JPWO2019146304A1 - Sustained-release composite agent containing an interlayer-modified layered inorganic compound and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To appropriately interact with a desired functional compound to be sustained-release by introducing a chemically stable organic-inorganic composite group having various chemical structures between layers of a layered inorganic compound. An object of the present invention is to provide a sustained-release composite agent and a method for producing the same, in which an environment is designed and constructed between layers, and a functional compound is inserted between layers and then released over a long period of time. SOLUTION: The interlayer-modified layered inorganic compound having an organic-inorganic composite group represented by the following formula (1) or the following formula (2) is inserted between layers of the layered inorganic compound and the interlayer-modified layered inorganic compound. A sustained-release complex containing the above compounds. [Chemical 1] [Chemical 2]

Description

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

As the sustained-release material that releases the functional compound inserted between the layers of the layered inorganic compound, an unmodified layered inorganic compound is used as the host compound, and the ionized functional compound is used as the guest compound and exists between the layers of the host compound. The functional compound is inserted between the layers by ion exchange between the exchangeable ion and the ionized guest compound, and the complex agent is released slowly, and the exchangeable metal cation existing between the layers of the layered inorganic compound is exchanged with alkylammonium. There is known a composite agent that organically (hydrophobicizes), inserts a functional compound between layers, and releases it slowly.

For example, in Patent Document 1, a layered double hydroxide having no modification between layers is used as a host compound, and anionized capsaicin as a guest compound is mixed with the layered double hydroxide, which is an anion existing between layers and nitrate ion. A layered double hydroxide-anionized capsaicin (host-guest) complex is prepared by exchange, and a complex agent in which the guest compound capsaicin is slowly released from the complex and a method for producing the same are described.

Further, in Patent Document 2, as a host compound, an organic bentonite in which the layers are organicized by cation exchange between an exchangeable metal cation between layers of the clay mineral montmorillonite and dimethyldioctadecylammonium is used, and neutral cymethrin is used as a guest compound. A mixed sustained-release simethrin granule and a method for producing the same are described.

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

However, when an unmodified layered inorganic compound containing an exchangeable metal cation described in Patent Document 1 is used as a host compound, only an ionized guest compound can be applied as a sustained-release compound, and a nonionic compound can be applied. Since it is not possible to insert the compound and release it slowly, and it is not possible to control the sustained release by designing the environment between the layers as desired according to the guest compound, the release rate of any compound can be adjusted according to the purpose. It cannot be adjusted and sustained.

Further, in the organic modification with alkylammonium described in Patent Document 2, since the interlayer environment of the host compound is only made hydrophobic and cannot be given diversity, any desired guest compound and layered inorganic material can be used according to the intended use. It is not possible to control the interaction with the compound, and it is difficult to design and synthesize the interlayer environment so that the insertion into and from the layers and the sustained release rate from the layers are optimized. Limited.
Further, since the interlayer is modified with alkylammonium, the cation exchange reaction between the layers proceeds easily under the influence of the usage environment such as acidic conditions, and the desorption of the alkylammonium group from the layers easily proceeds. Therefore, the conditions for using the sustained-release agent using such an organically modified host compound are limited, and the interlayer-modified structure of the organically modified inorganic compound can be maintained during relatively long-term use. It becomes difficult and is not practical as a sustained-release agent.

Further, since the layers of the layered inorganic compound which is the host compound of Patent Document 1 and Patent Document 2 are not crosslinked, the layered structure collapses and peels off depending on the usage environment, and the inserted guest compound is released at once. The uses and environments in which the compound is used as a sustained release agent are extremely limited, not versatile, and not industrially useful.

In view of the above situation, the present invention has been made after inserting a desired compound to be sustained-release between layers of a layered inorganic compound that is crosslinked via a covalent bond or a layered inorganic compound that has been interlayer-modified via a covalent bond. An object of the present invention is to provide a sustained-release composite agent released over a relatively long period of time and a method for producing the same.

As a result of diligent studies to solve the above problems, the present inventor has an interlayer cross-linked layered inorganic compound having an organic-inorganic composite cross-linked structure between layers of the layered inorganic compound, or an organic layer such as a silyl group between the layers of the layered inorganic compound. We have found that a sustained-release composite agent in which an interlayer-modified layered inorganic compound modified with an inorganic composite group is used as a host compound and a functional compound is inserted as a guest compound between the layers can solve the above problems, and the present invention is completed. I arrived.

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

(In the formula (1), M ¹ and M ² each independently represent Si, Al, Ti or Zr, and R ^a and R ^b are independent linear or branched chains having 1 to 20 carbon atoms, respectively. Saturated or unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branch of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms or aralkylene group of 7 to 20 carbon atoms, R ^c Indicates an organic group consisting of 1 to 40 carbon atoms and may contain a heteroatom, a linear structure, a branched structure, a cyclic structure, an unsaturated bond and an aromatic structure, and R is a linear or linear group having 1 to 20 carbon atoms. Indicates a saturated or unsaturated alkyl group having a branched chain, a saturated or unsaturated cycloalkyl group which may have a branched chain having 3 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms. , Vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, saturated or unsaturated mono or dialkylamino group of linear or branched chain with 1 to 20 carbon atoms, carbon number 6 to 20 mono or diarylamino groups, 7 to 20 carbons mono or dialalkylamino groups, primary, secondary, tertiary or quaternary ammonium groups, thiol groups, isocyanurate groups, ureido groups , Isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group or halogen atom may be substituted. Hydrogen atom, saturated or unsaturated alkyloxy group with 1 to 8 carbon atoms, saturated or unsaturated cycloalkyloxy group with 3 to 8 carbon atoms, trimethylsilyloxy group, dimethylsilyloxy group, carbon number Saturated or unsaturated heterocycloalkyloxy groups, which may have 1 to 8 branched chains, halogen atoms, hydroxyl groups, amino groups, linear or branched saturated or unsaturated alkylamino groups having 1 to 6 carbon atoms, Indicates an oxygen atom derived from a saturated or unsaturated dialkylamino group or layered inorganic compound of a linear or branched chain having 1 to 6 carbon atoms, and when M ¹ and M ² are either Si, Ti or Zr, The corresponding x is 2 and n is an integer of 0 to 2, and when M ¹ and M ² are Al, the corresponding x is 1 and n is 0 or 1, and n is. In the case of 2, R may be the same or different, and p, q and And r are integers of 0 or 1, at least one of which is 1. )

（式（２）において、Ｒは、炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和アルキル基、炭素数３〜８の分岐鎖があっても良い飽和もしくは不飽和シクロアルキル基、炭素数６〜２０のアリール基または炭素数７〜２０のアラルキル基を示し、それぞれビニル基、エポキシ基、オキセタニル基、エーテル基、アクリロキシ基、メタクリロキシ基、水酸基、アミノ基、炭素数１〜２０の直鎖または分岐鎖の飽和もしくは不飽和のモノもしくはジアルキルアミノ基、炭素数６〜２０のモノもしくはジアリールアミノ基、炭素数７〜２０のモノもしくはジアラルキルアミノ基、第１級、第２級、第３級もしくは第４級アンモニウム基、チオール基、イソシアヌレート基、ウレイド基、イソシアナート基、カルボニル基、アルデヒド基、カルボキシル基、カルボン酸エステル基、リン酸基、リン酸エステル基、スルホン酸基、スルホン酸エステル基またはハロゲン原子で置換されていても良い。Ｍは、Ｓｉ、Ａｌ、ＴｉまたはＺｒを示し、Ｚは水素原子、炭素数１〜８の飽和もしくは不飽和アルキルオキシ基、炭素数３〜８の分岐鎖があっても良い飽和もしくは不飽和シクロアルキルオキシ基、トリメチルシリルオキシ基、ジメチルシリルオキシ基、炭素数１〜８の分岐鎖があっても良い飽和もしくは不飽和ヘテロシクロアルキルオキシ基、ハロゲン原子、水酸基、アミノ基、炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のアルキルアミノ基、炭素数１〜６の直鎖または分岐鎖の飽和もしくは不飽和のジアルキルアミノ基または層状無機化合物由来の酸素原子を示し、ＭがＳｉ、ＴｉまたはＺｒのいずれかの場合には、それに対応するｘは３で、かつｎは１〜３の整数であり、ＭがＡｌの場合には、それに対応するｘは２で、かつｎは１または２であり、ｎが２または３の場合には、Ｒは同一でも異なっても良い。）

(In the formula (2), R is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms, and the like. It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and has a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group and 1 to 20 carbon atoms, respectively. Saturated or unsaturated mono or dialkylamino groups of linear or branched chains, mono or diarylamino groups with 6 to 20 carbon atoms, mono or dialalkylamino groups with 7 to 20 carbon atoms, primary and secondary, Tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group , A sulfonic acid ester group or a halogen atom. M represents Si, Al, Ti or Zr, Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. Saturated or unsaturated cycloalkyloxy group which may have 3 to 8 branched chains, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy which may have branched chains having 1 to 8 carbon atoms. Group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms, saturated or unsaturated dialkylamino of linear or branched chain with 1 to 6 carbon atoms Indicates an oxygen atom derived from a group or layered inorganic compound, where M is any of Si, Ti or Zr, the corresponding x is 3 and n is an integer 1-3 and M is Al. In some cases, the corresponding x is 2, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.)

Further, the present invention is a method for producing a sustained-release composite agent, which comprises mixing an interlayer-modified layered inorganic compound and a compound inserted between layers of the interlayer-modified layered inorganic compound.

In the sustained-release composite agent of the present invention, the interlayer-crosslinked layered inorganic compound having an organic-inorganic composite crosslinked structure represented by the above formula (1) between layers has various crosslinked structures, so that various interlayer distances are constructed. Since it is possible to construct an appropriate space between the layers according to the purpose, it is possible to control the insertion of the guest compound into the layers and further control the release rate from the layers. Furthermore, since the iso-interlayer cross-linking agent itself having a long-chain alkylene structure has flexibility, even if it is the same interlayer-crosslinked layered inorganic compound, the interlayer distance can be flexibly adjusted according to various guest compounds to be sustained-release. Can be varied.
In addition, since the crosslinked structure itself has various functional groups, the diversity of the interlayer environment (the place where it interacts with the guest compound) is very wide, and it is possible to insert and sustained release of various desired functional compounds between layers. A variety of suitable interacting groups such as hydrophobic and hydrophilic groups such as saturated or unsaturated aliphatic groups, aromatic and heterocyclic structural groups, hydrogen bond-forming groups, coordination-bond-forming groups and ionic-bond-forming groups. An organic-inorganic composite crosslinked structure can be designed by selecting various functional groups and introduced between layers, and various desired functional compounds (guest compounds) according to the purpose can be inserted between the layers, and guests can be used according to the application. The rate at which the compound is released can be controlled, and the compound can be slowly released depending on the purpose.

Furthermore, since the layers are cross-linked by covalent bonds via a cross-linked structure, it is difficult to cut even in the coexistence of alkali or acid.
Further, the interlayer crosslinked type layered inorganic compound having an organic-inorganic composite crosslinked structure between layers is M ¹ or M ² (M ¹ or M ² is Si, Ti, Zr or Al, respectively) -O-Si (Si is a layered inorganic compound). Origin) Since the layers are cross-linked via covalent bonds such as bonds, the chemical stability is very high in various environments such as acidic and alkaline conditions, and it is difficult to cut. Therefore, the crosslinked structure can exist between the layers for a sufficiently long period of time practically without being affected by the usage environment not only under strong alkaline and acidic conditions but also under weak alkaline and acidic conditions. The structure does not collapse and peel off, and the inserted guest compound is not released at once, and it can be used in various environments and applications. The compound inserted between the layers is practically retained for a long period of time and released slowly. can do.

Furthermore, since the interlayer crosslinked layered inorganic compound has extremely high chemical stability as described above, the compound inserted between the interlayers can be protected from the external environment, and has heat resistance, water resistance, ultraviolet resistance, etc. In addition to the sustained release of compounds with low heat resistance, water resistance, ultraviolet resistance, etc., the sustained release composite agent can be kneaded and molded into a resin or the like, or under water or humidified conditions. It can be used in various environments such as outdoors where it is exposed to sunlight.
Therefore, since various crosslinked structures can be introduced between the layers, the interlayer distance can be set widely according to the purpose, and the sustained-release composite agent can insert and release various compounds.

On the other hand, in the sustained-release composite agent of the present invention, the interlayer-modified layered inorganic compound in which the interlayers represented by the following formula (2) are modified with an organic-inorganic composite group is a silyl having various functional groups as an interlayer modifier. Due to the availability of organic-inorganic composite modifiers such as agents, the diversity of the interlayer environment (where they interact with guest compounds) is very wide, and the insertion and gradual insertion of various desired compounds between layers. Interaction groups suitable for release, such as hydrophobic and hydrophilic groups such as saturated or unsaturated aliphatic groups, aromatic groups and heterocyclic structural groups, hydrogen bond forming groups, coordination bond forming groups and ionic bond forming groups. Various functional groups such as those can be selected to design and modify the layers, and various desired functional compounds (guest compounds) according to the purpose can be inserted between the layers and sustained-release.

Further, the interlayer-modified layered inorganic compound is a functional group that interacts with the guest compound through a covalent bond such as an M (M is Si, Ti, Zr or Al) -O-Si (Si is derived from the layered inorganic compound) bond. Since it is modified with (interlayer modifying group), it has very high chemical stability in various environments such as acidic and alkaline conditions. Therefore, the modifying group can be practically present between the layers for a sufficiently long period of time without being affected by the usage environment, and the compound inserted between the layers is practically retained for a long period of time and slowly released. be able to.

Furthermore, since the interlayer-modified layered inorganic compound has extremely high chemical stability as described above, the compound inserted between the interlayers can be protected from the external environment, and heat resistance, water resistance, ultraviolet resistance, etc. can be improved. Since it can be imparted, not only the sustained release of compounds having low heat resistance, water resistance, ultraviolet resistance, etc., but also the sustained release composite agent can be kneaded into a resin or the like for molding, or under water or humidified conditions. It can be used in various environments such as an environment exposed to outdoor sunlight.
Therefore, since various modifying groups can be introduced between the layers, the interlayer distance can be set widely according to the purpose, and the sustained-release composite agent can insert and release various compounds.

Hereinafter, the sustained-release composite agent of the present invention will be described.
The layered inorganic compound in the present invention is not particularly limited, but is graphite, layered metal kaolinite, layered metal oxide (for example, titanium oxide, layered perovskite compound mainly composed of niobide oxide, titanium niobate, molybdenate). Etc.), layered metal oxyhalides, layered metal phosphates (eg, layered antimonate phosphates, etc.), layered clay minerals, layered silicates (eg, mica, smectites (montmorillonite, saponite, hectrite, fluorohect) Wright, etc.), kaolin (kaolinite, etc.), magadite, kenyaite, kanemite, etc.) and layered double hydroxides.
Among these, layered silicates, layered clay minerals and layered metal oxides are preferably used because of their availability, etc., but these may be either naturally produced or artificially synthesized. May be good.

Next, the organic-inorganic composite group existing between the layers of the layered inorganic compound will be described.
One of the organic-inorganic composite groups in the present invention has an organic-inorganic composite crosslinked structure represented by the above formula (1).
In the above formula (1), M ¹ and M ² are metals capable of forming a covalent bond with an oxygen atom derived from a layered inorganic compound, and the covalent bond is unlikely to cause a decomposition reaction such as hydrolysis and is easily available. From Si (silicon), Al (aluminum), Ti (titanium) and Zr (zyroxide), Si is preferable because it is easily available for introducing various interacting groups.

In the organic-inorganic composite crosslinked structure represented by the formula (1) introduced between layers via a covalent bond with a layered inorganic compound, the organic-inorganic composite crosslinked structure and the layered inorganic compound are bonded via a plurality of covalent bonds. It is more preferable from the viewpoint of the chemical stability of the bond connecting the layers, and when M ¹ and M ² in the above formula (1) are Si, Ti and Zr, n is 0 or 1 more. Preferably, in the case of Al, n is more preferably 0, and in any case, at least one of Z is more preferably containing an oxygen atom derived from a layered inorganic compound. Also be generated together organic-inorganic composite crosslinking structure Z between the vicinity engaged hydrolysis and condensation M ¹ -O-M ¹ bonds, M ¹ -O-M ² bond or M ² -O-M ² bond good.

Since the interaction with the guest compound can be appropriately designed in the organic-inorganic composite crosslinked structure, a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structural group, a hydrogen bond forming group, and a coordination can be appropriately designed. It preferably contains either a bond-forming group or an ionic bond-forming group. As a result, non-covalent interactions with guest compounds (for example, van der Waals force, π-π interaction, hydrophobic interaction, hydrogen bond, coordination bond, ionic bond, etc.) are appropriately adjusted and imparted. Any compound can be inserted between layers and sustained-release according to the purpose.

