JPH09295809A - Clay compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a clay compound capable of providing desired rheological characteristics to a matrix compound such as a solvent by a small amount of addition by introducing a specific surface-treating agent onto the surface of a swelling silicate and keeping average layer thickness of the swelling silicate to a prescribed thickness. SOLUTION: A surfactant [e.g. γ-(2-aminoethyl)aminopropyltrimethoxysilane] having a functional group, preferably one or more compounds selected from silane-based, titanate-based and alumina-based coupling agent is introduced onto the surface of a swelling silicate, preferably being smectite group clay mineral or a swelling mica by covalent bond to provide the objective clay compound having <=200Å average layer thickness or the objective clay compound in which clay compound having <=100Å average layer thickness occupies >=30%, preferably >=50% based on total clay compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel clay composite and a method for producing the same, and more particularly to a clay composite which gives a desired rheological property to a matrix compound even when added in a small amount, and a method for producing the same.

[0002]

2. Description of the Related Art Layered silicates have the property of being dispersed in various compounds serving as a matrix to adjust or improve rheological properties. Therefore, for example, the viscosity of fluid fine chemical products such as paints, printing inks and cosmetics can be adjusted. It is used as an agent. The layered silicate is also used as a filler or a reinforcing agent for the purpose of improving rigidity, mechanical properties, and physical properties such as heat distortion resistance of polymer materials such as rubber and plastics.

The layered silicate has a laminated structure in which a large number of unit layers are laminated. The thickness of the unit layer is around 10Å, but when a large number of the unit layers are laminated, the layer thickness is usually on the order of μm, although it depends on the number of laminated unit layers. Since the aspect ratio and the specific surface area of such a layered silicate are small, even if a layered silicate in which a number of unit layers are laminated is blended as a viscosity modifier, a small amount of the blending ratio will result in a rheology modifying effect and The thickening effect cannot be obtained sufficiently. As described above, it is necessary to increase the dispersion concentration in order to obtain a sufficient effect, but there are problems that the cost becomes high and the color tone of the product is impaired. On the other hand, among the layered silicates, swelling silicates such as smectite group clay minerals, swelling mica, and vermiculite have a property of swelling by taking in water between layers, and effectively increase the viscosity of water. Since it has the effect of increasing, it is possible to adjust the rheological properties of a fluid containing water as a main component. For improving the rheological properties of a solvent other than water or a mixed solvent containing a solvent other than water as a main component, and improving resin properties, the following techniques for treating and modifying swelling silicate are known.

(1) Organic cations, which are obtained by exchanging exchangeable cations such as alkali metals existing between unit layers of a smectite group clay mineral with other organic cations, are ionically bonded to the surface of the clay layer. A complex composed of, specifically, dodecylamine and a smectite group clay mineral 1
A dodecylammonium ionically bonded bentonite composite obtained from the seed bentonite is described in US Pat. No. 2,531,427. (2) A complex in which dimethyloctadecyl ammonium ion is introduced as a cation between unit layers of a smectite group clay mineral is industrially produced by NL Industry Co. or Coop Chemical Co., and is used as a thickener for paints. . (3) In the field of fluid products containing organic solvents such as alkyd resin paints and other synthetic resin paints, printing inks and sealants, a compound composed of a quaternary ammonium ion and a nonionic organic compound is used. New organic modified bentonite introduced into bentonite has been developed. This modified bentonite is dispersed in an organic solvent and used for the purpose of adjusting rheological properties (Japanese Patent 2).
44306). Further, in the field of the same fluid product, a novel organic modified bentonite in which both organic ammonium ion and organic anion are introduced into bentonite is known, and it is used for the same purpose as described above (Japanese Patent Laid-Open Publication No. Sho. 57
-111371 gazette). (4) A modified bentonite that is dispersed in an organic solvent by surface-treating purified bentonite with an alkyltrialkoxysilane has been developed (Japanese Patent Publication No. 7-23).
No. 211). The method for producing this modified bentonite is as follows. The purified bentonite is extracted from the suspension of crude bentonite by removing non-clay substances by the natural sedimentation method or the centrifugation method. This purified bentonite sol is preheated and subjected to humidity control drying, and finally dried sufficiently at 150 to 200 ° C. to prepare anhydrous purified bentonite. Then, a sufficient amount of alkyltrialkoxysilane is added to the anhydrous bentonite in an anhydrous atmosphere to stir the product so that the product does not exhibit water repellency, and the product is crushed to produce a modified bentonite.

However, the solvents whose rheological properties can be adjusted by the smectite group clay-mineral composites obtained by the methods of the prior arts (1) to (3) are limited to aromatic organic solvents such as benzene and toluene, and aliphatic solvents. When used as a hydrocarbon-based solvent, an appropriate amount of polar compounds such as methanol, ethanol, and acetone must be added. Such a method is complicated, and there is a problem that a polar solvent such as methanol is mixed in a dispersion composed of a smectite group clay mineral and an aliphatic hydrocarbon solvent.

