CN111511868A

CN111511868A - Slow-release complex agent comprising interlaminar-modified layered inorganic compound and method for producing same

Info

Publication number: CN111511868A
Application number: CN201880083490.2A
Authority: CN
Inventors: 北村昭宪; 熊谷伸哉; 桥本真由子
Original assignee: Toagosei Co Ltd
Current assignee: Toagosei Co Ltd
Priority date: 2018-01-23
Filing date: 2018-12-13
Publication date: 2020-08-07
Anticipated expiration: 2038-12-13
Also published as: KR20200112817A; CN111511868B; WO2019146304A1; JP7028263B2; JPWO2019146304A1; KR102662678B1

Abstract

The purpose of the present invention is to provide a sustained-release composite agent which is designed between layers by introducing a chemically stable organic-inorganic composite group having various chemical structures between the layers of a layered inorganic compound, creates an environment in which a desired functional compound to be sustained-released interacts appropriately between the layers, and releases the functional compound over a long period of time after the functional compound is inserted between the layers, and a method for producing the same. A sustained-release complex agent is provided in a layer of a layered inorganic compoundThe interlayer contains an interlayer modified layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) and a compound interposed between the layers of the interlayer modified layered inorganic compound.

Description

Slow-release complex agent comprising interlaminar-modified layered inorganic compound and method for producing same

[ technical field ]

The present invention relates to a sustained-release complex agent in which a compound is inserted between layers of a layered inorganic compound which has been modified between layers, and a method for producing the same.

[ background art ]

As sustained-release materials for releasing a functional compound inserted between layers of a layered inorganic compound, there are known: a complexing agent which uses a non-modified lamellar inorganic compound as a host compound and an ionized functional compound as a guest compound, and inserts the functional compound between the layers of the host compound by ion exchange between exchangeable ions present between the layers and the ionized guest compound, thereby achieving sustained release; and a complexing agent which is prepared by exchanging exchangeable metal cations present between the layers of the layered inorganic compound with alkylammonium to organize (hydrophobize) the layers, inserting a functional compound between the layers, and releasing the functional compound.

For example, patent document 1 describes a complexing agent and a method for producing the same, as follows: the layered double hydroxide having no modification between layers is used as a host compound, and an anionic capsaicin is mixed therein as a guest compound, and a nitrate ion, which is an anion present between layers, is exchanged to prepare a layered double hydroxide-anionic capsaicin (host-guest) complex, whereby the capsaicin as a guest compound is slowly released.

Patent document 2 describes sustained-release simetryn granules using organized bentonite that has been organized interlaminar by cation exchange between exchangeable metal cations between layers of the clay mineral montmorillonite and dimethyldioctadecylammonium as a host compound and containing neutral simetryn as a guest compound, and a method for producing the same.

Documents of the prior art

Patent document

Patent document 1: japanese patent No. 5688727

Patent document 2: japanese patent laid-open publication No. 2004-26705

[ summary of the invention ]

Problems to be solved by the invention

However, in the case of using a layered inorganic compound containing no modification and exchangeable metal cations as a host compound described in patent document 1, only an ionized guest compound is used as a compound to be slowly released, a nonionic compound cannot be inserted to perform slow release, and the slow release cannot be controlled by designing the interlayer environment as desired depending on the guest compound, and therefore, the release rate cannot be adjusted to an arbitrary compound to perform slow release.

In addition, in the organic modification based on alkylammonium described in patent document 2, since the interlayer environment of the host compound cannot be diversified only by hydrophobization, the interaction between any desired guest compound and the layered inorganic compound cannot be controlled depending on the use application, it is difficult to design and synthesize the interlayer environment so that the insertion into the interlayer and the rate of sustained release from the interlayer become optimal, and the compound capable of sustained release is limited.

Further, since interlayer modification is based on alkylammonium, a cation exchange reaction between layers is likely to proceed under the influence of a use environment such as acidic conditions, and the alkylammonium group is likely to be released from between layers. Therefore, the conditions for using such a sustained-release agent using an organically modified host compound are limited, and it is difficult to maintain the interlayer modified structure of the organically modified layered inorganic compound in use for a relatively long time, and thus it is not practical as a sustained-release agent.

Further, since the interlayer of the layered inorganic compound as the host compound of patent document 1 and patent document 2 is not crosslinked, the layered structure is broken and peeled off depending on the use environment, and the inserted guest compound is released immediately, and thus the use and environment of using the complexing agent as a sustained-release agent are extremely limited, not general-purpose, and not industrially useful.

In view of the above circumstances, an object of the present invention is to provide a sustained-release composite which is released over a long period of time after a desired compound to be sustained-released is inserted between layers of a layered inorganic compound which is interlaminar crosslinked via a covalent bond or a layered inorganic compound which is interlaminar modified via a covalent bond, and a method for producing the same.

Means for solving the problems

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a sustained-release complexing agent which comprises an interlayer crosslinked layered inorganic compound having an organic-inorganic complex crosslinked structure between layers of the layered inorganic compound, or an interlayer modified layered inorganic compound obtained by modifying an interlayer of the layered inorganic compound with an organic-inorganic complex group such as a silyl group as a host compound and inserting a functional compound between the layers as a guest compound can solve the above-mentioned problems, and have accomplished the present invention.

That is, the present invention is a sustained-release composite agent comprising an interlayer modified layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) and a compound interposed between the layers of the interlayer modified inorganic compound, between the layers of the layered inorganic compound.

[ chemical formula 1]

(in the formula (1), M¹And M²Each independently represents Si, Al, Ti or Zr; r^aAnd R^bEach independently represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 3 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms; r^cRepresents an organic group having 1 to 40 carbon atoms, and optionally contains a hetero atom, a linear chain structure, a branched chain structure, a cyclic structure, an unsaturated bond and an aromatic structure; r represents a straight chain or branched chain of 1 to 20 carbon atomsA saturated or unsaturated alkyl group in a chain, a saturated or unsaturated cycloalkyl group optionally having a branched chain of 3 to 8 carbon atoms, an aryl group of 6 to 20 carbon atoms, or an aralkyl group of 7 to 20 carbon atoms, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group of 1 to 20 carbon atoms, a monoarylamino group or diarylamino group of 6 to 20 carbon atoms, a monoaralkyl amino group or diaralkylamino group of 7 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid group, a sulfonate group. Z represents a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group optionally having a branched chain having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group optionally having 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, 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; at M¹And M²When any one of Si, Ti or Zr, x corresponding to the Si, Ti or Zr is 2, and n is an integer of 0-2; at M¹And M²In the case of Al, x corresponding thereto is 1, and n is 0 or 1; in case n is 2, R is optionally the same or different; p, q and r are integers of 0 or 1, and at least one of them is 1. )

[ chemical formula 2]

(in the formula (2), R represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and is substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, a monoarylamino group or diarylamino group having 6 to 20 carbon atoms, a monoarylamino group or diarylamino group having 7 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an isocyanato group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, an ester group, a carboxyl group, a salt group, a, Sulfonic acid group, sulfonate group or halogen atom. M represents Si, Al, Ti or Zr; z represents a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group optionally having a branched chain having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group optionally having 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, 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; when M is any one of Si, Ti or Zr, x corresponding to M is 3, and n is an integer of 1-3; in the case where M is Al, x corresponding thereto is 2, and n is 1 or 2; in case n is 2 or 3, R is optionally the same or different. )

The present invention also provides a method for producing a sustained-release composite agent, characterized by mixing an interlayer modified layered inorganic compound with a compound inserted between the interlayers of the interlayer modified layered inorganic compound.

[ Effect of the invention ]

In the sustained-release composite of the present invention, the interlayer crosslinking-type layered inorganic compound having the organic-inorganic composite crosslinked structure represented by the above formula (1) between the layers has various crosslinked structures, and thus various interlayer distances can be established, and an appropriate space can be established between the layers according to the purpose, so that the insertion of the guest compound into the layers can be controlled, and the release rate from the layers can be controlled. Further, since the interlayer crosslinking agent itself having a long-chain alkylene structure or the like has flexibility, even if it is the same interlayer crosslinking-type layered inorganic compound, the interlayer distance can be flexibly changed depending on various guest compounds to be controlled to release a desired amount of time.

Further, since the crosslinked structure itself has various functional groups, the interlayer environment (atmosphere in which the crosslinked structure interacts with the guest compound) is very diverse, and various functional groups suitable for insertion and sustained release of desired various functional compounds into the interlayer, for example, a hydrophobic group or a hydrophilic group such as a saturated or unsaturated aliphatic group, an aromatic group or a heterocyclic group, a hydrogen bond-forming group, a coordinate bond-forming group, an ionic bond-forming group, and the like can be selected to design an organic-inorganic composite crosslinked structure and introduced into the interlayer, and various desired functional compounds (guest compounds) according to the purpose can be inserted into the interlayer, and the rate of releasing the guest compounds can be controlled according to the purpose, thereby enabling sustained release according to the purpose.

Further, since the interlayer is crosslinked by covalent bonds via the crosslinked structure, it is difficult to cleave the interlayer even in the presence of alkali, acid, or the like.

Further, the interlayer crosslinking type layered inorganic compound having an organic-inorganic composite crosslinked structure between layers is obtained by passing M¹Or M²(M¹Or M²Since covalent bonds such as Si, Ti, Zr, or Al) -O-Si (Si is derived from a layered inorganic compound) bond crosslink the interlayer, chemical stability is very high in various environments such as acidic and alkaline conditions, and cleavage is difficult. Therefore, the crosslinked structure can be present between the layers for a practically sufficient time, the intercalated guest compound can be released immediately without breaking and peeling the layer structure, and the compound intercalated between the layers can be retained for a practically prolonged period of time and sustained release can be achieved in various environments and applications.

Further, as described above, since the interlayer crosslinking type lamellar inorganic compound has extremely high chemical stability, the compound interposed between the layers can be protected from the external environment, and heat resistance, water resistance, ultraviolet resistance and the like can be imparted, not only the compound having low heat resistance, water resistance, ultraviolet resistance and the like can be slowly released, but also the slow-release compound can be kneaded and molded in a resin or the like and used in various environments such as an environment in which the compound is used in water or under humid conditions, or under outdoor sunlight irradiation.

Therefore, various crosslinked structures can be introduced between layers, so that the interlayer distance can be set widely according to the purpose, and the sustained-release composite agent can realize 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 whose interlayer is modified with the organic-inorganic composite group represented by the following formula (2) can be obtained as an organic-inorganic composite modifier including a silylating agent having various functional groups as an interlayer modifier, therefore, the interlayer environment (atmosphere in which the guest compound interacts) is very diverse, and various interacting groups suitable for insertion and sustained release of desired various compounds into the interlayer, for example, a hydrophobic group or a hydrophilic group such as a saturated or unsaturated aliphatic group, an aromatic group or a heterocyclic structure group, a hydrogen bond-forming group, a coordinate bond-forming group, an ionic bond-forming group, and other various functional groups can be selected to design and modify the interlayer, and various desired functional compounds (guest compounds) according to the purpose can be inserted into the interlayer to achieve sustained release.

Further, since the interlayer modified layered inorganic compound is modified with a functional group (interlayer modifying group) that interacts with a guest compound via a covalent bond such as a M (M is Si, Ti, Zr, or Al) -O-Si (Si is derived from a layered inorganic compound) bond, chemical stability under various environments such as acidic and alkaline conditions is very high. Therefore, the modifier group can be present between layers for a practically sufficient time without being affected by the use environment, and the compound inserted between layers can be retained for a practically long time to achieve sustained release.

Further, as described above, since the interlayer modified layered inorganic compound has extremely high chemical stability, the compound interposed between the layers can be protected from the external environment, and heat resistance, water resistance, ultraviolet resistance and the like can be imparted, not only can the compound having low heat resistance, water resistance, ultraviolet resistance and the like be slowly released, but also the slow-release composite agent can be kneaded and molded with a resin or the like and used in various environments such as water, humid conditions, or outdoor sunlight irradiation environments.

Therefore, various modifying groups can be introduced between layers, so that the interlayer distance can be set widely according to the purpose, and the sustained-release composite agent can realize insertion and sustained release of various compounds.

[ detailed description of the invention ]

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

The layered inorganic compound in the present invention is not particularly limited, and examples thereof include graphite, layered metal chalcogenides, layered metal oxides (for example, layered perovskite compounds mainly composed of titanium oxide and niobium oxide, titanium niobate, molybdate, and the like), layered metal oxyhalides, layered metal phosphates (for example, layered antimony phosphate and the like), layered clay minerals, layered silicates (for example, mica, smectite groups (montmorillonite, saponite, hectorite, fluorohectorite, and the like), kaolinite groups (kaolin and the like), magadiite, kenyaite, and the like), layered double hydroxides, and the like.

Among them, from the viewpoint of easiness of obtaining, it is preferable to use a layered silicate, a layered clay mineral, and a layered metal oxide, and natural products or synthetic products thereof may be used.

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

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

In the above formula (1), M¹And M²Is a metal capable of forming a covalent bond with an oxygen atom derived from a layered inorganic compound, and is less likely to undergo hydrolysis due to the covalent bondThe Si (silicon), Al (aluminum), Ti (titanium), and Zr (zirconium) are any of Si (silicon), Al (aluminum), Ti (titanium), and Zr (zirconium), and Si which is easily available is preferable for introducing various interacting groups.

In the organic-inorganic composite crosslinked structure represented by the above formula (1) in which the organic-inorganic composite crosslinked structure is introduced into the interlayer via a covalent bond with the lamellar inorganic compound, it is more preferable that the organic-inorganic composite crosslinked structure is bonded to the lamellar inorganic compound via a plurality of covalent bonds and M in the above formula (1) is bonded to the lamellar inorganic compound from the viewpoint of chemical stability of the bond connecting the interlayers¹And M²In the case of Si, Ti and Zr, n is more preferably 0 or 1, and M in the formula (1)¹And M²In the case of Al, n is more preferably 0, and in any case, it is more preferable that at least one Z contains an oxygen atom derived from the layered inorganic compound. Further, Z of mutually adjacent organic-inorganic composite crosslinked structures may be hydrolyzed and condensed to form M¹-O-M¹Key, M¹-O-M²Key or M²-O-M²A key.

In the organic-inorganic composite crosslinked structure, it is preferable that the organic-inorganic composite crosslinked structure contains any of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond-forming group, a coordinate bond-forming group, and an ionic bond-forming group, from the viewpoint of enabling the interaction with the guest compound to be appropriately designed. Thus, non-covalent bond interactions (for example, van der waals forces, pi-pi interactions, hydrophobic interactions, hydrogen bonds, coordinate bonds, ionic bonds, and the like) with the guest compound can be appropriately adjusted and imparted, and an arbitrary compound can be inserted between layers to achieve sustained release depending on the purpose.

