JP2514780B2 - New organoclay complex - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organoclay composite having affinity for an organic solvent and useful as a thickener or a gelling agent, a process 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 layers are magnesium octahedral layers. Alternatively, it has a sandwich-type three-layer structure in which an aluminum octahedron layer is sandwiched, and this has a structure in which several to several tens of 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 one of the swelling layered silicates, are fine particles having cation exchange ability,
The layers have a property of easily spreading, forming a sol having a thixotropic property by dispersing in water, and forming a gel when the concentration is increased.

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 xylene. 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, examples in which they are used by dispersing them in esters, ketones, alcohols and the like are also disclosed, but 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]

The above-mentioned conventional thickeners are
The above organic solvents have the drawbacks that they do not have a sufficient thickening effect on organic solvents such as ethers, halogenated hydrocarbons, alcohols, ketones, amides, etc., and cannot withstand long-term storage. There is a need for the development of an organoclay composite that has a high affinity with and can be used as a thickener that is stable for a long period of time.

[0007]

Means for Solving the Problems As a result of many years of intensive research on a novel organoclay composite having an excellent thickening effect, the present inventors have found that polyoxyethylene is formed between layers of a swellable layered silicate. By introducing both a quaternary ammonium ion having a group and a quaternary ammonium ion having a polyoxypropylene group, it has excellent affinity with organic solvents such as alcohols, ketones and amides, and is dispersed in these. It was found that they showed a high thickening effect.

That is, the present invention is an organoclay composite in which a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group are introduced between layers of a swelling layered silicate. Regarding the body More preferably, the quaternary ammonium ion having a polyoxyethylene group is represented by the general formula (I),
The quaternary ammonium ion having a polyoxypropylene group is represented by the general formula (II).

[0009]

Embedded image

[In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a benzyl group, and R ²
And R ³ is a (CH ₂ CH ₂ O) _n H group or has 1 to 3 carbon atoms.
0 represents an alkyl group, R ⁴ represents a (CH ₂ CH ₂ O) _n H group, and n is 1 to 50. In the formula (II), R ⁵
Represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a benzyl group, and R ⁶ and R ⁷ are (CH ₂ CH (CH ₃ ) O) _m H
_{Groups, (CH 2 CH 2 CH 2} O) m H group or 1 to 30 carbon atoms
And an alkyl group of R ⁸ is (CH ₂ CH (CH ₃ ) O) _m
Represents H group or a _{(CH 2 CH 2 CH 2)} m H group, m 1
50] The quaternary ammonium ion of the above formulas (I) and (II) may be introduced as two or more kinds.

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 As also swelling mica, Li-type fluorine taeniolite, Na-type fluorine taeniolite, Na-type tetrasilicic fluorine mica, natural or chemically synthesized swelling mica such as Li-type tetrasilicic fluorine mica, interlayer Li ions and N
Examples thereof include swelling mica having an a-ion, a substitution product or derivative thereof, or a mixture thereof, and natural or synthetic vermiculite, fluorine vermiculite and the like can also be used.

The synthetic smectite clay used in the present invention is preferably a synthetic smectite of the general formula (III) having a structure similar to the hectorite type clay mineral produced by the following production method, but is not limited to the following production method. Not something.

[0013]

Embedded image

The synthetic smectite is produced by the following method. That is, a homogeneous mixture of silicic acid and magnesium salt is reacted with an alkaline solution to synthesize a silicon-magnesium complex, and after removing the by-produced electrolyte, the complex is mixed with lithium ions and sodium ions as necessary. It is obtained by adding hydrofluoric acid and / or hydrothermally reacting at 100 ° C. to 350 ° C. and then drying.

More specifically, first, a homogeneous mixed solution of a silicic acid solution and a magnesium salt solution is prepared. The mixing ratio of silicic acid and magnesium salt is preferably the stoichiometric ratio of the general formula (III). The silicic acid solution is obtained by adding mineral acid to a sodium silicate solution to make it acidic. Sodium silicate is generally commercially available 1
Either No. 4 to No. 4 water glass or sodium metasilicate may be used. Nitric acid as the mineral acid,
Hydrochloric acid, sulfuric acid, etc. can be used. When a mineral acid is added to the silicate solution, gelation occurs when the amount of the mineral acid is small, so it is necessary to add the mineral acid so that the pH of the solution is 5 or less, preferably 1 to 3.

