JPH0227282B2 - MUKI * JUKIFUKUGOTAINOZORUOYOBISOREOGENRYOTOSURUFUIRUMU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a film made of an inorganic material, and more specifically, a tough and flexible inorganic/organic composite film with excellent heat resistance suitable as an electrical insulation film or a film for building materials, and an inorganic/organic composite film that is a raw material thereof. It concerns the sol. Conventionally, films made of inorganic materials and sols of raw materials thereof include sols of layered silicates. The crystals of layered silicates have an anisotropic layered structure, and cleave between the layers to form scale bodies. These scales are used to form a film with a parallel structure of scales, and in order to create a film that has self-bonding power, it is necessary to use a layered structure that can form a stable sol in water. Requires silicate. Conventionally, the layered silicates used to make such films and sols have been free swelling types such as sodium or lithium hectorite, which have weak interlayer bonding and form sol by drawing in large amounts of water molecules between the layers. Fluorine mica and montmorillonite are known. However, none of the conventional sols has the stability and fluidity necessary to form a film through flow spreading, and the films made from such sols have insufficient flexibility and strength. The disadvantages were that both the elongation was small and the toughness was not strong enough to withstand practical use. The purpose of the present invention is to eliminate the above-mentioned conventional drawbacks and provide a film that has excellent toughness, flexibility, and heat resistance, and a sol that is a raw material for the film and has excellent stability and fluidity. It is something to do. In order to achieve the above object, the present invention uses limited swelling type fluorinated mica as the basic material, whereas the conventional method uses free swelling type layered silicate as the basic material. The free-swelling type can obtain scales with a wall thickness of molecular units (150 Å or less) only by immersion in water, whereas the limited-swelling type swells and the interlayers expand slightly, weakening the interlayer strength, but they can be cleaved. It's not enough to do that. The present invention is to obtain a composition that can be converted into a sol by compounding a limited swelling type fluorine mica with an organic molecule, and to complete a film that is more suitable for the purpose than a sol with that composition. (1) The chemical composition is X _0.3~1.0 Y _2.5~3.0 (Z _3.5~4.5 0 ₁₀
)
F _{1.5 ~ 3.0} [X is an interlayer ion exchange organic cation,
An organic cation that is at least one selected from alkylamines, aminoalcohols, or amino acids and has 3 to 7 carbon atoms and 1 nitrogen; Y is an octahedral ion (Mg _{1.5 to 2.5}
Li _0~1 ) or a part of its Mg ²⁺ as Fe ²⁺ , Ni ²⁺ ,
Substituted with at least one ion selected from Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Z is an ion at a tetrahedral position, and Si ⁴ or Ge ⁴⁺ or a part thereof is replaced by Al ³⁺ ，
A sol consisting of a limited swelling type fluorinated mica organic complex represented by [substituted with at least one kind of ion selected from Fe ³⁺ and B ³⁺ ], and the sol consists of a fluorinated mica organic complex substituted with at least one type of ion selected from Fe 3+ and B 3+ , and the sol consists of a Law average particle size is 0.1~15μ
m, an inorganic-organic composite sol characterized by a rotational viscosity of 10 centipoise or more, and (2) a chemical composition of X _0.3-1.0 Y _2.5-3.0 (Z _3.5-4.5 O ₁₀ ) F _1.5-3.0
(X is an interlayer ion exchange organic cation, at least one selected from alkyl amines, amino alcohols, and amino acids, and has 3 to 3 carbon atoms.
7. An organic cation in which the number of nitrogen atoms is 1, Y is an octahedral position ion (Mg _1.5~2.5 Li _0~1 ) or its
A part of Mg ²⁺ is converted into Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺
Z is an ion at a tetrahedral position, and Si ⁴⁺ or Ge ⁴⁺ or a part thereof is substituted with at least one ion selected from among Al ³⁺ , Fe ³⁺ , B ³⁺ A film consisting of a limited swelling type fluorinated mica organic composite represented by (substituted with at least one type of ion selected from 0.43
〜0.85, and the crystal size of the inorganic-organic composite in the film is 150 to 300 Å.
