KR20200112817A - Sustained-release composite agent containing interlayer modified layered inorganic compound and its manufacturing method - Google Patents

Abstract

In the present invention, by introducing a chemically stable organic-inorganic complex group having a variety of chemical structures between the layers of the layered inorganic compound, an environment that properly interacts with the desired functional compound to be slow-released is designed and constructed between the layers. It is an object of the present invention to provide a sustained-release composite agent that is released over a long period of time after being inserted between layers, and a method for producing the same. A sustained-release composite agent comprising an interlayered layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) between the layers of the layered inorganic compound, and a compound inserted between the layers of the layered inorganic compound As a solution.

Description

Sustained-release composite agent containing interlayer modified layered inorganic compound and its manufacturing method

The present invention relates to a sustained-release composite agent in which a compound is inserted between layers of a layered inorganic compound subjected to interlayer modification, and a method for producing the same.

As a sustained-release material that releases a functional compound inserted between layers of a layered inorganic compound, an anhydrous layered inorganic compound is used as a host compound, and an ionized functional compound is used as a guest compound. The functional compound is inserted between the layers by ion exchange between the exchangeable ions present between the layers of the compound and the ionized guest compound, and the exchangeable metal cations present between the layers of the sustained-release composite agent and the layered inorganic compound are exchanged with alkyl ammonium. [0003] A composite agent is known in which layers are organic (hydrogenated), and a functional compound is inserted between the layers for sustained release.

For example, in Patent Document 1, a layered double oxide having an anhydrous interlayer is used as a host compound, and capsaicin anionized as a guest compound is mixed therewith to exchange layered multioxide-anionization with nitrate ions, an anion present between the layers. A complex preparation for preparing a capsaicin (host-guest) complex preparation and sustained release of capsaicin as a guest compound therefrom, and a method for producing the same are described.

In addition, Patent Document 2 discloses that as a host compound, an interlayer exchangeable metal cation of the clay mineral montmorillonite and organicated bentonite obtained by cation exchange between the layers by cation exchange with dimethyldioctadecyl ammonium are used as a guest compound, as a neutral cymethrin ( Simetryn) mixed with sustained-release simethrin granules and a method for producing the same are described.

Japanese Patent No. 5688727 Japanese Patent Application Publication No. 2004-26705

However, when a layered inorganic compound containing an anhydrous exchangeable metal cation described in Patent Document 1 is used as a host compound, only an ionized guest compound can be applied as a sustained-release compound, and a nonionic compound is used. Since it cannot be inserted and sustained release, and the sustained release cannot be controlled by designing the interlayer environment as desired for the guest compound, it is not possible to sustained release by controlling the release rate according to the purpose.

In addition, since the interlayer environment of the host compound only hydrophobizes, but cannot have diversity, with the formula for organizing the alkyl ammonium described in Patent Document 2, the interaction of any desired guest compound and the layered inorganic compound depending on the intended use It cannot be controlled, and it is difficult to design and synthesize an interlayer environment so that the interlayer intercalation and the sustained release rate from the interlayer are optimal, and compounds capable of sustained release are limited.

In addition, since it is an interlayer modification by alkyl ammonium, it is easily affected by the use environment such as under acidic conditions, and the cation exchange reaction proceeds between the layers, and the alkylammonium group is easily separated from the interlayer. For this reason, the conditions of use of the sustained-release agent using such an organically modified host compound are limited, and when used for a relatively long period of time, it becomes difficult to maintain the interlayer modified structure of the organically modified layered inorganic compound, which is not practical as a sustained-release agent.

In addition, since the interlayers of the layered inorganic compound, which is the host compound of Patent Document 1 and Patent Document 2, are not crosslinked, depending on the usage environment, the layered structure collapses and peels off, releasing the inserted guest compound at once. The use and environment of zero use are extremely limited and not universal, and thus not industrially useful.

In view of the above situation, the present invention inserts the desired compound for sustained release between the layers of the layered inorganic compound cross-linked through covalent bonds or the layered inorganic compound modified through covalent bonds, It is an object of the present invention to provide a sustained-release composite agent and a method for producing the same.

As a result of the inventor's hard research to solve the above problems, the interlayer crosslinked layered inorganic compound or the layered inorganic compound having an organic-inorganic composite crosslinked structure between the layers of the layered inorganic compound is modified with an organic-inorganic complex such as silyl group. The present invention was completed by finding that a sustained-release composite agent in which the interlayered layered inorganic compound was used as a host compound and a functional compound was inserted as a guest compound between the layers could solve the above problems.

That is, the present invention includes an interlayered layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) between the layers of the layered inorganic compound, and a compound inserted between the layers of the layered inorganic compound. It is a sustained-release combination drug.

[Formula 1]

(In formula (1), M ¹ and M ² each independently represent Si, Al, Ti or Zr, and R ^a and R ^b are each independently a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, A saturated or unsaturated cycloalkylene group, which may have a branched chain having 3 to 20 carbon atoms, an allylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, R ^c represents an organic group consisting of 1 to 40 carbon atoms, and a hetero atom , A linear structure, a branched structure, a cyclic structure, an unsaturated bond, and an aromatic structure may be included, and R is a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and a saturated may have a branched chain having 3 to 8 carbon atoms. Or an unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, respectively, a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a carbon number 1 to 20 linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, first Grade, secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphate ester group, sulfonic acid May be substituted with a group, a sulfonic acid ester group, or a halogen atom Z is a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, or a saturated or unsaturated cycloalkyl which may have a branched chain having 3 to 8 carbon atoms. Oxy group, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy group, which may have a branched chain having 1 to 8 carbon atoms, halogen atom, hydroxyl group, amino group, linear or branched chain saturated with 1 to 6 carbon atoms Or an unsaturated alkylamino group, a straight or branched chain having 1 to 6 carbon atoms Represents an oxygen atom derived from a substituted or unsaturated dialkylamino group or a layered inorganic compound, and when M ¹ and M ² are either Si, Ti or Zr, the corresponding x is 2 and n is an integer of 0 to 2 (integer), and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1, and when n is 2, R may be the same or different, and p, q and r are 0 Or an integer of 1, and at least one of them is 1.)

[Formula 2]

(In formula (2), R is a C 1 to C 20 linear or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, a C 6 to C 20 aryl group or a C 7 to C Represents an aralkyl group of 20, each of which is a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group having 1 to 20 carbon atoms. Or a dialkylamino group, a monoarylamino group or diarylamino group having 6 to 20 carbon atoms, a monoaralkylamino group or diarylamino group having 7 to 20 carbon atoms, a primary, secondary, tertiary or quaternary ammonium group, thiol Group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom may be substituted. , Al, Ti or Zr, Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 branched chains, trimethylsilyloxy group, dimethyl A silyloxy group, a saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated alkylamino group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Represents an oxygen atom derived from a linear or branched saturated or unsaturated dialkylamino group or a layered inorganic compound, and when M is any one of Si, Ti or Zr, the corresponding x is 3, and n is 1 to It is an integer of 3, and when M is Al, the corresponding x is 2, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.)

In addition, the present invention is a method for producing a sustained-release composite agent, characterized in that the interlayered layered inorganic compound is mixed with a compound inserted between the layers of the interlayered layered inorganic compound.

In the sustained-release composite agent of the present invention, since the interlayer crosslinkable layered inorganic compound having an organic-inorganic composite crosslinked structure represented by the above formula (1) between layers has various crosslinking structures, various interlayer distances can be established, and the purpose According to this, since an appropriate space can be constructed between layers, the insertion of the guest compound into the layers can be controlled, and further, the release rate from the layers can be controlled. In addition, since the homogeneous interlayer crosslinking agent itself having a long chain alkylene structure has flexibility, even if it is the same interlayer crosslinkable layered inorganic compound, it can be flexibly adapted to various guest compounds desired for sustained release. You can change the distance between floors.

In addition, by having various functional groups in the crosslinked structure itself, the diversity of the interlayer environment (the environment that interacts with the guest compound) is very wide, and the interaction group suitable for insertion and sustained release of various desired functional compounds into the layer, for example, saturation Or design organic-inorganic complex crosslinking structure by selecting various functional groups such as hydrophobic groups such as unsaturated aliphatic groups, hydrophilic groups, aromatic groups or heterocyclic structure groups, hydrogen bond generators, coordination bond generators and ionic bond generators. And, it can be introduced between layers, and depending on the purpose, various functional compounds (guest compounds) desired according to the purpose can be inserted between the layers to control the rate at which the guest compound is released according to the purpose, so it can be sustained release according to the purpose.

In addition, since interlayers are crosslinked by covalent bonds through a crosslinked structure, it is difficult to cut even in the presence of alkalis or acids.

In addition, the interlayer crosslinkable layered inorganic compound having an organic-inorganic complex crosslinked structure between the layers is M ¹ or M ² (M ¹ or M ² is Si, Ti, Zr or Al, respectively)-O-Si (Si is derived from a layered inorganic compound. ) Since the layers are cross-linked through covalent bonds such as bonds, it is difficult to cut because the chemical stability is very high in various environments such as acidic or alkaline conditions. Therefore, under strong alkaline and acidic conditions, as well as under weak alkaline and acidic conditions, a crosslinked structure can exist between the layers for a sufficiently long period of time practically without being affected by the use environment, and the layer structure collapsed and peeled off and inserted. Since the compound is not released at once and can be used in various environments and uses, the compound inserted between the layers can be practically maintained for a long period of time and sustained release.

In addition, since the interlayer crosslinkable layered inorganic compound has very high chemical stability as described above, the compound inserted between the layers can be protected from the external environment, thereby imparting heat resistance, water resistance, and ultraviolet resistance, etc., so that heat resistance, water resistance, and In addition to sustained release of compounds having low UV resistance, etc., the sustained-release composite agent can be mixed/molded with resins, used underwater or under humidified conditions, or used in various environments such as an environment exposed to sunlight outdoors.

Therefore, since various crosslinked structures can be introduced between layers, the interlayer distance can be widely set according to the purpose, and it is a sustained-release composite agent capable of insertion and sustained release of various compounds.

On the other hand, in the sustained-release composite agent of the present invention, the interlayer modified layered inorganic compound represented by the above formula (2) is an organic-inorganic composite modifier including silylating agents having various functional groups as an interlayer modifier. Since it is available, there is a wide variety of interlayer environments (environments that interact with guest compounds), and a small number of interaction groups suitable for intercalation and sustained release of various compounds of interest, such as saturated or unsaturated aliphatic groups. Interlayers can be designed and modified by selecting various functional groups such as (疎水) group, hydrophilic group, aromatic group or heterocyclic structure group, hydrogen bond generator, coordination bond generator, and ionic bond generator. A functional compound (guest compound) can be inserted between layers for sustained release.

In addition, the interlayer modification layered inorganic compound is a functional group that interacts with the guest compound through covalent bonds such as M (M is Si, Ti, Zr or Al)-O-Si (Si is derived from a layered inorganic compound). ), the chemical stability is very high in various environments, such as under acidic or alkaline conditions. Therefore, the modifier can be present between the layers for a sufficiently long period of time practically without being affected by the use environment, and the compound inserted between the layers can be practically maintained for a long period of time and sustained release.

In addition, since the interlayered layered inorganic compound has very high chemical stability as described above, the compound inserted between the layers can be protected from the external environment and can impart heat resistance, water resistance, UV resistance, etc., so that heat resistance, water resistance, and In addition to sustained release of compounds having low UV resistance, etc., this sustained-release composite agent can be mixed with resins and molded, used underwater and under humidified conditions, or used in various environments such as an environment exposed to sunlight outdoors.

Therefore, since various modifiers can be introduced between layers, the interlayer distance can be widely set according to the purpose, and it is a sustained-release composite agent capable of inserting/sustaining various compounds.

Hereinafter, the sustained-release composite agent of the present invention will be described.

The layered inorganic compound of the present invention is not particularly limited, but graphite, layered metal chalcogenide, layered metal oxide (e.g., layered perovskite compound mainly composed of titanium oxide, niobium oxide, titanium niobate, molybdate, etc. ), layered metal oxyhalides, layered metal phosphates (eg, layered antimony phosphate), layered clay minerals, layered silicates (eg, mica, smectite group (montmorillonite, saponite, hectorite, fluorohectorite, etc.) , Kaolin group (kaolinite, etc.), magadite, kenyaite, kanemite, etc.), and layered double hydroxides.

Among these, layered silicates, layered clay minerals, and layered metal oxides are preferably used for reasons of availability and the like. These may be naturally produced or artificially synthesized.

Next, the organic-inorganic composite group existing between the layers of the layered inorganic compound will be described.

One of the organic-inorganic composite groups of the present invention has an organic-inorganic composite crosslinked structure represented by the above formula (1).

In the above formula (1), M ¹ and M ² are metals that can generate a covalent bond with an oxygen atom derived from a layered inorganic compound, and the covalent bond is difficult to cause decomposition reactions such as hydrolysis, and Si Si, which is any one of (silicon), Al (aluminum), Ti (titanium), and Zr (zirconium), is preferable to be readily available in order to introduce various interaction groups.

In the organic-inorganic composite crosslinked structure represented by the above formula (1) introduced between the layers through covalent bonds with the layered inorganic compound, the organic-inorganic composite crosslinked structure and the layered inorganic compound are bonded through a plurality of covalent bonds. It is more preferable from the viewpoint of the chemical stability of the bond that connects to, and when M ¹ and M ² in the above formula (1) are Si, Ti and Zr, n is more preferably 0 or 1, and in the case of Al, n is 0 is more preferable, and in any case, it is more preferable that at least one of Z contains an oxygen atom derived from a layered inorganic compound. In addition, Z may be hydrolyzed/condensed between organic-inorganic complex cross-linked structures close to each other to form M ¹ -OM ¹ bond, M ¹ -OM ² bond, or M ² -OM ² bond.

Since the interaction with the guest compound in the organic-inorganic complex crosslinked structure can be properly designed, any one of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond generator, a coordination bond generator, and an ionic bond generator It is preferable to include. Accordingly, non-covalent interactions with guest compounds (for example, van der Waals' force, π-π interactions, hydrophobic interactions, hydrogen bonds, coordination bonds, ionic bonds, etc.) It can be given by appropriately adjusting, and can be sustained release according to the purpose by inserting an arbitrary compound between the layers.

The non-covalent interaction group is not particularly limited, and for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-octyl group, decyl group, dodecyl group, Saturated or unsaturated groups such as octadecyl group, methylene group, ethylene group, propylene group, octamethylene group, cyclohexyl group, cyclohexylene group, vinyl group, allyl group, and other aliphatic groups such as alkyl, alkylene, cycloalkyl and cycloalkylene groups , Aryl groups such as styryl group, phenyl group, naphthyl group, phenylene group, naphthylene group, biphenylene group, benzyl group and benzylen group, aralkyl group, arylene group and aralkylene group such as aromatic group, pyridinyl group, piperidinyl group, Azole groups such as pyrrolidinyl group, pyrimidinyl group, and imidazolyl group, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, dioxanyl group, molhorinyl group, thiazinyl group, indole group, nucleic acid Heterocyclic structural groups such as bases, acrylicoxy groups, methacryloxy groups, acetyl groups, benzoyl groups, hydroxyl groups, thiol groups, aldehyde groups, carboxyl groups, methyl carboxylate groups, phosphoric acid groups, ethyl phosphate groups, sulfonic acid groups, methyl sulfonate groups, amino groups , Hydrogen bonds and coordination groups such as methylamino group, dimethylamino group, isocyanurate group, ureide group, isocyanate group, ethylammonium group, dimethylammonium group and trimethylammonium group ionic bond generator, etc. It includes an acid ester structure, a urethane structure, a urea structure, an amine structure, an ether structure, a thioether structure, and a disulfide structure, and it is a structure included in the main chain skeleton constituting the organic-inorganic complex crosslinked structure in that it is easy to obtain. Is a methylene group, ethylene group, propylene group, butylene group, octamethylene group, phenylene group, biphenylene group, benzylene group, carboxylic acid ester structure, urethane structure, urea structure, amine structure, ether structure, thioether structure and It is preferred to have a disulfide structure.

Among the organic-inorganic complex crosslinked structures represented by the above formula (1), those that can be constructed by reacting the crosslinkable functional groups of various coupling agents are universal and preferred, and the following formulas (3) to (17) from the viewpoint of ease of introduction into layers It is more preferable that it is represented by ).

