CN101374766A - Clay film and method for producing same - Google Patents

Abstract

Disclosed is a transparent clay film wherein a clay and an additive are uniformly dispersed and the haze value hardly increases over time even when the film is left in the air. In addition, the transparent clay film hardly suffers from defects such as breakage and cracking. Also disclosed is a method for producing such a transparent clay film. Specifically, a clay dispersion is obtained by mixing a synthetic saponite as the clay and water as the solvent. Meanwhile, an additive-containing solution is obtained by mixing sodium polyacrylate as the additive and water as the solvent. Then, a uniform clay-containing solution is obtained by mixing the clay dispersion and the additive-containing solution. After that, the clay-containing solution is deaerated in vacuum, and the deaerated clay-containing solution is applied over a flat portion of the surface of a polypropylene tray. After drying, a thus-formed clay film is separated from the tray.

Description

Clay membrane and manufacture method thereof

Technical field

The present invention relates to a kind of clay membrane and manufacture method thereof.Also relate to Electronic Paper (Electricity ペ-パ-), substrate and choke film that at least a portion is made of clay membrane.

Background technology

Generally, in most chemical industrial field, using the various production processes under the hot conditions.In pipeline linking part of these production lines etc., take for example to wait the countermeasure of the leakage that prevents liquid or gas by sealing member or welding.So far, flexible good sealing member is to use for example organic polymer material or asbestos etc. to make.Yet when using organic polymer material, the teflon that its thermotolerance is the highest (registered trademark) is about 250 ℃, and its above temperature just must be used metal sealing member., metal sealing member is compared with the occasion of using organic polymer material, and is flexible inferior, and existing has powerful aggressive problem to the mask relative with sealing member.Again, though it is good to contain the material thermotolerance and the resistance of asbestos, problem is that asbestos are big to the toxicity of human body, wishes to develop as early as possible equivalent material.

On the other hand, in recent years, be that the manufacturing technology of the flat-panel monitor (following note is made FPD) of representative is developed by leaps and bounds with the liquid-crystal display, the slim indicating meter that how also can't finish with former Braun tube becomes a reality.Present FPD forms device on glass substrate, do not have the FPD of the practicality of using the substrate except that glass substrate.As reason, it is high heat resistance that glass substrate is arranged for example, is suitable for forming the driving loop or the member of the indicating meter that needs high temperature formation; Linear expansivity is little, can suppress the stress to these driving loops or member, and the fracture of distribution or the characteristics fluctuation of component are less; Because in the visible region is transparent, so obtain light easily; And the gas barrier property height, can be used as prevention and use from the oxygen of outside and the gas-barrier material that enters of water vapour, can keep high vacuum etc. as required.

, glass substrate does not have flexibility, breaks easily.Again, there is the problem of base plate deformation or difficult treatment in Heavy Weight.Again, glass substrate can not be used to imagine the such elasticity indicating meter of flexible Electronic Paper with purposes that bending moves etc., because also have following shortcoming, promptly impacted and break easily, device damages easily when falling, so less be appropriate to mobile purposes.From such viewpoint, wish to have the substrate that the indicating meter of the thermotolerance equal with glass, linear expansivity, the transparency, gas barrier property etc. uses or the practicability of choke film.

Again, about the loop substrate of the electronic component that install to constitute the so electrified goods of indicating meter, mobile phone terminal, computer, the requirement of the densification that component are installed improves.Again, because the requirement of mobile phone terminal representative is rotated and the increase of the electrified goods of distortion, so the requirement of elastification is also improved.Therefore, the demand of elasticity loop substrate or copper-clad laminate and requirement also increase.

As the elasticity loop substrate, use now by the substrate of the resin formation of polyethylene terephthalate, polycarbonate, poly-imines etc., special glass epoxy substrate.Yet, use the such conductive ink of electroconductibility slurry, make when adopting printing or coating to form the printed base plate of loop distribution, in order to obtain the distribution of fully high specific conductivity, behind the coating conductive ink, generally need calcine at the high temperature more than 300 ℃, when being to use the elasticity loop substrate by the substrate of aforesaid resin formation, because the thermotolerance of resin is low, linear expansivity is also generally bigger, so can not carry out above-mentioned high-temperature calcination, must under lower temperature, carry out.

Yet,,, generally have the inferior such problem of conductivity so compare with tinsel or with the distribution that vacuum evaporation obtains because the sintering of conductive ink can not carry out fully at low temperatures.Poly-imide resin has than higher thermotolerance, but because high price, so be difficult to use in RFID (Radio frequency identification) the such purposes of paying attention to cost most of label.From such viewpoint, wish both to have had insulativity and had high heat resistance and the practicability of the elasticity printed base plate of the cheapness of flame retardancy.

On the other hand, clay is present in occurring in nature in large quantities, is the mineral with cheapness, harmless, the feature of not firing etc.Though viewed umbrinaceous " ashen " most of impurity by organism or iron etc. causes in the most natural clay, also can not contained the colourless clay of these impurity by chemosynthesis again.Clay mineral is roughly divided into crystalline mineral and amorphous mineral, and crystalline partly is to mean all be the phyllosilicate of " lobate ", because it becomes the foliate shape, so have lamellated structure basically.That is, the mineral that are commonly referred to as layered silicate are included in the category of the mineral that are defined as clay.Most clay is made of the big laminar layered inorganic compound of aspect ratio of the size with the long axis direction about tens of nm～5 μ m, this laminar layered inorganic compound by 1～3 layer be that tetrahedron thin slice that the center was constituted, the about 0.2nm to 0.5nm of thickness or octahedra tab laminate form with oxygen (O), silicon (Si), aluminium (Al).

Tetrahedron thin slice in such layered silicate or octahedra thin slice are described in more detail.4 O of the last coordination of Si form SiO ₄Tetrahedron, this tetrahedron has its 3 O, connects into the netted of hexagonal, thereby forms the tetrahedron thin slice.According to circumstances, also replace Si to form AlO sometimes with Al ₄Tetrahedron.In addition, iron (Fe) etc. also forms tetrahedron sometimes.And octahedra thin slice 6 hydroxyls of coordination (OH) or O and form on Al also use magnesium (Mg) or Fe etc. to replace Al to form sometimes.Again, because Si is replaced as Al etc. in the tetrahedron thin slice, perhaps Al is replaced as Mg etc. in octahedra thin slice, so the charge generation of thin slice is too not enough, thin slice carries permanent charge sometimes.Also carry out following trial, can and import element outside above-mentioned, the various rerum naturas of magnetic properties or optical characteristics etc. are changed toward the control of tetrahedron thin slice or octahedra thin slice artificially.

