JPH10168182A - Dispersion and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a dispersion usable as a raw material for an organic high molecular polymer expected to have more functional properties by dispersing a complex of lubricant laminar silicate with a compound containing phosphorus and a metal element as a fine particle in a liquid. SOLUTION: This dispersion is obtained by mixing (A) a lubricant laminar silicate with (B) a phosphoric acid salt and/or a polyphosphoric acid salt, (C) polyvalent metal salt and/or multinuclear metal complex salt, (D) a solvent and preferably (E) a high molecular monomer. A solid material dispersing in the dispersion is a complex of a compound obtained by the reaction of the component B with the component C and containing phosphorus and a metal element, with the component A, and forms regular laminar structure in the liquid. The above complex is very uniformly dispersed in a monomer when synthesizing an organic polymer compound, and used for improvement of various kinds of characteristics of the produced organic polymer compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dispersion useful for an organic polymer or as another raw material and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, inorganic materials such as calcium carbonate, clay minerals, and mica have been mixed and kneaded in order to improve various characteristics of organic polymer materials such as polyester and polyamide, especially mechanical characteristics and heat resistance. Is being done. However, simply mixing and kneading these inorganic materials does not readily disperse the inorganic materials into fine particles and do not disperse them. Therefore, a material having satisfactory properties has not been obtained. For this reason, many patent applications have been filed for inventions aiming at uniform dispersion in an organic polymer, in which montmorillonite and a fluoromica-based swelling clay mineral are chemically treated to form fine particles, and are dispersed uniformly in an organic polymer. Examples thereof are JP-A-62-74957, JP-A-2-173160, and JP-A-3-77.
No. 29, JP-A-3-41149, JP-A-8-
3310, JP-A-8-59822, JP-A-8-120071, and JP-A-8-134205. However, at present, even with these methods, sufficiently satisfactory dispersibility has not been obtained.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a dispersion which is useful as a raw material for an organic polymer which is expected to further improve the dispersibility obtained by a conventionally reported method and which is expected to have more functionality. It is something to offer.

[0004]

In order to uniformly disperse an inorganic material in an organic polymer, it is extremely important that the inorganic material be uniformly dispersed in a monomer which is a raw material of the organic polymer. Based on the knowledge obtained from the conventional experience that is, various tests are repeated, a dispersion produced under certain conditions is a composite of a swellable layered silicate and a compound containing phosphorus and a metal element The present invention has been found to have properties which have not existed in the past, and to be able to expect unprecedented advantages in terms of functionality, and have completed the present invention.

That is, the present invention includes the following inventions. (1) A dispersion obtained by mixing a swellable layered silicate, a phosphate and / or a polyphosphate, a polyvalent metal salt and / or a polynuclear metal complex salt, and a solvent. (2) a compound containing phosphorus and a metal element formed by the reaction of a phosphate and / or polyphosphate with a polyvalent metal salt and / or a polynuclear metal complex and a swellable layered silica; The dispersion according to the above (1), comprising a complex with an acid salt. (3) A dispersion obtained by further mixing a polymer monomer with the dispersion according to (1) or (2).

(4) A solid obtained by separating a solid from the dispersion described in the above (1) or (2), and mixing the separated solid with a polymer monomer or a polymer monomer and a solvent. liquid. (5) The swellable layered silicate is dispersed in a solvent, a phosphate and / or a polyphosphate is added thereto, and then a polyvalent metal salt and / or a polynuclear metal complex dissolved in the solvent is added and dispersed. The method for producing a dispersion according to the above (3), wherein the liquid (S) is prepared, and a polymer monomer is further mixed therein. (6) The solid content is separated from the dispersion (S) according to (5), and the separated solid is mixed with a polymer monomer or a polymer monomer and a solvent. )).

[0007]

DETAILED DESCRIPTION OF THE INVENTION As described above, the present invention comprises a swellable layered silicate, a phosphate and / or polyphosphate, a polyvalent metal salt and / or a polynuclear metal complex, and a solvent. The present invention relates to a dispersion obtained by mixing and a dispersion obtained by further mixing a polymer monomer. Also,
The present invention separates a solid content from a dispersion obtained by mixing a swellable layered silicate, a phosphate and / or a polyphosphate, a polyvalent metal salt and / or a polynuclear metal complex, and a solvent. The present invention relates to a dispersion obtained by mixing a polymer monomer or a polymer monomer and a solvent with a separated solid substance.