The homogeneous mixed solution thus obtained and the alkaline solution are mixed to obtain a homogeneous precipitate. The alkaline solution is preferably a solution of ammonia, sodium hydroxide, lithium hydroxide, potassium hydroxide or a mixture thereof. The amount of the alkaline solution added is such that the pH after mixing becomes 10 or more. Then, the generated 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 (50 to 5,000 Reynolds nozzles, average fineness of filtration membrane) is used. 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 alkali hydroxide than sodium hydroxide are used in the produced homogeneous precipitate, sodium ions are further added, and fluorine ions are further added if necessary, 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.

The lithium ion, sodium ion and fluorine ion to be added are, for example, 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 reaction product is dried and, if necessary, pulverized to obtain a synthetic smectite of the general formula (III).

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 meq or more, preferably 60 meq or more per 100 g of the swellable layered silicate. In the case of the synthetic smectite of the general formula (III), it is 85 to 130 meq, and the larger the exchange capacity, the better. Swellable layered silicate is 50%
The following non-clay impurities may be contained, but the amount of non-clay impurities is preferably 10% or less.

The alkyl group having 1 to 30 carbon atoms in the quaternary ammonium ion represented by the general formulas (I) and (II) is, for example, methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl can be mentioned.

R ¹ , R ² and R ³ in the general formula (I)
At least one of the alkyl groups has 10 to 2 carbon atoms.
It is preferably 0 . More preferably, R ¹ is a methyl group or a benzyl group and R ² has 10 to 20 carbon atoms.
An alkyl group, R ³及beauty R ⁴ is (CH ₂ CH ₂
O) _n . Number of added moles of polyoxyethylene unit n
Is preferably 1 to 30, particularly preferably 1 to 20.
It is. And when a plurality of polyoxyethylene groups are substituted, the total of those polyoxyethylene group units is
2-50 is preferable.

R ⁵ , R ⁶ and R in the general formula (II)
The alkyl group of ⁷ preferably has 1 to 4 carbon atoms .
More preferably, R ⁵ is a methyl group or a benzyl group, R ⁶ and R ⁷ are alkyl groups having 1 to 4 carbon atoms, and R
⁸ is a (CH ₂ CH (CH ₃ ) O) _m H group or (CH ₂ C
H ₂ CH ₂ O) _m H group.

Number of moles of polyoxypropylene group units added
m is preferably 1 to 50, more preferably 5 to 5.
It is 0, more preferably 20 to 50. With that
When the number of moles exceeds 50, dispersibility in organic solvents
Is improved, but the quaternary anneal occurs between the layers of the swellable layered silicate.
Some of the monium ion chains squeeze out, resulting in a product
Aggravates the solid properties of.

[0026] introducing the quaternary ammonium ion is represented by the general formula (I) and (II), but quaternary ammonium salts containing the ions used as such salts, for example Cl ^- , Br ⁻ , NO ₃ ⁻ , OH ⁻ , CH
_{An example} is a salt with an anion such as ₃ COO ⁻ .

Specific examples of the salt containing the quaternary ammonium ion represented by the general formula (I) include polyoxyethylene / trialkylammonium chloride polyoxyethylene / trialkylammonium bromide polyoxyethylene / dialkylammonium chloride polyoxy. Ethylene / dialkylammonium acetate Di (polyoxyethylene) / dialkylammonium chloride Di (polyoxyethylene) / dialkylammonium bromide Di (polyoxyethylene) / alkylammonium chloride Di (polyoxyethylene) / alkylammonium acetate Tri (polyoxyethylene ) ・ Alkylammonium chloride Tri (polyoxyethylene) ・ Alkylammonium bromide Tri (polyoxyethylene) ・ Alky Ammonium acetate and the like.

Specific examples of the salt containing the quaternary ammonium ion represented by the general formula (II) include polyoxypropylene trialkylammonium chloride polyoxypropylene trialkylammonium bromide di (polyoxypropylene) dialkyl. Examples include ammonium chloride di (polyoxypropylene) / dialkylammonium bromide tri (polyoxypropylene) / alkylammonium chloride tri (polyoxypropylene) / alkylammonium bromide.

In the organoclay composite of the present invention, a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group are introduced between the layers of the swelling layered silicate by ion exchange. Manufactured by the above, further various quaternary alkyl ammonium ions other than the above, even if mixed and introduced with various inorganic cations, without defeating the purpose of the present invention,
The total introduced amount of the quaternary ammonium ion having a polyoxyethylene group and the quaternary ammonium ion having a polyoxypropylene group is 50% of the ion exchange capacity.
The above is preferable, and 95% or more is particularly preferable.