The non-covalently interactive group is not particularly limited, and examples thereof include: aliphatic groups such as a saturated or unsaturated alkyl group, an alkylene group, a cycloalkyl group and a cycloalkylene group, such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, a n-octyl group, a decyl group, a dodecyl group, an octadecyl group, a methylene group, an ethylene group, a propylene group, an octamethylene group, a cyclohexyl group, a cyclohexylene group, a vinyl group and an allyl group; aromatic groups such as styryl, phenyl, naphthyl, phenylene, naphthylene, biphenylene, benzyl, and benzylene as aryl, aralkyl, arylene, and aralkylene groups; heterocyclic structural groups such as a pyridyl group, a piperidyl group, a pyrrolidinyl group (ピロジニル yl group), a pyrimidyl group, an imidazolyl group, and the like, a pyrrolyl group, an epoxy group, an oxetanyl group, a tetrahydrofuryl group, a tetrahydrothienyl group, a dioxanyl group, a morpholinyl group, a thiazinyl group, an indolyl group, a nucleic acid base group, and the like; a hydrogen bond and coordinate bond-forming group such as an acryloyloxy group, a methacryloyloxy group, an acetyl group, a benzoyl group, a hydroxyl group, a thiol group, an aldehyde group, a carboxyl group, a carboxylate methyl group, a phosphate ethyl group, a sulfonate methyl group, an amino group, a methylamino group, a dimethylamino group, an isocyanurate group, an ureido group, an isocyanate group, and an ionic bond-forming group such as an ethylammonium group, a dimethylammonium group, and a trimethylammonium group, and a carboxylate structure, a carbamate structure, a urea structure, an amine structure, an ether structure, a thioether structure, and a disulfide structure in a cross-linked main chain skeleton. From the viewpoint of ease of obtaining, methylene, ethylene, propylene, butylene, octamethylene, phenylene, biphenylene, benzylidene, carboxylate structure, carbamate structure, urea structure, amine structure, ether structure, thioether structure, and disulfide structure are preferably contained in the main chain skeleton constituting the organic-inorganic composite crosslinked structure.

Among the organic-inorganic composite crosslinked structures represented by the above formula (1), organic-inorganic composite crosslinked structures that can be constructed by reacting crosslinkable functional groups of various coupling agents are common, and therefore, the organic-inorganic composite crosslinked structures are preferable from the viewpoint of ease of introduction into the interlayer, and the organic-inorganic composite crosslinked structures represented by the following formulae (3) to (17) are more preferable.

[ chemical formula 3]

[ chemical formula 4]

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

[ chemical formula 13]

[ chemical formula 14]

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

(in formulae (3) to (17), R¹Represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched, saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, 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 ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid ester group or a halogen atom. R²And R¹³Each independently represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms; r³、R⁵、R⁶And R⁷Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r⁴Represents an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkylene group having 7 to 10 carbon atoms; r⁸、R⁹、R¹⁰And R¹²Each independently represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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; r¹¹Represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 3 to 20 carbon atoms, an arylene 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, any one of R¹¹Optionally substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, and a substituent comprising 1 to 10 atoms inclusive of these atoms; z represents a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a branched saturated or unsaturated cycloalkyloxy group optionally having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a branched saturated or unsaturated heterocycloalkyloxy group optionally 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 an oxygen atom derived from a layered inorganic compound; i is a group derived from a polymerization initiator and may be the same or different; y is a group derived from a conjugate base derived from an acid; n represents an integer of 0 to 2; m and h represent an integer of 0 or 1; k represents an integer of 0 to 4. )

The organic-inorganic composite crosslinked structure can be constructed by treating the interlayer with a coupling agent, modifying the interlayer with silylation or the like, and then subjecting the crosslinkable functional group to crosslinking reaction between the layers, and can also be constructed by: the organic-inorganic composite crosslinking agent having two or more hydrolyzable sites is prepared by crosslinking crosslinkable functional groups of a coupling agent in advance, or reacting a grignard reagent with a hydrolyzable metal compound, and the organic-inorganic composite crosslinking agent is inserted between layers and undergoes a modification reaction with a hydroxyl group derived from a layered inorganic compound. However, the former method of reacting crosslinkable functional groups derived from a coupling agent between layers is preferable in that there is no side reaction and no by-product gel component.

Since the production steps are less and industrially more advantageous when the crosslinkable functional groups are reacted between the layers after the layers are modified by silylation or the like to construct a crosslinked structure, and then the layers are modified with the same coupling agent and then subjected to a crosslinking reaction, the organic-inorganic composite crosslinked structure is more preferably represented by the formulae (3) to (7) and the formulae (12) to (16), and the formulae (3) to (7) and the formulae (14) to (16) are further more preferable because the crosslinking reaction is easily performed under mild conditions, various chemical structures, flexibility and rigidity can be introduced, and the crosslinking length is more diversified.

Next, the production method of the interlayer crosslinking layered inorganic compound of the present invention having the organic-inorganic composite group represented by the above formula (1) will be described in detail. Unless otherwise specified, parts represent parts by mass and% represents% by mass.

In the present invention, the lamellar inorganic compound having enlarged interlayer which is obtained by reacting exchangeable cations such as alkali metals such as sodium and potassium, and metal cations such as alkaline earth metals such as magnesium and calcium, which are present in the lamellar inorganic compound, with an organic onium salt or the like is a precursor (in the case of silylation, a silylated lamellar inorganic compound) which is silylated with a coupling agent such as a silane coupling agent and a crosslinking agent having two or more hydrolyzable silyl groups.

The precursor is a compound in which the exchangeable cations of the layered inorganic compound are substituted with onium groups in an arbitrary proportion in terms of ion exchange capacity, and when the reaction rate of silylation or the like is increased, the proportion of the onium groups is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and still more preferably 35 to 70 mol%.

Here, the ion exchange capacity means an ion exchange amount per unit weight of the ion exchanger, and is usually expressed in terms of milliequivalents per 1g of the ion exchanger (meq/g), milliequivalents per 100g of the ion exchanger (meq/100g), and a molar amount per 1kg of the ion exchanger (mol)_cPer kg), centimolar amount per 1kg of ion exchanger (cmol)_c/kg), etc.

For exampleThe chemical formula of the sodium-magadiite is Na₂Si₁₄O₂₉·nH₂O here, when n is 0, the formula weight is 903.2, and all sodium can be regarded as exchangeable cations, so the ion exchange capacity at this time can be expressed as 2.21mol_c/kg。

When a metal cation is present between layers as an exchangeable cation, the interlayer modification ratio (silylation ratio in the case of a silane coupling agent) by a coupling agent such as a silane coupling agent or a crosslinking agent is reduced, and therefore, it is preferable to reduce the metal cation by acid treatment.

Therefore, as a method for introducing an onium group between layers of the layered inorganic compound, there are a method of reacting with an onium salt having a cation exchange capacity of equivalent or more and then allowing an acid to act, a method of reacting an onium salt having a cation exchange capacity of equivalent or less in advance, and the like.

In addition, as a method for adjusting the amount of onium groups introduced between layers of the layered inorganic compound, a mixture obtained by mixing an onium salt and an acid in appropriate amounts may be reacted with the layered inorganic compound, or the onium salt may be reacted after reacting the acid in an appropriate amount (preferably, an equivalent amount lower than the cation exchange capacity) first.

In the present invention, the onium salt used for producing the precursor is not particularly limited, but organic onium salts such as organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic sulfonium, organic oxysulfonium, organic selenonium, organic non-classical carbonium (carbonium), organic azonium, organic iodonium, organic pyrylium, organic pyrrolidinium, organic classical carbonium (carbenium), organic acylonium, organic thiazolium, organic arsonium, organic antimonium, and organic tellurium are preferable, and among them, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, and organic sulfonium salts are preferable, and two or more of these onium salts may be used alone or in combination.

The organic group in the onium salt is not particularly limited, and may beExamples thereof include alkyl groups having 1 to 22 carbon atoms, aralkyl groups having 7 to 22 carbon atoms, aryl groups having 6 to 22 carbon atoms, - (CH)₂-CH(CH₃)O)_p-H radical, - (CH)₂-CH₂-O)_qAn H group, p and q are integers of 1 to 20, and are optionally substituted with a functional group such as a vinyl group, an epoxy group, an ether group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, a thiol group, an isocyanate group, a halogen atom, an amino group, a basic group such as an alkylamino group, an acidic group such as a carboxyl group, a photo-acid generating group, a thermal acid generating group, a photo-base, a thermal base, a photo-radical generating group, a thermal radical generating group, or the like.

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

R¹⁴R¹⁵R¹⁶R¹⁷N⁺X^-(18)

(in formula (18), R¹⁴、R¹⁵、R¹⁶And R¹⁷Independently represent an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms and- (CH)₂-CH(CH₃)O)_p-H radical or- (CH)₂-CH₂-O)_q-H, p and q are integers from 1 to 20, X^-Is a halide ion. )

The organic onium salt represented by the formula (18) is not particularly limited, and examples thereof include dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, triethylbenzylammonium chloride, dodecylammonium chloride, dimethyldipolyethyleneammonium chloride, dimethyldiepoxyelammonium chloride, dimethylpolyethylenepropyleneoxide ammonium chloride, dimethylstearylpolyethyleneoxide ammonium chloride, dimethylstearylpolypropyleneoxide ammonium chloride, methylstearylpolyethyleneoxide ammonium chloride, methylstearylpolypropyleneoxide ammonium chloride, benzylmethyldimethylpropyleneoxide ammonium chloride, 1-ethylpyridinium bromide, 1-octadecylpyridinium chloride, cetylpyridinium chloride, and the like, 3-methyl-1-propylimidazolium bromide, 3-methyl-1- (2-naphthyl) imidazolium chloride, triphenyl (tetradecyl) phosphonium bromide, ethyldimethylsulfonium chloride, triphenylsulfonium bromide, etc.

Among them, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, eicosyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, triethylbenzylammonium chloride and dodecylammonium chloride are preferable.

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

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

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

The water used as the solvent for the cation exchange reaction may be any of neutral, acidic and basic, and is not particularly limited, but is 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, and is 1 to 100 times by mass, more preferably 5 to 70 times by mass, and still more preferably 10 to 50 times by mass based on the layered inorganic compound used as a raw material.

In order to adjust the ratio of onium groups in the aforementioned precursor having an organic onium group, the following method is preferred: after the organic onium salt is reacted with the lamellar inorganic compound, a part of the onium groups in the lamellar inorganic compound is converted into hydroxyl groups by an acid.

The amount of the acid to be used may be arbitrarily set according to the purpose, but when the cation exchange capacity of the lamellar inorganic compound is set to 100 mol%, it is preferably set to 100 mol% - [ the proportion (mol%) of the organic onium groups to be left between the layers ], and more preferably the amount of the acid is appropriately increased or decreased.

The acid is not particularly limited, and known acids such as hydrochloric acid (hydrogen chloride), bromic acid (hydrogen bromide), carboxylic acids (for example, formic acid, acetic acid, oxalic acid, etc.), phosphoric acid, nitric acid, sulfuric acid, sulfonic acids such as methanesulfonic acid, etc. are exemplified, and among them, hydrochloric acid (hydrogen chloride) is preferable in terms of excellent reactivity.

When the amount of onium salt present between the layers is adjusted to a specific range by reacting with onium salt between the layers using these acids, hydroxyl groups such as silanol between the layers are formed, and the reaction site for modification such as silylation is increased, which is preferable.

When an onium salt is used in an amount smaller than the equivalent of the cation exchange capacity, metal cations such as sodium remain between layers, and therefore, an alkoxide (アルコシラート) derived from a hydroxyl group such as silanol which becomes a reaction point is strongly bonded to the metal cations, and there is a possibility that an interlayer modification reaction such as a silylation reaction is inhibited.

The organic solvent used in converting a part of the onium salt into a hydroxyl group is not particularly limited, and examples thereof include: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-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 methyl ethyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane; aromatic compounds such as benzene and toluene; esters such as ethyl acetate; and halogen-based hydrocarbons such as chloroform and methylene chloride.

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

The reaction temperature in the acid treatment is not particularly limited, but is preferably 0 to 200 ℃, more preferably 50 to 160 ℃, and still more preferably 70 to 150 ℃. It is generally preferable to react the organic solvent used as the reaction solvent at the boiling point (under reflux with heating).

The precursor obtained by the aforementioned cation exchange reaction and acid treatment is preferably dried after separation and washing. The method for separating, washing, and drying is not particularly limited, and a known method for separating, washing, and drying a layered inorganic compound, inorganic fine particles, and the like can be used.

Examples of the separation method include the following: after the reaction solution is subjected to solid-liquid separation by standing or centrifugal separation, the supernatant is removed by decantation; the reaction solution is subjected to filtration operations such as natural filtration, pressure filtration, and reduced pressure filtration to obtain a lamellar inorganic compound.

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

Examples of the cleaning method include the following methods: the solid obtained after decantation is redispersed in water, an organic solvent, or the like, and then water or an organic solvent is similarly injected from above the solid obtained by decantation or filtration to wash the solid.

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

The organic solvent used for washing is not particularly limited, and examples thereof include: alcohols such as methanol and ethanol; ketones such as acetone and methyl ethyl ketone; alkanes such as hexane; aromatic compounds such as toluene. In this case, an organic solvent such as an appropriate polar solvent may be used in combination in order to make the lamellar inorganic compound contact water well.

The solid obtained above may be dried at normal temperature and normal pressure, or the organic solvent may be removed under reduced pressure and normal temperature with heating or cooling as appropriate.

The pressure at the time of the pressure reduction is not particularly limited, and may be, for example, in the range of 0 to 1 atm. The temperature is not particularly limited, but is preferably-10 to 200 ℃, more preferably 0 to 150 ℃, and particularly preferably 10 to 100 ℃.

As described above, the precursor may be a compound obtained by replacing the exchangeable cations of the lamellar inorganic compound with onium groups in any ratio, and is preferably a compound obtained by replacing the exchangeable cations of the lamellar inorganic compound with onium groups in a ratio of 25 to 75 mol% in terms of ion exchange capacity.

When the proportion of the onium salt as the precursor is 25 to 75 mol%, hydroxyl groups as modification reaction sites for silylation or the like increase, and a space is generated between layers, so that a silylation agent or the like is easily inserted between layers, and the silylation rate or the like is improved.

Then, all or a part of the counter anions (alkoxylates) 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 to produce a layered inorganic compound having a crosslinkable functional group via a covalent bond between layers.

The coupling agent is not particularly limited as long as it is an organic-inorganic composite agent having an organic functional group capable of undergoing a crosslinking reaction with a hydrolyzable group in the same molecule, and examples thereof include a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent, and a compound represented by the following formula (19) is preferable.

