JP2006117477A - Layered structured body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered structured body finely dispersible without applying high shearing and excellent in reinforcing effects as a filler for polymer materials. <P>SOLUTION: The layered structured body is composed of a surfactant layer (A) and a platy compositional layer (B) containing a residual group of a coupling agent (D). In its X-ray diffraction pattern, there are two peaks satisfying formula (1): dn=(1/n)d1 [wherein dn is the lattice plane spacing (nm) at the peak number n; d1 is the lattice plane spacing (nm) at the peak number 1; among peaks satisfying formula (1), the peak number of the peak with the smallest diffraction angle (2θ) is designated as n=1, and the peak number increases in order as n=2, 3, etc., according to an increase of the diffraction angle (2θ)] and the lattice plane spacing of the smallest diffraction angle (2θ) d1 is 1-100 nm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a layered structure. More specifically, the present invention relates to a layered structure utilizing self-assembly of a surfactant and a sol-gel reaction of metal alkoxide or metal halide.

In the past, inorganic fillers have been widely added and mixed in order to improve the mechanical properties of organic polymer materials. Examples of the inorganic filler include metal oxides such as silica, and layered structures such as talc and mica. However, when a layered structure is added and mixed, if the dispersibility is poor, the smoothness of the molding surface may be lowered or the toughness may be lowered.
For this reason, it has been considered to be important to improve the aspect ratio or fine dispersion of the filler, that is, to make the layered structure thinner. As a method for finely dispersing the filler, for example, there is a method of dispersing a layered compound in a thermosetting polymer such as nylon, vinyl polymer, epoxy, or rubber (Patent Document 1, Patent Document 2, Non-Patent Document). Reference 1).
These are a method of organicizing a layered compound with an organic onium ion to initiate monomer polymerization between viscosity layers, a method of incorporating clay into a growing species, or a method of kneading clay with a polymer and putting the polymer between the layers. All of these are methods in which an organic onium ion is inserted between layers of a viscous mineral to increase the interlayer distance and to apply a shearing force to the organized clay to separate and disperse it (Patent Document 1).
JP-A-62-74957 JP-A-1-198645 E. P. Giannelis, Chem. Mater. 5, 1694-1696 (1993)

  However, when these layered structures are dispersed in a polymer material, the dispersibility and the reinforcing effect are not always sufficient. An object of the present invention is to provide a layered structure having excellent dispersibility in a polymer material and excellent reinforcing effect on the polymer material.

As a result of intensive studies to solve such problems, the present inventors have reached the present invention.
That is, the present invention comprises a plate-like composition layer (B) containing residues of a surfactant layer (A) and a coupling agent (D), and the following relational expression (1) is expressed in the X-ray diffraction measurement pattern. A layered structure characterized in that there are two or more peaks to be satisfied, and the lattice plane distance d1 of the peak having the smallest diffraction angle (2θ) is 1 to 100 nm; an interface containing a coupling agent (D) The precursor (C) of the plate-like composition layer (B) is added to the layered micelle solution of the activator (a), and (C) and (D) are hydrolyzed and polycondensed on the micelle surface. (B) containing a residue, and in the pattern of X-ray diffraction measurement, there are two or more peaks satisfying the following relational expression (2), and the grating having the smallest diffraction angle (2θ) Surfactant layer having a surface spacing d1 of 1 to 100 nm Method of producing a layer structure consisting of A) a plate-like composition layer (B); a.
dn = (1 / n) d1 (1)
[Wherein, dn represents the lattice spacing (nm) at the peak number n, and d1 represents the lattice spacing (nm) when n is 1; provided that the diffraction angle (2θ) is the largest among the peaks satisfying the formula (1). The peak number of a peak with a small value is n = 1, and n = 2, 3,... In order as the diffraction angle (2θ) increases. ]

  When the layered structure of the present invention is used as a filler for a polymer material, it can be mixed and dispersed in the polymer material, and the layer can be easily separated and dispersed uniformly by applying a shearing force. There is an effect of imparting an effect.

The layered structure of the present invention is produced by utilizing a self-organization (micelle formation) of a surfactant and a sol-gel reaction of a metal alkoxide or metal halide.
In the solution of the surfactant (a) containing the coupling agent (D), the layered micelle is formed, and then the precursor (C) of the plate-like composition layer (B) is added to the hydrophilic group of the layered micelle. Oriented partly, hydrolyzed (C) and (D), partially polycondensed to form a hydrous sol solution. Furthermore, dehydration polycondensation is performed to form a gel (plate-like composition layer (B)), and a layered structure composed of (A) and (B) can be obtained.
When (C) is subjected to hydrolysis and polycondensation reaction, all or part of (D) contained in (a) undergoes condensation reaction with (C) to form (B) containing the residue of (D) Is done.

  The surfactant (a) used in the present invention is not particularly limited as long as it forms a layered micelle in water. Anionic surfactant (a1), cationic surfactant (a2), nonionic surfactant (A3) and amphoteric surfactant (a4) can be used. However, a surfactant having a long molecular chain is preferable for expanding the interlayer, and an alkylene oxide addition type nonionic surfactant is more preferable.

  As (a1), carboxylic acid and its salt (a1-1), sulfate ester and its salt (a1-2), carboxymethylated product and its salt (a1-3), sulfonic acid and its salt (a1-4) Moreover, phosphate ester and its salt (a1-5) etc. can be used.

As (a1-1), a saturated or unsaturated fatty acid having 8 to 22 carbon atoms, a higher fatty acid derived from a natural product, an aromatic carboxylic acid having 8 to 22 carbon atoms, and a salt thereof can be used.
Examples of saturated fatty acids include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid.
Examples of unsaturated fatty acids include oleic acid, linoleic acid, and ricinoleic acid.

Examples of higher fatty acids derived from natural products include fatty acids obtained by saponifying palm oil, palm kernel oil, rice bran oil, peanut oil, whale oil, beef tallow, and the like.
Examples of the aromatic carboxylic acid include 4-methylsalicylic acid.

Moreover, as these salts, the salt which combines the anion which consists of said carboxylic acid, and the following cations can be used.
As the cation forming the salt, alkali metal ions, ammonium ions and the like can be used.