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

(In formulas (3) to (17), R ¹ is a C 1 to C 20 linear or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, or a C 6 to C 20 aryl A group or an aralkyl group having 7 to 20 carbon atoms, respectively, a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or branched chain having 1 to 20 carbon atoms, or Unsaturated monoalkylamino group or dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, primary, secondary, tertiary or tertiary Even if it is substituted with a quaternary ammonium group, thiol group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom. R ² and R ¹³ are each independently a C 1 to C 20 linear or branched saturated or unsaturated alkylene group, a C 1 to C 8 branched saturated or unsaturated cycloalkylene group, or a C 6 to C 20 allylene group. Or an aralkylene group having 7 to 20 carbon atoms, R ³ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, phenyl Represents a ren group or an aralkylene group having 7 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branch having 3 to 8 carbon atoms Represents a saturated or unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, which may have a chain, and R ¹¹ is a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, 3 to carbon atoms A saturated or unsaturated cycloalkylene group which may have 20 branches, Represents an allylene group having 6 to 20 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or a polyphenylene group having 6 to 24 carbon atoms, and any R ¹¹ is a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, and the number of atoms including the same 1 May be substituted with a substituent consisting of 10 to 10, Z is a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group which may have a branched chain having 3 to 8 carbon atoms , A trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated chain having 1 to 6 carbon atoms Represents an oxygen atom derived from an alkylamino group or a layered inorganic compound, I is a group derived from a polymerization initiator, may be the same or different, Y is a group derived from a conjugated base derived from an acid, n is an integer of 0 to 2, m And h represents an integer of 0 or 1, and k represents an integer of 0 to 4.)

The organic-inorganic complex crosslinked structure can be constructed by treating the interlayers with a coupling agent to modify the silylation, etc., and then crosslinking the crosslinkable functional groups between the layers. Also, crosslinking the crosslinkable functional groups of the coupling agent in advance or By reacting a grignard reagent with a hydrolyzable metal compound, an organic-inorganic complex crosslinking agent having two or more hydrolyzable sites is prepared, and it is inserted between the layers to react with the hydroxyl group derived from the layered inorganic compound. Although it may be constructed, a method of reacting a crosslinkable functional group derived from a coupling agent between the former layers is preferable in that there is no side reaction and the gel component is not incidentally generated.

In order to build a crosslinked structure by reacting the crosslinkable functional groups between the layers after modifying the interlayer by silylation, etc., if the interlayer is modified with the same coupling agent and then crosslinked, the manufacturing process is less and industrially more advantageous. As the organic-inorganic complex crosslinking structure, the above formulas (3) to (7) and the above formulas (12) to (16) are more preferable, and the crosslinking reaction proceeds easily under mild conditions, and various chemical structures, flexibility and rigidity can be introduced. And the crosslinking length is also varied, the formulas (3) to (7) and the formulas (14) to (16) are more preferable.

Next, in the present invention, an interlayer crosslinkable layered inorganic compound having an organic-inorganic composite group represented by Formula (1) will be described in detail according to a manufacturing method. Here, unless otherwise specified, the number of copies represents parts by mass, and% represents% by mass.

In the present invention, an interlayered layered inorganic compound obtained by reacting an exchangeable cation such as an alkali metal such as sodium and potassium and a metal cation such as an alkaline earth metal such as magnesium and calcium with an organic onium salt, etc. It is a precursor that performs silylation or the like (in the case of silylation, a silylated layered inorganic compound) with a coupling agent such as a silane coupling agent and a crosslinking agent having two or more hydrolyzable silyl moieties.

The precursor is a compound substituted with an onium group in an arbitrary ratio in terms of ion exchange capacity with respect to the exchangeable cation of the layered inorganic compound, and when increasing the reaction rate such as silylation, the ratio of the onium group is preferably 25 to 75 mol%. , It is more preferable that it is 30-70 mol%, and it is still more preferable that it is 35-70 mol%.

Here, the ion exchange capacity refers to the amount of ion exchange per unit weight of the ion exchanger, and is usually milli-equivalent per 1 g of ion exchanger (meq/g) or milli-equivalent per 100 g of ion exchanger (meq/100g) and ion exchanger It is expressed as a molar amount per 1 kg (mol _c /kg) or centimolar amount per 1 kg of ion exchanger (cmol _c /kg).

For example, the formula of sodium-magadite is Na ₂ Si ₁₄ O ₂₉ ·nH ₂ O, where n = 0, the food is 903.2 and all sodium can be regarded as exchangeable cations. , In this case, the ion exchange capacity can be expressed as 2.21 mol _c /kg.

If metal cations exist between the layers as exchangeable cations, the interlayer modification rate (silylation rate in the case of a silane coupling agent) by a coupling agent or crosslinking agent such as a silane coupling agent decreases. Therefore, the metal cations are treated with acid. It is desirable to reduce

Therefore, as a method of introducing an onium group between the layers of a layered inorganic compound, a method of reacting an acid after reacting a cation exchange capacity and an onium salt of a corresponding amount or more, and a method of reacting an onium salt less than the corresponding amount of the cation exchange capacity in advance. However, in order to further improve the interlayer modification rate, a method of reacting an onium salt of an equivalent amount or more of the former and then reacting with an acid is more preferable.

In addition, as a method of introducing by adjusting the amount of interlayered onium groups of the layered inorganic compound, a mixture of an onium salt and an acid in an appropriate amount may be reacted with the layered inorganic compound, and first, an appropriate amount of acid (preferably Is less than the corresponding amount of the cation exchange capacity), and then the onium salt may be reacted.

The onium salt used for the preparation of the precursor in the present invention is not particularly limited, but organic onium is preferable, and for example, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic alcohol Phonium, organic sulfoxynium, organic selenium, organic carbonium, organic diazonium, organic iodonium, organic pyryllium, organic pyroridinium, organic carbenium, organic acyllium, organic thiazolinium, organic arsenium, Salts such as organic stibonium and organic terlonium, among which salts of organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium and organic sulfonium are preferable, and these onium salts are either alone or It is used in combination of two or more.

) 발생기, 열염기(

) 발생기, 광　라디칼 발생기, 열　라디칼 발생기 등의 작용기로 치환되어 있어도 된다.The organic group of the onium salt is not particularly limited, but, for example, an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, an allyl group having 6 to 22 carbon atoms, -(CH ₂ -CH(CH ₃ )O) _p -H group, -(CH ₂ -CH ₂ -O) _q -H group, p and q are integers of 1 to 20, vinyl group, epoxy group, ether group, oxetanyl group, acryloxy group, meta Krilloxy group, hydroxyl group, thiol group, isocyanate group, halogen atom, basic group such as amino group or alkylamino group, acidic group such as carboxyl group, photoacid generator, thermal acid generator, photobase (

) Generator, hot base (

) May be substituted with a functional group such as a generator, an optical radical generator, or a thermal radical generator.

As the organic onium salt, an organic onium salt represented by the following formula (18) is more preferable.

^{R 14 R 15 R 16 R 17} N + X - (18)

(In formula (18), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, an allyl group having 6 to 22 carbon atoms, and -(CH _2- CH(CH ₃ )O) _p -H group or -(CH ₂ -CH ₂ -O) _q -H group, p and q are integers from 1 to 20, and X ^- is a halide ion.)

The organic onium salt represented by the above formula (18) is not particularly limited, but for example, dodecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, dihexadecyldimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, dimethyloctadecylphenyl chloride Ammonium, triethylbenzyl ammonium chloride, dodecyl ammonium chloride, ammonium chloride dimethyldipolyethylene oxide, ammonium chloride dimethyldipropylene oxide, ammonium chloride dimethylpolyethylene oxide polypropylene oxide ammonium, dimethyl stearyl chloride ammonium polyethylene oxide, ammonium chloride Ammonium dimethylstearylpolypropylene oxide, ammonium chloride methylstearyldipolyethylene oxide, ammonium chloride methylstearyldipolypropylene oxide, ammonium chloride benzylmethyldipolyethylene oxide, ammonium chloride benzylmethyldipolypropylene oxide, brominated 1-ethylpyridinium, 1-octadecylpyridinium chloride, 3-methyl-1-propylimidazolium bromide, 3-methyl-1 (2-naphthyl) imidazolium chloride, triphenyl bromide (tetradecyl) Phosphonium, ethyldimethylsulfonium chloride, triphenylsulfonium bromide, and the like.

Among these, preferred are dodecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, dihexadecyldimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, icosyltrimethyl ammonium chloride, dimethyloctadecylphenyl ammonium chloride, triethylbenzyl ammonium chloride, and chloride. It is dodecyl ammonium.

A method of reacting with an onium salt to modify the interlayer of the layered compound with an onium group is not particularly limited, and a known method can be used. For example, by mixing salts such as organic onium, chloride ions, bromide ions, and halide ions such as iodide ions with a layered inorganic compound in a solvent such as water, alcohol such as methanol, or a polar solvent such as acetonitrile. Interlayers can be modified with onium groups by a cation exchange reaction between an exchangeable cation in a compound and an organic onium.

The amount of the organic onium salt in the cation exchange reaction is not particularly limited and can be arbitrarily set according to the purpose, but is preferably 20 to 2000 mol% (0.2 to 20 equivalent), more preferably, with respect to the cation exchange capacity of the layered inorganic compound. Is 50 to 1000 mol% (0.5 to 10 equivalents), more preferably 100 to 500 mol% (1 to 5 equivalents).

The reaction temperature in the cation exchange reaction is not particularly limited, but is preferably 0 to 100°C, more preferably 10 to 60°C, and still more preferably 15 to 40°C.

As water used as a solvent for the cation exchange reaction, neutral, acidic, and alkaline can all be used, and although not particularly limited, preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The amount of the solvent used in the cation exchange reaction is not particularly limited, but is 1 to 100 times by mass, more preferably 5 to 70 times by mass, and even more preferably 10 to 50 times by mass relative to the layered inorganic compound used as a raw material. to be.

In order to adjust the ratio of the onium group in the precursor having the organic onium group, after reacting the organic onium salt with the layered inorganic compound, a method of converting a part of the onium group in the layered inorganic compound to a hydroxyl group with an acid This is desirable.

The amount of acid to be reacted can be arbitrarily set according to the purpose, but preferably, when the cation exchange capacity of the layered inorganic compound is 100 mol%, 100 mol%-[the ratio of organic onium groups to be left between the layers (mol%)] It is more preferable to set to and increase or decrease the amount of acid appropriately.

The acid is not particularly limited, and known acids such as hydrochloric acid, hydrogen bromide, carboxylic acids (for example, formic acid, acetic acid, oxalic acid, etc.), phosphoric acid, nitric acid, sulfuric acid and methanesulfonic acid, and other sulfonic acids. Among these, hydrochloric acid is preferred because of its excellent reactivity.

If the amount of the onium salt present between the layers is adjusted to a specific range by reacting with the interlayer onium salt using these acids, hydroxyl groups such as interlayer silanol are generated, which is preferable because the modified reaction point such as silylation increases. Do.

When an onium salt in an amount less than the corresponding amount of the cation exchange capacity is used, metal cations such as sodium remain between layers, so the alkoxylate derived from hydroxyl groups such as silanol, which is a reaction point, is firmly bound with the metal cations. As a result, there is a concern that interlayer modification reactions such as silylation reaction may be disturbed.

The organic solvent used when converting a part of the onium salt to a hydroxyl group is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2- Alcohols such as methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, tetrahydrofuran, etc. Ethers, ketones such as acetone, ethyl methyl ketone, amides such as N,N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, ethyl acetate, etc. Halogen-based hydrocarbons, such as esters, chloroform, and dichloromethane, etc. are mentioned.

Among these, alcohols, aprotic polar solvents such as ethers, nitriles and ketones are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2- Alcohols such as propanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol are more preferable, and have a high boiling point. From the viewpoint of high polarity, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 1-methoxy-2-propanol are more preferable.

In the acid treatment, the reaction temperature is not particularly limited, but is preferably 0 to 200°C, more preferably 50 to 160°C, and still more preferably 70 to 150°C. Usually, it is preferable to react at the boiling point of the organic solvent used as the reaction solvent (under heating and reflux).

The precursor obtained by the cation exchange reaction and acid treatment is preferably dried after isolation and washing. A method of isolating, washing, and drying is not particularly limited, and a known method of isolating, washing and drying a layered inorganic compound and inorganic fine particles may be used.

For example, as an isolation method, the reaction solution is allowed to stand or centrifuge to separate solid and liquid, and then the supernatant is removed by decantation or natural filtration, pressurized filtration, or reduced pressure filtration. These include filtering and filtering layered inorganic compounds by filtration operations such as.

The pressure at the time of pressure filtration is not particularly limited, and may be, for example, in the range of 1 to 5 atmospheres. The pressure during filtration under reduced pressure is not particularly limited, and may be in the range of 0 to 1 atmosphere.

As a washing method, the solid obtained after decanting is re-dispersed with water or an organic solvent, etc., and then decanted or filtered, and then water or an organic solvent is poured on the filtered solid. There are methods of washing.

The water used for washing may be neutral, acidic or alkaline, and is not particularly limited, but preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The organic solvent used for washing is not particularly limited, but alcohols such as methanol and ethanol, ketones such as acetone and ethylmethylketone, alkanes such as hexane, and aromatics such as toluene may be mentioned. At this time, in order to improve the contact between the layered inorganic compound and water, an appropriate organic solvent such as a polar solvent may be used in combination.

As a drying method of the solid obtained above, the organic solvent may be removed by air drying at room temperature and pressure, or heating or cooling appropriately at room temperature under reduced pressure.

The pressure at the time of decompression is not particularly limited, and may be, for example, in the range of 0 to 1 atmosphere. Further, the temperature is also not particularly limited, and is preferably -10 to 200°C, more preferably 0 to 150°C, and particularly preferably 10 to 100°C.

As described above, the precursor may be a compound substituted with an onium group in an arbitrary ratio with respect to the exchangeable cation of the layered inorganic compound, but is preferably a compound substituted with an onium group at a ratio of 25 to 75 mol% in terms of ion exchange capacity. .

If the ratio of the onium salt of the precursor is 25 to 75 mol%, the hydroxyl group, which is a modified reaction point such as silylation, increases, and at the same time, a space is created between the layers, so that the silylation agent is easily inserted between the layers. The silylation rate and the like are improved.

Next, all or part of the pairing anion (pairing anion (alkoxylate)) of the hydroxyl group and the onium group of the precursor is subjected to an interlayer modification reaction with a coupling agent such as a silane coupling agent, thereby crosslinking through covalent bonds between layers. To prepare a layered inorganic compound having a functional group.

The coupling agent is not particularly limited, and may be an organic-inorganic composite agent having an organic functional group capable of crosslinking with a hydrolyzable group in the same molecule. For example, a silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent, etc. These are mentioned, Preferably it is a compound represented by following formula (19).

[Formula 18]

(In formula (19), R ¹ is a C 1 to C 20 straight or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, a C 6 to C 20 aryl group, or a C Represents an aralkyl group of 7 to 20, each of which is a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched C1 to C20 saturated or unsaturated mono Alkylamino group or dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, primary, secondary, tertiary or quaternary ammonium group , Thiol group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphate ester group, sulfonic acid group, sulfonic acid ester group, or halogen atom. Is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group that may have a branched chain having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Represents a group, each vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, alkylamino group, arylamino group, aralkylamino group, ammonium group, thiol group, isocyanurate group, It may be substituted with a ureide group, an isocyanate group, a carboxyl group or a halogen atom, D is a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, or a saturated or unsaturated branched chain having 3 to 8 carbon atoms. Cycloalkyloxy group, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, halogen atom, hydroxyl group, amino group, straight or branched chain having 1 to 6 carbon atoms Of a saturated or unsaturated alkylamino group or a linear or branched chain having 1 to 6 carbon atoms, or Represents an unsaturated dialkylamino group, M represents Si, Al, Ti or Zr, and when M is any one of Si, Ti or Zr, p is 3 and n is an integer of 0 to 2, and M is Al. In this case, p is 2 and n is 0 or 1.)

