JPH06287014A - Organic material-clay complex - Google Patents

Abstract

PURPOSE:To obtain an organic material-clay complex having high affinity to organic solvents and polysiloxanes and usable as a thickener stable over a long period by introducing a specific quaternary ammonium ion between layers of a swelling laminar silicate. CONSTITUTION:The organic material-clay complex has a structure containing a quaternary ammonium ion expressed by formula between layers of a swelling laminar silicate. In the formula, R<1> is 1-30C alkyl or benzyl; R<2> and R<3> are (CH2CH(CH3)O)nH, (CH2CH2CH2O)nH or 1-30C alkyl; R<4> is (CH2CH(CH3)O)nH or (CH2CH2CH2O)nH; (n) is 1-50. The organic material-clay complex can be produced by reacting a swelling laminar silicate with 0.5-1.5 times equivalent (in terms of m-equivalent, based on the cation exchange capacity of the laminar silicate) of a quaternary ammonium salt having the quaternary ammonium ion of formula.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organoclay composite having an affinity for organic solvents and polysiloxanes and useful as a thickener or a gelling agent, a method for producing the same and a composition thereof.

[0002]

2. Description of the Related Art Layered silicate minerals are typical minerals constituting clay, and in a 2: 1 type layered silicate mineral, two silica tetrahedral silicate layers are made of magnesium. It has a sandwich type three-layer structure in which an octahedral layer or an aluminum octahedral layer is sandwiched, and this has a structure in which several to several tens layers are laminated.

The silicate layer of the swellable layered silicate has a negative charge, but since the charge is neutralized by the alkali metal cations and alkaline earth metal cations existing between the layers, As the charge is balanced. Smectite clay and swelling mica which are these swelling layered silicates are fine particles having a cation exchange ability, the layers are easily spread, and a sol having a thixotropic property is dispersed in water to form a sol having a high concentration. Then, it has a property of forming a gel.

The swellable layered silicate can be made into an organoclay composite by reacting with various cationic organic compounds. As an example of such an organoclay composite, a product in which dimethyl dioctadecyl ammonium ion is introduced by cation exchange between smectite layers is industrially produced and used as a thickener for a paint. However, organic solvents capable of dispersing and thickening this are limited to a part of aromatic hydrocarbons such as toluene and benzene. In addition, as a thickening agent for highly polar organic solvents, dimethyl benzyl octadecyl
Organoclay composites having ammonium ions introduced are also known, but they do not have a sufficient thickening effect and their dispersibility is poor.
Further, although examples in which they are used by dispersing them in ethyl acetate, ketones, alcohols, etc. are disclosed, none of these solvents has poor dispersibility and does not have a sufficient thickening effect.

On the other hand, a thickener for an organic solvent which is made organic by modifying the surface of delicate silica with an organic substance is also known, but the thickening effect cannot be obtained unless it is used in a large amount.
Further, since it has a low affinity with an organic solvent, it has a drawback that part of it precipitates and redispersion becomes difficult when stored for a long time.
Further, no thickening agent effective for polysiloxanes has been reported so far.

[0006] EP Patent Publication No. 0133071 discloses
A modified organophilic clay is described in which a smectite clay is modified using a combination of a quaternary ammonium salt having an alkyl group or a benzyl group and a mono- or polyhydroxylated nitrogen-containing organic surfactant. However, these are intended as thickeners for organic solvents such as toluene and white spirits, and their dispersibility in other organic solvents is not described.

Japanese Unexamined Patent Publication No. 5-57288 (USP 5,
No. 130,028), in smectite clay,
[Methyl / diethyl / polyoxypropylene (25)]
Organoclays obtained by reacting ammonium chloride are described. However, since this organoclay is organic (hydrophobic), it does not function as a non-adhesive agent by itself, and in order to use it as a non-adhesive agent for paints, it improves organophilicity. It is stated that it must be used in combination with a highly hydrophobic ammonium salt for the purpose.

[0008]

The above-mentioned conventional thickeners are
The drawback is that it does not have a sufficient thickening effect on organic solvents such as ethers, halogenated hydrocarbons, alcohols, ketones, amides, esters, etc. and polysiloxanes, and cannot withstand long-term storage. Therefore, it is required to develop an organoclay composite that has a high affinity with organic solvents and polysiloxanes and can be used as a thickener that is stable for a long period of time.

