / charge], delamination of an intercalation compound obtained from such an ion-exchangeable inorganic substance is likely to occur. The physical properties of the composite material formed into a composite can be further increased. This charge density is determined by determining the lattice constant from the result of structural analysis by observation with a transmission electron microscope or the result of structural analysis by the Liberty method of powder X-ray diffraction. It shows the charge of the ions present.

<Organic compounds>
The organic compound is inserted between the above-described layers of the ion-exchangeable inorganic material in a non-ionized state, whereby the layers of the ion-exchangeable inorganic material are modified. Such an organic compound is preferably an additive for a polymer material from the viewpoint that functionality can be imparted to the composite polymer material. Examples of additives that can be used as the organic compound of the present embodiment include flame retardants, plasticizers, anti-aging agents, ultraviolet absorbers, and damping agents.

  Specific examples of the organic compound include at least one selected from triazine compounds, phosphorus compounds, and α-amino acids. Further, since the triazine compound or the phosphorus compound is a flame retardant for the polymer material, it is preferable from the viewpoint that the flame retardancy of the composite material formed by combining the polymer material and the interlayer compound can be increased. is there.

  Examples of triazine compounds include melamine compounds and cyanuric acid compounds. Examples of the melamine compound include melamine, N-ethylenemelamine, N, N ′, N ″ -triphenylmelamine, melamine sulfate, melamine phosphate, melamine polyphosphate, melamine pyrophosphate, melamine cyanurate, and the like. As cyanuric acid, isocyanuric acid, trimethyl cyanurate, trismethyl isocyanurate, triethyl cyanurate, trisethyl isocyanurate, tri (n-propyl) cyanurate, tris (n-propyl) isocyanurate, diethyl cyanurate, N, N'-diethyl isocyanurate, methyl cyanurate, methyl isocyanurate and the like can be mentioned.

  Examples of the phosphorus compound include aromatic phosphate esters, aromatic condensed phosphate esters, halogen phosphate esters, halogen condensed phosphate esters, and red phosphorus. Aromatic phosphate esters include triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (i-propylated phenyl) phosphate, 2- Examples include ethyl hexyl diphenyl phosphate. Examples of the aromatic condensed phosphates include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl) phosphate, bisphenol A bis (diphenyl phosphate), and the like. Examples of the halogen phosphate esters include tris (dichloropropyl) phosphate, tris (β-chloropropyl) phosphate, tris (chloroethyl) phosphate, and the like. Examples of the halogen condensed phosphate esters include 2,2-bis (chloromethyl) trimethylene bis (bis (2-chloroethyl) phosphate), polyoxyalkylene bisdichloroalkyl phosphate, and the like. Examples of organic halogen compounds include tetrabromobisphenol A (TBA), decabromodiphenyl oxide (DBDPO), hexabromocyclododecane (HBCD), tribromophenol (TBP), ethylenebistetrabromophthalimide, TBA polycarbonate oligomer, brominated polystyrene. And bromine compounds such as TBA epoxy oligomer and ethylene bispentabromodiphenyl, and chlorine compounds such as chlorinated paraffin.

α-amino acids include α-amino acids or α-amino acid salts. An α-amino acid is an amino acid having an amino group (—NH ₂ ) and a carboxyl group (—COOH) in the molecule, and the carboxyl group and the amino group are bonded to the same carbon atom. Examples of the α-amino acid include alanine, arginine, glycine, cysteine, serine, tyrosine, valine, leucine, isoleucine, proline, tryptophan, methionine, threonine, asparagine, aspartic acid, glutamine, glutamic acid, lysine, and phenylalanine. Examples of the α-amino acid salt include potassium salt, sodium salt, magnesium salt and the like of α-amino acid.

<Interlayer compound>
An organic compound inserted in a non-ionized state is interposed between layers of the inorganic layered substance constituting the interlayer compound.

  The intercalation amount of the organic compound is preferably 1 milligram equivalent / 100 g or more, more preferably 5 milligram equivalent / 100 g or more, and further preferably 10 milligram equivalent / 100 g or more. When the intercalation amount of the organic compound is less than 1 milligram equivalent / 100 g, the interlayer of the ion-exchangeable inorganic substance may not be sufficiently modified. On the other hand, the upper limit of the intercalation amount of the organic compound is not particularly limited, but is, for example, 200 milligram equivalent / 100 g or less.