Examples of alkali metal ions include lithium ions, sodium ions, and potassium ions.
Examples of ammonium ions include NH4 ⁺ , ammonium ions composed of alkanolamines, ammonium ions composed of primary amines, ammonium ions composed of secondary amines, ammonium ions composed of tertiary amines, and quaternary ammonium ions. Can be used.
As (a1-1), one or a mixture of two or more of these carboxylic acids and salts thereof can be used.

  As (a1-2), higher alcohol sulfates, higher alkyl ether sulfates, sulfated oils, sulfated fatty acid esters, sulfated olefins, and salts thereof can be used. As these salts, a salt formed by combining an anion comprising a sulfate ester and a cation exemplified in (a1-1) can be used.

  As the higher alcohol sulfate, a sulfuric monoester of an aliphatic alcohol (8 to 22 carbon atoms) can be used. For example, octyl alcohol sulfate monoester, decyl alcohol sulfate monoester, lauryl alcohol sulfate monoester, stearyl alcohol sulfate monoester. Examples include esters.

As higher alkyl ether sulfates, sulfuric acid monoesters of adducts of alcohol (8 to 22 carbon atoms) alkylene oxide (2 to 4 carbon atoms and 2 to 20 added moles) can be used.
Examples of the alkylene oxide (hereinafter abbreviated as AO) include alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, and tetrahydro. Examples include francs.
Of these, EO and PO are preferable, and EO and EO and PO are used in combination (random and / or block).

  Examples of the higher alkyl ether sulfate include lauryl alcohol EO 2 mol adduct sulfate monoester, octyl alcohol EO 3 mol adduct sulfate monoester, and oleyl alcohol EO 10 mol adduct.

  As the sulfated oil, sulfated oils of natural fats and oils having a carboxylic acid residue having 8 to 22 carbon atoms can be used. For example, natural fats and oils such as castor oil, peanut oil, olive oil, rapeseed oil, beef tallow or sheep fat Of the sulfated oil.

  As the sulfated fatty acid ester, an unsaturated fatty acid ester (carbon number 8 to 30) sulfate can be used, for example, butyl oleate sulfate, butyl ricinoleate sulfate and butyl linoleate sulfate. Can be mentioned.

  Examples of sulfated olefins include olefin (carbon number 8 to 22) sulfates and the like, and examples thereof include sulfates such as octene, dodecene, and octadecene (for example, tee pole, manufactured by Shell).

As (a1-3), a carboxymethylated product of an aliphatic alcohol, a carboxymethylated product of an aliphatic alcohol AO adduct, and a salt thereof can be used.
As these salts, a salt formed by combining an anion composed of a carboxymethyl compound and a cation exemplified in (a1-1) can be used.

  As a carboxymethylated product of an aliphatic alcohol, a carboxymethylated product of an aliphatic alcohol (8 to 22 carbon atoms) can be used. For example, octyl alcohol carboxymethylated product, decyl alcohol carboxymethylated product, lauryl alcohol carboxymethylated product, etc. Can be mentioned.

  As a carboxymethylated product of an aliphatic alcohol AO adduct, a carboxymethylated product of an AO (addition mole number 2 to 20) adduct of an aliphatic alcohol (carbon number 8 to 22) can be used, for example, octyl alcohol EO 3 mol. Examples thereof include carboxymethylated products of adducts, carboxymethylated products of lauryl alcohol EO 4 mol adducts, and the like.

As (a1-4), alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, sulfo fatty acid diester, α-olefin sulfonic acid, Igepon T-type sulfonic acid and salts thereof can be used.
As these salts, a salt formed by combining an anion composed of sulfonic acid and a cation exemplified in (a1-1) can be used.

  As the alkylbenzenesulfonic acid, alkylbenzenesulfonic acid having an alkyl group having 8 to 22 carbon atoms can be used, and examples thereof include octylbenzenesulfonic acid, dodecylbenzenesulfonic acid and octadecylbenzenesulfonic acid.

  As the alkyl naphthalene sulfonic acid, alkyl naphthalene sulfonic acid having an alkyl group having 8 to 22 carbon atoms can be used, and examples thereof include octyl naphthalene sulfonic acid, dodecyl naphthalene sulfonic acid, and octadecyl naphthalene sulfonic acid.

  As the sulfo fatty acid diester, a sulfo fatty acid dialkyl ester having an alkyl group having 8 to 22 carbon atoms can be used, and examples thereof include sulfosuccinic acid di-2-ethylhexyl ester and sulfosuccinic acid dioctadecyl ester.

  As the α-olefin sulfonic acid, a sulfonic acid obtained by reacting sulfuric acid anhydride with an α-olefin having 8 to 22 carbon atoms can be used. P. 189 (manufactured by DuPont) and Worolate (manufactured by Bayer).

  The Igepon T-type sulfonic acid is a sulfonic acid obtained by reacting a fatty acid having 8 to 22 carbon atoms with N-methyltaurine. For example, Ceramide (manufactured by Carlstadt Chem. Co.), Igepon T (IG) And Alipon CT (manufactured by IG).

As (a1-5), higher alcohol phosphates, higher alcohol AO adduct phosphates, salts thereof and the like can be used.
As these salts, a salt formed by combining an anion composed of a phosphate ester and the cation exemplified in (a1-1) can be used.

  As the higher alcohol phosphate ester, a phosphate mono- or diester of alcohol (8 to 22 carbon atoms) can be used. For example, lauryl alcohol phosphate monoester, lauryl alcohol phosphate diester, oleyl alcohol phosphate monoester and oleyl Examples thereof include alcohol phosphoric acid diesters.

  As the higher alcohol AO adduct phosphate ester, phosphate mono- or di-ester of alcohol (8 to 22 carbon atoms) AO (addition mole number 2 to 20) adduct can be used, for example, 10 mol of lauryl alcohol EO Examples include adduct phosphate monoester, lauryl alcohol EO 10 mol adduct phosphate diester, and oleyl alcohol EO 5 mol adduct phosphate monoester.