[0009]

Means for Solving the Problems The present inventors have conducted extensive studies for many years to develop an organoclay composite useful as a thickener for organic solvents and polysiloxanes. Organoclay composites in which a quaternary ammonium ion having the following general formula (I) having a propylene group is introduced between the layers of the swelling layered silicate are aromatic hydrocarbons, ethers, halogenated hydrocarbons. It has been found that it has a good affinity with organic solvents such as alcohols, ketones, amides and esters, and polysiloxanes, and has a sufficient thickening effect when dispersed in these.

That is, the present invention relates to an organoclay composite in which a quaternary ammonium ion represented by the general formula (I) is introduced between layers of a swellable layered silicate.

[Chemical 3]

The swellable layered silicate used as a raw material for the organoclay composite of the present invention is a layered silicate having a cation exchange ability and having a unique property of swelling by taking in water between layers. , Smectite-type clay, swelling mica, and the like. For example, examples of the smectite clay include hectorite, saponite, stevensite, beidellite, montmorillonite, nontronite, bentonite, and other naturally or chemically synthesized substances, or substitution products, derivatives thereof, or a mixture thereof. You can The swelling mica is a natural or chemically synthesized swelling mica such as Li-type fluoro-teniolite, Na-type fluoro-teniolite, Na-type tetrasilicon-fluorine mica, Li-type tetra-silicon-mica, etc., with Li ion or Na ion between the layers. Swellable mica having, or a substitution product thereof, a derivative or a mixture thereof, vermiculite,
Fluorine vermiculite or the like can also be used.

The synthetic smectite clay used in the present invention has a general formula having a structure similar to that of a hectorite type clay mineral produced by the production method described in Japanese Patent Publication No. 61-12848 or a production method similar thereto. (II)
Synthetic smectites are preferred, but are not limited to the following production methods.

[Chemical 4]

The synthetic smectite is produced by the following method. That is, a homogeneous mixture of silicate and magnesium salt is reacted with an alkaline solution to synthesize a silicon-magnesium complex, the by-produced electrolyte is removed, and then lithium ion and sodium ion are optionally added to the complex. as well as/
Or add fluoride ion, 100 ℃ -350 ℃
It is obtained by hydrothermally reacting with and then drying.

More specifically, first, a homogeneous mixed solution of a silicate solution and a magnesium salt solution is prepared. The mixing ratio of the silicate and the magnesium salt is preferably the stoichiometric ratio of the general formula (II). The silicate solution is obtained by mixing sodium silicate and mineral acid and acidifying the mixed solution. As the sodium silicate, any of commercially available No. 1 to No. 4 water glass and sodium metasilicate may be used.
As the mineral acid, nitric acid, hydrochloric acid, sulfuric acid or the like can be used. When a silicate and a mineral acid are mixed, a gel is often formed when the amount of the mineral acid is small. Therefore, the pH of the solution is 5 or less, preferably 1 to 3
It is necessary to add a mineral acid so that

An alkaline solution is mixed with the obtained homogeneous mixed solution at room temperature to obtain a homogeneous precipitate. As the alkaline solution, ammonia, sodium hydroxide, lithium hydroxide,
Solutions of potassium hydroxide and mixtures thereof are preferred.
The amount of the alkaline solution added is such that the pH after mixing becomes 10 or more. Next, the formed precipitate is filtered and washed with water repeatedly to sufficiently remove the by-produced electrolyte.

As a method for removing the by-produced electrolyte as completely as possible, an ultrafiltration method by a cross-flow method described in JP-A-5-279012 (Rey nozzle number 50 to 5,000, average fineness of filtration membrane). Pore size 0.1-5
μm) is preferred, but if similar separation / removal is possible,
The method is not limited to this.

When lithium ions and other than sodium hydroxide are used as the alkaline solution in the produced homogeneous precipitate, sodium ions are further added, and if necessary, fluorine ions are added, and the mixture is pressurized in an autoclave or the like. It is charged in a reactor and reacted at 100 to 350 ° C. Regarding the reaction time, generally, the higher the reaction temperature, the higher the reaction rate, and the longer the reaction time, the better the crystallization. Under the conditions of 41 kg / cm ² and 250 ° C., a reaction time of 1 to 3 hours is sufficient.