[ chemical formula 18]

(in formula (19), R¹Represents a linear or branched chain saturated with 1 to 20 carbon atomsAnd/or an unsaturated alkyl group, a saturated or unsaturated cycloalkyl group optionally having a branched chain of 3 to 8 carbon atoms, an aryl group of 6 to 20 carbon atoms or an aralkyl group of 7 to 20 carbon atoms, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group of 1 to 20 carbon atoms, a monoarylamino group or diarylamino group of 6 to 20 carbon atoms, a monoarylamino group or diarylamino group of 7 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphate group, a sulfonic acid group, a sulfonate group or a. A represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carboxyl group or a halogen atom; d represents a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a branched saturated or unsaturated cycloalkyloxy group optionally having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a branched saturated or unsaturated heterocycloalkyloxy group optionally 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 a linear or branched saturated or unsaturated dialkylamino group having 1 to 6 carbon atoms; m represents Si, Al, Ti or Zr; when M is any one of Si, Ti or Zr, p is 3, and n is an integer of 0-2; in the case where M is Al, p is 2, and n is 0 or 1. )

Among the coupling agents, silane coupling agents are more preferable in terms of abundance of species, easiness of availability, easiness of handling, and easiness of controlling hydrolysis reaction. The silane coupling agent is not particularly limited, and is preferably a compound represented by the following formula (20), for example.

[ chemical formula 19]

(in the formula (20), R¹Represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched, saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, 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 ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid ester group or a halogen atom. A represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carboxyl group or a halogen atom; d represents a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group optionally having a branched chain having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group optionally having a branched chain having 1 to 8 carbon atoms, a halogen atom, a hydroxyl group, an amino group, a linear or branched saturated heterocycloalkyloxy group having 1 to 6 carbon atoms, a hydroxyl group, an amino group, a linear or branched saturated heterocycloalkyloxy group having 1 to 6 carbon atomsOr an unsaturated alkylamino group or a linear or branched, saturated or unsaturated dialkylamino group having 1 to 6 carbon atoms; n represents an integer of 0 to 2. )

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

Among the silane coupling agents, preferred are alkoxysilanes which have a very low possibility of side reactions to the crosslinkable functional group due to the fact that the hydrolyzable group does not by-produce an acid such as hydrogen chloride, do not cause corrosion of the reaction apparatus, and do not require disposal of the by-produced acid, more preferred are silanes of methoxy group, ethoxy group, and propoxy group which are excellent in silylation reactivity, and particularly preferred are silanes of methoxy group and ethoxy group.

The alkoxysilane coupling agent represented by the formula (20) includes, for example, vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, divinyltrimethoxysilane, divinyldimethoxysilane, di-or tri-vinyl-methoxysilane, di-or tri-, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, Tris- (trimethoxysilylpropyl) isocyanurate, 3-uredepropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 8-glycidooctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 4- (trimethoxysilyl) butyric acid, 1-dimethylethyl 4- (trimethoxysilyl) butyrate, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, and triethoxysilane, etc.

Further, silane coupling agents other than alkoxysilanes may also be used. Examples thereof include hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonate, triethylchlorosilane, t-butyldimethylchlorosilane, chlorotriisopropylsilane, 1, 3-dichloro-1, 1,3, 3-tetraisopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, allyltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, tris (N, N-dimethylamino) methylsilane, bis (N, N-dimethylamino) dimethylsilane and (N, N-dimethylamino) trimethylsilane.

In these silane coupling agents, when a plurality of hydrolyzable groups are present in one molecule, the hydrolyzable groups such as alkoxy group, halogen atom, alkylamino group, dialkylamino group, etc. may be present singly or in combination.

In addition, instead of the silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, and the like can be used in the same manner.

The organic solvent used in the reaction with the coupling agent is not particularly limited, and examples thereof include: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-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 methyl ethyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane; aromatic compounds such as benzene and toluene; esters such as ethyl acetate; and halogen-based hydrocarbons such as chloroform and methylene chloride. Among them, alcohols, ethers, nitriles and ketones as aprotic polar solvents are preferable.

More preferably an aprotic polar solvent or a secondary or tertiary alcohol, preferably an organic solvent having a boiling point of 80 ℃ or higher, more preferably 90 ℃ or higher, and still more preferably 100 ℃ or higher.

Examples of the aprotic polar solvent include: nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isopropyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide.

The secondary alcohol or tertiary alcohol is not particularly limited, and examples thereof include aromatic alcohols such as 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 1-ethoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol, and phenol.

Among them, 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 are preferable, and 2-butanol, 1-methoxy-2-propanol and 1-butoxy-2-propanol are more preferable.

The following is inferred: when an aprotic polar solvent or a secondary alcohol or tertiary alcohol is used as the organic solvent for the above reaction, an O-alkylation reaction, which is a side reaction of a hydroxyl group and an alkoxylate derived from the lamellar inorganic compound, is less likely to occur, and since the boiling point of the organic solvent used is high, the silylation reaction temperature rises, an interlayer modification reaction such as silylation reaction is accelerated, and the interlayer modification rate such as silylation rate increases.

Further, the use of secondary alcohols or tertiary alcohols is preferable because side reactions such as by-production of hydroxyl groups such as silanol by hydrolysis of a coupling agent such as a silane coupling agent described later and condensation of the coupling agent such as a silane coupling agent can be suppressed. This is presumed to be 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 any of neutral, acidic and basic, and is not particularly limited, but is preferably ion-exchanged water, distilled water, pure water and ultrapure water.

The amount of water added is preferably 0.05 to 4.0 mol times, and particularly preferably 0.1 to 3.0 mol times, relative to the total amount of the alkoxylates as the counter anions of the onium groups and the hydroxyl groups as the reaction sites of the layered inorganic compound, i.e., the ion exchange capacity.

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

The amount of the coupling agent such as a silane coupling agent in the reaction is not particularly limited, but is preferably 0.1 to 30 times by mole, more preferably 0.05 to 20 times by mole, and still more preferably 1.0 to 10 times by mole, based on the total amount of the hydroxyl groups as reaction sites and the alkoxylates as counter anions of the onium groups, that is, the ion exchange capacity.

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

The interlayer modification rate such as a silylation rate with respect to the interlayer reaction point of the layered inorganic compound, that is, the ion exchange capacity, is not particularly limited and may be selected according to the purpose, but the interlayer modification rate such as a silylation rate is preferably 15 mol% or more, and more preferably 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 lamellar inorganic compound may be excessively covered with the component 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 ℃, more preferably 50 to 180 ℃, and still more preferably 70 to 170 ℃. The reaction is usually carried out at the boiling point of the organic solvent used as the reaction solvent (under reflux by heating).

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

The interlayer modification reaction such as the silylation reaction using the coupling agent of the present invention may be carried out using a catalyst, or without using a catalyst, and known acids such as hydrogen chloride, carboxylic acids such as formic acid, acetic acid, and oxalic acid, sulfonic acids such as phosphoric acid, nitric acid, sulfuric acid, and methanesulfonic acid, and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide may be added as catalysts.

In this case, the amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 1.0 times by mole, and more preferably 0.01 to 0.1 times by mole, based on the total amount of the hydroxyl groups as reaction sites and the alkoxylates as counter anions of the onium groups, that is, the ion exchange capacity.

The interlayer modified layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction is preferably separated, washed and then dried. The method for separating, washing, and drying is not particularly limited, and a known method for separating, washing, and drying a layered inorganic compound and inorganic fine particles can be used.

When the exchangeable cations such as onium groups and metal cations remaining after the interlayer modification reaction such as silylation reaction are reduced or removed, the acid treatment can be performed using a known acid and a known solvent in the same manner as described above.

Next, a method for producing an interlayer-crosslinkable layered inorganic compound by reacting a crosslinkable functional group derived from the coupling agent with a layered inorganic compound having an interlayer modified with the coupling agent will be described.

The crosslinking reaction based on the crosslinkable functional group derived from a coupling agent such as a silane coupling agent is not particularly limited, and various generally known chemical reactions such as an addition reaction, a substitution reaction, a condensation reaction, an ionic reaction, an electrophilic reaction, a nucleophilic reaction, a peri-cyclic reaction, and a radical reaction may be used, and a so-called click reaction may also be used. Further, the following crosslinking reaction and the like can be mentioned: generating a radical from the alkyl group to cause a crosslinking reaction; taking alkyl halide and the like as Grignard reagents and converting the reagents into anion species to carry out nucleophilic reaction; alternatively, nucleophilic substitution reaction is carried out by allowing a nucleophilic species such as a hydroxyl group, an alkoxy group, or an amino group to act on an alkyl halide or the like. From the viewpoint that the reactions represented by the following formulae (21) to (35) are preferable in order to easily obtain a coupling agent and to allow the crosslinking reaction to proceed under relatively mild conditions, and if the interlayer is modified with the same coupling agent and then the crosslinking reaction is performed, the production process is less and the crosslinking reaction is industrially more advantageous, the crosslinking reactions represented by the formulae (21) to (25) and the formulae (30) to (34) are more preferable, and the crosslinking reactions represented by the formulae (21) to (25) and the formulae (32) to (34) are further preferable in that the crosslinking reaction is easily performed under mild conditions, various chemical structures, flexibility and rigidity can be introduced, and the length of the crosslinking can be diversified.

When the crosslinking reactions represented by the formulae (21) to (23) and (32) are used, they have the following characteristics: the cross-linked functional groups have the same or similar structures, the cross-linked structure generated by reaction is simpler and can be determined according to R²、R⁴And R¹³The structure of (3) makes it easier to control the interlayer distance and interlayer environment (hydrophobicity, hydrophilicity, aromaticity, etc.) of the lamellar inorganic compound.

In addition, in the use of formula (24), formula (25), formula (33) and formula (34) shown in the crosslinking reaction, not only can be according to R²、R⁴And R¹³The structure of (3) can easily control the interlayer distance, flexibility, and interlayer environment (hydrophobicity, hydrophilicity, aromaticity, hydrogen bond formation, etc.) of the lamellar inorganic compound, and various available amines and diamines can be introduced into the crosslinked structure, and therefore has the following characteristics: the interlayer distance, flexibility, and interlayer environment (hydrophobicity, hydrophilicity, aromaticity, hydrogen bond formation, heterocyclic structure, ionic bond, coordinate covalent bond, etc.) of the layered inorganic compound can be easily and freely controlled.

[ chemical formula 20]

[ chemical formula 21]

[ chemical formula 22]

[ chemical formula 23]

[ chemical formula 24]

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

[ chemical formula 32]

[ chemical formula 33]

[ chemical formula 34]

(in formulae (21) to (35), R¹Represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and each of which is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched, saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, 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 ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid ester group or a halogen atom.And (4) substitution. R²And R¹³Each independently represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 3 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms; r³、R⁵、R⁶And R⁷Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; r⁴Represents an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkylene group having 7 to 10 carbon atoms; r⁸、R⁹、R¹⁰And R¹²Each independently represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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; r¹¹Represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 3 to 20 carbon atoms, an arylene 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, any one of R¹¹Optionally substituted with a substituent comprising 1 to 10 atoms such as a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, etc.; z represents a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a branched saturated or unsaturated cycloalkyloxy group optionally having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a branched saturated or unsaturated heterocycloalkyloxy group optionally 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, 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; i is a group derived from a polymerization initiator and may be the same or different; y is a group derived from a conjugate base derived from an acid; n represents an integer of 0 to 2; m and h represent an integer of 0 or 1; k represents an integer of 0 to 4.

In the crosslinking reactions represented by the above formulae (21) to (35), crosslinking reactions derived from crosslinkable functional groups of coupling agents containing titanium (Ti), aluminum (Al), zirconium (Zr), etc. in place of silicon atoms (Si) may be used.

In the above-mentioned crosslinking reaction, the crosslinking point in the crosslinking reaction of the carbon-carbon double bond 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 the oxetanyl group may be either one of the carbon atoms existing on the two carbon atoms adjacent to the oxygen atom of the cyclic ether group.

In order to accelerate the crosslinking reaction, a known thermal radical generator, a photoradical generator, a thermal anion generator, a photocation generator, a thermal acid generator, a photoacid generator, a thermal base generator, a photobase generator, a known inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, a known organic acid such as formic acid, acetic acid, oxalic acid, citric acid, methanesulfonic acid, or p-toluenesulfonic acid, a known inorganic base such as ammonia, sodium hydroxide, potassium hydroxide, or calcium hydroxide, an organic base such as a known organic amine such as methylamine, diethylamine, or triethylamine, a known ammonium salt such as tetramethylammonium hydroxide, a known catalyst such as succinic anhydride, phthalic anhydride, or maleic anhydride, a known catalyst such as a curing agent, bromine, or an oxidizing agent such as iodine may be used in combination as necessary.

The polymerization initiator is not particularly limited, and a known polymerization initiator used in polymerization reaction of a polymerizable monomer may be used, and a thermal polymerization initiator and/or a photopolymerization initiator may be used, but a thermal polymerization initiator is more preferable in that a crosslinking reaction system including a layered inorganic compound after interlayer modification with a coupling agent is suspended and light such as ultraviolet rays is hardly transmitted.

Various compounds can be used as the thermal polymerization initiator, and in the case where 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.

Specific examples of the peroxide include hydrogen peroxide, inorganic peroxides such as sodium persulfate, ammonium persulfate and potassium persulfate, 1-bis (t-butylperoxy) 2-methylcyclohexane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-hexylperoxy) cyclohexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 1-bis (t-butylperoxy) cyclohexane, 2-bis (4, 4-di-butylperoxycyclohexyl) propane, 1-bis (t-butylperoxy) cyclododecane, t-butylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3, 5, 5-trimethylhexanoate, t-butylperoxy laurate, 2, 5-dimethyl-2, 5-di (m-toluoylperoxy) hexane, isopropyl monocarbonate, 2-ethylhexylmonocarbonate, t-butylperoxybenzoic acid, t-butylperoxy, 2, 5-dimethyl-2, 5-di (m-tolylperoxyperoxy) hexane, isopropyl monocarbonate, 2-ethylhexylperoxydicarbonate, 5-di (t-butylperoxy) hexane, di (t-butylperoxy) hydroperoxide, di (t-butylperoxy) hexane, di-butyl-tert-butyl peroxydicarbonate, di (3, 5-butyl-tert-butyl peroxybenzene, di-butyl-5-butyl) hydroperoxide, di (tert-butyl-tert-butyl) benzene, di-5-butyl-tert-butyl-5, di (tert-butyl) hydroperoxide, di-butyl-tert-butyl-peroxybenzene, di (tert-butyl-peroxybenzene, di-tert-butyl-hydroperoxide), di-butyl-peroxybenzene, di-tert-butyl-tert-3, di-butyl-tert-.

Specific examples of the azo initiator include azo compounds such as 2,2 '-azobisisobutyronitrile, 1' -azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2, 4-dimethylvaleronitrile, azobis-tert-octane, and azobis-tert-butane, and these azo initiators may be used alone or in combination of two or more.