In these dispersions, the solids dispersed therein are phosphate and / or polyphosphate and polyvalent metal salts and / or
Another feature of the present invention resides in that it contains a complex of a compound containing phosphorus and a metal element formed by a reaction with a polynuclear metal complex and a swellable layered silicate. Further, these dispersions have a second characteristic in that dispersed solids are regularly laminated in the liquid.

A swellable (swellable means that water enters between crystal layers and swells in water) layered silicate, phosphate and / or polyphosphate, which is a raw material of these dispersions,
The details of the polyvalent metal salt and / or polynuclear metal complex salt, the solvent, and the polymer monomer are shown below.

Swellable layered silicates Natural or synthetic hectorite, saponite, stevensite, beidellite, montmorillonite, nontronite, bentonite and other smectite clay minerals and Na
Swelling mica clay minerals such as type tetrasilicic mica, Li type tetrasilicic mica, Na type fluorine teniolite, Li type fluorine teniolite, and vermiculite, or a mixture thereof.

Commercially available products include Laponite XLG (a synthetic hectorite-like substance manufactured by LaPort, UK), Laponite RD (a synthetic hectorite-like substance manufactured by LaPorte, UK), and Thermabis (similar to a hectorite manufactured by Henkel, Germany) Substance), smecton SA-1 (a saponite-like substance manufactured by Kunimine Industry Co., Ltd.), wenger (natural montmorillonite sold by Toyshun Yoko Co., Ltd.), kunipia F (natural montmorillonite sold by Kunimine Industry Co., Ltd.), veegum (US Natural hectorite manufactured by Vanderbilt Co., Ltd., dimonite (synthetic swelling mica manufactured by Topy Industries, Ltd.), somasif (synthetic swelling mica manufactured by Corp Chemical Co., Ltd.), SWN (manufactured by Corp Chemical Co., Ltd.) Synthetic smectite) and SWF (synthetic smectite manufactured by Corp Chemical Co., Ltd.).

As the swellable layered silicate used in the present invention, sodium and / or lithium obtained by heating a fine powder obtained by mixing talc with sodium and / or lithium silicofluoride to 700 to 1200 ° C. Alkali metals, magnesium, silicon, oxygen,
A swellable layered silicate containing fluorine as a main constituent element is desirable. The swellable layered silicate produced by the method is described in detail in Japanese Patent Publication No. Hei 6-27002, and Somasif (ME-1) by Corp Chemical Co., Ltd.
00), it may be used.

[0013] The swellable layered silicate used in the present invention comprises:
It is desirable that the average particle size is from 0.1 to 50 μm, and when the particle size is large, it is preferable to grind. The cation exchange capacity (methylene blue adsorption amount) of the swellable layered silicate is 15
~ 150 meq (milliequivalent) / 100 g is preferable, and 5
0 to 150 meq (milliequivalent) / 100 g is more preferable.

Phosphates and / or polyphosphates alkali metal or ammonium salts of orthophosphoric acid, alkali metal or ammonium salts of pyrophosphoric acid, alkali metal or ammonium salts of tripolyphosphoric acid, alkali metal or ammonium salts of trimetaphosphoric acid, tetrametaline Examples include alkali metal or ammonium salts of acids, and other water-soluble phosphates and / or polyphosphates.

As specific examples, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium pyrophosphate,
Disodium dihydrogen pyrophosphate and sodium tripolyphosphate are mentioned. Preferably sodium pyrophosphate,
Polyphosphates such as disodium dihydrogen pyrophosphate and sodium tripolyphosphate are used.

Polyvalent metal salts and / or polynuclear metal complex salts Divalent or higher valent metal salts are considered. Preferably, a trivalent or tetravalent metal salt such as an Al salt, a Zr salt, a Ti salt, a trivalent Fe salt, and a Cr salt are exemplified. Preferred specific examples include aluminum nitrate (Al (NO ₃ ) ₃ ), aluminum chloride (AlCl ₃ ), zirconium oxychloride (Z
rCl ₂ O).