The mixing ratio of the quaternary ammonium ion having a polyoxyethylene group and the quaternary ammonium ion having a polyoxypropylene group can be freely set. The amount of introduced ions (% in terms of mol) is preferably
Is 5 to 95%, most preferably 35 to 90 %.

The organoclay composite of the present invention comprises a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group,
It is obtained by cation exchange with interlayer ions of the swelling layered silicate. Specifically, it can be produced by the following method, but the present invention is not limited to the following production method. As a first step, a quaternary ammonium salt solution having a polyoxyethylene group and a quaternary ammonium salt solution having a polyoxypropylene group are mixed,
The mixed aqueous solution is 5 to 50% by weight. Alternatively, they may be used as separate solutions. In the second step, the swellable layered silicate is dispersed in water, and the solid dispersion concentration thereof is usually 1 to 1.
5 wt% is desirable, but the swelling layered silicate can be freely set within a concentration range where it can be sufficiently dispersed.
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 third 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. Further, in the reaction of the quaternary ammonium salt solution and the swellable layered silicate suspension, an organic solvent such as alcohol may be added and the reaction may be carried out in an organic solvent-containing liquid.

The total amount of the quaternary ammonium salt added is preferably equivalent to the cation exchange capacity of the swelling layered silicate as the quaternary ammonium ion, but a smaller amount is also possible 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, ground to obtain a final product.

The general properties of the organoclay composite thus obtained 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 (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 001 bottom surface reflection by X-ray diffraction. When synthetic smectite type clay is used as a raw material, it has a bottom spacing of 10Å in a dehydrated state and 12 to 15Å under normal temperature and humidity.
The organoclay composite of the present invention depends on the number of carbon atoms of the alkyl group in the quaternary ammonium ion and the number of moles of addition of the polyoxyethylene group and the polyoxypropylene group,
Since the bottom surface spacing is 15 Å or more, 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 and dispersed by stirring or the like. The thicker the amount added, the higher the thickening effect. The addition amount of the organoclay complex varies depending on the type of organic solvent and its application, but generally, it can be used for various applications by dispersing it in the range of 0.1 to 20% by weight.

The organoclay composite of the present invention can be dispersed in various organic solvents to give an organoclay composite composition. As the organic solvent, various organic solvents having high polarity, low polarity or non-polarity, specifically, aromatic hydrocarbons such as benzene and toluene; ethers such as tetrahydrofuran, ketones such as acetone and methyl ethyl ketone;
Alcohols such as methanol, ethanol, propanol; alcohol derivatives such as cellosolve; chloroform,
Halogenated hydrocarbons such as perchlorethylene and chlorobenzene; amides such as dimethylformamide; dimethylsulfoxide; and N-methyl-2-pyrrolidone. It can also be used as a mixture of two or more of the above-mentioned solvents, or various solvents obtained by mixing the above-mentioned solvent with another inorganic solvent such as water. If necessary, a polar additive such as water may be added to increase the viscosity.

[0038]

The organoclay composite of the present invention is a novel organoclay composite having two or more kinds of quaternary ammonium ions introduced between the layers of the swelling layered silicate and has a polyoxyethylene group. Compared with organoclay composites containing only quaternary ammonium ions, organoclay composites containing only quaternary ammonium ions having a polyoxypropylene group, and organoclay composites in which these are physically mixed The characteristic is that the viscosity with respect to the organic solvent is remarkably improved. The organoclay composite of the present invention has an affinity for an organic solvent, and further exhibits a dispersion and thickening effect by quaternary ammonium ion having a polyoxyethylene group and quaternary ammonium ion having a polyoxypropylene group. When ammonium ions are present between the layers, the hydrophilic / hydrophobic balance of the layer space of the organoclay complex depends on the carbon number of the alkyl group of the combined quaternary ammonium ion, the addition moles of the polyoxyethylene group and polyoxypropylene group. This is because it is controlled by the number. Organic solvent molecules are dissolved between layers due to the matching hydrophilic / hydrophobic balance of the layer space, and are sequentially solvated with oxygen and hydroxyl groups of polyoxyethylene groups and polyoxypropylene groups to spread the layers and further stack silicic acid. It is believed to separate the salt layers. It is considered that the separated silicate layers form a gel structure by irregularly bonding to each other due to the negative charge remaining on the layer surface and the positive charge on the end surface. In particular, an organoclay complex in which a quaternary ammonium ion having a polyoxyethylene group and a polyoxypropylene group is introduced between the layers of the synthetic smectite represented by the general formula (III) is used as an aromatic hydrocarbon or halogenated hydrocarbon. When dispersed in alcohols, alcohols, ketones, amides, N-methyl-2-pyrrolidone, etc., a transparent and highly viscous sol or gel can be obtained because these combinations are homogeneous. It is considered that this is because it has an extremely advantageous effect on the formation of various gel structures.