The non-covalent interacting group is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-hexyl group, an n-octyl group, a decyl group, and the like. Saturated or unsaturated alkyl groups such as dodecyl group, octadecyl group, methylene group, ethylene group, propylene group, octamethylene group, cyclohexyl group, cyclohexylene group, vinyl group, allyl group, alkylene group, cycloalkyl group and cyclo Aryl groups such as aliphatic groups, styryl groups, phenyl groups, naphthyl groups, phenylene groups, naphthylene groups, biphenylene groups, benzyl groups and benzylene groups, which are alkylene groups, aromatic groups which are aralkyl groups, arylene groups and aralkylene groups, Azol groups such as pyridinyl group, piperidinyl group, pyrozinyl group, pyrimidinyl group, imidazolyl group, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, dioxanyl group, morpholinyl group, thiazinyl group, indol group, nucleic acid base and the like. Heterocyclic structural group, acryloxy group, methacryloxy group, acetyl group, benzoyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, methyl carboxylate group, phosphate group, ethyl phosphate group, sulfonic acid group, methyl sulfonate group , Amino group, methylamino group, dimethylamino group, isocyanurate group, ureido group, isocyanato group and other hydrogen bond and coordination bond generation groups, ethylammonium group, dimethylammonium group and trimethylammonium group ion bond generation group, etc. , A carboxylic acid ester structure, a urethane structure, a urea structure, an amine structure, an ether structure, a thioether structure, and a disulfide structure in the crosslinked main chain skeleton. The structures contained therein include methylene group, ethylene group, propylene group, butylene group, octamethylene group, phenylene group, biphenylene group, benzylene group, carboxylic acid ester structure, urethane structure, urea structure, amine structure and ether structure. It preferably has a thioether structure and a disulfide structure.

Among the organic-inorganic composite crosslinked structures represented by the formula (1), those capable of being constructed by reacting the crosslinkable functional groups of various coupling agents are general and preferable, and easy to introduce into layers. Therefore, those represented by the following formulas (3) to (17) are more preferable.

(In formulas (3) to (17), R ¹ is a saturated or unsaturated alkyl group of a linear or branched chain having 1 to 20 carbon atoms, and may have a branched chain having 3 to 8 carbon atoms. Saturated cycloalkyl group, aryl group with 6 to 20 carbon atoms or aralkyl group with 7 to 20 carbon atoms, vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, carbon Saturated or unsaturated mono or dialkylamino group of linear or branched chain of number 1 to 20, mono or diarylamino group of 6 to 20 carbon number, mono or dialalkylamino group of 7 to 20 carbon number, primary , Secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester It may be substituted with a group, a sulfonic acid group, a sulfonic acid ester group or a halogen atom. R ² and R ¹³ are independent linear or branched saturated or unsaturated alkylene groups having 1 to 20 carbon atoms, respectively. , Saturated or unsaturated cycloalkylene groups that may have branches with 1 to 8 carbon atoms, arylene groups with 6 to 20 carbon atoms or aralkylene groups with 7 to 20 carbon atoms, R ³ , R ⁵ , R ⁶ and R ⁷ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkyl group having 7 to 10 carbon atoms, and R ⁸ , R ⁹ , R ¹⁰ and R ¹² may each independently have a hydrogen atom, a linear or unsaturated alkyl group having 1 to 20 carbon atoms, or a branched chain having 3 to 8 carbon atoms. A saturated or unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkylene group which may have a branch of 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. R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and a substituent consisting of 1 to 10 atoms containing the halogen atom, and Z is a hydrogen atom and a linear chain having 1 to 8 carbon atoms. Or a saturated or unsaturated alkyl group of branched chains Saturated or unsaturated cycloalkyloxy group, trimethylsilyloxy group, dimethylsilyloxy group, may have branched chains having 3 to 8 carbon atoms Saturated or unsaturated Saturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms or oxygen atom derived from layered inorganic compound, I indicates polymerization initiation The agent-derived groups may be the same or different, where Y is an acid-derived conjugated base-derived group, n is an integer of 0-2, m and h are 0 or 1, and k is 0-4. Indicates an integer of. )

The organic-inorganic composite crosslinked structure can be constructed by treating the layers with a coupling agent, modifying the layers by silylation or the like, and then crosslinking the crosslinkable functional groups between the layers to form a crosslink of the coupling agent. An organic-inorganic composite cross-linking agent having two or more hydrolyzable sites is prepared by cross-linking a sex functional group in advance or reacting a greeninal reagent with a hydrolyzable metal compound, and this is inserted between layers to form a layered inorganic substance. Although it can be constructed by a modification reaction with a hydroxyl group derived from a compound, the former method of reacting a crosslinkable functional group derived from a coupling agent between layers is preferable because there is no side reaction and no gel component is produced as a by-product.

In order to construct a crosslinked structure by modifying the layers with a silylation or the like and then reacting the crosslinkable functional groups between the layers, if the layers are modified with the same coupling agent and then subjected to a crosslink reaction, the manufacturing process becomes more complete. The above formulas (3) to (7) and the above formulas (12) to (16) are more preferable as the organic-inorganic composite crosslinked structure because the amount is small and industrially more advantageous, and the crosslinking reaction can be easily carried out under mild conditions. The formulas (3) to (7) and the formulas (14) to (16) are further expanded because various chemical structures, flexibility and rigidity can be introduced and the length of the crosslink is also varied. preferable.

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

In the present invention, it is obtained by reacting an alkali metal such as sodium and potassium present in a layered inorganic compound and an exchangeable cation such as a metal cation such as an alkaline earth metal such as magnesium and calcium with an organic onium salt or the like. , The layered inorganic compound having wide layers is silylated with a coupling agent such as a silane coupling agent and a cross-linking agent having two or more hydrolyzable silyl sites (in the case of silylation, the silylated layered inorganic compound). It is a precursor (of a compound).
The precursor is a compound in which an arbitrary ratio of onium groups is substituted as an ion exchange capacity with respect to the exchangeable cations of the layered inorganic compound, and the ratio of onium groups is used when increasing the reaction rate such as silylation. Is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and even more preferably 35 to 70 mol%.

Here, the ion exchange capacity represents the amount of ion exchange per unit weight of the ion exchanger, and is usually the milliequivalent per 1 g of the ion exchanger (meq / g) or the milliequivalent per 100 g of the ion exchanger (meq / 100 g). , And the molar amount per 1 kg of the ion exchanger (mol _c / kg), the centimeter amount per 1 kg of the ion exchanger (cmol _c / kg), and the like.
For example, the chemical formula of sodium-magadiate is Na ₂ Si ₁₄ O ₂₉ · nH ₂ O, where n = 0, the formula quantity is 903.2, and all sodium can be regarded as exchange cations. Therefore, the ion exchange capacity in this case can be expressed as 2.21 mol _c / kg.

If a metal cation is present between layers as an exchangeable cation, the interlayer modification rate (silylation rate in the case of a silane coupling agent) due to a coupling agent such as a silane coupling agent or a cross-linking agent decreases. It is preferable to reduce the metal cations.
Therefore, as a method of introducing an onium group between layers of a layered inorganic compound, a method of reacting an onium salt having an equivalent amount or more with a cation exchange capacity and then allowing an acid to act, and an onium having an equivalent amount less than the cation exchange capacity in advance. There are methods such as reacting with a salt, but in order to further improve the interlayer modification rate, a method in which an acid is allowed to act after reacting with an onium salt equal to or more than the former equivalent is more preferable.
Further, as a method for adjusting and introducing the amount of onium groups between the layers of the layered inorganic compound, a mixture of an onium salt and an acid in an appropriate amount may be reacted with the layered inorganic compound, and the acid may be added in an appropriate amount first. After the reaction (preferably less than the equivalent of the cation exchange capacity), the onium salt may be reacted.

In the present invention, the onium salt used for producing the precursor is not particularly limited, but organic onium is preferable, and for example, organic ammonium, organic pyridinium, organic imidazolium, organic phosphonium, organic oxonium, organic sulfonium, and organic sulfoxonium. , Organic selenonium, organic carbonium, organic diazonium, organic iodonium, organic pyririnium, organic pyrrolidinium, organic carvenium, organic asylium, organic thiazolinium, organic arsonium, organic sulphonium, organic telluronium and other salts. Salts of organic pyridinium, organic imidazolium, organic phosphonium and organic sulfonium are preferable, and these onium salts are used alone or in combination of two or more.
The organic group in the onium salt is not particularly limited, but for example, an alkyl group having 1 to 22 carbon atoms, an aralkyl group having 7 to 22 carbon atoms, an aryl group having 6 to 22 carbon atoms, and-(CH _2- CH). (CH ₃ ) O) _p −H group, − (CH ₂ −CH ₂ −O) _q −H group, p and q are integers from 1 to 20, vinyl group, epoxy group, ether group, Oxetanyl group, acryloxy group, metharoxy group, hydroxyl group, thiol group, isocyanato group, halogen atom, basic group such as amino group and alkylamino group, acidic group such as carboxyl group, photoacid generating group, thermoacid generating group, It may be substituted with a functional group such as a photobase generating group, a thermal base generating group, a photoradical generating group and a thermal radical generating group.

As the organic onium salt, an organic onium salt represented by the following formula (18) is more preferable.
^{R 14 R 15 R 16 R 17} N + X - (18)
(In the formula (18), R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently alkyl groups having 1 to 22 carbon atoms, aralkyl groups having 7 to 22 carbon atoms, and aryl groups having 6 to 22 carbon atoms, respectively. And − (CH ₂ −CH (CH ₃ ) O) _p −H group or − (CH ₂ −CH ₂ −O) _q −H group, p and q are integers from 1 to 20, and X ^- is Indicates a halide ion.)

The organic onium salt represented by the formula (18) is not particularly limited, and for example, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, and the like. Triethyl benzyl ammonium chloride, dodecyl ammonium chloride, dimethyl dipolyethylene oxide ammonium chloride, dimethyl dipropylene oxide ammonium chloride, dimethyl polyethylene oxide polypropylene oxide ammonium chloride, dimethyl stearyl polyethylene oxide ammonium chloride, dimethyl stearyl polypropylene oxide ammonium chloride, methyl stearyl dipoly chloride Ammonium ethylene oxide, methylstearyl dipolypropylene oxide ammonium chloride, benzylmethyldipolyethylene oxideammonium chloride, benzylmethyldipolypropylene oxideammonium chloride, 1-ethylpyridinium bromide, 1-octadecylpyridinium chloride, 3-methyl-1-propylimidazole bromide Examples thereof include rium, 3-methyl-1- (2-naphthyl) imidazolium, triphenyl (tetradecyl) phosphonium bromide, ethyldimethylsulfonium chloride, and triphenylsulfonium bromide.
Among these, preferably dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, dihexadecyldimethylammonium chloride, octadecyltrimethylammonium chloride, icosyltrimethylammonium chloride, dimethyloctadecylphenylammonium chloride, triethylbenzylammonium chloride and dodecyl chloride. It is ammonium.

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

The amount of the organic onium salt in the cation exchange reaction is not particularly limited and can be arbitrarily set depending on the intended purpose, but is preferably 20 to 2000 mol% (preferably 20 to 2000 mol%) based on the cation exchange capacity of the layered inorganic compound. It is 0.2 to 20 equivalents), more preferably 50 to 1000 mol% (0.5 to 10 equivalents), and even more preferably 100 to 500 mol% (1 to 5 equivalents).
The reaction temperature in the cation exchange reaction is not particularly limited, but is preferably 0 to 100 ° C, more preferably 10 to 60 ° C, and even more preferably 15 to 40 ° C.

The water used as the solvent for the cation exchange reaction may be neutral, acidic or alkaline, and is not particularly limited, but ion-exchanged water, distilled water, pure water and ultrapure water are preferable.
The amount of the solvent used in the cation exchange reaction is not particularly limited, but is 1 to 100 times by mass, more preferably 5 to 70 times by mass, still more preferably 10 times by mass with respect to the layered inorganic compound used as a raw material. ~ 50 times by mass.

In order to adjust the proportion of onium groups in the precursor having an organic onium group, the layered inorganic compound is reacted with an organic onium salt, and then a part of the onium groups in the layered inorganic compound is converted into a hydroxyl group by an acid. The method of causing is preferable.
The amount of the acid to act can be arbitrarily set according to the purpose, but preferably, when the cation exchange capacity of the layered inorganic compound is 100 mol%, 100 mol%-[organic onium group to be left between layers It is more preferable to set the ratio (mol%)] and increase or decrease the amount of acid as appropriate.

The acid is not particularly limited, and includes hydrochloric acid (hydrogen chloride), bromide (hydrogen bromide), carboxylic acid (for example, formic acid, acetic acid and oxalic acid), phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid and the like. Known acids such as sulfonic acids can be mentioned, and among these, hydrochloric acid (hydrogen chloride) is preferable because of its excellent reactivity.
When the amount of onium salt existing between layers is adjusted to a specific range by reacting with the onium salt between layers using these acids, hydroxyl groups such as interlayer silanol are generated and the number of modification reaction points such as silylation increases. Therefore, it is preferable.
When an onium salt in an amount smaller than the equivalent of the cation exchange capacity is used, a metal cation such as sodium remains between the layers, so that the hydroxyl group-derived alcoholate such as silanol, which is the reaction point, is firmly bonded to the metal cation. Therefore, it may interfere with the interlayer modification reaction such as the silylation reaction.

The organic solvent used for converting a part of the onium salt into a hydroxyl group is not particularly limited, but is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2. -Alcohols such as propanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, tetrahydrofuran and the like. Ethers, ketones such as acetone and ethyl methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alcohols such as hexane, aromatics such as benzene and toluene, ethyl acetate Examples thereof include esters such as, and halogen-based hydrocarbons such as chloroform and dichloromethane.

Among these, alcohols and ethers, nitriles and ketones which are aprotonic polar solvents are preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol and 2-methyl-2 are preferable. Alcohols such as -propanol, 2-methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol are more preferred, with higher boiling points and higher polarity. Therefore, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol and 1-methoxy-2-propanol are more preferable.

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

The precursor obtained by the cation exchange reaction and acid treatment is preferably dried after isolation and washing. The method for isolating, washing and drying is not particularly limited, and known methods for isolating, washing and drying layered inorganic compounds, inorganic fine particles and the like can be used.
For example, as an isolation method, the reaction solution is allowed to stand, or after centrifugation to separate solid and liquid, the supernatant is removed by decantation, or by filtration operations such as natural filtration, pressure filtration, and vacuum filtration. Examples include filtering the layered inorganic compound.
The pressure during pressure filtration is not particularly limited, and may be in the range of 1 to 5 atm, for example. The pressure during vacuum filtration is not particularly limited and may be in the range of 0 to 1 atm.

As a cleaning method, the solid obtained after decantation is redispersed in water or an organic solvent, and then the solid is washed by pouring water or an organic solvent over the decantation or the filtered solid. The method etc. can be mentioned.
The water used for cleaning may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion-exchanged water, distilled water, pure water and ultrapure water.
The organic solvent used for cleaning is not particularly limited, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and ethyl methyl ketone, alkanes such as hexane, and aromatics such as toluene. At this time, in order to improve the contact between the layered inorganic compound and water, an organic solvent such as an appropriate polar solvent can be used in combination.

As a method for drying the solid obtained above, the organic solvent can be air-dried at normal temperature and pressure, or the organic solvent can be removed while appropriately heating or cooling at room temperature under reduced pressure.
The pressure at the time of depressurization is not particularly limited, and may be in the range of 0 to 1 atm, for example. The temperature is also not particularly limited, preferably −10 to 200 ° C., more preferably 0 to 150 ° C., and particularly preferably 10 to 100 ° C.

As described above, the precursor may be a compound in which the exchangeable cations of the layered inorganic compound are substituted with an arbitrary ratio of onium groups, but the onium is at a ratio of 25 to 75 mol% in terms of ion exchange capacity. It is preferably a compound substituted with a group.
When the ratio of the onium salt of the precursor is 25 to 75 mol%, the number of hydroxyl groups, which are modification reaction points for silylation and the like, increases, and a space is created between the layers, which makes it easier for the silylating agent and the like to be inserted between the layers. The silylation rate and the like are improved.

Next, all or a part of the counter anion (alkoxylate) of the hydroxyl group and the onium group of the precursor is subjected to an interlayer modification reaction with a coupling agent such as a silane coupling agent, and crosslinkable functionality is performed between the layers via a covalent bond. A layered inorganic compound having a group is produced.

The coupling agent is not particularly limited as long as it is an inorganic composite agent having an organic functional group capable of cross-linking with a hydrolyzable group in the same molecule. For example, a silane coupling agent or a titanium-based cup. Examples thereof include a ring agent, an aluminum-based coupling agent and a zirconium-based coupling agent, and a compound represented by the following formula (19) is preferable.