As the cationic surfactant (a2), a quaternary ammonium salt type cationic surfactant (a2-1), an amine salt type cationic surfactant (a2-2) and the like can be used.
As (a2-1), a tetraalkylammonium cation, an ammonium cation having a benzyl group and an alkyl group, a pyridinium cation, or a quaternary ammonium salt comprising an ammonium cation having a polyoxyalkylene group and an alkyl group can be used. . As anions constituting these quaternary ammonium salts, hydroxide ions, halogen ions (for example, fluorine ions, chlorine ions, bromine ions and iodine ions), nitrate ions, nitrite ions, methosulphate ions, and carbon number 1 ~ 8 carboxyl anions (for example, anions derived from formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, lactic acid, malic acid, gluconic acid, etc.) and the like can be used.

  As the tetraalkylammonium cation, an ammonium cation having an alkyl group (8 to 22 carbon atoms) or the like can be used. Examples of ammonium salts comprising these include lauryltrimethylammonium chloride, didecyldimethylammonium chloride, and cetyltrimethylammonium chloride. , Dioctyl dimethyl ammonium bromide, stearyl trimethyl ammonium bromide, cetyl trimethyl ammonium methosulfate, stearamide ethyl diethyl methyl ammonium methosulfate, lauryl amidoethyl diethyl methyl ammonium methosulfate and the like.

  As an ammonium cation having a benzyl group and an alkyl group, an ammonium cation having a benzyl group and an alkyl group having 8 to 22 carbon atoms can be used. As an ammonium salt comprising these, for example, lauryldimethylbenzylammonium chloride ( Benzalkonium chloride) and octyldimethylbenzylammonium methosulfate.

  As the pyridinium cation, a pyridinium cation having an alkyl group (8 to 22 carbon atoms) can be used, and examples of the ammonium salt thereof include cetylpyridinium chloride, oleylpyridinium chloride, and laurylpyridinium methosulfate.

  As an ammonium cation having a polyoxyalkylene group and an alkyl group, an ammonium cation having a polyoxyalkylene group (alkylene group having 2 to 4 carbon atoms) (molecular weight: 120 to 1200) and an alkyl group having 1 to 22 carbon atoms. Examples of ammonium salts composed of these include polyoxyethylene (molecular weight: 120 to 1,200) trimethylammonium chloride, polyoxyethylene (molecular weight: 120 to 1,200) lauryldimethylammonium chloride and polyoxy Examples include ethylene (molecular weight: 120 to 1,200) lauryldimethylammonium methosulfate.

  (A2-1) is a tertiary amine and a quaternizing agent (an alkylating agent such as methyl chloride, methyl bromide, ethyl chloride, benzyl chloride, dimethyl sulfate, diazomethane; 2 to 4 carbon atoms such as EO and PO). AO; a dialkyl carbonate such as dimethyl carbonate).

  As (a2-2), primary amine salts, secondary amine salts, tertiary amine salts and the like can be used. As anions constituting these amine salts, hydroxide ions, halogen ions (for example, fluorine ions, chlorine ions, bromine ions, iodine ions), nitrate ions, nitrite ions, methosulphate ions and those having 1 to 8 carbon atoms. Carboxylic anions (for example, anions derived from formic acid, acetic acid, propionic acid, 2-ethylhexanoic acid, lactic acid, malic acid, gluconic acid, etc.) can be used.

  As the primary amine salt, a primary higher amine salt having an alkyl group (8 to 22 carbon atoms) can be used. For example, laurylamine chloride, stearylamine bromide, cetylamine methosulfate, cured beef tallow amine chloride and Examples include rosinamine acetate.

  As the secondary amine salt, a secondary higher amine salt having an alkyl group (8 to 22 carbon atoms) can be used. For example, laurylmethylamine chloride, stearylethylamine bromide, dilaurylamine methosulfate, laurylpropylamine Examples include acetate, dioctylamine chloride, and octadecylethylamine hydroxide.

  As the tertiary amine salt, a tertiary amine salt having an alkyl group (8 to 22 carbon atoms) can be used, and examples thereof include lauryl diethylamine chloride, laurylethylmethylamine bromide, octadecyl diethylamine methosulfate, and the like.

  As nonionic surfactant (a3), AO addition type nonionic surfactant (a3-1), polyhydric alcohol type nonionic surfactant (a3-2), etc. can be used.

As (a3-1), higher alcohol AO adduct, carboxylic acid AO adduct, (a3-2) as polyhydric alcohol AO adduct, polyhydric alcohol carboxylic ester AO adduct, polyhydric alcohol alkyl ether AO adducts and the like can be used.
As the higher alcohol AO adduct, an AO adduct of saturated or unsaturated aliphatic alcohol (carbon number of 8 to 22, including primary or secondary alcohol) can be used. For example, octyl alcohol EO adduct (addition mole number 10-50 mol), lauryl alcohol EO adduct (addition mole number 10-50 mol), stearyl alcohol EO adduct (addition mole number 10-50 mol), oleyl alcohol EO Examples include adducts (addition mole number 10 to 50 mol), lauryl alcohol EO (addition mole number 10 to 50 mol) PO (addition mole number 10 to 50 mol) block adduct, and the like. The number of AO added is preferably 3 or more per active hydrogen, more preferably 5 or more, particularly preferably 10 or more, and preferably 100 or less, more preferably 70 or less, and particularly preferably 50 or less. . In AO, the amount of EO is preferably 50 to 100% by weight based on the total weight of AO.

  As the carboxylic acid AO adduct, an AO adduct of a saturated or unsaturated carboxylic acid (having 8 to 22 carbon atoms) can be used. For example, stearic acid EO adduct (addition mole number 10 to 50 mol), lauric acid EO adduct (addition mole number 10 to 50 mol), oleic acid EO adduct (addition mole number 10 to 50 mol), polyethylene glycol ( Examples thereof include lauric acid diesters having a polymerization degree of 10 to 50), oleic acid diesters of polyethylene glycol (polymerization degree of 10 to 50), and stearic acid diesters of polyethylene glycol (polymerization degree of 10 to 50).

As the polyhydric alcohol AO adduct, polyhydric alcohol (2 to 8 valence, C2 to C22) AO adduct (addition mole number 10 to 50) and the like can be used. Polyhydric alcohols include ethylene glycol, propylene glycol, glycerin, diglycerin, tetraglycerin, trimethylolpropane, ditrimethylolpropane, neopentyl alcohol, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, sucrose And glucose etc. can be used.
The preferred range of AO is the same as above. The number of added AOs is preferably 20 or more per active hydrogen, more preferably 25 or more, particularly preferably 30 or more, and preferably 320 or less, more preferably 300 or less, particularly preferably 280 or less. . Of AO, the amount of EO is preferably 10 to 70% by weight based on the total weight of AO.