It is an organic composite film. The crystal structure of fluorine mica is that silicic acid tetrahedral layers (ZO ₄ ) are arranged in parallel with the apex oxygen facing each other, and in between, six-coordinated ions (Y) are narrowed in a sandwich-like pattern to form an octahedral structure. form. The three-layer lattice of tetrahedral layer, octahedral layer, and tetrahedral layer formed in this way is used as a unit layer, and this is called a tablet. Cations liberated due to charge balance in the three-layer lattice are coordinated between the unit layers, and are called interlayer ions. In the case of swellable fluorinated mica, interlayer ions are ion-exchangeable. The limited swelling type fluorinated mica organic composite of the present invention has the following chemical composition. X _0.3-1.0 Y _2.5-3.0 (Z _3.5-4.5 O ₁₀ ) F _1.5-3.0 X is an interlayer ion exchange cation, and this X is (a)
It is an organic cation molecule with a strong dipole moment, (b) it can penetrate between layers in a form that solvates with water molecules, and (c) the formed inorganic-organic complex maintains affinity with polar solvents. It is necessary that the X that satisfies (a), (b), and (c) above is at least one selected from alkylamines, aminoalcohols, and cationized amino acids, and is an organic molecule. The number of carbon atoms inside is 3 to 7 and the number of nitrogen atoms is 1. Specific examples thereof include cations of n-butylamine, n-propylamine, iso-amylamine, triethanolamine, and 6-amino-n-caproic acid. Unless the organic cation is used as described above, a stable sol cannot be obtained, and a film made of the sol has poor flexibility and toughness, which is not preferable. The index of X in the above chemical composition is 0.3~
Must be 1.0. This range is determined by the relationship with the indices of Y and Z, but
If it is larger or smaller than this range, a sol having both stability and fluidity cannot be obtained, and a film made from the sol will have poor toughness and flexibility. Y _2.5-3.0 (Z _3.5-4.5 O ₁₀ ) in the above chemical composition
The portion represented by F _{1.5 to 3.0} is the tablet portion of the limited swelling type fluorine mica organic composite and forms the skeleton of the crystal. Y is a six-coordinated ~hedral ion represented by (Mg _1.5-2.5 Li _0-1 ), preferably (Mg _1.8-2.2 Li _0.7-1.0 ). In addition, a part of Mg ²⁺ may be replaced with Fe ²⁺ or
Substitution may be made with Ni ²⁺ , Mn ²⁺ , Al ³⁺ , or Fe ³⁺ . Y
The exponent of should be between 2.5 and 3.0. Further, Z is an ion at a tetrahedral position and is Si ⁴⁺ or Ge ⁴⁺ , but it may also be Al ³⁺ or Fe ³ within a range (within 10% of Si ⁴⁺ or Ge ⁴⁺ ) that does not impede the purpose of the present invention. ⁺ , B ³⁺ may be substituted. The index of Z is 3.5 to 4.5. Furthermore, if the composition of the tablet portion is outside the above range, it will be difficult to form a scale crystal structure, and good sol and film will not be obtained. The rotational viscosity of the sol of the present invention must be 10 centipoise or more, preferably 15 centipoise or more. This is a parameter that determines the stability of the sol and the cleavage in the thickness direction of the organic/inorganic composite. If the rotational viscosity is smaller than the above range, the cleavage will be insufficient and the sol will not be stable, and the sol for film will It is inappropriate as such. The sedimentation method average particle diameter of the sol constituent particles of the present invention is
It needs to be 0.1-15 μm, preferably 0.2-10 μm. If the average particle size is smaller than the above range,
The scales are composed of small scale diameters in the planar direction, which is not preferable for use in film production, and conversely, if the scale diameters are large, the stability of the sol will be poor. In the present invention, organic cations X, which are interlayer ions of a limited swelling type fluorine-mica organic composite, can be ion-exchanged with inorganic cations. This application of inorganic cation exchange is useful for improving the heat resistance of the film, preventing deterioration over time, and improving the dielectric constant. The inorganic cation that can be used for ion exchange preferably has an ionic index (product of ion valence and ionic radius) of 1.25 or more. In this case, if the ionic index is smaller than the above range, ion exchange is difficult, and the interlayer is unstable and hygroscopicity remains, which is not preferable. The thickness of the film made of the limited swelling type fluorine mica composite of the present invention is 1 to 100 μm (preferably 2 to 100 μm).