Solvent Water is a base, and alcohol (methanol,
And lower alcohols such as ethanol and propanol) and / or polyhydric alcohols.

Polymer Monomer There is no particular limitation as long as it is a raw material for producing a polymer compound such as a synthetic resin. In the present invention, the polymer monomer is a concept including a polymer having a low degree of polymerization, which is a raw material for producing a polymer compound, in addition to a general monomer. In the present invention, one or more kinds of polymer monomers are used. The monomers of polyamide and polyester, which are typical polymer compounds, are described below.

Specific examples of polyamide monomers: amino acids such as 6-amino-n-caproic acid and 12-aminododecanoic acid; nylon salts such as hexamethylenediamine adipate; ε-caprolactam, butyrolactam, valerolactam, caprylactam And lactams such as dodecanolactam.

Specific examples of polyester monomers: adipic acid, suberic acid, azelaic acid,
Sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid Acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid, diglycolic acid and the like;
As the diol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, neopentyl glycol, diethylene glycol, 1,4-bis (β-hydroxyethoxy) benzene, Polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.

The method for producing the dispersion of the present invention is described below, but is not limited thereto. First, the swellable layered silicate is dispersed in a solvent. Water is usually used as the solvent, but an alcohol (lower alcohol such as methanol, ethanol, propanol and the like) and / or a polyhydric alcohol may be mixed in some cases. The concentration of the swellable phyllosilicate is not particularly limited, but is usually mixed so as to be a dispersion of 1 to 20% by weight. Stirring is sufficient to improve dispersion.

Next, phosphate and / or polyphosphate are added to the dispersion containing the swellable layered silicate. The amount of the phosphate and / or polyphosphate to be added is usually 0.05 to 5.00 mol per 1 mol of the swellable layered silicate. It is necessary to dissolve the added phosphate and / or polyphosphate in a solvent. Therefore, if the solvent is insufficient, it is added. Alternatively, the phosphate and / or polyphosphate may be added after dissolving in a solvent.

Thereto, a polyvalent metal salt and / or a polynuclear metal complex salt is added as a solution dissolved in the above-mentioned solvent. If a polyvalent metal salt and / or a polynuclear metal complex salt is added as a powder, a good dispersion cannot be obtained. Therefore, it is preferable to add the polyvalent metal salt and the polynuclear metal complex as a solution dissolved in a solvent. The amount of the polyvalent metal salt and / or polynuclear metal complex salt to be added is usually 0.1 to 1 mol of the swellable layered silicate.
An amount is added so as to be 10 to 10.00 mol.

The dispersion (S) of the present invention thus obtained contains the phosphorus element contained in the phosphate and / or the polyphosphate and the polyvalent metal salt and / or the polynuclear metal complex salt. (A) containing the metal element (M)
It forms a complex (B) with the swellable layered silicate, and is determined to be dispersed as a fine solid in the liquid.
The basis is that the solid content in the dispersion liquid is centrifuged, washed with water, dried at 50 to 90 ° C., left at room temperature, and subjected to elemental analysis or chemical analysis. And the presence of the metal element (M) can be confirmed. In the X-ray diffraction spectrum by the powder method, the (001) diffraction line region near the bottom spacing value (d ₀₀₁ ) characteristic of the swellable phyllosilicate as the raw material is observed. The reflection peak value (9.5 to 15 °) of the solid (C) is 3 to 3 times higher than the value of the raw material swellable phyllosilicate.
This is a point that is larger by 0 °. These results show that the compound (A) exists between the crystal layers, and the presence of the compound (A) between the crystal layers indicates that some bonding force with the swellable layered silicate is present. It is a result of working, and it can be determined that a complex (B) of the swellable layered silicate and the compound (A) has been formed. In some cases, the compound (A) exists alone without forming the complex (B) with the swellable layered silicate depending on the reaction conditions.