By such thin slice, perhaps by lamination in conjunction with these thin slices, generate various layered inorganic compounds.In the present invention, this thin slice bonded unit layer is defined as the clay crystallization.For example, as by being the material that the clay crystallization of unit layer constitutes with the tetrahedron thin slice only, can give an example generally is called a series of mineral (as magadiite) of the poly-silicic acid of stratiform.And known between the octahedra thin slice of positively charged and octahedra thin slice, having the negative ion of carbonate etc., form the clay mineral that is called the hydrotalcite class.

Generally be called kaolin mineral with 1:1 in conjunction with the clay crystalline clay mineral that lamination forms as the unit layer of mineral by tetrahedron thin slice and octahedra thin slice, famous is kaolinite, halloysite.And in conjunction with the clay crystalline clay mineral that lamination (being tetrahedron thin slice-octahedra thin slice-tetrahedron thin slice) forms as unit layer pyrophyllite, talcum, montmorillonite family clay, vermiculite, mica clay mineral etc. are arranged with 2:1 by tetrahedron thin slice and octahedra thin slice.It is said, especially the clay (for example polynite, saponite, hectorite, rich magnesium montmorillonite etc.) that belongs to montmorillonite family is the situation that has the general material of inorganic cation between two-layer, can be dispersed in equably in the so high polar solvent of water or alcohol (especially water), even be considered to be dispersed in (for example with reference to non-patent literature 1) in the high polar solvent in 11 ground of unit layer scattered here and therely.

As above-mentioned such clay utilize one of method, carry out extensive studies for the nano composite material of in resin, adding the clay of a small amount of (generally below about 5 quality %), a part is at practicability (for example, with reference to non-patent literature 2).Add in the series of nano composite material material of small amount of clay at these, can confirm the raising effect of intensity or flame retardant resistance or the raising effect of gas barrier property.

Yet, in these nano composite materials,, do not improve gas barrier property or flame retardant resistance in essence significantly because the ratio of clay is few.For example, if try to get gas barrier property,, also there is the transmitance of gas to become example about part, but almost do not have gas barrier property to improve the above example of one digit number then by adding clay.Again, the mobile route of the gas when prolonging gas permeation and improve the purpose of gas barrier property, great majority use the big natural montmorillonite of crystallizations or synthetic mica but this situation, because the major cause of the scattering of light that the yellow coloring that natural montmorillonite causes or the size of synthetic mica cause etc. is difficult to obtain little, the colourless and transparent high films of all spendable mist (turbidity) such as indicating meter.Equally, the addition of clay after a little while, be difficult to improve other rerum naturas, the dimensional stability when for example improving thermotolerance or temperature variation significantly except that gas barrier property, the characteristic of the essence of the clay of hardly high heat-resisting and excellent size stability is fully utilized.

We think, make closely and the to heavens nano composite material body of orientation of clay crystalline layer in order to improve gas barrier property and to suppress scattering of light and improve the transparency, importantly forming.Thus, dimensional stability is improved.In the past, known for example by Dispersion of Clay liquid is spread out on the sheet glass, standing and drying formed the consistent film of particulate orientation, formed by this film, adjusted the orientation sample (with reference to non-patent literature 3) of X-ray diffraction method.Use the making (for example with reference to non-patent literature 4) of the clay thin film of Langmuir-Blodgett method again., in the method, clay thin film is to form on the substrate surface of being made by the material of glass etc., is not the clay thin film that has as independent film strength.

Again, in the past, relevant for the various reports of the inflation method of functional clay thin film etc.For example, existing hydrotalcite is to carry out drying after membranaceousization of aqueous dispersions of intercalation compound and the manufacture method (referring to Patent Document 1) of the transparent clay membrane that constitutes; A kind of manufacture method of layered clay mineral film (referring to Patent Document 2), this manufacture method is utilized the reaction between layered clay mineral and phosphoric acid or the phosphate, by implementing to promote the thermal treatment of this reaction, the integrated structure orientation that layered clay mineral is had is fixing; A kind of montmorillonite that contains is that the epithelium of the complex compound of the above metal of clay mineral and divalent is handled use composition (referring to Patent Document 3); And other example., the membranaceous clay form thing in these existing documents all forms on some support, is not the clay alignment films that the lamination that has the physical strength that can be used as the independent film utilization, make clay particle is orientated to heavens.

Again, as the transparent film that uses clay, have will synthetic saponite or the aqueous dispersions of synthetic li-montmorillonite be coated on the film as the example of the phasic difference film of liquid-crystal display etc.This transparent film is bigger poor by the specific refractory power between direction and the sheet thickness direction in the clay crystalline sheet plane that effectively utilizes synthetic saponite or synthetic li-montmorillonite and have, is endowed the phasic difference of advancing with respect to light.In such transparent film, also some is peeled off the clay membrane that is formed on the support and obtains (referring to Patent Document 4).

; peeling off the clay membrane that obtains of patent documentation 4 records from support; unique amount that is inferred to be the clay that is contained in the clay membrane with the physical strength that can be used as the independent film utilization is approximately 47 quality %, and the additive by polymkeric substance etc. over half constitutes.Therefore, be film hardly based on clay, deduction gas barrier properties etc. are not enough.Again, form thick film if increase the amount of clay, then, lost the suitability of the phasic difference film of using as liquid-crystal display because the phasic difference between interior direction of the face of film and the thickness direction is excessive, so when making has the such thick film of independence, must have to reduce the ratio of clay.

Also developed a kind of that constitute by transparent poly-imines and hydrophobicity clay, high strength and have water-proof transparent clay film again.Thereby the mineral ion that this hydrophobicity clay is the hydrophilic clay that will be dispersed in the montmorillonite family in the water to have is exchanged for the hydrophobicity clay that organic ammonium salt etc. improves the dispersiveness in organic solvent.This clay membrane is different with the clay membrane that above-mentioned patent documentation 4 is put down in writing, and also can not dissolve even meet water.

Yet, patent documentation 5 put down in writing if the content of clay less than 20 quality %, part clay cohesion in manufacturing process.Mist increases as a result, and becoming is transparent state (the mist value is more than 50%) hardly, demonstrates toughness simultaneously and significantly descends.That is, these are the equal materials of nano composite material with former interpolation small amount of clay, are by being the film that main body improves gas barrier property or dimensional stability significantly with the clay hardly.

Under such situation, the inventor about make clay crystalline layer closely and to heavens the making of the clay alignment films of orientation carried out various trials, in this process, find that the clay membrane clay particle orientation, that have the intensity of the independent film of can be used as use can obtain by method as described below.Promptly, this method is to adjust clay dispersion, obtain the dispersion liquid of homogeneous, level leaves standstill this dispersion liquid, make clay particle deposition, use various solid-liquid separating method (for example centrifugation, filtration, vacuum-drying, freeze vacuum-drying or heating vaporization) to separate simultaneously, form membranaceous as the liquid of dispersion agent, then, it is peeled off (referring to Patent Document 6) from support.