If the film thickness is smaller than the above range, the heat resistance will be poor, and conversely, if the film thickness is larger than the above range, the flexibility will be poor. This is not desirable. The density index of the film is in the range of 0.43 to 0.85, preferably 0.50 to 0.78. If the density index of the film is smaller than the above range, the toughness of the film will be poor, while if the density index is larger than the above range, the flexibility will be poor, which is not preferable. In addition, the crystal size of the limited swelling type fluorine mica organic composite in the film is 150 to 300 Å, preferably 200 to 300 Å.
It is in the range of 300 Å. If the crystal size is smaller or larger than the above range, the film will have poor toughness, which is not preferable. In order to further improve the moisture resistance of the film of the present invention, it is effective to exchange the interlayer ions of the limited swelling type fluorine mica organic composite with inorganic cations having an ionic index of 1.25 or more. A film exchanged with a cation having an ionic index smaller than the above range is not preferable because it becomes water-absorbing and remains hygroscopic due to the instability of interlayer ions. In order to further improve the tear strength of the film made of the limited swelling type fluorine-mica organic composite of the present invention, this can be achieved by laminating an organic polymer film on at least one side of the film. This organic molecular film preferably has a temperature at 5% weight loss of 400°C, preferably 450°C or higher. In this case, if the temperature at 5% weight loss is lower than the above range, the adhesiveness of the laminated film will be poor when used at high temperatures, which is not preferable. In addition, the lamination thickness ratio of the organic polymer film and the limited swelling type fluorine mica organic composite is 0.01 to 0.2, preferably 0.05.
A range of ~0.15 is desirable. In this case, if the lamination thickness ratio is smaller than the above range, the tear strength of the film will be poor, which is not preferable, and if it is too large, the heat resistance will be poor, which is not preferable. Next, the method for producing the sol and film of the present invention will be explained. The raw material for the limited swelling type fluorinated mica organic composite constituting the present invention is limited swelling type fluorinated mica represented by the following chemical composition. Na _0.5-1.0 Y _2.5-3.0 (Z _3.5-4.5 0 ₁₀ ) F _1.5-3.0 Na is an interlayer ion, Y is an ion at a six-coordinated octahedral position, (Mg _1.5-2.5 Li _0-1.0 ) Preferably, it is represented by (Mg _1.8-2.2 Li _0.7-1.0 ). In addition, a part of Mg ²⁺ may be replaced by isomorphic substitution within a range that does not impede the purpose of the present invention (within 20% of Mg ²⁺ ).
It may be substituted with Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Al ³⁺ , Fe ³⁺ . The index of Z needs to be between 3.5 and 4.5. If the Na index is less than 0.5, or if the above chemical composition applies, a free-swelling type such as sodium hectorite Na1/3Mg ₂ 2/3Li1/3
(Si ₄ O ₁₀ ), Sodium Tetrasilicon Mica Na Mg _2.5
(Si ₄ O ₁₀ ) F ₂ , Lithium Taeniolite LiMg ₂ Li
Sols made from (Si ₄ O ₁₀ )F ₂ or the like are not preferred because they do not have both stability and fluidity, and films made from such sols have poor toughness and flexibility. Furthermore, sols made from natural minerals such as vermiculite and montmorillonite do not have both stability and fluidity, and are not preferred as raw materials for films. Regarding the cleavage method of limited swelling type fluorine mica,
Conventionally, rapid heating at 500° C. or higher has been used, but this method requires repeated heating and decantation many times, which is inefficient and the resulting sol is unstable. There is also another method of cleaving using a lithium salt (for example, lithium chloride), but the sol produced by this method does not have both stability and fluidity. The manufacturing method of the product of the present invention is different from conventional methods,
Based on the investigation of the swelling mechanism of limited swelling type fluorine mica, the so-called intercalation (INTER CALA-
It utilizes the reaction of forming a complex called TION, which is formed by the coordination of an organic compound to the interlayer region of a layered compound. In other words, the limited swelling type fluorine mica that is the host
This takes the form of an ion exchange reaction between Na ⁺ and a guest organic cation. The specific method of cleavage in the present invention is as follows. (1) A synthetic melt of limited swelling type fluorine mica is made into hydrated small particles by a known method. The method for making particles into small particles may be either a method of immersion in water or a method of weathering in water vapor. (2) React the hydrated small particles with the organic cation that is the guest of the present invention. This reaction is carried out in an aqueous solution with a pH of 1 to 6. The reaction means may be a dipping method or a stirring method. (3) After ion exchange, excess organic cations and unnecessary
Remove Na ⁺ . In this step, the composite of the present invention incorporates a large amount of water between its layers and becomes a sol. (4) Next, the sol-like organic-inorganic composite obtained in (3) is cleaved using rotational viscosity until a sol of at least 10 centipoise is obtained. As this means, it is effective to use a device having a shearing action, such as a mixer, homogenizer, or ball mill. (5) Next, coarse particles in the sol constituent particles are separated. After completion of this step, the average particle size of the sol by sedimentation method must be 15 μm or less, preferably 10 μm or less. Through the above steps, it is possible to obtain an organic-inorganic composite sol made of a limited swelling type fluorine mica organic composite that has both stability and fluidity. The sol of the organic/inorganic composite obtained by the above method can be treated with other polar solvents such as formamide, dimethyl sulfoxide, etc. by a known phase inversion method.
