JP4793713B2 - Inorganic / organic composite nanosheet, manufacturing method thereof, coating agent, filler, layered inorganic / organic composite, and thin film - Google Patents

Description

The present invention, no machine / organic composite nanosheet, manufacturing method thereof, a coating agent, a filler, to a layered inorganic / organic composite and the thin film.

Many intercalation compounds in which an organic substance is introduced by intercalation reaction between layers of inorganic layered compounds such as clay minerals have been reported .

  In addition, a method for producing a nanosheet by peeling a layered compound such as a layered titanate is already known (for example, Patent Documents 3 and 4 and Non-Patent Document 1). In recent years, development of a large number of layered oxide nanosheets has been promoted due to the widespread expectation of development of new materials using nanosheets.

If the layered inorganic / organic composite can be made into a nanosheet in the same manner as the inorganic layered compound, it can be expected to exert a great ripple effect on the development of new materials. In addition, development of lipophilic nanosheets has been awaited for purposes such as use as a filler for organic general-purpose resins and paints, and for the production of thin films on lipophilic substrates.

However, it is useless to simply apply the above-described method for obtaining nanosheets from inorganic layered compounds to the production of inorganic / organic composite nanosheets. This is because when the layered inorganic / organic composite is peeled off and separated to the nano level, and finally separated into a single layer, it is naturally separated into an inorganic substance and an organic substance. The object is no longer an inorganic / organic composite nanosheet, but merely a mixture of inorganic nanosheet and organic material.

Japanese Patent Laid-Open No. 06-200034 JP 2004-107494 A JP 09-175816 A Japanese Patent Laid-Open No. 10-087320 J. et al. Am. Chem. Soc. , 1996, 118, 8329

The present invention, problems to solve the problems of the prior art as described above, be provisionally monolayered, as well as to be able to continue as inorganic / organic composite nano-sheet, a Rukoto Kyosu Hisage its manufacturing method It is said.

A layered organosilicon polymer (Patent Document 1) in which an organic part and an inorganic part are combined through a strong joint such as a covalent bond, and a thermoplastic layered alkylsiloxane invented by the present inventors (Patent Document 2) It is known.
As a result of intensive studies to solve such problems, the present inventors have found that a method of applying a layered inorganic / organic composite in which an organic part and an inorganic part are combined through a strong joint such as a covalent bond is effective. I found something. In other words, as described above, most of the layered inorganic / organic composites, even if the method of obtaining the inorganic nanosheet is applied, eventually becomes a simple mixture of the inorganic nanosheet and the organic material, but both are robust through covalent bonds. I realized that this is not the case for composites with complex interfaces. As described above, a plurality of compounds are already known as the complex via the corresponding covalent bond.

  The conditions for the complex used in the present invention are as follows. 1. The organic part and the inorganic part have a robust interface through a covalent bond. 2. High affinity for the solvent used for nanosheet formation. It is stable under nanosheet forming operation conditions. It has been found that it is optimal to use a composite (for example, Patent Document 2; JP-A-2004-107494) already developed by the present inventors as a layered inorganic / organic composite satisfying these conditions.

  As a method for forming a nanosheet, 1. 1. It is simpler. 2. No expensive equipment is used. It was considered that a nanosheet forming method with a wider application range can be provided if it is performed under mild conditions such as near room temperature, normal pressure, and not using a highly active reagent.

  Further, as the swelling treatment method, a method that can be continuously performed with nanosheets is more desirable. For example, it is very convenient if the process from the swollen state to the nanosheet can be carried out as a series of processes only by changing the mixing ratio of the solvent in the same solvent and container.

  The method satisfying the above conditions succeeded in obtaining an inorganic / organic composite nanosheet as shown below, while maintaining the bond between the inorganic part and the organic part of the layered silicate / organic composite and the layered organosiloxane. It has succeeded in swelling.

The inorganic / organic composite nanosheet of the invention 1 is an inorganic / organic composite nanosheet in which an organic group is added to a nanosheet made of an inorganic silicon compound , and two of the three sides are 0.1 a ～2Myuemu, a thickness of one side remains is 1 to 3 nm, the inorganic silicon compound Ri name combinators of silicon constituting and the coupling element of the organic groups are covalently bonded to the inorganic silicon compound The nanosheet is characterized by having a tetrahedral sheet .