  In the inorganic layered substance, it is preferable that the exchangeable ion amount of the ion-exchangeable inorganic substance is maintained from the viewpoint of securing the characteristics inherent to the ion-exchangeable inorganic substance. The difference between the ion exchange capacity of the ion-exchangeable inorganic substance used as the raw material and the ion exchange capacity of the inorganic layered substance constituting the intercalation compound is preferably, for example, less than 10 milligram equivalent / 100 g. .

  For the insertion of an organic compound between layers of an ion-exchangeable inorganic substance, for example, shearing force and organic compound can be applied to the ion-exchangeable inorganic substance and the organic compound in a state where the ion-exchangeable inorganic substance and the solid-state organic compound are in contact with each other. It can be manufactured by applying an impact force. That is, an organic compound is inserted between layers of an ion-exchangeable inorganic substance by applying an external force to the ion-exchangeable inorganic substance and the organic compound without using ion exchange of ions existing between the layers of the ion-exchangeable inorganic substance. . In the thus obtained intercalation compound, the exchangeable ion content of the ion exchangeable inorganic substance is maintained between the layers of the inorganic layered substance. A ball mill, a hammer mill, a jet mill, a kneader, or the like is preferably used for inserting such an organic compound. In addition, by carrying out a treatment in which the ion-exchangeable inorganic substance is previously brought into contact with an electron-donating organic solvent, the organic compound is easily inserted between the layers of the ion-exchangeable inorganic substance, and the amount of intercalation of the organic compound is increased. Is possible. That is, it is presumed that the electron donating organic solvent activates the outer surface and inner surface of the ion-exchangeable inorganic substance, and increases the affinity between the ion-exchangeable inorganic substance and the organic compound inserted between the layers. . As such an electron-donating organic solvent, for example, tetrahydrofuran is preferable.

  The compounding amount of the organic compound with respect to the ion-exchangeable inorganic substance is preferably 0.1 to 100 parts by mass, more preferably 0.1 to 70 parts by mass, and still more preferably 0 with respect to 100 parts by mass of the ion-exchangeable inorganic substance. .1 to 50 parts by mass. When this compounding quantity is less than 0.1 mass part, there exists a possibility that it may become difficult to ensure the interlayer insertion amount of an organic compound enough. On the other hand, when it mixes exceeding 100 mass parts, since the fall of the improvement rate of an intercalation amount is caused, there exists a possibility of becoming uneconomical.

<Composite material>
The composite material is a material in which the above-described intercalation compound and a polymer material are combined. The polymer material is contained as a base material of the composite material, and the polymer material is classified into a thermoplastic resin, a thermosetting resin, and rubbers. Examples of the thermoplastic resin include olefin resin, polyester resin, polyamide resin, styrene / acrylonitrile resin, polycarbonate, polysulfone, polyphenylene ether, polyoxymethylene, polyvinyl chloride, and polyvinylidene chloride. Examples of olefin resins include high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-vinyl acetate copolymer. Examples thereof include a polymer, an ethylene-methacrylate copolymer, and an ionomer resin. Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, and various polyester elastomers. Examples of the polyamide-based resin include polyamide 6, polyamide 66, polyamide 11, polyamide 12, amorphous polyamide, polymethacrylamide and the like. Examples of the styrene / acrylonitrile resin include polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene copolymer, and polyacrylonitrile.

Examples of the thermosetting resin include an epoxy resin, a phenol resin, an unsaturated polyester resin, a melamine resin, a urethane resin, and a urea resin.
Examples of rubbers include urethane rubber, silicone rubber, ethylene-propylene rubber, chloroprene rubber, butyl rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylic rubber, and natural rubber.