The method for producing a modified bentonite according to the prior art (4) requires a great deal of labor and cost for drying and crushing, and in an anhydrous atmosphere, purified bentonite has a thickness of the order of μm in which unit layers are laminated in multiple layers. Only separate. Therefore, the alkyltrialkoxysilane is
It only reacts with the surface of the layered silicate laminate of the m-order size. Further, in order to efficiently obtain a silane-modified purified bentonite by directly reacting an anhydrous purified bentonite and an alkyltrialkoxysilane in an anhydrous atmosphere, a catalyst such as an amine compound is usually required. In the method described in Japanese Patent Publication No. 7-23211 of (4), since no catalyst is used, it is difficult to efficiently obtain silane-modified purified bentonite.
Therefore, it is difficult to industrially utilize the method (4). Further, the surface of the alkyltrialkoxysilane used in the above method (4) is made hydrophobic by a saturated alkyl group having 1 to 22 carbon atoms. The affinity between the hydrophobized bentonite and highly polar solvents such as alcohols, ethers, and amine compounds is low, and sufficient fine dispersion is difficult. Therefore, the modified bentonite obtained by the method (4) is limited in use in a highly polar solvent.

As described above, at present, a modified layered silicate which can be well uniformly dispersed in various solvents and whose rheological properties of the solvent can be adjusted even when added in a small amount has not yet been provided.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems, and a clay complex which can give various rheological properties to a matrix compound even when added in a small amount, It is to provide the manufacturing method.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have introduced a surface-treating agent having a functional group onto the surface of a swelling silicate by a covalent bond, It has been found that a clay composite in which the above-mentioned problems are solved can be provided by making the average layer thickness into a flaky shape having a specific thickness or less, and the present invention has been completed.

That is, according to the present invention, the surface-treating agent (B) having a functional group is covalently introduced onto the surface of the swelling silicate (A), and the total average layer thickness is 200 Å or less. A clay composite is provided (claim 1). Further, according to the present invention, the surface-treating agent (B) having a functional group is introduced onto the surface of the swelling silicate (A) by a covalent bond,
A clay composite having a layer thickness of 100 Å or less occupying 30% or more of the whole is provided (claim 2). In a preferred embodiment, 50% of the total layer thickness is 100Å or less.
It occupies the above (claim 3). Further, according to the present invention, there is provided a clay complex in which the average bottom surface interval is expanded by introducing the surface treatment agent (B) onto the surface of the swelling silicate (A) by covalent bond (claim) Item 4). In a preferred embodiment, the bottom surface spacing is expanded by a factor of 2 or more (claim 5). In a further preferred embodiment, claims 1, 3,
Or 2 or more of any of the clay composites according to 4 (claim 6). In a further preferred embodiment, those having a layer thickness of 50Å or less occupy 10% or more of the whole (claim 7). In a further preferred embodiment, those having a layer thickness of 50 Å or less account for 20% or more of the whole (claim 8). In a further preferred embodiment, the swellable silicate (A) is a smectite group clay mineral (claim 9).
In a further preferred embodiment, the swellable silicate (A) is swellable mica (claim 10). In a further preferred embodiment, the surface treatment agent (B) is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an alumina coupling agent (claim 11). . In a further preferred embodiment, the surface-treating agent (B) has the general formula (I)

[0011]

Embedded image Y _n SiX _4-n (I)

(However, n is an integer of 0 to 3, and Y
Is a hydrocarbon group having 1 to 25 carbon atoms, and 1 to 25 carbon atoms
Is at least one selected from the group consisting of an organic functional group composed of a hydrocarbon group and a substituent, and X is a hydrolyzable group and / or a hydroxyl group. The n Y's and the 4-n X's may be the same or different. ) Is a silane coupling agent represented by () (claim 12). Further, according to the present invention, there is provided a clay complex having a function of increasing the viscosity of at least one solvent selected from the group consisting of water and an organic solvent, which is used in a concentration of 3.5% by weight in the solvent. A clay complex is provided which increases the apparent viscosity at 25 ° C. and 6 rpm to 5 times or more the value of the viscosity of the solvent when dispersed in the composition (claim 13). The method for producing the clay composite of the present invention is a surface treatment agent having a functional group on the surface of the swollen silicate (A) which is swollen by dispersing the swellable silicate (A) in a dispersion medium. It is a method of covalently bonding (B) (claim 14). In a preferred embodiment, the surface treatment agent (B) is covalently bonded while stirring at 1000 rpm or more (claim 15). In a further preferred embodiment, the surface treatment agent (B) is covalently bonded while stirring at a shear rate of 500 (1 / s) or more (claim 16).

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The swelling silicate (A) which is a raw material of the clay composite of the present invention is mainly composed of a tetrahedral sheet of silicon oxide and an octahedral sheet of metal hydroxide. Examples include swelling clay minerals such as smectite group clay minerals, vermiculite, and swelling mica.