As the polyhydric alcohol AO adduct, for example, an AO block adduct of ethylene glycol or propylene glycol is used.
As a propylene glycol EO block adduct, a compound represented by EOx-POy-EOx (x is an integer of usually 5 to 110, preferably 10 to 100, y is an integer of 5 to 100, preferably 10 For example, EO5-PO70-EO5, EO106-PO70-EO106, EO100-PO39-EO100, EO20-PO70-EO20, EO17-PO85-EO17, EO20-PO30-EO20, and the like. EO26-PO39-EO26, EO20-PO30-EO20, EO80-PO30-EO80, etc. are mentioned.

  As an ethylene glycol PO block adduct, a compound represented by POx-EOy-POx (x is usually an integer of 5 to 110, preferably 10 to 100, y is an integer of 5 to 100, preferably 10 For example, PO19-EO33-PO19, PO30-EO50-PO30, PO25-EO80-PO25, and the like.

  Examples of the polyhydric alcohol carboxylate AO adduct include sorbitan monolaurate EO adduct (addition mole number 10 to 50 mol), sorbitan trioleate ester EO adduct (addition mole number 10 to 50 mol), glycerin, and the like. Monooleate EO adduct (addition mole number 10-50 mol), trimethylolpropane monostearate EO (addition mole number 10-50 mol) PO (addition mole number 10-50 mol) random adduct, sorbitan monostea Rate EO adduct (addition mol number 10-50 mol), sorbitan distearate EO adduct (addition mol number 10-50 mol) and sorbitan dilaurate EO (addition mol number 10-50 mol) PO (addition mol number 10 50 mol) random adducts and the like

  Examples of the polyhydric alcohol alkyl ether AO adduct include pentaerythritol monobutyl ether EO adduct (addition mole number 10 to 50 mol), pentaerythritol monolauryl ether EO adduct (addition mole number 10 to 50 mol), and sorbitan monomethyl. Ether EO adduct (addition mol number 10-50 mol), sorbitan monostearyl ether EO adduct (addition mol number 10-50 mol), methyl glycoside EO (addition mol number 10-50 mol) PO (addition mol number 10 50 mol) random adduct, lauryl glycoside EO adduct (10 to 50 mol added), stearyl glycoside EO (10 to 50 mol added), PO (10 to 50 mol added) random adduct, and the like. It is done.

As the amphoteric surfactant (a4), amino acid type amphoteric surfactant (a4-1), betaine type amphoteric surfactant (a4-2), imidazoline type amphoteric surfactant (a4-3) and the like can be used.
(A4-1) is an amphoteric surfactant having an amino group and a carboxyl group in the molecule, an alkylaminopropionic acid type amphoteric surfactant (sodium stearylaminopropionate, potassium laurylaminopropionate, etc.) and Examples thereof include alkylaminoacetic acid type amphoteric surfactants (sodium laurylaminoacetate, ammonium stearylaminoacetate and the like).

  (A4-2) is an amphoteric surfactant having a quaternary ammonium salt type cation moiety and a carboxylic acid type anion moiety in the molecule, and alkyldimethylbetaine (stearyldimethylaminoacetic acid betaine, lauryl). Dimethylaminoacetic acid betaine), amide betaine (coconut oil fatty acid amide propyl betaine etc.), alkyl dihydroxyalkyl betaine (lauryl dihydroxyethyl betaine etc.), etc. are mentioned.

  Examples of (a4-3) include 2-undecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine and 2-heptadecenyl-hydroxyethylimidazoline.

Among these (a), (a3) is preferable, (a3-2b) is more preferable, and an AO block adduct of ethylene glycol or propylene glycol is particularly preferable.
(A) can use the commercial item as it is, and what was manufactured by the publicly known method may be used for it. Moreover, you may use 2 or more types of mixtures.

  The amount of (a) used (parts by weight) is preferably 5 or more, more preferably 10 or more, particularly preferably 20 or more, most preferably 30 or more, and preferably 900 or less, relative to 100 parts by weight of the solvent. More preferably, it is 500 or less, particularly preferably 200 or less, and most preferably 100 or less. If it is in this range, a lamellar structure is formed, and the viscosity becomes an appropriate viscosity that does not hinder the progress of the sol-gel reaction by the alkoxide required for forming the plate-like composition layer.

The plate-like composition layer (B) constituting the layered structure of the present invention comprises a silicate or silica layer (B1), an inorganic oxide layer (B2), an organic / inorganic composite layer (B3), and combinations thereof. .
These (B1), (B2), or (B3) can be obtained by hydrolyzing and polycondensing the precursor (C).
Among these, as the precursor of (B1) or (B2), at least one selected from the group consisting of inorganic alkoxide (C1) and inorganic halide (C2) can be used.
As (C1) and (C2), a compound represented by the general formula (2) can be used.
In formula (2), M represents an n-valent inorganic atom, n is an integer of 1 to 7, preferably an integer of 2 to 5, such as the availability and ease of handling of (C1) From the viewpoint, an integer of 3 to 5 is more preferable, an integer of 3 to 4 is particularly preferable, and 4 is most preferable. The n ROs may be the same or different. M is used without limitation as long as it is a metal atom that can stably exist as an inorganic alkoxide and an inorganic halide. Specifically, Group II (zinc), Group III (indium, aluminum), Group IV (tin, silicon, Zirconium, titanium), group V (vanadium, antimony), group VI (tungsten), group VII (manganese), inorganic group atoms such as group VIII (iron), and combinations thereof. Among these, from the viewpoint of availability of (C1) and (C2), a group IV atom, particularly silicon and titanium are preferable, and silicon is more preferable.

  Moreover, in Formula (2), R represents an alkyl group and a C1-C30 alkyl group etc. are used. Specific examples of the alkyl having 1 to 30 carbon atoms include methyl, ethyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, 2-ethylhexyl, decyl, hexadecyl, eicosyl and tricosyl. Can be mentioned. Of these, propyl, n-butyl and t-butyl are preferred from the viewpoints of availability and ease of handling of (C1) and (C2), more preferred is methyl, and particularly preferred is ethyl.