It can be phase inverted to n-methyl-pyrrolidone, propylene carbonate, ethyl alcohol, etc. The sol obtained by phase inversion can be easily kneaded into resins and the like. The concentration of the inorganic/organic composite sol obtained by the above method is 1 to 20% by weight, preferably 2 to 10% by weight.
The solution prepared in the following manner is spread on a releasable substrate by a casting method or a spraying method so that the sol has a uniform thickness. 25~
After drying at a temperature of 250°C to form a film, the film is peeled off from the substrate to obtain a single inorganic/organic composite film. In this case, an infrared heater or the like may be used to shorten the drying time.
Alternatively, excess solvent may be removed using centrifugation or reduced pressure drying. Further, if it is desired to continuously form a film, a rotating drum or an endless belt can be used as the substrate. When forming into a film, other known solution casting methods and wet casting methods can be used. In addition, a method of depositing an inorganic/organic composite film on an electrode surface using electrophoresis and forming a film by taking advantage of the fact that the inorganic/organic composite of the present invention is negatively charged in a solution is used. Good too. Next, the film is heat treated if necessary. In this case, the heat treatment is preferably carried out at a temperature in the range of 200 to 550°C. Moreover, by pressurizing the film of the present invention,
A film with even greater toughness can be produced. The pressurizing step in this case may be carried out before, during or after drying the film, or may be carried out by applying pressure while heating. In this case, the pressure is 100 when applying pressure on a surface.
Kg/cm ² or more, line pressure 100 in case of roll rolling etc.
It is preferable that it is Kg/cm or more. The present invention is characterized by the above, and the inorganic/organic composite of the present invention has a
By adding up to 30% by weight of a polar linear polymer compound, a film with even better toughness can be obtained. The polar linear polymer compound in this case is a compound having a degree of polymerization of 100 or more, and refers to a linear polymer compound having at least one polar group in the repeating unit of the polymer. Here, the polar group refers to a group having at least one bond having a bond moment of 0.7 debye or more, preferably 1.0 debye or more. Specific examples of bonds with a bond moment of 0.7 debye or more include N-H, O-H, H-F, H-Cl, C=O,
C≡N, etc., and examples of polar compounds having at least one of these bonds include hydroxyl group, amino group,
Examples include, but are not limited to, carbonyl groups, ether groups, nitrile groups, carboxyl groups, and amide groups. Note that the bond moment refers to the dipole moment that acts between two bonded atoms, and its numerical value is given in the Basics of Chemistry Handbook,
The values shown in P.1406, Table 11173 (1975) (Maruzen) were adopted. Debye, the unit of bond moment, is 10 ^-18 cgs・esu・cm. In addition, the linear polymer compound referred to here refers to a monomer polymerized almost linearly with some branching, or a linear polymer chain formed after linear polymerization. A polymer compound that is cross-linked and does not contain a cyclic structure such as an aromatic ring or a cyclohexane ring in the polymer main chain. Linear polymer compounds do not include those whose polymerization occurs dimensionally or three-dimensionally through a crosslinking reaction. Specific examples of polar linear polymeric compounds suitable for this purpose include polyvinyl alcohol, polyacrylamide, polyethylene oxide, polyacrylonitrile, and the like. Further, the addition method may be either a method of adding a linear polymer compound with a predetermined degree of polymerization from the beginning, or a method of adding a polymerizable monomer and then polymerizing it to form a polymer compound. As for the timing of addition, it may be added to a sol and then formed into a film, or it may be impregnated into a film. As a method for laminating the inorganic/organic composite film obtained by the above method and the organic polymer film, known lamination methods can be used, but the most preferred method is to laminate the organic polymer film on the surface of the organic polymer film. Corona discharge treatment (in air, nitrogen gas,