In addition, among the coupling agents, a silane coupling agent is more preferable from the viewpoint of having a wide variety of types, and from the viewpoint of being easy to obtain, handle, and control the hydrolysis reaction. Although it does not specifically limit as a silane coupling agent, For example, the compound represented by following formula (20) is preferable.

[Formula 19]

(In formula (20), R ¹ is a C 1 to C 20 linear or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, a C 6 to C 20 aryl group or a C 7 Aralkyl groups of to 20, respectively vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, linear or branched saturated or unsaturated monoalkylamino group having 1 to 20 carbon atoms or Dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, primary, secondary, tertiary or quaternary ammonium group, thiol group , Isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom, A is a hydrogen atom, Represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group which may have a branched chain having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, respectively Vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, alkylamino group, arylamino group, aralkylamino group, ammonium group, thiol group, isocyanurate group, ureide group, May be substituted with an isocyanate group, carboxyl group or halogen atom, D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having a branched chain having 3 to 8 carbon atoms, or a trimethylsilyloxy group , A dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated alkylamino group having 1 to 6 carbon atoms or 1 To 6 linear or branched saturated or unsaturated dialkylamino groups, n is 0 It represents the integer of 2 to. ）

In the silane coupling agent represented by the above formula (20), the crosslinkable functional group may be protected by an appropriate protecting group.

Among the silane coupling agents, the hydrolyzable group does not produce incidental acids such as hydrogen chloride, so the risk of side reaction to the crosslinkable functional group is very low, does not cause corrosion of the reaction device, and incidentally generated acid. It is preferable that it is an alkoxysilane which also does not require waste treatment, more preferably a methoxy group, an ethoxy group and a propoxy group having excellent silylation reactivity, and particularly preferably a methoxy group and an ethoxy group.

The silane coupling agent represented by the above formula (20) is alkoxysilanes, such as vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3- Glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrie Toxoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxycillin, 3-methacryl Oxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butyly) Den)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris-(trimethoxysilylpropyl )Isocyanurate, 3-ureidepropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 8-glycidoxyoxy Tyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 4-(trimethoxysilyl )Butyric acid, 4-(trimethoxysilyl)butyric acid 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrie Oxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, Dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxy Methylsilane, triethoxysilane, etc. Can be lifted.

Further, silane coupling agents other than alkoxysilanes can be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonic acid, triethylchlorosilane, tertiarybutyldimethylchlorosilane, chlorotriisopropylsilane, 1,3-dichloro -1,1,3,3-tetraisopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, aryltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, tris( N,N-dimethylamino)methylsilane, bis(N,N-dimethylamino)dimethylsilane, (N,N-dimethylamino)trimethylsilane, etc. are mentioned.

In such a silane coupling agent, when a plurality of hydrolyzable groups are present in one molecule, a single hydrolyzable group such as an alkoxy group, a halogen atom, an alkylamino group, or a dialkylamino group may be present, or a plurality of hydrolyzable groups may be present.

In addition, instead of the silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent may be used.

The organic solvent used for the reaction with the coupling agent is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1 -Alcohols such as propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran , Ketones such as acetone, ethyl methyl ketone, amides such as N,N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate , Halogen-based hydrocarbons such as chloroform and dichloromethane. Among these, alcohols and ethers, nitriles and ketones which are aprotic polar solvents are preferable.

More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol, and the boiling point is preferably 80°C or higher, more preferably 90°C or higher, and still more preferably 100°C or higher.

Aprotic polar solvents include nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethyl methyl ketone, diethyl ketone, methylene isopropyl ketone, and N,N. -Amides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide.

In addition, the secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3- Aromatic alcohols, such as hexanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol, and phenol, etc. are mentioned.

Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and 1-propoxy-2-propanol are preferred. And 2-butanol and 1-methoxy-2-propanol are more preferred.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the reaction, the O-alkylation reaction, which is a side reaction of the hydroxyl group and the alkoxylate derived from the layered inorganic compound, is difficult to occur, and is used. Since the boiling point of the organic solvent is high, it is inferred that the silylation reaction temperature increases, accelerating the interlayer modification reaction such as the silylation reaction, thereby increasing the interlayer modification rate such as the silylation rate.

In addition, if secondary or tertiary alcohols are used, such as condensation of hydroxyl groups such as silanol by hydrolysis of coupling agents such as silane coupling agents described later, or condensation between coupling agents such as silane coupling agents. It is preferable because side reactions are suppressed. It is inferred that this is a solvent effect due to alcoholic hydroxyl groups.

It is preferable to add water to the reaction system during the reaction. The water to be added may be neutral, acidic or alkaline, and is not particularly limited, but preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The amount of water added is preferably 0.05 to 4.0 mole times, and particularly preferably 0.1 to 3.0 mole times, with respect to the total amount of the alkoxylate, that is, the ion exchange capacity, which is the pairing anion of the hydroxyl group and the onium group, which is the reaction point of the layered inorganic compound. .

If the amount of water added is less than 0.05 mole times, the effect of addition is small, and if it exceeds 4.0 mole times, there is a concern that side reactions such as hydrolysis/condensation between coupling agents such as silane coupling agents may proceed.

In the above reaction, the amount of a coupling agent such as a silane coupling agent is not particularly limited, but the total amount of the alkoxylate, which is the pairing anion of the hydroxyl group and the onium group, which is the reaction point, that is, preferably 0.1 to 30 mol with respect to the ion exchange capacity. Times, more preferably 0.05 to 20 mole times, and still more preferably 1.0 to 10 mole times.

If the amount of the coupling agent used is less than 0.1 mole times, the silylation reaction rate becomes small, while if it exceeds 30 mole times, it is industrially disadvantageous in terms of raw material cost.

The reaction point between the layers of the layered inorganic compound, that is, the interlayer modification rate such as the silylation rate with respect to the ion exchange capacity, is not particularly limited because it is selected according to the purpose, but the interlayer modification rate such as the silylation rate is 15 mol% or more. It is preferable, and it is more preferable that it is 25 mol% or more.

On the other hand, if the interlayer modification rate such as the silylation rate exceeds 200 mol%, the interlayer of the layered inorganic compound may be excessively covered with components derived from the coupling agent, which is not preferable.

The reaction temperature in the interlayer modification reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 50 to 180°C, and still more preferably 70 to 170°C. Usually, the reaction is carried out at the boiling point (under heating and reflux) of the organic solvent used as the reaction solvent.

The amount of the organic solvent used in the interlayer modification reaction is not particularly limited, but is 1 to 30 times by mass, more preferably 5 to 25 times by mass, and even more preferably 10 with respect to the layered inorganic compound used as a raw material. To 20 times by mass.

Interlayer modification reaction such as silylation reaction by the coupling agent of the present invention may or may not use a catalyst, but carboxylic acids such as hydrogen chloride, formic acid, acetoic acid, oxalic acid, phosphoric acid, nitric acid, sulfuric acid, methane Known acids such as sulfonic acids such as sulfonic acid and known bases such as ammonia, trimethylamine, triethylamine, tetramethyl ammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as a catalyst.

In this case, the amount of the catalyst to be added is not particularly limited, but the total amount of the alkoxylate, which is the pairing anion of the hydroxyl group and the onium group, is preferably 0.001 to 1.0 mole times the ion exchange capacity, and more preferably It is 0.01 to 0.1 mole times.

It is preferable to dry the layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction after isolation and washing. A method of isolating, washing and drying is not particularly limited, and a known method of isolating, washing and drying the layered inorganic compound and inorganic fine particles may be used.

For example, as an isolation method, the reaction solution is allowed to stand or centrifuge to separate solid and liquid, and then the supernatant is removed by decantation or natural filtration, pressurized filtration, and reduced pressure filtration. And those that filter and filter the layered inorganic compound by a filtration operation such as.

The pressure at the time of pressure filtration is not particularly limited, and may be, for example, in the range of 1 to 5 atmospheres. The pressure during filtration under reduced pressure is not particularly limited and may be in the range of 0 to 1 atmosphere.

As a cleaning method, the solid obtained after decanting is redispersed with water or an organic solvent, and then the solid is washed by decanting or pouring water or an organic solvent on the filtered solid in the same way. I can.

The water used for washing may be any of neutral, acidic, and alkaline, and is not particularly limited, but preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The organic solvent used for washing is not particularly limited, but examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and ethylmethylketone, alkanes such as hexane, and aromatics such as toluene. At this time, in order to improve the contact between the layered inorganic compound and water, an appropriate organic solvent such as a polar solvent may be used in combination.

As a method of drying the solid obtained as described above, the organic solvent may be removed by air drying at room temperature and pressure, or heating or cooling appropriately at room temperature under reduced pressure.

The pressure at the time of decompression is not particularly limited and may be in the range of 0 to 1 atmosphere. Further, the temperature is not particularly limited, and is preferably -10 to 200°C, more preferably 0 to 150°C, and particularly preferably 10 to 100°C.

In the case of reducing or removing exchangeable cations such as onium groups or metal cations that remain after interlayer modification reactions such as silylation, etc., acid treatment may be performed using a known acid and solvent as above. I can.

Next, a method of preparing an interlayer crosslinkable layered inorganic compound by reacting a crosslinkable functional group derived from this coupling agent with a layered inorganic compound modified with a coupling agent is described.

The crosslinking reaction by a crosslinkable functional group derived from a coupling agent such as a silane coupling agent is not particularly limited, and an addition reaction, substitution reaction, condensation reaction, ionic reaction, electrophilic reaction Various commonly known chemical reactions such as (electrophilic reaction), nucleophilic reaction, pericyclic reaction, and radical reaction can be used, and so-called click reactions can also be used. Nucleophilic substitution by generating a radical from an alkyl group for crosslinking reaction, or by converting a halogenated alkyl group into anionic species with a Grignard reagent for nucleophilic reaction, or by reacting nucleated species such as hydroxyl, alkoxy, and amino groups on halogenated alkyl groups. Crosslinking methods to make the reaction are also mentioned. However, since it is easy to obtain a coupling agent and the crosslinking reaction proceeds under relatively mild conditions, the reaction represented by the following formulas (21) to (35) is preferable, and the crosslinking reaction after modifying the layers with the same coupling agent. Because the manufacturing process is less and industrially advantageous, the crosslinking reaction represented by formulas (21) to (25) and (30) to (34) is more preferable, and the crosslinking reaction proceeds easily under mild conditions. Since a variety of chemical structures, flexibility and rigidity can be introduced, the crosslinking length can also be varied, and thus the crosslinking reaction represented by the formulas (21) to (25) and (32) to (34) is more preferable.

When using the crosslinking reaction represented by formulas (21) to (23) and (32), the functional groups to be crosslinked have the same or similar structure, and the crosslinked structure to be reacted or generated is relatively simple, and R ² , R ⁴ and R ^{According to} the structure of ¹³ , the interlayer distance or interlayer environment (hydrophobicity, hydrophilicity, aromaticity, etc.) of the layered inorganic compound can be controlled relatively easily.

In addition, in the case of using the crosslinking reaction represented by formulas (24), (25), (33) and (34), the interlayer distance or flexibility of the layered inorganic compound is relatively easy depending on the structure of R ² , R ⁴ and R ¹³ . , In addition to being able to control the interlayer environment (hydrophobicity, hydrophilicity, aromaticity, hydrogen bond formation, etc.), various amines and diamines can be introduced into the crosslinked structure, so the interlayer distance of the layered inorganic compound can be easily and freely B. Flexibility, the interlayer environment (hydrophobicity, hydrophilicity, aromaticity, hydrogen bond generation, heterocyclic structure, ionic defects, coordination covalent (配位共有) bonds, etc.) have the characteristics of being able to control.

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Chemical Formula 29]

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

(In formulas (21) to (35), R ¹ is a C 1 to C 20 linear or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, or a C 6 to C 20 aryl A group or an aralkyl group having 7 to 20 carbon atoms, respectively, a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or branched chain having 1 to 20 carbon atoms, or Unsaturated monoalkylamino group or dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, primary, secondary, tertiary or tertiary Even if it is substituted with a quaternary ammonium group, thiol group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom. R ² and R ¹³ are each independently a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkylene group having 3 to 8 carbon atoms, or an allylene group having 6 to 20 carbon atoms. Or an aralkylene group having 7 to 20 carbon atoms, R ³ , R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴ is an alkylene group having 1 to 6 carbon atoms, phenyl Represents a ren group or an aralkylene group having 7 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and having 3 to 8 carbon atoms. Represents a saturated or unsaturated cycloalkyl group having a branched chain, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, 3 carbon atoms Saturated or unsaturated cycloalkylene which may be branched from to 20 A group, an allylene group having 6 to 20 carbon atoms, an aralkylene group having 7 to 20 carbon atoms, or a polyphenylene group having 6 to 24 carbon atoms, and any R ¹¹ is a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, and an atom containing the same May be substituted with a substituent consisting of 1 to 10 carbon atoms, Z is a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyl which may have a branched chain having 3 to 8 carbon atoms Oxy group, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy group, which may have a branched chain having 1 to 8 carbon atoms, halogen atom, hydroxyl group, amino group, linear or branched chain saturated with 1 to 6 carbon atoms Or an unsaturated alkylamino group, a linear or branched saturated or unsaturated dialkylamino group having 1 to 6 carbon atoms, or an oxygen atom derived from a layered inorganic compound, and I may be the same or different as a group derived from a polymerization initiator, and Y Is a group derived from an acid-derived conjugated base, n is an integer of 0 to 2, m and h represent an integer of 0 or 1, and k represents an integer of 0 to 4.)

In addition, in the crosslinking reaction represented by the above formulas (21) to (35), a crosslinking reaction of a crosslinkable functional group derived from a coupling agent composed of titanium (Ti), aluminum (Al), zirconium (Zr), etc. instead of a silicon atom (Si) Can be used.

The crosslinking point of the crosslinking reaction of the carbon-carbon double bond in the crosslinking reaction may be either the head or the tail of the double bond, and the crosslinking point in the ring opening crosslinking reaction of the epoxy group and oxetanyl group is the oxygen of the cyclic ether group Any one on a carbon atom having two adjacent atoms may be used.

)발생제 및 광염기(

)발생제, 염화수소산, 황산, 질산 등 공지된 무기산, 포름산, 아세트산, 옥살산, 시트르산, 메탄술폰산, 파라톨루엔술폰산 등 공지된 유기산, 암모니아, 수산화나트륨, 수산화칼륨, 수산화칼슘 등의 공지된 무기 염기, 메틸아민, 디에틸아민, 트리에틸아민 등 공지된 유기아민 등의 유기염기, 테트라메틸 암모늄 히드록시 등의 공지된 암모늄염 및 무수숙신산, 무수프탈산, 무수말레인산 등 공지된 산무수물 등의 공지된 촉매나 경화제, 브롬이나 요오드 등의 산화제를 병용할 수 있다.Thermal radical generator, photo radical generator, thermal anion generator, photo cation generator, thermal acid generator, photoacid generator, which are known polymerization initiators as needed to promote the crosslinking reaction , Thermal base (

) Generator and photobase (

) Generators, known inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, known organic acids such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, paratoluenesulfonic acid, known inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide and calcium hydroxide, Known catalysts such as organic bases such as known organic amines such as methylamine, diethylamine, and triethylamine, known ammonium salts such as tetramethyl ammonium hydroxy, and known acid anhydrides such as succinic anhydride, phthalic anhydride, and maleic anhydride A curing agent and an oxidizing agent such as bromine or iodine can be used in combination.

The polymerization initiator is not particularly limited, and a known polymerization initiator used in the polymerization reaction of the polymerizable monomer is used, and a thermal polymerization initiator and/or a photopolymerization initiator are used, but interlayer coupling A thermal polymerization initiator is more preferable because a crosslinking reaction system including a zero-modified layered inorganic compound is suspended and it is difficult to pass light such as ultraviolet rays.

Various compounds can be used as the thermal polymerization initiator, and when the polymerizable group is a radical polymerizable group, for example, in the case of the formula (21) and the formula (31), a peroxide and an azo initiator are preferable.