The composition of the compound (A) is not clear, but, for example, NaH ₂ PO ₄ , Na ₄ P ₂ O ₇ or Na ₅ P as a phosphate and / or polyphosphate.
_When 3O ₁₀ is used and Al (NO ₃ ) ₃ is used as a polyvalent metal salt and / or polynuclear metal complex salt, the following compounds are presumed.

In the case of NaH ₂ PO ₄ and Al (NO ₃ ) ₃ , Al _1−X Na _Y (H ₃ O) _Z PO ₄ (0 ≦ X <1, Y +
Z = 3X) In the case of Na ₄ P ₂ O ₇ and Al (NO ₃ ) ₃ AlNa _{1 -X} (H ₃ O) _X P ₂ O ₇ (X = 0 to 1) Na ₅ P ₃ O ₁₀ and Al (NO ₃ ) In the case of ₃ , AlNa _2-x (H ₃ O) _x P ₃ O ₁₀ (X = 0 to 2) In the case of other combinations, the metal elements are different,
Compounds similar to are envisioned.

In the above formulas, (P
O ₄ ), (P ₂ O ₇ ) and (P ₃ O ₁₀ ) are partially (OH)
When a polyphosphate is used or when a polyphosphate is used, the compound (A) may be formed after a part of the polyphosphate or the orthophosphate has a lower polymerization degree.

The swellable phyllosilicate and the compound (A)
To form the complex (B) with the hydrogen ion concentration of the liquid (p
H) affects, generally, it is necessary to adjust the pH of the solution to about 1 to 6 to form the complex (B). For example, as a polyvalent metal salt and / or a polynuclear metal complex salt, A
When 1 salt, Zr salt, Ti salt, Cr salt, trivalent Fe salt or the like is used, the pH is particularly preferably about 1 to 4. therefore,
In some cases, before or after the addition of the polyvalent metal salt and / or the polynuclear metal complex, it is necessary to adjust the pH by adding an alkaline solution such as a NaOH or KOH solution.

In the above series of operations, there is no particular problem as long as the liquid temperature is about 0 to 60 ° C. Also,
As a characteristic of the dispersion (S), in the dispersion obtained by dispersing only the raw material swellable layered silicate in a solvent mainly composed of water, the bottom of the swellable layered silicate is determined by an X-ray diffraction spectrum in order to form a card house structure. Although the reflection peak value (9.5 to 15 °) near the (001) diffraction line region, which is the interval value (d ₀₀₁ ), is not recognized, in the X-ray diffraction spectrum of the dispersion liquid (S), (0)
01) The reflection peak value in the vicinity of the diffraction line region is obtained as a value 1 to 15 ° larger than the reflection peak value of the solid (C). This indicates that the solvent is intercalated in addition to the compound (A) between the crystal layers, and that it is regularly laminated. This is considered to be a remarkable property of the dispersion (S), and it is determined that this property greatly affects the good dispersibility of the dispersion (S).

The dispersion (T _A ) of the present invention can be obtained by mixing a polymer monomer with the dispersion (S) containing the composite (B) obtained by the above method. The mixing ratio of the dispersion liquid (S) and the polymer monomer can be arbitrarily selected depending on the purpose. In general, the amount of the polymer monomer is 5 to 1000 (weight ratio) with respect to the raw material swellable phyllosilicate 1. ).

Since the dispersion liquid (S) contains dissolved electrolytes, if they are judged to be disadvantageous substances, they are separated. Separation may be carried out by conventional means such as centrifugation, decantation, and filtration. If a certain amount of dissolved electrolyte is to be removed, it may be removed by decantation. Since the separated solid contains an attached electrolyte, the solid substance is washed with water when it is desired to sufficiently remove the attached electrolyte. The solid thus obtained is mainly composed of the complex (B), and a polymer monomer and, if necessary, a solvent are mixed therewith to obtain the dispersion (T _B ) of the present invention.
Is obtained. At this time, when the polymer monomer is a liquid, the solvent may not be used. The mixing ratio between the separated solid and the polymer monomer can be arbitrarily selected depending on the purpose, but generally, the swellable layered silicate 1 used as a raw material contained in the separated solid is used in comparison with the polymer monomer. Quantity 5
１０００1000 (weight ratio). When the separated solid is suddenly mixed with a polymer monomer, it often does not disperse well. Generally, the separated solid is first dispersed in the above-mentioned solvent (the dispersion concentration of the solid is not particularly limited; About 1 to 50% by weight), and then a high molecular monomer is mixed. When dispersing the separated solids in the solvent,
A small amount (5% by weight or less of the solvent) of a phosphate and / or polyphosphate may be dissolved in a solvent and then dispersed.