These polymer materials may be used alone, or may be used as a polymer alloy or a block copolymer in which a plurality of types are combined.
The compounding amount of the intercalation compound in the composite material is preferably 0.1 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and further preferably 1 to 60 parts by mass with respect to 100 parts by mass of the polymer material. It is. When this compounding quantity is less than 0.1 mass part, there exists a possibility that the physical property of a composite material may not be improved significantly. On the other hand, when it mixes exceeding 200 mass parts, there exists a possibility that the moldability of a composite material may not fully be obtained.

This composite material may contain a filler, a flame retardant, a corrosion inhibitor, a colorant, an antistatic agent, a wetting agent, and the like as components other than the intercalation compound as necessary.
The composite of the polymer material and the intercalation compound can be performed, for example, by mixing the intercalation compound with the polymer material and mixing the polymer material and the intercalation compound. For example, it can also carry out by mix | blending an interlayer compound with a monomer and polymerizing the monomer. The composite material may be configured as a master batch in which a polymer material and an intercalation compound are combined, and the master batch may be diluted with the polymer material.

  When the polymer material and the intercalation compound are combined, it is possible to use a dissolver and various extruders in addition to known mixers such as a Banbury mixer, a planetary mixer, a Glen mill, and a kneader. The compounding can be performed by heating as necessary.

  In such a composite, a part or the whole of the intercalation compound is delaminated, so that a part or the whole of the intercalation compound becomes fine particles, and these fine particles are dispersed (nanodispersed) in a nano-order level in the polymer material. At this time, exchangeable ions exist between layers of the interlayer compound of the present embodiment, and the organic compound is inserted in a non-ionized state. In the inorganic layered substance constituting the intercalation compound, the exchangeable ion amount of the ion exchangeable inorganic substance is maintained. For this reason, it is presumed that the intercalation compound becomes easy to delaminate, the dispersibility of the fine particles formed by the delamination is improved, and the interface state between the nano-dispersed fine particles and the polymer material is modified.

  The composite material thus obtained can be used as various molded articles in, for example, the electric / electronic field, the automobile field, and the building field. In a molded product molded from this composite material, excellent mechanical properties are exhibited.

The effects exhibited by this embodiment will be described below.
(1) Interchangeable ions exist between layers of the interlayer compound of this embodiment, and an organic compound is inserted in a non-ionized state. That is, exchangeable ions and an organic compound inserted in a non-ionized state coexist between layers of the inorganic layered substance constituting the interlayer compound. For this reason, it is presumed that the intercalation compound becomes easy to delaminate, the dispersibility of the fine particles formed by the delamination is improved, and the interface state between the nano-dispersed fine particles and the polymer material is modified. Therefore, the physical properties of the composite material obtained by combining the intercalation compound and the polymer material can be enhanced.

  (2) The inorganic layered material constituting the intercalation compound preferably retains the exchangeable ion content of the ion-exchangeable inorganic material. In this case, the characteristics inherent to the ion-exchangeable inorganic substance used as a raw material can be ensured. The difference between the ion exchange capacity of the ion-exchangeable inorganic substance and the ion exchange capacity of the inorganic layered substance is preferably less than 10 milligram equivalent / 100 g.

  (3) The ion exchange capacity of the ion exchangeable inorganic substance is preferably 25 to 195 milligram equivalent / 100 g. In this intercalation compound, delamination is likely to occur, so that the physical properties of a composite material obtained by combining a polymer material and an intercalation compound can be further enhanced.

  (4) The composite material of the present embodiment is configured by combining the above-described intercalation compound and a polymer material. Such a composite material can exhibit enhanced physical properties based on compounding with an intercalation compound. Therefore, in a molded product molded from this composite material, for example, mechanical properties and the like can be enhanced, and thus the utility value of this composite material is extremely high.

Next, the technical idea that can be grasped from the above embodiment will be described below.
An intercalation compound in which the ion-exchangeable inorganic substance is at least one selected from swellable mica (swellable mica), smectite group clay mineral, vermiculite group clay mineral, zeolite, sepiolite, and hydrotalcites.

An intercalation compound in which the organic compound is an additive for a polymer material.
An intercalation compound in which the organic compound is a triazine compound or a phosphorus compound.
An intercalation compound in which the intercalation amount of the organic compound with respect to the inorganic layered material is 1 milligram equivalent / 100 g or more.