Examples of the lithium ion, sodium ion and fluorine ion to be added include lithium hydroxide,
It can be selected from sodium hydroxide, hydrofluoric acid, sodium fluoride and the like. The reaction can be easily achieved without adding fluorine ion. After completion of the reaction, the content of the reactor is dried and pulverized to obtain the synthetic smectite of the general formula (II).

The swellable mica used in the present invention can be prepared, for example, by the method described in JP-A-2-149415.
It is obtained by heat-treating a mixture of sodium silicofluoride or lithium silicofluoride and talc, or a mixture of sodium silicofluoride or lithium silicofluoride and sodium fluoride or lithium fluoride and talc at 700 to 1,000 ° C.

The cation exchange capacity of the swellable layered silicate used for producing the organoclay composite of the present invention is 10 milliequivalents or more, preferably 60 milliequivalents or more per 100 g of clay. In the case of the synthetic smectite of (II), it is 85 to 130 meq, and the larger the exchange capacity, the better. The swellable layered silicate may contain up to 50% non-clay impurities, but the amount of non-clay impurities is 10%.
% Or less is desirable.

The alkyl group in the quaternary ammonium ion represented by the general formula (I) has 1 to 30 carbon atoms, for example, methyl, ethyl, propyl, isopropyl,
Examples thereof include butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl and the like.

Polyoxypropylene group [(CH ₂ CH
_{N of} (CH ₃ ) O) _n H or (CH ₂ CH ₂ CH ₂ O) _n H]
Is from 1 to 50, preferably from 5 to 50, and the greater the number of added moles, the better the dispersibility in the organic solvent, but if it is excessive, the product becomes tacky. When the dispersibility in the solvent is emphasized, the number of n is more preferably 20 to 50. Also, the number of n is 5
When it is 20, the product is non-tacky and has excellent grindability. From the viewpoint of dispersibility and handling, the total number of n in the whole quaternary ammonium is preferably 5 to 50.

In order to introduce the quaternary ammonium ion represented by the general formula (I) between the layers of the layered silicate, a quaternary ammonium salt containing the ion is used. Examples of such a salt include: For example, Cl ⁻ , Br ⁻ , NO ₃ ⁻ , OH
^-, CH ₃ COO ^- it can be exemplified salts with such anions.

Specific examples of the quaternary ammonium salt include polyoxypropylene / trialkylammonium chloride polyoxypropylene / trialkylammonium bromide di (polyoxypropylene) / dialkylammonium chloride di (polyoxypropylene) / dialkyl. Examples thereof include ammonium bromide tri (polyoxypropylene) / alkylammonium chloride tri (polyoxypropylene) / alkylammonium bromide.

In the quaternary ammonium ion of the general formula (I), the preferable one for R ¹ is methyl group or benzyl group. R ² is preferably an alkyl group having 1 to 12 carbon atoms, particularly preferably an alkyl group having 1 to 4 carbon atoms, and most preferably an ethyl group. R
Preferred as ³ is an alkyl group having 1 to 4 carbon atoms,
Particularly preferred is the ethyl group. R ⁴ is preferably a (CH ₂ CH (CH ₃ ) O) _n H group or (CH ₂ CH ₂
CH ₂ O) _n H group. It is preferable that n is 5 to 50.

The organoclay composite of the present invention is obtained by cation exchange between layers, and can be produced, for example, by the following method. In the first step, the swellable layered silicate is dispersed in water, and the solid dispersion concentration is usually desired to be 1 to 15 wt%, but it is freely set as long as the concentration of the swellable layered silicate is sufficiently dispersible. It is possible. In this case, it is effective to use the swellable layered silicate that has been previously freeze-dried in order to easily produce the organoclay composite. In the second step, the quaternary ammonium salt solution is added to the swellable layered silicate suspension, or conversely, the swellable layered silicate suspension is added to the quaternary ammonium salt solution. It is also possible to produce an organoclay composite by adding.

The amount of the quaternary ammonium salt added is preferably equivalent to the cation exchange capacity of the swellable layered silicate as the quaternary ammonium ion, but a smaller amount than this can be used for production. There is no problem even if an excessive amount is added to the cation exchange capacity. The amount thereof is preferably 0.5 to 1.5 times (milliequivalent) the cation exchange capacity of the layered silicate, and particularly preferably 0.8 to 1.4 times.