[0039]

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. , A halogenated hydrocarbon, a ketone, an alcohol, a derivative thereof, an amide, or the like, or a solvent containing them, and can be used as a thickener.

The organoclay composite of the present invention has an affinity for an organic solvent, is easily dispersed, and has an excellent thickening property even when added in a small amount.
Viscosity modifiers, dispersants, and emulsifiers for various products and industrial processes such as cosmetics, pharmaceuticals, sanitizers, adhesives, paints, coating materials, various plastic products, textile industry, etc. that require viscosity adjustment to show gelation effect. It is extremely useful because it can be used as a composition such as a binder. Furthermore, since this organoclay composite contains a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group, it is an antistatic agent for plastics and fibers, a bactericide, a dyeing aid, and a leveling agent. It can also be used as a dyeing 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.

In particular, the organoclay composite of the present invention synthesized by using the synthetic smectite represented by the general formula (III) has high transparency and forms a uniform sol or gel when combined with an organic solvent. It is particularly useful for applications such as cosmetics and pharmaceuticals in which the homogeneity and stability of the dispersion system are required. 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.

[0042]

【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 the cross flow method manufactured by NGK Insulators Ltd. [Cross flow filter (ceramic membrane filter: pore size 2 μ
m, tubular type, filtration area 400 cm ² )] and thoroughly washed with water, then 200 ml of water and Li (OH) · H
_A solution consisting of 14.5 g of ₂ O was added to form a slurry. This is transferred to an autoclave, 41kg / cm ² , 25
Hydrothermal reaction was carried out at 0 ° C. for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and pulverized to obtain a synthetic smectite of the following formula. This synthetic smectite had a bottom spacing of 12.5Å in air and a cation exchange capacity of 110 meq / 100 g as measured by X-ray diffraction. 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 Organoclay Complexes A to E 100 g of the synthetic smectite synthesized in Synthesis Example 1 was dispersed in 5000 ml of tap water to obtain a suspension. 20-80% of the formula (IV) corresponding to the cation exchange capacity (110 meq / 100 g) of the synthetic smectite

[0045]

Embedded image

Quaternary ammonium salt of 80 to 20%
A considerable amount of the following formula (V)

[0047]

[Chemical 6]

300 ml of an aqueous solution in which each of the quaternary ammonium salt of was dissolved was added to the above-mentioned synthetic smectite suspension, and the mixture was reacted at room temperature for 2 hours with stirring. The product was subjected to solid-liquid separation, washed to remove by-product salts, and dried to obtain each of the synthetic smectite-based organoclay composites A to E shown in Table 1. According to X-ray diffraction measurement of the product,
01 The bottom distance calculated from the bottom reflection position is 25 to 3
It was 9Å, and formation of the smectite-based organoclay composite of the present invention was confirmed.

[0049]

[Table 1]

Example 2 Production of Organoclay Complex F 100 g of the synthetic swelling mica obtained in Synthesis Example 2 was added to 5 parts of tap water.
Disperse into 000 ml and add 50% of the exchange capacity to the quaternary ammonium salt of formula (IV) and 50% of the exchange capacity.
3000 ml of an aqueous solution in which a considerable amount of the quaternary ammonium salt of the formula (V) was dissolved was added, and the mixture was reacted at room temperature for 2 hours while stirring. The product was solid-liquid separated, washed, and dried to synthesize a synthetic mica-based organoclay complex.

Example 3 100 g of the synthetic smectite synthesized in Synthesis Example 1 was dispersed in 5000 ml of tap water to obtain a suspension. 50% of the cation exchange capacity (110 meq / 100 g) of the synthetic smectite, and a quaternary ammonium salt of the formula (IV);
0% equivalent amount of quaternary ammonium salt of formula (V) and 10
% Equivalent formula (VI)

[0052]

[Chemical 7]

Mixed solution 300 of quaternary ammonium salt
0 ml was added, and the mixture was reacted at room temperature for 2 hours with stirring. The product was subjected to solid-liquid separation, washed to remove by-product salts, and then dried to obtain an organoclay complex G.