(In the formula (19), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms, and the like. It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and has a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group and 1 to 20 carbon atoms, respectively. Saturated or unsaturated mono or dialkylamino groups of linear or branched chains, mono or diarylamino groups with 6 to 20 carbon atoms, mono or dialalkylamino groups with 7 to 20 carbon atoms, primary and secondary, Tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group , A sulfonic acid ester group or a halogen atom may be substituted. A has a hydrogen atom, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms, and a branched chain having 3 to 8 carbon atoms. Saturated or unsaturated cycloalkyl groups may be represented, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, which are a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, respectively. It may be substituted with a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an aralkylamino group, an ammonium group, a thiol group, an isocyanurate group, a ureido group, an isocyanato group, a carboxyl group or a halogen atom, and D is hydrogen. Saturated or unsaturated alkyloxy group of atomic, linear or branched chain having 1 to 8 carbon atoms, saturated or unsaturated cycloalkyloxy group which may have branched chain having 3 to 8 carbon atoms, trimethylsilyloxy group, dimethylsilyl Oxy group, saturated or unsaturated heterocycloalkyloxy group which may have a branched chain having 1 to 8 carbon atoms, halogen atom, hydroxyl group, amino group, saturated or unsaturated linear or branched chain having 1 to 6 carbon atoms Indicates a saturated or unsaturated dialkylamino group of an alkylamino group or a linear or branched chain having 1 to 6 carbon atoms, M represents Si, Al, Ti or Zr, and M is any of Si, Ti or Zr. In the case of, p is 3 and n is an integer of 0 to 2, and when M is Al, p is 2 and n is 0 or 1.)

Further, among the coupling agents, the silane coupling agent is more preferable because of the abundance of types, availability, handling and controllability of the hydrolysis reaction. The silane coupling agent is not particularly limited, but for example, a compound represented by the following formula (20) is preferable.

(In the formula (20), R ¹ is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms. , An aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, respectively, a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group, and 1 to 20 carbon atoms. Saturated or unsaturated mono or dialkylamino group of linear or branched chain, mono or diarylamino group with 6 to 20 carbon atoms, mono or dialalkylamino group with 7 to 20 carbon atoms, primary and secondary , Tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid It may be substituted with a group, a sulfonic acid ester group or a halogen atom. A is a hydrogen atom, a linear or unsaturated alkyl group having 1 to 20 carbon atoms, or a branched chain having 3 to 8 carbon atoms. Saturated or unsaturated cycloalkyl groups may be present, aryl groups having 6 to 20 carbon atoms or aralkyl groups having 7 to 20 carbon atoms, which are vinyl groups, epoxy groups, oxetanyl groups, ether groups, acryloxy groups and methacryloxy groups, respectively. It may be substituted with a 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, a ureido group, an isocyanato group, a carboxyl group or a halogen atom. Is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having 3 to 8 carbon atoms, a trimethylsilyloxy group, a dimethylsilyloxy group, and carbon. Saturated or unsaturated heterocycloalkyloxy group, which may have a branched chain of 1 to 8, a halogen atom, a hydroxyl group, an amino group, a linear or branched alkylamino group having 1 to 6 carbon atoms, which is saturated or unsaturated. Alternatively, it represents a saturated or unsaturated dialkylamino group of a linear or branched chain having 1 to 6 carbon atoms, and 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, the hydrolyzable group has an extremely low risk of causing a side reaction with the crosslinkable functional group because it does not generate an acid such as hydrogen chloride as a by-product, and does not cause corrosion of the reactor and is a by-product. Alkoxysilanes that do not require the disposal treatment of the acid are preferable, those having a methoxy group, an ethoxy group and a propoxy group having excellent silylation reactivity are more preferable, and those having a methoxy group and an ethoxy group are particularly preferable.

Examples of the silane coupling agent represented by the formula (20) include vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, and 2- (3,4-epyl). Cyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycydoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxy Silane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, tris- (trimethoxysilylpropyl) isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxy Silane, 3-Mercaptopropyltrimethoxysilane, 3-Ixionpropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyl Trimethoxysilane, 7-octenyltrimethoxysilane, 4- (trimethoxysilyl) butyric acid, 4- (trimethoxysilyl) butyrate 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, Methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethyl Examples thereof include silane, dimethoxydimethylsilane, trimethoxymethylsilane and triethoxysilane.

Further, silane coupling agents other than alkoxysilanes can also be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonate, triethylchlorosilane, tertiarybutyldimethylchlorosilane, chlorotriisopropylsilane, 1,3-dichloro-1,1,3,3-tetra. Isopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, allyltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosisilane, tris (N, N-dimethylamino) methylsilane, bis (N, N) -Dimethylamino) dimethylsilane and (N, N-dimethylamino) trimethylsilane and the like.
In these silane coupling agents, when a plurality of hydrolyzable groups are present in one molecule, a single hydrolyzable group such as an alkoxy group, a halogen atom, an alkylamino group and a dialkylamino group is present. However, a plurality of things may be mixed.

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

The organic solvent used for the reaction with the coupling agent is not particularly limited, but is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl. Alcohols such as -1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and ethyl Ketones such as methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxyode, alcohols such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform And halogen-based hydrocarbons such as dichloromethane are mentioned, and among these, alcohols and ethers, nitriles and ketones which are aprotonic polar solvents are preferable.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol having a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher.
Examples of the aprotonic polar solvent include nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethylmethyl ketone, diethyl ketone and methylene isopropyl ketone, and amides such as N, N-dimethylformamide. Examples include sulfoxides such as dimethylsulfoxide.

The secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-. Examples include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol and phenol.
Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol and 1-butoxy-2-propanol Is preferred, and 2-butanol, 1-methoxy-2-propanol and 1-butoxy-2-propanol are even more preferred.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the reaction, the O-alkylation reaction, which is a side reaction of the hydroxyl group and the alkoxylate derived from the layered inorganic compound, is unlikely to occur, and the O-alkylation reaction is unlikely to occur. It is inferred that since the boiling point of the organic solvent used is high, the silylation reaction temperature rises, the interlayer modification reaction such as the silylation reaction is accelerated, and the interlayer modification rate such as the silylation rate increases.
Further, when secondary or tertiary alcohols are used, hydroxyl groups such as silanol are produced by hydrolysis of the coupling agent such as the silane coupling agent described later, and the coupling agents such as the silane coupling agent are used as by-products. This is preferable because side reactions such as condensation are suppressed. It is inferred that this is the solvent effect due to the alcoholic hydroxyl group.

During the reaction, it is preferable to add water to the reaction system. The water to be added may be neutral, acidic or alkaline, and is not particularly limited, but ion-exchanged water, distilled water, pure water and ultrapure water are preferable.
The amount of water added is preferably 0.05 to 4.0 mol times the total amount of the hydroxyl group, which is the reaction point of the layered inorganic compound, and the alkoxylate, which is the counter anion of the onium group, that is, the ion exchange capacity. , 0.1 to 3.0 mol times is particularly preferable.
If the amount of water added is less than 0.05 mol times, the addition effect is small, and if it exceeds 4.0 mol times, side reactions such as hydrolysis and condensation between coupling agents such as silane coupling agents proceed. There is a fear.

The amount of the coupling agent such as the silane coupling agent in the reaction is not particularly limited, but is preferably relative to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. It is 0.1 to 30 mol times, more preferably 0.05 to 20 mol times, and even more preferably 1.0 to 10 mol times.
If the amount of the coupling agent used is less than 0.1 mol times, the silylation reaction rate becomes low, while if it exceeds 30 mol times, it is industrially disadvantageous in terms of raw material cost.

The reaction point between the layers of the layered inorganic compound, that is, the interlayer modification rate such as the silylation rate with respect to the ion exchange capacity is selected according to the purpose and is not particularly limited, but the interlayer modification rate such as the silylation rate is 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 layers of the layered inorganic compound may be excessively covered with the components derived from the coupling agent, which is not preferable.

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

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

The interlayer modification reaction such as the silylation reaction with the coupling agent of the present invention may or may not use a catalyst, but carboxylic acids such as hydrogen chloride, formic acid, acetic acid and oxalic acid, phosphoric acid, nitrate, sulfuric acid and Known acids such as sulfonic acids such as methanesulfonic acid and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as catalysts.
In that case, the amount of the catalyst to be added is not particularly limited, but is 0.001 to 1.0 mol with respect to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. It is preferably double, more preferably 0.01 to 0.1 molar times.

The interlayer-modified layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction is preferably isolated, washed and then dried. The method for isolation, washing and drying is not particularly limited, and known methods for isolating, washing and drying layered inorganic compounds and inorganic fine particles can be used.
For example, as an isolation method, the reaction solution is allowed to stand, or after centrifugation to separate solid and liquid, the supernatant is removed by decantation, or by filtration operations such as natural filtration, pressure filtration, and vacuum filtration. Examples include filtering the layered inorganic compound.
The pressure during pressure filtration is not particularly limited, and may be in the range of 1 to 5 atm, for example. The pressure during vacuum filtration is not particularly limited and may be in the range of 0 to 1 atm.

As a cleaning method, the solid obtained after decantation is redispersed in water or an organic solvent, and then the solid is washed by pouring water or an organic solvent over the decantation or the filtered solid. The method etc. can be mentioned.
The water used for cleaning may be neutral, acidic or alkaline, and is not particularly limited, but is preferably ion-exchanged water, distilled water, pure water and ultrapure water.
The organic solvent used for cleaning is not particularly limited, and examples thereof include alcohols such as methanol and ethanol, ketones such as acetone and ethyl methyl ketone, alkanes such as hexane, and aromatics such as toluene. At this time, in order to improve the contact between the layered inorganic compound and water, an organic solvent such as an appropriate polar solvent can be used in combination.

As a method for drying the solid obtained above, the organic solvent can be air-dried at normal temperature and pressure, or the organic solvent can be removed while appropriately heating or cooling at room temperature under reduced pressure.
The pressure at the time of depressurization is not particularly limited and may be in the range of 0 to 1 atm. The temperature is also not particularly limited, preferably −10 to 200 ° C., more preferably 0 to 150 ° C., and particularly preferably 10 to 100 ° C.
When reducing or removing exchangeable cations such as onium groups and metal cations remaining after an interlayer modification reaction such as a silylation reaction, acid treatment can be carried out using a known acid and solvent in the same manner as described above. ..

Next, a method for producing an interlayer crosslinked layered inorganic compound by reacting a layered inorganic compound having layers modified with a coupling agent with a crosslinkable functional group derived from the coupling agent will be described.
The cross-linking reaction by a cross-linking functional group derived from a coupling agent such as a silane coupling agent is not particularly limited, and is an addition reaction, a substitution reaction, a condensation reaction, an ionic reaction, an electron electrophilic reaction, a nucleophilic reaction, and a pericyclic reaction. Various generally known chemical reactions such as reactions and radical reactions can be used, and so-called click reactions can also be used. A radical is generated from an alkyl group for a cross-linking reaction, an alkyl halide group is converted into an anionic species as a greeninal reagent for a nucleophilic reaction, or a hydroxyl group, an alkoxy group or an amino group is subjected to a alkyl halide group or the like. A cross-linking method in which a nucleophilic substitution reaction is carried out by allowing a nucleophilic species such as the above to act can be mentioned, but since the coupling agent is easily available and the cross-linking reaction proceeds under relatively mild conditions, the following formula (21) to The reaction represented by (35) is preferable, and if the layers are modified with the same coupling agent and then crosslinked, the number of manufacturing steps is reduced, which is more industrially advantageous. Therefore, the formulas (21) to (25) and The cross-linking reactions represented by the formulas (30) to (34) are more preferable, the cross-linking reaction proceeds easily under mild conditions, various chemical structures, flexibility and rigidity can be introduced, and the length of the cross-linking varies. The cross-linking reactions represented by the formulas (21) to (25) and the formulas (32) to (34) are more preferable because they can have a property.

When the cross-linking reactions represented by the formulas (21) to (23) and the formula (32) are used, the cross-linking functional groups have a similar or similar structure, and the cross-linking structure to be reacted or produced is relatively simple. It has a feature that the interlayer distance and the interlayer environment (hydrophobicity, hydrophilicity, aromaticity, etc.) of the layered inorganic compound can be controlled relatively easily according to the structures of R ² , R ⁴ and R ¹³ .
Further, when the cross-linking reactions represented by the formulas (24), (25), (33) and (34) are used, the layers are relatively easily layered according to the structures of R ² , R ⁴ and R ^13. Not only can the interlayer distance and flexibility of inorganic compounds and the environment between layers (hydrophilicity, hydrophilicity, aromaticity, hydrogen bond formation, etc.) be controlled, but also various available amines and diamines can be crosslinked. Since it can be introduced into the layered inorganic compound easily and freely, the interlayer distance and flexibility of the layered inorganic compound, the environment between the layers (hydrophilicity, hydrophilicity, aromaticity, hydrogen bond formation, heterocyclic structure, ionic bond, arrangement) It has the feature of being able to control covalent bonds).

(In formulas (21) to (35), R ¹ is a saturated or unsaturated alkyl group of a linear or branched chain having 1 to 20 carbon atoms, and may have a branched chain having 3 to 8 carbon atoms. Cycloalkyl group, aryl group with 6 to 20 carbon atoms or aralkyl group with 7 to 20 carbon atoms, vinyl group, epoxy group, oxetanyl group, ether group, acryloxy group, methacryloxy group, hydroxyl group, amino group, carbon number Saturated or unsaturated mono or dialkylamino groups of 1 to 20 linear or branched chains, mono or diarylamino groups of 6 to 20 carbon atoms, mono or dialalkylamino groups of 7 to 20 carbon atoms, primary, Secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group , A sulfonic acid group, a sulfonic acid ester group or a halogen atom. R ² and R ¹³ are independent linear or branched saturated or unsaturated alkylene groups having 1 to 20 carbon atoms, respectively. It represents a saturated or unsaturated cycloalkylene group which may have a branch of 3 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms or an aralkylene group having 7 to 20 carbon atoms, and R ³ , R ⁵ , R ⁶ and R. ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ⁴ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group or an aralkyl group having 7 to 10 carbon atoms, and R ⁸ ,. R ⁹ , R ¹⁰ and R ¹² are each independently saturated or saturated with a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a branched chain having 3 to 8 carbon atoms. Alternatively, an unsaturated cycloalkyl group, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and R ¹¹ is a linear or branched saturated or unsaturated alkylene group having 1 to 20 carbon atoms. It represents a saturated or unsaturated cycloalkylene group which may have a branch of 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. R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom, etc. and a substituent consisting of 1 to 10 atoms containing the same, and Z is a hydrogen atom and 1 to 8 carbon atoms. Saturated or unsaturated al of linear or branched chains of Kiroxy group, saturated or unsaturated cycloalkyloxy group which may have a branched chain having 3 to 8 carbon atoms, trimethylsilyloxy group, dimethylsilyloxy group, which may have a branched chain having 1 to 8 carbon atoms Saturated or unsaturated Saturated heterocycloalkyloxy group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms, saturated or saturated linear or branched chain with 1 to 6 carbon atoms It represents an unsaturated dialkylamino group or an oxygen atom derived from a layered inorganic compound, where I is a group derived from a polymerization initiator and may be the same or different, Y is a group derived from an acid-derived conjugated base, and n is 0 to 0. An integer of 2, m and h represent an integer of 0 or 1, and k represents an integer of 0-4.

Further, in the cross-linking reactions represented by the formulas (21) to (35), cross-linking derived from a coupling agent composed of titanium (Ti), aluminum (Al), zirconium (Zr) or the like instead of silicon atom (Si). Cross-linking reactions of sex functional groups can be utilized.

In the above-mentioned cross-linking reaction, the cross-linking point in the carbon-carbon double bond cross-linking reaction may be either the head or the tail of the double bond, and the cross-linking point in the ring-opening cross-linking reaction of the epoxy group and the oxetanyl group is a cyclic ether group. It may be any of two carbon atoms existing adjacent to each other.

In order to promote the cross-linking reaction, if necessary, known polymerization initiators such as thermal radical generators, photoradical generators, thermal anion generators, photocation generators, thermoacid generators, photoacid generators, etc. Thermobase generators and photobase generators, known inorganic acids such as hydrochloric acid, sulfuric acid, nitrate, formic acids, acetic acid, oxalic acid, citric acid, methanesulfonic acid, paratoluenesulfonic acid and other known organic acids, ammonia, water Known inorganic bases such as sodium oxide, potassium hydroxide and calcium hydroxide, organic bases such as known organic amines such as methylamine, diethylamine and triethylamine, known ammonium salts such as tetramethylammonium hydroxy and succinic anhydride, anhydrous. Known catalysts such as known acid anhydrides such as phthalic acid and maleic anhydride, curing agents, and oxidizing agents such as bromine and iodine can be used in combination.