,

’-비스(t-부틸퍼옥시)디이소프로필벤젠, 디큐밀퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, t-부틸쿠밀퍼옥시드, 디-t-부틸퍼옥시드, p-멘탄히드로퍼옥시드, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥신-3, 디이소프로필벤젠히드로퍼옥시드, t-부틸트리메틸실릴퍼옥시드, 1,1,3,3-테트라메틸부틸히드로퍼옥시드, 쿠멘히드로퍼옥시드, t-헥실히드로퍼옥시드, t-부틸히드로퍼옥시드 등의 유기과산화물을 들 수 있다.Specific examples of peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate and potassium persulfate; 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hex) Silperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclo Hexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclo Dodecane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5- Dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxyisopropylmonocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, t-hexylperoxybenzoate, 2,5 -Dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2,2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4, 4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate,

,

'-Bis(t-butylperoxy)diisopropylbenzene, dicumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumylperoxide, di-t -Butyl peroxide, p-mentane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, Organic peroxides, such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide, are mentioned.

Specific examples of the azo initiator include 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, Azo compounds such as 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane, and these may be used alone or in two types. You may use the above together.

In addition, reducing agents such as peroxide and ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and ferric chloride are used in combination. It is also possible to make a redox reaction by combining it with one redox polymerization initiator.

The amount of the thermal polymerization initiator to be used is selected depending on the type and polymerization conditions, but is usually 1 to 1000 moles per 100 moles of the polymerizable functional group, more preferably 5 to 500 moles, and even more preferably 50 to 200 moles. to be.

Specific examples of the photopolymerization initiator include benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4 when the polymerizable group is a radical polymerizable group. -(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1-(methylvinyl) )Phenyl]-propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-methyl -1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, Acetophenone compounds such as 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one; Benzoin compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1-[4-( 4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(di Benzophenone compounds such as ethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone; Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine Acylphosphine oxide compounds such as pinoxide; And thioxanthone, 2-chloro thioxanthone, 2,4-diethyl thioxanthone, isopropyl thioxanthone, 1-chloro-4-propyl thioxanthone, 3-[3,4-dimethyl-9- And thioxanthone compounds such as oxo-9H-thioxanthone-2-yl-oxy]-2-hydroxypropyl-N,N,N-trimethyl ammonium chloride and fluorothioxanthone.

Examples of compounds other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl)phenylphosphinate, methyl phenylglyoxylate, ethylanthraquinone, phenanthrenequinone, camphorquinone, and the like.

The amount of the photopolymerization initiator used is selected depending on the type and polymerization conditions, and the amount is 1 to 1000 moles per 100 moles of the polymerizable functional group, more preferably 5 to 500 moles, and still more preferably 50 to 200 moles.

In addition, when the polymerizable group is a cationic polymerizable group, for example, in the case of the formula (22), the formula (23) and the formula (32), various known cationic polymerization initiators can be used, and as a thermal cationic polymerization initiator Is sulfonium salts, phosphonium salts, and quaternary ammonium salts. Among these, a sulfonium salt is preferable.

A pair anion (pairing anion) of the thermal cationic polymerization initiator is, for example, AsF ₆ ^-, and the like ^{_{-, SbF 6 -, PF 6}} -, B (C 6 F 5) 4.

Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, triphenylsulfonium arsenic hexafluoride, tri(4-methoxyphenyl)sulfonium arsenic hexafluoride, diphenyl(4-phenylthio Phenyl) sulfonium hexafluoride and the like.

In addition, the sulfonium salt may be commercially available. Specifically, for example, ADEKA's product "Adeka Opton CP-66" (brand name) and "Adeka Opton CP-77" (brand name), SANSHIN Chemical Industry's product " Sunade SI-60L” (brand name), “Sunade SI-80L” (brand name), and “Sunade SI-100L” (brand name).

Examples of the phosphonium salt include ethyltriphenylphosphonium antimony hexafluoride, tetrabutylphosphonium antimony hexafluoride, and the like.

Examples of the quaternary ammonium salt include N,N-dimethyl-N-benzylanilinium hexafluoride antimony, N,N-diethyl-N-benzylanilinium tetrafluoride, NN-dimethyl-N-benzylpyridinium hexafluoride antimony , N,N-diethyl-N-benzylpyridiniumtrifluoromethanesulfonic acid, N,N-dimethyl-N-(4-methoxybenzyl)pyridinium hexafluoride antimony, N,N-diethyl-N-( 4-methoxybenzyl)pyridinium hexafluoride antimony, N,N-diethyl-N-(4-methoxybenzyl) toluidinium hexafluoride antimony, N,N-dimethyl-N-(4-me Oxybenzyl) toluidinium hexafluoride antimony, and the like.

Examples of the photo cationic polymerization initiator include onium salts such as iodonium salts, sulfonium salts, diazonium salts, selenium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among these, iodonium salts and sulfonium salts are preferred.

If the photo cationic polymerization initiator is an iodonium salt or sulfonium salt, paired anion as (pairing anion), for example, _{^{BF 4 -, AsF 6 -,}} SbF 6 -, PF 6 -, B (C 6 F 5) 4 - And the like.

The iodonium salts include (tricumyl) iodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetra Fluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis( Dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoro Phosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, 4-methylphenyl-4 -(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate, etc. are mentioned.

In addition, the iodine salt may be commercially available. Specifically, for example, "UV-9380C" (brand name), a product of Momentive Performance Materials Japan, "PHOTOINITIATOR2074" (brand name), a product of Solvay Japan, and Fujifilm Waco The products of pure pharmacist “WPI-116” (brand name) and “WPI-113” (brand name) are listed.

As the sulfonium salts, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimony Acid salt, bis[4-(diphenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl -4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, Diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, diphenyl-4-(phenylthio)phenylsulfonium tetrakis( Pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(di(4-(2-hydroxyethoxy))) Phenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis [4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, and the like.

In addition, sulfonium salts may be commercially available products, specifically, for example, “Silacure UVI-6990” (brand name), “Silacure UVI-6992” (brand name), which are products of Dow Chemical Japan, and “Silacure UVI-6974”, “Adeka Offtomer SP-150” (brand name), “Adeka Offtomer SP-152” (brand name), “Adeka Offtomer SP-170” (brand name) , And “Adeka Optomer SP-172” (brand name), “WPAG-370” (brand name) and “WPAG-638” (brand name), which are products of Fujifilm Wako Pure Pharmacy.

Examples of the diazonium salt include benzene diazonium hexafluoroantimonate, benzene diazonium hexafluorophosphate, and benzene diazonium hexafluoroborate.

In addition, when the polymerizable group is an anionic polymerizable group, for example, in the case of the above formula (21), various known anionic polymerization initiators can be used, and as the thermal cationic polymerization initiator, for example, amines, thiols, imidas Sols, etc. can be used. Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis(3-aminopropyl)glycoluril, and the like. , As thiols, trimethylolpropane tris (3-mercaptopropionic acid ester), tris (2-mercaptoethyl) isocyanurate, 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril And the like, and examples of the imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole.

As a photoanionic polymerization initiator, for example, acetphenone O-benzoyloxime, nifedipine, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4,4,0]deca- 5-ene, 2-nitrophenylmethyl4-methacryloyloxypiperidine-1-carboxylic acid, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3 -Benzoylphenyl)propionic acid, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, and the like.

The amine represented by the following formula (36) that can be used for crosslinking the epoxy group represented by the formula (24) and the formula (33) is not particularly limited, but, for example, ammonia, methylamine, ethylamine, propylamine, butylamine , Pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, icosylamine, isopropylamine, arylamine, alkylamines such as 2-cyclohexylethylamine, cyclopentylamine, cyclohexyl Cyclic alkylamines such as amine, cyclooctylamine, and 3-cyclohexenylamine, phenylamine, 1-naphthylamine, 2-naphthylamine, 2-aminoanthracene, 1-aminopyrene, 3-aminobiphenyl, etc. Arylamine, benzylamine, 2-phenylethyl group, 1-(1-naphthyl)ethylamine, 1-(2-naphthyl)ethylamine, 2-(7-methoxy-1-naphthyl)ethylamine, etc. Of aralkylamine, etc. are mentioned.

H ₂ NR ⁸ (36)

(In formula (36), R ⁸ is a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group which may have a branched chain having 3 to 8 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Or an aralkyl group having 7 to 20 carbon atoms.)

The diamine represented by the following formula (37) that can be used for crosslinking the epoxy group represented by the formula (25) and the formula (34) is not particularly limited, but, for example, diaminomethane, urea, thiourea, 1,2- Diaminoethane, 1,2-bis(methylamino)ethane, N-methylmethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1 ,4-diaminobutane, 1,4-bis(methylamino)-2-butene, 1,6-diaminohexane, 1,8-dimethyloctane, N,N-bis(2-aminoethyl)methylamine, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 3-aminopyrrolidine, 4,4'-methylenebis(2-methylcyclohexylamine), beads(aminomethyl)bicyclo[2.2 .1]heptane, 1,3-phenylenediamine, 1,4-phenylenediamine, 1,2,4-triaminobenzene, N,N'-diphenyl-1,4-phenylenediamine, 2-chloro -1,4-phenylenediamine, 2,7-diaminofluorene, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3' ,4,4'-tetraaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diaminoanthraquinone, 1,6-diaminopyrene, 1,8-diaminopyrene, 3-(aminomethyl) Benzylamine, 4-(aminomethyl)benzylamine, and the like.

R ⁹ HR ¹¹ NHR ¹⁰ (37)

(In formula (37), R ⁹ and R ¹⁰ are each independently a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group which may have a branched chain having 3 to 8 carbon atoms, or Represents a 6 to 20 aryl group or a C 7 to C 20 aralkyl group, R ¹¹ is a C 1 to C 20 linear or branched saturated or unsaturated alkylene group, a C 3 to C 20 branched saturated or unsaturated cycloalkyl Represents a ene group, an arylene group having 6 to 20 carbon atoms, an alkylene group having 7 to 20 carbon atoms or a polyphenylene group having 6 to 24 carbon atoms, and any R ¹¹ is a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and an atom containing the same It may be substituted with a number of 1 to 10 substituents.)

In the case of the reaction represented by the above formula (30), an oxidizing agent can be used in combination, and a known oxidizing agent that accelerates the disulfide formation reaction, such as using bromine or iodine under basic conditions, can be used.

In the case of carrying out the crosslinking reaction between layers by heating, the reaction temperature is not particularly limited and may be appropriately selected. For example, 0 to 200°C is preferable, 25 to 180°C is more preferable, and 40 to 170°C is More preferable. At this time, it is preferable to appropriately contain a thermal polymerization initiator in the reaction system from the viewpoint of ease of crosslinking and cost.

Examples of active energy rays for performing crosslinking reaction between layers by irradiation with active energy rays include ultraviolet rays, visible rays, and electron rays. When ultraviolet rays or visible rays are used as active energy rays, it is preferable to contain a photopolymerization initiator from the viewpoint of easiness of crosslinking and cost.

Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).

The irradiation energy can be appropriately set according to the type or composition of active energy rays, and may vary depending on the thickness or illuminance of the reaction system. For example, when a high-pressure mercury lamp is used, irradiation in the UV-A area As the energy, 5 to 10,000 mJ/cm ² is preferred, for example. In addition, when using a UV-LED, the emission peak wavelength is preferably 350 to 420 nm, and the irradiation energy is preferably 5 to 10,000 mJ/cm ² , for example.

In the case of using an electron beam as an active energy ray, it is possible to cure it by an electron beam without containing a photopolymerization initiator, but a small amount may be blended if necessary to improve curability.

Various devices may be used as the electron beam irradiation device, and examples thereof include Cockcroft-Walton type, Van de Graaff type and resonance transformer type devices.

The absorbed dose of the electron beam is preferably 1 to 1000 kGy, for example.

The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, and more preferably 300 ppm or less.

When performing a crosslinking reaction between layers, a reaction solvent may be used. Such a solvent is not particularly limited and may be appropriately selected, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1-propanol, 1 -Alcohols such as methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol, and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone, ethyl Ketones such as methyl ketone, amides such as N,N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetoate, chloroform , Halogen-based hydrocarbons such as dichloromethane, and the like. Among these, alcohols and aprotic polar solvents such as ethers, nitriles and ketones are preferable.

More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol, and the boiling point is preferably 80°C or higher, more preferably 90°C or higher, and still more preferably 100°C or higher.

The aprotic polar solvent is not particularly limited, but nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, acetone, ethyl methyl ketone, diethyl ketone, and methylene isopropyl ketone. Ketones, amides such as N,N-dimethylformamide, and sulfoxides such as dimethyl sulfoxide are mentioned.

In addition, the secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3 -Aromatic alcohols, such as hexanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol, and phenol, etc. are mentioned. .

Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and 1-propoxy-2-propanol are preferred. And 2-butanol and 1-methoxy-2-propanol are more preferred.

The reaction concentration of the crosslinking reaction between layers is not particularly limited and may be appropriately selected. For example, 1 to 50% by mass is preferable, 3 to 40% by mass is more preferable, and 5 to 40% by mass as the mass% of the interlayered layered inorganic compound. 30 mass% is more preferable.

In addition, in addition to the organic-inorganic composite crosslinked structure, arbitrary functional groups and modifiers may exist between the layers of the interlayer crosslinkable layered inorganic compound of the present invention. For example, exchangeable metal cations such as sodium, potassium, and calcium may be present, or may be modified with an organic onium group such as alkyl ammonium or alkylphosphonium, and a hydroxyl group derived from a layered inorganic compound may be present, and this hydroxyl group May be enclosed/converted into an alkoxy group such as a methoxy group, and an organic silyl group such as an alkylsilyl group, an arylsilyl group, an aralkylsilyl group, and a group derived from an uncrosslinked silane coupling agent, and a metal such as titanium, aluminum, zirconium, etc. It may be modified as an organic-inorganic compound modifier (修飾基).

The timing of introducing an arbitrary functional group or modifier other than the organic-inorganic composite crosslinked structure present between the layers may be both before, after, and at the same time, before and after the interlayer modification by the coupling agent for constructing the crosslinked structure. It may be before or after the interlayer crosslinking reaction of the crosslinkable functional group derived from the introduced coupling agent, and may be arbitrarily selected in consideration of various functional groups, modifiers, and reactivity of the coupling agent.

In the case of introducing a crosslinked structure through covalent bonds between layers of a layered inorganic compound using an organic-inorganic composite crosslinking agent having two or more hydrolyzable metal sites, use the organic-inorganic composite crosslinking agent in the same manner instead of the coupling agent for the above-described precursor. Just react.

The organic-inorganic composite crosslinking agent having two or more hydrolyzable metal moieties is not particularly limited, and examples thereof include 1,4-bis(triethoxysilyl)benzene, 1,6-bis(trimethoxysilyl)hexane, etc. I can.

Next, the interlayer type layered inorganic compound having the organic-inorganic composite group represented by the above formula (2) will be described.

In the above formula (2), M is a metal capable of generating a covalent bond with an oxygen atom derived from a layered inorganic compound, and the covalent bond is difficult to cause decomposition reactions such as hydrolysis and is easily available, so Si (silicon), Al Si, which is any one of (aluminum), Ti (titanium), and Zr (zirconium), is preferred because it is readily available in order to introduce various interaction groups.

In the organic-inorganic complex device represented by the above formula (2) introduced between the layers through covalent bonds with the layered inorganic compound, the combination of the organic-inorganic complex group and the layered inorganic compound through a plurality of covalent bonds is the chemical of the bond that connects the layers. It is more preferable from the viewpoint of stability, and in the above formula (2), when M is Si, Ti, and Zr, n is more preferably 1 or 2, in the case of Al, n is more preferably 1, and in any case, Z It is more preferable that at least one of these contains an oxygen atom derived from a layered inorganic compound. Further, Z of the organic-inorganic composite groups close to each other may be hydrolyzed/condensed to form an M-O-M bond.

Since the interaction with the guest compound in the organic-inorganic composite group can be appropriately designed, any one of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond generator, a coordination bond generator, and an ionic bond generator It is preferable to include. Through this, non-covalent interactions with guest compounds (e.g., van der Waals' force, π-π interactions, hydrophobic interactions, hydrogen bonds, coordination bonds, ionic bonds, etc.) are properly controlled. It can be given, and an arbitrary compound can be inserted between layers and sustained release according to the purpose.