  The compound represented by the general formula (2) includes tetraalkoxysilane, tetraalkoxytitanium, trialkoxyaluminum and the like. Examples of the tetraalkoxysilane include dimethoxydiethoxysilane, methoxytriethoxysilane, tetramethoxysilane, tetraethoxysilane (hereinafter abbreviated as TEOS), tetrapropoxysilane, tetrabutoxysilane, and tetraisopropoxysilane. Examples of tetraalkoxytitanium include dimethoxydiethoxytitanium, tetraethoxytitanium, and tetraisopropoxytitanium. Examples of trialkoxyaluminum include triethoxyaluminum and triisopropoxyaluminum. Of these, tetraalkoxysilane and trialkoxyaluminum are preferable from the viewpoint of availability and the like, more preferably tetraalkoxysilane, and particularly preferably tetramethoxysilane, TEOS, tetrapropoxysilane, and tetrabutoxysilane.

As the inorganic halide (C2), a compound represented by the general formula (3) can be used.
In the formula (3), M and n are the same as those in the general formula (2). The n Xs may be the same or different.
Examples of the compound represented by the general formula (3) include silane tetrahalide, titanium tetrahalide, and aluminum trihalide. Examples of the silane tetrahalide include silane tetrachloride, silane tetrabromide, silane tetrafluoride, and silane tetraiodide. Examples of the titanium tetrahalide include titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium tetraiodide, and the like. Examples of the aluminum trihalide include aluminum trichloride, aluminum tribromide, aluminum trifluoride, and aluminum triiodide. Of these, silane tetrahalide and aluminum trihalide are preferable from the viewpoint of availability and the like, more preferably silane tetrahalide, and particularly preferably silane tetrachloride and silane tetrabromide.

  The precursor of the organic / inorganic composite layer (B3) forming the plate-like composition layer (B) is an organic / metal composite alkoxide (C3) and an organic / inorganic composite halide (C4), each of (C1) An alkoxy group and a part of the halogen atom of (C2) are substituted with an organic group (or bonded through an organic group), and compounds represented by the general formulas (4) and (5) are used. it can.

In the formulas (4) and (5), M and n are the same as those in the general formulas (2) and (3). m is 0 or a positive integer not exceeding (n−2), j is 1 or 2, R1 is an organic group having 1 to 20 carbon atoms that forms a chemical bond with j M, and R2 is hydrogen An atom, a hydroxyl group or a hydrocarbon group having 1 to 8 carbon atoms, R3 is a hydrocarbon group having 1 to 8 carbon atoms, and X is a halogen atom. ]
Of these, M is preferably titanium and more preferably silicon from the viewpoints of availability of (C3) and (C4).

  In formulas (4) and (5), R1 is a j-valent organic group having 1 to 20 carbon atoms, and is a monovalent hydrocarbon group such as an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms. Group, an allyl group having 6 to 12 carbon atoms, and an aralkyl group having 7 to 12 carbon atoms; and a divalent hydrocarbon group such as an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and a carbon number A 2-20 alkynylene group, a C6-C20 arylene group, a C7-C20 aralkylene group, etc. are contained.

  Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, n-butyl group, i-butyl group, t-butyl group, hexyl group, 2-ethylhexyl group and n-octyl group. It is done. Examples of the alkenyl group having 2 to 8 carbon atoms include vinyl group, propenyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 2-octenyl group and 7-octenyl group. Is mentioned. Examples of the allyl group having 6 to 12 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, 3,5-dimethylphenyl group and dimethylnaphthyl group. Examples of the aralkyl group having 7 to 12 carbon atoms include benzyl group, phenylethyl group, methylbenzyl group and naphthylmethyl group. Examples of the alkylene group having 1 to 20 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, 1,2-butylene group, 1,3-butylene group, 1 , 2-hexylene group, 1,3-hexylene group, 1,4-hexylene group, 1,5-hexylene group, 1,2-octylene group and the like. Examples of the alkenylene group having 2 to 20 carbon atoms include vinylene group, propenylene group, 1-ethylvinylene group, 1,2-dimethylvinylene group, 1-butylvinylene group, and 1-hexylvinylene group.

Examples of the alkynylene group having 2 to 20 carbon atoms include ethynylene group, propynylene group, 1-ethylethynylene group, 1,2-dimethylethynylene group, 1-butylethynylene group, 1-hexylethynylene group and 1-octylethynylene group Is mentioned. Examples of the arylene group having 6 to 20 carbon atoms include an o-phenylene group, an m-phenylene group, a p-phenylene group, and a 2,7-naphthylene group. Examples of the aralkylene group having 7 to 20 carbon atoms include an organic group represented by the general formula (6).
In Formula (6), -Ph- is an o-, m- or p-phenylene group, q and r are 0 or an integer of 1 to 14 where q + r is 1 to 14.

  Among these, from the viewpoint of availability as (C3) and (C4), an alkylene group and an arylene group are preferable, and a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, Octamethylene group, decamethylene group, 1,2-butylene group, 1,3-butylene group, 1,2-hexylene group, 1,3-hexylene group, 1,4-hexylene group, 1,5-hexylene group, 1 , 2-octylene group, o-phenylene group, m-phenylene group, p-phenylene group and 2,7-naphthylene group, particularly preferably methylene group, ethylene group and p-phenylene group.

  In formulas (4) and (5), R2 is a hydrogen atom, a hydroxyl group or a hydrocarbon group having 1 to 8 carbon atoms, and R3 is a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms include those having 1 to 8 carbon atoms among the aforementioned monovalent hydrocarbon groups for R1. Among these, from the viewpoint of availability of (C3) and (C4), R2 is preferably methyl, ethyl and phenyl, more preferably methyl and phenyl. R3 is preferably methyl, ethyl, propyl, n-butyl and t-butyl, more preferably methyl, and particularly preferably ethyl.