The polymerization initiator is not particularly limited, and a known polymerization initiator used in the polymerization reaction of the polymerizable monomer is used, and a thermal polymerization initiator and / or a photopolymerization initiator is used. A thermal polymerization initiator is more preferable because a cross-linking reaction system containing a layered inorganic compound modified with a coupling agent may be suspended between layers and light such as ultraviolet rays may not easily pass through.

Various compounds can be used as the thermal polymerization initiator, and when the polymerizable group is a radically polymerizable group, for example, in the case of the above formula (21) and the above formula (31), it is excessive. Oxide and azo-based initiators are preferred.

Specific examples of peroxides include hydrogen peroxide; inorganic peroxides such as sodium persulfate, ammonium persulfate, and potassium persulfate; 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1. -Bis (t-hexyl peroxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3 5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,5-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) Cyclododecane, t-hexyl peroxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl -2,5-di (m-toluole peroxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2 , 5-Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t) -Butyl peroxy) valerate, di-t-butyl peroxyisophthalate, α, α'-bis (t-butyl peroxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di ( t-Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, p-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin- 3. Diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide, etc. Includes organic peroxides.

Specific examples of the azo-based initiator include 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, and 2-. Examples thereof include azo compounds such as phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi-t-octane, and azodi-t-butane, which may be used alone or in combination of two or more. Is also good.
In addition, peroxides, ascorbic acid, sodium ascorbate, sodium erythorbate, tartaric acid, citric acid, metal salts of formaldehyde sulfoxylate, sodium thiosulfate, sodium sulfite, sodium bisulfite, sodium metabisulfite, bisulfite chloride It is also possible to carry out a redox reaction by combining it with a redox polymerization initiation system in which a reducing agent such as iron is used in combination.

The amount of the thermal polymerization initiator used is selected depending on the type, polymerization conditions, etc., but is usually 1 to 1000 molars, more preferably 5 to 500 molars, relative to 100 molars of the polymerizable functional group. It is more preferably 50 to 200 molar quantities.

Specific examples of the photopolymerization initiator include benzyldimethylketal, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one when the polymerizable group is a radically polymerizable group. , 1- [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methyl) Vinyl) 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-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one and 2-dimethylamino-2-one Acetphenone compounds such as (4-methylbenzyl) -1- (4-morpholine-4-yl-phenyl) butane-1-one; benzophenone compounds such as benzoin, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, methyl-2-benzophenone, 1- [4- (4-benzoylphenyl sulfanyl) phenyl ] -2-Methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 4-methoxy-4' -Benzophenone compounds such as dimethylaminobenzophenone;
Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Acylphosphine oxide compounds; as well as thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2 -Il-oxy] -2-hydroxypropyl-N, N, N-trimethylammonium chloride, fluorothioxanthone and other thioxanthone compounds can be mentioned.
Examples of compounds other than the above include benzyl, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate, methyl phenylglioxyate, ethyl anthraquinone, phenanthrenequinone, camphorquinone and the like.

The amount of the photopolymerization initiator used is selected depending on its type, polymerization conditions, etc., but is 1 to 1000 molars, more preferably 5 to 500 molars, relative to 100 molars of the polymerizable functional group. More preferably, the amount is 50 to 200 mol.

When the polymerizable group is a cationically polymerizable group, for example, in the cases of the above formula (22), the above formula (23) and the above formula (32), various known cationic polymerization initiators are used. Examples of the thermal cationic polymerization initiator include sulfonium salts, phosphonium salts, and quaternary ammonium salts. Of these, sulfonium salts are preferred.
Examples of the counter anion in the thermal cationic polymerization initiator include AsF ₆ ⁻ , SbF ₆ ⁻ , PF ₆ ⁻ , B (C ₆ F ₅ ) ₄ ^{− and the} like.

Examples of the sulfonium salt include triphenylsulfonium boron tetrafluoride, triphenylsulfonium hexafluoride antimony, triphenylsulfonium arsenic pentafluoride, tri (4-methoxyphenyl) sulfonium arsenic pentafluoride, and diphenyl (4-phenylthiophenyl). ) Sulfonium arsenic pentafluoride and the like.
Commercially available products can also be used as the sulfonium salt. Specifically, for example, "ADEKA OPTON CP-66" (trade name) and "ADEKA OPTON CP-77" (trade name) manufactured by ADEKA, Sanshin Chemical Co., Ltd. Examples thereof include "Sun Aid SI-60L" (trade name), "Sun Aid SI-80L" (trade name) and "Sun Aid SI-100L" (trade name) manufactured by Kogyo Co., Ltd.

Examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoride antimony and tetrabutylphosphonium hexafluoride antimony.
Examples of the quaternary ammonium salt include N, N-dimethyl-N-benzylanilinium hexafluoride antimony pentafluoride, N, N-diethyl-N-benzylanilinium tetrafluoride boron, and N, N-dimethyl-N-benzyl. Antimony pentafluoride, N, N-diethyl-N-benzylpyridinium trifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) Antimony pentafluoride, N, N-diethyl-N- ( 4-methoxybenzyl) pyridinium hexafluoride antimony, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony, N, N-dimethyl-N- (4-methoxybenzyl) toluidinium hexafluoride antimony And so on.

Examples of the photocationic polymerization initiator include onium salts such as iodonium salt, sulfonium salt, diazonium salt, selenium salt, pyridinium salt, ferrosenium salt and phosphonium salt. Among these, iodonium salt and sulfonium salt are preferable.
When the cationic photopolymerization initiator is an iodonium salt or sulfonium salt, as a counter anion, for _{^{example, BF 4 -, AsF 6 -}} , SbF 6 -, PF 6 -, B (C 6 F 5) 4 - and the like include Be done.

Examples of the iodonium salt include (tricmil) iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, diphenyl iodonium tetrafluoroborate, and diphenyl iodonium 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-( Examples thereof include 1-methylethyl) phenyliodonium tetrafluoroborate and 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate.
As the iodonium salt, a commercially available product can be used. Specifically, for example, "UV-9380C" (trade name) manufactured by Momentive Performance Materials Japan Co., Ltd. and "PHOTOINITIATOR 2074" manufactured by Solvay Japan Co., Ltd. ( (Product name), "WPI-116" (trade name) and "WPI-113" (trade name) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. and the like.

Examples of the sulfonium salt include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (diphenylsulfonium). Nio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfonio) 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, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] Sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] Sulfide bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonium) Ethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, etc. Be done.
Commercially available products can also be used as the sulfonium salt. Specifically, for example, "Cyracure UVI-6990" (trade name), "Cyracure UVI-6992" (trade name) and "Cyracure UVI-6992" (trade name) manufactured by Dow Chemical Japan Co., Ltd. Cyracure UVI-6974 ", ADEKA's" Adeka Putmer SP-150 "(trade name)," Adeka Putmer SP-152 "(trade name)," Adeka Putmer SP-170 "(trade name) and" Adeka Examples thereof include "Optomer SP-172" (trade name), "WPAG-370" (trade name) manufactured by Fujifilm Wako Junyaku Co., Ltd., and "WPAG-638" (trade name).

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

When the polymerizable group is an anionic polymerizable group, for example, in the case of the above formula (21), various known anionic polymerization initiators can be used, and the thermal cationic polymerization initiator may be used. For example, amines, thiols, imidazoles and the like can be used. Examples of amines include diethylenetriamine, triethylenetetramine, isophoronediamine, xylylenediamine, diaminodiphenylmethane, 1,3,4,6-tetrakis (3-aminopropyl) glycoluryl and the like, and examples of thiols include trimethylol. Propyltris (3-mercaptopropionate), tris (2-mercaptoethyl) isocyanurate, 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluryl and the like can be mentioned, and imidazoles include 2-. Examples thereof include methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.

Examples of the photoanion polymerization initiator include acetphenone O-benzoyloxime, nifedipine, and 2- (9-oxoxanthen-2-yl) propionic acid 1,5,7-triazabicyclo [4,4,0] deca-. 5-ene, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, 1,2-diisopropyl-3- [bis (dimethylamino) methylene] guanidium 2- (3-benzoylphenyl) propionate, 1,2 -Dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate and the like can be mentioned.

The amine represented by the following formula (36) that can be used for cross-linking the epoxy group represented by the formula (24) and the formula (33) is not particularly limited, but for example, ammonia, methylamine, ethylamine, propylamine, etc. Butylamine, pentylamine, hexylamine, octylamine, dodecylamine, hexadecylamine, octadecylamine, icosylamine, isopropylamine, allylamine, alkylamines such as 2-cyclohexylethylamine, cyclopentylamine, cyclohexylamine, cyclooctylamine, 3-cyclo Cyclic alkylamines such as hexenylamine, phenylamines, 1-naphthylamines, 2-naphthylamines, 2-aminoanthracenes, 1-aminopyrene, 3-aminobiphenyls and other arylamines, benzylamines, 2-phenylethyl groups, 1- (1) Examples thereof include aralkylamines such as −naphthyl) ethylamine, 1- (2-naphthyl) ethylamine, and 2- (7-methoxy-1-naphthyl) ethylamine.

H ₂ NR ⁸ (36)
(In formula (36), R ⁸ is a hydrogen atom, a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, and a saturated or unsaturated cyclo having a branched chain having 3 to 8 carbon atoms. It indicates an alkyl group, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.)

The amine represented by the following formula (37) that can be used for cross-linking the epoxy group represented by the formula (25) and the formula (34) is not particularly limited, but for example, diaminomethane, urea, thiourea, and the like. 1,2-diaminoethane, 1,2-bis (methylamino) ethane, N-methylmethylenediamine, 1,3-diaminopropane, 1,2-diaminopropane, 1,2-diamino-2-methylpropane, 1, , 4-Diaminobutane, 1,4-bis (methylamino) -2-butene, 1,6-diamihexane, 1,8-dimethyloctane, N, N-bis (2-aminoethyl) methylamine, 1,3 −Diaminocyclohexane, 1,4-diaminocyclohexane, 3-aminopyrrolidin, 4,4′-methylenebis (2-methylcyclohexylamine), bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3-phenylene Diamine, 1,4-phenylenediamine, 1,2,4-triaminobenzene, N, N'-diphenyl-1,4-phenylenediamine, 2-chloro-1,4-phenylenediamine, 2,7-diaminofluorene , 4,4'-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethylbiphenyl, 3,3', 4,4'-tetraaminobiphenyl, 1,5-diaminonaphthalene, 2,6-diamino Examples thereof include anthraquinone, 1,6-diaminopyrene, 1,8-diaminopyrene, 3- (aminomethyl) benzylamine, 4- (aminomethyl) benzylamine and the like.

R ⁹ HR ¹¹ NHR ¹⁰ (37)
(In the formula (37), R ⁹ and R ¹⁰ each independently have a hydrogen atom, a linear or unsaturated alkyl group having 1 to 20 carbon atoms, and a branched chain having 3 to 8 carbon atoms. Saturated or unsaturated cycloalkyl groups may be represented, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, where R ¹¹ is a saturated or unsaturated linear or branched chain having 1 to 20 carbon atoms. Saturated alkylene group, saturated or unsaturated cycloalkylene group which may have branching of 3 to 20 carbon atoms, arylene group of 6 to 20 carbon atoms, aralkylene group of 7 to 20 carbon atoms or polyphenylene group of 6 to 24 carbon atoms. R ¹¹ may be substituted with a sulfur atom, an oxygen atom, a nitrogen atom, a halogen atom and a substituent consisting of 1 to 10 atoms containing the same.)

In the case of the reaction represented by the above formula (30), an oxidizing agent can be used in combination, and a known oxidizing agent that promotes the disulfide formation reaction, for example, using bromine or iodine under basic conditions, is used. Can be done.

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

Examples of the active energy ray for irradiating the active energy ray to carry out the cross-linking reaction between the layers include ultraviolet rays, visible light, and electron beam. When ultraviolet rays or visible rays are used as the active energy rays, it is preferable to contain a photopolymerization initiator from the viewpoint of ease of crosslinking and cost.

Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet electrodeless lamp, and an ultraviolet light emitting diode (UV-LED).
The irradiation energy may be appropriately set according to the type of active energy ray and the compounding composition, and varies depending on the thickness and illuminance of the reaction system. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is used. For example, 5 to 10,000 mJ / cm ² is preferable. When a UV-LED is used, its emission peak wavelength is preferably 350 to 420 nm, and the irradiation energy is preferably 5 to 10,000 mJ / cm ² .

When an electron beam is used as the active energy ray, it can be cured by an electron beam without containing a photopolymerization initiator, but it can also be added in a small amount if necessary in order to improve the curability.
Various devices can be used as the electron beam irradiation device, and examples thereof include Cockcroft-Walton type, Van de Graaff type, and resonant transformer type devices.
The absorbed dose of the electron beam is preferably 1 to 1000 kGy, for example.
The oxygen concentration in the electron beam irradiation atmosphere is preferably 500 ppm or less, more preferably 300 ppm or less.

A reaction solvent can be used when carrying out a cross-linking reaction between layers. Such a solvent is not particularly limited and may be appropriately selected, but methanol, ethanol, 1-propanol, 2-propanol, 1-propanol, 2-butanol, 2-methyl-2-propanol, 2- Alcohols such as methyl-1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and Ketones such as ethyl methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alkanes such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, Halogen-based hydrocarbons such as chloroform and dichloromethane can be mentioned, and among these, alcohols and ethers, nitriles and ketones which are aprotonic polar solvents are preferable.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol having a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher.

The aprotonic polar solvent is not particularly limited, but is limited to nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethylmethyl ketone, diethyl ketone and methylene isopropyl ketone, N, N-. Examples thereof include amides such as dimethylformamide and sulfoxides such as dimethylsulfoxide.

The secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-. Examples include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol and phenol.
Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol and 1-butoxy-2- Propanol is preferred, with 2-butanol, 1-methoxy-2-propanol and 1-butoxy-2-propanol being even more preferred.

The reaction concentration in the cross-linking reaction between layers is not particularly limited and may be appropriately selected. For example, the mass% of the interlayer-modified layered inorganic compound is preferably 1 to 50% by mass, more preferably 3 to 40% by mass. It is preferable, and more preferably 5 to 30% by mass.

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

The time for introducing any functional group or modifying group other than the organic-inorganic composite crosslinked structure existing between the above layers may be before, after, or at the same time as the interlayer modification with the coupling agent for constructing the crosslinked structure. Further, it may be before or after the interlayer cross-linking reaction of the cross-linking functional group derived from the coupling agent introduced between the layers, and it may be arbitrarily selected in consideration of the reactivity of various functional groups, modifying groups and the coupling agent. be able to.

When a cross-linked structure is introduced between layers of a layered inorganic compound via a covalent bond using an organic-inorganic composite cross-linking agent having two or more hydrolyzable metal sites, the coupling agent is used with respect to the above-mentioned precursor. Instead, the organic-inorganic composite cross-linking agent may be reacted in the same manner.

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

Next, an interlayer-modified layered inorganic compound having an organic-inorganic composite group represented by the formula (2) will be described.
In the above formula (2), M is a metal capable of forming a covalent bond with an oxygen atom derived from a layered inorganic compound, and the covalent bond is unlikely to cause a decomposition reaction such as hydrolysis and is easily available. Si is preferred because it is any of silicon), Al (aluminum), Ti (titanium) and Zr (zyrosine) and is readily available for introducing various interacting groups.

In the organic-inorganic composite group represented by the formula (2) introduced between layers via a covalent bond with a layered inorganic compound, the organic-inorganic composite group and the layered inorganic compound are bonded via a plurality of covalent bonds. It is more preferable from the viewpoint of the chemical stability of the bond connecting the layers, and when M in the above formula (2) is Si, Ti and Zr, n is more preferably 1 or 2, and when Al. In any case, n is more preferably 1, and in any case, at least one of Z is more preferably containing an oxygen atom derived from a layered inorganic compound. Further, Z of organic-inorganic composite groups in the vicinity of each other may be hydrolyzed and condensed to form an MOM bond.

Since the interaction with the guest compound can be appropriately designed in the organic-inorganic composite group, a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structural group, a hydrogen bond forming group, and a coordination bond can be appropriately designed. It preferably contains either a producing group or an ionic bond generating group. As a result, non-covalent interactions with guest compounds (for example, van der Waals force, π-π interaction, hydrophobic interaction, hydrogen bond, coordination bond, ionic bond, etc.) are appropriately adjusted and imparted. Any compound can be inserted between layers and sustained-release according to the purpose.