A composite material in which the polymer material is at least one selected from thermoplastic resins, thermosetting resins, and rubbers.
-The composite material by which 0.1-200 mass parts of said interlayer compounds are mix | blended with respect to 100 mass parts of said polymeric materials.

Next, the embodiment will be described more specifically with reference to examples and comparative examples.
<A. Interlayer compound>
Example 1-A
Tetrahydrofuran (THF, reagent grade 1, Wako Pure Chemical Industries, Ltd.) with respect to 100 parts by mass of synthetic mica [Na-type tetralithic fluoric mica: Somasif (trade name) ME-100, manufactured by Coop Chemical Co., Ltd.] as an ion-exchangeable inorganic substance 10 parts by mass of Kogyo Co., Ltd.) was blended, and synthetic mica was pulverized for 45 minutes at room temperature using a ball mill. Next, 150 mg equivalent number / 100 g of melamine as an organic compound was blended, and synthetic mica and melamine were co-ground for 2 hours at room temperature using a ball mill. Thereby, the intercalation compound was prepared by inserting melamine into the interlayer of synthetic mica in the non-ionized state.

(Comparative Example 1-A)
1 kg of synthetic mica [Na-type tetralithic fluorine mica: Somasif (trade name) ME-100, manufactured by Coop Chemical Co., Ltd.] as an ion-exchangeable inorganic substance is poured into 20 L of ion-exchanged water, and the synthetic mica is infinitely swollen. A 5% mica suspension was prepared. On the other hand, a melamine hydrochloric acid solution was prepared by dissolving 138.8 g of melamine in an acid solution in which 91.7 mL of concentrated hydrochloric acid was dissolved in 2.5 L of ion-exchanged water. This melamine hydrochloric acid solution is added dropwise to a mica suspension kept at 60 ° C. and stirred for 2.5 hours to convert exchangeable ions present between synthetic mica layers and melamine hydrochloride. I exchanged it. Thereafter, the supernatant was removed and filtered to obtain a wet intercalation compound. The obtained intercalation compound was dried at 80 ° C. for 20 hours and then pulverized using a blender mixer to obtain an intercalation compound.

(Measurement of ion exchange capacity)
About the synthetic mica used as a raw material and the intercalation compound of each example, the measurement of the ion exchange capacity was performed in the following procedures. The measurement results are shown in Table 1.

(Procedure 1) A dispersion liquid is prepared by dispersing 2 g of a sample in 100 mL of pure water.
(Procedure 2) Add 100 mL of 2M potassium acetate solution to the dispersion and shake for 1 hour. Next, the dispersion is subjected to solid-liquid separation using a centrifuge, the supernatant is removed, and the solid is collected.

(Procedure 3) After adding 100 mL of 1M potassium acetate solution to the obtained solid and shaking for 1 hour, solid-liquid separation is performed again using a centrifuge.
(Procedure 4) The above procedure 3 is performed once more.

(Procedure 5) After adding 100 mL of pure water to the obtained solid and shaking for 1 hour, solid-liquid separation is performed using a centrifuge.
(Procedure 6) The above procedure 5 is repeated twice more.

(Procedure 7) The obtained solid is dried at 70 ° C. and then pulverized.
(Procedure 8) Using a fluorescent X-ray apparatus, potassium (K) in the solid is quantified.
(Procedure 9) Potassium is converted into the number of moles per 4 moles of silicon (Si). Taking the formula weight of the sample as 390, milligram equivalent (meq) / 100 g is calculated from the number of moles of potassium.

(Measurement of intercalation amount)
For the intercalation compounds of Example 1-A and Comparative Example 1-A, the intercalation amount of the organic compound was measured by the following procedure. The measurement results are shown in Table 1.