Comparative Example Production of Comparative Organoclay Complex (1) Production of Comparative Organoclay Complex O In the same manner as in Example 1, the synthetic smectite of Synthetic Example 1 contained only the quaternary ammonium salt of the formula (IV). The replacement capacity 110
Comparative organoclay composite O was prepared using milliequivalents. (2) Production of Comparative Organoclay Complex P In the same manner as in Example 1, the synthetic smectite of Synthesis Example 1 was replaced with only the quaternary ammonium salt of the formula (V) with an exchange capacity of 110.
Comparative organoclay composite P was prepared using milliequivalents. (3) Production of Comparative Organoclay Complex Q In the same manner as in Example 1, the synthetic smectite obtained in Synthesis Example 1 was mixed with dimethyl dioctadecyl ammonium salt (trade name: Arcard 2HT, Lion Akzo strain) with an exchange capacity of 110.
Comparative organoclay composite Q was prepared using milliequivalents. (4) Production of Comparative Physically Mixed Organoclay Complex 10 g of the comparative organoclay complex O and 10 g of the comparative organoclay complex P produced in Comparative Examples (1) and (2) were mixed with a mixer to give a comparative physical property. A mixed organoclay composite was prepared. (5) Production of Comparative Organoclay Complex R A Comparative Organoclay Complex R was produced in the same manner as in Example 2 using the quaternary ammonium salt of the formula (IV) in an amount equivalent to 70 milliequivalent. . (6) Production of Comparative Organoclay Complex S A Comparative Organoclay Complex S was produced in the same manner as in Example 1 using the quaternary ammonium salt of the formula (V) in an amount equivalent to 70 milliequivalent exchange capacity. .

Test Example 1 Dispersibility / Transparency Test [Dispersion Test] The organoclay composites C and F of the present invention and the comparative organoclay organic composite Q were added to various solvents at a concentration of 2 wt%, 30 g of this dispersion was placed in a 50 ml screw tube bottle and shaken vigorously to homogenize it.
The dispersibility was visually determined by allowing the mixture to stand at 0 ° C. for 1 week. The results are shown in Tables 2 and 3. The dispersed state was represented by the following criteria. Completely dispersed: ○ Dispersed but some sediment formed: △ Not swelled and not dispersed: ×

[Transparency Test] The organoclay composites C and F of the present invention and the comparative organoclay composite Q were added to various solvents so as to have a concentration of 4 wt%, and 30 g of this dispersion was added to a 50 ml screw tube. The mixture was placed in a bottle, shaken vigorously to homogenize it, and left to stand overnight at 25 ° C. The light transmittance of the dispersion was measured using a Hitachi spectrophotometer to measure the absorbance at 500 nm using pure water as a control. Those with a rate of 70% or more were made transparent. The test results are shown in Tables 2, 3 and 4.

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

From the results shown in Tables 2 to 4, the organoclay composites C and F of the present invention are dispersed in various organic solvents, and in particular, the organoclay composite C is benzene, toluene, methanol and perchloro. A transparent liquid for ethylene, chlorobenzene, dimethyl sulfoxide, methyl cellosolve, and N-methyl-2-pyrrolidone, and an organoclay complex F for a perchlorethylene, were obtained. Did not disperse but precipitated.

Test Example 2 Viscosity Test [Viscosity Test] The organic clay complex was dispersed in various organic solvents at various concentrations,
Using a rotational viscometer (B-type viscometer manufactured by Tokyo Keiki Co., Ltd.), 6
The apparent viscosity (mPa · s) at rotations / minute (shear rate 5.58 / s) and 60 rotations / minute (shear rate 55.8 / s) was measured. Tables 5 to 9 show the test results when the organic clay composites A to G of the present invention, the comparative organic clay composites O and P, and the comparative physically mixed organic clay composites were dispersed in various organic solvents. .