Further, the redox reaction can be carried out by combining with a redox polymerization initiator system using a peroxide and a reducing agent such as ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, a metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, or ferric chloride in combination.

The amount of the thermal polymerization initiator to be used may be selected depending on the kind thereof, polymerization conditions, and the like, and is usually 1 to 1000 mol, more preferably 5 to 500 mol, and still more preferably 50 to 200 mol, based on 100 mol of the polymerizable functional group.

Specific examples of the photopolymerization initiator include, when the polymerizable group is a radical polymerizable group: benzildimethyl ketal, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (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, Acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 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-based compounds such as 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 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone and 4-methoxy-4 ' -dimethylaminobenzophenone;

acylphosphine oxide compounds such as bis (2,4, 6-trimethylbenzoyl) phenylphosphine oxide, 2,4, 6-trimethylbenzoyl diphenylphosphine oxide and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide; and thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2, 4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3, 4-dimethyl-9-oxo-9H-thioxanthone-2-yl-oxy ] -2-hydroxypropyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

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

The amount of the photopolymerization initiator to be used may be selected depending on the kind and polymerization conditions thereof, and is 1 to 1000 mol, more preferably 5 to 500 mol, and still more preferably 50 to 200 mol, based on 100 mol of the polymerizable functional group.

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 examples of the thermal cationic polymerization initiator include sulfonium salts, phosphonium salts, quaternary ammonium salts and the like. Among them, sulfonium salts are preferred.

Examples of the counter anion in the thermal cationic polymerization initiator include AsF₆ ^-、SbF₆ ^-、PF₆ ^-、B(C₆F₅)₄ ^-And the like.

Examples of the sulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, tris (4-methoxyphenyl) sulfonium hexafluoroarsenate, and diphenyl (4-phenylthiophenyl) sulfonium hexafluoroarsenate.

As the sulfonium salt, commercially available ones can be used, and specific examples thereof include "Adeka Opton CP-66" (trade name) and "Adeka Opton CP-77" (trade name) manufactured by ADEKA, and "San-AidSI-60L" (trade name), "San-AidSI-80L" (trade name) and "San-Aid SI-100L" (trade name) manufactured by Sanxin chemical industries, for example.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the quaternary ammonium salts include N, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N-diethyl-N-benzylanilinium tetrafluoroborate, N-dimethyl-N-benzylpyridinium hexafluoroantimonate, N-diethyl-N-benzylpyridinium trifluoromethanesulfonate, n, N-dimethyl-N- (4-methoxybenzyl) pyridinium hexafluoroantimonate, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoroantimonate, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexafluoroantimonate, and the like.

Examples of the photo cation polymerization initiator include onium salts such as iodonium salts, sulfonium salts, azoonium salts, selenonium salts, pyridinium salts, ferrocenium salts, and phosphonium salts. Among them, iodonium salts and sulfonium salts are preferable.

When the photo cation polymerization initiator is an iodonium salt or a sulfonium salt, examples of the counter anion include BF₄ ^-、AsF₆ ^-、SbF₆ ^-、PF₆ ^-、B(C₆F₅)₄ ^-And the like.

Examples of the iodonium salts include (triisopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, 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 hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, and the like, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate, and the like.

Further, commercially available iodonium salts may be used, and specific examples thereof include "UV-9380C" (trade name) manufactured by MomentivePerformance Materials Japan, and "Photonitiator 2074" (trade name) manufactured by SO L VAY JAPAN, and "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Fuji film and Wako pure chemical industries.

Examples of the sulfonium salt include bis [4- (diphenylsulfonium) phenyl ] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonium) phenyl ] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonium) phenyl ] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonium) phenyl ] sulfide tetrakis (pentafluorophenyl) borate, 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, triphenylsulfonium hexafluoroantimonate, and triphenylsulfonium salts, Bis [4- (bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl ] sulfide bis hexafluorophosphate, bis [4- (bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl ] sulfide bis hexafluoroantimonate, bis [4- (bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl ] sulfide bis tetrafluoroborate, bis [4- (bis (4- (2-hydroxyethoxy)) phenylsulfonium) phenyl ] sulfide bis pentafluorophenyl borate, and the like.

Further, commercially available sulfonium salts can be used, and specific examples thereof include: "Cyracure UVI-6990" (trade name), "Cyracure UVI-6992" (trade name), and "Cyracure UVI-6974" manufactured by the Dow chemical Japan company; "Adeka Optomer SP-150" (trade name), "Adeka Optomer SP-152" (trade name), "Adeka Optomer SP-170" (trade name), and "Adeka Optomer SP-172" (trade name) manufactured by ADEKA corporation; fuji film and Wako pure chemical industries, Ltd. "WPAG-370" (trade name), "WPAG-638" (trade name), and the like.

Examples of the azoonium salt include phenylazoium hexafluoroantimonate, phenylazoium hexafluorophosphate, and phenylazoium hexafluoroborate.

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

Examples of the photo-anionic polymerization initiator include acetophenone O-benzoyl oxime, nifedipine, 1,5, 7-triazabicyclo [4,4,0] dec-5-ene-2- (9-oxoxanthen-2-yl) propionate, 2-nitrophenylmethyl 4-methacryloxypiperidine-1-carboxylate, 1, 2-diisopropyl-3- [ bis (dimethylamino) methylene ] guanidinium 2- (3-benzoylphenyl) propionate, and 1, 2-dicyclohexyl-4, 4,5, 5-tetramethylbiguanidinium n-butyltriphenylborate.

The amine represented by the following formula (36) that can be used for crosslinking the epoxy groups represented by the formulae (24) and (33) is not particularly limited, and examples thereof include: alkylamines such as ammonia, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, eicosylamine, isopropylamine, allylamine, and 2-cyclohexylethylamine; cyclic alkylamines such as cyclopentylamine, cyclohexylamine, cyclooctylamine, and 3-cyclohexenylamine; arylamines such as phenylamine, 1-naphthylamine, 2-aminoanthracene, 1-aminopyrene and 3-aminobiphenyl; aralkyl amines such as benzylamine, 2-phenylethyl, 1- (1-naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, and 2- (7-methoxy-1-naphthyl) ethylamine.

H₂NR⁸(36)

(in the formula (36), R⁸Represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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. )

The diamine represented by the following formula (37) that can be used for crosslinking the epoxy group represented by the above formula (25) and the above formula (34) is not particularly limited, and examples thereof include diaminomethane, urea, thiourea, 1, 2-diaminoethane, 1, 2-bis (methylamino) ethane, N-methylmethylenediamine, 1, 3-diaminopropane, 1, 2-diamino-2-methylpropane, 1, 4-diaminobutane, 1, 4-bis (methylamino) -2-butene, 1, 6-hexanediamine, 1, 8-dimethyloctane, N-bis (2-aminoethyl) methylamine, 1, 3-cyclohexanediamine, 1, 4-cyclohexanediamine, 3-aminopyrrolidine, and mixtures thereof, 4, 4' -methylenebis (2-methylcyclohexylamine), bis (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 ' -diaminodiphenylmethane, 4 ' -diamino-3, 3 ' -dimethylbiphenyl, 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.

R⁹HR¹¹NHR¹⁰(37)

(in the formula (37), R⁹And R¹⁰Each independently represents a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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; r¹¹Represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkylene group optionally having 3 to 20 carbon atoms, an arylene 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, any one of R¹¹Optionally substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, and a substituent comprising 1 to 10 atoms inclusive of these atoms. )

In the case of the reaction represented by the above formula (30), an oxidizing agent may be used in combination, and for example, a known oxidizing agent which promotes a disulfide formation reaction under an alkaline condition, such as bromine or iodine, may be used.

When the crosslinking reaction between layers is carried out by heating, the reaction temperature is not particularly limited as long as it is appropriately selected, and is, for example, preferably 0 to 200 ℃, more preferably 25 to 180 ℃, and still more preferably 40 to 170 ℃. In this case, it is preferable that the reaction system contains a thermal polymerization initiator as appropriate from the viewpoint of ease of crosslinking and cost.

The active energy ray for the crosslinking reaction between layers by irradiation with an active energy ray includes ultraviolet rays, visible rays, and electron beams. When ultraviolet light or visible light is used as the active energy ray, a photopolymerization initiator is preferably contained from the viewpoint of ease of crosslinking and cost.

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

The irradiation energy may be appropriately set depending on the kind and the compounding composition of the active energy ray, and may vary depending on the thickness, the illuminance and the like of the reaction system, and for example, in the case of using a high-pressure mercury lamp, it is preferable that the irradiation energy is, for example, 5 to 10,000mJ/cm in terms of the UV-A region²When UV-L ED is used, the emission peak wavelength is preferably 350 to 420nm, and the emission peak wavelength is preferably 5 to 10,000mJ/cm in terms of irradiation energy²。

When an electron beam is used as the active energy ray, the curing can be performed by an electron beam without containing a photopolymerization initiator, but a small amount of a photopolymerization initiator may be added as necessary to improve curability.

Various electron beam irradiation apparatuses can be used, and examples thereof include Cockcroft-Walton type, Van de Graff type, and resonant transformer type apparatuses.

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

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

In the case of performing the crosslinking reaction between layers, a reaction solvent may be used, and such a solvent is not particularly limited as long as it is appropriately selected, and there may be mentioned: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-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 methyl ethyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane; aromatic compounds such as benzene and toluene; esters such as ethyl acetate; and halogen-based hydrocarbons such as chloroform and methylene chloride. Among them, alcohols, ethers, nitriles and ketones as aprotic polar solvents are preferable.

More preferably an aprotic polar solvent or a secondary or tertiary alcohol, preferably a solvent having a boiling point of 80 ℃ or higher, more preferably 90 ℃ or higher, and still more preferably 100 ℃ or higher.

The aprotic polar solvent is not particularly limited, and includes: nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isopropyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide.

The reaction concentration in the interlayer crosslinking reaction is not particularly limited, and may be appropriately selected, and for example, the mass% of the interlayer modified layered inorganic compound is preferably 1 to 50 mass%, more preferably 3 to 40 mass%, and further preferably 5 to 30 mass%.

In addition, in the interlayer of the interlayer crosslinking type layered inorganic compound of the present invention, an arbitrary functional group or modifying group may be present in addition to the organic-inorganic composite crosslinking structure. For example, exchangeable metal cations such as sodium, potassium and calcium may be present, and the cation may be modified with an organic onium group such as an alkylammonium or alkylphosphonium group, or a hydroxyl group derived from a lamellar inorganic compound, and the hydroxyl group may be terminated and converted with an alkoxy group such as a methoxy group, or may be modified with an organic silyl group such as an alkylsilyl group, arylsilyl group, aralkylsilyl group and a group derived from an uncrosslinked silane coupling agent, or an organic-inorganic complex modifying group containing a metal such as titanium, aluminum and zirconium.

The time for introducing the optional functional group or modifying group other than the organic-inorganic composite crosslinked structure present between the layers may be before, after, or simultaneously with the interlayer modification of the coupling agent for constructing the crosslinked structure, or may be before or after the interlayer crosslinking reaction of the crosslinkable functional group derived from the coupling agent introduced between the layers, and may be arbitrarily selected in consideration of the reactivity of the various functional groups, modifying groups, and coupling agent.

When the organic-inorganic composite crosslinking agent having two or more hydrolyzable metal sites is used to introduce a crosslinked structure between layers of the layered inorganic compound via covalent bonds, the organic-inorganic composite crosslinking agent may be reacted with the above precursor in the same manner as the coupling agent.

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

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

In the formula (2), M is a metal capable of forming a covalent bond with an oxygen atom derived from the layered inorganic compound, and is any of Si (silicon), Al (aluminum), Ti (titanium), and Zr (zirconium), from the viewpoint that this covalent bond hardly causes a decomposition reaction such as hydrolysis and is easily obtained, and Si which is easily obtained is preferable for introducing various interacting groups.

In the organic-inorganic composite group represented by the formula (2) in which the organic-inorganic composite group and the lamellar inorganic compound are introduced into the interlayer via a covalent bond, it is more preferable that the organic-inorganic composite group and the lamellar inorganic compound are bonded via a plurality of covalent bonds from the viewpoint of chemical stability of the bond connecting the interlayers, and n is more preferably 1 or2 in the case where M in the formula (2) is Si, Ti, or Zr, n is more preferably 1 in the case where M in the formula (2) is Al, and in either case, it is more preferable that at least one Z includes an oxygen atom derived from the lamellar inorganic compound. Further, Z of the organic-inorganic composite groups adjacent to each other may be hydrolyzed and condensed to form an M-O-M bond.

The organic-inorganic complex group preferably contains any of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond-forming group, a coordinate bond-forming group, and an ionic bond-forming group, from the viewpoint of appropriately designing the interaction with the guest compound. Thus, non-covalent bond interactions (for example, van der waals forces, pi-pi interactions, hydrophobic interactions, hydrogen bonds, coordinate bonds, ionic bonds, and the like) with the guest compound can be appropriately adjusted and imparted, and an arbitrary compound can be inserted between layers to achieve sustained release depending on the purpose.

The non-covalently interactive group is not particularly limited, and examples thereof include: saturated or unsaturated aliphatic groups such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-hexyl, n-octyl, decyl, dodecyl, octadecyl, methylene, propylene, cyclohexyl, vinyl, and allyl; aromatic groups such as styryl, phenyl, naphthyl, and phenylene; heterocyclic structural groups such as a pyrrolyl group such as a pyridyl group, piperidyl group, pyrrolidinyl group, pyrimidinyl group, imidazolyl group, etc., an epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothienyl group, dioxanyl group, morpholinyl group, thiazinyl group, indolyl group, nucleic acid base group, etc.; hydrogen bond and coordinate bond-forming groups such as acryloyloxy group, methacryloyloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, carboxylic acid methyl group, phosphoric acid group, phosphoethyl group, sulfonic acid methyl group, amino group, methylamino group, dimethylamino group, isocyanurate group, ureide group, and isocyanate group; and an ionic bond-forming group of an ethylammonium group, a dimethylammonium group, and a trimethylammonium group. From the viewpoint of ease of availability, methyl, ethyl, n-propyl, n-hexyl, decyl, octadecyl, methylene, propylene, cyclohexyl, vinyl, allyl, styryl, phenyl, phenylene, epoxy, oxetanyl, acryloyloxy, methacryloyloxy, acetyl, benzoyl, benzyl, hydroxyl, thiol, carboxyl, amino, methylamino, dimethylamino, trimethylammonium, isocyanurate, ureide, and isocyanate groups are preferable.

These non-covalently bonded interacting groups can form a crosslinked structure by a crosslinking reaction between layers.

Next, the interlayer modified layered inorganic compound of the present invention will be described in detail according to the production method.