Examples of the smectite group clay mineral include, for example, naturally or chemically synthesized hectorite, saponite, montmorillonite, stevensite, beidellite, nontronite, bentonite, etc., or their substitution products, derivatives, or these. A mixture of

The swelling mica is a substance having a property of swelling in water, a polar solvent which is compatible with water at an arbitrary ratio, and a mixed solvent of water and the polar solvent, and examples thereof include lithium-type teniolite and sodium. -Type teniolite, lithium-type tetrasilicic mica, and sodium-type tetrasilicic mica, which are natural or chemically synthesized swellable mica having lithium ion or sodium ion between layers, or a substitution product thereof. , Derivatives, or mixtures thereof. Vermiculite equivalents, which will be described later, can also be used.

Vermiculite has a trioctahedral type and a dioctahedral type, and has the following general formula (II).

[0017]

Embedded image _{(Mg, Fe, Al) 2} ■ 3 (Si 4-X Al X) O 10 (OH) 2 · (M +, M 2+ 1/2) X · nH 2 O (II)

(Where M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6
~ 0.9, n = 3.5-5) natural or synthetic vermiculite may be used.

The swelling silicate (A) is used alone or in combination of two or more. The crystal structure of the swelling silicate (A) is preferably one that is regularly stacked in the c-axis direction and has a high degree of purity, but the crystal cycle is disturbed, and so-called mixed layer minerals in which multiple types of crystal structures are mixed are also used. Can be done. Among the swelling silicates (A), smectite group clay minerals and swelling mica are preferably used.

As the surface-treating agent (B) which is a raw material of the clay composite of the present invention, a generally-used surface-treating agent is used, for example, a silane coupling agent, a titanate coupling agent, and alumina. Examples include system coupling treatment agents.

The silane coupling agent is preferably the following general formula (I):

[0022]

Embedded image Y _n SiX _4-n (I)

A silane coupling treatment agent represented by: Here, n is an integer of 0-3. Y has 1 carbon atom
Is at least one selected from the group consisting of a hydrocarbon group having 25 to 25 carbon atoms, a hydrocarbon group having 1 to 25 carbon atoms and a substituent, and the substituent is an ester group or an ether. A functional group selected from the group consisting of a group, an epoxy group, an amino group, a carboxyl group, a carbonyl group, an amide group, a mercapto group, a sulfonyl group, a sulfinyl group, a nitro group, a nitroso group, a nitrile group, a halogen atom, and a hydroxyl group. At least one kind. X is a hydrolyzable group and / or a hydroxyl group, and the hydrolyzable group is selected from the group consisting of an alkoxy group, an alkenyloxy group, a ketoxime group, an acyloxy group, an amino group, an aminoxy group, an amide group, and a halogen. It is at least one kind. The n Y's or the 4-n X's may be the same or different.

In the present specification, the hydrocarbon group means a linear or branched (that is, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aliphatic hydrocarbon group. It means a cyclic hydrocarbon group, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, a phenyl group, a naphthyl group, and a cycloalkyl group. In the present specification, an alkyl group includes a polyvalent hydrocarbon group such as an alkylene group unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like, respectively.

In the above general formula (I), Y has 1 carbon atom.
Examples of the hydrocarbon groups having a lower alkyl group such as decyltrimethoxysilane, those having a lower alkyl group such as methyltrimethoxysilane, 2
Those having an unsaturated hydrocarbon group such as -hexenyltrimethoxysilane, those having a side chain such as 2-ethylhexyltrimethoxysilane, those having a phenyl group such as phenyltriethoxysilane, and 3-β-naphthyl Examples thereof include those having a naphthyl group such as propyltrimethoxysilane, and those having a phenylene group such as p-vinylbenzyltrimethoxysilane. Examples of the case where Y is a group having a vinyl group include vinyltrimethoxysilane, vinyltrichlorosilane, and vinyltriacetoxysilane. Examples of the case where Y is a group having an ester group include γ-methacryloxypropyltrimethoxysilane. Examples of the case where Y is a group having an ether group include γ-polyoxyethylenepropyltrimethoxysilane and 2-ethoxyethyltrimethoxysilane. Examples of the case where Y is a group having an epoxy group include γ-glycidoxypropyltrimethoxysilane. Examples of a case where Y is a group having an amino group include γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-anilinopropyltrimethoxysilane. Examples of the case where Y is a group having a carboxyl group include γ- (4-
Carboxyphenyl) propyltrimethoxysilane. Examples of a case where Y is a group having a carbonyl group include γ-ureidopropyltriethoxysilane. Examples of the case where Y is a group having a mercapto group include γ-mercaptopropyltrimethoxysilane. Examples of the case where Y is a group having a halogen include γ-chloropropyltriethoxysilane. Examples of the case where Y is a group having a sulfonyl group include γ-phenylsulfonylpropyltrimethoxysilane. Examples of the case where Y is a group having a sulfinyl group include γ-phenylsulfinylpropyltrimethoxysilane. Examples of the case where Y is a group having a nitro group include γ-nitropropyltriethoxysilane. Examples of the case where Y is a group having a nitroso group include γ-nitrosopropyltriethoxysilane. Examples of the case where Y is a group having a nitrile group include γ-cyanoethyltriethoxysilane and γ-cyanopropyltriethoxysilane.