[0062]

[Table 5]

[0063]

[Table 6]

[0064]

[Table 7]

[0065]

[Table 8]

[0066]

[Table 9]

From the results shown in Tables 5 to 8, only the comparative organoclay complex O in which only the quaternary ammonium ion having a polyoxyethylene group was introduced and only the quaternary ammonium ion having a polyoxypropylene group were introduced. Compared with the introduced comparative organoclay complex P, or the comparative physically mixed organoclay complex which is a mixture thereof, the organoclay complexes A to E of the present invention have ethanol, methanol, dimethylformamide, N- It can be seen that a high viscosity can be obtained for methyl-2-pyrrolidone. Organoclay complex G
Shows that a high viscosity can be obtained for N-methyl-2-pyrrolidone. Further, from the results in Table 9, it is understood that the organoclay composite F of the present invention also has a higher viscosity with respect to perchlorethylene than the comparative organoclay composites R and S.

Front Page Continuation (72) Inventor Takahiro Sekimoto 4278-1 Katsurazuka, Hoei-shi, Niigata Corp. Kohei Chemical Hoeisha 203 (72) Inventor Toshikazu Fujisaki 1-2-7 Hayatominami, Hoei-shi, Niigata (72) Inventor Yuyasu Nikaido 4-10-32 Botansan, Niigata City, Niigata Prefecture Corpus Kido 303 (72) Inventor Kanako Saito 5-9-2 Daiei-cho, Shibata City, Niigata Prefecture (72) Innovator, Seinosuke Ando 3-24 Inokashira, Mitaka City, Tokyo 1 (72) Inventor Ko Honma 5-25-7 Tajima, Urawa-shi, Saitama Cresent Town 107 Examiner Koji Amamiya

Claims (9)

(57) [Claims] 1. An organoclay composite in which a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group are introduced between layers of a swelling layered silicate. 2. A quaternary ammonium ion having a polyoxyethylene group is an ion represented by general formula (I), and a quaternary ammonium ion having a polyoxypropylene group is represented by general formula (II). The organic clay complex according to claim 1, wherein the organoclay composite is an ion. Embedded image [In the formula (I), R ¹ is a hydrogen atom and has 1 to 30 carbon atoms.
Represents an alkyl group or a benzyl group, R ² and R ³ represent a (CH ₂ CH ₂ O) _n H group or an alkyl group having 1 to 30 carbon atoms, and R ⁴ represents a (CH ₂ CH ₂ O) _n H group. Represents n
Is 1 to 50. In the formula (II), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a benzyl group, R ⁶ and R ⁷ represent a (CH ₂ CH (CH ₃ ) O) _m H group,
_{(CH 2 CH 2 CH 2 O} ) represents an _m H group or an alkyl group having 1 to 30 carbon atoms, R ⁸ is _{(CH 2 CH (CH 3)} O) m H group or a _{(CH 2 CH 2 CH 2)} m Represents a H group, m is 1 to 50
Is] 3. In the general formula (I), R ¹ is a methyl group or a benzyl group, R ² is an alkyl group having 10 to 20 carbon atoms, and R ³ and R ⁴ are (CH ₂ CH ₂ O ) _n
H group, the total number of n is 2 to 50, in the general formula (II), R ⁵ is a methyl group or a benzyl group, and R ⁶ and R ⁷ are alkyl groups having 1 to 4 carbon atoms. ,
R ⁸ is a (CH ₂ CH (CH ₃ ) O) _m H group or (CH ₂ C
H ₂ CH are ₂ O) _m H group, organoclay composite according to claim 2 m is 5-50. 4. The organoclay composite of claim 1, wherein the swellable layered silicate is a smectite clay. 5. A smectite clay is prepared by reacting an alkaline solution with a homogeneous mixture of silicic acid and magnesium salt to synthesize a silicon-magnesium complex, removing the by-produced electrolyte, and then adding lithium ion to the complex. And adding sodium ion and / or fluorine ion as needed, 1
The organoclay composite according to claim 4, which is a synthetic smectite of the general formula (III) obtained by hydrothermal reaction at 00 ° C to 350 ° C and then drying. Embedded image 6. The organoclay composite of claim 1, wherein the swellable layered silicate is a swellable mica. 7. A cation of the layered silicate in a total amount of a quaternary ammonium ion having a polyoxyethylene group and a quaternary ammonium ion having a polyoxypropylene group in the swelling layered silicate. Exchange capacity 0.5 ~
The method for producing an organoclay composite according to claim 1, wherein the reaction is performed in a 1.5- fold amount (milliequivalent conversion). 8. A thickener or gelling agent for an organic solvent, which comprises the organoclay composite according to any one of claims 1 to 6. 9. An organoclay composite composition in which the organoclay composite according to any one of claims 1 to 6 is dispersed in an organic solvent.