A preferred method is to cast the inorganic/organic composite sol onto an organic polymer film and dry it to form a film. The characteristic values of the sols and films of the Examples described below are based on the following measurement method. (1) Index of ion-exchanged cations The index used in the present invention is the amount of organic cations coordinated between layers through ion-exchange reactions (JIS
The total carbon content was measured according to the Strelein carbon determination method (G1211), and the molar ratio was calculated by calculating the amount of organic cations. (2) Average particle diameter by sedimentation method 50% average particle diameter measured by a light transmission particle size distribution analyzer. (3) Rotational viscosity Using a rotational viscometer, the rotational viscosity was measured at pH 9, water temperature 20°C, and shear rate 7.2/sec. (4) Stability The layer separation of a suspension of a 3% by weight sol was observed after it was left to stand for 48 hours. Those with no layer separation were evaluated as good, and those with layer separation were evaluated as poor. (5) Fluidity This is an observation of the spreadability when a 5% by weight sol is spread on a glass surface.Those that spread evenly and form a uniform film are considered good, and those that spread evenly and form a uniform film are considered good. Those that occur were considered defective. (6) Strength and elongation of film Strength and elongation as used in the present invention refer to breaking strength and elongation when tensile, and are based on JIS-Z-1702.
Measurement was performed at 25°C and 65% RH using an Instron type tensile tester according to the method specified in . (7) Toughness (P) In order to quantitatively express toughness, it is defined by the following formula, and the larger P is, the better the toughness is. P=1/2×A×B Here, A is the strength of the film (Kg/mm ² ), B
is the elongation (%). In addition, when P was 10 or more, the toughness was determined to be good, and when it was less than 10, the toughness was determined to be poor. (8) Flexibility After repeating the operation of bending a film with a length of 150 mm and a width of 10 mm in half 180 degrees along the longitudinal direction 20 times, observe the film. If there is no change, the flexibility is good. If there is a crack or breaks at the bent part, the flexibility is judged to be poor. (9) Heat resistance A capacitor element is made by layering a 15 mm thick film as a dielectric layer, layering 6 mm aluminum foil, and wrapping two sets of this so that the total area of the dielectric layer is 10,000 mm ² . A DC voltage is applied to this in air at a rate of 100 V/sec, and the voltage at which the capacitor breaks down is defined as the dielectric breakdown voltage. This measurement was carried out at 25℃.
Performed at 0%RH and 400℃, 0%RH. 400
When the dielectric breakdown voltage value at °C was 80% or more of the value at 25 °C, the heat resistance was determined to be good, and when it was less than 80%, the heat resistance was determined to be poor. (10) Moisture resistance The above dielectric breakdown voltage was measured at 25℃, 0%RH.
If the dielectric breakdown voltage value at 80%RH is 80% or more of the value at 0%RH, the moisture resistance is good; if it is less than 80%, the moisture resistance is poor. It was determined that (11) Tear strength 25
The tear propagation resistance of the film was measured at ℃ and 65%RH. When the tear propagation resistance was 100 g/mm or more, the tear strength was determined to be good, and when it was less than 100 g/mm, the tear strength was determined to be poor. (12) Adhesion The laminated film was placed in a gear oven at 250℃.
After processing for 30 minutes, apply cellophane tape to the organic/inorganic composite film and quickly peel it off. If the peeling rate of the organic/inorganic composite layer is less than 10% of the total area of the cellophane tape, the adhesiveness is good; if the peeling rate is 10% or more, the adhesiveness is good.