The method for producing a precursor for silylation or the like, which is a layered inorganic compound having an enlarged interlayer, from a layered inorganic compound is the same as the method described in the above paragraphs 0047 to 0064.

Then, all or a part of the hydroxyl group and counter anion (alkoxide) of the onium group of the precursor is subjected to an interlayer modification reaction with an organic-inorganic composite modifier such as a silylating agent represented by the following formula (38), thereby producing an interlayer modified layered inorganic compound having an organic-inorganic composite group represented by the following formula (2) between layers through a covalent bond.

The modifier for introducing the organic-inorganic composite group represented by the above formula (2) into the interlayer may be any organic-inorganic composite modifier having a functional group capable of interacting with the hydrolyzable group and the functional compound in the same molecule, and examples thereof include a silylating agent containing a silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent, and a compound represented by the following formula (38) is preferable.

R_nMD_y-n(38)

(in the formula (38), R represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, a monoarylamino group or diarylamino group having 1 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an isocyanato group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a salt group, a, Sulfonic acid group, sulfonate group or halogen atom; m represents Si, Al, Ti or Zr; d represents a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group optionally having a branched chain having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group optionally having 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, a linear or branched saturated or unsaturated dialkylamino group having 1 to 6 carbon atoms; 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; in the case where M is Al, y corresponding thereto is 3, and n is 1 or 2; in case n is 2 or 3, R is optionally the same or different. )

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

Among the organic-inorganic composite modifiers, a silylation agent in which M is Si is more preferable in terms of the abundance of species, the availability, the ease of handling, and the ease of controlling the hydrolysis reaction.

Among the silylating agents, preferred are alkoxysilanes which have a very low possibility of causing side reactions to functional groups due to the fact that an acid such as hydrogen chloride is not by-produced from a hydrolyzable group, do not cause corrosion of a reaction apparatus, and do not require disposal of the by-produced acid, more preferred are silanes of methoxy group, ethoxy group, and propoxy group which are excellent in silylation reactivity, and particularly preferred are silanes of methoxy group and ethoxy group.

The silylating agent is not particularly limited, and examples of the alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-vinyltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyldimethoxysilane, vinyldimethoxysilane, vinyl, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1, 3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, Tris- (trimethoxysilylpropyl) isocyanurate, 3-uredepropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 8-glycidooctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7-octenyltrimethoxysilane, 4- (trimethoxysilyl) butyric acid 1, 1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldimethoxy, Phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxydimethylsilane, trimethoxymethylsilane, and triethoxysilane, etc.

In addition, silylating agents other than alkoxysilanes may be used. Examples thereof include hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonate, triethylchlorosilane, t-butyldimethylchlorosilane, chlorotriisopropylsilane, 1, 3-dichloro-1, 1,3, 3-tetraisopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, allyltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosilane, tris (N, N-dimethylamino) methylsilane, bis (N, N-dimethylamino) dimethylsilane and (N, N-dimethylamino) trimethylsilane.

In these silylating agents, when a plurality of hydrolyzable groups are present in one molecule, the hydrolyzable groups such as an alkoxy group, a halogen atom, an alkylamino group, and a dialkylamino group may be present singly or in combination.

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

The organic solvent used in the reaction with the silylating agent is not particularly limited, and examples thereof include: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-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 methyl ethyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane; aromatic compounds such as benzene and toluene; esters such as ethyl acetate; and halogen-based hydrocarbons such as chloroform and methylene chloride. Among them, alcohols, ethers, nitriles and ketones as aprotic polar solvents are preferable.

Further, the use of secondary alcohols or tertiary alcohols is preferable because side reactions such as by-production of hydroxyl groups such as silanol and condensation of coupling agents such as silane coupling agents, which are caused by hydrolysis of organic-inorganic composite modifiers such as silylating agents described later, can be suppressed. This is presumed to be a solvent effect due to alcoholic hydroxyl groups.

The amount of the organic-inorganic composite modifier such as a silylating agent in the reaction is not particularly limited, but is preferably 0.1 to 30 times by mole, more preferably 0.05 to 20 times by mole, and still more preferably 1.0 to 10 times by mole, based on the total amount of the hydroxyl groups as the reaction sites and the alkoxylates as counter anions of the onium groups, that is, the ion exchange capacity.

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

The interlayer modification reaction such as silylation reaction using the organic-inorganic composite modifier of the present invention may or may not use a catalyst, and known acids such as hydrogen chloride, carboxylic acids such as formic acid, acetic acid, and oxalic acid, sulfonic acids such as phosphoric acid, nitric acid, sulfuric acid, and methanesulfonic acid, and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide, and potassium hydroxide may be added as catalysts.

The interlayer modified layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction is preferably separated, washed and then dried. The method for separating, washing, and drying is not particularly limited, and a known method for separating, washing, and drying the layered inorganic compound and the inorganic fine particles may be used, and for example, a method using the precursor described above may be used.

Z present in the organic-inorganic composite group represented by the aforementioned formula (2) may also participate in the interaction with a guest compound. For example, in the case of a hydroxyl group, hydrogen bonding with a guest compound can be caused to participate in insertion and sustained release, and the interaction with the guest compound can be controlled by the kind of Z, for example, a hydroxyl group, a methoxy group, or the like, and the amount of Z present.

In addition, the interlayer of the interlayer modified layered inorganic compound of the present invention may have an optional functional group or modifying group in addition to the organic-inorganic composite group. For example, exchangeable metal cations such as sodium, potassium and calcium may be present, and the cation may be modified with an organic onium group such as an alkylammonium or an alkylphosphonium group, or a hydroxyl group derived from a lamellar inorganic compound may be present, and the hydroxyl group may be sealed and converted in an end-capping state by an alkoxy group such as a methoxy group. And also participate in controlling the interaction with guest compounds by their presence.

The compound (also referred to as a guest compound) to be inserted between layers of the organic-inorganic composite base represented by the formula (1) or the formula (2) of the present invention to be controlled in a sustained manner is not particularly limited and may be arbitrarily selected depending on the intended use, and for example, the compound may have a linear or branched, saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched, saturated or unsaturated cycloalkyl group having optionally 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and may be optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched, saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, a monoarylamino group or a diarylamino group having 6 to 20 carbon atoms, a cyclic or a cyclic amino group having 1 to 20 carbon atoms, or a cyclic amino, A monoaralkylamino group or a diaralkylamino group having 7 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid group, a sulfonate group, a ketone group, a functional group of an ether group, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a halogen atom, or the like, and may have various heterocyclic structural groups.

Among them, from the viewpoint of easy control of interaction with the organic-inorganic complex group, compounds containing any of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond-forming group, a coordinate bond-forming group, or an ionic bond-forming group are preferable, and examples thereof include, but are not particularly limited to, compounds containing a saturated or unsaturated aliphatic group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a tert-butyl group, a n-hexyl group, a n-octyl group, a decyl group, a dodecyl group, an octadecyl group, a methylene group, a propylene group, a cyclohexyl group, a vinyl group, or an allyl group; aromatic groups such as styryl, phenyl, phenolic, naphthyl, and phenylene; a pyrrolyl group such as a pyridyl group, a piperidyl group, a pyrrolidinyl group, a pyrimidinyl group, a pyrazinyl group, and an imidazolyl group; heterocyclic structural groups such as thiazolinyl, thiazolyl, thiazolinonyl, isothiazolinonyl, epoxy, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, dioxanyl, morpholinyl, thiazinyl, indolyl, and nucleic acid salt groups; hydrogen bond and coordinate bond-forming groups such as acryloyloxy group, methacryloyloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, carboxylic acid methyl group, phosphoric acid group, phosphoethyl group, sulfonic acid methyl group, amino group, methylamino group, dimethylamino group, isocyanurate group, ureide group, and isocyanate group; and an ionic bond-forming group of an ethylammonium group, a dimethylammonium group, and a trimethylammonium group. These functional groups may also be present in combination in the same compound.

The molecular weight of the compound is not particularly limited and may be arbitrarily selected according to the intended use, but from the viewpoint of ease of intercalation into the interlayer and maintenance of a stable host-guest complexing agent structure, the molecular weight is preferably 2,000 or less, more preferably 1,000 or less, and further preferably 500 or less.

The method for producing the sustained-release composite agent having the functional compound inserted between the layers of the interlayer-modified layered inorganic compound is not particularly limited, and examples thereof include: a method of mixing an interlaminar modification layered inorganic compound with a compound in the absence of a solvent; a method of mixing the interlayer modified layered inorganic compound in the presence of a solvent which makes the compound soluble or insoluble.

In the case where the compound is a gas or a liquid, a method of mixing in the absence of a solvent is economical and is therefore preferred. On the other hand, when the compound is a highly viscous liquid or solid, it is preferable to use a method of mixing the compound with the interlayer-modified layered inorganic compound in the presence of a solvent which makes the compound soluble because the compound is efficiently intercalated between the layers. In addition, when the compound is a solid, a method of heating the compound to a temperature higher than its melting point to liquefy the compound and mixing the compound with the interlayer modified layered inorganic compound is efficient without using a solvent.

The temperature of the mixture of the interlayer modifying layered inorganic compound and the compound is not particularly limited, and is usually in the range of 0 to 200 ℃, preferably 10 to 150 ℃, and more preferably 15 to 100 ℃.

The solvent used in the production of the sustained-release composition is not particularly limited, and examples thereof include: alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-2-propanol, 2-methyl-1-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 methyl ethyl ketone; amides such as N, N-dimethylformamide; sulfoxides such as dimethyl sulfoxide; alkanes such as hexane; aromatic compounds such as benzene and toluene; esters such as ethyl acetate; and halogen-based hydrocarbons such as chloroform and methylene chloride. The solubility of the guest compound and the hydrophilicity and hydrophobicity of the interlayer modification group of the host compound may be appropriately selected in consideration of these properties.

The mixing ratio of the interlayer modified layered inorganic compound as the host compound and the compound as the guest compound in the production of the sustained-release composite agent is not particularly limited, and may be arbitrarily set according to the purpose, and in the case of a sustained-release agent for a long period of time, it is preferably mixed with a maximum amount of the compound capable of being inserted between the interlayers of the layered inorganic compound or more. For example, when 10 parts of the functional compound can be inserted between layers per 100 parts of the interlayer modifying layered inorganic compound, it is preferably mixed with 10 parts or more.

The sustained-release complex agent obtained by mixing the interlaminar modified layered inorganic compound and the compound can be used as a sustained-release agent as it is, or can be used as a sustained-release agent after removing an excessive amount of the compound and the solvent. The excess compound or solvent may be removed by filtration through a known filtration operation such as natural filtration, reduced pressure filtration, or pressure filtration, in the case where the compound is a liquid or in the case where a soluble solvent is used in combination with the compound. When the compound is a liquid or a solid having sublimability, it can be removed by air drying, evaporation by heating, or distillation under reduced pressure. When the compound is a solid and a solvent is used in combination, the unnecessary solvent may be removed by air drying, evaporation by heating, or distillation under reduced pressure.

The method of using the slow-release composite agent comprising the interlayer-modified layered inorganic compound and the compound inserted between the interlayers of the interlayer-modified layered inorganic compound of the present invention is not particularly limited, and for example, the composite agent may be used as a slow-release agent as it is, or may be used by being mixed with a resin to prepare a structural material, a coating agent, a fiber, a film, a sheet, a plate, a particle, a block, or the like, or may be used as a coating material by being dispersed in a solvent, a polymerizable monomer, or the like.

The sustained-release composition of the present invention can be compounded with various materials to impart an effect corresponding to the function of the guest compound. Examples of materials that can be blended include: rubbers such as silicone and acrylic resin; various plastics such as polyvinyl chloride, polyolefin, polyurethane, ABS, polystyrene, polyvinyl acetate, polycarbonate, polyester, polyurethane, polyacrylic acid, and the like.

The sustained-release complexing agent of the present invention may be suspended in a liquid medium such as water or an organic solvent in the presence or absence of a binder, and then applied to the surface of various metals, plastics, ceramics, or the like by a usual coating method such as spray coating, coater coating, dipping, brush coating, roll coating, or the like to form a coating film, whereby an effect corresponding to the function of the guest compound can be imparted to articles of various materials.

The preferable ratio of the sustained-release composite agent of the present invention to be blended with each material is not particularly limited, and may be arbitrarily selected depending on the use environment and the purpose.

Specific applications of the material or the molded article to which the sustained-release composition, or the like of the present invention is blended or coated include: fiber products such as towels, carpets, curtains, clothes, mosquito nets, bedding and the like; electrical products such as leather, refrigerators, washing machines, dish dryers, dust collectors, air conditioners, televisions, telephones, personal computers, and the like; wall paper, ceramic tile, brick, concrete, screw, joint and other building materials; daily miscellaneous goods such as face washing devices, toothbrushes, brooms, hoses, slippers, garbage bins, brushes and the like; kitchen supplies such as chopping boards, triangular corners, chopping knives, and the like; a cosmetic product; mobile articles such as automobiles, airplanes, ships, and the like; agricultural products such as agricultural chemicals and plant hormones; medical and health care products such as medicines and quasi-medicines; a dispenser; a cosmetic; a fragrance; an antioxidant; a lubricant; a humectant; repellents for insects or animals, etc.; physiological active agents such as insecticides, bactericides, insect-proofing agents, preservatives, mildewproofing agents, antiviral agents, and the like; food additives and the like; various coating agents; coating; and adhesives, etc. However, it is not limited to these uses.

Examples

The present invention will be described in detail below with reference to examples and comparative examples.

EXAMPLE 1 Synthesis of a sustained-release complex agent in which 2-methyl-2-thiazoline (hereinafter referred to as 2MT) was inserted between layers of magadiite which had been subjected to interlayer modification with methacryl-type crosslinks and phenylsilyl groups, and evaluation of sustained-release properties thereof.

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

18.34g of sodium silicate (product name: No. 4 sodium silicate, manufactured by Fuji chemical Co., Ltd.), 7.28g of silica gel (product name: Wakogel Q-63, manufactured by Fuji film and Wako pure chemical industries, Ltd.), and 54.37g of pure water were mixed, and the mixture was sealed in a high-pressure reaction decomposition vessel (product name: HU-100, manufactured by Sanai science Co., Ltd.) and heated at 170 ℃ for 30 hours. The resultant was collected by suction filtration, washed with a dilute aqueous NaOH solution (pH 9 to 10) and pure water, and dried at 40 ℃ for 2 days to obtain 15.9g of Na-magadiite.

The composition of Na-magadiite was calculated using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu corporation) and a thermogravimetric analyzer (TG/DTA 6300, manufactured by Hitachi High-Tech Science), and the result was Na₂Si₁₄O₂₉·nH₂O, ion exchange capacity calculated as n 0 is 2.21mol_c/kg。

The spacing between the bottom surfaces of the obtained Na-magadiite was determined to be 1.54nm using an X-ray diffraction apparatus (product name: D8 ADVANCE, manufactured by BRUKER Co.).