  (Nm-1) is preferably an integer of 2 to 6, more preferably an integer of 2 to 5, particularly preferably an integer of 2 to 3, from the viewpoint of ease of forming the plate-like composition layer. . n is an integer of 0 to 7, and is preferably an integer of 0 to 5, more preferably an integer of 0 to 2, particularly preferably 0 or 1, from the viewpoint of ease of forming the plate-like composition layer. is there. j is an integer of 1 to 2, and 1 is preferable from the viewpoint of ease of forming the plate-like composition layer.

  (C3) includes an organic / inorganic composite alkoxide (C3-1) in which j = 1, an organic / inorganic composite alkoxide in which j = 2 (C3-2), a mixture thereof, and the like.

  (C3-1) includes the following methoxysilane, ethoxysilane (eg, triethoxymethylsilane), butoxysilane, octoxysilane, phenoxysilane, methoxytitanium, ethoxytitanium, butoxytitanium, octoxytitanium, and phenoxytitanium. Etc. are included.

  Examples of methoxysilane, butoxysilane, octoxysilane, and phenoxysilane include those corresponding to ethoxysilane (with ethoxy groups substituted by methoxy, butoxy, octoxy, and phenoxy groups, respectively).

  Examples of methoxytitanium, ethoxytitanium, butoxytitanium, octoxytitanium, and phenoxytitanium include those corresponding to methoxysilane, ethoxysilane, butoxysilane, octoxysilane, and phenoxysilane (wherein silane is substituted with titanium).

  Organic / metal composite alkoxides (C3-2) where j = 2 include methoxysilane, ethoxysilane, butoxysilane, octoxysilane, phenoxysilane, methoxytitanium, ethoxytitanium, butoxytitanium, octoxytitanium, phenoxytitanium, etc. Is included. Methoxysilane includes trimethoxysilane, dimethoxysilane and monomethoxysilane.

    Examples of methoxysilane, butoxysilane, octoxysilane, and phenoxysilane include those corresponding to ethoxysilane (with ethoxy groups substituted by methoxy, butoxy, octoxy, and phenoxy groups, respectively).

  Examples of methoxytitanium, ethoxytitanium, butoxytitanium, octoxytitanium, and phenoxytitanium include those corresponding to methoxysilane, ethoxysilane, butoxysilane, octoxysilane, and phenoxysilane (wherein silane is substituted with titanium).

  The organic / inorganic composite halide (C4) includes an organic / inorganic composite halide (C4-1) in which j = 1, an organic / inorganic composite halide (A4-2) in which j = 2, and a mixture thereof. Is included.

Examples of (C4-1) in which j = 1 includes the following trihalosilane (for example, trichloromethylsilane), dihalosilane (for example, dichlorodimethylsilane), trihalotitanium, dihalotitanium, and the like.
And bromosilane in which chloro is replaced by bromine.

  Examples of trihalotitanium and dihalotitanium include those corresponding to the above-mentioned trihalosilane and dihalosilane (wherein each silane is substituted with titanium).

The organic / inorganic composite halide (C4-2) where j = 2 includes the following trihalosilane (eg, bis (trichlorosilyl) methylene), dihalosilane (eg, bis (dichloromethylsilyl) methylene), Monohalosilanes such as bis (chlorodimethylsilyl) methylene), trihalotitanium, dihalotitanium and monohalotitanium.
In addition, bromotitanium in which chloro corresponding to the above is substituted with bromine can be mentioned.

Examples of trihalotitanium, dihalotitanium, and monohalotitanium include those corresponding to the above-mentioned trihalosilane and dihalosilane (wherein each silane is substituted with titanium).
Of these (C), (C1) and (C2) are preferable, (C1) is more preferable, and (C1) is particularly preferably composed of silicon and titanium as a metal atom, for example, tetraethylalkoxysilane.

The amount (parts by weight) of (C) used is about 0.1 to 10% by weight, more preferably 0.3 to 5% by weight, particularly preferably 0.6 to 5%, based on the surfactant (a). 3% by weight. If it exists in this range, since a plate-shaped composition layer (B) is formed and the sol-gel reaction by an alkoxide becomes easy to occur on the lamellar layer of surfactant, it is preferable.

  The coupling agent (D) used in the present invention is used for improving the adhesion strength with a polymer when a layered structure is added as a filler component to a polymer material. Examples of the coupling agent used in the present invention include a silane coupling agent containing Si in the hydrophilic group portion, a titanate coupling agent containing Ti in the hydrophilic group portion, and an aluminum coupling agent containing Al in the hydrophilic group portion. . The structure of the coupling agent is roughly classified into a hydrophilic group composed of an alkoxy group bonded to a metal element such as Ti or Al or Si, and a hydrophobic group that interacts with the resin. The alkoxy group is hydrolyzed and condensed. It is possible to combine with the plate-like composition (B).

  (D) includes 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2-aminoethyltrimethoxysilane, 3-aminopropyl Trimethoxysilane, 3-aminopropyltriethoxysilane, 3- [N- (2-aminoethyl) amino] ethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltri Toxisilane, 3- [N- (2-aminoethyl) amino] propylmethyldimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-acryloxyethyltrimethoxysilane, 3-methacryl Roxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, methyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltri Ethoxysilane, vinylacetoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxy Orchids, .gamma. anilino trimethoxysilane, isopropyl tri (N- aminoethyl-aminoethyl) titanate, isopropyl titanate, isopropyl tridecyl benzenesulfonyl titanate, and the like acetyl alkoxy ammonium diisopropylate. Of these, a silane coupling agent and a titanate coupling agent are preferable from the viewpoint of availability and the like, and a silane coupling agent is more preferable.

  The amount of (D) added is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the surfactant (a). If the amount added is less than 0.1 parts by weight, the surface of the layered structure tends to be insufficiently coated with the coupling agent, and if it exceeds 20 parts by weight, the layered structure cannot be sufficiently formed. Become a trend.

  The X-ray diffraction (hereinafter abbreviated as XRD) pattern in the present invention is obtained, for example, by a small angle scattering measurement method. The diffraction pattern obtained by these measurements is a plot of the scattering intensity of the measurement substance at each diffraction angle, with the vertical axis representing the scattering intensity and the horizontal axis representing the diffraction angle (2θ).