It was determined to be defective. (13) Film density index The value obtained by dividing the film density measured at 25°C by the density gradient tube method by the particle density of the raw material is the film density index. The particle density of the raw material was measured using the pycnometer method. (14) Crystal size Calculated using Scherrer's formula from the half-width of the diffraction peak at 2θ = 6° by wide-angle X-ray diffraction (reflection) method. The measurement was performed at 35KV and 15mA, and the slit system used was DS, SS = 1/6°, and RS = 0.3mm. (15) Ion index Product of ion valence Q and ion radius γ (Q×
It is an index defined by
The value of 11・175 (1795) (Maruzen) was used. (16) Temperature at 5% weight loss The thermal weight loss curve was measured in an air atmosphere using a thermogravimetric analyzer, and the temperature at which the weight loss rate reached the initial 5% was defined as the temperature at 5% weight loss. The temperature increase rate was 10°C/min. According to the present invention, the following excellent effects can be obtained. (1) The sol has excellent stability, fluidity, and particle uniformity, as well as excellent electrodeposition and miscibility with other solvents. (2) The film has excellent toughness and flexibility as well as excellent heat resistance.
(3) The film exhibits excellent moisture resistance. (4) The laminated film has strong tear strength and excellent adhesive properties, and also exhibits excellent heat resistance. Utilizing the above-mentioned excellent properties, the films and laminated films of the present invention can be applied to all the applications for which paper and plastic films were conventionally used, such as electrical insulation, dielectric materials for capacitors, and construction applications. It is particularly suitable for use in electrically insulating capacitors. Example 1 Starting material sodium taeniolite [Na _0.9
Mg _1.9 Li _0.9 (Si ₄ O ₁₀ ) F _2.3 ] 100g, 0.25 mol/
An organic-inorganic composite was produced by immersing the sample in 200 ml of a hydrochloric acid solution of n-butylamine for 30 minutes. Next, after washing several times with distilled water and allowing it to swell sufficiently, it is uniformly dispersed using a homogenizer (rotation speed 10,000 rpm), coarse particles are removed using a 325 mesh sieve, and then centrifugal separator (rotation speed 10000 rpm) is used to remove coarse particles. 3000 rpm) to obtain the upper layer as a sol. The coordination index of organic cations between the layers of this sol was 0.6, the rotational viscosity was 26 c.p., and the average sedimentation particle diameter was 0.3 μm. As shown in Table 1, this sol had good stability and fluidity. However, even if the starting material sodium taeniolite is the same as that of the present invention, the index n rotational viscosity of the sol and the average particle diameter of the sedimentation method are outside the scope of the present invention (Comparative Examples 1 to 5), as shown in Table 1. As expected, stability and fluidity were poor. In addition, when the starting material is outside the scope of the present invention (Comparative Examples 6 to 8), as shown in Table 1, a sol that has both stability and fluidity can be obtained even if the exponential rotational viscosity and average particle diameter of the sedimentation method are modified. I couldn't get it.

【table】

[Table] Example 2 (Comparative Examples 9 to 18) The concentration of the inorganic/organic composite sol obtained in Example 1 was adjusted to 3 Wt%. This sol was cast onto a glass plate to a uniform thickness of 1 mm, and dried at room temperature for 24 hours, then in a gear oven at 70°C for 1 hour and at 120°C for 1 hour. Thereafter, the film formed on the glass plate was peeled off to obtain a film with a thickness of 15 μm. This film had a density index of 0.61 and a crystal size of 240 Å. As shown in Table 2, this film had good toughness and flexibility as well as good heat resistance. However, even if the type of inorganic/organic composite is the same as that of the present invention, the thickness of the film
When the density index and crystal size were outside the scope of the present invention (Comparative Examples 9 to 14), as shown in Table 2, no film was obtained that had both toughness, flexibility, and heat resistance. In addition, when the inorganic/organic composite is outside the scope of the present invention (Comparative Examples 15 to 18), even if the thickness, density, and crystal size of the film are modified as shown in the table, the toughness, flexibility, A film having both heat resistance could not be obtained.

【table】

[Table] Example 3 (Comparative Examples 19-20) The inorganic/organic composite film of Example 2 was immersed in a barium chloride saturated solution for 96 hours, and then immersed in a water stream for 20 hours.