The non-covalent interaction group is not particularly limited, and for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-octyl group, decyl group, dodecyl group, Saturated or unsaturated aliphatic groups such as octadecyl group, methylene group, propylene group, cyclohexyl group, vinyl group, allyl group, styryl group, phenyl group, naphthyl group, aromatic group such as phenylene group, pyridinyl group, piperidinyl group, Azole groups such as pyrrolidinyl group, pyrimidinyl group, and imidazolyl group, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, dioxanyl group, molhorinyl group, thiazinyl group, indole group, nucleic acid Heterocyclic structural groups such as base, acrylicoxy group, methacryloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, methyl carboxylate group, phosphoric acid group, ethyl phosphate group, sulfonic acid group, sulfonic acid Hydrogen bonds and coordination bond generators such as methyl group, amino group, methylamino group, dimethylamino group, isocyanurate group, ureide group, and isocyanate group, ethyl ammonium group, dimethylammonium group and trimethylammonium group ion bond generator, etc. In terms of ease of use, methyl group, ethyl group, n-propyl group, n-hexyl group, decyl group, octadecyl group, methylene group, propylene group, cyclohexyl group, vinyl group, aryl group, styryl group, phenyl group, phenylene group, Epoxy group, oxetanyl group, acryloxy group, methacryloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, carboxyl group, amino group, methylamino group, dimethylamino group, trimethylammonium group, isocyanurate group, ureide Groups and isocyanate groups are preferred.

These non-covalent interaction groups may form a crosslinked structure by a crosslinking reaction between layers.

Next, the interlayered layered inorganic compound of the present invention will be described in detail according to the manufacturing method.

For reference, a method of preparing a precursor for performing silylation, which is a layered inorganic compound having an interlayer widened from the layered inorganic compound, is the same as the method described in paragraphs [0074] to [0109].

Next, all or part of the pairing anion (pairing anion (alkoxylate)) of the hydroxyl group and the onium group of the precursor is subjected to an interlayer modification reaction with an organic-inorganic complex formulating agent such as a silylation agent represented by the following formula (38), An interlayer type layered inorganic compound having an organic-inorganic composite group represented by the above formula (2) is prepared through covalent bonds between the layers.

The modifier for introducing the organic-inorganic composite group represented by the above formula (2) between the layers may be an organic-inorganic composite modifier having a hydrolyzable group in the same molecule and a functional group capable of interacting with a functional compound. For example, a silane couple And a silylating agent including a ring agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent, and the like, preferably a compound represented by the following formula (38).

R _n MD _yn (38)

(In formula (38), R is a C 1 to C 20 straight or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, a C 6 to C 20 aryl group or a C 7 to C Represents an aralkyl group of 20, each of which is a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group having 1 to 20 carbon atoms. Or a dialkylamino group, a C1-C20 monoarylamino group or a diarylamino group, a C1-C20 monoaralkylamino group or a diaralkylamino group, a primary, secondary, tertiary or quaternary ammonium group, thiol Group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom may be substituted, M is Si , Al, Ti or Zr, D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 branched chains, trimethylsilyloxy group, dimethyl A silyloxy group, a saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated alkylamino group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Represents a linear or branched saturated or unsaturated dialkylamino group of, M represents Si, Al, Ti or Zr, and when M is any one of Si, Ti or Zr, the corresponding y is 4, and n is an integer of 1 to 3, and when M is Al, the corresponding y is 3, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.)

In the organic-inorganic composite modifier represented by the above formula (38), the functional group represented by R may be protected with an appropriate protecting group.

Among the above organic-inorganic complex modifiers, a silylating agent in which M is Si is more preferable because of its abundant variety and ease of acquisition, handling and control of hydrolysis reactions.

Among the silylating agents, hydrolyzable groups do not generate incidental acids such as hydrogen chloride, so there is a very low risk of causing side reactions to functional groups, and does not cause corrosion of the reaction device, and does not require disposal of incidental acids. It is preferably an alkoxysilane, more preferably a methoxy group, an ethoxy group, and a propoxy group having excellent silylation reactivity, and particularly preferably a methoxy group and an ethoxy group.

The silylating agent is not particularly limited, but examples of the alkoxysilanes include vinyl trimethoxysilane, vinyl triethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane 2-(3,4-epoxycyclohexyl). ) Ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane , 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxycillin, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- Hydrochloric acid salt of (1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane , Tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidepropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanate propyltrier Toxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 7-octenyltrimethoxy Silane, 4-(trimethoxysilyl)butyric acid, 4-(trimethoxysilyl)butyric acid 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane , Dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane Silane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane , Dimethoxydimethylsilane, Trimethoxymethylsilane, triethoxysilane, etc. are mentioned.

Further, silylating agents other than alkoxysilanes can also be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonic acid, triethylchlorosilane, tertiarybutyldimethylchlorosilane, chlorotriisopropylsilane, 1,3-dichloro -1,1,3,3-tetraisopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, aryltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, tris( N,N-dimethylamino)methylsilane, bis(N,N-dimethylamino)dimethylsilane, (N,N-dimethylamino)trimethylsilane, etc. are mentioned.

In such a silylating agent, when a plurality of hydrolyzable groups are present in one molecule, a single hydrolyzable group such as an alkoxy group, a halogen atom, an alkylamino group, or a dialkylamino group may be present, or a plurality of hydrolyzable groups may be present.

In addition, instead of the silylating agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, or the like may be used.

The organic solvent used for the reaction with the silylating agent is not particularly limited, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1 -Alcohols such as propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran , Ketones such as acetone, ethyl methyl ketone, amides such as N,N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate , Halogen-based hydrocarbons such as chloroform and dichloromethane. Among these, alcohols and ethers, nitriles and ketones which are aprotic polar solvents are preferable.

More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol, and the boiling point is preferably 80°C or higher, more preferably 90°C or higher, and still more preferably 100°C or higher.

Aprotic polar solvents include nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethyl methyl ketone, diethyl ketone, methylene isopropyl ketone, and N,N. -Amides such as dimethylformamide, and sulfoxides such as dimethyl sulfoxide.

In addition, the secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3- And aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol, and phenol.

Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, and 1-butoxy-2-propanol is preferred, and 2-butanol, 1-methoxy-2-propanol and 1-butoxy-2-propanol are more preferred.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the reaction, the O-alkylation reaction, which is a side reaction of the hydroxyl group and the alkoxylate derived from the layered inorganic compound, is difficult to occur, and is used. Since the boiling point of the organic solvent is high, it is inferred that the silylation reaction temperature increases, accelerating the interlayer modification reaction such as the silylation reaction, thereby increasing the interlayer modification rate such as the silylation rate.

In addition, when secondary or tertiary alcohols are used, the concomitant formation of hydroxyl groups such as silanol or condensation between coupling agents such as silane coupling agents by hydrolysis of organic-inorganic complex formulating agents such as silylating agents described later This is preferable because side reactions such as are suppressed. It is inferred that this is a solvent effect due to alcoholic hydroxyl groups.

It is preferable to add water to the reaction system during the reaction. The water to be added may be either neutral, acidic, or alkaline, and is not particularly limited, but preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The amount of water added is preferably 0.05 to 4.0 mole times, and particularly preferably 0.1 to 3.0 mole times, with respect to the total amount of the alkoxylate, that is, the ion exchange capacity, which is the pairing anion of the hydroxyl group and the onium group, which is the reaction point of the layered inorganic compound. .

If the amount of water added is less than 0.05 mole times, the effect of addition is small, and if it exceeds 4.0 mole times, there is a concern that side reactions such as hydrolysis/condensation between coupling agents such as silane coupling agents may proceed.

In the above reaction, the amount of the organic-inorganic complex modifier such as a silylating agent is not particularly limited, but the total amount of the alkoxylate, which is the pairing anion of the hydroxyl group and the onium group, which is the reaction point, that is, preferably 0.1 to It is 30 mole times, more preferably 0.05 to 20 mole times, and still more preferably 1.0 to 10 mole times.

If the amount of the coupling agent is less than 0.1 mole times, the silylation reaction rate becomes small, while if it exceeds 30 mole times, it is industrially disadvantageous in terms of the cost of raw materials.

Since the reaction point between the layers of the layered inorganic compound, that is, the interlayer modification rate such as the silylation rate relative to the ion exchange capacity, is selected according to the purpose, it is not particularly limited, but the interlayer modification rate such as the silylation rate is 15 mol% or more. It is preferable, and it is more preferable that it is 25 mol% or more.

On the other hand, if the interlayer modification rate such as the silylation rate exceeds 200 mol%, the interlayer of the layered inorganic compound may be excessively covered with components derived from the organic-inorganic complex modification agent, which is not preferable.

The reaction temperature in the interlayer modification reaction is not particularly limited, but is preferably 0 to 200°C, more preferably 50 to 180°C, and still more preferably 70 to 170°C. Usually, the reaction is carried out at the boiling point (under heating and reflux) of the organic solvent used as the reaction solvent.

The amount of the organic solvent used in the interlayer modification reaction is not particularly limited, but is 1 to 30 times by mass, more preferably 5 to 25 times by mass, more preferably with respect to the layered inorganic compound used as a raw material. It is 10 to 20 times by mass.

The interlayer modification reaction, such as the silylation reaction with the organic-inorganic compound modifier of the present invention, may or may not use a catalyst, but carboxylic acids such as hydrogen chloride, formic acid, acetoic acid, and oxalic acid, phosphoric acid, nitric acid, etc. Known acids such as sulfonic acids such as sulfuric acid and methanesulfonic acid, and known bases such as ammonia, trimethylamine, triethylamine, tetramethyl ammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as a catalyst.

In this case, the amount of the catalyst to be added is not particularly limited, but the total amount of the alkoxylate, which is the pairing anion of the hydroxyl group and the onium group, which is the reaction point, that is, it is preferably 0.001 to 1.0 mole times the ion exchange capacity, and more preferably Is 0.01 to 0.1 molar times.

It is preferable to dry the layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction after isolation and washing. The method of isolating, washing and drying is not particularly limited, and a known method of isolating, washing and drying the layered inorganic compound and inorganic fine particles may be used. For example, a method in the precursor may be used.

Z present in the organic-inorganic composite group represented by the above formula (2) may be involved in the interaction with the guest compound. For example, if it is a hydroxyl group, it can be involved in insertion and sustained release by generating hydrogen bonds with the guest compound, and it is involved in controlling the interaction with the guest compound depending on the type of Z, for example, a hydroxyl group, a methoxy group, etc. You may.

In addition, in addition to the organic-inorganic composite group, arbitrary functional groups and modifier groups may exist between the layers of the interlayer modified layered inorganic compound in the present invention. For example, exchangeable metal cations such as sodium, potassium, and calcium may be present, or may be modified with an organic onium group such as alkyl ammonium or alkylphosphonium, or a hydroxyl group derived from a layered inorganic compound may be present, and the hydroxyl group may be methoxide. It may be encapsulated/converted by alkoxy groups such as timing. Depending on the amount of these, it may be involved in controlling the interaction with the guest compound.

The compound (also referred to as a guest compound) that is inserted into the interlayered layered inorganic compound having an organic-inorganic composite group represented by the above formula (1) or (2) of the present invention for sustained release is not particularly limited, and depends on the intended use. It can be selected arbitrarily, for example, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having 3 to 8 branched carbon atoms, an aryl group having 6 to 20 carbon atoms, or a carbon number in the compound. Represents an aralkyl group of 7 to 20, each of which is a vinyl group, an epoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group having 1 to 20 carbon atoms, or Dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, primary, secondary, tertiary or quaternary ammonium group, thiol group , Isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphate ester group, sulfonic acid group, sulfonic acid ester group, ketone group, functional group or oxygen atom of ether group, It may be substituted with a hetero atom such as a nitrogen atom, a sulfur atom, a phosphoric acid atom, or a halogen atom, or may have various heterocyclic structural groups.

Among these, since it is easy to control the interaction with the organic-inorganic composite group, it is more preferable to include any one of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond generator, a coordination bond generator, or an ionic bond generator. Preferred, but not particularly limited, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-hexyl group, n-octyl group, decyl group, dodecyl group, octadecyl group, methylene Group, propylene group, cyclohexyl group, vinyl group, saturated or unsaturated aliphatic group such as allyl group, styryl group, phenyl group, phenol group, naphthyl group, aromatic group such as phenylene group, pyridinyl group, piperidinyl group, pyrroly An azole group such as a denil group, a pyrimidinyl group, a pyridinyl group, and an imidazolyl group, thiazolinyl group, thiazole group, thiazolinone group, isothiazolinone group, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothio Heterocyclic structural groups such as phenyl group, dioxanyl group, molholinyl group, thiazinyl group, indole group, and nucleotide group, acryloxy group, methacryloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, Hydrogen bonds and coordination bond generators such as aldehyde group, carboxyl group, methyl carboxylic acid group, phosphoric acid group, ethyl phosphate group, sulfonic acid group, methyl sulfonate group, amino group, methylamino group, dimethylamino group, isocyanurate group, ureide group, isocyanate group, ethyl Those containing an ammonium group, a dimethylammonium group, and an ionic bond generator of a trimethylammonium group, and the like. These functional groups may be present in combination in the same compound.

There is no particular limitation on the molecular weight of the compound, and it can be arbitrarily selected according to the intended use, but since interlayer insertion is easy and the host-guest composite structure is stably maintained, its molecular weight is preferably 2,000 or less, and 1,000 or less. Is more preferable, and 500 or less is still more preferable.

The method of preparing the sustained-release composite agent in which the functional compound is inserted between the layers of the interlayered layered inorganic compound is not particularly limited, and for example, a method of mixing the interlayered layered inorganic compound and the compound in the absence of a solvent, or the compound is soluble ( Or a method of mixing an interlayer type layered inorganic compound in the presence of an insoluble solvent or the like.

When the compound is a gas or a liquid, a method of mixing in the absence of a solvent is economical and preferable. On the other hand, when the compound is a liquid or solid having high viscosity, a method of mixing the compound with the interlayer type inorganic compound in the presence of a soluble solvent is preferable because the compound is efficiently intercalated between the layers. In addition, when the compound is a solid, the method of mixing it with the interlayer type layered inorganic compound by heating to the melting point or higher and mixing it with the layered inorganic compound is efficient without requiring a solvent.

The temperature at which the interlayered layered inorganic compound and the compound are mixed is not particularly limited, and is usually in the range of 0 to 200°C, preferably 10 to 150°C, and more preferably 15 to 100°C.

The solvent used when preparing the sustained-release composite agent is not particularly limited, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl-1- Alcohols such as propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, Ketones such as acetone and ethylmethylketone, amides such as N and N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate , Halogen-based hydrocarbons such as chloroform and dichloromethane, and the like, and may be appropriately selected in consideration of the solubility of the guest compound and the hydrophilicity and hydrophobicity of the interlayer modifier of the host compound.

When preparing the sustained-release composite agent, the mixing ratio of the interlayered layered inorganic compound as a host compound and the compound as a guest compound is not particularly limited, and is arbitrarily set according to the purpose. However, in the case of a sustained release agent over a long period of time, the layered inorganic compound is interlayered. It is preferred to mix with at least the maximum amount of compounds that may be incorporated. For example, when 10 parts of the functional compound can be intercalated with respect to 100 parts of the interlayered layered inorganic compound, it is preferable to mix with 10 parts or more.

The sustained-release composite agent obtained by mixing the interlayered layered inorganic compound and the compound may be used as it is, or may be used as a sustained-release agent after removing excess compound or solvent. Excessive compounds or solvents can be removed by filtration by known filtration operations such as natural filtration, reduced pressure filtration, or pressure filtration when the compound is a liquid or when a soluble solvent of the compound is used in combination. . If the compound is a liquid or a sublimable solid, it may be removed by air drying, evaporation by heating, or distillation under reduced pressure. When the compound is solid and a solvent is used in combination, an unnecessary solvent can be dried by air, or removed by heat evaporation or vacuum distillation.

The method of using the sustained-release composite agent including the interlayered layered inorganic compound of the present invention and the compound inserted between the layers of the interlayered layered inorganic compound is not particularly limited, and for example, the composite agent may be used as a sustained release agent. , In addition, it may be mixed with a resin and used as a structural material, a coating agent, a fiber, a film, a sheet, a plate, a particle, a block, or the like, or may be dispersed in a solvent or a polymerizable monomer to be used as a paint.