Again, find not have only clay, in clay dispersion, add the argillaceous liquid of minor amounts of additives, can improve the flexibility or the intensity (referring to Patent Document 7) of clay membrane by use; By using the clay slip of the solid ratio that improves argillaceous liquid, can make clay membrane (referring to Patent Document 8) at short notice; Also have by using synthesis of clay, can make transparent clay membrane in the visible region based on the non-coloring of clay.

And, affirmation is based on clay and make closely and the to heavens clay membrane of orientation of clay crystalline layer, few the comparing of ratio with former clay, possess jointly and be characterised in that, (1) has high heat resistance, (2) inorganic gas to oxygen or hydrogen etc. has high gas barrier property, (3) pore-free in the film, (4) has flexibility, (5) have resistance, (6) linear expansivity is low, and (7) have flame retardant resistance, (8) have insulativity, find to be suitable for use in the material that constitutes above-mentioned sealing member or aforementioned display device purposes with the electronic material of member, elasticity loop substrate etc.

Yet, in the former method, mix, sometimes because the cohesion of additive clay if in clay dispersion, add additive.Perhaps, the viscosity of clay dispersion rises rapidly and is dispersed in the clay dispersion with making the additive heterogeneity sometimes, produces inhomogenous aggregate in clay dispersion, perhaps also sometimes clay condense and separate out particulate state, the clay membrane heterogeneity that obtains.Sometimes make the clay solvability in the dispersive dispersion solvent or dispersed when low aptly when additive, additive is insufficient too to be disperseed equably, produces and above-mentioned similar problem.The result, in transparent clay membrane, the interior spot that produces of the area surface that the transparency is low, perhaps be condensed into granular clay or additive and make scattering of light, the problem of generation mist increase etc., even so want that the kind of additive or addition are also restricted sometimes by adding the rerum natura of additive raising clay membrane.

In addition, we know if clay crystalline layer closely and to heavens is orientated by the ratio that increases the clay membrane medium clay soil always, then be difficult to remove gaseous constituent remaining in the clay membrane from clay membranes.That is, sneak into bubble (space) that the gaseous constituent of argillaceous liquid causes when being included in the clay membrane, have following problem, heating even rapidly, then bubble rapid expansion and produce circular expansion on the surface of clay membrane is destroyed clay membrane; Perhaps the space becomes the reason of the scattering-in of light in transparent clay membrane, and clay membrane is fuzzy, and mist increases.

We consider, owing to remain in gaseous constituent in the clay membrane from the gaseous constituent that comprises in the argillaceous liquid, so importantly after the gaseous constituent in removing argillaceous liquid fully, form membranaceously on support, carry out drying and obtain clay membrane.Especially, when making the big clay membrane of the ratio of clay, promptly when the ratio of clay dispersion medium clay soil is big,,, be difficult to remove these gaseous constituents so the flowability of clay dispersion descends owing to manifest viscosity or the thixotropy that clay causes significantly.Therefore, making the gaseous constituent minimizing in the argillaceous liquid is important problem for making the big clay membrane of clay ratio, requires its effective gimmick of exploitation.

Again, as the method that makes clay particles disperse in solvent, the general method of vibrating with diverting device etc. of using is especially divided under the high situation of concentration solid formation, need vibrate for a long time with diverting device.Again, owing to be subjected to the concentration of clay dispersion of the fluidity boundary constraint of clay that the upper limit is generally arranged, so be difficult to the solid formation branch concentration of clay dispersion is brought up to more than the value that the fluidity boundary sets.

Again, the former transparent clay membrane that is made of clay and additive is if be placed in the atmosphere for a long time, and then mist increases sometimes, and clay membrane is fuzzy, and the transparency descends.This mist increase to be to be produced owing to the surface of clay membrane uneven increases with the passing of time with the passing of time.

Also carried out such discussion, promptly, improves mist the transparency of clay membrane for being descended, the surface ground make its smoothing, form the layer that is different from the such clay of transparent resin and form clay membrane etc., because smoothing need be carried out with nano level precision, and have problem of clay film strength and weather resistance etc., so physical grinding is difficult.Again, produce following problem sometimes: because the above-mentioned heat resisting temperature that gives layer is low, so the thermotolerance of clay membrane declines to a great extent, perhaps because different with respect to the linear expansivity of temperature variation and clay membrane, so the film warpage is perhaps because stress produces defective etc. on the clay membrane.Like this, it is many to form in the method for the layer that is different from the such clay of resin the problem that exists.

Again, by easy and be the heating vaporization of general gimmick, remove and to desolvate when making clay membrane, owing to solidify and produce volumetric shrinkage in the exsiccant process, so the stress of following above-mentioned volumetric shrinkage is on clay membrane at evaporation, clay dispersion along with solvent.Therefore, there is following problem: when the clay film strength can not be born this stress, produce the crack at drying process medium clay soil film sometimes.

Therefore, problem of the present invention is to provide a kind of clay membrane and manufacture method thereof, and this clay membrane has solved the problem points that aforesaid technology in the past exists, and clay and additive disperse equably, be not easy to crack, the defective in crack etc., have the intensity that the independent film of can be used as is utilized.Again, and, even simultaneously problem is also to provide that a kind of transmittance height and mist are little is placed on that mist in the atmosphere also is difficult in time and the transparent clay membrane and the manufacture method thereof that increase.Again, problem also is to provide in the lump Electronic Paper substrate and the choke film that possesses such clay membrane.

Patent documentation 1: Japan's patent disclosure communique is put down into 6 years No. 95290

Patent documentation 2: Japan's patent disclosure communique is put down into 5 years No. 254824

Patent documentation 3: Japan's patent disclosure communique 2002 No. 30255

Patent documentation 4: No. the 3060744th, Japan's patent gazette

Patent documentation 5: Japan's patent disclosure communique 2006 No. 37079

Patent documentation 6: Japan's patent disclosure communique 2005 No. 104133

Patent documentation 7: Japan's patent disclosure communique 2005 No. 313604

Patent documentation 8: Japan's patent disclosure communique 2006 No. 265088

Non-patent literature 1: must compile " clay science ヘ reception-clay by the rattan klatch

Face と glamour-(to the true qualities and the glamour of the invitation-clay of clay science) ", Japan, three publish p.6 (2000) altogether

Non-patent literature 2: the clear volume of discal patch, " Port リ マ-

ノ コ Application Port ジ ッ ト System Pin development (product development of polymer system nano composite material) ", Japan, publish in the border, and p.25～90 (2004)

Non-patent literature 3: the fine hero of plain boiled water, " Nian Tu Mining thing-clay Ke Ji Foundation-(basis of clay mineralogy-clay science-) ", and Japan, towards storehouse bookstore, p.57 (1988)

Non-patent literature 4: Mei Zetaishi, " clay science ", Japan, the 42nd volume, No. 4,218～222 (2003)

Summary of the invention

In order to solve described problem, the present invention by following constitute form.Promptly, the manufacture method of clay membrane of the present invention, it is characterized in that, have: argillaceous liquid is adjusted operation, respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, described clay dispersion and the described additive liquid that contains are mixed, make the described additive in the total amount of described clay and described additive ratio for surpass 0 quality %, below the 50 quality %, thereby obtain argillaceous liquid; Drying process is configured in the surface of support with this argillaceous liquid, removes described solvent then, carries out drying.