An example of the coupling treatment agent when Y is a group having a hydroxyl group is N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane. The hydroxyl groups may also be in the form of silanol groups (SiOH). Examples of the group having a silanol group include an oligomer of dimethyldihydroxysilane represented by the following formula (III). n is preferably in the range of 2 to 30 from the viewpoint of handleability of the silane treating agent and reactivity with the swelling silicate.

[0027]

Embedded image

Substitutes or derivatives of the above-mentioned silane coupling agent can also be used. These silane coupling agents are used alone or in combination of two or more.

Examples of the titanate coupling treatment agent include the following general formulas (IV) to (VI)

[0030]

[Chemical 6]

A titanate-based coupling treatment agent represented by: Where R ¹ , R ² , R ³ , R ⁴ , and R ⁵
Is preferably a hydrocarbon group having 1 to 25 carbon atoms, a vinyl group, an ester group, an ether group, an epoxy group, an amino group,
A functional group having at least one group selected from the group consisting of a carbonyl group, a mercapto group, a halogen, a hydroxyl group, a phosphoric acid ester group, and a polyphosphoric acid ester group,
R ^{1 to} R ⁵ may be the same or different. Z
Is preferably a methylene group or a carbonyl group.

Examples of the monoalkoxy type titanate type treating agent represented by the general formula (IV) include isopropyl tris-isostearoyl titanate, isopropyl tris-n-dodecylbenzene sulfonyl titanate, and isopropyl dimethacryloyl isostearoyl titanate. To be Examples of the chelate-type titanate treating agent represented by the general formula (V) include, for example, bis (dioctylpyrophosphate) -oxyacetate titanate, bis (dioctylpyrophosphate) -ethylene titanate, and dicumylphenyloxyacetate titanate. Is mentioned. Examples of the coordination type titanate treating agent represented by the general formula (VI) include tetraisopropyl-bis (ditridecylphosphite) titanate and tetraoctyl-bis (ditridecylphosphite) titanate. .

A substitution product of the titanate treating agent as described above,
Or derivatives may also be used. These titanate coupling agents are used alone or in combination of two or more.

Examples of the alumina-based coupling treatment agent used in the present invention include the following general formula (VII)

[0035]

Embedded image

(In the formula, R is a hydrocarbon group having 1 to 25 carbon atoms.) Acetoalkoxy aluminum diisopropylate and the like can be mentioned. Substitutes or derivatives of these alumina-based coupling agents may also be used. These alumina-based coupling agents are used alone or in combination of two or more.

Among the above surface treatment agents (B), a silane coupling treatment agent is preferably used.

In the clay composite of the present invention, the surface treating agent (B) having a functional group is introduced by covalent bond. When not covalently bonded, the surface treatment agent (B) separates when the clay complex is dispersed in the matrix, and as a result,
The desired rheology modifying effect cannot be obtained. When the functional group species introduced into the swelling silicate (A) by a covalent bond or a plurality of functional groups introduced by a covalent bond, the ratio thereof is calculated by Fourier transform (FT) -IR. Can be measured. After the clay complex is made into a powder in a mortar or the like, the components not covalently bound are washed with an organic solvent such as tetrahydrofuran. After washing, a sufficiently dried clay complex and a window material such as powdered potassium bromide (KBr), etc. are thoroughly mixed in a predetermined ratio using a mortar or the like, and compressed into tablets. , Can be measured by a transmission method. When more accurate measurement is desired, or when the amount of covalently bonded functional groups is small, a sufficiently dried powdery clay complex is directly subjected to the diffuse reflection method (DR).
It is desirable to measure with IFT).

The amount of the above-mentioned surface treatment agent (B) can be adjusted so as to increase the affinity with the matrix compound. If necessary, a plurality of types of surface treatment agents (B) having different functional groups may be used in combination. Therefore, the amount of the surface-treating agent (B) added is not generally specified, but preferably 0.1 to 20 relative to 100 parts by weight of the swelling silicate (A).
The amount is 0 parts by weight, more preferably 0.2 to 160 parts by weight, and particularly preferably 0.3 to 120 parts by weight. If the amount of the surface-treating agent (B) is less than 0.1 part by weight, the effect of finely dispersing the obtained clay complex tends to be insufficient, which is not preferable. Further, even if the amount of the surface treatment agent (B) added exceeds 200 parts by weight, the effect does not change, so there is no need to add more than 200 parts by weight, which is rather uneconomical.