The reaction proceeds sufficiently at room temperature, but may be heated. The maximum temperature of heating is governed by the heat resistance of the quaternary ammonium salt used, and can be arbitrarily set as long as it is below its decomposition point. Then, the solid-liquid is separated, and the produced organoclay composite is washed with water to sufficiently remove the by-product electrolyte. This is dried and, if necessary, crushed to obtain a final product.

The general characteristics of the thus obtained organoclay composite can be evaluated by selecting from the following items according to the purpose or by carrying out a combination of these. (1) Chemical analysis (2) X-ray diffraction (powder method or oriented method) (3) NMR (4) Infrared absorption spectrum (5) Thermobalance / differential thermal analysis (6) Rheology measurement of organic solvent system (7) ) Color tone (8) Swelling power in organic solvent

For example, the formation of the organoclay composite of the present invention is
It can be easily confirmed by measuring the position of the (001) bottom surface reflection by X-ray diffraction. The raw material, synthetic smectite, is 10Å in dehydrated state, and 1 in normal temperature and humidity.
It has a bottom spacing of 2 to 15 Å, but the organoclay composite of the present invention has 15 Å or more, depending on the number of carbon atoms of the alkyl group in the quaternary ammonium ion and the number of addition condensation of polyoxypropylene groups. From this, it can be seen that the organoclay composite is formed. The function as a thickener can be easily confirmed by visually observing the viscosity by dispersing it in an organic solvent such as alcohol, but the rheological properties of the resulting dispersion are measured with a viscometer. You can know it.

To use the organoclay composite of the present invention as a thickener or gelling agent, the organoclay composite is added to an organic solvent or polysiloxane and dispersed by stirring or the like. The thicker the amount is, the higher the thickening effect is.
The amount of the organoclay complex added varies depending on the type and application of the organic solvent or polysiloxane, but generally 0.1 to
By dispersing in the range of 20% by weight, it can be used for various purposes.

The organoclay composite of the present invention can be dispersed in various organic solvents and / or polysiloxanes to give an organoclay composite composition. As the organic solvent, various high-polarity, low-polarity or non-polar organic solvents, specifically, aromatic hydrocarbons such as benzene, toluene, xylene; ethers such as tetrahydrofuran, acetone, methyl ethyl ketone, methyl isobutyl ketone Such as ketones; lower alcohols such as methanol, ethanol, propanol and isopropanol; higher alcohols such as decanol, hexanol and decanol; halogenated carbonization such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, perchloroethylene and chlorobenzene Hydrogens; amides such as dimethylformamide; esters such as ethyl acetate and dioctide phthalate, dimethylsulfoxide, methylcellosolve, N
-Disperse in a solvent such as methyl-2-pyrrolidone. Further, it can be dispersed in polysiloxanes such as various silicone oils.

[0033]

The organoclay composite of the present invention has an affinity for organic solvents and polysiloxanes, and further exhibits the effect of dispersing and thickening that the oxygen of the polyoxypropylene group or the terminal hydroxyl group and the organic solvent And, because the hydroxyl group or oxygen of the polysiloxane is hydrogen-bonded, or because the hydrophilicity and the hydrophobicity balance between the interlayer organic substance and the organic solvent and the polysiloxane are the same, the solvent molecule is formed between the layers of the swelling layered silicate. It is considered that this is because it penetrates and spreads the layers to separate the further laminated silicate layers. It is presumed that the separated silicate layers form a gel structure by irregularly bonding to each other due to the negative charges remaining on the layer surfaces and the positive charges on the end surfaces.

[0034]

INDUSTRIAL APPLICABILITY The organoclay composite of the present invention is different from the conventional organoclay composites in that the use thereof is limited to aromatic hydrocarbons and halogenated hydrocarbons. It can be used as a thickener by dispersing it in an organic solvent such as compounds, halogenated hydrocarbons, ketones, alcohols, amides and esters, and polysiloxanes or a solvent containing them.