Again, the manufacture method of clay membrane of the present invention, it is characterized in that, have: argillaceous liquid is adjusted operation, modulate respectively clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, described clay dispersion and the described additive liquid that contains are mixed, make the described additive in the total amount of described clay and described additive ratio for surpass 0 quality %, below the 30 quality %, thereby obtain argillaceous liquid; Drying process is configured in the surface of support with this argillaceous liquid, then, removes described solvent, carries out drying.

In the manufacture method of such clay membrane of the present invention, it is desirable to have the degassing process that gas that described argillaceous liquid contained is reduced.Also have, also can have the stripping process that the dry thing that obtains by described drying process is peeled off from described support.

Again, adjust in the operation, it is desirable under the temperature higher, described clay dispersion and the described additive liquid that contains are mixed, obtain described argillaceous liquid than normal temperature at described argillaceous liquid.

Further, it is desirable to described argillaceous liquid is located at than placing under the high temperature of normal temperature and under reduced pressure, the gas that described argillaceous liquid is contained reduces, better is by stirring described argillaceous liquid under temperature higher than normal temperature and decompression, the gas minimizing that described argillaceous liquid is contained.

Further, in the manufacture method of clay membrane of the present invention, described support can have flexibility, in this case, after it is desirable to carry out drying under the deformable state of described support, described dry thing is peeled off from described support.Described support can be the resin type film.Again, can peel off facilitation to described support and handle, also can carry out hydrophobic processing treatment.

Further, the manufacture method of clay membrane of the present invention is that the surface configuration at the dry thing that obtains by described drying process makes the liquid of described clay swelling or makes described additive dissolving or dispersive liquid, also can have to make it exsiccant drying process more again.At this moment, can at the described liquid of the surface configuration of described dry thing, also can pass through the described liquid of spraying, by being immersed in the described liquid at the described liquid of the surface configuration of described dry thing.

Further, in described drying process again, the described dry thing by make near surface part swelling at least at the described liquid of surface configuration is contacted with the level and smooth member of surface smoothing, after its surface smoothingization, carry out again dry described liquid.This level and smooth member can be to have flexibility and deformable member, in this case, it is desirable to carry out dry to described liquid under described dry thing and described level and smooth member state of contact again.

Further, in the manufacture method of clay membrane of the present invention, it is desirable to described clay and be for water the affinity height, be dispersed in hydrophilic clay in the water easily.Again, described clay can be to organic solvent the affinity height, be dispersed in hydrophobicity clay in the organic solvent easily.It is the situation of hydrophobicity clay, it is desirable to be exchanged into organic ion and make, it is desirable to described organic ion and contain at least a in ammonium ion, phosphorus (Off オ ス Off オ ニ ウ system) ion, the imidazol ion the affinity of organic solvent and the dispersed hydrophobicity clay that improves by the mineral ion that hydrophilic clay is had.

Further, in the manufacture method of clay membrane of the present invention, the clay membrane that obtains can be transparent.

Further, clay membrane of the present invention is characterised in that, is a kind of clay membrane of manufacture method manufacturing of aforesaid clay membrane of the present invention, and lamellated clay crystallization lamination on film thickness direction forms.And, it is desirable to from 30 ℃ to 250 ℃ average coefficient of linear expansion below 10ppm.

Again, it is desirable to, the mist of clay membrane of the present invention is below 5%, and total light transmittance is more than 85% simultaneously, and the transmittance in the wavelength region more than 400nm, below the 800nm is more than 85%, below 95%.About mist, better is mist further it is desirable to mist less than 1% below 2%.Further, the mist under 24 ℃, the environment of 1 air pressure, humidity 45% lasts variation more than-2%, below 2%.Further, it is thick to it is desirable to the Film Thickness Ratio 15 μ m of clay membrane of the present invention.

Further, Electronic Paper of the present invention is characterised in that its at least a portion is to be made of the clay membrane of the manufacture method manufacturing of aforesaid clay membrane of the present invention or aforesaid clay membrane of the present invention.

Further, elastic base plate of the present invention is characterised in that its at least a portion is to be made of the clay membrane of the manufacture method manufacturing of aforesaid clay membrane of the present invention or aforesaid clay membrane of the present invention.

Further, elasticity printed base plate of the present invention is characterised in that its at least a portion is to be made of the clay membrane of the manufacture method manufacturing of aforesaid clay membrane of the present invention or aforesaid clay membrane of the present invention.

Further, substrate of the present invention is characterised in that, be the substrate with gas barrier property that the electronics with non-luminous organic semiconductor or amorphous inorganic semiconductor is installed, its at least a portion is to be made of the clay membrane of the manufacture method manufacturing of aforesaid clay membrane of the present invention or aforesaid clay membrane of the present invention.

Further; choke film of the present invention is characterised in that; be the choke film that has the electronics of non-luminous organic semiconductor or amorphous inorganic semiconductor from gas aspect protection, its at least a portion is that clay membrane or the aforesaid clay membrane of the present invention that the manufacture method by aforesaid clay membrane of the present invention obtains constitutes.

Description of drawings

Fig. 1 is the figure of the ultraviolet-visible absorption spectroscopy of expression clay membrane;

Fig. 2 is the X-ray diffraction spectrographic figure of the transparent clay membrane of expression.

Fig. 3 is the figure of cross sectional photograph of the TEM of the transparent clay membrane of expression;

Fig. 3 is the figure of cross sectional photograph of the SEM of expression clay membrane;

Fig. 5 is the X-ray diffraction spectrographic figure of expression clay membrane.

Fig. 6 is the figure of cross sectional photograph of the TEM of expression clay membrane;

Fig. 7 is the figure of cross sectional photograph of the SEM of expression clay membrane.

Embodiment

Clay membrane of the present invention is the film that is made of clay and additive, but the ratio of the additive in the total amount of clay and additive need surpass 0 quality %, below the 50 quality %, it is desirable to surpass 0 quality %, below the 40 quality %.And, in order to obtain characteristic preferably as clay membrane, the ratio of better is additive surpasses 0 quality %, below the 30 quality %, further it is desirable to above 0 quality %, less than below the 30 quality %, it is desirable to surpass 0 quality % especially, below the 15 quality %, it would be desirable above 0 quality %, below the 10 quality %.