Invention 2 is an inorganic / organic composite nanosheet of Invention 1 , wherein the inorganic sheet has a structure in which an octahedral sheet made of an inorganic compound is sandwiched between two tetrahedral sheets.

Invention 3 is the inorganic / organic composite nanosheet of Invention 2 , the composition of which is represented by the general formula R _h M _{6 / i} Si _j O _k (OH) _l (where R is an organic group, M is Mg, Al, Fe At least one element among them, 0.1 ≦ h ≦ 1, i represents the valence of the element M, 2 ≦ j ≦ 4, 6 ≦ k ≦ 10, 2 ≦ l ≦ 6). It is characterized by being expressed.

The invention 4 has a composition in which a part of M in the general formula R _h M _{6 / i} Si _j O _k (OH) ₁ of the invention 3 is substituted with at least one element among alkali metals, and the composition is R _h (M _{( 6 / i-m) L m} ) Si j O k (OH) l ( where, L is at least one element among alkali metals, characterized by being represented by 0.005 ≦ m ≦ 1) And

Invention 5 is characterized in that in the inorganic / organic composite nanosheet of Invention 4 , the organic group is a propyloctadecyldimethylammonium group .

Invention 6 is an inorganic / organic composite nanosheet according to Invention 1 , wherein the composition is represented by the general formula [R ′ _n Si _p O _q (O J ) _r ] _s (where R ′ represents an organic group, J represents H, Si Or a group in which an OJ group can be easily changed to an OH group in a solution or suspension, 0.5 ≦ n ≦ 2, 1.5 ≦ p ≦ 3, 2.5 ≦ q ≦ 4, 1 ≦ r ≦ 2.5, 2 ≦ s ≦ 200)).
Invention 7 is the inorganic / organic composite nanosheet of Invention 6 , wherein R ′ is an octadecyl group or a hexadecyl group.

Invention 8 is a method for producing an inorganic / organic composite nanosheet according to any one of Inventions 1 to 7 , wherein a silicon bond and an organic group bond are covalently bonded to a nanosheet made of an inorganic silicon compound. The layered inorganic / organic composite material is peeled off by applying an organic solvent.
Invention 9 is a method for producing an inorganic / organic composite nanosheet of Invention 8 , wherein the layered silicate / organic composite is acted on with an organic solvent before the layered silicate / organic composite is peeled off to form a layered silicate. / Swelling of organic complex.

The coating agent of the invention 10 contains the inorganic / organic composite nanosheet of any of the inventions 1 to 7 as an active ingredient.

The filler of the invention 11 is characterized in that at least a part thereof is constituted by using the inorganic / organic composite nanosheet of any of the inventions 1 to 7 .

The layered inorganic / organic composite of the invention 12 is that the inorganic / organic composite nanosheet of any one of the inventions 1 to 7 constitutes at least a part thereof, and is constructed using the inorganic / organic composite nanosheet. Features.

The thin film of the invention 13 is obtained by aligning the inorganic / organic composite nanosheet of any one of the inventions 1 to 7 on a substrate.

The reason why the inorganic / organic composite nanosheet is formed by the methods of the ninth and tenth aspects of the present invention is considered as follows. Due to the affinity between the organic solvent molecules and the organic portion, the organic solvent molecules are taken in between the layers of the composite, and the composite swells. Furthermore, when the mixing ratio of the organic solvent is increased and an excess organic solvent is present in the system, the affinity between the organic part and the organic solvent is strong, and the affinity between the layered composite and the organic solvent is an appropriate combination. The organic solvent solvates the organic portion of the composite, and the layered composite peels. The affinity between the organic solvent and the organic part is thought to be mainly due to van der Waals forces. It is thought that dipole-dipole attractive force also works between the organic solvent and the whole complex.

  The solving means of the present invention is as described above, and the inorganic / organic composite nanosheet can be produced by these solving means. Also, instead of using nanosheets as a single species, multiple layered inorganic / organic composites can be reconstructed by combining and recombining multiple different types of composite nanosheets in which the organic and / or inorganic portions are different chemical species. Manufacture is possible. Thereby, for example, two or more different organic portions can exist in the same two-dimensional field (interlayer formed by a pair of adjacent sheet-like inorganic portions). There is a possibility that segregation, which has been a problem with conventional layered silicate / organic composites obtained by an intercalation reaction or the like, can also be solved.