In order to obtain the rheology modifying effect, the form of the clay composite of the present invention needs to be any one or more of the following three forms. That is, the average layer thickness of the clay composite is 200 Å or less, preferably 180 Å or less, and particularly preferably 150 Å or less. Average layer thickness is 200Å
If it is larger, not only the rheology modifying effect is difficult to be obtained, but also the physical properties of the matrix are made non-uniform. The lower limit of the average layer thickness is not particularly limited, but about 10Å is preferable. In addition, it is preferable that the clay composite layer having a layer thickness of 100 Å or less accounts for 30% or more of the whole, and 50% of the whole.
It is more preferable to occupy the above. If the layer thickness is less than 100Å less than 30% of the whole, the effect of modifying the rheology of the matrix tends to be difficult to obtain, which is not preferable. In addition, the bottom spacing of the clay complex is larger than that of the initial swelling silicate (A) due to the presence of the surface-treating agent (B) covalently bonded, and the bottom spacing is preferably The initial value is enlarged by 2 times or more, more preferably 3 times or more. As described above, by increasing the spacing between the bottom surfaces, the affinity with the matrix compound is increased, and the rheological properties can be efficiently improved. The clay composite of the present invention may contain two or more kinds of the above-mentioned clay composites.

In order to obtain the rheology modifying effect more efficiently, the ratio of the clay composite having a layer thickness of 50 Å or less is preferably 10% or more of the entire clay composite, and further 20
% Or more, and particularly preferably 30% or more.

The layer thickness of the clay complex can be obtained, for example, by measuring with an electron microscope or the like. In addition, the bottom surface spacing is (001) by the small-angle X-ray diffraction method (SAXS).
It can be easily confirmed from the measurement of the bottom distance between the surfaces. The bottom surface spacing can be obtained by applying the diffraction peak angle value in SAXS to the Bragg equation and calculating it.

The clay composite of the present invention has the function of increasing the viscosity of at least one solvent selected from the group consisting of water and an organic solvent. For example, 3.5% by weight of the clay composite of the present invention is used. %, The apparent viscosity at 25 ° C. and 6 rpm depends on the types and amounts of the swelling silicate (A) and the surface treatment agent (B) and the type of solvent to be dispersed. Is more than 5 times the initial solvent value. Examples of the organic solvent include aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethers such as tetrahydrofuran and dioxane, ketones such as acetone and methyl ethyl ketone and methyl isobutyl ketone, and methanol and Lower alcohols such as ethanol, propanol and isopropanol, higher alcohols such as decanol and hexanol, halogenated hydrocarbon compounds such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, perchloroethylene and chlorobenzene, dimethyl. Examples include amide compounds such as formamide, ester compounds such as ethyl acetate, and other solvents such as dioctyl phthalate, dimethyl sulfoxide, methyl cellosolve, and N-methyl-2-pyrrolidone. . These solvents are used alone or in combination of two or more.

The clay composite of the present invention has a thickening effect on various solvents, because the clay composite has an affinity for various solvents serving as a matrix, and is excellent in various matrices. It is considered that this is because the particles are dispersed, and they are uniformly finely dispersed without agglomerating in the matrix, and even if added in a small amount, they have an excellent thickening effect on the matrix and a modifying / modifying action such as rheological properties. Therefore, the clay composite of the present invention is used in various applications as a thickening agent or gelling agent for various solvent systems having various polarities. This object can be easily achieved by adding the clay complex to an arbitrary solvent system and dispersing it by an operation such as ordinary stirring. The dispersed concentration of the clay complex is
The thicker the concentration that can be dispersed in the solvent, the higher the thickening effect. The specific dispersion concentration cannot be specified unconditionally because it depends on the application, but it is generally in the range of 0.01 to 50% by weight, preferably 0.05 to 35% by weight, and more preferably 0.1 to 20% by weight. is there.

The clay composite of the present invention comprises a step of swelling the swelling silicate (A) to increase the bottom spacing (swelling step) and a surface of the swelling silicate (A) in a swollen state. It is produced by a method including a step of introducing the surface treating agent (B) having a functional group by a covalent bond (functional group introducing step). In the step of swelling the swelling silicate (A), the swelling silicate (A) is dispersed in a dispersion medium, or the swelling silicate (A) is cleaved by applying a physical external force. It is done by

When a dispersion medium is used in the swelling step,
For example, it can be performed by the method shown below. First, the swelling silicate (A) is swollen by stirring in a dispersion medium. As the dispersion medium, water or a polar solvent compatible with water at an arbitrary ratio, or a mixed solvent of the polar solvent and water may be used. The polar solvent that is compatible with the above water at an arbitrary ratio includes alcohols such as methanol and ethanol, glycols such as ethylene glycol and propylene glycol, acetone, and ketones such as methyl ethyl ketone, diethyl ether, and tetrahydrofuran. Ethers and the like are used. The solid dispersion concentration of the swellable silicate (A) dispersed in the dispersion medium can be freely set as long as it is within the concentration range in which the swellable silicate (A) can be sufficiently dispersed.

In the swelling step, when a physical external force is applied to cleave the swelling silicate (A), the physical external force can be applied by using a commonly used pulverizing method of filler. As a general method of finely pulverizing a filler, for example, a method of utilizing hard particles can be mentioned. In this method, hard particles and swelling silicate (A)
And an arbitrary solvent are mixed and stirred, and the swelling silicate (A) is separated by physical collision between the hard particles and the swelling silicate (A). The hard particles usually used are beads for crushing filler, and examples thereof include glass beads and zirconia beads. These grinding beads are selected in consideration of the hardness of the swelling silicate (A) or the material of the stirrer, and are not limited to the above-mentioned glass or zirconia. The particle size is also not specified because it is determined in consideration of the swelling silicate (A), but it is preferably in the range of 0.1 to 6.0 mm. The solvent used here is not particularly limited, but a solvent preferable for surface-treating the swelling silicate (A) in the functional group introducing step, such as water, or a mixed solvent of water and the polar solvent is preferable.