If the ratio of additive is big, the quantitative change that then enters the additive between the unit layer of clay is many and open bigger between the clay crystalline layer, upset clay crystalline orientation further, be subjected to above-mentioned the influence, following various bad situation takes place sometimes, promptly the transparency descends, the stable on heating decline that the thermolysis of additive causes, the decline of the gas barrier property that the gas permeation by additive causes, the increase of the dimensional change amount of the clay membrane that temperature variation causes etc., thus according to rerum natura and with the significant different disappearances of former nano composite material.If the ratio of additive then can obtain the former nano composite material visibly different feature less with the clay ratio (for example, low linear expansion coefficient and high gas barrier property) (if special below 30 quality %) below the 50 quality %.

Generally, by clay will only being contained or containing clay and surface that the argillaceous liquid of additive is configured in support makes it dry, obtain clay membrane.The effect of the additive in the clay membrane is different and varied according to function of wanting to make it to show and purposes, but only obtains can be used as generally difficulty comparatively of intensity that independent film utilizes with clay, so require additive more or less to have the function of the intensity of giving.Clay crystalline average aspect ratio (aspect) for example uses average aspect ratio when the natural montmorillonite more than 300 when big, also can obtain having and can doing even without additive

The clay membrane of the intensity of utilizing for independent film, but the clay membrane that obtains is crisp, the highly desirable additive that is to use.In the present invention, the most important effect of additive is to improve the clay film strength.

Therefore, if increase the ratio of the additive (for example polymkeric substance and polymerizable monomer) with the effect that improves intensity, then the clay film strength also improves usually.We infer: the situation that the ratio of additive was big as former nano composite material body (surpassing 50 quality %), if do not consider the key element of the clay crystalline orientation of a part, the embedding (inserting desired substance) of additive, degree of advancing and the dispersive degree that clay crystalline layer is peeled off, the removal of sneaking into the gaseous constituent in the argillaceous liquid etc. at clay crystalline interlayer, effect that gives intensity that causes by additive etc., having can be from the intensity of support extent of exfoliation or certain transparency.

; when making the big clay membrane of clay ratio; especially in the clay ratio when 70 quality % are above; because with the method clay known in the past with additive is insufficient is dispersed in equably in the argillaceous liquid; the gaseous constituent of perhaps sneaking in the argillaceous liquid can not fully be removed, so the clay membrane heterogeneity that obtains sometimes.The result is the physical strength and the flexible deficiency of clay membrane sometimes.Again, the concentration of dividing owing to the solid formation in the input of additive or the clay dispersion increases and produces cohesion, transparent deficiency in transparent clay membrane sometimes.Under these circumstances, in order further to improve the transparency, consider to implement to be different from the countermeasure of layer of composition of the clay of surface smoothing layer etc., but probably can produce owing to increase manufacturing process or the above-mentioned layer problem that makes degradation under the thermotolerance that give is set.Even implement such countermeasure, can not avoid being created in the rerum natura that the inhomogenous structure of the inside of clay membrane causes and descend again.

Therefore, the inventor attentively studies in order to solve above-mentioned such issue, found that the suitableeest manufacture method that can access the clay membrane that is dispersed with clay and additive equably.Promptly, the manufacture method of clay membrane of the present invention, it is characterized in that, have: (a) argillaceous liquid is adjusted operation, respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, above-mentioned clay dispersion and the above-mentioned additive liquid that contains are mixed, make that the ratio of the above-mentioned additive in the total amount of above-mentioned clay and above-mentioned additive surpasses 0 quality %, below the 50 quality %, thereby obtain argillaceous liquid; (b) drying process is configured in the surface of support with this argillaceous liquid, then, removes above-mentioned solvent, carries out drying.

By suitably selecting the kind of clay and additive, can make the clay membrane that obtains transparent again.In addition, the transparent meaning among the present invention be total light transmittance more than 70%, mist is below 5%, the transmittance in the wavelength region more than 400nm, below the 800nm is more than 75%, below 95%.Yet this transparency is a bottom line, it is desirable to total light transmittance more than 80%, and better is more than 85%, and better is more than 88%.Again, the value of mist it is desirable to below 3%, and better is below 2%, and better is less than 1%.Again, the transmittance in the wavelength region more than 400nm, below the 800nm it is desirable to more than 80%, below 95%, and better is more than 85%, below 95%.Said here in addition total light transmittance and mist are that the method JIS K 7136 that asks according to the mist of the optical test method JIS K 7105 of the test method JIS K 7361 of the total light transmittance of the plastic transparent material of JIS regulation, plastics, plastic transparent material tries to achieve.

In the past, during such clay membrane of making that manufacture method by clay membrane of the present invention obtains, when 70 quality % are above, also additive directly added to make in the clay dispersion of clay dispersion in solvent and modulated argillaceous liquid in the ratio of clay., in the method, because the solid formation of the clay in the clay dispersion divides concentration high more, then the viscosity of clay dispersion rises more, and thixotropy is remarkable more, and the remarkable more decline of the flowability of clay dispersion is so be difficult to make additive to be dispersed or dissolved in equably in the argillaceous liquid.Especially have when making the situation of additive (for example polyacrylate) of the effect of argillaceous liquid tackify more difficult by interpolation.

And method of the present invention, since respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, mix both and modulate argillaceous liquid, so no matter be to show the additive of tackify effect, dispersiveness in solvent or the low additive of solvability that still clay dispersion is used, all can make it to be dispersed in equably in the argillaceous liquid in process that is dissolved in solvent and dispersion process.Therefore, limit the kind and the addition of spendable additive hardly.Owing under the state that clay and additive are dispersed or dissolved respectively fully, mix, suppress to make the clay cohesion form inhomogenous because of the effect of additive again.

In the method, it is desirable to, be dispersed or dissolved in the solvent, modulate clay dispersion and contain additive liquid by under being higher than the temperature of normal temperature, making clay and additive.Like this, additive is is more dispersed or dissolved to homogeneous and high density.Again, it is desirable to, by obtaining argillaceous liquid being higher than under the temperature of normal temperature the mixed clay dispersion liquid and containing additive liquid.Like this, can modulate the high argillaceous liquid of solid formation branch concentration, and the clay in this argillaceous liquid disperses more equably, additive disperses or dissolves more equably simultaneously.

As the method that clay and additive is dispersed or dissolved in modulate clay dispersion in the solvent and contain additive liquid, following method is arranged for example, method 1 is to add clay or additive in solvent, stirs, vibrates and mix after heating with gimmicks such as well heater, warm wind, water-baths; Method 2 heats with above-mentioned gimmick for the limit, and stir on the limit, vibration, mixes; Method 3 energizes with ultrasonic dispersing device, homogenizer etc. for the limit, makes to contain additive liquid heating itself, and stir on the limit, vibration, mixes.