  Furthermore, since the present invention also provides a swelling treatment method for a layered silicon compound / organic composite in which an inorganic part and an organic part are bonded by a covalent bond, a wide range from a layered silicon compound to an inorganic / organic composite nanosheet through its swelling state It can be formed using the technique of the present invention over a range.

The present invention has the features as described above, and an embodiment thereof will be described below. The inventors focused on the importance of refining to the nano level and achieving both inorganic / organic bonding in order to obtain an inorganic / organic composite nanosheet. As a layered composite that is a starting material that gives a composite nanosheet that can achieve both, 1. 1. The inorganic part and the organic part have a robust interface through a covalent bond; 2. It can be subdivided to nano level under relatively mild conditions. Even if it is subdivided to the nano level, the structure in the two-dimensional direction of the inorganic part is stable, that is, the bond in one direction (stacking direction) is weak, but the bond in the remaining two directions (in the layer) seems to be robust. 3. It has characteristics. Those that are stable even after the nanosheeting operation are desirable.
From such knowledge, the layered silicon compound / organic compound complex previously developed by the present inventors (for example, Patent Document 2; JP-A-2004-107494) is optimal.

  That is, the inorganic / organic composite nanosheet provided by the first and second inventions of the present application is, as described above, two of the three sides are 0.1 to 2 μm and the remaining one side is 1 to 3 nm. Although it is a nano-order thick sheet, since the inorganic part and the organic part are covalently bonded, the inorganic / organic interface is maintained even if it is subdivided by being surrounded by the solvent to the nano level, and the nano level Succeeded in producing the composite.

The composition of the inorganic / organic composite nano-sheets by the general formula _{R h M 6 / i Si j} O k (OH) l ( wherein, R represents an organic radical, M is Mg, Al, at least one of Fe 0.1 ≦ h ≦ 1, i represents the valence of the element M, 2 ≦ j ≦ 4, 6 ≦ k ≦ 10, 2 ≦ l ≦ 6). The inorganic part has a structure similar to a 2: 1 type layered clay mineral in which the element M forms an octahedral sheet, and the octahedral sheet is sandwiched between two tetrahedral sheets formed by Si. Therefore, even if it is subdivided to the nano level, the structure in the layer is kept stable, and the size in the two directions is 0.1 to 2 μm, which is relatively large in the thickness direction, and thus has a sheet-like form. Also, such inorganic part, organic part and inorganic / organic interface are stable after the nanosheeting operation provided in the present invention.

Further, as the onset bright provided, it is possible to obtain a partially substituted inorganic / organic composite nano-sheet with the element M is the element L forming the octahedral sheet. Here, L represents at least one element of alkali metal as described above. Since various alkali metals are included and the charge of the inorganic portion can be changed, there is a possibility of designing a nanosheet that can be freely adapted to the application.

  In the present invention, the coefficient h of the organic group R must be greater than 0, theoretically up to 4. However, in view of the structural stability of the inorganic silicate portion, it is more practically set to 1 or less.

The organic group R in the onset bright, such as an alkyl group or an alkyl ammonium group, are considered to be particularly because it is relatively stable and lipophilic groups useful, of course not limited thereto. The inorganic portion of the inorganic / organic composite nanosheet provided in the present invention can be a siloxane sheet having a two-dimensional extension.

Inorganic / As a method for producing an organic composite nanosheet, as the onset bright provides, represented by the composition formula similar to the inorganic / organic composite nanosheet purposes, layered silicon compound is a structure as stacked is nanosheets object / An organic solvent is allowed to act on the organic composite because it is the most convenient and widely applicable. Further, prior to peeling by acting organic solvents may be swollen by the action of an organic solvent.

The organic solvent used is: 1. High affinity with the layered inorganic / organic composite to be used, particularly with the organic moiety; The layered inorganic / organic composite to be used and the target inorganic / organic composite nanosheet must not be decomposed. Moreover, since it is desirable that the operation can be performed under a mild condition near room temperature, a liquid which is liquid near room temperature is preferable. Further, if the volatility is too high, a special environment is required for the nanosheet forming operation, and if it is too low, the purification treatment of the intended composite nanosheet obtained becomes troublesome. For example, using a toluene and xylene, is very easy when the action of organic solvents at room temperature.

Next, a method for swelling the layered silicon compound / organic composite will be described . As a result, the solid layered silicon compound / organic composite, its swollen state, and composites in various states ranging from composite nanosheets can be used continuously, which is very convenient in practice. For example, when used as a viscosity modifier, the layered silicon compound / organic composite can be added in a swollen state according to the target viscosity.