The non-covalent interacting group is not particularly limited, and for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-hexyl group, an n-octyl group, a decyl group, and the like. Saturated or unsaturated aliphatic groups such as dodecyl group, octadecyl group, methylene group, propylene group, cyclohexyl group, vinyl group and allyl group, aromatic groups such as styryl group, phenyl group, naphthyl group and phenylene group, pyridinyl group. , Piperidinyl group, pyrodinyl group, pyrimidinyl group, imidazolyl group and other azole groups, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, dioxanyl group, morpholinyl group, thiazinyl group, indol group, nucleic acid base and other heterocycles. Structural group, acryloxy group, methacryloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, methyl carboxylate group, phosphate group, ethyl phosphate group, sulfonic acid group, methyl sulfonate group Group, amino group, methylamino group, dimethylamino group, isocyanurate group, ureido group, isocyanato group and other hydrogen bond and coordination bond generation groups, ethylammonium group, dimethylammonium group and trimethylammonium group ion bond generation group Etc., and because of their availability, methyl group, ethyl group, n-propyl group, n-hexyl group, decyl group, octadecyl group, methylene group, propylene group, cyclohexyl group, vinyl group, allyl group, styryl group , Phenyl group, phenylene group, epoxy group, oxetanyl group, acryloxy group, metharoxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, carboxyl group, amino group, methylamino group, dimethylamino group, trimethylammonium group , Isocyanurate group, ureido group and isocyanato group are preferable.
These non-covalent interacting groups may form a crosslinked structure by a crosslinking reaction between layers.

Next, the interlayer-modified layered inorganic compound in the present invention will be described in detail along with the production method.
The method for producing a precursor from a layered inorganic compound, which is a layered inorganic compound having wide layers, such as silylation, is the same as the method described in paragraphs 0047 to 0064 above.

Next, all or part of the counter anion (alkoxylate) of the hydroxyl group and 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). Then, an interlayer-modified layered inorganic compound having an organic-inorganic composite group represented by the above formula (2) is produced through a covalent bond between the layers.

The modifier for introducing the organic-inorganic composite group represented by the formula (2) between layers is an organic-inorganic composite having a hydrolyzable group and a functional group capable of interacting with a functional compound in the same molecule. Any modifier may be used, and examples thereof include a silylating agent containing a silane coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, and the like, preferably represented by the following formula (38). It is a compound to be used.

R _n MD _yn (38)
(In the formula (38), R is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms, and the like. It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and has a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group and 1 to 20 carbon atoms, respectively. Saturated or unsaturated mono or dialkylamino groups of linear or branched chains, mono or diarylamino groups with 1 to 20 carbon atoms, mono or dialalkylamino groups with 1 to 20 carbon atoms, primary and secondary, Tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group , Sulphonic acid ester group or halogen atom may be substituted, M represents Si, Al, Ti or Zr, D is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, carbon. Saturated or unsaturated cycloalkyloxy group may have 3 to 8 branched chains, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyl may have 1 to 8 branched chains Oxy group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms, saturated or unsaturated dialkyl of linear or branched chain with 1 to 6 carbon atoms It represents an amino group, M represents Si, Al, Ti or Zr, and when M is any of Si, Ti or Zr, the corresponding y is 4 and n is an integer of 1-3. , When M is Al, the corresponding y is 3, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.)

In the organic-inorganic composite modifier represented by the formula (38), the functional group represented by R may be protected by an appropriate protecting group.
Among the organic-inorganic composite modifiers, a silylating agent having M as Si is more preferable because of its abundance of types, availability, handling, and ease of controlling hydrolysis reaction.

Among the silylating agents, the hydrolyzable group has an extremely low risk of causing a side reaction with the functional group because it does not by-produce an acid such as hydrogen chloride, does not corrode the reactor, and is a by-product of the acid. It is preferably an alkoxysilane that does not require a disposal treatment, more preferably a methoxy group, an ethoxy group and a propoxy group having excellent silylation reactivity, and particularly preferably a methoxy group and an ethoxy group.

The silylating agent is not particularly limited, and examples of the alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, divinyldimethoxysilane, trivinylmethoxysilane, and 2- (3,4-epylcyclohexyl) ethyltrimethoxy. Silane, 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Ethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacry Loxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 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-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-Ixionpropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, 7 − Octenyltrimethoxysilane, 4- (trimethoxysilyl) butyric acid, 4- (trimethoxysilyl) butyrate 1,1-dimethylethyl, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, Dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, Octyltriethoxysilane, decyltrimethoxysilane, undecyltrimethoxysilane, dodecyltrimethoxysilane, tetradecyltrimethoxysilane, hexadecyltrimethoxysilane, octadecyltrimethoxysilane, trifluoropropyltrimethoxysilane, methoxytrimethylsilane, dimethoxy Examples thereof include dimethylsilane, trimethoxymethylsilane and triethoxysilane.

In addition, silylating agents other than alkoxysilanes can also be used. For example, hexamethyldisilazane, chlorotrimethylsilane, hexamethyldisilazane, trimethylsilyltrifluoromethanesulfonate, triethylchlorosilane, tertiarybutyldimethylchlorosilane, chlorotriisopropylsilane, 1,3-dichloro-1,1,3,3-tetra. Isopropyldisiloxane, chloromethyltrimethylsilane, triethylsilane, allyltrimethylsilane, 3-methacryloxypropyltrichlorosilane, 3-methacryloxypropylmethyldichlorosisilane, tris (N, N-dimethylamino) methylsilane, bis (N, N) -Dimethylamino) dimethylsilane and (N, N-dimethylamino) trimethylsilane and the like.
In these silylating agents, when a plurality of hydrolyzable groups are present in one molecule, even if a single hydrolyzable group such as an alkoxy group, a halogen atom, an alkylamino group or a dialkylamino group is present. , Multiple things may be mixed.

Further, instead of the silylating agent, a titanium-based coupling agent, an aluminum-based coupling agent, a zirconium-based coupling agent, or the like can be used in the same manner.

The organic solvent used for the reaction with the silylating agent is not particularly limited, but is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl. Alcohols such as -1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and ethyl Ketones such as methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxyode, alcohols such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform And halogen-based hydrocarbons such as dichloromethane are mentioned, and among these, alcohols and ethers, nitriles and ketones which are aprotonic polar solvents are preferable.
More preferably, it is an aprotic polar solvent or a secondary or tertiary alcohol having a boiling point of 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 100 ° C. or higher.

Examples of the aprotonic polar solvent include nitriles such as acetonitrile and propionitrile, ethers such as tetrahydrofuran, ketones such as acetone, ethylmethyl ketone, diethyl ketone and methylene isopropyl ketone, and amides such as N, N-dimethylformamide. Examples include sulfoxides such as dimethylsulfoxide.

The secondary or tertiary alcohol is not particularly limited, but 2-propanol, 2-butanol, 1-methoxy-2-propanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-. Examples include aromatic alcohols such as hexanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol, 1-butoxy-2-propanol, 2-methyl-2-propanol and phenol.
Among these, acetonitrile, tetrahydrofuran, methyl isopropyl ketone, 2-propanol, 2-butanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-propanol-2-propanol and 1-butoxy-2- Propanol is preferred, with 2-butanol, 1-methoxy-2-propanol and 1-butoxy-2-propanol being even more preferred.

When an aprotic polar solvent or a secondary or tertiary alcohol is used as the organic solvent for the reaction, the O-alkylation reaction, which is a side reaction of the hydroxyl group and the alkoxylate derived from the layered inorganic compound, is unlikely to occur, and the O-alkylation reaction is unlikely to occur. It is inferred that since the boiling point of the organic solvent used is high, the silylation reaction temperature rises, the interlayer modification reaction such as the silylation reaction is accelerated, and the interlayer modification rate such as the silylation rate increases.
Further, when secondary or tertiary alcohols are used, hydroxyl groups such as silanol are produced by hydrolysis of an organic-inorganic composite modifier such as a silylating agent described later, and coupling agents such as a silane coupling agent are used with each other. This is preferable because side reactions such as condensation are suppressed. It is inferred that this is the solvent effect due to the alcoholic hydroxyl group.

During the reaction, it is preferable to add water to the reaction system. The water to be added may be neutral, acidic or alkaline, and is not particularly limited, but ion-exchanged water, distilled water, pure water and ultrapure water are preferable.
The amount of water added is preferably 0.05 to 4.0 mol times the total amount of the hydroxyl group, which is the reaction point of the layered inorganic compound, and the alkoxylate, which is the counter anion of the onium group, that is, the ion exchange capacity. , 0.1 to 3.0 mol times is particularly preferable.
If the amount of water added is less than 0.05 mol times, the addition effect is small, and if it exceeds 4.0 mol times, side reactions such as hydrolysis and condensation between coupling agents such as silane coupling agents may proceed. There is.

The amount of the organic-inorganic composite modifier such as the silylating agent in the reaction is not particularly limited, but is preferable with respect to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. Is 0.1 to 30 mol times, more preferably 0.05 to 20 mol times, still more preferably 1.0 to 10 mol times.
If the amount of the coupling agent used is less than 0.1 mol times, the silylation reaction rate becomes low, while if it exceeds 30 mol times, it is industrially disadvantageous in terms of raw material cost.

The reaction point between the layers of the layered inorganic compound, that is, the interlayer modification rate such as the silylation rate with respect to the ion exchange capacity is selected according to the purpose and is not particularly limited, but the interlayer modification rate such as the silylation rate is 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 layers of the layered inorganic compound may be excessively covered with the components derived from the organic-inorganic composite modifier, which is not preferable.

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

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

The interlayer modification reaction such as the silylation reaction with the organic-inorganic composite modifier in the present invention may or may not use a catalyst, but carboxylic acids such as hydrogen chloride, formic acid, acetic acid and oxalic acid, phosphoric acid, nitrate, etc. Known acids such as sulfonic acids such as sulfuric acid and methanesulfonic acid, and known bases such as ammonia, trimethylamine, triethylamine, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide can be added as catalysts.
In that case, the amount of the catalyst to be added is not particularly limited, but is 0.001 to 1.0 mol with respect to the total amount of the hydroxyl group as the reaction point and the alkoxylate as the counter anion of the onium group, that is, the ion exchange capacity. It is preferably double, more preferably 0.01 to 0.1 molar times.

The interlayer-modified layered inorganic compound obtained by the interlayer modification reaction such as the silylation reaction is preferably isolated, washed and then dried. The method for isolation, washing and drying is not particularly limited, and a known method for isolating, washing and drying layered inorganic compounds and inorganic fine particles can be used, for example, the method for the precursor and the like. Can be used.

Z present in the organic-inorganic composite group represented by the formula (2) can also participate in the interaction with the guest compound. For example, if it is a hydroxyl group, it can generate a hydrogen bond with a guest compound and participate in insertion and sustained release, and it can interact with a guest compound depending on the type of Z, for example, a hydroxyl group, a methoxy group, etc. It can also be involved in control.

Further, any functional group or modifying group may be present between the layers of the interlayer-modified layered inorganic compound in the present invention in addition to the organic-inorganic composite group. For example, exchangeable metal cations such as sodium, potassium and calcium may be present, modified with organic onium groups such as alkylammonium and alkylphosphonium, and hydroxyl groups derived from layered inorganic compounds may be present. Often, the hydroxyl group may be sealed / converted by an alkoxy group such as a methoxy group. These abundances can also be involved in controlling the interaction with guest compounds.

In the present invention, there are no particular restrictions on the compound (also referred to as guest compound) that is inserted into the interlayer-modified layered inorganic compound having an organic-inorganic composite group represented by the formula (1) or the formula (2) and slowly released. However, it can be arbitrarily selected according to the intended use, but for example, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms and a branched chain having 3 to 8 carbon atoms are contained in the compound. Saturated or unsaturated cycloalkyl groups may be present, aryl groups having 6 to 20 carbon atoms or aralkyl groups having 7 to 20 carbon atoms are shown, and vinyl groups, epoxy groups, oxetanyl groups, acryloxy groups, metharoxy groups, hydroxyl groups, respectively. Amino group, saturated or unsaturated mono or dialkylamino group of linear or branched chain with 1 to 20 carbon atoms, mono or diarylamino group with 6 to 20 carbon atoms, mono or dialalkylamino group with 7 to 20 carbon atoms , Primary, secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group , Phosphoric acid ester group, sulfonic acid group, sulfonic acid ester group, ketone group, ether group functional group or heteroatomic atom such as oxygen atom, nitrogen atom, sulfur atom, phosphorus atom, halogen atom, etc. It may have various heterocyclic structural groups.

Among these, since it is easy to control the interaction with the organic-inorganic composite group, a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structural group, a hydrogen bond forming group, a coordination bond forming group or an ionic bond forming Those containing any of the groups are more preferable, and there is no particular limitation, but for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-hexyl group, an n-octyl group, a decyl group, etc. Saturated or unsaturated aliphatic groups such as dodecyl group, octadecyl group, methylene group, propylene group, cyclohexyl group, vinyl group and allyl group, aromatic groups such as styryl group, phenyl group, phenol group, naphthyl group and phenylene group. , Azol groups such as pyridinyl group, piperidinyl group, pyrodinyl group, pyrimidinyl group, pyraziniryl group, imidazolyl group, thiazolinyl group, thiazole group, thiazolinone group, isothiazolinone group, epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydrothiophenyl group, Dioxanyl group, morpholinyl group, thiazinyl group, indol group, heterocyclic structural group such as nucleic acid base, acryloxy group, methacryloxy group, acetyl group, benzoyl group, benzyl group, hydroxyl group, thiol group, aldehyde group, carboxyl group, methyl carboxylate Hydrogen bond and coordination bond formation of groups, phosphate groups, ethyl phosphate groups, sulfonic acid groups, methyl sulfonate groups, amino groups, methylamino groups, dimethylamino groups, isocyanurate groups, ureido groups, isocyanato groups, etc. Examples thereof include those containing an ionic bond-forming group of a group, an ethylammonium group, a dimethylammonium group and a trimethylammonium group. These functional groups may be present in combination in the same compound.

The molecular weight of the compound is not particularly limited and can be arbitrarily selected according to the intended use. However, since it is easy to insert into layers and the host-guest composite agent structure is kept stable, the compound is used. The molecular weight is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 500 or less.

The method for producing a sustained-release composite agent in which a functional compound is inserted between layers of an interlayer-modified layered inorganic compound is not particularly limited. For example, a method of mixing an interlayer-modified layered inorganic compound and a compound in the absence of a solvent. Alternatively, a method of mixing the layer-interlayer modified layered inorganic compound in the presence of a solvent in which the compound is soluble or insoluble can be mentioned.
When the compound is a gas or a liquid, a method of mixing in the absence of a solvent is economical and preferable. On the other hand, when the compound is a 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 soluble solvent because the compound is efficiently inserted between the layers. When the compound is a solid, the method of heating it above its melting point to liquefy it and mixing it with the interlayer-modified layered inorganic compound is efficient because it does not require a solvent.

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

The solvent used for producing the sustained-release complex is not particularly limited, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, 2-methyl. Alcohols such as -1-propanol, 1-methoxy-2-propanol, 1-pentanol, 2-pentanol, 1-hexanol and 2-hexanol, nitriles such as acetonitrile, ethers such as tetrahydrofuran, acetone and ethyl Ketones such as methyl ketone, amides such as N, N-dimethylformamide, sulfoxides such as dimethyl sulfoxide, alcohols such as hexane, aromatics such as benzene and toluene, esters such as ethyl acetate, chloroform And halogen-based hydrocarbons such as dichloromethane may be mentioned, and may be appropriately selected in consideration of properties such as solubility of the guest compound and hydrophilicity and hydrophobicity of the interlayer modifying group of the host compound.

The mixing ratio of the interlayer-modified layered inorganic compound, which is a host compound when producing a sustained-release composite agent, and the compound, which is a guest compound, is not particularly limited and is arbitrarily set according to the purpose, but over a long period of time. When it is used as a sustained-release agent, it is desirable to mix it with the maximum amount or more of the compound that can be inserted between the layers of the layered inorganic compound. For example, when 10 parts of the functional compound can be inserted between layers with respect to 100 parts of the interlayer-modified layered inorganic compound, it is preferable to mix with 10 parts or more.

The sustained-release composite agent obtained by mixing the interlayer-modified layered inorganic compound and the compound can be used as it is as a sustained-release compound, or can be used as a sustained-release agent after removing excess compounds and solvents. When the compound is a liquid or a soluble solvent of the compound is used in combination, the excess compound or solvent can be removed by filtration by a known filtration operation such as natural filtration, vacuum filtration, or pressure filtration. When the compound is a liquid or a sublimable solid, it can be removed by air drying, heating evaporation, vacuum distillation operation or the like. When the compound is a solid and a solvent is used in combination, unnecessary solvent can be removed by air drying, heat evaporation, or vacuum distillation operation.