In the functional group introducing step, a silane coupling treatment agent and a titanate coupling treatment agent are added to a dispersion composed of the swelling silicate (A) swollen in the swelling step and a dispersion medium. , And at least one surface-treating agent (B) selected from the group consisting of alumina-based coupling agents, and stirred to introduce the covalent bond onto the surface of the swollen swelling silicate (A). To do. When it is desired to more efficiently covalently bond the surface treatment agent (B), the stirring speed is set to 1000 rpm or more, or 500
A shear rate of (1 / s) or more is applied. The upper limit of rotation speed is 25,000 rpm, and the upper limit of shear rate is 5000.
It is 00 (1 / s). Even if stirring is performed at a value higher than the upper limit, the effect tends not to change any more, so it is not necessary to perform stirring at a value higher than the upper limit.

The above-mentioned functional group introduction step is performed in a single step or multi-step.

In the case of a single step, the surface-treating agent (B) forms a covalent bond by a reaction with a hydroxyl group existing on the surface of the swelling silicate (A), whereby the swelling silicate (A) is formed. The surface treatment agent (B) having at least one functional group is introduced on the surface of (1). In the case of multiple steps, for example, in the first step, the surface treatment agent (B) having a reactive functional group such as a hydroxyl group, a carboxyl group, an amino group, an epoxy group, or a vinyl group is introduced. Next, as a second step, a compound having a functional group that reacts with the reactive functional group introduced in the first step is newly added and reacted. By this second step, it is possible to lengthen the chain length of the introduced group or to change the polarity. The compound added in the second step is not limited to the surface treatment agent (B) described above, and any compound may be used according to the purpose.
Examples thereof include an epoxy group-containing compound, an amino group-containing compound, a carboxyl group-containing compound, an acid anhydride group-containing compound, and a hydroxyl group-containing compound, and these may be used alone or in combination of two or more.

When water or a polar solvent is used as the dispersion medium in the swelling step, the dispersion obtained there can be used as it is as a reaction system with the surface treatment agent (B).
Also, when using a physical external force in the swelling process,
The swelling silicate (A) thus obtained can be dispersed in water or a mixed solvent of water and a polar solvent to prepare a dispersion, which can react with the surface treatment agent (B). The clay complex obtained as described above is isolated, dried and optionally ground.

The reaction in the step of introducing a functional group proceeds sufficiently at room temperature, but may be heated if necessary. The maximum temperature during heating is governed by the heat resistance of the surface treatment agent (B) used, and can be set arbitrarily as long as it is below the decomposition temperature.

It is considered that the clay composite of the present invention has a layer space. By utilizing this layer space, it is also possible to utilize the clay complex as an organic substance storage agent, sustained-release agent, catalyst, adsorbent, carrier, filler and the like.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The raw materials used in the following examples and comparative examples, and the method of measuring characteristic values are as follows.

[Swellable silicate (A)] Montmorillonite is a natural montmorillonite produced in Akita Prefecture (bottom surface interval = 13).
Å) was used as is without purification. The swelling mica used was synthesized as follows. Mix 25.4 g of talc and 4.7 g of sodium silicofluoride, and mix.
After heat treatment at 00 ° C., 28.2 g of swelling mica was obtained (bottom surface interval = 12Å).

[Surface Treatment Agent (B)] The following three types of silane coupling agents were used as they were without purification. γ- (2-aminoethyl) aminopropyltrimethoxysilane γ-polyoxyethylenepropyltrimethoxysilane N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane

[Identification of Covalently Bonded Functional Group in Clay Complex by FT-IR] The above-mentioned clay complex was added to tetrahydrofuran (THF) and stirred for 15 minutes to physically adsorb the surface treatment agent. (B) was washed. The supernatant was separated by centrifugation. This washing operation was repeated three times. About 1 mg of the sufficiently dried clay complex and about 200 mg of KBr powder were thoroughly mixed in a mortar, and then a KBr disk for measurement was prepared using a tabletop press. Then, it measured by the transmission method using an infrared spectroscope. An MCT detector was used as a detector, and the resolution was 4 cm ⁻¹ and the number of scans was 100 times.

[Measurement of Layer Thickness of Clay Complex by Transmission Electron Microscope (TEM)] Transmission electron microscope (JEOL J
EM-1200EX) and the acceleration voltage was 80 kV. A sample was prepared by an epoxy embedding method in which the clay complex was sufficiently stirred and dispersed in an epoxy compound so as not to aggregate and then cured. An ultrathin section was cut out from the cured product and stained with ruthenium oxide to prepare a sample.