The polymer monomer to be mixed can be selected arbitrarily, and typical examples thereof include the above-mentioned polyamide monomer and polyester monomer. In addition, in the dispersions (T _A ) and (T _B ) of the present invention, the reflection peak value near the (001) diffraction line region is the same as that of the solid (C) as in the X-ray diffraction spectrum of the dispersion (S). From 1 to 15 ° C. larger than the reflection peak value. This is dispersion (T _A), in addition to the (T _B) characteristics of the dispersion (S) is maintained even at, Dispersed complex (B) is compound crystal layers (A), the solvent and This indicates that the polymer monomers are regularly stacked in an intercalated form. This is the dispersion of the invention (T
_A ) and (T _B ) are considered to be remarkable properties, and it is determined that these properties greatly affect the dispersibility of the dispersions (T _A ) and (T _B ).

_A simple polymerization test was carried out on the dispersion (T _A ) of the present invention. The solids dispersed in the dispersion (T _A ) were uniformly dispersed in the polymer obtained by polymerizing the monomers. I was able to confirm that. In addition, a pigment, an antibacterial agent, an ultraviolet absorber and the like can be added to the dispersion of the present invention, if necessary, in addition to the components described above, as long as the properties are not significantly impaired.

[0034]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the present invention. In addition, in the following examples, the numbers of the raw materials indicate weight basis.

Example 1 As a swellable layered silicate, Somasif (ME-100) manufactured by Corp Chemical Co., Ltd. was used. The details of Somasif are described below.

[0036]

_Embedded image General formula: Na _{2X + 2a} Mg _3.0-X [(Si _4.0-a Mg _a )
O ₁₀ ] (F, OH) ₂ (where 0 ≦ X ≦ 0.5, 0 ≦ a <0.50, 0.15
≦ X + is a ≦ 0.5, Na coordination number 12 cations in the interlayer; Mg _3.0-X in Mg cation coordination number 6 forming the octahedral sheet; (Si _4.0- Si and Mg in _a Mg _a ) are cations having a coordination number of 4 forming a tetrahedral sheet. )

Cation exchange capacity (amount of methylene blue adsorbed): 70 meq / 100 g Average particle size 3 μm Somasif (swellable layered silicate) 4 and water 96 were thoroughly mixed, and a 4% by weight Somasif dispersion was prepared. Prepared. Take 150 g of it and add sodium tripolyphosphate (N
a ₅ P ₃ O ₁₀ , phosphate and / or polyphosphate) 3 g
Was added and mixed well to completely dissolve the sodium tripolyphosphate. Aluminum nitrate (Al (NO
_{3) 3} · 9H ₂ O, was added and mixed for about 30 minutes 100ml substantial amount of polyvalent metal salt and / or polynuclear metal complex) 7.5 g as 0.2 mol / 1000 ml solution, dispersion of the present invention (S ₁ ) Got it. The pH of the dispersion (S ₁ ) is 2.
Nine.

The dispersion (S ₁ ) 25 was mixed with ethylene glycol (polymer monomer) at a ratio of 30 to obtain a dispersion (T _A1 ) of the present invention. For the dispersion (S ₁ ) 25,
The mixture was mixed at a ratio of 60 of ε-caprolactam (polymer monomer) to obtain a dispersion (T _A2 ) of the present invention. Dispersion (S ₁ )
Was rinsed three times with a centrifuge, and one part of the separated cake was dried at 60 ° C. for 12 hours to obtain a solid (C
₁ ) Got it.