The method of using the sustained-release composite agent containing the interlayer-modified layered inorganic compound and the compound inserted between the layers of the interlayer-modified layered inorganic compound in the present invention is not particularly limited, and for example, the composite agent is sustained-release as it is. It can be used as an agent, or it can be mixed with a resin and used as a structural material, a coating agent, a fiber, a film, a sheet, a plate, particles, a block, etc., and further dispersed in a solvent, a polymerizable monomer, or the like. It can also be used as a paint.

The sustained-release composite agent of the present invention can be blended 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, and various plastics such as polyvinyl chloride, polyolefin, polyurethane, ABS, polystyrene, polyvinyl acetate, polycarbonate, polyester, polyurethane, and polyacrylic acid. Be done.

Further, the sustained-release composite agent of the present invention is a compound suspended in a liquid medium such as water or an organic solvent in the presence or absence of a binder, and is spray-coated, coater-coated, dipping, brush-coated. It is also possible to apply it to the surface of various metals, plastics, ceramics, etc. by ordinary coating means such as roll coating to form a film, thus providing an article of various materials with an effect corresponding to the function of the guest compound. Can be granted.

The preferable ratio of the sustained-release composite agent of the present invention when blended with various materials is not particularly limited and can be arbitrarily selected depending on the usage environment and purpose.

Specific uses of the material or molded body to which the sustained-release composite agent and the sustained-release composite agent of the present invention are blended or applied include textile products such as towels, carpets, curtains, clothing, mosquito nets, bedding, leather, etc. Refrigerators, washing machines, dish dryers, vacuum cleaners, air fresheners, TVs, telephones, electrical appliances such as personal computers, building materials such as wallpaper, tiles, bricks, concrete, screws, joints, face washers, toothbrushes, brooms, hoses, Daily miscellaneous goods such as slippers, garbage boxes, scrubbing brushes, cutting boards, triangular corners, kitchen supplies such as kitchen towels, toiletry supplies, mobility supplies such as automobiles, aircraft, ships, agricultural supplies such as pesticides and plant hormones, pharmaceuticals, outside the pharmaceutical department Medical and hygiene products such as products, drug delivery, cosmetics, air fresheners, antioxidants, lubricants, moisturizers, repellents for insects and animals, insecticides, bactericides, insect repellents, preservatives, fungicides , Physiological activators such as anti-virus agents, foods such as food additives, various coating agents, paints and adhesives, etc., but are not limited thereto.

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

<Example 1> Synthesis of a sustained-release composite agent in which 2-methyl-2-thiazolin (hereinafter referred to as 2MT) is inserted between layers of a methacrylolyl-type crosslinked and a magadiate interlayer-modified with a phenylsilyl group, and its sustained-release property. Evaluation.
(1) Synthesis of sodium-magadite (hereinafter referred to as Na-magadite).
Mix 18.34 g of sodium silicate (manufactured by Fuji Chemical Co., Ltd., trade name: No. 4 sodium silicate), 7.28 g of silica gel (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: Wakogel Q-63) and 54.37 g of pure water. After that, it was sealed in a high-pressure reaction decomposition container (manufactured by San-ai Kagaku Co., Ltd., trade name: HU-100) and heated at 170 ° C. for 30 hours. The product was collected by suction filtration, washed with a dilute aqueous NaOH solution (pH: 9-10) and pure water, and dried at 40 ° C. for 2 days to obtain 15.9 g of Na-magadiate.
As a result of calculating the composition of Na-magadiate using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu Corporation) and a thermogravimetric analyzer (TG / DTA6300, manufactured by Hitachi High-Tech Science), Na ₂ Si ₁₄ O ₂₉ -NH ₂ O, and the ion exchange capacity calculated assuming n = 0 was 2.21 mol _c / kg.
Further, as a result of determining the bottom surface spacing of Na-magadite obtained by using an X-ray diffractometer (manufactured by BRUKER, trade name: D8 ADVANCE), it was 1.54 nm.

(2) Synthesis of dodecyltrimethylammonium (hereinafter referred to as DTMA) -magadiate (synthesis of silylation precursor by interlayer ammonium formation by dodecyltrimethylammonium chloride treatment of Na-magadite).
100 g of Na-magadiate, 6500 g of pure water and 175 g of dodecyltrimethylammonium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) obtained as described above 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 ° C. to obtain 94 g of DTMA-magadiate.
As a result of measuring the mass of Na in the obtained DTMA-magadite using an atomic absorption spectrometer (AA-6200, manufactured by Shimadzu Corporation), the Na content was less than 0.04% by mass, and almost all cations were exchanged. I confirmed that it was done.
As a result of calculating the composition of DTMA-magadiate obtained by using an elemental analyzer (manufactured by Yanako Analytical Industry Co., Ltd., CHN coder MT-5) and a thermogravimetric analyzer (manufactured by Hitachi High-Tech Science Corporation, TG / DTA6300), DTMA _{It was 1.72} H _0.28 Si ₁₄ O ₂₉ · nH ₂ O.
Further, in the same manner as described above, the bottom surface spacing of the obtained DTMA-magadiaite was determined to be 2.89 nm.

(3) Interlayer silylation of DTMA-magadiaite by 3-methacryloyloxypropyltrimethoxysilane (hereinafter referred to as MAC-TRIMS) treatment (introduction of methacryloyloxypropyl group).
100 g of DTMA-magadiate obtained as described above was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, and then 1850 g of 1-methoxy-2-propanol (hereinafter referred to as PGM) dried with molecular sieve 3A, pure. 3.4 g of water and 39.2 g of MAC-TRIMS (0.5 mol times with respect to the reaction site, manufactured by Shin-Etsu Chemical Co., Ltd.) were mixed, and the mixture was stirred for 4 days while heating under reflux in a nitrogen atmosphere. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain 105 g of silylated magadite (hereinafter referred to as MACPS-magadite).
As a result of calculating the composition of the obtained MACPS-magadiate in the same manner as described above, it was methacryloyloxypropylsilyl (MACPS) _0.43 DTMA _0.56 Me _1.01 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing was 2.12 nm. It was.

(4) Synthesis of interlayer cross-linked layered inorganic compound by cross-linking reaction of MACPS-magadiate.
100 g of MACPS-magadiate and 1450 g of toluene obtained as described above were mixed, and nitrogen gas was bubbled for 1 hour while cooling in an ice bath to remove oxygen in the system. Then, 7.88 g of 2,2'-azobisisobutyronitrile (hereinafter referred to as AIBN) was added, and the mixture was stirred at 60 ° C. for 24 hours. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C. to obtain 95 g of magadiate (hereinafter referred to as P-MACPS-magadiate) crosslinked with a methacryloxy group.
As a result of calculating the composition of the P-MACPS-magadiaite obtained in the same manner as above, the crosslinked methacryloyloxypropyl group (P-MACPS) _0.06 MACPS _0.38 DTMA _0.56 Me _1.00 Si ₁₄ O ₂₉ · nH ₂ O. The bottom spacing was 1.94 nm.

(5) Interlayer silylation (introduction of phenyl group) by phenyltrimethoxysilane (hereinafter referred to as Ph-TRIMS) treatment of P-MACPS-magadiaite.
Except that 100 g of DTMA-magadiate was changed to 100 g of P-MACPS-magadiate and 39.2 g of MAC-TRIMS was changed to 263 g of Ph-TRIMS (7 mol times relative to the reaction point, manufactured by Shin-Etsu Chemical Co., Ltd.). By performing interlayer silylation in the same manner as in Example 1 (3), 96 g of silylated magadite (hereinafter referred to as P-MACPS-PhS-magadite) was obtained.
As before, the result of calculating the composition of the resulting P-MACPS-PhS- magadiite, a _{P-MACPS 0.06 MACPS 0.38 PhS 0.38} DTMA 0.02 Me 1.16 Si 14 O 29 · nH 2 O, the basal spacing 1 It was .95 nm.

(6) Preparation of a complex agent of P-MACPS-PhS-magadiate and 2MT.
30 g of the P-MACPS-PhS-magadite obtained above was mixed with 150 g of 2MT (manufactured by Tokyo Kasei Kagaku Kogyo Co., Ltd.) and stirred at 25 ° C. for 2 days. Then, the solid was collected by suction filtration and dried at 25 ° C. to obtain 33 g of a composite agent of P-MACPS-PhS-magadiate and 2MT (hereinafter referred to as P-MACPS-PhS-magadiate / 2MT composite agent). .. The bottom spacing was 1.98 nm.
Calculate the 2MT weight adsorbed in 1g of the composite agent obtained using an elemental analyzer (Yanako Analytical Industry Co., Ltd., CHN coder MT-5) and a thermogravimetric analyzer (Hitachi High-Tech Science Co., Ltd., TG / DTA6300). As a result, it was 83.4 mg.

(7) 2MT release test from P-MACPS-PhS-magadiate / 2MT complex.
40 mg of the P-MACPS-PhS-magadiate / 2MT complex obtained above was mixed with 2.8 g of Octane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and stirred at 25 ° C.
After the start of stirring, sampling was performed over time, the sampling solution was centrifuged, and the 2MT concentration in the supernatant was analyzed using 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 a sustained-release composite agent in which 2MT is inserted between layers of a phenylsilyl group-modified magadite and evaluation of its sustained-release (1) Partially protonated DTMA by hydrochloric acid treatment of DTMA-magadiate -Synthesis of magadite (silylation precursor).
100 g of DTMA-magadiate obtained as in Example 1 (2) and 655 g of 0.1 mol · dm- ³ hydrochloric acid were mixed and stirred at room temperature for 1 day. Then, the solid was sucked and collected, washed with pure water, and dried at 60 ° C. to obtain 86 g of partially protonated DTMA-magadiate.
In the same manner as above, the composition of the obtained partially protonated DTMA-magadiaite was calculated to be DTMA _1.11 H _0.89 Si ₁₄ O ₂₉ · nH ₂ O, and the proportion of ammonium groups was 56 mol% with respect to the ion exchange capacity. Met.
As a result of analyzing the bottom spacing of the partially protonated DTMA-magadiaite in the same manner as described above, no clear diffraction peak was observed. It is presumed that this is because most of the layered structure of the obtained partially protonated DTMA-magadiaite is broken.

(2) Interlayer silylation of partially protonated DTMA-magadite by Ph-TRIMS treatment (introduction of phenyl group).
Cyrilized magadite by performing interlayer silylation in the same manner as in Example 1 (5) except that 100 g of P-MACPS-magadite was converted to 100 g of partially protonated DTMA-magadite obtained as described above. 102 g (hereinafter referred to as PhS-magadiate) was obtained.
As a result of calculating the composition of the obtained PhS-magadiaite in the same manner as described above, it was found that phenylsilyl (PhS) _1.13 DTMA _0.40 Me _0.47 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 2.16 nm.

(3) Removal of residual DTMA group of PhS-magadiate and introduction of methyl group using hydrogen chloride and methanol (sealing of silanol).
100 g of PhS-magadiate obtained as described above was dried under reduced pressure at 100 ° C. and about 100 Pa for 2 hours, and then 1650 g of PGM dried with molecular sieve 3A and 78.5 g of a 5% hydrogen chloride methanol solution were mixed to create a nitrogen atmosphere. It was stirred for 3 days with heating under reflux. Then, the solid was collected by suction filtration, washed with methanol, and dried at 60 ° C.
The entire amount of the obtained solid was mixed with 1980 g of methanol and stirred for 2 days while heating under reflux in a nitrogen atmosphere. Then, the solid was collected by suction filtration and dried at 60 ° C., and the DTMA group was removed, and the silanol derived from magadiaite was O-methylated PhS-magadiate (hereinafter referred to as PhS-magadiaite-PPMe) 76 g. Got
As a result of calculating the composition of the obtained PhS-magadiaite-PPMe in the same manner as described above, it was PhS _1.13 DTMA _0.04 Me _0.83 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 1.69 nm.

(4) Preparation of a composite agent of PhS-magadiate-PPMe and 2MT.
A composite agent of PhS-magadite-PPMe and 2MT in the same manner as in Example 1 (6) except that 30 g of P-MACPS-PhS-magadiaite was changed to 30 g of PhS-magadiaite-PPMe obtained above. Hereinafter, 34 g (referred to as PhS-magadiate-PPMe / 2MT complex) was obtained. The bottom spacing was 2.11 nm.
As a result of calculating the weight of 2MT adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 122.6 mg.

(5) 2MT release test from PhS-magadiate-PPMe / 2MT complex.
P-MACPS-PhS-magadiate / 2MT complex 40 mg was changed to 40 mg of the PhS-magadiaite-PPMe / 2MT complex obtained above, but in the same manner as in Example 1 (7). 2MT concentration was analyzed.
The results are shown in Tables 1 and 2.

<Example 3> Synthesis of a sustained-release complex agent in which 2MT is inserted between layers of magadiaite (MACPS-magadiaite) interlayer-modified with a 3-methacryloyloxypropylsilyl group, and evaluation of the sustained-release complexing.
(1) Preparation of a complex agent of MACPS-magadiate and 2MT.
MACPS-magadite and 2MT in the same manner as in Example 1 (6) except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of MACPS-magadite obtained as in Example 1 (3). 31 g of the complex agent (hereinafter referred to as MACPS-magadite / 2MT complex agent) was obtained. The bottom spacing was 2.20 nm.
As a result of calculating the weight of 2MT adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 46.2 mg.

(2) 2MT release test from MACPS-magadiate / 2MT complex.
The 2MT concentration in the octane was the same as in Example 1 (7), except that the P-MACPS-PhS-magadiate / 2MT complex 40 mg was changed to the MACPS-magadiate / 2MT complex 40 mg obtained above. Was analyzed.
The results are shown in Tables 1 and 2.

<Comparative Example 1> Preparation of a sustained-release composite agent in which 2MT is inserted between layers of unmodified Na-magadite.
With Na-magadite in the same manner as in Example 1 (6), except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of Na-magadite obtained as in Example 1 (1). 30 g of a 2MT composite agent (hereinafter referred to as Na-magadite / 2MT composite agent) was obtained. The bottom spacing was 1.56 nm.
As a result of calculating the weight of 2MT adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 12.9 mg. The results are shown in Table 1.

<Comparative Example 2> Synthesis of a sustained-release complex agent in which 2MT is inserted between layers of magadites interlayer-modified with a DTMA group and evaluation of the sustained-release complexing.
(1) Preparation of a composite agent of DTMA-magadiate and 2MT.
With DTMA-magadite in the same manner as in Example 1 (6), except that 30 g of P-MACPS-PhS-magadite was changed to 30 g of DTMA-magadite obtained as in Example 1 (2). 30 g of a 2MT complex (hereinafter referred to as DTMA-magadiate / 2MT complex) was obtained. The bottom spacing was 2.89 nm.
As a result of calculating the weight of 2MT adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 12.0 mg.

(2) 2MT release test from DTMA-magadiate / 2MT complex.
The 2MT concentration in the octane was adjusted in the same manner as in Example 1 (7), except that the P-MACPS-PhS-magadiate / 2MT complex 40 mg was changed to the DTMA-magadiaite / 2MT complex 40 mg obtained above. analyzed. The results are shown in Tables 1 and 2.

As shown in Table 1, the unmodified and conventional alkylammonium-interlayered host compounds shown in Comparative Examples 1 and 2 cannot control the interaction with the guest compound, so that the amount of 2MT is very small. Not able to adsorb. On the other hand, when the interlayer-modified layered inorganic compound having the organic-inorganic composite group of the present invention shown in Examples 1 to 3 as a host compound is used, 2MT, which is a guest compound, is effectively adsorbed. Can be held. In Example 2, 11.5 times as much guest compound as in Comparative Example 2 can be adsorbed per unit host compound.
Further, since the space between the bottom surfaces of the layered inorganic compound is expanded after the compounding with the guest compound, it is shown that most of the adsorbed guest compounds are intercalated between the layers.

In the 2MT release test carried out using the composite agents of Examples 1 to 3 and Comparative Example 2 in Table 1, it was adsorbed into the initial host-guest composite agent based on the measured 2MT concentration in the octane. The ratio of the guest compound released from the host-guest complex to the amount of 2MT was calculated as the release rate, and Table 2 shows the time-dependent representation.