  The intercalation compound was washed using THF as a washing solution. First, the washing | cleaning used in the ratio of 100 ml of THF with respect to 100 mass parts of layered clay minerals was repeated 3 times, and it was set as preliminary washing. Next, while using an aspirator to suck the intercalation compound, the washing using 100 ml of THF with respect to 100 parts by mass of the layered clay mineral was repeated three times to obtain the main washing. Thereafter, the intercalation compound was vacuum-dried to obtain a sample for measuring intercalation amount. The weight change when the sample was heated from room temperature to 600 ° C. at a rate of temperature increase of 10 ° C./min was measured with a thermogravimetric apparatus (SSC 5200, manufactured by Seiko Instruments Inc.), and the intercalation of organic compounds was performed. The amount was calculated.

実施例１−Ａの層間化合物では、合成マイカが有しているイオン交換容量と、原料として用いた合成マイカのイオン交換容量とは同程度である。すなわち、実施例１−Ａの層間化合物では、原料として用いた合成マイカの有するイオン交換容量が保持されている。これに対して、比較例１−Ａの層間化合物では、原料として用いた合成マイカの有するイオン交換容量は保持されていない。すなわち比較例１−Ａの層間化合物は、イオン化したメラミン塩酸塩と合成マイカの層間に存在する交換性イオンとが交換されて構成されているため、原料として用いた合成マイカのイオン交換容量は保持されていない。

In the intercalation compound of Example 1-A, the ion exchange capacity of synthetic mica is approximately the same as the ion exchange capacity of synthetic mica used as a raw material. That is, the intercalation compound of Example 1-A retains the ion exchange capacity of the synthetic mica used as a raw material. On the other hand, in the intercalation compound of Comparative Example 1-A, the ion exchange capacity of the synthetic mica used as a raw material is not retained. That is, since the intercalation compound of Comparative Example 1-A is constituted by exchanging ionized melamine hydrochloride and exchangeable ions existing between the layers of synthetic mica, the ion exchange capacity of the synthetic mica used as a raw material is maintained. It has not been.

<B. Composite materials>
(Example 1-B)
As a polymer material, 3 parts by mass of the intercalation compound of Example 1-A is blended with 97 parts by mass of polyamide 6 (1911FB, manufactured by Ube Industries, Ltd., hereinafter referred to as “PA6”). A composite material was prepared by kneading using TEX30α (manufactured by Nippon Steel Co., Ltd.) at a resin temperature of 250 ° C. and a screw rotation number of 50 rotations / minute.

(Comparative Example 1-B)
A composite material was prepared in the same manner as in Example 1-B, except that the intercalation compound of Comparative Example 1-A was used as the intercalation compound to be blended with PA6.

(Comparative Example 2)
PA6 (1911FB, manufactured by Ube Industries) was used as Comparative Example 2.
(Measurement of physical properties)
The flexural modulus of the composite material of each example and the flexural modulus of the material of Comparative Example 2 were measured according to JIS K 7171-1994. The measurement results are shown in Table 2.

表２の結果から明らかなように、実施例１−Ｂの曲げ弾性率は、比較例１−Ｂの曲げ弾性率よりも高い値を示していることから、実施例１−Ｂの複合材料では、実施例１−Ａの層間化合物による複合化に基づいて物性が高められることがわかる。

As is clear from the results in Table 2, the flexural modulus of Example 1-B shows a higher value than the flexural modulus of Comparative Example 1-B. Therefore, in the composite material of Example 1-B, It can be seen that the physical properties are enhanced on the basis of the compounding of the intercalation compound of Example 1-A.

Claims (5)

An intercalation compound in which an organic compound is inserted between layers of an inorganic layered substance,
An intercalation compound obtained by inserting the organic compound in a non-ionized state between layers of an ion exchangeable inorganic substance in which exchangeable ions exist between layers. The intercalation compound according to claim 1, wherein the exchangeable ion amount of the ion exchangeable inorganic substance is retained in the inorganic layered substance. The intercalation compound according to claim 2, wherein the difference between the ion exchange capacity of the ion exchangeable inorganic substance and the ion exchange capacity of the inorganic layered substance is less than 10 milligram equivalent / 100 g. The intercalation compound according to any one of claims 1 to 3, wherein the ion-exchange capacity of the ion-exchangeable inorganic substance is 25 to 195 milligram equivalent / 100 g. A composite material comprising the intercalation compound according to any one of claims 1 to 4 and a polymer material.