[Measurement of Bottom Surface Spacing by Small Angle X-Ray Diffraction (SAXS)] X-ray generator (RU-20 manufactured by Rigaku Denki Co., Ltd.)
0B), target CuKα ray, Ni filter, voltage 40 kV, current 200 mA, scanning angle 2θ = 0.
Under the measurement conditions of 2-16.0 ° and step angle = 0.02, the swelling silicate (A) and the bottom spacing of the clay composite of the present invention were measured.

[Apparent Viscosity] The apparent viscosity at 25 ° C. of the clay composite dispersion obtained by dispersing the clay composite in various solvents is
The measurement was performed using a B-type viscometer manufactured by Tokyo Seiki. Depending on the viscosity of the dispersion, the rotor is no. 1, No. 2, No.
3 and BL adapters were used. The clay complex was added to 400 ml of the solvent shown in Table 2, and the dispersion concentration was 3.5% by weight.
And the mixture was stirred at 5000 rpm for 15 minutes to prepare a clay complex dispersion. The resulting dispersion is 50
Transfer to a 0 ml mayonnaise bottle and let stand for 3 hours,
The rotor was put up to the marked line, and the apparent viscosity was measured at a rotor rotation speed of 6 rpm.

Examples 1 to 11 The layer thicknesses and bottom spacings of the clay composites a to d obtained by the following production method were measured. The results are shown in Table 1. Further, 25 g of the clay composites a to d were dispersed in 700 g of the solvent shown in Table 1 and the apparent viscosity at 25 ° C was measured. The results are shown in Table 1.

Clay Complex a 140 g of montmorillonite was dispersed in 3500 g of pure water using a high speed stirrer. Thereafter, 14 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane was gradually added dropwise with a simple pipette, and stirring was continued at 5000 rpm for 2 hours. Clay composite a was obtained by filtering, drying and crushing.
In addition, as a result of measuring the clay complex a by FT-IR,
Absorption bands derived from the primary amino group, secondary amino group, and ethylene group were observed.

Clay Complex b 140 g of montmorillonite was dispersed in 3500 g of pure water using a high-speed stirrer. Thereafter, 14 g of γ-polyoxyethylenepropyltrimethoxysilane hydrolyzed with water adjusted to pH 4 with hydrochloric acid was gradually added dropwise using a simple pipette, and stirring was continued for 3 hours at a shear rate of 4000 (1 / s). It was filtered, dried and crushed to obtain a clay complex b.
In addition, as a result of measuring the clay composite b by FT-IR,
Absorption bands derived from ether groups and ethylene groups were observed.

Clay Complex c 140 g of montmorillonite was dispersed in 3500 g of pure water using a high speed stirrer. Then, N, N-di (2-hydroxyethyl) amino-3 hydrolyzed with an ethanol / water (3/7 weight ratio) mixed solvent adjusted to pH 4 with hydrochloric acid.
14 g of -propyltriethoxysilane was gradually added dropwise using a simple pipette, and the mixture was stirred at 5000 rpm for 3 hours. It was filtered, dried and crushed to obtain a clay complex c. In addition, as a result of measuring the clay complex c by FT-IR, absorption bands derived from a tertiary amino group and an ethylene group were observed.

Clay complex d 140 g of swelling mica was dispersed in 3500 g of pure water using a high speed stirrer. Then, γ- (2-aminoethyl)
Aminopropyltrimethoxysilane (14 g) was gradually dropped using a simple pipette, and the shear rate was 4000 (1 / s).
The stirring was continued for 3 hours. It was filtered, dried and crushed to obtain a clay complex d. As a result of measuring the clay composite d by FT-IR, absorption bands derived from primary amino groups, secondary amino groups, and ethylene groups were observed.

Comparative Examples 1 to 11 Silane-treated montmorillonite a'obtained by the following method
.About.c ', the layer thickness of the silane-treated swellable mica d', and the bottom spacing were measured. The results are shown in Table 1. Further, 25 g of silane-treated montmorillonite a ′ to c ′ and silane-treated swellable mica d ′ was dispersed in 700 g of the solvent shown in Table 1 and the apparent viscosity of the system at 25 ° C. was measured. The results are shown in Table 1.

Silane-treated montmorillonite a ′ 140 g of montmorillonite was sprayed with 14 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane using a sprayer and mixed for 1 hour. The bottom spacing of the silane-treated montmorillonite a ′ was 13Å. still,
As a result of measuring the silane-treated montmorillonite a'by FT-IR, absorption bands derived from the primary amino group, secondary amino group, and ethylene group were observed.

Silane-treated montmorillonite b ′ 140 g of montmorillonite was sprayed with 14 g of γ-polyoxyethylenepropyltrimethoxysilane hydrolyzed with a methoxy group, and mixed for 1 hour.
The silane-treated montmorillonite b'was measured by FT-IR, and as a result, absorption bands derived from ether groups and ethylene groups were observed.

Silane-treated montmorillonite c ′ 140 g of montmorillonite was sprayed with 14 g of N, N-di (2-hydroxyethyl) amino-3-propyltriethoxysilane having a hydrolyzed ethoxy group, and mixed for 1 hour. did. As a result of measuring silane-treated montmorillonite c ′ by FT-IR, absorption bands derived from a tertiary amino group and an ethylene group were observed.