The inorganic / organic composite nanosheet of the present invention are conceivable variety of applications but, as a co computing agents and fillers, or can be used as part of their construction material.

In addition, when the inorganic / organic composite nanosheet of the present invention is used, various new materials as described above can be designed . And new layered inorganic / organic composite obtained by the rebuild double focus nanosheet thin film is one of the new material.

Examples will be shown below, and the embodiments of the present invention will be described in more detail.
9.13 g of silica sol, 45.26 g of 50 wt% methanol solution of octadecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride, 3.50 g of magnesium hydroxide and 0.31 g of lithium fluoride were weighed and sufficiently dispersed in ion-exchanged water. A reaction solution was prepared. The reaction solution was kept at 200 ° C. for 3 days, and the product was filtered off, and then washed with methanol and then with ion-exchanged water. The obtained sample was dried to obtain a powder.

This powder has a 2: 1 structure in which the inorganic part is similar to hectorite, that is, a structure in which one octahedron sheet is sandwiched between two Si tetrahedron sheets and a layer is further laminated. Is an aliphatic quaternary ammonium group, the organic part is present between the layers of the inorganic part, and is further complexed via a covalent bond. The composition is R _0.43 Li _0.009 (Mg _2.99 Li _{0. 009} ) Si _3.22 O _k (OH) _{1 and} was a layered silicate / alkylammonium complex. This powder was used as starting material. When 200 mg of the powder of the layered silicate / alkylammonium complex was added to 1 ml of toluene and stirred for about 30 minutes at room temperature, a colloidal mixed solution (mixed solution A) was obtained.

  Further, an X-ray diffraction pattern of a mixed colloid solution having a concentration of 20 mg / 1 ml, which was obtained by diluting the mixture 10 times with toluene, was measured (FIG. 1 (a)). Reflection corresponding to a d value of 4.4 nm was observed on the low angle side. The reflection corresponding to 2.3 nm is considered to be secondary reflection. Since the interplanar spacing of the layered silicate / alkylammonium complex, which is the starting material, is about 2.3 nm, it can be seen that the complex was swollen by the action of toluene.

  The interplanar spacing discussed here is the interplanar spacing and is the sum of the thickness of one 2: 1 layer and the distance between layers. The mixed colloidal solution was dropped on the substrate and dried, and then observed with a scanning electron microscope (SEM). As shown in FIG. 2A, a laminated layered image was observed.

  To the colloidal mixed solution (mixed solution A) obtained in Example 1, toluene was further added to dilute the mixed solution A by about 67 times to obtain a mixed colloidal solution having a concentration of 3 mg / 1 ml. The XRD pattern was measured in the same manner for the sample thus obtained, but as shown in FIG. 1B, no reflection was observed, suggesting the formation of a nanosheet.

Further, a sample diluted to 100 times to a concentration of 3 × 10 ⁻² mg / 1 ml was dropped on the substrate, dried, and then subjected to SEM observation. As shown in FIG. the variance in different people direction nanosheets, observed aggregated image, very different image is observed with the 10-fold dilution of the sample (FIG. 2 (a)). It is considered that toluene molecules are excessively intercalated between the layers of the composite in the mixed solution, further solvate the organic part (alkyl ammonium group), and finally peel off the layers. It is considered that the inorganic / organic composite nanosheet formed into a nanosheet by peeling off was deposited on the substrate during the drying process on the substrate. From these results, it was shown that a lipophilic inorganic / organic composite nanosheet can be obtained in a toluene solution.

As in Example 1, a layered silicate / alkylammonium complex was used as a starting material. When 200 mg of powder of the layered silicate / alkylammonium complex was added to 1 ml of 1-octanol and stirred at room temperature for about 1 hour, a colloidal mixed solution was obtained. When the XRD pattern of the mixed solution was measured, reflection corresponding to about 4 nm was observed, suggesting swelling of the layered composite. This swollen state was very stable, and the swollen state was maintained even if it was dried on a slide glass in a dry nitrogen atmosphere for a whole day. FIG. 3 shows an XRD pattern of the drying process. FIG. 3 (a) shows immediately after dropping (swelled state), FIG. 3 (b) shows after drying for 1 day, and FIG. 3 (c) shows after 2 days of drying.