The dispersion (S ₁ ) is subjected to cake rinsing three times with a centrifuge, and one part of the separated cake is taken, and water is added to prepare a 20% solution of solid (C ₁ ). Liquid 1
Was mixed with ethylene glycol at a ratio of 4 to obtain a dispersion (T _B1 ) of the present invention. The dispersion (S ₁ ) is subjected to cake rinsing three times with a centrifugal separator, one part of the separated cake is taken, and water is added to prepare a 20% solution of solid (C ₁ ).
The prepared liquid 1 was mixed at a ratio of ε-caprolactam 4 to obtain a dispersion liquid (T _B2 ) of the present invention.

The swellable phyllosilicate (A), phosphate and / or polyphosphate (B), polyvalent metal salt and / or polynucleate for producing the dispersion (S ₁ ) of the present invention. The molar ratio of the metal complex salt (C) is A: B: C = 1.00: 0.53:
It was set to 1.33.

[0041] (Example 2) sodium tripolyphosphate (Na ₅ P ₃ O ₁₀₎ to 3g to 1.5g, aluminum nitrate _{(Al (NO 3) 3 ·} 9H 2 O) and 7.5 g 3.5 g
Was obtained in the same manner as in Example 1 except that the dispersion liquid (S ₂ ) of the present invention was obtained. The dispersion (S ₂ ) had a pH of 3.4.

The dispersion (S ₂ ) 25 was mixed with ethylene glycol at a ratio of 30 to obtain a dispersion (T _A3 ) of the present invention. The dispersion (S ₂ ) 25 was mixed with ε-caprolactam 60 at a ratio of 25 to obtain a dispersion (T _A4 ) of the present invention.
The dispersion (S ₂ ) was subjected to cake rinsing three times with a centrifuge, and one part of the separated cake was taken and dried at 60 ° C. for 12 hours to obtain a solid (C ₂ ).

The dispersion (S ₂ ) was subjected to cake rinsing three times with a centrifugal separator. One part of the separated cake was taken, and water was added to prepare a 20% solution of solid (C ₂ ). Liquid 1
Was mixed with ethylene glycol at a ratio of 4 to obtain a dispersion (T _B3 ) of the present invention. The dispersion (S ₂ ) is subjected to cake rinsing three times with a centrifugal separator, one part of the separated cake is taken, and water is added to prepare a 20% solution of solid (C ₂ ).
The prepared liquid 1 was mixed at a ratio of ε-caprolactam 4 to obtain a dispersion liquid (T _B4 ) of the present invention.

The swellable phyllosilicate (A), phosphate and / or polyphosphate (B), polyvalent metal salt and / or polynucleate used in producing the dispersion (S ₂ ) of the present invention. The molar ratio of the metal complex salt (C) is A: B: C = 1.00: 0.27:
0.61 was set. X-ray diffraction spectra of the dispersions and solids obtained in Examples 1 and 2 were measured, and a (001) diffraction line region having a bottom surface spacing value (d ₀₀₁ ) specific to the swellable phyllosilicate as a raw material was obtained. The near reflection peak values were measured and are shown in Table 1.

[0045]

[Table 1]

The solid (C ₁ ) obtained in Examples 1 and 2,
The solid (C ₂ ) and the raw material Somasif were subjected to X-ray fluorescence analysis to determine the chemical composition (% by weight). In addition,
Si, Mg, Na, Al, and P are oxide equivalent values.

[0047]

Table 2 Chemical composition of solids-1 (% by weight) Raw material Somasif Solid (C ₁ ) Solid (C ₂ ) 1 SiO ₂ 59.8 48.9 55.3 2 MgO 28.6 23.0 26 5.5 3 Na ₂ O 5.5 1.3 1.8 4 F 10.0 7.9 9.1 5 Al ₂ O ₃ 0.5 7.2 4.9 6 P ₂ O ₅ 0.0 8. 2 4.4

Example 3 A mixture of Somasif 4 and water 96 was sufficiently mixed to prepare a 4% by weight Somasif dispersion. A 150 g portion thereof was taken, and 0.5 g of sodium tripolyphosphate (Na ₅ P ₃ O ₁₀ ) was added thereto and mixed well to completely dissolve the sodium tripolyphosphate. 6.4 g of zirconium oxychloride (ZrCl ₂ O, polyvalent metal salt and / or polynuclear metal complex salt) was added thereto at 0.2 mol / 100.
A 0 ml aqueous solution was added and mixed in an amount of 100 ml in about 30 minutes to obtain a dispersion (S ₃ ) of the present invention. Dispersion (S
₃ ) The pH was 1.5.