  The X-ray diffraction pattern has at least two peaks, and the diffraction angle (2θ) of these peaks is expressed by the equation (1). For example, d1 is 10 nm and d2 is 5 nm. This shows that d) is a structure regularly arranged at intervals of 10 nm.

In the present invention, the layered structure is obtained using layered micelles formed by self-assembly of a surfactant. Formation of layered micelles can be confirmed by using X-ray diffraction.
The self-assembly of the surfactant means that the shape of the micelle is controlled by the balance between the size of the hydrophilic group and the size of the hydrophobic group in the surfactant (a). Details are described in the literature (Supramolecular Science, Tokyo Science Doujin, 1998). For example, in an aqueous system, as the volume occupied by a hydrophobic group generally increases with respect to the length of the hydrophobic group, the volume changes from a spherical micelle to a rod-like micelle and from a rod-like micelle to a layered micelle.

  The temperature and concentration conditions for the surfactant to form layered micelles in water vary depending on the structure of the surfactant, but by setting the temperature and concentration conditions suitable for the surfactant used, the surfactant in the solvent Has a lamellar structure regularly arranged in layers. For example, in the case of polyethylene glycol (PE6200; manufactured by Sanyo Chemical Industries, Ltd.) which is a nonionic surfactant in water, the temperature is 40 to 60 ° C. at a concentration of 5 to 75%.

  The coupling agent (D) is arranged in such a manner that hydrophilic groups are dispersed on the surface of the layered micelle due to the interaction with the layered micelle, and has a layered micelle structure including the coupling agent. After adding HCl and the like to acid conditions and adding an alkoxysilane such as TEOS as a precursor (C) to an aqueous solution containing a surfactant having a layered micelle structure, the alkoxysilyl group is hydrolyzed and dehydrated. By condensing, a plate-like composition layer (B) is formed, and a layered structure comprising the surfactant layers (A) and (B) is obtained. At this time, the alkoxy group in (D) is polycondensed with (C) to form (B). This is because a hydrophilic group is present on the surface of the layered micelle, so that the terminal silanol group of the alkoxide undergoes a sol-gel condensation reaction with the surface of the layered micelle, resulting in the formation of a plate-like composition layer (B), A layered structure composed of the activator layer (A) and the plate-like composition layer (B) is formed.

  HCl is added as a catalyst for the sol-gel reaction, and is 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 10% by weight from the viewpoint of reactivity.

  Factors for obtaining the layered compound include reaction temperature, reaction time, surfactant concentration, weight ratio of surfactant to inorganic alkoxide, HCl concentration, and the like.

  The lower the reaction temperature, the higher the regularity of the product tends to be. On the other hand, the higher the reaction temperature, the higher the degree of polymerization and the higher the structural stability. Therefore, the reaction temperature is preferably in the range of 20 to 80 ° C. A more preferable temperature range is 30 ° C to 70 ° C. A particularly preferred temperature range is 40-60 ° C.

  In addition, the reaction time is an important condition for crystal formation. If the time is too short, the crystal becomes amorphous and a high-quality crystal cannot be obtained. The reaction time is preferably 1 hour or longer, more preferably 3 hours or longer, particularly preferably 6 hours or longer.

  The dealcoholization condensation reaction can be performed in a solvent or without a solvent. The solvent is not particularly limited as long as it is an organic solvent that dissolves the surfactant (a) and the precursor (C) and is inactive thereto. Examples of such an organic solvent include aprotic polar solvents such as dimethylformamide, dimethylacetamide, tetrahydrofuran, and methyl ethyl ketone.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In the following, parts indicate parts by weight and% indicates% by weight.
[Example 1]

Nonionic surfactant PE6200 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) 5.2 parts, 100 parts of ion-exchanged water, 0.5 part of 2-glycidoxyethyltrimethoxysilane, 24 parts of 37 wt% HCl were charged into a reaction vessel at 55 ° C. And stirred until uniform. Next, 4.0 parts of tetraethoxysilane (TEOS) was added and stirred at 55 ° C. for 6 hours to obtain a white precipitate. The precipitate was filtered and air dried. After drying, the obtained precipitate was measured by XRD, and the presence of two peaks indicating a layered structure could be confirmed. d1 and d2 satisfied the formula (1), and the interlayer distance was 7.6 nm.
[Example 2]

Nonionic surfactant PE6200 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) 5.0 parts, ion exchange water 100 parts, 2-glycidoxyethyltrimethoxysilane 0.5 part, 37 wt% HCl 23.4 parts were charged in a reaction vessel, The mixture was heated to 55 ° C. and stirred until uniform. Next, 4.2 parts of TEOS was added and stirred at 55 ° C. for 6 hours to obtain a white precipitate. The precipitate was filtered and air dried. After drying, the obtained precipitate was measured by XRD, and the presence of two peaks indicating a layered structure could be confirmed. d1 and d2 satisfied the formula (1), and the interlayer distance was 7.6 nm.
[Example 3]

40.7 parts of cationic surfactant tetrastearyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 parts of ion exchanged water, 3.5 parts of 2-glycidoxyethyltrimethoxysilane, 1.7 parts of 1 mol / L NaOH And stirred at 25 ° C. until uniform. Next, 21.5 parts of TEOS was added and stirred for 20 hours to obtain a white precipitate. The precipitate was filtered and air dried. After drying, the obtained precipitate was measured by XRD, and the presence of two peaks indicating a layered structure could be confirmed. d1 and d2 satisfied the formula (1), and the interlayer distance was 4.5 nm.
[Comparative Example 1]

Nonionic surfactant PE6200 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) 5.2 parts, 100 parts of ion-exchanged water and 24 parts of 37 wt% HCl were placed in a test tube, heated to 55 ° C., and stirred until uniform. Next, 4.0 parts of TEOS was added and stirred at 55 ° C. for 6 hours to obtain a white precipitate. The precipitate was filtered and air dried. After drying, the obtained precipitate was measured by XRD, and the presence of two peaks indicating a layered structure could be confirmed. d1 and d2 satisfied the formula (1), and the interlayer distance was 7.6 nm.
[Comparative Example 2]

  40.7 parts of cationic surfactant tetrastearyl ammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 100 parts of ion-exchanged water and 1.7 parts of 1 mol / L NaOH were charged in a reaction vessel and stirred at 25 ° C. until uniform. Next, 21.5 parts of TEOS was added and stirred for 20 hours to obtain a white precipitate. The precipitate was filtered and air dried. After drying, the presence of two peaks indicating a layered structure was confirmed by XRD. d1 and d2 satisfied the formula (1), and the interlayer distance was 4.5 nm.