In the present invention, mixed clay dispersion liquid and when containing additive liquid, mix at normal temperatures and also can, but divide the angle of concentration to consider from the argillaceous liquid of making homogeneous and the solid formation that improves argillaceous liquid, to modulate the such method of argillaceous liquid better being higher than under the temperature of normal temperature the mixed clay dispersion liquid and containing additive liquid.As such method, following method is arranged for example, method 1 is for the mixed clay dispersion liquid and contain additive liquid, stirs, vibrates and mix after heating with gimmicks such as well heater, warm wind, water-baths; Method 2 heats with above-mentioned gimmick for the limit, and stir on the limit, vibration, mixes; Method 3 energizes with ultrasonic dispersing device, homogenizer etc. for the limit, makes to contain additive liquid heating itself, and stir on the limit, vibration, mixes.

In addition, the clay that contains in the clay dispersion can be a kind, also can be that the different clays more than 2 kinds mixes use.Equally, containing the additive that contains in the additive liquid can be a kind, also can be that the different clays more than 2 kinds mixes use.Further, can use the different clay dispersions such as kind of the clay more than 2 kinds to make argillaceous liquid, also can use the different additive liquid that contain such as kind of the additive more than 2 kinds to make argillaceous liquid.Perhaps, can mix multiple clay dispersion respectively and the multiple additive liquid that contains is made argillaceous liquid.

Like this, because by being higher than each liquid of adjustment under the temperature of normal temperature, the argillaceous liquid of clay and additive obtains being scattered here and there more equably, so can suppress the generation of condensation product, form in the operation at clay membrane, embed (intercalate) additive fifty-fifty at clay crystalline interlayer, the result can make has sufficient mechanical and flexible clay membrane, can give transparent clay membrane with the sufficient transparency.

By being higher than under the temperature of normal temperature, the solid formation branch concentration of argillaceous liquid is uprised respectively with clay and additive and solvent again.If the solid formation branch concentration of argillaceous liquid is uprised, then shorten time of drying etc., make thick clay membrane easily.Again, low viscous argillaceous liquid can only be configured in the surface of support with the rectangular horizontal plane of gravity direction on, if be configured on the scarp and then can flow down, and but the solid formation branch concentration of argillaceous liquid is uprised become pulpous state, then also can be configured on the scarp.Again, because mobile decline, thereby can prevent that argillaceous liquid from flowing out from support, so need not implement to manage in order to prevent to flow out (for example need not to be provided with frame etc.) to support.

In the present invention, while at clay dispersion, contain mixing in the modulation of additive liquid, argillaceous liquid and can use around the revolve round the sun such method of container of rotation of axle.Promptly be a kind of like this method, when making the clay membrane that constitutes by clay and additive, clay dispersion, contain at least a of additive liquid, argillaceous liquid, use said vesse to modulate argillaceous liquid.

Clay dispersion, contain the blending means in the modulation of additive liquid, argillaceous liquid, so long as can make clay and additive dispersive method fully, just have no particular limits, but use the method for said vesse owing to not only can disperse or dissolve at short notice by powerful whipping force and degassing ability, even under the state of the gelation that surpasses the fluidity boundary, also can stir, so very suitable to being used to obtain the high solid argillaceous liquid that forms branch concentration.

Especially,, under reduced pressure argillaceous liquid is stirred, then can carry out vacuum outgas simultaneously at blended if make in the container decompression state for vacuum etc.Therefore, can be fully and effectively to because of forming branchs concentration height admittedly, outgasing for high viscosity is difficult to make the argillaceous liquid of the gaseous constituent minimizing of sneaking into.

In addition, also can use the method for the above-mentioned a plurality of methods of combination, carry out the manufacturing of clay membrane.

In the clay membrane made from manufacture method of the present invention, the ratio of additive is when 30 quality % are following, probably can produce following problem, even sneak into bubble (space), then air bubble expansion and destroy clay membrane during heat drying, perhaps degradation in transparent film because under the transparencys such as scattering of light.Again, usually, because the solid formation of argillaceous liquid divides concentration high more, then viscosity rises more, and thixotropy is got over grow, so if stop to stir then mobile forfeiture, this tendency is strong more.The result is difficult to remove the gaseous constituent of sneaking in the argillaceous liquid.In the argillaceous liquid of the solid formation branch concentration that obtains practical rate of drying, this tendency is especially high, and sneaking into the gaseous constituent of argillaceous liquid is to be difficult to make it reduce if do not remove operation by some.

In the high clay membrane of clay ratio,,, when being difficult to remove film forming, the result remains in the bubble of the inside of clay membrane so gas barrier property improves because clay compact crystallization ground is orientated, lamination again.Therefore, the operation of removing the gaseous constituent that argillaceous liquid contained fully is very important, is substantially necessary operation in the high clay membrane of clay ratio.

Further, in order to give the high clay membrane of clay ratio, need above to a certain degree thickness can be used as the intensity that independent film is utilized.The ideal thickness of clay membrane be thicker than 10 μ m, better is thicker than 15 μ m, better is thicker than 20 μ m, it is desirable to thicklyer than 30 μ m especially, it would be desirable thicker than 50 μ m.This is the bigger difference of the purposes of itself and coat film, and coat film does not need independence, even thickness is below number μ m, in most occasion still effectively.

Yet, in order to improve intensity, the thickness of clay membrane to be made thick like that as described above, its thickness is thick more, difficultly more during film forming removes the gaseous constituent of sneaking into argillaceous liquid from clay membrane inside, the easy more inside that remains in clay membrane of this gaseous constituent.This expression thickness is thick more, and then owing to remain in the defective that the bubble etc. of the inside of clay membrane causes, for example the transparency that causes such as scattering of light descends and the breakage of the clay membrane during heating in easy more generation.

In order to make the thickness thickening of the clay membrane that will obtain, adopt any one of the concentration of the clay that improves argillaceous liquid and the method for thickening the liquid film that is configured in the argillaceous liquid on the support usually.When adopting the former method, owing to the increase that divides concentration along with the solid formation of clay, the viscosity of argillaceous liquid rises, further, thixotropy also becomes significantly, and the flowability of argillaceous liquid descends, and becomes very important so remove the gaseous constituent of sneaking into fully with some method.Also have, when adopting the latter's method, because a thickening is configured in the thickness of the liquid film on the support, it is many that the amount of the gaseous constituent of sneaking into just becomes, so it is very important to remove the gaseous constituent of sneaking into fully with some method.

As such method of removing the gaseous constituent that is contained in the argillaceous liquid fully, can be by centrifugation from argillaceous liquid the method for divided gas flow composition, it is desirable to especially carry out the method for vacuum outgas by argillaceous liquid being placed reduce pressure.The then high solid argillaceous liquid that forms branch concentration at this moment,, makes viscosity degradation, even also can outgas well if be higher than normal temperature by the temperature that makes argillaceous liquid.Just, it is desirable to before argillaceous liquid is configured in the surface of support, make the temperature that clay contains liquid be higher than normal temperature, place under reduced pressure simultaneously, remove clay and contain the bubble that liquid contains.At this moment, if under reduced pressure argillaceous liquid is stirred, then owing to not only the entrap bubble of argillaceous liquid inside is moved near the liquid level, discharge from argillaceous liquid easily, can also suppress thixotropic manifesting, can suppress the rising of the viscosity of argillaceous liquid, so further improve degasifying effect.