  As described above in detail, according to the present invention, an inorganic / organic composite nanosheet having both the characteristics of an inorganic silicon compound and an organic substance can be provided. In other words, it has become possible to obtain a completely new composite material having both inorganic and organic characteristics and a nano-level size. Thereby, since the lipophilic nanosheet, ie, the nanosheet which can exist in the lipophilic solvent, can be produced, it can be used in a wide range as a coating agent, a filler and a viscosity modifier.

In Example 1 and 2, the XRD pattern of the mixed solution of a layered silicate / alkyl ammonium complex and toluene. (A) 20 mg / 1 ml, (b) 3 mg / 1 ml. In Example 1 and 2, the drawing substitute SEM image of the observation sample obtained by dripping and drying the mixed solution of a layered silicate / alkylammonium complex and toluene. (A) 20 mg / 1 ml, (b) 3 × 10 ⁻² mg / 1 ml. In Example 3, the XRD pattern of the drying process of the layered silicate / alkyl ammonium complex swollen with 1-octanol. (A) Immediately after dropping (swelled state), (b) after drying for 1 day, (c) after drying for 2 days.

Claims (13)

An inorganic / organic composite nanosheet obtained by adding an organic group to a nanosheet made of an inorganic silicon compound,
In the inorganic / organic composite nanosheet, two of the three sides are 0.1 to 2 μm, and the remaining one side is 1 to 3 nm in thickness,
Ri name and combinators of the organic group as connectives silicon constituting the inorganic silicon compound is covalently bonded,
The nanosheet made of an inorganic silicon compound has a tetrahedral sheet, and is an inorganic / organic composite nanosheet. Inorganic / organic composite nanosheet according to claim 1, nanosheet consisting said inorganic silicon compound is characterized by having an octahedral sheet is sandwiched structure consisting of an inorganic compound between a two tetrahedral sheets Inorganic / organic composite nanosheet. Inorganic / organic composite nanosheet according to claim 2, the composition, in the general formula _{R h M 6 / i Si j} O k (OH) l ( wherein, R represents an organic radical, M is Mg, Al, the Fe At least one of these elements, 0.1 ≦ h ≦ 1, i represents the valence of the element M, 2 ≦ j ≦ 4, 6 ≦ k ≦ 10, 2 ≦ l ≦ 6) An inorganic / organic composite nanosheet characterized by the above. The composition in which a part of M in the general formula R _h M _{6 / i} Si _j O _k (OH) _{1 according} to claim 3 is substituted with at least one element among alkali metals is R _h (M _{( 6 / i-m) L m)} Si j O k (OH) l ( where, L is at least one element among alkali metals, inorganic / organic composite represented by 0.005 ≦ m ≦ 1) Nanosheet. The inorganic / organic composite nanosheet according to claim 4 , wherein the organic group is a propyloctadecyldimethylammonium group . Inorganic / organic composite nanosheet according to claim 1, composition formula _{[R 'n Si p O q} (O J) r] s ( where, R' represents an organic group, J is H, Si, Or a group in which an OJ group can be easily changed to an OH group in a solution or suspension, 0.5 ≦ n ≦ 2, 1.5 ≦ p ≦ 3, 2.5 ≦ q ≦ 4, 1 ≦ r ≦ 2.5, 2 ≦ s ≦ 200)). The inorganic / organic composite nanosheet according to claim 6 , wherein R 'is an octadecyl group or a hexadecyl group. The method for producing an inorganic / organic composite nanosheet according to any one of claims 1 to 7 , wherein the silicon binder and the organic group binder are covalently bonded to the nanosheet made of an inorganic silicon compound. A method for producing an inorganic / organic composite nanosheet, characterized in that an organic solvent is allowed to act on the inorganic / organic composite of the material to separate it. 9. The method for producing an inorganic / organic composite nanosheet according to claim 8 , wherein an organic solvent is allowed to act on the layered silicate / organic composite to cause release of the layered silicate / organic composite. A method for producing an inorganic / organic composite nanosheet characterized by swelling an organic composite. Coating agent characterized by containing as an active ingredient one of the inorganic / organic composite nanosheet of claims 1 to 7. Fillers, characterized by being configured at least partially with one of the inorganic / organic composite nanosheet of claims 1 to 7. Either inorganic / organic composite nanosheets constitutes at least a part, said to inorganic / organic composite nanosheet layered inorganic / organic composite constructed using of claims 1 to 7. Either inorganic / organic thin film obtained by the composite nanosheet is aligned on the substrate of claims 1 to 7.

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