The organoclay composite of the present invention has an affinity for organic solvents and polysiloxanes, disperses easily, and exhibits excellent thickening and gelling effects even when added in a small amount. Use as a composition of viscosity modifier, dispersant, emulsifier, binder, etc. in various products and industrial processes such as various cosmetics, pharmaceuticals, sanitizers, adhesives, paints, coating materials, various plastic products, textile industry, etc. It is possible and extremely useful. Furthermore, since this organoclay composite contains a polyoxypropylene group, it can be used as an antistatic agent for plastics and fibers, a bactericidal agent, a dyeing auxiliary agent, a leveling agent, and a coupling agent. Further, the layer space can be utilized as an organic substance storage agent, sustained release agent, catalyst, separating agent, adsorbent, resin stabilizer, polymerization initiator, carrier, filler and the like.

Particularly, an organic clay complex in which a preferable quaternary ammonium ion among the quaternary ammonium ions of the general formula (I) is introduced between the layers of synthetic smectite is used as an aromatic hydrocarbon or a halogenated hydrocarbon. When used by dispersing it in alcohols, alcohols, ketones, amides or N-methyl-2-pyrrolidone, a sol or gel having a high degree of dispersion is required because it disperses transparently and does not form a precipitate. This is especially useful in some cases. In addition, since the organoclay composite produced by using swelling mica as a raw material has a structure different from that of smectite clay, cosmetics, resin fillers, catalysts, paints, greases, etc. are particularly utilized by taking advantage of these characteristics. Can be expected to be used for various purposes.

[0037]

【Example】

Synthesis Example 1 Synthesis of synthetic smectite 4 L of water was placed in a 10 L beaker, and water glass No. 3 (Si
O ₂ 28%, Na ₂ O 9%, molar ratio 3.22) 860 g
Is dissolved and 162 g of 95% sulfuric acid are added at once with stirring to obtain a silicate solution. Then add 1 L of water to MgCl ₂ · 6
560 g of H ₂ O primary reagent (purity 98%) was dissolved and added to the silicic acid solution to prepare a homogeneous mixed solution. This was dropped into 3.6 L of 2N-NaOH solution with stirring for 5 minutes. The reaction precipitate obtained was immediately filtered by NGK Insulators Co., Ltd. using a cross-flow filtration system [Cross-flow filter (ceramic membrane filter: pore size 2 μm
m, tubular type, filtration area 400 cm ² ), pressurization:
2 kg / cm ² , filter cloth: Tetron 1310], and after thoroughly washing with water, 200 ml of water and Li (OH) · H ₂ O 1
A solution of 4.5 g was added to form a slurry. This was transferred to an autoclave, 41kg / cm ² , 3 at 250 ℃
It was hydrothermally reacted for a time. After cooling, the reaction product is taken out, and the temperature is 80 ° C.
And then pulverized to obtain a synthetic smectite of the following formula.
This synthetic smectite had a bottom distance measured by X-ray diffraction of 12.5Å in air and a cation exchange capacity of 110 meq / 100 g. Na _0.4 Mg _2.6 Li _0.4
Si ₄ O ₁₀ (OH) ₂

Synthesis Example 2 Synthesis of synthetic swelling mica According to the method described in JP-A-2-149415, 13.5 g of talc and 2.5 g of sodium silicofluoride.
The finely pulverized products of 1. were mixed and heat-treated at 800 ° C. to obtain 15.0 g of synthetic swelling mica. The cation exchange capacity of this synthetic swellable mica was 70 meq / 100 g.

Example 1 Production of Synthetic Smectite Organoclay Complex A 10 g of the synthetic smectite synthesized in Synthesis Example 1 was added to tap water 5
It was dispersed in 00 ml to give a suspension. The cation exchange capacity equivalent amount of the synthetic smectite represented by the following formula (III)

[Chemical 5] 300 ml of an aqueous solution containing 17.7 g (98% content) of the quaternary ammonium salt of was dissolved in the synthetic smectite suspension, and the mixture was reacted for 2 hours at room temperature with stirring. The product was subjected to solid-liquid separation, washed to remove by-product salts, and then dried to obtain a synthetic smectite-based organoclay complex A. According to X-ray diffraction measurement of the product, the basal plane distance calculated from the position of the (001) basal plane reflection was 44Å, confirming the formation of the synthetic smectite-based organoclay composite of the present invention.