[Comparative Example 3]
100 parts of a 3 wt% aqueous solution of montmorillonite (Kunipia F) and 30 parts of a 10 wt% aqueous solution of a surfactant (trimethylcetylammonium chloride) are heated to 80 ° C. and then mixed and stirred. After stirring for 2 hours, the precipitate was filtered off and washed twice with 80 ° C. water. Thereafter, water was evaporated to obtain a gray organic clay in which trimethylcetylammonium ions were inserted between montmorillonite layers. As a result of obtaining the interlayer distance from the XRD diffraction pattern, d1 and d2 satisfy the formula (1), but the obtained interlayer distance was 2.0 nm.

<Test example>
Using each of the layered structures obtained in Examples 1 to 3 and Comparative Examples 1 to 3, resin films were prepared according to the following formulation, and the linear expansion coefficient was measured. (Test Examples 1-3, Comparative Test Examples 1-3)
<Creation of cured film>
(1) Into a planetary mixer, 42 parts of Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.) and 58 parts of the layered structure obtained in Examples or Comparative Examples were charged and kneaded for 30 minutes.
(2) 44 parts of MEK solution (solid content 50%) of glycidyl methacrylate / styrene / 2-ethylhexyl acrylate copolymer (Mw = 30,000, Tg = 57 ° C., epoxy equivalent = 322), phenolic curing agent ( Phenol novolac resin, 32 parts of PSM-4326 manufactured by Gunei Chemical Industry Co., Ltd., 8 parts of flame retardant (brominated epoxy resin, YDB-500 manufactured by Tohto Kasei Co., Ltd.), epoxy ring-opening catalyst (manufactured by San Apro, SA-102) 4 Part and 26 parts of methyl ethyl ketone were charged and mixed for 15 minutes to obtain a curable resin composition.
(3) Next, this resin solution was applied to a PET film (600 mm × 600 mm) having a thickness of 50 μm by a roll coater so that the resin thickness after drying was 50 μm, and then dried at 90 ° C. for 7 minutes. A curable resin film was obtained. This curable resin film was cured by heating at 170 ° C. for 90 minutes to obtain a cured product in which the layered structure of the present invention was dispersed, and the linear expansion coefficient was measured by the following measurement method.

<Measurement of linear expansion coefficient>
The cured film at 25 ° C. (length) 15 mm × (width) 2 mm × (thickness) 0. Cut to a size of 04 mm. The length and width of the cut sample were measured with a caliper, and the thickness was measured with a film thickness meter, each measuring up to an order of 0.001 mm.
Using a TMA / SS6100 manufactured by Seiko Instruments Inc., a load of 49 mN was applied to the measurement sample, the inside of the measurement cell was held at 30 ° C. for 30 minutes, and then the measurement cell temperature was changed from 30 ° C. to 230 ° C. at 10 ° C./min. The temperature rose. The length at 30 ° C. was (L ₃₀ ) [mm], the length at 100 ° C. was (L ₁₀₀ ) [mm], and the linear expansion coefficient was determined from the following formula. The results are shown in Table 1.
Linear expansion coefficient (X) = ((L ₁₀₀ ) − (L ₃₀ )) × 10 ⁶ / {140 × L ₃₀ } [ppm]

  Examples 1 to 3 show that the thermal expansion coefficient is smaller than that of the comparative example and the reinforcing effect as a filler is excellent.

The layered structure produced in this way can be uniformly and finely dispersed in the polymer, so even if the amount of clay dispersed is very small, it is a great reinforcement that cannot be achieved with other fillers and other reinforcing materials. The layered structure exhibits the effect and can exhibit high mechanical strength. In particular, a polymer composition excellent in mechanical properties such as strength and elastic modulus, heat resistance, thermal deformation temperature, low temperature embrittlement temperature, and the like can be obtained.

Claims (6)

2 or more which satisfy | fills the following relational expression (1) in the pattern of the X-ray-diffraction measurement which consists of a surfactant layer (A) and the plate-shaped composition layer (B) containing the residue of a coupling agent (D) A layered structure characterized in that the lattice plane spacing d1 of the peak having the smallest diffraction angle (2θ) is 1 to 100 nm.
dn = (1 / n) d1 (1)
[Wherein, dn represents the lattice spacing (nm) at the peak number n, and d1 represents the lattice spacing (nm) when n is 1; provided that the diffraction angle (2θ) is the largest among the peaks satisfying the formula (1). The peak number of a peak with a small value is n = 1, and n = 2, 3,... In order as the diffraction angle (2θ) increases. ]   2. (B) is one selected from the group consisting of a silicate or silica layer (B1), a metal oxide layer (B2), and an organic / inorganic composite layer (B3). Layered structure.   3. The layered structure according to claim 1, wherein (B) is (B1).   3. The layered structure according to claim 2, wherein (B3) is formed by bonding a metal atom, an oxygen atom, and an organic group containing at least one or more carbon atoms.   (D) is a silane coupling agent, The layered structure in any one of Claims 1-4. The precursor (C) of the plate-like composition layer (B) is added to the layered micelle solution of the surfactant (a) containing the coupling agent (D), and (C) and (D) are hydrolyzed on the micelle surface. And (B) containing the residue of (D) is formed by polycondensation, and in the X-ray diffraction measurement pattern, there are two or more peaks satisfying the following relational expression (2), and most of them are diffracted. A method for producing a layered structure comprising a surfactant layer (A) and a plate-like composition layer (B), wherein the lattice spacing d1 of the peak having a small angle (2θ) is 1 to 100 nm.
dn = (1 / n) d1 (2)
[Wherein, dn represents the lattice spacing (nm) at the peak number n, and d1 represents the lattice spacing (nm) when n is 1; provided that the diffraction angle (2θ) is the largest among the peaks satisfying the formula (1). The peak number of a peak with a small value is n = 1, and n = 2, 3,... In order as the diffraction angle (2θ) increases. ]