Silane-treated swellable mica d ′ 140 g of swellable mica was sprayed with 14 g of γ- (2-aminoethyl) aminopropyltrimethoxysilane using a sprayer and mixed for 1 hour. As a result of measuring the silane-treated swellable mica d'by FT-IR, an absorption band derived from a primary amino group, a secondary amino group, and an ethylene group was observed.

[0071]

[Table 1]

Reference Examples 1 to 10 Montmorillonite used in Examples 1 to 10 and the swelling mica and the solvent of Table 2 were sufficiently stirred and mixed to prepare a system containing montmorillonite and the solvent. The apparent viscosity of the system at 25 ° C was measured. Table 2 shows the results.

[0073]

[Table 2]

Reference Examples 11-19 140 g of montmorillonite was dispersed in 3500 g of pure water using a high-speed stirrer. 28 g of trimethyloctadecyl ammonium chloride was added, and the mixture was stirred at room temperature for 1 hour. Then, it was sufficiently washed with water, suction filtered, and dried and pulverized to obtain a montmorillonite-ammonium salt complex. The bottom distance was 25Å. 25 g of the above complex was dispersed in 700 g of the solvent shown in Table 3, and the apparent viscosity at 25 ° C. was measured. The results are shown in Table 3.

[0075]

[Table 3]

[0076]

As described above, according to the present invention, there is provided a clay composite which can give a desired rheological property to a matrix compound such as a solvent even when added in a small amount, and a method for producing the same. According to the present invention, the affinity between the matrix compound such as various solvents and the clay complex can be increased by selecting the type and combination of the functional groups to be introduced on the surface of the swelling silicate. Therefore, for example, since it has an excellent rheology modifying effect even when added in a small amount, various products such as cosmetics, pharmaceuticals, sanitizers, adhesives, paints, coating materials, various plastic products, textile industry, etc. that require viscosity adjustment, or It can be used as a composition such as a viscosity modifier, a dispersant, an emulsifier, a binder in an industrial process, and is extremely useful. The clay composite of the present invention can be easily obtained with a commonly used surface treatment agent such as a silane coupling agent.

Claims (16)

[Claims] 1. A surface treating agent (B) having a functional group is introduced onto the surface of the swelling silicate (A) by a covalent bond,
A clay composite having an average layer thickness of 200 Å or less. 2. A surface treating agent (B) having a functional group is introduced onto the surface of the swelling silicate (A) by a covalent bond,
A clay composite having a layer thickness of 100 Å or less occupying 30% or more of the whole. 3. The total thickness is 50 Å or less.
The clay composite according to claim 2, which accounts for at least%. 4. A clay composite characterized in that the surface treatment agent (B) is introduced into the surface of the swelling silicate (A) by a covalent bond to increase the bottom spacing. 5. The bottom surface spacing is enlarged by a factor of 2 or more.
The described clay complex. 6. A clay composite comprising two or more of any one of the clay composites according to claim 1, 3, or 4. 7. A layer having a layer thickness of 50Å or less is 10% of the whole.
The clay composite according to any one of claims 1 to 6, which occupies the above. 8. A layer having a layer thickness of 50Å or less is 20% of the whole.
The clay composite according to claim 7, which occupies the above. 9. The clay composite according to claim 1, wherein the swelling silicate (A) is a smectite group clay mineral. 10. The clay composite according to claim 1, wherein the swelling silicate (A) is a swelling mica. 11. The surface treatment agent (B) is at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent, and an alumina coupling agent.
The clay composite according to any one of claims 1 to 10, which is a seed. 12. The surface-treating agent (B) has the general formula (I): Y _n SiX _4-n (I) (wherein n is an integer of 0 to 3 and Y is 1 carbon atom). ~
25 hydrocarbon groups, and at least one selected from the group consisting of a hydrocarbon group having 1 to 25 carbon atoms and an organic functional group consisting of a substituent, and X is a hydrolyzable group and / or
Or it is a hydroxyl group. The n Y's and the 4-n X's may be the same or different. ) The clay composite according to any one of claims 1 to 11, which is a silane coupling agent represented by the formula (1). 13. A clay complex having a function of increasing the viscosity of at least one solvent selected from the group consisting of water and an organic solvent, the clay complex being present at a concentration of 3.5% by weight. Clay composite characterized by increasing the apparent viscosity at 25 ° C. and 6 rpm when dispersed therein to 5 times or more the value of the viscosity of the solvent. 14. A swelling silicate (A) is swelled by dispersing it in a dispersion medium, and a surface treating agent (B) having a functional group is covalently bonded to the surface of the swelling silicate (A). A method for producing a viscosity complex, comprising: 15. The method according to claim 14, wherein the surface treatment agent (B) is covalently bonded while stirring at 1000 rpm or more. 16. The production method according to claim 14, wherein the surface treatment agent (B) is covalently bonded while stirring at a shear rate of 500 (1 / s) or more.