After washing with water for a minute, heat to 100℃ using a gear oven.
The film was dried for 2 hours at 170° C. and for 3 hours at 170° C. to produce a film in which the interlayer ions of the inorganic/organic composite of Example 2 were replaced with barium (Ba ²⁺ ). As shown in Table 3, this film had toughness, flexibility, and heat resistance, as well as excellent moisture resistance. However, when the interlayer ions of the inorganic-organic composite were exchanged with ions other than those of the present invention (Comparative Examples 19 and 20), films with excellent moisture resistance as shown in the table could not be obtained. Example 4 (Comparative Examples 21 to 23) The sol of the inorganic/organic composite used in Example 2 was previously subjected to corona discharge treatment (in air) to a thickness of 2 μm.
24 hours at room temperature, then dried in a gear oven at 70°C for 1 hour and at 120°C for 1 hour to adjust the lamination thickness ratio of polyimide and inorganic/organic composite. I made a laminated film of 0.13. This laminated film had excellent heat resistance and adhesion, and also exhibited excellent tear strength. However, with laminated films other than those of the present invention, it was not possible to obtain a film that had all of the heat resistance, adhesiveness, and tear strength as shown in Table 4.

【table】

【table】

Claims (1)

[Claims] 1. Chemical composition: X _0.3-1.0 Y _2.5-3.0 (Z _3.5-4.5 O ₁₀ )
F _{1.5 ~ 3.0} [X is an interlayer ion exchange organic cation,
It is at least one kind selected from alkyl amines, amino alcohols, or amino acids, and is an organic cation having 3 to 7 carbon atoms and 1 nitrogen; Y is an octahedral ion; (Mg _{1.5 to 2.5}
Li _0~1 ) or a part of its Mg ²⁺ as Fe ²⁺ , Ni ²⁺ ,
Substituted with at least one ion selected from Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Z is an ion at a tetrahedral position, and Si ⁴ or Ge ⁴⁺ or a part thereof is substituted with
At least one selected from Al ³⁺ , Fe ³⁺ , B ³⁺
A sol consisting of a limited swelling type fluorinated mica organic composite represented by
An inorganic/organic composite sol with a rotational viscosity of 0.1 to 15 μm and a rotational viscosity of 10 centipoise or more. 2. Claim 1, wherein the interlayer ions of the limited swelling type fluorine-mica organic composite of the sol are ion-exchanged with inorganic cations having an ionic index (product of ion valence and ionic radius) of 1.25 or more. Sols of inorganic/organic composites described in section. 3 Chemical composition is X _0.3~1.0 Y _2.5~3.0 (Z _3.5~4.5 O ₁₀ )
F _{1.5 ~ 3.0} [X is an interlayer ion exchange organic cation,
It is at least one kind selected from alkyl amines, amino alcohols, or amino acids, and is an organic cation having 3 to 7 carbon atoms and 1 nitrogen; Y is an octahedral ion; (Mg _{1.5 to 2.5}
Li _0~1 ) or a part of its Mg ²⁺ as Fe ²⁺ , Ni ²⁺ ,
Substituted with at least one ion selected from Mn ²⁺ , Al ³⁺ , Fe ³⁺ , Z is an ion at a tetrahedral position, and Si ⁴ or Ge ⁴⁺ or a part thereof is substituted with
At least one selected from Al ³⁺ , Fe ³⁺ , B ³⁺
A film consisting of a limited swelling type fluorinated mica organic composite represented by [substituted with species ions], the film having a thickness of 1 to 100 μm,
An inorganic/organic composite film characterized in that the density index of the film is 0.43 to 0.85, and the crystal size of the inorganic/organic composite in the film is 150 to 300 Å. 4. The inorganic-organic composite according to claim 3, wherein interlayer ions of the limited swelling type fluorine-mica organic composite in the film are ion-exchanged with inorganic cations having an ionic index of 1.25 or more. film. 5 A film in which an organic polymer film with a temperature at 5% weight loss of 400°C or higher is laminated on at least one side of an inorganic/organic composite film, and the lamination thickness of the organic polymer film and the inorganic/organic composite film is The laminated film according to claim 3 or 4, characterized in that the thickness ratio is in the range of 0.01 to 0.2.