The sustained-release composite agent of the present invention can be blended with various materials to provide an effect corresponding to the function of the guest compound. Materials that can be blended include various plastics such as rubber such as silicone and acrylic, polyvinyl chloride, polyolefin, polyurethane, ABS, polystyrene, polyvinyl acetate, polycarbonate, polyester, polyurethane, polyacrylic acid, etc. Can be mentioned.

In addition, the sustained-release composite agent of the present invention, suspended in a liquid medium such as water or an organic solvent, in the presence or absence of a binder, is spray coating, coater coating, dipping, brush It is also possible to form a film by applying it to the surface of various metals, plastics, ceramics, etc. by general application means such as brush coating and roll coating. Corresponding effects can be given.

The preferred ratio when blending the sustained-release composite agent of the present invention into various materials is not particularly limited, and can be arbitrarily selected according to the use environment or purpose.

As a specific use of a material or molded article blended or coated with the sustained-release composite agent and the sustained-release composite agent of the present invention, textile products such as towels, carpets, curtains, clothes, mosquito nets, bedding, leather, refrigerators, washing machines, dish dryers, vacuum cleaners, Electronic products such as air conditioners, televisions, telephones, PCs, building materials such as wallpaper, tiles, bricks, concrete, screws, and filling materials, daily necessities such as washing machines, toothbrushes, brooms, hoses, slippers, trash cans, scrubbers, cutting boards, Triangular corners, kitchen utensils such as kitchen knives, toilet utensils, mobility supplies such as automobiles, aircraft, and ships, agricultural products such as pesticides and plant hormones, medical and health hygiene products such as medicines and quasi-drugs, drug delivery, cosmetics, and air fresheners , Antioxidants, lubricants, moisturizers, repellents for insects and animals, insecticides, fungicides, insect repellents, preservatives, mold removers, bioactive agents such as antiviral agents, foods such as food additives, various coatings, paints and adhesives, etc. However, it is not limited to these.

Example

Hereinafter, the present invention will be specifically described according to Examples and Comparative Examples.

<Example 1> Synthesis of a sustained-release composite agent in which 2-methyl-2-thiazoline (hereinafter referred to as 2MT) was inserted between the layers of a methacryloyl-type crosslinked and interlayer modified magadite with a phenylsilyl group and its sustained release evaluation

(1) Synthesis of sodium-magadite (hereinafter referred to as Na-magadite)

After mixing 18.34g of sodium silicate (product of Fuji Chemical, brand name: Soda 4 silicate), 7.28g of silica gel (product of Fujifilm Wako Pure Chemicals, brand name: Oekkogel Q-63) and 54.37g of pure water, reaction for high pressure It was enclosed in a decomposition container (product of SANAI Scientific, brand name: HU-100) and heated at 170° C. for 30 hours. The product was filtered off by suction, washed with a diluted aqueous NaOH solution (pH:9-10) and pure water, and dried at 40° C. for 2 days to obtain 15.9 g of Na-magadite.

As a result of calculating the composition of Na-magadite using an atomic absorption analyzer (product of Shimadzu Corporation, AA-6200) and a thermogravimetric analyzer (product of Hitachi Hi-Tech Science, TG/DTA6300), Na ₂ Si ₁₄ O ₂₉ It was nH ₂ O, and the ion exchange capacity calculated by setting n = 0 was 2.21 mol c/kg.

In addition, the bottom surface spacing of the Na-magadite obtained using an X-ray diffraction device (BRUKER's product, brand name: D8 ADVANCE) was calculated and found to be 1.54 nm.

(2) Synthesis of dodecyltrimethylammonium (hereinafter referred to as DTMA)-magadite (synthesis of silylation precursors by interlaminarization by treatment of Na-magadite with dodecyltrimethylammonium chloride)

100 g of Na-magadite obtained as described above, 6500 g of pure water, and 175 g of dodecyltrimethyl ammonium chloride (manufactured by Fujifilm Wako Sun Pharmaceutical) were mixed and stirred at room temperature for 7 days. Then, the solid was sucked out, washed with methanol, and dried at 60° C. to obtain 94 g of DTMA-magadite.

As a result of measuring the Na mass in the DTMA-magadite obtained using an atomic absorption analyzer (product of Shimadzu Corporation, AA-6200), it was confirmed that the Na content was less than 0.04 mass%, and most of the cation exchange was performed.

As a result of calculating the composition of DTMA-magadite obtained using an elemental analysis device (product of Yanako Analysis Corporation, CHN coder MT-5) and a thermogravimetric analysis device (product of Hitachi Hi-Tech Science, TG/DTA6300), DTMA _1.72 It was H _0.28 Si ₁₄ O ₂₉ ·nH ₂ 0.

In addition, as above, the bottom surface spacing of the obtained DTMA-magadite was calculated and found to be 2.89 nm.

(3) Interlayer silylation by treatment of 3-methacryloyloxypropyl trimethoxysilane (hereinafter referred to as MAC-TRIMS) of DTMA-magadite (introduction of methacryloyloxypropyl group)

100 g of DTMA-magadite obtained as described above was dried under reduced pressure at 100° C. and about 100 Pa for 2 hours, and then 1850 g of 1-methoxy-2-propanol (hereinafter referred to as PGM) dried with a molecular sieve 3A , 3.4 g of pure water and 39.2 g of MAC-TRIMS (0.5 mol times to the reaction point, manufactured by Shin-Etsu Chemical Industries) were mixed and stirred for 4 days while performing heating and refluxing under a nitrogen atmosphere. Thereafter, the solid was sucked out, washed with methanol, and dried at 60° C. to obtain 105 g of silylation magadite (hereinafter referred to as MACPS-magadite).

As described above, the composition of the obtained MACPS-magadite was calculated, and as a result, methacryloyloxypropylsilyl (MACPS) _0.43 DTMA _0.56 Me _1.01 Si ₁₄ O ₂₉ nH ₂ O was found, and the bottom surface spacing was 2.12 nm.

(4) Synthesis of interlayer crosslinked layered inorganic compounds by crosslinking reaction of MACPS-magadite

100 g of MACPS-magadite obtained as described above and 1450 g of toluene were mixed, cooled with ice, and nitrogen gas was bubbled for 1 hour to remove oxygen in the system. Then, 7.88 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, followed by stirring at 60° C. for 24 hours. Then, the solid was sucked out, washed with methanol, and dried at 60° C. to obtain 95 g of magadite crosslinked with a methacryloxy group (hereinafter referred to as P-MACPS-magadite).

As described above, the composition of the obtained P-MACPS-magadite was calculated, and as a result, the crosslinked methacryloyloxypropyl group (P-MACPS) _0.06 MACPS _0.38 DTMA _0.56 Me _1.00 Si ₁₄ O ₂₉ nH ₂ O, and the bottom The spacing was 1.94 nm.

(5) Interlayer silylation by treatment of P-MACPS-magadite with phenyltrimethoxysilane (hereinafter referred to as Ph-TRIMS) (introduction of a phenyl group)

Except that DTMA-magadite 100g was changed to P-MACPS-magadite 100g, and MAC-TRIMS 39.2g was changed to Ph-TRIMS 263g (7 mole times the reaction point, product of Shin-Etsu Chemical Co., Ltd.), In the same manner as in Example 1 (3), 96 g of interlayer silylated magadite (hereinafter referred to as P-MACPS-PhS-magadite) was obtained.

As described above, the composition of the obtained P-MACPS-PhS-magadite was calculated, as a result, P-MACPS _0.06 MACPS _0.38 PhS _0.38 DTMA _0.02 Me _1.16 Si ₁₄ O ₂₉ nH ₂ O, and the bottom surface spacing was 1.95 nm.

(6) Preparation of a combination of P-MACPS-PhS-magadite and 2MT

30 g of P-MACPS-PhS-magadite obtained above was mixed with 150 g of 2MT (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 25° C. for 2 days. Thereafter, the solid was filtered off by suction and dried at 25°C to obtain 33 g of a combination of P-MACPS-PhS-magadite and 2MT (hereinafter referred to as a P-MACPS-PhS-magadite/2MT combination). The bottom surface spacing was 1.98 nm.

Calculate the weight of 2MT adsorbed in 1 g of the composite agent obtained by using an elemental analysis device (product of Yanako Analysis Industries, CHN coder MT-5) and a thermogravimetric analysis device (product of Hitachi Hi-Tech Science, TG/DTA6300). Was.

(7) 2MT release test from P-MACPS-PhS-magadite/2MT combination

40 mg of the P-MACPS-PhS-magadite/2MT composite agent obtained above was mixed with 2.8 g of octane (manufactured by Fujifilm Wako Sun Pharmaceutical Co., Ltd.) and stirred at 25°C.

After starting the stirring, sampling was performed over time, and the sample solution was centrifuged, and the concentration of 2MT in the supernatant was analyzed using gas chromatography (7820A, a column: CP-Sil 5 CB, manufactured by Agilent Technologies).

The results are shown in FIGS. 1 and 2.

<Example 2> Synthesis of a sustained-release composite agent in which 2MT was inserted between layers of margadite modified with a phenylsilyl group and evaluation of the sustained-release property

(1) Synthesis of partially protonated DTMA-magadite (silylation precursor) by treatment of DTMA-magadite with hydrochloric acid

100 g of DTMA-magadite obtained in the same manner as in Example 1(2) and 655 g of 0.1 mol·dm ⁻³ hydrochloric acid were mixed, and stirred at room temperature for 1 day. Then, the solid was sucked out, washed with pure water, and dried at 60° C. to obtain 86 g of partially protonated DTMA-magadite.

As described above, the composition of the obtained partially protonated DTMA-magadite was calculated, and as a result, DTMA was _1.11 H _0.89 Si ₁₄ O ₂₉ ·nH ₂ O, and the proportion of ammonium groups was 56 mol% with respect to the ion exchange capacity.

Similarly to the above, as a result of analyzing the bottom surface spacing of the partially protonated DTMA-magadite, no clear diffraction peak was observed. This is presumed to be due to the collapse of most of the layered structure of the obtained partially protonated DTMA-magadite.

(2) Interlayer silylation of partially protonated DTMA-magadite by Ph-TRIMS treatment (introduction of phenyl group)

Silylation margadite (hereafter, by performing interlayer silylation in the same manner as in Example 1 (5), except that 100 g of P-MACPS-magadite was used as 100 g of partially protonated DTMA-magadite obtained as described above. PhS-magadite) 102g was obtained.

As above, the obtained PhS-magadite composition was calculated, and as a result, phenylsilyl (PhS) _1.13 DTMA _0.40 Me _0.47 Si ₁₄ O ₂₉ ·nH ₂ O was found, and the bottom surface spacing was 2.16 nm.

(3) Removal of residual DTMA group of PhS-magadite using hydrogen chloride and methanol and introduction of methyl group (encapsulation of silanol)

100 g of PhS-magadite obtained as described above was dried under reduced pressure at 100° C. and about 100 Pa for 2 hours, and then PGM1650 g dried with molecular sieve 3A and 78.5 g of 5% hydrogen chloride methanol solution were mixed under nitrogen atmosphere. The mixture was stirred for 3 days while heating to reflux. Then, the solid was sucked out, washed with methanol, and dried at 60°C.

The total amount of the obtained solid was mixed with 1980 g of methanol, and stirred for 2 days while heating to reflux under a nitrogen atmosphere. Thereafter, the solid was aspirated, filtered, and dried at 60° C. to remove DTMA groups and O-methylated PhS-magadite (hereinafter referred to as PhS-magadite-PPMe) 76 g of magadite-derived silanol was obtained.

As described above, the composition of the obtained PhS-magadite-PPMe was calculated, and as a result, PhS _1.13 DTMA _0.04 Me _0.83 Si ₁₄ O ₂₉ ·nH ₂ O was found, and the bottom surface spacing was 1.69 nm.

(4) Preparation of a combination of PhS-magadite-PPMe and 2MT

In the same manner as in Example 1(6), except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of PhS-magadite-PPMe obtained above, a combination of PhS-magadite-PPMe and 2MT ( Since then, it is referred to as PhS-magadite-PPMe/2MT combination) 34g was obtained. The bottom surface spacing was 2.11 nm.

Similarly to the above, the weight of 2MT adsorbed in 1 g of the obtained composite agent was calculated and found to be 122.6 mg.

(5) 2MT release test from PhS-magadite-PPMe/2MT combination

In the same manner as in Example 1(7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 40 mg of the PhS-magadite-PPMe/2MT combination drug obtained above, the 2MT concentration in the octane was Analyzed.

The results are shown in Tables 1 and 2.

<Example 3> Synthesis of a sustained-release composite agent in which 2MT was interposed between layers of magadite (MACPS-magadite) modified with 3-methacryloyloxypropylsilyl group and its sustained-release evaluation

(1) Preparation of a combination of MACPS-magadite and 2 MT

In the same manner as in Example 1 (6), except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of MACPS-magadite obtained in the same manner as in Example 1 (3), and MACPS-magadite and 31 g of a 2MT combination preparation (hereinafter referred to as MACPS-magadite/2MT combination preparation) was obtained. The bottom surface spacing was 2.20 nm.

As described above, the weight of 2MT adsorbed in 1 g of the obtained composite agent was calculated and found to be 46.2 mg.

(2) 2MT release test from MACPS-magadite/2MT combination

In the same manner as in Example 1 (7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 40 mg of the MACPS-magadite/2MT combination drug obtained above, the 2MT concentration in the octane was analyzed as in Example 1 (7). .

The results are shown in Tables 1 and 2.

<Comparative Example 1> Preparation of a sustained-release composite agent in which 2MT is inserted between layers of anhydrous Na-magadite

In the same manner as in Example 1 (6), except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of Na-magadite obtained in the same manner as in Example 1 (1). 30 g of a 2MT composite agent (hereinafter referred to as Na-magadite/2MT composite agent) was obtained. The bottom surface spacing was 1.56 nm.

As described above, the weight of 2MT adsorbed in 1 g of the obtained composite agent was calculated and found to be 12.9 mg. The results are shown in Table 1.

<Comparative Example 2> Synthesis of a sustained-release composite agent in which 2MT is inserted between layers of magadite modified with DTMA group and its sustained-release evaluation

(1) DTMA-Preparation of a combination of magadite and 2 MT

In the same manner as in Example 1 (6) except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of DTMA-magadite obtained in the same manner as in Example 1 (2), DTMA-magadite and 30 g of a 2MT combination preparation (hereinafter referred to as DTMA-magadite/2MT combination preparation) was obtained. The bottom surface spacing was 2.89 nm.

As described above, the weight of 2MT adsorbed in 1 g of the obtained composite agent was calculated and found to be 12.0 mg.

(2) DTMA-2MT release test from magadite/2MT combination

In the same manner as in Example 1 (7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 40 mg of the DTMA-magadite/2MT combination drug obtained above, the 2MT concentration in the octane was analyzed. . The results are shown in Tables 1 and 2.

[Table 1]

As shown in Table 1, both the anhydrous type and the host compound organically interlayered with the conventional alkylammonium shown in Comparative Examples 1 and 2 could not control the interaction with the guest compound, so that only a small amount of 2MT was adsorbed. . On the other hand, when the interlayer type layered inorganic compound having the organic-inorganic composite group of the present invention shown in Examples 1 to 3 is used as the host compound, 2MT as the guest compound can be effectively adsorbed and maintained. Per unit host compound, Example 2 can adsorb 11.5 times more guest compounds than Comparative Example 2.

In addition, since the spacing of the bottom surface of the layered inorganic compound was enlarged after complexing with the guest compound, most of the adsorbed guest compounds were intercalated between the layers.

In the 2MT release test conducted using the combination agents of Examples 1 to 3 and Comparative Example 2 in Table 1, based on the measured 2MT concentration in the octane, the host-guest combination agent for the amount of 2MT adsorbed in the initial host-guest combination agent Table 2 shows that the ratio of the guest compound released from was calculated as the release rate and expressed over time.

[Table 2]

In all cases of Examples 1 to 3, the 2MT release rate gradually increased as time passed, indicating that the guest compound was sustained release in the test solvent octane.

On the other hand, in the case of using the layered inorganic compound organicated with alkyl ammonium (DTMA), which is a conventional technique shown in Comparative Example 2, as the host compound, 18.5% of the guest compound was released until 1 hour later, but after that, the guest compound was a layered inorganic compound. It was not released in a state adsorbed inside and was not sustained release.