In addition, if at high temperature outgas, so then because the viscosity step-down can outgas well as mentioned above, but owing to the solvent of argillaceous liquid in the degassing evaporates easily, so especially near the solid formation branch concentration the liquid level of solvent evaporation rises easily, the result causes separating out of solid substance easily.Therefore, while further outgas by stirring, the partial solid rising that forms branch concentration of argillaceous liquid can not take place, and prevent from again can at high temperature outgas aptly because thixotropy viscosity rises.

After can heating argillaceous liquid in the gimmick with well heater, warm wind, water-bath etc., aforesaid degassing operation carries out, also can be while using above-mentioned gimmick heating to carry out, Yi Bian also can argillaceous liquid heating itself be carried out on one side energizing with ultrasonic dispersing device, homogenizer etc.Again, when under reduced pressure argillaceous liquid being stirred, can use stirrer or agitating vane, also can use the container of above-mentioned one side around axle revolution one side autobiography.

After can also being configured in argillaceous liquid on the support, carry out above-mentioned degassing operation.At this moment, can make thin liquid film on the support by argillaceous liquid is configured in, and be that the situation that enters the operation that outgases in the groove (tank) etc. under the state of thick tunicle is compared at argillaceous liquid, and gaseous constituent is reduced.

In the present invention, when making argillaceous liquid, the solid formation branch concentration that it is desirable to argillaceous liquid is more than the 0.5 quality %, below the 20 quality %.Because divide concentration by improving solid formation, can shorten the dry time that needs, so it is desirable to more than 0.5 quality %.Be set in below the 20 quality % argillaceous liquid of be scattered here and there well clay and additive by forming branch concentration admittedly again.Again, because the viscosity that suppresses argillaceous liquid can suppress thixotropic manifesting, so remove the gaseous constituent of sneaking in the argillaceous liquid easily below prescribed value.The result improves clay crystalline orientation and the homogeneity in the resulting clay membrane, improves the transparency, gas barrier property and the dimensional stability etc. of clay membrane.In order to obtain these effects fully, what the solid formation branch concentration of argillaceous liquid was better is more than the 1 quality %, below the 15 quality %, and better is more than the 1 quality %, below the 12 quality %.

In addition, in the present invention, also can use argillaceous liquid through the pulpous state of following processing, promptly under reduced pressure stir etc. after the gaseous constituent that argillaceous liquid is contained reduces, heating etc. reduces solvent, further improves solid formation and divides concentration, thereby obtain the argillaceous liquid of pulpous state.Compare with above-mentioned suitable scope, this situation also can further improve the solid formation branch concentration of argillaceous liquid.Because can remove the gaseous constituent that contains in the argillaceous liquid in view of the above and can shorten time of drying, so obtain to improve the effect of the batch process of clay membrane.

Again, improve viscosity, according to circumstances, can manifest significantly, can make mobile decline thus, so can remove the restriction of support as described above by making thixotropy.That is,,, need not to use such having such as container of dividing plate to prevent the support of effusive structure so the argillaceous liquid that is coated on the support can not flow out because the argillaceous liquid of pulpous state is mobile low.Again, the argillaceous liquid of pulpous state has and also can be coated on the first-class advantage in scarp.In addition, in argillaceous liquid, add tackifier etc., make pulp, also can play above-mentioned effect.

Method as the solvent that makes in the argillaceous liquid reduces it is desirable to heating vaporization, and there is no particular limitation, can use known solid-liquid separation techniques such as centrifugation, filtration, squeezing.The enrichment process that above-mentioned raising forms branch concentration admittedly can under reduced pressure carry out, especially if make the thickness attenuation of argillaceous liquid, and carry out on one side by stirring to wait argillaceous liquid to be produced flow on one side, then the evaporation quantitative change of solvent is many and can concentrate at short notice, so has effect.If under reduced pressure implement to concentrate, then, therefore be fit to owing to also can outgas in the spissated while again.Just, owing to, then as mentioned above, be difficult to remove the gaseous constituent that remains in the argillaceous liquid, therefore importantly must after reducing fully, the gaseous constituent that argillaceous liquid is contained concentrate again if concentrated argillaceous liquid.Again, not only concentrated but also when outgasing, and importantly must finish the degassing before carrying out concentrating.

The argillaceous liquid that obtains like this is coated on certain thickness remove at leisure after the surface of support and desolvates, thereby form clay membrane.Remove the method desolvate and limit especially, but for example it is desirable to centrifugation, filtration, vacuum-drying, freeze vacuum-drying, inert gas atmosphere places down and heating vaporization.Perhaps, also can make up several different methods in these methods.

When using for example heating vaporization in these methods, for example be advisable to use smooth tray to be coated with argillaceous liquid thereon as support.The material of support is limited especially, but the temperature when needing anti-heating.For example, film, substrate, glass and the silicon chip that is made of polyethylene terephthalate (PET), the such resin of polypropylene arranged for example.Again, the substrate that also can have brass, copper, stainless steel, the such metal of aluminium to constitute for example.The thermal conductivity height of support is generally more satisfactory.In addition, the viscosity height or the thixotropy of argillaceous liquid are strong, and the not effusive situation of the argillaceous liquid of coating need not the such container that prevents the effusive structure of argillaceous liquid of tray, also can use the smooth support that is made of above-mentioned material.

In the exsiccant process, occurring volumetric shrinkage along with evaporation liquid-solidization of argillaceous of solvent, the stress that is accompanied by above-mentioned volumetric shrinkage is on the clay membrane that obtains.Therefore, when the clay film strength cannot stand this stress, have following problem, split at drying process medium clay soil film sometimes, be difficult to make large-area clay membrane this moment, and the purposes that can be suitable for is limited.In this case, in order to absorb the stress of following volumetric shrinkage and producing, it is desirable to use support with flexibility, easy deformation.Like this, because can be along with support be out of shape at dry medium clay soil film itself, Yi Bian support is deformed into can relax the shape of the stress that volumetric shrinkage brings, Yi Bian carry out drying, so can relax the stress that remains in clay membrane inside, suppress clay membrane and crackle occurs.

As long as support has flexibility, easy deformation, there is no particular limitation, but if consider dried clay membrane separability, make cylinder shape continuous production clay membrane and to the influence of the manufacturing cost of clay membrane, the resin manufacture film of the cheapness of PET etc. is proper.