The dispersion (S ₃ ) 25 was mixed with ethylene glycol at a ratio of 60 to obtain a dispersion (T _A5 ) of the present invention. The dispersion (S ₃ ) 25 was mixed with ε-caprolactam 30 at a ratio of 25 to obtain a dispersion (T _A6 ) of the present invention.
The dispersion (S ₃ ) was subjected to cake rinsing three times with a centrifuge, and one part of the separated cake was taken and dried at 60 ° C. for 12 hours to obtain a solid (C ₃ ).

The dispersion (S ₃ ) was subjected to cake rinsing three times by a centrifugal separator, one part of the separated cake was taken, and water was added to prepare a 20% solution of solid (C ₃ ). Liquid 1
Was mixed with ethylene glycol at a ratio of 2 to give a dispersion liquid (T _B5 ) of the present invention. The dispersion (S ₃ ) is subjected to cake rinsing three times with a centrifuge, one part of the separated cake is taken, and water is added to prepare a 20% solution of solid (C ₃ ).
The prepared liquid 1 was mixed at a ratio of ε-caprolactam 4 to obtain a dispersion liquid (T _B6 ) of the present invention.

The swellable phyllosilicate (A), phosphate and / or polyphosphate (B), polyvalent metal salt and / or polynucleate for producing the dispersion (S ₃ ) of the present invention. The molar ratio of the metal complex salt (C) is A: B: C = 1.00: 0.09:
It was set to 1.33.

Example 4 A dispersion (S ₄ ) of the present invention was obtained in the same manner as in Example 3 except that 0.5 g of sodium tripolyphosphate (Na ₅ P ₃ O ₁₀ ) was changed to 1.5 g. Was. The dispersion (S ₄ ) had a pH of 2.0.

The dispersion (S ₄ ) 25 was mixed with ethylene glycol at a ratio of 60 to obtain a dispersion (T _A7 ) of the present invention. Dispersion (S ₄ ) 25 was mixed with ε-caprolactam 30 at a ratio of 25 to obtain a dispersion (T _A8 ) of the present invention.
The dispersion (S ₄ ) was subjected to cake rinsing three times with a centrifuge, and one part of the separated cake was taken and dried at 60 ° C. for 12 hours to obtain a solid (C ₄ ).

The dispersion (S ₄ ) was rinsed with a cake three times by a centrifuge. One part of the separated cake was taken, and water was added to prepare a 20% solution of the solid (C ₄ ). Liquid 1
Was mixed with ethylene glycol at a ratio of 2 to obtain a dispersion (T _B7 ) of the present invention. The dispersion (S ₄ ) is subjected to cake rinsing three times by a centrifugal separator, a part of the separated cake is taken, and water is added to prepare a 20% solution of a solid (C ₄ ).
The prepared liquid 1 was mixed at a ratio of ε-caprolactam 4 to obtain a dispersion liquid (T _B8 ) of the present invention.

The swellable phyllosilicate (A), phosphate and / or polyphosphate (B), polyvalent metal salt and / or polynucleate used in the production of the dispersion (S ₄ ) of the present invention. The molar ratio of the metal complex salt (C) is A: B: C = 1.00: 0.27:
It was set to 1.33. X-ray diffraction spectra of the dispersions and solids obtained in Examples 3 and 4 were measured, and a (001) diffraction line region having a bottom surface spacing value (d ₀₀₁ ) specific to the raw material swellable phyllosilicate. The near reflection peak values were measured and are shown in Table 3.

[0056]

[Table 3]

The solid (C ₃ ) obtained in Examples 3 and 4,
The solid (C ₄ ) and the raw material Somasif were subjected to X-ray fluorescence analysis to determine the chemical composition (% by weight). In addition,
Si, Mg, Na, Zr, and P are oxide equivalents.