In addition, Example 1 uses a layered inorganic compound crosslinked by an organic-inorganic composite crosslinked structure as a host compound, whereas in Examples 2 and 3, the interlayer is modified with a phenylsilyl group or a methacryloxy group, and the interlayer This is the case where a non-crosslinked layered inorganic compound is used as a host compound. In Example 2, when paying attention to the release rate of 2MT (the slope of the release rate), 21.9% was released until 1 hour later, and even after that, it was larger than that of Example 1. Also in Example 3, when paying attention to the release rate of 2MT (the slope of the release rate), 38.7% was already released by 1 hour, and even after that, it was larger than that of Example 1.

On the other hand, Example 1 is a case where the layered inorganic compound crosslinked between layers was used as a host compound by introducing methacryloxy between the layers and crosslinking it.When focusing on the release rate of 2MT (the slope of the release rate), 1.9% even after 1 hour It was very small and very small after that, and 2MT was sustained very slowly. That is, even by appropriately maintaining the interlayer distance by interlayer crosslinking, the interaction of the guest compound between the layers can be controlled, so that the release rate can be appropriately controlled and the function derived from the guest compound can be expressed over a long period of time (long To enable longevity).

In this way, by using the layered inorganic compound modified between layers with the organic-inorganic multi-function device of the present invention as a host compound, the desired guest compound can be stored more efficiently than the conventional method, and the release rate can be controlled to effectively sustain the release over a long period of time. have.

<Example 4> Synthesis of a sustained-release composite agent in which 2,3,5-trimethylpyrazine (hereinafter referred to as 235 TMP) was inserted between the interlayer-modified magadite layers with 3-methacryloyloxypropylsilyl group and its sustained-release evaluation

(1) Preparation of a combination of MACPS-magadite and 235TMP

In the same manner as in Example 3(2), except that 150g of 2MT was changed to 150g of 235TMP (manufactured by Tokyo Chemical Industry Co., Ltd.), a combination of MACPS-magadite and 235TMP (hereinafter referred to as MACPS-magadite/235TMP combination) ) 49g was obtained. The spacing of the bottom surface was 3.20 nm.

Similarly to the above, the weight of 235 TMP adsorbed in 1 g of the obtained composite agent was calculated and found to be 381.5 mg.

(2) 235TMP release test from MACPS-magadite/235TMP combination

The concentration of 235TMP in the octane was analyzed in the same manner as in Example 1 (7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 40 mg of the MACPS-magadite/235TMP combination drug obtained above. .

The results are shown in Tables 3 and 4.

<Comparative Example 3> Synthesis of a sustained-release composite agent in which 235TMP was inserted between the layers of magadite modified between layers with a DTMA machine and its sustained-release evaluation

(1) DTMA-Preparation of a combination of magadite and 235TMP

In the same manner as in Example 4 (1), except that 30 g of MACPS-magadite was changed to 30 g of DTMA-magadite obtained in the same manner as in Example 1 (2), a combination of DTMA-magadite and 235 TMP ( Thereafter, 34 g of DTMA-magadite/235TMP combination) was obtained. The spacing of the bottom surface was 3.83 nm.

As described above, the weight of 235 TMP adsorbed in 1 g of the obtained composite agent was calculated and found to be 126.8 mg.

(2) 235TMP release test from DTMA-magadite/235TMP combination

In the same manner as in Example 1 (7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 40 m of the obtained DTMA-magadite/235TMP combination drug, the concentration of 235TMP in the octane was analyzed as in Example 1(7). . The results are shown in Tables 3 and 4.

[Table 3]

As shown in Table 3, when the interlayer modified layered inorganic compound modified with the organic-inorganic multi-layer of the present invention shown in Example 4 was used as the host compound, compared to that of the conventional alkylammonium organicized as shown in Comparative Example 3 , 235TMP, a guest compound, can be effectively adsorbed and maintained, and in Example 4, 4.2 times the guest compound of Comparative Example 3 can be adsorbed per unit host compound. In addition, since the spacing of the bottom surface of the layered inorganic compound was enlarged after the guest compound was complexed, most of the adsorbed guests were intercalated between the layers.

In the 235TMP release test performed using the combination agents of Example 4 and Comparative Example 3 in Table 3, based on the measured 235 TMP concentration in the octane, the amount of 235 TMP adsorbed in the initial host-guest combination agent was determined from the host-guest combination agent. Table 4 shows that the ratio of the released guest compound was calculated as the release rate and expressed over time.

[Table 4]

In Table 4, in Example 4, the release rate of 235TMP gradually increased with the passage of time, and it is shown that the guest compound was sustained in the test solvent octane.

On the other hand, according to the conventional technique of Comparative Example 3, after many guest compounds were released until 1 hour later, the guest compounds were not released in a state adsorbed in the layered inorganic compound and were not released sustained.

As described above, by using the layered inorganic compound modified between layers with the organic-inorganic multi-function device of the present invention as a host compound, a desired guest compound can be efficiently stored and the release rate thereof can be controlled for sustained release.

<Example 5> Synthesis of a sustained-release composite agent in which 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as OIT) was inserted between the layers of magadite modified with a phenylsilyl group and its sustained release evaluation

(1) Preparation of a combination of PhS-magadite-PPMe and OIT

90 g of PhS-magadite-PPMe obtained in the same manner as in Example 2(4) was mixed with 200 g of methanol and 10 g of OIT, followed by stirring at 25°C for 24 hours. After that, the mixed solution was transferred to a petri dish and dried at 25°C for 16 hours to remove methanol, a solvent, and a combination of PhS-magadite-PPMe and OIT (hereinafter, PhS-magadite-PPMe/OIT). It was called a combination drug, and the active ingredient concentration of OIT: 10wt%) 　99g was obtained. The bottom surface spacing was 2.77 nm.

(2) OIT release test from PhS-magadite-PPMe/OIT combination

Example 1 (7), except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 20 mg of the PhS-magadite-PPMe/OIT combination drug obtained above, and 2.8 g of octane was changed to 20 g of octane. ), the OIT concentration in octane was analyzed.

The results are shown in Tables 5 and 6.

<Example 6> Synthesis of a sustained-release composite agent in which OIT was inserted between the layers of the interlayer modified magadite with a phenylsilyl group and a hexylsilyl group and its sustained-release evaluation

(1) Interlayer silylation by treatment of partially protonated DTMA-magadite with Ph-TRIMS and hexylsilyltrimethoxysilane (hereinafter referred to as Hx-TRIMS) (introduction of phenyl and hexyl groups)

DTMA-magadite 100g was changed to partially protonated DTMA-magadite 100g obtained in the same manner as in Example 2(1), and MAC-TRIMS 39.2g was changed to Ph-TRIMS 132g and Hx-TRIMS (Tokyo Chemical Industry Co., Ltd. (Product of) silylation (hereinafter referred to as PhS-HxS-magadite) 108 g was obtained by performing interlayer silylation in the same manner as in Example 1 (3) except having changed to 137 g.

As a result of calculating the composition of PhS-HxS-magadite obtained using the above elemental analyzer, thermogravimetric analyzer, and nuclear magnetic resonance device (JNM-ECA400, manufactured by Japan Electronics Co., Ltd.), PhS _0.45 HxS _0.24 DTMA _0.71 Me _0.60 Si ₁₄ O ₂₉ ·nH ₂ 0.

In addition, as above, the bottom surface spacing of the obtained PhS-HxS-magadite was calculated and found to be 2.35 nm.

(2) Removal of residual DTMA group of Ph-HxS-magadite using hydrogen chloride and methanol and introduction of methyl group (encapsulation of silanol)

The DTMA group was removed in the same manner as in Example 2(3), except that 100 g of PhS-magadite was changed to 100 g of PhS-HxS-magadite, and silanol derived from magadite was O-methylated PhS-HxS -76 g of magadite (hereinafter referred to as PhS-HxS-magadite-PPMe) was obtained.

As described above, the composition of the obtained PhS-HxS-magadite-PPMe was calculated, and as a result, PhS _0.45 HxS _0.24 DTMA _0.18 Me _1.13 Si ₁₄ O ₂₉ nH ₂ O was found, and the bottom surface spacing was 1.95 nm.

(3) Preparation of a combination of PhS-HxS-magadite-PPMe and OIT

A combination of PhS-HxS-magadite-PPMe and OIT in the same manner as in Example 5(1), except that 90 g of PhS-magadite-PPMe was changed to 90 g of PhS-HxS-magadite-PPMe (hereinafter It was called PhS-HxS-magadite-PPMe/OIT complex and the active ingredient concentration of OIT: 10 wt%) 95 g was obtained. The spacing of the bottom surface was 2.66 nm.

(4) OIT release test from PhS-HxS-magadite-PPMe/OIT complex

The OIT concentration in octane was adjusted in the same manner as in Example 5(2), except that 20 mg of the PhS-magadite-PPMe/OIT composite agent was changed to 20 mg of the PhS-HxS-magadite-PPMe/OIT composite agent obtained above. Analyzed.

The results are shown in Tables 5 and 6.

<Example 7> Synthesis of a sustained-release composite agent in which OIT was inserted between layers of margadite modified with a phenylsilyl group and a 3-mercaptopropylsilyl group, and its sustained-release evaluation

(1) Ph-TRIMS of partially protonated DTMA-magadite and 3-mercaptopropylsilyltrimethoxysilane (hereinafter referred to as MP-TRIMS) interlayer silylation (introduction of phenyl group and mercaptopropyl group) )

Silylation magadite (later PhS-MPS-Maga) was carried out in the same manner as in Example 6(1), except that 137 g of Hx-TRIMS was changed to 123 g of MP-TRIMS (manufactured by Shin-Etsu Chemical Co., Ltd.). It is called Dite) 104g was obtained.

As described above, the composition of the obtained PhS-MPS-magadite was calculated, as a result, PhS _0.62 mercaptopropylsilyl (MPS) _0.61 DTMA _0.27 Me _0.50 Si ₁₄ O ₂₉ ·nH ₂ O, and the bottom surface spacing was 2.15 nm.

(2) Removal of residual DTMA group in PhS-MPS-magadite using hydrogen chloride and methanol and introduction of methyl group (encapsulation of silanol)

The DTMA group was removed in the same manner as in Example 2(3), except that 100 g of PhS-magadite was changed to 100 g of PhS-MPS-magadite, and the silanol derived from magadite was O-methylated PhS-MPS -93 g of magadite (hereinafter referred to as PhS-MPS-magadite-PPMe) was obtained.

As described above, the composition of the obtained PhS-HxS-magadite-PPMe was calculated, and as a result, PhS _0.62 MPS _0.61 DTMA _0.19 Me _0.58 Si ₁₄ O ₂₉ nH ₂ O was found, and the bottom surface spacing was 2.15 nm.

(3) Preparation of a combination of PhS-MPS-magadite-PPMe and OIT

A combination of PhS-MPS-magadite-PPMe and OIT in the same manner as in Example 5(1), except for changing PhS-magadite-PPMe 90g to PhS-MPS-magadite-PPMe 90g (hereinafter , PhS-MPS-magadite-PPMe/OIT complex, and the active ingredient concentration of OIT: 10 wt%) 98 g was obtained. The spacing of the bottom surface was 2.48 nm.

(4) OIT release test from PhS-MPS-magadite-PPMe/OIT complex

The OIT concentration in octane was adjusted in the same manner as in Example 5(2), except that 20 mg of the PhS-magadite-PPMe/OIT composite agent was changed to 20 mg of the PhS-MPS-magadite-PPMe/OIT composite agent obtained above. Analyzed.

The results are shown in Tables 5 and 6.

<Example 8> Synthesis of a sustained-release composite agent in which OIT was inserted between layers of margadite modified with 3-mercaptopropylsilyl group and its sustained-release evaluation

(1) Interlayer silylation by MP-TRIMS treatment of partially protonated DTMA-magadite (introduction of mercaptopropyl group)

Examples except that 100 g of DTMA-magadite was changed to 100 g of partially protonated DTMA-magadite obtained in the same manner as in Example 2 (1), and 39.2 g of MAC-TRIMS was changed to 245 g of MP-TRIMS. In the same manner as in 1(3), interlayer silylation was performed to obtain 97 g of silylated magadite (hereinafter referred to as MPS-magadite).

As described above, the composition of the obtained MPS-magadite was calculated, and as a result, MPS _0.95 DTMA _0.30 Me _0.75 Si ₁₄ 0 ₂₉ nH ₂ O was found, and the bottom surface spacing was 2.22 nm.

(2) Removal of residual DTMA group of MPS-magadite using hydrogen chloride and methanol and introduction of methyl group (encapsulation of silanol)

The DTMA group was removed in the same manner as in Example 2(3), except that 100 g of PhS-magadite was changed to 100 g of MPS-magadite, and the silanol derived from magadite was O-methylated MPS-magadite. 93 g (hereinafter referred to as MPS-magadite-PPMe) was obtained.

As described above, the composition of the obtained MPS-magadite-PPMe was calculated, and as a result, MPS _0.95 DTMA _0.23 Me _0.82 Si ₁₄ O ₂₉ nH ₂ O was found, and the bottom surface spacing was 2.21 nm.

(3) Preparation of a combination of MPS-magadite-PPMe and OIT

In the same manner as in Example 5(1), except that 90g of PhS-magadite-PPMe was changed to 90g of MPS-magadite-PPMe, a combination of MPS-magadite-PPMe and OIT (hereinafter, MPS-magaite It was called Dite-PPMe/OIT complex and the active ingredient concentration of OIT: 10 wt%) 95 g was obtained. The bottom surface spacing was 2.51 nm.

(4) OIT release test from MPS-magadite-PPMe/OIT complex

The OIT concentration in octane was analyzed in the same manner as in Example 5(2), except that 20 mg of the PhS-magadite-PPMe/OIT composite agent was changed to 20 mg of the MPS-magadite-PPMe/OIT composite agent obtained above. .

The results are shown in Tables 5 and 6.

<Comparative Example 4> Synthesis of a sustained-release composite agent in which OIT is inserted between layers of magadite modified between layers with a DTMA machine and its sustained-release evaluation

(1) DTMA-Preparation of a combination of magadite and OIT

A combination of DTMA-magadite and OIT in the same manner as in Example 5 (1), except that 90 g of PhS-magadite-PPMe was obtained as in Example 1(2) and changed to DTMA-magadite 90g. (After that, it was referred to as DTMA-magadite/OIT complex and OIT active ingredient concentration: 10 wt%) 99 g was obtained. The bottom surface spacing was 3.99 nm.

(2) OIT release test from DTMA-magadite/OIT combination

The OIT concentration in octane was analyzed in the same manner as in Example 5(2), except that 20 mg of the PhS-magadite-PPMe/OIT composite agent was changed to 20 mg of the DTMA-magadite/OIT composite agent obtained above.

The results are shown in Tables 5 and 6.

[Table 5]

As shown in Table 5, when the layered inorganic compound modified between layers with the organic-inorganic composite group of the present invention is used as the host compound, and when the layered inorganic compound is interlayered with the conventional alkyl ammonium group is used as the host compound, the guest compound is It can be seen that all OITs are intercalated between the layers.

In the OIT emission test conducted using the combination agents of Examples 5 to 8 and Comparative Example 4 in Table 5, based on the measured OIT concentration in the octane, the amount of OIT adsorbed in the initial host-guest combination -Table 6 shows the ratio of the guest compound released from the guest combination agent as the release rate and expressed over time.

[Table 6]

In Table 6, in Examples 5 to 8, the release rate of the guest compound, OIT, gradually increased with the passage of time, indicating that the guest compound was sustained release in the test solvent, octane.

On the other hand, in the conventional technique of Comparative Example 4, almost all of the guest compounds were released until 1 hour later, and sustained release was not possible.

In addition, comparing Examples 5 to 8 shows that the sustained release rate of the guest compound can be changed by changing the interlayer modifier of the host compound and appropriately combining a plurality of modifiers.

As described above, by using the layered inorganic compound modified between layers with the organic-inorganic multi-function device of the present invention as a host compound, a desired guest compound can be efficiently stored and the release rate thereof can be controlled for sustained release.