Example 2 Production of Synthetic Smectite Organoclay Complexes B, C and D 10 g of the synthetic smectite synthesized in Synthesis Example 1 was added to 5 parts of tap water.
It was dispersed in 00 ml to give a suspension. The following formulas (IV), (V) and (VI) corresponding to the cation exchange capacity of the synthetic smectite

[Chemical 6]

[Chemical 7]

[Chemical 8] Aqueous solution 3 in which each of the quaternary ammonium salts of
00 ml was added to the above synthetic smectite suspension, and the mixture was reacted for 2 hours at room temperature with stirring. Solid-liquid separation of products,
After washing to remove by-product salts, it was dried to obtain synthetic smectite-based organoclay composites B, C and D, respectively.

Example 3 Production of Synthetic Swellable Mica-based Organoclay Complexes A and B 15 g of the synthetic swellable mica synthesized in Synthetic Example 2 was added to 50 parts of tap water.
It was dispersed in 0 ml to give a suspension. 17.7 g (9) each of the quaternary ammonium salts of formulas (III) and (V) above
300 ml of an aqueous solution in which 8% content product) was dissolved was added to the swelling mica suspension and reacted at room temperature for 2 hours while stirring. The product is subjected to solid-liquid separation, washed to remove by-product salts, and then dried to produce a synthetic swelling mica-based organoclay complex A and B.
Respectively obtained.

Example 4 Production of Other Organoclay Composites 10 g of the swellable layered silicate described in Table 1 was added to tap water 500
It was dispersed in ml to give a suspension. 300 ml of an aqueous solution in which an amount equivalent to the cation exchange capacity of the organoclay complex was dissolved in the quaternary ammonium salt of the formula (III) was added to the swellable layered silicate suspension and stirred at room temperature. The reaction was carried out for 2 hours. The product is subjected to solid-liquid separation, washed to remove by-product salts, and then dried to obtain other organoclay complexes A, B, C, D,
E, F, G and H were obtained respectively.

[Table 1] Comparative Example 1 The same procedure as in Example 1 was carried out except that 7.7 g of dimethyl dioctadecyl ammonium salt (trade name: Arcard 2HT, Lion Akzo strain) was used in place of the quaternary ammonium salt used in Example 1. A comparative organoclay composite was prepared.

Test Example 1 Dispersibility Test The smectite-based organoclay composites A and B of the present invention and the other organoclay composites A to H were added to various organic solvents so as to have a concentration of 2 wt%, and the dispersion was conducted. 50g of liquid 30g
The mixture was placed in a screw tube bottle of No. 1 and shaken vigorously to make it uniform, and then allowed to stand at 25 ° C. for 1 week, and the dispersibility was visually measured. The results are shown in Table 2. The dispersed state was represented by the following criteria. Completely dispersed: A, dispersed but some sediment is formed: B, not swelled and not dispersed: C

[Table 2]

As can be seen from Table 2, the dispersibility of the synthetic smectite type organic clay composites A and B and the other organic clay composites A to H was A rank or B rank in various organic solvents. In particular, it is understood that the synthetic smectite-based organoclay composite produced from the synthetic smectite produced in Synthesis Example 1 has excellent dispersibility in various organic solvents.

Test Example 2 Dispersibility / Transparency / Sol-Gel Property Test [Dispersion Test] The test was performed in the same manner as in Test Example 1 except that the concentration of the organoclay composite in Test Example 1 was changed to 4 wt%. [Transparency test] Synthetic smectite-based organoclay composites A to D and synthetic swellable mica-based organoclay composite B of the present invention
Add various organic solvents and polysiloxane solutions to a wt% concentration, add 30 g of this dispersion into a 50 ml screw tube bottle, shake vigorously to homogenize, and then
The light transmittance of the dispersion liquid left at 5 ° C. overnight was measured using a spectrophotometer manufactured by Hitachi, and the absorbance at 500 nm was measured with pure water as a control, and those having a transmittance of 70% or more were made transparent. [Sol-gel property test] The above organic clay complex was added to various organic solvents and polysiloxane solutions so as to have a concentration of 4 wt%, and 30 g of this dispersion was put into a 50 ml screw tube bottle and shaken vigorously. Then, the mixture was left to stand overnight at 25 ° C., slowly rotated 180 ° upside down, and the state of the dispersion was examined according to the following criteria. Dispersion drops when the bottle is turned upside down-
--- Even if the sol-bin is turned upside down, the dispersion does not hang down --- Gel test results are shown in Tables 3 to 7.