In all of Examples 1 to 3, the release rate of 2MT slowly increased with the passage of time, indicating that the guest compound was slowly released into the octane as the test solvent.
On the other hand, when the layered inorganic compound organicized with alkylammonium (DTMA), which is the conventional technique shown in Comparative Example 2, is used as the host compound, 18.5% of the guest compound is released by 1 hour. However, after that, the guest compound was not released as it was adsorbed in the layered inorganic compound, and could not be released slowly.
Further, while Example 1 uses a layered inorganic compound in which layers are crosslinked by an organic-inorganic composite crosslinked structure as a host compound, in Examples 2 and 3, the layers are modified with a phenylsilyl group or a methacryloxy group. This is a case where a layered inorganic compound that has not been crosslinked between layers is used as a host compound. Focusing on the release rate of 2 MT (slope of release rate) in Example 2, 21.9% was released by 1 hour, which is still larger than that in Example 1. In Example 3, focusing on the release rate of 2MT (slope of release rate), 38.7% was already released by 1 hour, which is still larger than that of Example 1.
On the other hand, Example 1 is a case where a layered inorganic compound cross-linked between layers is used as a host compound by introducing methacryloxy between layers and cross-linking the mixture, but the release rate (slope of release rate) of 2 MT is obtained. Focusing on it, it is very small at 1.9% even after 1 hour, and it is also very small after that, and 2MT is released very slowly. That is, the interaction between the guest compounds can be controlled by appropriately maintaining the interlayer distance by the interlayer crosslinking, so that the release rate can be appropriately controlled, and the function derived from the guest compound is extended. It is shown that it can be expressed over a period of time (the life can be extended).
By using the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention as the host compound in this way, the desired guest compound can be stored more efficiently than the conventional methods, and the release rate thereof. Can be effectively sustained over a long period of time.

<Example 4> Synthesis of a sustained-release composite agent in which 2,3,5-trimethylpyrazine (hereinafter referred to as 235TMP) is inserted between layers of magadiaite layer-modified with a 3-methacryloyloxypropylsilyl group, and its gradual release. Release evaluation.
(1) Preparation of a complex agent of MACPS-magadiate and 235 TMP.
A composite agent of MACPS-magadiate and 235 TMP (hereinafter referred to as MACPS-magadiate / 235 TMP complex agent) in the same manner as in Example 3 (2) except that 2MT 150 g was changed to 235 TMP (manufactured by Tokyo Kasei Chemical Industry Co., Ltd.). ) 49 g was obtained. The bottom spacing was 3.20 nm.
As a result of calculating the weight of 235 TMP adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 381.5 mg.

(2) 235 TMP release test from MACPS-Magadiate / 235 TMP complex.
The 235 TMP concentration in the octane was adjusted in the same manner as in Example 1 (7), except that the P-MACPS-PhS-magadiate / 2MT complex 40 mg was changed to the MACPS-magadiate / 235 TMP complex 40 mg obtained above. analyzed.
The results are shown in Tables 3 and 4.

<Comparative Example 3> Synthesis of a sustained-release complex agent in which 235 TMP is inserted between layers of magadiaite interlayer-modified with a DTMA group and evaluation of its sustained-release property.
(1) Preparation of a composite agent of DTMA-magadiate and 235 TMP.
A composite agent of DTMA-magadiate and 235 TMP in the same manner as in Example 4 (1), except that 30 g of MACPS-magadiate was changed to 30 g of DTMA-magadite obtained as in Example 1 (2). (Hereinafter referred to as DTMA-magadiate / 235TMP complex agent) 34 g was obtained. The bottom spacing was 3.83 nm.
As a result of calculating the weight of 235 TMP adsorbed in 1 g of the obtained composite agent in the same manner as described above, it was 126.8 mg.

(2) 235 TMP release test from DTMA-magadiate / 235 TMP complex.
235 TMP concentration in octane in the same manner as in Example 1 (7) except that 40 mg of the P-MACPS-PhS-magadiate / 2MT complex was changed to 40 m of the DTMA-magadiate / 235 TMP complex obtained above. Was analyzed. The results are shown in Tables 3 and 4.

As shown in Table 3, when the interlayer-modified layered inorganic compound which is interlayer-modified with the organic-inorganic composite group of the present invention shown in Example 4 is used as the host compound, the conventional alkylammonium shown in Comparative Example 3 is used. Compared with the interlayer organic compound, the guest compound 235 TMP can be effectively adsorbed and retained, and in Example 4, 4.2 times as many guest compounds as in Comparative Example 3 per unit host compound. Can be adsorbed. Further, since the space between the bottom surfaces of the layered inorganic compound is expanded after the compounding of the guest compounds, it is shown that most of the adsorbed guests are intercalated between the layers.

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

表４において、実施例４では時間の経過とともに２３５ＴＭＰの放出率が徐々に増加しており、試験溶媒であるオクタン中にゲスト化合物が徐放されていることを示している。
一方、比較例３の従来技術では１時間後までに多くのゲスト化合物が放出された後は、ゲスト化合物は層状無機化合物中に吸着されたまま放出されておらず、徐放化できていない。

In Table 4, in Example 4, the release rate of 235 TMP gradually increased with the passage of time, indicating that the guest compound was slowly released into the octane as the test solvent.
On the other hand, in the prior art of Comparative Example 3, after a large number of guest compounds were released within 1 hour, the guest compounds were not released while being adsorbed in the layered inorganic compound, and could not be released slowly.

By using the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention as the host compound in this way, the desired guest compound can be efficiently stored, and the release rate thereof can be adjusted for sustained release. Can be transformed into.

<Example 5> Synthesis of a sustained-release complex agent in which 2-n-octyl-4-isothiazolin-3-one (hereinafter referred to as OIT) is inserted between layers of magadiate interlayer-modified with a phenylsilyl group, and its use. Sustained release evaluation.
(1) Preparation of a complex agent of PhS-magadiate-PPMe and OIT.
90 g of PhS-magadiate-PPMe obtained as in Example 2 (4) was mixed with 200 g of methanol and 10 g of OIT, and the mixture was stirred at 25 ° C. for 24 hours. Then, the mixed solution was transferred to a petri dish and dried at 25 ° C. for 16 hours to remove methanol as a solvent, and a composite agent of PhS-magadiate-PPMe and OIT (hereinafter, PhS-magadiaite-PPMe / OIT composite agent) was used. As described, the active ingredient concentration of OIT: 10 wt%) 99 g was obtained. The bottom spacing was 2.77 nm.

(2) OIT release test from PhS-magadiate-PPMe / OIT complex.
Example 1 except that 40 mg of the P-MACPS-PhS-magadiaite / 2MT complex was changed to 20 mg of the PhS-magadiaite-PPMe / OIT complex obtained above, and 2.8 g of octane was changed to 20 g of octane. The OIT concentration in the octane was analyzed in the same manner as in (7).
The results are shown in Tables 5 and 6.

<Example 6> Synthesis of a sustained-release composite agent in which OIT is inserted between layers of magadiates modified with a phenylsilyl group and a hexylsilyl group, and evaluation of the sustained-release complexing thereof.
(1) Interlayer silylation (introduction of phenyl group and hexyl group) by Ph-TRIMS and hexylsilyltrimethoxysilane (hereinafter referred to as Hx-TRIMS) treatment of partially protonated DTMA-magadiaite.
100 g of DTMA-magadiate was changed to 100 g of partially protonated DTMA-magadiaite obtained as in Example 2 (1), and 39.2 g of MAC-TRIMS was changed to 132 g of Ph-TRIMS and Hx-TRIMS (Tokyo Kasei Kagaku Kogyo Co., Ltd.). (Manufactured) 108 g of silylated magadite (hereinafter referred to as PhS-HxS-magadiate) was obtained by performing interlayer silylation in the same manner as in Example 1 (3) except that the weight was changed to 137 g.
As a result of calculating the composition of PhS-HxS-magadiite obtained by using the above-mentioned elemental analyzer, thermogravimetric analyzer and nuclear magnetic resonance apparatus (JNM-ECA400, manufactured by JEOL Ltd.), PhS _0.45 HxS _0.24 DTMA _{It was 0.71} Me _0.60 Si ₁₄ O ₂₉ · nH ₂ O.
Further, in the same manner as described above, the bottom surface spacing of the obtained PhS-HxS-magadiaite was determined and found to be 2.35 nm.

(2) Removal of residual DTMA group of Ph-HxS-magadiate and introduction of methyl group using hydrogen chloride and methanol (sealing of silanol).
PhS-HxS in which the DTMA group was removed and silanol derived from magadiaite was O-methylated in the same manner as in Example 2 (3) except that 100 g of PhS-magadiate was changed to 100 g of PhS-HxS-magadiaite. -Magadiate (hereinafter referred to as PhS-HxS-Magadiaite-PPMe) 76 g was obtained.
As a result of calculating the composition of the obtained PhS-HxS-magadiaite-PPMe in the same manner as described above, the result was PhS _0.45 HxS _0.24 DTMA _0.18 Me _1.13 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 1.95 nm. It was.

(3) Preparation of a complex agent of PhS-HxS-magadiate-PPMe and OIT.
A composite agent of PhS-HxS-magadiaite-PPMe and OIT (hereinafter, PhS-HxS) in the same manner as in Example 5 (1) except that PhS-magadiaite-PPMe90g was changed to PhS-HxS-magadiaite-PPMe90g. 95 g (concentration of active ingredient of OIT: 10 wt%), which is described as -magadite-PPMe / OIT complex, was obtained. The bottom spacing was 2.66 nm.

(4) OIT release test from PhS-HxS-magadiate-PPMe / OIT complex.
OIT in octane in the same manner as in Example 5 (2), except that the PhS-magadiaite-PPMe / OIT complex 20 mg was changed to the PhS-HxS-magadiaite-PPMe / OIT complex 20 mg obtained above. The concentration was analyzed.
The results are shown in Tables 5 and 6.

<Example 7> Synthesis of a sustained-release composite agent in which OIT is inserted between layers of magadites interlayer-modified with a phenylsilyl group and a 3-mercaptopropylsilyl group, and evaluation of the sustained-release complexing thereof.
(1) Interlayer silylation of partially protonated DTMA-magadiaite by Ph-TRIMS and 3-mercaptopropylsilyltrimethoxysilane (hereinafter referred to as MP-TRIMS) treatment (introduction of phenyl group and mercaptopropyl group).
Cyrilized magadiaite (hereinafter PhS-MPS-magadia) by performing interlayer silylation in the same manner as in Example 6 (1) except that 137 g of Hx-TRIMS was changed to 123 g of MP-TRIMS (manufactured by Shin-Etsu Chemical Co., Ltd.). 104 g (denoted as Ito) was obtained.
As a result of calculating the composition of the obtained PhS-MPS-magadiaite in the same manner as described above, PhS _0.62 mercaptopropylsilyl (MPS) _0.61 DTMA _0.27 Me _0.50 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing is 2. It was 15 nm.

(2) Removal of residual DTMA group and introduction of methyl group of PhS-MPS-magadiate using hydrogen chloride and methanol (sealing of silanol).
PhS-MPS in which the DTMA group was removed and silanol derived from magadiaite was O-methylated in the same manner as in Example 2 (3) except that 100 g of PhS-magadiaite was changed to 100 g of PhS-MPS-magadiaite. -Magadiate (hereinafter referred to as PhS-MPS-Magadiaite-PPMe) 93 g was obtained.
As a result of calculating the composition of the obtained PhS-HxS-magadiate-PPMe in the same manner as described above, PhS _0.62 MPS _0.61 DTMA _0.19 Me _0.58 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 2.15 nm. It was.

(3) Preparation of a complex agent of PhS-MPS-magadiate-PPMe and OIT.
A composite agent of PhS-MPS-magadiaite-PPMe and OIT (hereinafter, PhS-MPS) in the same manner as in Example 5 (1) except that PhS-magadiaite-PPMe90g was changed to PhS-MPS-magadiaite-PPMe90g. 98 g (concentration of active ingredient of OIT: 10 wt%), which is described as -magadite-PPMe / OIT complex, was obtained. The bottom spacing was 2.48 nm.

(4) OIT release test from PhS-MPS-magadiaite-PPMe / OIT complex.
OIT in octane in the same manner as in Example 5 (2), except that the PhS-magdiaite-PPMe / OIT complex 20 mg was changed to the PhS-MPS-magadiaite-PPMe / OIT complex 20 mg obtained above. The concentration was analyzed.
The results are shown in Tables 5 and 6.

<Example 8> Synthesis of a sustained-release complex agent in which OIT is inserted between layers of magadiaite interlayer-modified with a 3-mercaptopropylsilyl group, and evaluation of the sustained-release complexing.
(1) Interlayer silylation of partially protonated DTMA-magadiaite by MP-TRIMS treatment (introduction of mercaptopropyl group).
Example 1 (Except that 100 g of DTMA-magadiate was changed to 100 g of partially protonated DTMA-magadiate obtained as in Example 2 (1) and 39.2 g of MAC-TRIMS was changed to 245 g of MP-TRIMS. By carrying out interlayer silylation in the same manner as in 3), 97 g of silylated magadite (hereinafter referred to as MPS-magadiate) was obtained.

As a result of calculating the composition of the obtained MPS-magadiaite in the same manner as described above, the MPS was _0.95 DTMA _0.30 Me _0.75 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom surface spacing was 2.22 nm.

(2) Removal of residual DTMA group and introduction of methyl group of MPS-magadiate using hydrogen chloride and methanol (sealing of silanol).
MPS-Magdiaite (MPS-Magdiaite in which the DTMA group was removed and silanol derived from magadiaite was O-methylated in the same manner as in Example 2 (3), except that 100 g of PhS-magadiate was changed to MPS-magadiaite 100 g. Hereinafter, 93 g (referred to as MPS-magadite-PPMe) was obtained.
As a result of calculating the composition of the obtained MPS-magadiaite-PPMe in the same manner as described above, the MPS was _0.95 DTMA _0.23 Me _0.82 Si ₁₄ O ₂₉ · nH ₂ O, and the bottom spacing was 2.21 nm.

(3) Preparation of a composite agent of MPS-magadiate-PPMe and OIT.
A composite agent of MPS-magadiaite-PPMe and OIT (hereinafter, MPS-magadiaite-PPMe /) in the same manner as in Example 5 (1) except that PhS-magadiaite-PPMe90g was changed to MPS-magadiaite-PPMe90g. 95 g of OIT active ingredient concentration (10 wt%), which is described as an OIT composite agent, was obtained. The bottom spacing was 2.51 nm.

(4) OIT release test from MPS-magadiate-PPMe / OIT complex.
The OIT concentration in the octane was adjusted in the same manner as in Example 5 (2), except that the PhS-magadiate-PPMe / OIT complex 20 mg was changed to the MPS-magadiaite-PPMe / OIT complex 20 mg obtained above. analyzed.
The results are shown in Tables 5 and 6.

<Comparative Example 4> Synthesis of a sustained-release complex agent in which OIT is inserted between layers of magadiaite interlayer-modified with a DTMA group and evaluation of its sustained-release property.
(1) Preparation of Complex Agent of DTMA-Magadiaite and OIT Example 5 (1) except that 90 g of PhS-magadiaite-PPMe was changed to 90 g of DTMA-magadiaite obtained as in Example 1 (2). ), 99 g of a complex agent of DTMA-magadiaite and OIT (hereinafter referred to as DTMA-magadiaite / OIT complex agent, effective concentration of OIT: 10 wt%) was obtained. The bottom spacing was 3.99 nm.

(2) OIT release test from DTMA-magadiate / OIT complex.
The OIT concentration in the octane was analyzed in the same manner as in Example 5 (2), except that 20 mg of the PhS-magadiate-PPMe / OIT complex was changed to 20 mg of the DTMA-magadiaite / OIT complex obtained above. ..
The results are shown in Tables 5 and 6.

As shown in Table 5, when the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention is used as the host compound, and when the layered inorganic compound interlayer-organized with the conventional alkylammonium group is used as the host compound. It can be seen that all of the guest compounds, OIT, were intercalated between the layers.
In the OIT release test carried out using the composite agents of Examples 5 to 8 and Comparative Example 4 in Table 5, it was adsorbed into the initial host-guest composite agent based on the measured OIT concentration in the octane. Table 6 shows the ratio of the guest compound released from the host-guest complex to the amount of OIT calculated as the release rate and expressed over time.

In Table 6, in Examples 5 to 8, the release rate of the guest compound OIT gradually increased with the passage of time, indicating that the guest compound was slowly released into the octane as the test solvent. ing.
On the other hand, in the prior art of Comparative Example 4, almost all the guest compounds were released by 1 hour, and the sustained release could not be achieved.

Further, when Examples 5 to 8 are compared, it is shown that the sustained release rate of the guest compound can be changed by changing the interlayer modifying group of the host compound and appropriately combining a plurality of modifying groups.

By using the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention as the host compound in this way, the desired guest compound can be efficiently stored, and the release rate thereof can be adjusted for sustained release. Can be transformed into.

<Example 9> 1- (1-methylpropoxycarbonyl) -2- (2-hydroxyethyl) piperidine (hereinafter referred to as icaridin) is inserted between layers of magadiate modified with a phenylsilyl group and a hexylsilyl group. Synthesis of sustained-release complex agents and evaluation of their sustained-release properties.
(1) Preparation of a complex agent of PhS-HxS-magadiate-PPMe and icaridin.
A composite agent of PhS-HxS-magadiate-PPMe and icaridin (hereinafter PhS-HxS-magadiaite-PPMe) in the same manner as in Example 6 (3) except that 10 g of OIT was changed to 10 g of icaridin (manufactured by Combiblock). / 97 g of icaridin active ingredient concentration (10 wt%), which is described as an icaridin complex, was obtained. The bottom spacing was 2.28 nm.