<Example 9> 1-(1-methylpropoxycarbonyl)-2-(2-hydroxyethyl)piperidine (hereinafter, icaridine) between the layers of magadite modified with a phenylsilyl group and a hexylsilyl group (referred to as icaridin)) and its sustained-release evaluation

(1) Preparation of a combination of PhS-HxS-magadite-PPMe and icaridine

In the same manner as in Example 6(3), except that 10 g of OIT was changed to 10 g of icaridine (manufactured by CombiBloc), a combination of PhS-HxS-magadite-PPMe and igoridine (hereinafter, PhS-HxS-Maga It was called Dite-PPMe/icaridine complex, and the active ingredient concentration of Igaridine: 10 wt%) 97 g was obtained. The spacing of the bottom surface was 2.28 nm.

(2) Icaridine release test from PhS-HxS-magadite-PPMe/icaridine combination drug

40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 20 mg of the PhS-HxS-magadite-PPMe/icaridine combination drug obtained above, and 2.8 g of octane was replaced with a 2.4% aqueous citric acid solution (2.5 g of citric acid was 100 g of pure water. Dissolved and prepared)) The concentration of icaridine in the 2.4% citric acid aqueous solution was analyzed in the same manner as in Example 1 (7), except that the stirring temperature was changed to 20 g and the stirring temperature was changed from 25°C to 40°C.

The results are shown in Tables 7 and 8.

<Comparative Example 5>

Synthesis of a sustained-release composite with icaridine inserted between layers of interlayer modified magadite with DTMA and its sustained-release evaluation

(1) Preparation of a combination of DTMA-magadite and icaridine

In the same manner as in Example 3(1), except that 10 g of OIT was changed to 10 g of icaridine, a combination drug of DTMA-magadite and icaridine (hereinafter referred to as a DTMA-magadite/icaridine combination drug, and the effectiveness of icaridine Ingredient concentration: 10wt%) to obtain 96g. The bottom surface spacing was 3.55 nm.

(2) DTMA-magadite/icaridine release test from combination drug

Icaridine concentration in 2.4% citric acid aqueous solution was analyzed in the same manner as in Example 7(2), except that 20 mg of the DTMA-magadite/OIT combination drug was changed to 20 mg of the DTMA-magadite/icaridine combination drug obtained above. did.

The results are shown in Tables 7 and 8.

[Table 7]

As shown in Table 7, when the host compound is a layered inorganic compound modified between layers with the organic-inorganic composite group of the present invention, and when the layered inorganic compound is interlayered with a conventional alkyl ammonium group is used as the host compound, the guest compound is It can be seen that all of the icaridines are intercalated between the layers.

In the icaridine release test conducted using the combination agents of Example 9 and Comparative Example 4 in Table 7, based on the measured concentration of icaridine in the 2.4% citric acid aqueous solution, the amount of icaridine adsorbed in the initial host-guest combination agent On the other hand, the ratio of the guest compound released from the host-guest combination agent was calculated as the release rate and expressed over time is shown in Table 8.

[Table 8]

As shown in Example 9 of Table 8, the composite formulation containing the layered inorganic compound modified between the layers through covalent bonds by the organic-inorganic composite group of the present invention as a host compound, sustained release while effectively maintaining the guest compound icaridine in an acidic solution. did. On the other hand, in the case of the conventional alkyl ammonium of Comparative Example 5 using a layered inorganic compound as a host compound, the guest compound, icaridine, was released in a considerable amount of citric acid aqueous solution after 1 hour compared to Example 7. Was not sustained release, but rather the concentration in the citric acid aqueous solution decreased. This is inferred from Comparative Example 5 because the interlayer is modified with alkyl ammonium through ionic bonds, so it is easy to be influenced by the pH environment around the composite agent, and the release of alkylammonium from the interlayer or re-adsorption of icaridine occurred. Indicates that the material is not suitable.

<Example 10> Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (hereinafter referred to as Irganox 1010) between layers of margadite modified with a phenylsilyl group. The synthesis of a sustained-release combination drug with insert) and its sustained-release evaluation

(1) Preparation of a combination of PhS-magadite-PPMe and Irganox 1010

A combination of PhS-magadite-PPMe and Irganox 1010 (hereinafter, PhS-magadite-PPMe) was carried out in the same manner as in Example 5(1), except that 10 g of OIT was changed to 10 g of Irganox 1010 (product of BASF Japan). /Irganox 1010 combination drug, and the active ingredient concentration of the Irganox 1010 combination drug: 10 wt%) 97 g was obtained. The bottom surface spacing was 1.93 nm.

(2) Irganox 1010 release test from PhS-magadite-PPMe/Irganox 1010 combination

Example 1 except that 40 mg of the P-MACPS-PhS-magadite/2MT combination drug was changed to 20 mg of the PhS-magadite-PPMe/Irganox 1010 combination drug obtained above, and 2.8 g of octane was changed to 20 g of octane. As in 7), the concentration of Irganox 1010 in octane was analyzed. The results are shown in Table 9 and Table 10.

<Comparative Example 6>

Synthesis of a sustained-release combination drug in which Irganox 1010 is combined between layers of interlayer modified magadite with DTMA and its sustained-release evaluation

(1) DTMA-Preparation of a combination of magadite and Irganox 1010

In the same manner as in Example 3(1), except for changing OIT 10g to Irganox 1010 10g, a combination of DTMA-magadite and Irganox 1010 (hereinafter referred to as a combination of DTMA-magadite/Irganox 1010 and called Irganox 1010 combination The active ingredient concentration of: 10wt%) to obtain 95g. The spacing of the bottom surface was 2.86 nm.

(2) DTMA-Irganox 1010 release test from magadite/Irganox 1010 combination drug

In the same manner as in Example 10(2), the concentration of Irganox 1010 in the octane was analyzed as in Example 10(2), except that 20 mg of the PhS-magadite-PPMe/Irganox 1010 combination drug was changed to 20 mg of the obtained DTMA-magadite/Irganox 1010 combination drug. did. The results are shown in Table 9 and Table 10.

[Table 9]

As shown in Table 9, when the layered inorganic compound modified with the organic-inorganic multi-layer of the present invention of Example 10 was used as the host compound, the spacing of the bottom surface was increased before and after adsorption of the guest compound Irganox 1010, and between the layers It can be seen that Irganox 1010 is intercalated.

On the other hand, when the layered inorganic compound organically interlayered with the conventional alkyl ammonium of Comparative Example 6 was used as the host compound, the spacing of the bottom surface did not change before and after the adsorption of the guest compound Irganox 1010, and Irganox 1010 intercalated between the layers. It cannot be judged that it is, and there is a possibility that the intercalation will not occur.

In the Irganox 1010 release test conducted using the combination agents of Example 10 and Comparative Example 6 in Table 9, based on the measured concentration of Irganox 1010 in the octane, the amount of Irganox 1010 adsorbed in the initial host-guest combination -The ratio of the guest compound released from the guest composite agent was calculated as the release rate, and the values expressed over time are shown in Table 10.

[Table 10]

In Table 10, in Example 10, the release rate of Irganox 1010 gradually increased with the passage of time, indicating that the guest compound was sustained in octane, which is a test solvent.

On the other hand, in the conventional technique of Comparative Example 6, almost all of the guest compounds were released until 1 hour later and were not sustained release.

As described above, by using the layered inorganic compound modified between layers with the organic-inorganic multifunction device of the present invention as a host compound, even very large molecules such as Irganox 1010 can be efficiently stored between the layers, and sustained release can be performed by controlling the release rate. .

<Example 11> Mold removal test of a resin injected by kneading a PhS-HxS-magadite-PPMe/OIT composite agent (sustained-release mold remover)

(1) Preparation of resin test piece

2.5cm

2mm 크기의 시험편을 잘라냈다.40 g of polyethylene resin (UBE polyethylene J3519 manufactured by Ube Maruzen Polyethylene, hereinafter referred to as PP resin) was dissolved in a heating mill, while stirring at 140°C. To this, 0.4 g of the PhS-HxS-magadite-PPMe/OIT composite agent synthesized in Example 6 was added and stirred for 15 minutes, and the obtained mixture was put into a mold, pressed at 160° C. for 5 minutes, and then allowed to cool (放冷) To form a 2mm thick plate. 2.5cm in this

2.5cm

A 2 mm-sized test piece was cut out.

(2) Heat deterioration treatment of resin test piece

The test piece prepared in the above (1) was allowed to stand for 96 hours in a ventilating dryer at 80° C., and then allowed to stand at 25° C. for 17 days.

(3) Hot water immersion deterioration treatment of resin test piece

The test piece prepared in (1) was weighed and placed in a 1L poly bottle containing 1L of pure water, and the test piece was completely immersed in water, and then the lid of the polybottle was closed and heated at 60°C for 120 hours. In the meantime, hot water immersion was started, and water was replaced with pure water after 24 hours and 96 hours, respectively.

(4) Mold removal test (Halo test)

: 발육 저지대가 형성되었음(곰팡이 제거효과 있음),

: 발육 저지대가 형성되지 않았음(곰팡이 제거효과 없음)을 의미한다.The molds used for the evaluation of mold removal were black mold (Cladosporium cladospolioides), blue mold (Penicillium funiculosum), and black yeast mold (Aspergills niger), and spores were added to the inorganic salt solution of the composition shown in Table 11, and each The number of spores was adjusted to be around 10 ⁵ /mL to obtain a spore mixed suspension. 150 μL of the spore mixture suspension was inoculated evenly on an agar medium of potato glucose having a diameter of 9 cm, and the test pieces prepared in the above (1) to (3) were placed in close contact with each other near the center of the above. This was cultured for 3 days at 25° C. and a humidity of 90% or more to check whether or not a growth inhibition zone was formed, thereby evaluating the mold removal property. Table 12 shows the evaluation results. The symbols in the table are,

: Growth inhibition zone was formed (fungus removal effect),

: It means that the growth retardation zone was not formed (no mold removal effect).

<Comparative Example 7> Mold removal test of resin injected by kneading OIT (a mold-removing organic compound as a guest compound)

A test piece was prepared in the same manner as in Example 11, except that 0.4 g of the PhS-HxS-magadite-PPMe/OIT composite was changed to 0.04 g of OIT, and accelerated deterioration treatment and hot water immersion treatment were performed. It carried out the mold removal test. The results are shown in Table 12.

<Comparative Example 8> Mold removal test of resin injected by kneading PhS-HxS-magadite-PPMe (interlayered layered inorganic compound as a host compound)

A test piece was prepared in the same manner as in Example 11, except that 0.4 g of the PhS-HxS-magadite-PPMe/OIT composite agent was changed to 0.36 g of PhS-HxS-magadite-PPMe, and accelerated deterioration treatment and hot water immersion Deterioration treatment was performed to perform a mold removal test. The results are shown in Table 12.

[Table 11]

[Table 12]

As shown in Table 12, the test piece obtained by kneading and injecting the OIT of Comparative Example 7 alone into PP resin initially exhibited a mold-removing effect by observing a mold-removal effect, but after a deterioration test by heating and hot water immersion All of the lowlands were not observed at all and did not show the effect of removing mold. On the other hand, in the test specimen in which the sustained-release mold remover of the present invention of Example 11 was kneaded and injected into PP resin, low-lying zones were observed not only in the initial stage but also after deterioration treatment by heating and hot water immersion, and the mold removal effect was confirmed. This indicates that when the layered inorganic compound modified between layers with the organic-inorganic multi-function device of the present invention is used as a host compound, it is possible to impart sustained release properties to the mold-removing organic compound, while providing heat resistance and hot water resistance, and practical sustained-release mold It indicates that it can be used as a remover.

As described above, by using the layered inorganic compound modified with the organic-inorganic multi-layer of the present invention as the host compound, it is possible to appropriately design the interlayer environment corresponding to the guest compounds having various structures or molecular weights, so the application range is very wide and the desired guest The compound can be intercalated between layers, and a sustained-release composite agent capable of controlling the sustained-release rate according to the purpose. In addition, since the host compound is a layered inorganic compound modified between layers by an organic-inorganic composite group through a covalent bond, environmental resistance such as heat resistance, water resistance, and acid resistance can be imparted to the guest compound. According to the present invention, the function derived from the guest compound can be effectively expressed depending on the conditions of use.

Claims (6)

A sustained-release comprising a layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) between the layers of the layered inorganic compound, and a compound inserted between the layers of the layered inorganic compound (徐放性) combination drug.
[Formula 1]

(In formula (1), M ¹ and M ² each independently represent Si, Al, Ti or Zr, and R ^a and R ^b are each independently a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, A saturated or unsaturated cycloalkylene group, which may have a branched chain having 3 to 20 carbon atoms, an allylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms, R ^c represents an organic group consisting of 1 to 40 carbon atoms, and a hetero atom , A linear structure, a branched structure, a cyclic structure, an unsaturated bond, and an aromatic structure may be included, and R is a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and a saturated may have a branched chain having 3 to 8 carbon atoms. Or an unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, respectively, a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a carbon number 1 to 20 linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group, monoarylamino group or diarylamino group having 6 to 20 carbon atoms, monoaralkylamino group or diarylalkylamino group having 7 to 20 carbon atoms, first Grade, secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphate ester group, sulfonic acid May be substituted with a group, a sulfonic acid ester group, or a halogen atom Z is a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, or a saturated or unsaturated cycloalkyl which may have a branched chain having 3 to 8 carbon atoms. Oxy group, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy group, which may have a branched chain having 1 to 8 carbon atoms, halogen atom, hydroxyl group, amino group, linear or branched chain saturated with 1 to 6 carbon atoms Or an unsaturated alkylamino group, a straight or branched chain having 1 to 6 carbon atoms Represents an oxygen atom derived from a substituted or unsaturated dialkylamino group or a layered inorganic compound, and when M ¹ and M ² are either Si, Ti or Zr, the corresponding x is 2 and n is an integer of 0 to 2 (integer), and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1, and when n is 2, R may be the same or different, and p, q and r are 0 Or an integer of 1, and at least one of them is 1.)
[Formula 2]

(In formula (2), R is a C 1 to C 20 linear or branched saturated or unsaturated alkyl group, a C 3 to C 8 branched saturated or unsaturated cycloalkyl group, a C 6 to C 20 aryl group or a C 7 to C Represents an aralkyl group of 20, each of which is a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group having 1 to 20 carbon atoms. Or a dialkylamino group, a monoarylamino group or diarylamino group having 6 to 20 carbon atoms, a monoaralkylamino group or diarylamino group having 7 to 20 carbon atoms, a primary, secondary, tertiary or quaternary ammonium group, thiol Group, isocyanurate group, ureide group, isocyanate group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphate ester group, sulfonic acid group, sulfonic acid ester group or halogen atom may be substituted. , Al, Ti or Zr, Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 branched chains, trimethylsilyloxy group, dimethyl A silyloxy group, a saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated alkylamino group having 1 to 6 carbon atoms, and 1 to 6 carbon atoms Represents an oxygen atom derived from a linear or branched saturated or unsaturated dialkylamino group or a layered inorganic compound, and when M is any one of Si, Ti or Zr, the corresponding x is 3, and n is 1 to It is an integer of 3, and when M is Al, the corresponding x is 2, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.) The method of claim 1,
In the organic-inorganic composite group, both of M ¹ and M ² in the formula (1) are Si or M in the formula (2) is Si. The method according to claim 1 or 2,
Sustained release containing at least one selected from the group consisting of a carboxylic acid ester structure, a urethane structure, a urea structure, an amine structure, an ether structure, a thioether structure, a disulfide structure, and a hydroxyl group in the organic-inorganic composite group represented by formula (1) Sex combination. The method according to any one of claims 1 to 3,
The compound inserted between the layers of the interlayered layered inorganic compound comprises at least one selected from the group consisting of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond generator, a coordination bond generator, and an ionic bond generator. A compound sustained-release combination. The method according to any one of claims 1 to 4,
The sustained-release composite agent, wherein the layered inorganic compound comprises one selected from the group consisting of layered silicates, layered clay minerals, and layered metal oxides. In the manufacturing method of the sustained-release composite agent according to any one of claims 1 to 5,
The method for producing a sustained-release composite agent, characterized in that mixing the interlayered layered inorganic compound and a compound inserted between the layers of the interlayered layered inorganic compound.