(2) Dodecyltrimethylammonium (hereinafter DTMA) -synthesis of magadiite (synthesis of silylated precursor of Na-magadiite by interlayer ammonification based on dodecyltrimethylammonium chloride treatment).

100g of Na-magadiite obtained as described above, 6500g of pure water, and 175g of dodecyltrimethylammonium chloride (Fuji film, Wako pure chemical industries, Ltd.) were mixed and stirred at room temperature for 7 days. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ℃ to obtain 94g of DTMA-magadiite.

The Na content of the obtained DTMA-magadiite was measured by using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu corporation), and it was confirmed that most of the obtained DTMA-magadiite had undergone cation exchange, when the Na content was less than 0.04 mass%.

The composition of the obtained DTMA-magadiite was calculated using an elemental analyzer (CHN recorder MT-5 manufactured by YANACO analysis industries, Ltd.) and a thermogravimetric analyzer (TG/DTA 6300 manufactured by Hitachi High-Tech Science, Ltd.), and as a result, DTMA-magadiite was obtained_1.72H_0.28Si₁₄O₂₉·nH₂O。

The distance between the bottoms of the obtained DTMA-magadiite was determined in the same manner as described above, and found to be 2.89 nm.

(3) Interlayer silylation (introduction of methacryloxypropyl group) by 3-methacryloxypropyltrimethoxysilane (hereinafter referred to as MAC-TRIMS) treatment of DTMA-magadiite.

After drying 100g of the DTMA-magadiite obtained as described above at 100 ℃ under a reduced pressure of about 100Pa for 2 hours, 1850g of dried 1-methoxy-2-propanol (hereinafter, PGM), 3.4g of pure water, and MAC-TRIMS39.2g (0.5 molar times the reaction point, manufactured by shin-Etsu chemical Co., Ltd.) were mixed with molecular sieves 3A, and the mixture was stirred for 4 days under reflux with heating in a nitrogen atmosphere. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ℃ to obtain 105g of silylated magadiite (hereinafter referred to as MACPS-magadiite).

The composition of the obtained MACPS-magadiite was calculated in the same manner as described above, and the result was Methacryloyloxypropylsilyl (MACPS)_0.43DTMA_0.56Me_1.01Si₁₄O₂₉·nH₂O, bottom spacing of 2.12 nm.

(4) Synthesis of lamellar inorganic Compound of the interlaminar crosslinking type by crosslinking reaction of MACPS-magadiite.

100g of MACPS-magadiite obtained as described above and 1450g of toluene were mixed, and nitrogen gas was bubbled through the mixture for 1 hour while cooling the mixture in an ice bath to remove oxygen in the system. Then, 7.88g of 2, 2' -azobisisobutyronitrile (hereinafter referred to as AIBN) was added thereto, and the mixture was stirred at 60 ℃ for 24 hours. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ℃ to obtain 95g of methacryloxy-crosslinked magadiite (hereinafter referred to as P-MACPS-magadiite).

The composition of the resulting P-MACPS-magadiite was calculated as described above, resulting in a crosslinked methacryloyloxypropyl group (P-MACPS)_0.06MACPS_0.38DTMA_0.56Me_1.00Si₁₄O₂₉·nH₂O, bottom spacing of 1.94 nm.

(5) Interlayer silylation (incorporation of phenyl groups) by treatment of P-MACPS-magadiite with phenyltrimethoxysilane (hereinafter Ph-TRIMS).

Interlayer silylation was carried out in the same manner as in example 1(3) except that 100g of DTMA-magadiite was changed to 100g of the above-described P-MACPS-magadiite and MAC-TRIMS39.2g was changed to Ph-TRIMS263g (7 times the reaction point, manufactured by shin-Etsu chemical Co., Ltd.), thereby obtaining 96g of silylated magadiite (hereinafter referred to as P-MACPS-PhS-magadiite).

The composition of the resulting P-MACPS-PhS-magadiite was calculated in the same manner as described above, and the result was P-MACPS_0.0 ₆MACPS_0.38PhS_0.38DTMA_0.02Me_1.16Si₁₄O₂₉·nH₂O, bottom spacing of 1.95 nm.

(6) Preparing a complexing agent of P-MACPS-PhS-magadiite and 2 MT.

30g of the P-MACPS-PhS-magadiite obtained above was mixed with 150g of 2MT (manufactured by Tokyo chemical industry Co., Ltd.), and the mixture was stirred at 25 ℃ for 2 days. Then, the solid was collected by suction filtration and dried at 25 ℃ to obtain 33g of a P-MACPS-PhS-magadiite-2 MT complexing agent (hereinafter referred to as P-MACPS-PhS-magadiite/2 MT complexing agent). The interval between the bottom surfaces is 1.98 nm.

The weight of 2MT adsorbed to 1g of the obtained complexing agent was calculated using an elemental analyzer (CHN recorder MT-5 manufactured by YANACO analysis industries, Ltd.) and a thermogravimetric analyzer (TG/DTA 6300 manufactured by Hitachi High-Tech Science, Ltd.), and the result was 83.4 mg.

(7) 2MT release test from P-MACPS-PhS-magadiite/2 MT complexing agent.

40mg of the P-MACPS-PhS-magadiite/2 MT complex obtained above was mixed with 2.8g of octane (manufactured by Fuji film and Wako pure chemical industries, Ltd.), and the mixture was stirred at 25 ℃.

After the start of stirring, the sample was taken over time, the sampled solution was centrifuged, and the 2MT concentration in the supernatant was analyzed by gas chromatography (7820A, manufactured by Agilent technologies, column: CP-Sil 5 CB).

The results are shown in tables 1 and 2.

EXAMPLE 2 Synthesis of sustained Release Complex agent having 2MT inserted between layers of magadiite modified with phenylsilyl group and evaluation of sustained Release thereof

(1) Synthesis of partially protonated DTMA-magadiite (silylated precursor) by HCl treatment of DTMA-magadiite.

The DTMA-magadiite obtained in example 1(2) was mixed with 0.1mol dm^-3655g of hydrochloric acid was mixed, and the mixture was stirred at room temperature for 1 day. Then, the solid was collected by suction filtration, washed with pure water, and dried at 60 ℃ to obtain 86g of partially protonated DTMA-magadiite.

The composition of the obtained partially protonated DTMA-magadiite was calculated in the same manner as described above, and as a result, DTMA was obtained_1.11H_0.89Si₁₄O₂₉·nH₂O, the proportion of ammonium groups was 56 mol% based on the ion exchange capacity.

The interval between the bottoms of the partially protonated DTMA-magadiite was analyzed in the same manner as described above, and no clear diffraction peak was observed. This is presumably due to the fact that most of the layered structure of the resulting partially protonated DTMA-magadiite is destroyed.

(2) Interlayer silylation (incorporation of phenyl groups) by a Ph-TRIMS treatment of partially protonated DTMA-magadiite.

Interlayer silylation was carried out in the same manner as in example 1(5) except that 100g of P-MACPS-magadiite was changed to 100g of partially protonated DTMA-magadiite obtained as described above, thereby obtaining 102g of silylated magadiite (hereinafter referred to as "PhS-magadiite").

The composition of the obtained PhS-magadiite was calculated in the same manner as described above, and as a result, it was phenylsilyl (PhS)_1.13DTMA_0.40Me_0.47Si₁₄O₂₉·nH₂O, bottom spacing of 2.16 nm.

(3) Removal of residual DTMA groups and introduction of methyl groups (silanol capping) of PhS-magadiite was performed using hydrogen chloride and methanol.

100g of PhS-magadiite obtained as described above was dried under reduced pressure at 100 ℃ and about 100Pa for 2 hours, and then PGM1650g and 78.5g of 5% methanol hydrogen chloride solution were mixed with molecular sieves 3A, and the mixture was stirred under reflux for 3 days under nitrogen atmosphere. Thereafter, the solid was collected by suction filtration, washed with methanol, and dried at 60 ℃.

The total amount of the obtained solid was mixed with 1980g of methanol, and stirred for 2 days while being heated under reflux under a nitrogen atmosphere. Then, the solid was collected by suction filtration, dried at 60 ℃ to remove DTMA groups, and 76g of PhS-magadiite (hereinafter referred to as PhS-magadiite-PPMe) in which silanol derived from magadiite was O-methylated was obtained.

The composition of the obtained PhS-magadiite-PPMe was calculated in the same manner as described above, and the result was PhS_1.13DTMA_0.04Me_0.83Si₁₄O₂₉·nH₂O, bottom spacing 1.69 nm.

(4) Preparation of a PhS-magadiite-PPMe and 2MT complexing agent.

34g of a composite agent of PhS-magadiite-PPMe and 2MT (hereinafter referred to as "PhS-magadiite-PPMe/2 MT composite agent") was obtained in the same manner as in example 1(6) except that 30g of P-MACPS-PhS-magadiite was changed to the above-obtained PhS-magadiite-PPMe 30 g. The interval between the bottom surfaces was 2.11 nm.

The weight of 2MT adsorbed in 1g of the obtained composite preparation was calculated in the same manner as described above, and the result was 122.6 mg.

(5) 2MT release test from PhS-magadiite-PPMe/2 MT complexing agent.

The concentration of 2MT in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complex was changed to 40mg of the PhS-magadiite-PPMe/2 MT complex obtained as described above.

The results are shown in tables 1 and 2.

EXAMPLE 3 Synthesis of a sustained-release complexing agent having 2MT inserted between the layers of magadiite (MACPS-magadiite) which had been modified with 3-methacryloyloxypropylsilyl group and its sustained-release property was evaluated.

(1) Preparing a composite agent of MACPS-magadiite and 2 MT.

A composite preparation of MACPS-magadiite and 2MT (hereinafter referred to as MACPS-magadiite/2 MT composite preparation) was obtained in the same manner as in example 1(6) except that 30g of P-MACPS-PhS-magadiite was changed to 30g of MACPS-magadiite obtained in example 1 (3). The interval between the bottom surfaces was 2.20 nm.

The weight of 2MT adsorbed in 1g of the obtained composite preparation was calculated in the same manner as described above, and found to be 46.2 mg.

(2) 2MT release test from MACPS-magadiite/2 MT complexing agent.

The concentration of 2MT in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complex was changed to 40mg of the MACPS-magadiite/2 MT complex obtained as described above.

The results are shown in tables 1 and 2.

COMPARATIVE EXAMPLE 1 preparation of sustained-release composite having 2MT inserted between layers of unmodified Na-magadiite.

A composite preparation of Na-magadiite and 2MT (hereinafter referred to as Na-magadiite/2 MT composite preparation) was obtained in the same manner as in example 1(6) except that 30g of P-MACPS-PhS-magadiite was changed to 30g of Na-magadiite obtained in example 1 (1). The bottom surface spacing was 1.56 nm.

The weight of 2MT adsorbed in 1g of the obtained composite preparation was calculated in the same manner as described above, and the result was 12.9 mg. The results are shown in table 1.

COMPARATIVE EXAMPLE 2 Synthesis of a sustained-release complex having 2MT inserted between layers of magadiite modified by DTMA intercalation and evaluation of sustained-release properties thereof.

(1) And (3) preparing a composite agent of DTMA-magadiite and 2 MT.

30g of a composite agent of DTMA-magadiite and 2MT (hereinafter referred to as a DTMA-magadiite/2 MT composite agent) was obtained in the same manner as in example 1(6) except that 30g of P-MACPS-PhS-magadiite was changed to 30g of DTMA-magadiite obtained in example 1 (2). The bottom surface spacing was 2.89 nm.

The weight of 2MT adsorbed in 1g of the obtained composite preparation was calculated in the same manner as described above, and the result was 12.0 mg.

(2) 2MT release test from DTMA-magadiite/2 MT complexing agent.

The concentration of 2MT in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complex was changed to 40mg of the above-obtained DTMA-magadiite/2 MT complex. The results are shown in tables 1 and 2.

[ Table 1]

As shown in Table 1, the host compounds of unmodified type shown in comparative examples 1 and 2 and of conventional type in which interlayer organization was carried out using alkylammonium did not control the interaction with the guest compound, and thus only a very small amount of 2MT was adsorbed. On the other hand, when the interlayer modified layered inorganic compound having the organic-inorganic composite group of the present invention between the layers as shown in examples 1 to 3 is used as a host compound, 2MT as a guest compound can be effectively adsorbed and held. In example 2, 11.5 times as much guest compound as in comparative example 2 can be adsorbed per unit host compound.

In addition, since the distance between the bottom surfaces of the layered inorganic compounds is increased after the layered inorganic compounds are combined with guest compounds, it means that many of the adsorbed guest compounds are inserted between the layers.

In the 2MT release test using the complexing agents of examples 1 to 3 in table 1 and comparative example 2, the release rate was calculated as the ratio of the guest compound released from the host-guest complexing agent to the amount of 2MT adsorbed in the initial host-guest complexing agent based on the measured 2MT concentration in octane, and the release rate indicated by the time course is shown in table 2.

[ Table 2]

In any of examples 1 to 3, the release rate of 2MT gradually increased with the passage of time, and this indicated that the guest compound was slowly released in octane as a test solvent.

On the other hand, when the layered inorganic compound organized with alkylammonium (DTMA) as a conventional technique shown in comparative example 2 was used as the host compound, 18.5% of the guest compound was released up to 1 hour later, but the guest compound remained adsorbed in the layered inorganic compound and was not released thereafter, and the sustained release was not achieved.

While example 1 used a layered inorganic compound in which the interlayer was crosslinked by an organic-inorganic composite crosslinked structure as a host compound, examples 2 and 3 used a layered inorganic compound in which the interlayer was modified with a phenylsilyl group or a methacryloxy group and was not crosslinked by the interlayer as a host compound. In example 2, when the release rate (gradient of release rate) of 2MT was observed, 21.9% was released up to 1 hour later, and thereafter, it was also larger than that in example 1. In example 3, when the release rate (gradient of release rate) of 2MT was observed, 38.7% was released even after 1 hour, and thereafter, the release rate was larger than that in example 1.

On the other hand, in example 1, a layered inorganic compound which is interlayer-crosslinked by introducing methacryloyloxy groups between layers and causing a crosslinking reaction is used as a main compound, but when the release rate (gradient of release rate) of 2MT is focused, the release rate is very small up to 1 hour and 1.9%, and thereafter, the release rate is very small, and 2MT is very slowly released. Namely, it means: by appropriately maintaining the interlayer distance by interlayer crosslinking, the interaction of the guest compound between layers can also be controlled, and therefore, the release rate can be appropriately controlled, and the function derived from the guest compound can be exhibited over a long period of time (the lifetime can be extended).

By using the layered inorganic compound modified between the organic-inorganic composite substrates of the present invention as a host compound, a desired guest compound can be contained more efficiently than in the conventional methods, and the release rate can be controlled to allow effective sustained release over a long period of time.