[0058]

Table 4 Chemical composition of solid -2 (% by weight) Raw material Somasif Solid (C ₁ ) Solid (C ₂ ) 1 SiO ₂ 59.8 50.2 42.8 2 MgO 28.6 25.0 20 0.83 Na ₂ O 5.5 0.9 0.74 F 10.0 8.5 7.1 5 Al ₂ O ₃ 0.5 0.4 0.46 ZrO ₂ 0.0 13.1 18 .47 P ₂ O ₅ 0.0 1.8 9.8

Example 5 One part of the dispersion (T _A2 ) of the present invention obtained in Example 1 was taken, and the dispersion well dispersed by ultrasonic treatment was placed in a test tube. The upper end was stretched with a gas burner to form a 1 mm capillary. The test tube was reacted at 255 ° C. for 10 hours in an air bath,
Then it was cooled. When observing the product, the dispersion (T _A2 )
It was confirmed that the solids dispersed therein were uniformly dispersed in the polymer obtained by polymerizing the monomers.

[0060]

The dispersion of the present invention comprises a compound containing phosphorus and a metal element formed by the reaction of a phosphate and / or polyphosphate with a polyvalent metal salt and / or a polynuclear metal complex, and a swellable layered material. Contains a solid consisting of a complex with silicate,
It is dispersed as fine particles in the liquid. In addition, the dispersed complex (solid material) has an extremely characteristic property in which a solvent and / or a high molecular monomer is intercalated regularly between the crystal layers. For this reason, when synthesizing an organic polymer compound, it is determined that this complex is extremely uniformly dispersed in the monomer, and can be effectively used for improving various characteristics of the resulting organic polymer compound.

The compound formed by the reaction of the phosphate and / or polyphosphate with the polyvalent metal salt and / or the polynuclear metal complex forms a complex with the swellable layered silicate, or Although they exist as a simple substance, they can be expected to provide various effects such as an effect of improving flame retardancy because they contain phosphorus and various polyvalent metal elements. In addition, the dispersion before mixing the polymer monomer can be expected to be used for purposes other than the polymer, and also as a raw material for, for example, paints and coating agents.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Akira Yu Abiko 169-5 Takadacho, Tosu City, Saga Prefecture (72) Inventor Masaru Oi 9-32, Suehirocho, Niigata City, Niigata Prefecture (72) Inventor Haruo Asai Otsu, Shiga Prefecture 2-1-1 Katata, City (72) Inventor Yoshiko Takino 2-1-1 Katata, Otsu-shi, Shiga Prefecture (72) Nobuyuki Kinan 2-1-1 Katata, Otsu-shi, Shiga Prefecture

Claims (6)

[Claims] 1. A swellable layered silicate, comprising a phosphate and / or
Alternatively, a dispersion obtained by mixing a polyphosphate, a polyvalent metal salt and / or a polynuclear metal complex, and a solvent. 2. The method according to claim 1, wherein the dispersed solid is phosphate and / or
The dispersion according to claim 1, further comprising a complex of a compound containing phosphorus and a metal element, which is formed by a reaction of a polyphosphate with a polyvalent metal salt and / or a polynuclear metal complex, and a swellable layered silicate. 3. A dispersion obtained by further mixing a polymer monomer with the dispersion according to claim 1 or 2. 4. A dispersion obtained by separating a solid from the dispersion according to claim 1 or 2, and mixing a polymer monomer or a polymer monomer and a solvent with the separated solid. 5. A swellable layered silicate is dispersed in a solvent, a phosphate and / or a polyphosphate are added thereto, and then a polyvalent metal salt and / or a polynuclear metal complex dissolved in the solvent is added. 4. The method for producing a dispersion according to claim 3, wherein the dispersion (S) is prepared by adding a polymer monomer to the dispersion. 6. A solid content is separated from the dispersion liquid (S) according to claim 5, and a polymer monomer or a polymer monomer and a solvent are mixed with the separated solid material. A method for producing the dispersion according to the above.