(2) Icaridin release test from PhS-HxS-magadiate-PPMe / icaridin complex.
40 mg of the P-MACPS-PhS-magadiate / 2MT complex was changed to 20 mg of the PhS-HxS-magadiaite-PPMe / icaridine complex obtained above, and 2.8 g of octane was added to a 2.4% aqueous citric acid solution (2.4% citric acid aqueous solution). Prepared by dissolving 2.5 g of citric acid in 100 g of pure water) 2.4% in the same manner as in Example 1 (7) except that the mixture was changed to 20 g and the stirring temperature was changed from 25 ° C to 40 ° C. The concentration of icaridine in the aqueous citric acid solution was analyzed.
The results are shown in Tables 7 and 8.

<Comparative example 5>
Synthesis of a sustained-release complex agent in which icaridin is inserted between layers of magadiaite interlayer-modified with a DTMA group and evaluation of its sustained-release property.
(1) Preparation of a complex agent of DTMA-magadiaite and icaridin.
The active ingredient concentration of icaridin, which is hereinafter referred to as DTMA-magadiaite / icaridin complex, is the same as in Example 3 (1) except that 10 g of OIT is changed to 10 g of icaridin. %) 96 g was obtained. The bottom spacing was 3.55 nm.

(2) Icaridin release test from DTMA-magadiaite / icaridin complex.
In the same manner as in Example 7 (2), in a 2.4% aqueous citric acid solution, except that 20 mg of the DTMA-magadiaite / OIT complex was changed to 20 mg of the DTMA-magadiaite / icaridin complex obtained above. Icaridin concentration was analyzed.
The results are shown in Tables 7 and 8.

As shown in Table 7, when the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention is used as the host compound, and when the layered inorganic compound interlayer-organized with the conventional alkylammonium group is used as the host compound. It can be seen that all of the guest compounds, icaridine, were intercalated between the layers.

In the icaridin release test performed using the composite agents of Example 9 and Comparative Example 4 in Table 7, it was adsorbed into the initial host-guest composite agent based on the measured icaridin concentration in the 2.4% aqueous citric acid solution. Table 8 shows the ratio of the guest compound released from the host-guest complex to the amount of icaridin that had been calculated as the release rate and expressed over time.

As shown in Example 9 of Table 8, the composite agent using the layered inorganic compound as the host compound, which is interlayer-modified with the organic-inorganic composite group of the present invention via a covalent bond, contains icaridin, which is a guest compound, even in an acidic solution. It is released slowly while holding it effectively. On the other hand, when the conventional layered inorganic compound interlayer-organized with alkylammonium of Comparative Example 5 was used as the host compound, the guest compound icaridine contained considerably more citric acid after 1 hour as compared with Example 7. It was released into the aqueous solution and has not been sustained since then, but rather the concentration in the citric acid aqueous solution has decreased. This is because Comparative Example 5 is susceptible to the influence of the pH environment around the composite agent because the layers are modified with alkylammonium via ionic bonds, and desorption of alkylammonium from the layers and readsorption of icaridin occur. It is presumed that this is due to the occurrence, indicating that it is not suitable as a sustained-release material.

<Example 10> Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] between layers of magadiate interlayer-modified with a phenylsilyl group (hereinafter referred to as Irganox 1010). Synthesis of sustained-release complex agent and evaluation of its sustained-release complex.
(1) Preparation of a composite agent of PhS-magadiate-PPMe and Irganox 1010.
In the same manner as in Example 5 (1) except that 10 g of OIT was changed to 10 g of Irganox 1010 (manufactured by BASF Japan Ltd.), a composite agent of PhS-magadite-PPMe and Irganox 1010 (hereinafter, PhS-magadite-PPMe /) 97 g of the active ingredient concentration of the Irganox 1010 complex, which is referred to as the Irganox 1010 complex, was obtained (10 wt%). The bottom spacing was 1.93 nm.

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

<Comparative Example 6>
Synthesis of a sustained-release composite agent in which Irganox 1010 is complexed between layers of magadiaite interlayer-modified with a DTMA group, and evaluation of its sustained-release property.
(1) Preparation of a combination drug of DTMA-magadiate and Irganox 1010.
Irganox 1010 complex, which is hereinafter referred to as DTMA-magadiate / Irganox 1010 composite, in the same manner as in Example 3 (1), except that OIT 10 g was changed to Irganox 1010 10 g. Active ingredient concentration: 10 wt%) 95 g was obtained. The bottom spacing was 2.86 nm.

(2) Irganox 1010 release test from DTMA-magadiate / Irganox 1010 complex.
Irganox 1010 concentration in octane in the same manner as in Example 10 (2), except that 20 mg of the PhS-magadiate-PPMe / Irganox 1010 complex was changed to 20 mg of the DTMA-magadiaite / Irganox 1010 complex obtained above. Was analyzed. The results are shown in Tables 9 and 10.

As shown in Table 9, when the layered inorganic compound intercalated with the organic-inorganic composite group of the present invention of Example 10 is used as the host compound, the bottom surface spacing increases before and after adsorption of the guest compound Irganox 1010. It can be seen that the Irganox 1010 was intercalated between the layers.
On the other hand, when the conventional layered inorganic compound intercalated with alkylammonium of Comparative Example 6 was used as the host compound, the bottom surface spacing did not change before and after the adsorption of the guest compound Irganox 1010, and the intercalation between the layers did not change. It cannot be determined that the Irganox 1010 has been intercalated, and it is possible that it has not been intercalated.

In the Irganox 1010 release test performed with the composites of Example 10 and Comparative Example 6 in Table 9, the Irganox 1010 adsorbed into the initial host-guest composite was based on the measured Irganox 1010 concentration in the octane. Table 10 shows the ratio of the guest compound released from the host-guest complex to the amount of the above calculated as the release rate and expressed over time.

In Table 10, in Example 10, the release rate of Irganox 1010 gradually increased with the passage of time, indicating that the guest compound was slowly released into the octane as the test solvent.
On the other hand, in the prior art of Comparative Example 6, almost all the guest compounds were released by 1 hour, and the sustained release could not be achieved.

By using the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention as a host compound in this way, even a very large molecule such as Irganox 1010 can be efficiently stored between the layers. In addition, the release rate can be adjusted for sustained release.

<Example 11> An antifungal test of a resin kneaded with a PhS-HxS-magadiate-PPMe / OIT composite agent (sustained release antifungal agent).
(1) Preparation of resin test piece.
40 g of polyethylene resin (UBE polyethylene J3519 manufactured by Ube Maruzen Polyethylene Co., Ltd., hereinafter referred to as PP resin) was dissolved in a heating mill at 140 ° C. with stirring. 0.4 g of the PhS-HxS-magadite-PPMe / OIT composite agent synthesized in Example 6 was added thereto and stirred for 15 minutes, then the obtained mixed solution was placed in a mold and pressed at 160 ° C. for 5 minutes. Then, it was allowed to cool and molded into a plate having a thickness of 2 mm. A test piece having a size of 2.5 cm × 2.5 cm × 2 mm was cut out from here.
(2) Heat deterioration treatment of the resin test piece.
The test piece prepared in (1) above was allowed to stand in a ventilation dryer at 80 ° C. for 96 hours and then allowed to stand at 25 ° C. for 17 days.
(3) Deterioration treatment of the resin test piece by immersion in warm water.
A metal weight is attached to the test piece prepared in (1) above, and the test piece is placed in a 1 L plastic bottle containing 1 L of pure water, the test piece is completely submerged in water, the lid of the plastic bottle is closed, and the temperature is 60 ° C. for 120 hours. It was heated. On the way, the water was replaced with pure water 24 hours and 96 hours after the start of hot water immersion.
(4) Antifungal test (hello test).
The molds used for the evaluation of antifungal properties were black mold (Cladosporium clados polioides), blue mold (Penicillium funiculosum) and black aspergillium (Aspergillus niger), and spores were added to the inorganic salt solution having the composition shown in Table 11, respectively. number was adjusted to spore mixed suspension so that 10 ⁵ cells / mL before and after. 150 μL of the spore mixed suspension was uniformly inoculated on a potato dextrose agar medium having a diameter of 9 cm, and the test pieces prepared in (1) to (3) above were placed near the center of the suspension and brought into close contact with each other. This was cultured at 25 ° C. and a humidity of 90% or more for 3 days, and the presence or absence of the formation of a growth inhibitory zone was confirmed to evaluate the antifungal property. The evaluation results are shown in Table 12. The symbols in the table mean that 〇: with the formation of a growth inhibitory zone (with antifungal effect), ×: without the formation of a growth inhibitory zone (without antifungal effect).

<Comparative Example 7> An antifungal test of a resin kneaded with OIT (an antifungal organic compound which is a guest compound).
A test piece was prepared in the same manner as in Example 11 except that 0.4 g of the PhS-HxS-magadiaite-PPMe / OIT composite agent was changed to 0.04 g of OIT, and accelerated deterioration treatment and hot water immersion deterioration treatment were performed. An antifungal test was conducted. The results are shown in Table 12.

<Comparative Example 8> Antifungal test of a resin kneaded with PhS-HxS-magadiate-PPMe (interlayer modified layered inorganic compound which is a host compound).
A test piece was prepared in the same manner as in Example 11 except that 0.4 g of the PhS-HxS-magadiaite-PPMe / OIT composite agent was changed to 0.36 g of PhS-HxS-magadiaite-PPMe, and accelerated deterioration treatment and warm water were prepared. Immersion deterioration treatment was performed and a mold resistance test was carried out. The results are shown in Table 12.

As shown in Table 12, in the test piece in which the OIT of Comparative Example 7 was kneaded alone into the PP resin, a mold blocking zone was observed at the initial stage and showed a mold-proofing effect, but a deterioration test by heating and immersion in warm water was performed. After that, no blocking zone was observed in any of them, and no antifungal effect was shown. On the other hand, in the test piece in which the sustained-release antifungal agent of the present invention of Example 11 was kneaded into the PP resin, a blocking band was observed not only at the initial stage but also after the deterioration treatment by heating and immersion in warm water, and the antifungal zone was observed. The effect was confirmed. This is because when the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention is used as the host compound, the antifungal organic compound can be imparted with sustained release property, as well as heat resistance and temperature resistance. It is shown that it can be a practical sustained-release fungicide.

As described above, by using the layered inorganic compound interlayer-modified with the organic-inorganic composite group of the present invention as the host compound, it is possible to appropriately design the interlayer environment corresponding to guest compounds having various structures and molecular weights. Therefore, a sustained-release composite agent having a very wide range of application and capable of intercalating a desired guest compound between layers and adjusting the sustained-release rate according to the purpose can be obtained. Furthermore, since the host compound is a layered inorganic compound that has been interlayer-modified with an organic-inorganic composite group via a covalent bond, it is possible to impart environmental resistance such as heat resistance, water resistance, and acid resistance to the guest compound. According to the present invention, the function derived from the guest compound can be effectively expressed according to the conditions of use.

Claims (6)

Between the layers of the layered inorganic compound, 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 inserted between the layers of the interlayer-modified layered inorganic compound, Sustained-release compounding agent containing.

(In the formula (1), M ¹ and M ² independently represent Si, Al, Ti or Zr, respectively, and R ^a and R ^b are independent linear or branched chains having 1 to 20 carbon atoms, respectively. Saturated or unsaturated alkylene group, saturated or unsaturated cycloalkylene group which may have a branched chain having 3 to 20 carbon atoms, arylene group having 6 to 20 carbon atoms or aralkylene group having 7 to 20 carbon atoms, R ^c represents an organic group consisting of 1 to 40 carbon atoms and may contain a heteroatom, a linear structure, a branched structure, a cyclic structure, an unsaturated bond and an aromatic structure, and R is 1 to 20 carbon atoms. Saturated or unsaturated alkyl group of linear or branched chain, saturated or unsaturated cycloalkyl group which may have branched chain having 3 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms or 7 to 20 carbon atoms. Indicates an aralkyl group, which is a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacrylox group, a hydroxyl group, an amino group, a linear or branched mono- or dialkylamino having 1 to 20 carbon atoms, respectively. Group, mono or diarylamino group with 6 to 20 carbon atoms, mono or dialalkylamino group with 7 to 20 carbon atoms, primary, secondary, tertiary or quaternary ammonium group, thiol group, isocyanurate It may be substituted with a group, a ureido group, an isocyanato group, a carbonyl group, an aldehyde group, a carboxyl group, a carboxylic acid ester group, a phosphoric acid group, a phosphoric acid ester group, a sulfonic acid group, a sulfonic acid ester group or a halogen atom. .Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having a linear or branched chain having 1 to 8 carbon atoms, a saturated or unsaturated cycloalkyloxy group having a branched chain having 3 to 8 carbon atoms, or trimethylsilyl. Oxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy group which may have branched chains having 1 to 8 carbon atoms, halogen atoms, hydroxyl groups, amino groups, linear or branched chains having 1 to 6 carbon atoms. Indicates an oxygen atom derived from a saturated or unsaturated alkylamino group, a linear or branched linear or branched dialkylamino group having 1 to 6 carbon atoms, or a layered inorganic compound, in which M ¹ and M ² are Si and Ti. Or, in any case of Zr, the corresponding x is 2 and n is an integer of 0 to 2, and when M ¹ and M ² are Al, the corresponding x is 1 and. When n is 0 or 1, and n is 2, even if R is the same. It may be different, where p, q and r are integers of 0 or 1 and at least one of them is 1. )

(In the formula (2), R is a saturated or unsaturated alkyl group having a linear or branched chain having 1 to 20 carbon atoms, a saturated or unsaturated cycloalkyl group having a branched chain having 3 to 8 carbon atoms, and the like. It represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and has a vinyl group, an epoxy group, an oxetanyl group, an ether group, an acryloxy group, a methacryloxy group, a hydroxyl group, an amino group and 1 to 20 carbon atoms, respectively. Saturated or unsaturated mono or dialkylamino groups of linear or branched chains, mono or diarylamino groups with 6 to 20 carbon atoms, mono or dialalkylamino groups with 7 to 20 carbon atoms, primary and secondary, Tertiary or quaternary ammonium group, thiol group, isocyanurate group, ureido group, isocyanato group, carbonyl group, aldehyde group, carboxyl group, carboxylic acid ester group, phosphoric acid group, phosphoric acid ester group, sulfonic acid group , A sulfonic acid ester group or a halogen atom. M represents Si, Al, Ti or Zr, Z is a hydrogen atom, a saturated or unsaturated alkyloxy group having 1 to 8 carbon atoms, and a carbon number of carbon atoms. Saturated or unsaturated cycloalkyloxy group which may have 3 to 8 branched chains, trimethylsilyloxy group, dimethylsilyloxy group, saturated or unsaturated heterocycloalkyloxy which may have branched chains having 1 to 8 carbon atoms. Group, halogen atom, hydroxyl group, amino group, saturated or unsaturated alkylamino group of linear or branched chain with 1 to 6 carbon atoms, saturated or unsaturated dialkylamino of linear or branched chain with 1 to 6 carbon atoms Indicates an oxygen atom derived from a group or layered inorganic compound, where M is any of Si, Ti or Zr, the corresponding x is 3 and n is an integer 1-3 and M is Al. In some cases, the corresponding x is 2, and n is 1 or 2, and when n is 2 or 3, R may be the same or different.) The sustained-release composite agent according to claim 1, wherein in the organic-inorganic composite group, both M ¹ and M ² in the formula (1) are Si, or M in the formula (2) is Si. .. In the organic-inorganic composite group represented by the formula (1), at least one selected from the group consisting of a carboxylic acid ester structure, a urethane structure, a urea structure, an amine structure, an ether structure, a thioether structure, a disulfide structure and a hydroxyl group is added. The sustained-release composite agent according to claim 1 or 2, which comprises. The compound inserted between the layers of the interlayer-modified layered inorganic compound is composed of a saturated or unsaturated aliphatic group, an aromatic group, a heterocyclic structural group, a hydrogen bond forming group, a coordination bond forming group and an ionic bond forming group. The sustained-release composite agent according to any one of claims 1 to 3, which is a compound containing at least one selected from the group. The sustained-release composite agent according to any one of claims 1 to 4, wherein the layered inorganic compound contains one selected from the group consisting of layered silicates, layered clay minerals and layered metal oxides. The sustained-release composite according to any one of claims 1 to 5, wherein the interlayer-modified layered inorganic compound and a compound inserted between layers of the interlayer-modified layered inorganic compound are mixed. Method of manufacturing the agent.