< example 4 > Synthesis of sustained-release complexing agent having 2,3, 5-trimethylpyrazine (hereinafter, referred to as 235TMP) inserted between layers of magadiite modified by 3-methacryloxypropylsilyl group and evaluation of sustained-release property thereof.

(1) Preparing a complexing agent of MACPS-magadiite and 235 TMP.

49g of a composite of MACPS-magadiite and 235TMP (hereinafter referred to as MACPS-magadiite/235 TMP composite) was obtained in the same manner as in example 3(2) except that 2MT150g was changed to 150g of 235TMP (manufactured by Tokyo chemical industries, Ltd.). The interval between the bottom surfaces was 3.20 nm.

The weight of 235TMP adsorbed to 1g of the obtained composite preparation was calculated in the same manner as described above, and found to be 381.5 mg.

(2) 235TMP release test from MACPS-magadiite/235 TMP complexing agent.

The 235TMP concentration in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complexing agent was changed to 40mg of the MACPS-magadiite/235 TMP complexing agent obtained above.

The results are shown in tables 3 and 4.

COMPARATIVE EXAMPLE 3 Synthesis of sustained Release Complex agent having 235TMP inserted between layers of magadiite modified by inter-DTMA layer and evaluation of sustained Release thereof.

(1) Preparing a complexing agent of DTMA-magadiite and 235 TMP.

34g of a composite agent of DTMA-magadiite and 235TMP (hereinafter referred to as "DTMA-magadiite/235 TMP composite agent") was obtained in the same manner as in example 4(1) except that 30g of MACPS-magadiite was changed to 30g of DTMA-magadiite obtained in example 1 (2). The interval between the bottom surfaces was 3.83 nm.

The weight of 235TMP adsorbed to 1g of the obtained composite preparation was calculated in the same manner as described above, and found to be 126.8 mg.

(2) 235TMP release test from DTMA-magadiite/235 TMP complexing agent.

The 235TMP concentration in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complexing agent was changed to 40m of the aforementioned DTMA-magadiite/235 TMP complexing agent. The results are shown in tables 3 and 4.

[ Table 3]

As shown in table 3, when the interlayer modified layered inorganic compound of the present invention modified between organic and inorganic composite substrates shown in example 4 was used as a host compound, 235TMP as a guest compound was adsorbed and retained more effectively than the conventional host compound after interlayer organization with alkylammonium shown in comparative example 3, and in example 4, 4.2 times as much guest compound as in comparative example 3 was adsorbed per unit host compound. In addition, since the distance between the bottom surfaces of the layered inorganic compound is increased after the layered inorganic compound is combined with the guest compound, it is shown that many of the adsorbed guest substances are inserted between the layers.

In the 235TMP release test using the complexing agents of example 4 and comparative example 3 of table 3, the ratio of the guest compound released from the host-guest complexing agent to the amount of 235TMP adsorbed in the initial host-guest complexing agent was calculated as a release rate based on the 235TMP concentration in the measured octane, and the release rate indicated by the time series is shown in table 4.

[ Table 4]

In table 4, the gradual increase of the release rate of 235TMP with the passage of time in example 4 indicates that the guest compound was slowly released in octane as a test solvent.

On the other hand, in the conventional technique of comparative example 3, after releasing a large amount of guest compound until 1 hour later, the guest compound remains adsorbed in the layered inorganic compound and is not released, and the sustained release cannot be achieved.

By using the layered inorganic compound modified between the organic-inorganic composite substrates of the present invention as a host compound in this way, a desired guest compound can be efficiently contained, and the release rate can be controlled to achieve sustained release.

EXAMPLE 5 Synthesis of a sustained-release composition having 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as OIT) inserted between layers of magadiite modified with phenylsilyl groups and evaluation of sustained-release property thereof.

(1) Preparation of a complex agent of PhS-magadiite-PPMe and OIT.

PhS-magadiite-PPMe 90g obtained as in example 2(4) was mixed with 200g of methanol and OIT10g and stirred at 25 ℃ for 24 hours. Then, the mixture was transferred to a shallow pan and dried at 25 ℃ for 16 hours, and methanol as a solvent was removed to obtain 99g of a complex agent of PhS-magadiite-PPMe and OIT (hereinafter referred to as a PhS-magadiite-PPMe/OIT complex agent, the concentration of the active ingredient of OIT: 10 wt%). The bottom surface spacing was 2.77 nm.

(2) OIT release test from the PhS-magadiite-PPMe/OIT complex.

The OIT concentration in octane was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complex agent was changed to 20mg of the above-obtained PhS-magadiite-PPMe/OIT complex agent, and 2.8g of octane was changed to 20g of octane.

The results are shown in tables 5 and 6.

EXAMPLE 6 Synthesis of a sustained-release complex agent having OIT inserted between layers of magadiite modified with phenylsilyl and hexylsilyl groups and evaluation of the sustained-release property thereof.

(1) Interlayer silylation (introduction of phenyl and hexyl groups) by treatment of partially protonated DTMS and hexylsilyltrimethoxysilane (hereinafter Hx-TRIMS) of DTMA-magadiite.

Interlayer silylation was carried out in the same manner as in example 1(3) except that 100g of DTMA-magadiite was changed to 100g of partially protonated DTMA-magadiite obtained as in example 2(1), and MAC-TRIMS39.2g was changed to Ph-TRIMS132g and Hx-TRIMS (manufactured by Tokyo chemical industries Co., Ltd.) to 137g, thereby obtaining 108g of silylated magadiite (hereinafter referred to as PhS-HxS-magadiite).

The composition of the obtained PhS-HxS-magadiite was calculated using the elemental analyzer, thermogravimetric analyzer and nuclear magnetic resonance apparatus (JNM-ECA 400, manufactured by Nippon electronics Co., Ltd.), and the result was PhS_0.45HxS_0.24DTMA_0.71Me_0.60Si₁₄O₂₉·nH₂O。

The bottom surface spacing of the obtained PhS-HxS-magadiite was determined in the same manner as described above, and found to be 2.35 nm.

(2) Removal of residual DTMA groups and introduction of methyl groups (silanol capping) from Ph-HxS-magadiite using hydrogen chloride and methanol.

PhS-HxS-magadiite (hereinafter referred to as PhS-HxS-magadiite-PPMe) 76g was obtained in the same manner as in example 2(3) except that 100g of PhS-magadiite was changed to 100g of PhS-HxS-magadiite, from which DTMA groups were removed and silanol derived from magadiite was O-methylated.

The composition of the obtained PhS-HxS-magadiite-PPMe was calculated in the same manner as described above, and the result was PhS_0.45HxS_0.24DTMA_0.18Me_1.13Si₁₄O₂₉·nH₂O, bottom spacing of 1.95 nm.

(3) Preparation of PhS-HxS-magadiite-PPMe/OIT composite.

95g of a composite agent of PhS-HxS-magadiite-PPMe and OIT (hereinafter referred to as "PhS-HxS-magadiite-PPMe/OIT composite agent", the concentration of the active ingredient in OIT: 10% by weight) was obtained in the same manner as in example 5(1) except that PhS-magadiite-PPMe 90g was changed to PhS-HxS-magadiite-PPMe 90 g. The bottom surface spacing was 2.66 nm.

(4) OIT Release test from PhS-HxS-magadiite-PPMe/OIT Complex.

The OIT concentration in octane was analyzed in the same manner as in example 5(2) except that 20mg of the PhS-magadiite-PPMe/OIT complex agent was changed to 20mg of the PhS-HxS-magadiite-PPMe/OIT complex agent obtained above.

The results are shown in tables 5 and 6.

EXAMPLE 7 Synthesis of a sustained-release composition having OIT inserted between layers of magadiite modified with phenylsilyl and 3-mercaptopropylsilyl and evaluation of the sustained-release property thereof.

(1) Interlayer silylation (introduction of phenyl and mercaptopropyl groups) by Ph-TRIMS of partially protonated DTMA-magadiite and treatment with 3-mercaptopropylsilyltrimethoxysilane (hereinafter referred to as MP-TRIMS).

Interlayer silylation was carried out in the same manner as in (1) of example 6 except that Hx-TRIMS137g was changed to MP-TRIMS (manufactured by shin-Etsu chemical Co., Ltd.) 123g, thereby obtaining 104g of silylated magadiite (hereinafter referred to as PhS-MPS-magadiite).

The composition of the obtained PhS-MPS-magadiite was calculated in the same manner as described above, and the result was PhS_0.62Mercaptopropylsilyl (MPS)_0.61DTMA_0.27Me_0.50Si₁₄O₂₉·nH₂O, bottom spacing of 2.15 nm.

(2) Removal of residual DTMA groups and introduction of methyl groups (silanol capping) of PhS-MPS-magadiite using hydrogen chloride and methanol.

In the same manner as in example 2(3), 93g of PhS-MPS-magadiite (hereinafter referred to as PhS-MPS-magadiite-PPMe) from which DTMA groups were removed and silanol derived from magadiite was O-methylated was obtained except that 100g of PhS-magadiite was changed to 100g of PhS-MPS-magadiite.

The composition of the obtained PhS-HxS-magadiite-PPMe was calculated in the same manner as described above, and the result was PhS_0.62MPS_0.61DTMA_0.19Me_0.58Si₁₄O₂₉·nH₂O, bottom spacing of 2.15 nm.

(3) Preparation of a PhS-MPS-magadiite-PPMe and OIT complexing agent.

98g of a composite agent of PhS-MPS-magadiite-PPMe and OIT (hereinafter referred to as "PhS-MPS-magadiite-PPMe/OIT composite agent", the concentration of the active ingredient of OIT: 10% by weight) was obtained in the same manner as in example 5(1) except that PhS-MPS-magadiite-PPMe 90g was changed to PhS-MPS-magadiite-PPMe 90 g. The interval between the bottom surfaces was 2.48 nm.

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

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

The results are shown in tables 5 and 6.

EXAMPLE 8 Synthesis of a sustained-release complexing agent having OIT inserted between layers of magadiite modified with 3-mercaptopropylsilyl groups and evaluation of the sustained-release property thereof.

(1) Interlayer silylation (introduction of mercaptopropyl groups) by MP-TRIMS treatment of partially protonated DTMA-magadiite.

Interlayer silylation was carried out in the same manner as in example 1(3) except that 100g of DTMA-magadiite was changed to 100g of partially protonated DTMA-magadiite obtained as in example 2(1) and MAC-TRIMS39.2g was changed to MP-TRIMS245g, thereby obtaining 97g of silylated magadiite (hereinafter referred to as MPs-magadiite).

The composition of the MPS-magadiite obtained was calculated in the same manner as described above, and as a result, MPS was obtained_0.95DTMA_0.30Me_0.75Si₁₄O₂₉·nH₂O, bottom spacing of 2.22 nm.

(2) MPS-magadiite removal of residual DTMA groups and introduction of methyl groups (silanol capping) using hydrogen chloride and methanol.

MPS-magadiite (hereinafter referred to as MPS-magadiite-PPMe) 93g from which DTMA groups were removed and silanol derived from magadiite was O-methylated was obtained in the same manner as in example 2(3) except that PhS-magadiite 100g was changed to MPS-magadiite 100 g.

The composition of the MPS-magadiite-PPMe thus obtained was calculated in the same manner as described above, and as a result, MPS was obtained_0.95DTMA_0.23Me_0.82Si₁₄O₂₉·nH₂O, bottom spacing of 2.21 nm.

(3) Preparing MPS-magadiite-PPMe and OIT composite agent.

95g of a composite agent of MPS-magadiite-PPMe and OIT (hereinafter referred to as MPS-magadiite-PPMe/OIT composite agent, the concentration of the active ingredient in OIT: 10% by weight) was obtained in the same manner as in example 5(1) except that PhS-magadiite-PPMe 90g was changed to MPS-magadiite-PPMe 90 g. The interval between the bottom surfaces was 2.51 nm.

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

The OIT concentration in octane was analyzed in the same manner as in example 5(2) except that 20mg of the PhS-magadiite-PPMe/OIT complex agent was changed to 20mg of the MPS-magadiite-PPMe/OIT complex agent thus obtained.

The results are shown in tables 5 and 6.

COMPARATIVE EXAMPLE 4 Synthesis of a sustained-release composition having OIT inserted between layers of magadiite modified by DTMA intercalation and evaluation of sustained-release property thereof.

(1) Preparation of DTMA-magadiite and OIT complexing agent

99g of a composite agent of DTMA-magadiite and OIT (hereinafter referred to as a DTMA-magadiite/OIT composite agent, the concentration of the effective component of OIT: 10 wt%) was obtained in the same manner as in example 5(1) except that PhS-magadiite-PPMe 90g was changed to 90g of DTMA-magadiite obtained in example 1 (2). The interval between the bottom surfaces was 3.99 nm.

(2) OIT release test from DTMA-magadiite/OIT complex.

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

The results are shown in tables 5 and 6.

[ Table 5]

As shown in table 5, it can be seen that: when the layered inorganic compound modified between the organic-inorganic composite interlayers of the present invention is used as a host compound, and when the layered inorganic compound organized between the conventional alkylammonium groups is used as a host compound, OIT as a guest compound is interposed between the layers.

In the OIT release test using the complexing agents of examples 5 to 8 of table 5 and comparative example 4, the release rate was calculated as the ratio of the guest compound released from the host-guest complexing agent to the amount of OIT adsorbed in the initial host-guest complexing agent based on the measured OIT concentration in octane, and the release rate indicated by the time course is shown in table 6.

[ Table 6]

In table 6, examples 5 to 8 showed that the guest compound was slowly released in octane as a test solvent by gradually increasing the release rate of OIT as the guest compound with the passage of time.

On the other hand, in the prior art of comparative example 4, almost all of the guest compound was released up to 1 hour, and sustained release was not possible.

Further, when examples 5 to 8 were compared, it was shown that: by changing the interlayer modification group of the host compound and appropriately combining a plurality of modification groups, the rate of sustained release of the guest compound can be changed.

EXAMPLE 9 Synthesis of a sustained-release composition comprising magadiite interlaminar modified with phenylsilyl and hexylsilyl groups and 1- (1-methylpropoxycarbonyl) -2- (2-hydroxyethyl) piperidine (hereinafter referred to as Icaritin) inserted between the layers, and evaluation of the sustained-release property thereof.

(1) Preparation of PhS-HxS-magadiite-PPMe and Escarin complexing agent.

97g of a PhS-HxS-magadiite-PPMe/Escarelin complex (hereinafter referred to as PhS-HxS-magadiite-PPMe/Escarelin complex, concentration of active ingredient of Escarelin: 10% by weight) was obtained in the same manner as in example 6(3) except that OIT10g was changed to 10g of Escarelin (manufactured by Combi-Blocks). The bottom surface spacing was 2.28 nm.