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

Test Example 3 Viscosity Test The following organic clay complex was dispersed in an organic solvent and polysiloxanes at various concentrations, and a rotational viscometer (B, manufactured by Tokyo Keiki Co., Ltd.) was used.
Type viscometer), 6 rotations (rpm) / min (shear rate 5.5
8 s-1) and 60 rotations (rpm) / min (shear rate 55.8
s-1. The apparent viscosity (mPa · S) was measured. (1) Dispersing the synthetic smectite-based organoclay composite A in ethyl acetate and methyl isobutyl ketone at various concentrations,
Table 8 shows the results of measuring the apparent viscosity at 6 revolutions / minute.

[Table 8] The dispersion liquid dispersed in ethyl acetate was transparent white and had thixotropy. The dispersion liquid in which methyl isobutyl ketone was dispersed was almost transparent and had thixotropy. (2) The synthetic swelling mica-based organoclay complex A was dispersed in methyl isobutyl ketone at various concentrations, and the apparent viscosity at 6 revolutions / minute was measured. The results are shown in Table 9.

[Table 9] The dispersion dispersed in methyl isobutyl ketone showed a very good thickening effect. The dispersion was transparent white and had a thixotropy.

Test Example 4 Viscosity Test Table 10 shows the results of the viscosity test when the synthetic smectite-based organoclay composites A and B were dispersed in various solvents and polysiloxanes at a concentration of 2 wt%.

[Table 10]

Test Example 5 Viscosity Test Synthetic smectite-based organoclay composites A, B and C were dispersed in ethanol, acetone, dimethylformamide, N-methyl-2-pyrrolidone and polysiloxane at various concentrations. The results are shown in Tables 11 to 13. In addition, in all the tests, it was completely dispersed.

[Table 11]

[Table 12]

[Table 13]

Test Example 6 Grindability Test Table 14 shows the results of the grindability test of the organic viscosity composite using a sample mill manufactured by Kyoritsu Riko Co., Ltd. The ones that were easy to pulverize were evaluated as ⊚, those that could be pulverized were rated as ◯, and those that could not be pulverized were rated as x.

[Table 14]

Claims (8)

[Claims] 1. An organoclay composite in which a quaternary ammonium ion represented by the general formula (I) is introduced between layers of a swelling layered silicate. [Chemical 1] Wherein, R ¹ represents an alkyl group or a benzyl group having 1 to 30 carbon atoms; R ² and R ³ is _{(CH 2 CH (CH 3)} O)
_n H group, (CH ₂ CH ₂ CH ₂ O) _n H group or 1 to 1 carbon atoms
30 is an alkyl group; R ⁴ is (CH ₂ CH (CH ₃ ).
O) _n H group or (CH ₂ CH ₂ CH ₂ O) _n H group;
Indicates 1 to 50] 2. The organoclay composite of claim 1, wherein the swellable layered silicate is a smectite clay. 3. Smectite is formed by reacting a homogeneous mixture of a silicate and a magnesium salt with an alkaline solution to obtain silicon.
After synthesizing the magnesium complex and removing the by-produced electrolyte, lithium ion and optionally sodium ion and / or fluorine ion are added to the complex to obtain 100
A synthetic smectite of the general formula (II) obtained by hydrothermal reaction at ℃ to 350 ℃, followed by drying.
Organic clay complex. [Chemical 2] 4. The organoclay composite of claim 1, wherein the swellable layered silicate is a swellable mica. 5. In the quaternary ammonium ion of the general formula (I), R ¹ is a methyl group or a benzyl group; R ² and R ³ are alkyl groups having 1 to 4 carbon atoms;
R ⁴ is a (CH ₂ CH (CH ₃ ) O) _n H group or (CH ₂ CH
It is ₂ CH ₂ O) _n H group; n is 5 to 50, organic clay complex of any one of claims 1-4. 6. A quaternary ammonium salt having a quaternary ammonium ion represented by the general formula (I) is added to the swelling layered silicate in an amount of 0.5 to 1 of the cation exchange capacity of the layered silicate. The method for producing an organoclay composite according to claim 1, wherein the reaction is carried out at a rate of 5 times equivalent (in terms of milliequivalent). 7. A thickener or gelling agent for organic solvents and / or polysiloxanes, which comprises the organoclay composite according to any one of claims 1 to 5. 8. An organoclay composite composition in which the organoclay composite according to any one of claims 1 to 5 is dispersed in an organic solvent and / or polysiloxane.