(2) Ecameratin release test from PhS-HxS-magadiite-PPMe/Ecameratin complex.

The concentration of escaroptin in the 2.4% citric acid aqueous solution was analyzed in the same manner as in example 1(7) except that 40mg of the P-MACPS-PhS-magadiite/2 MT complex was changed to 20mg of the above-obtained PhS-HxS-magadiite-PPMe/escaroptin complex, 2.8g of octane was changed to 20g of a 2.4% citric acid aqueous solution (a solution prepared by dissolving 2.5g of citric acid in 100g of pure water), and the stirring temperature was changed from 25 ℃ to 40 ℃.

The results are shown in tables 7 and 8.

Comparative example 5

The synthesis and the evaluation of the slow release performance of the slow release complexing agent of the escaroptin are inserted between the layers of the magadiite modified by the DTMA basal layer.

(1) And (3) preparing a compound agent of DTMA-magadiite and Escarin.

96g of a combination of DTMA-magadiite and Escarelin (hereinafter referred to as DTMA-magadiite/Escarelin combination, concentration of active ingredient of Escarelin: 10% by weight) was obtained in the same manner as in example 3(1) except that OIT10g was changed to 10g of Escarelin. The interval between the bottom surfaces was 3.55 nm.

(2) Escitin release test from DTMA-magadiite/Escitin complex.

The concentration of escargot in a 2.4% citric acid aqueous solution was analyzed in the same manner as in example 7(2) except that 20mg of the DTMA-magadiite/OIT complex was changed to 20mg of the DTMA-magadiite/escargot complex obtained as described above.

The results are shown in tables 7 and 8.

[ Table 7]

As shown in table 7, it can be seen that: when the layered inorganic compound modified between the organic-inorganic composite substrates of the present invention is used as a host compound and when a conventional layered inorganic compound organized between alkylammonium groups is used as a host compound, the intermediate layer is intercalated with the ercaprepin as a guest compound.

In the ekatin release test using the complexing agents of example 9 and comparative example 4 of table 7, the ratio of the guest compound released from the host-guest complexing agent to the amount of the adsorbed ekatin in the initial host-guest complexing agent was calculated as the release rate based on the measured ekatin concentration in the 2.4% citric acid aqueous solution, and the release rate indicated by the time course is shown in table 8.

[ Table 8]

As shown in example 9 of table 8, the complexing agent containing the layered inorganic compound as a host compound, which is interlaminar modified with an organic-inorganic complex group via a covalent bond, of the present invention effectively retains and slowly releases escoretin as a guest compound even in an acidic solution. On the other hand, in the case of comparative example 5 in which the conventional layered inorganic compound organized between the alkylammonium layers was used as the host compound, as compared with example 7, the escitalopram, which is the guest compound, was released into the aqueous citric acid solution after 1 hour to a greater extent, and was not released slowly thereafter, but rather the concentration in the aqueous citric acid solution decreased. It is presumed that in comparative example 5, since the interlayer is modified with alkylammonium via an ionic bond, the modification is easily affected by the pH environment around the complexing agent, and desorption of alkylammonium from the interlayer and re-adsorption of escaroptin occur, indicating that the modification is not suitable as a sustained-release material.

< example 10 > Synthesis of a sustained-release complexing agent having pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ] (hereinafter referred to as Irganox 1010) inserted between layers of magadiite modified with phenylsilyl groups and evaluation of sustained-release property thereof.

(1) Preparation of a PhS-magadiite-PPMe and Irganox1010 complexing agent.

97g of a composite preparation of PhS-magadiite-PPMe and Irganox1010 (hereinafter referred to as "PhS-magadiite-PPMe/Irganox 1010 composite preparation", the active ingredient concentration of Irganox1010 composite preparation: 10% by weight) was obtained in the same manner as in example 5(1) except that OIT10g was changed to Irganox1010 (manufactured by BASFJAPAN). The interval between the bottom surfaces was 1.93 nm.

(2) Irganox1010 release test from PhS-magadiite-PPMe/Irganox 1010 complexing agent.

The Irganox1010 concentration in octane was analyzed in the same manner as in example 1(7) except that 40mg of P-MACPS-PhS-magadiite/2 MT complex was changed to 20mg of the above-obtained PhS-magadiite-PPMe/Irganox 1010 complex, and 2.8g of octane was changed to 20g of octane. The results are shown in tables 9 and 10.

Comparative example 6

The synthesis of the Irganox1010 sustained-release complexing agent and the evaluation of the sustained-release property thereof were compounded between layers of magadiite modified by the DTMA interlayer.

(1) And (3) preparing a composite agent of DTMA-magadiite and Irganox 1010.

95g of a composite agent of DTMA-magadiite and Irganox1010 (hereinafter referred to as a DTMA-magadiite/Irganox 1010 composite agent, the active ingredient concentration of the Irganox1010 composite agent: 10% by weight) was obtained in the same manner as in example 3(1) except that OIT10g was changed to Irganox 101010 g. The bottom surface spacing was 2.86 nm.

(2) Irganox1010 release test from DTMA-magadiite/Irganox 1010 complexing agent.

The concentration of Irganox1010 in octane was analyzed in the same manner as in example 10(2) except that 20mg of the PhS-magadiite-PPMe/Irganox 1010 complex agent was changed to 20mg of the DTMA-magadiite/Irganox 1010 complex agent obtained above. The results are shown in tables 9 and 10.

[ Table 9]

As shown in table 9, it can be seen that: in the case of example 10 in which the layered inorganic compound modified between the organic-inorganic composite base layers of the present invention was used as the host compound, the gap between the front and rear bottom surfaces of Irganox1010 as the guest compound was enlarged before and after the adsorption, and Irganox1010 was inserted between the layers.

On the other hand, in the case of comparative example 6 in which a layered inorganic compound organized between layers by a conventional alkylammonium was used as a host compound, the gap between the bottom surfaces before and after the adsorption of Irganox1010 as a guest compound did not change, and it could not be determined that Irganox1010 was inserted between the layers and was not inserted.

In the Irganox1010 release test using the complexing agents of example 10 and comparative example 6 in table 9, the ratio of the guest compound released from the host-guest complexing agent to the amount of Irganox1010 adsorbed in the initial host-guest complexing agent was calculated as the release rate based on the measured Irganox1010 concentration in octane, and the release rate shown in a time series is shown in table 10.

[ Table 10]

In table 10, the gradual increase in the Irganox1010 release rate with time in example 10 indicates that the guest compound was slowly released in octane as a test solvent.

On the other hand, in the prior art of comparative example 6, almost all of the guest compound was released up to 1 hour, and sustained release was not possible.

By using the layered inorganic compound modified between the organic-inorganic composite base layers of the present invention as a host compound, even a very large molecule such as Irganox1010 can be efficiently held between the layers, and the release rate can be controlled to achieve sustained release.

EXAMPLE 11 mould resistance test of resin incorporating PhS-HxS-magadiite-PPMe/OIT complexing agent (slow release mould inhibitor).

(1) And (3) manufacturing a resin test piece.

40g of polyethylene resin (UBE polyethylene J3519, manufactured by Yusha polyethylene Co., Ltd., hereinafter referred to as PP resin) was dissolved by heating and milling at 140 ℃ under stirring, 0.4g of the PhS-HxS-magadiite-PPMe/OIT composite agent synthesized in example 6 was added thereto, and after stirring for 15 minutes, the resulting mixture was charged into a mold, and after pressing at 160 ℃ for 5 minutes, the mixture was naturally cooled to be molded into a 2mm thick sheet, and a test piece having a size of 2.5cm × 2.5.5 cm × 2mm was cut therefrom.

(2) And (3) performing heat deterioration treatment on the resin test piece.

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

(3) Hot water immersion degradation treatment of the resin test piece.

The test piece prepared in the above (1) was added with a metal weight, and the test piece was put into a 1L polyethylene bottle containing pure water 1L, the test piece was completely immersed in water, the polyethylene bottle was closed, and the bottle was heated at 60 ℃ for 120 hours, and during the process, the water was replaced with pure water 24 hours after the start of immersion in hot water and 96 hours after the start.

(4) Mildew resistance test (halo test).

The mold used for the evaluation of mold resistance was black mold (Cladosporium cladosporides), Penicillium Penicillium and Aspergillus niger (Aspergillus niger), spores were added to the inorganic salt solution having the composition shown in Table 11, and the number of each spore was adjusted to 10⁵The test pieces prepared in (1) to (3) above were placed in the vicinity of the center of a potato dextrose agar medium having a diameter of 9cm and adhered together, and the resulting mixture was cultured at 25 ℃ and 90% or more humidity for 3 days to confirm the presence or absence of the formation of a growth inhibitory band, thereby evaluating the mildew resistance, and the evaluation results are shown in Table 12.

Comparative example 7 is a mold test of a resin in which OIT (an antimildew organic compound as a guest compound) is mixed.

Test pieces were produced in the same manner as in example 11 except that 0.4g of PhS-HxS-magadiite-PPMe/OIT compound was changed to OIT0.04g, and subjected to accelerated deterioration treatment and hot-water immersion deterioration treatment to carry out a mold-proof test. The results are shown in table 12.

Comparative example 8 mould proof test of a resin containing PhS-HxS-magadiite-PPMe (interlayer modified layered inorganic compound as a main compound).

Test pieces were produced in the same manner as in example 11 except that 0.4g of PhS-HxS-magadiite-PPMe/OIT composite agent was changed to PhS-HxS-magadiite-PPMe0.36g, and subjected to accelerated deterioration treatment and hot water immersion deterioration treatment to carry out a mildew-proof test. The results are shown in table 12.

[ Table 11]

Sodium nitrate	2.0g
		Potassium dihydrogen phosphate	0.7g
Dipotassium hydrogen phosphate	0.3g
		Potassium chloride	0.5g
Magnesium sulfate heptahydrate	0.5g
		Iron (II) sulfate heptahydrate	0.01g
Distilled water	1000mL
		pH	6.0 to 6.5 (adjusted with sterile 0.01 mol/L sodium hydroxide solution)

[ Table 12]

As shown in table 12, the test piece in which OIT of comparative example 7 was mixed into PP resin alone exhibited a mold-inhibiting zone at the beginning, but no mold-inhibiting zone was observed at all and no mold-inhibiting effect was exhibited after the deterioration test by heating and hot water immersion. On the other hand, in the test piece of example 11 in which the sustained-release mildewcide of the present invention was mixed into the PP resin, the inhibition zone was observed not only at the beginning but also after the deterioration treatment by heating and hot water immersion, and the mildewproofing effect was confirmed. This indicates that when the layered inorganic compound modified between the organic-inorganic composite base layers of the present invention is used as a host compound, the antifungal organic compound can be imparted with sustained release properties, and heat resistance and hot water resistance can be imparted thereto, and that the layered inorganic compound can be used as a practically sustained-release antifungal agent.

As described above, by using the layered inorganic compound modified between organic-inorganic composite interlayers of the present invention as a host compound, it is possible to appropriately design an interlayer environment in accordance with a guest compound having various structures and molecular weights, and thus it is possible to prepare a sustained-release composite agent which has a very wide application range, which can interpose a desired guest compound between layers, and which can adjust the sustained-release rate according to the purpose. Further, since the layered inorganic compound in which interlayer modification is performed via a covalent bond via an organic-inorganic complex group is used as the host compound, 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 exhibited depending on the use conditions.

Claims

1. A sustained-release composite agent comprising an interlayer modified layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) and a compound interposed between the layers of the interlayer modified layered inorganic compound,

[ chemical formula 1]

In the formula (1), M¹And M²Each independently represents Si, Al, Ti or Zr; r^aAnd R^bEach independently represents a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms, and optionally has a branched chain having 3 to 20 carbon atomsA saturated or unsaturated cycloalkylene group, an arylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms; r^cRepresents an organic group having 1 to 40 carbon atoms, and optionally contains a hetero atom, a linear chain structure, a branched chain structure, a cyclic structure, an unsaturated bond and an aromatic structure; r represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, 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 ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an ureide group, an isocyanate group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, a sulfonic acid group, Sulfonate group or halogen atom; z represents a hydrogen atom, a linear or branched saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a branched saturated or unsaturated cycloalkyloxy group optionally having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a branched saturated or unsaturated heterocycloalkyloxy group optionally 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, 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; at M¹And M²When any one of Si, Ti or Zr, x corresponding to the Si, Ti or Zr is 2, and n is an integer of 0-2; at M¹And M²In the case of Al, x corresponding thereto is 1, and n is 0 or 1; in case n is 2, R is optionally the same or different; p, q and r are integers of 0 or 1, and at least one of them is 1;

[ chemical formula 2]

In the formula (2), R represents a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, a branched saturated or unsaturated cycloalkyl group optionally 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, and is optionally substituted with a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloyloxy group, a methacryloyloxy group, a hydroxyl group, an amino group, a linear or branched saturated or unsaturated monoalkylamino group or dialkylamino group having 1 to 20 carbon atoms, a monoarylamino group or diarylamino group having 6 to 20 carbon atoms, a monoarylamino group or diarylamino group having 7 to 20 carbon atoms, a primary ammonium group, a secondary ammonium group, a tertiary ammonium group or a quaternary ammonium group, a thiol group, an isocyanurate group, an isocyanato group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylate group, a phosphoric acid group, a phosphate group, an ester group, a carboxylic acid, Sulfonic acid group, sulfonate group or halogen atom; m represents Si, Al, Ti or Zr; z represents a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group optionally having a branched chain having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, a saturated or unsaturated heterocycloalkyloxy group optionally having 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, 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; when M is any one of Si, Ti or Zr, x corresponding to M is 3, and n is an integer of 1-3; in the case where M is Al, x corresponding thereto is 2, and n is 1 or 2; in case n is 2 or 3, R is optionally the same or different.

2. The sustained-release complex agent according to claim 1, wherein, in the organic-inorganic complex group, M in the formula (1)¹And M²All are Si, or M in the formula (2) is Si.

3. The sustained-release complex agent according to claim 1 or2, wherein at least one selected from a carboxylate structure, a carbamate structure, a urea structure, an amine structure, an ether structure, a thioether structure, a disulfide structure, and a hydroxyl group is contained in the organic-inorganic complex group represented by the formula (1).

4. The sustained-release composite agent according to any one of claims 1 to 3, wherein the compound inserted between the layers of the interlayer-modified layered inorganic compound is a compound containing at least one selected from a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structure group, a hydrogen bond-forming group, a coordinate bond-forming group, and an ionic bond-forming group.

5. The sustained-release composite agent according to any one of claims 1 to 4, wherein the layered inorganic compound comprises one selected from a layered silicate, a layered clay mineral, and a layered metal oxide か.

6. A method for producing a sustained-release composite agent according to any one of claims 1 to 5, wherein the interlayer modified layered inorganic compound is mixed with a compound interposed between the layers of the interlayer modified layered inorganic compound.