It is desirable to clay membrane be handled or hydrophobic processing treatment easily from the facilitation of peeling off that support is peeled off to the part that contacts with clay membrane at least in the surface of support.Perhaps, it is desirable to constitute support with the strong polypropylene of hydrophobicity, tetrafluoroethylene etc.Handle as peeling off facilitation, for example uviolizing processing, electron rays radiation treatment, ion beam irradiation processing, corona discharge process, Cement Composite Treated by Plasma (remote plasma treatment is for example arranged for example, the flame plasma processing), physical treatment (, making contact area reduce) for example to the mechanical treatment of surface working.Again, the processing of the resin that make being adjacent to property decline of coating as polyorganosiloxane resin is arranged for example, or being coated with the processing that separability gives agent, pliability or yang type modulus change or bubble this coating separability by the physical stimulation that is subjected to light, heat etc., make the decline of being adjacent to property.Perhaps, also can be with multiple the combining in these processing.

As hydrophobic processing treatment, in most cases, obtain same effect by the above-mentioned facilitation processing of peeling off, but, have fluororesin-coated for example and method titanium dioxide as suitable example again.

It is desirable to, the surface of support is level and smooth as far as possible.Rough words are because the surface of support coarse copies on the surface of clay membrane, so the surface smoothing decline of clay membrane.Concerning transparent film, the light diffuse-reflectance is to make the mist cause of increased further.

In the clay membrane that is made of hydrophilic clay, though it is dry bigger after intact just to be accompanied by the stress that dry shrinkage results from the clay membrane, most applications is that place a little while dry back, and then internal stress reduces.For example, the most transparent film that is made of hydrophilic clay finishes owing to internal stress curls in firm drying, but places about 10 minutes, and then internal stress is open, becomes smooth film.Therefore, during internal stress reduces,, the stress of generation is escaped, peels off clay membrane from support after internal stress is open by making the support distortion, can make thus internal stress few, do not have crackle and a curling clay membrane.As the reason of placing internal stress minimizing a little while after the drying, be because flexibility improves by absorbing airborne moisture.Therefore, keep a little while under the environment of clay membrane at controlling moisture that firm drying is finished, this is effective to the internal stress of removing the clay membrane that is made of hydrophilic clay.

As mentioned above, by using variable support, can suppress the volumetric shrinkage when making and the breakage of the caused clay membrane of stress that produces along with clay membrane.Thus, even because the larger area clay membrane, also can high yield rate manufacturing, so suit for the purposes of the so large-area film of needs of indicating meter.Again,, use the support that constitutes by the film that is rolled into the cylinder shape, when carrying out continuous production,, make long clay membrane (for example clay Belt) easily owing to obtain the successive clay membrane easily by cylinder according to the present invention.

When removing the solvent of argillaceous liquid, be advisable to use forced blowing type baking box etc. by heating vaporization.And, dry more than 10 minutes, below 7 hours if under the temperature condition more than 30 ℃, below 120 ℃, then obtain clay membrane.What temperature condition was better is more than 30 ℃, below 90 ℃, and better is more than 50 ℃, below 70 ℃.Again, what time of drying was better is more than 20 minutes, below 3 hours, and better is more than 20 minutes, below 2 hours.

Just, and change along with the difference of the thickness of clay membrane, the solid formation branch concentration of argillaceous liquid, the solvent types of use etc. the suitableeest time of drying.Because specific heat of water is big, dried floral is time-consuming, so as solvent, be advisable with organic solvent, especially is advisable with the lower solvent of boiling point.And, with an organic solvent be hopeful to shorten time of drying as the combination of clay as solvent, use hydrophobicity clay.In addition, if the boiling point of solvent is low excessively, and then not only when adjusting argillaceous liquid solvent evaporates solid formation branch concentration is risen, and the danger of lighting blast etc. also rises, so it is desirable to consider the property produced in batches and these two aspects of security, the kind of selective solvent aptly.

According to the manufacture method of such clay membrane of the present invention, can make clay membrane physical strength, that linear expansivity is little with the independent film of can be used as utilization.Again, during the clay of the non-coloring of use synthesis of clay etc., the spectral response curve of Yin Pingtan, non-coloring, the spot that can make transmitance or mist can not be used such clay membrane of Visual Confirmation on a large scale., in the former clay membrane, be placed on sometimes in the atmosphere, then the surface with the passing of time uneven and increase.Use hydrophilic synthetic saponite or synthetic li-montmorillonite as clay, use polyacrylate as additive, when making water as the solvent of argillaceous liquid, such phenomenon is particularly remarkable.The surface of clay membrane uneven is not only and given other films on the surface of clay membrane or form the isochronous bigger problem of electronics, and because by rough increase, mist increases, and clay membrane blurs and transparency decline, so be the important problem that should solve.

Such problem, can be by described argillaceous liquid so far being carried out clay membrane that drying obtains (afterwards, sometimes note is made the primary drying film) the surface on configuration make the liquid of clay swelling or make additive dissolving or dispersive liquid, carry out drying again and solve.Even do not produce such problem,, mist is descended owing to can make the surface smoothingization of clay membrane by such method again.

There is no particular limitation for the method for the surface configuration aforesaid liquid of the primary drying film that obtains in that argillaceous liquid is carried out drying (make the liquid of clay swelling or make additive dissolving or dispersive liquid), but for example can be with the method for primary drying film immersion in aforesaid liquid, also can be the such surface that aforesaid liquid is sprayed to the primary drying film of atomizer.Perhaps, also can be under the vapor atmosphere of the high density of aforesaid liquid, to place the primary drying film.

At this moment, if the overlong time that the primary drying film contacts with aforesaid liquid, then the part of primary drying film or whole redispersion are in aforesaid liquid sometimes, and perhaps the primary drying film absorbs aforesaid liquid and swelling.Therefore, it is shorter to it is desirable to the time ratio that the primary drying film contacts with aforesaid liquid, though hope be from the several seconds to long also in several minutes.

Again, most applications, the method on the surface by aforesaid liquid being sprayed to the primary drying film or in the aforesaid liquid that is flowing the method etc. of dipping primary drying film, the configuration aforesaid liquid makes its purge flow cross the surface of primary drying film, then can make the increase of film smoothing and the mist of inhibition through causing after a while effectively.At the surface configuration aforesaid liquid of primary drying film, rest on the surface of primary drying film for a long time in order not make aforesaid liquid, so that being adjusted into heeling condition and aforesaid liquid is flowed down from horizontality, the primary drying film is advisable.

Again, the primary drying film is remained heeling condition and configuration during aforesaid liquid from horizontality, it is desirable to mounting primary drying film on the latticed iron wire that uses when making paper etc., the configuration aforesaid liquid.Like this, because unnecessary aforesaid liquid flows away from the surface of primary drying film easily, so can suppress the part of primary drying film or whole redispersion in aforesaid liquid and swelling excessively.

The kind of aforesaid liquid is so long as that make the clay swelling or additive dissolving or dispersive are got final product, and there is no particular limitation, selects aptly to get final product according to the kind of clay and additive.Especially, if in water the hydrophilic clay of swelling or have the clay membrane of dissolved additive in water, water is suitable.

In addition, by aforesaid liquid being configured in the surface of primary drying film, this whole film easily absorbs this liquid and when being varied to gel, and along with the volume of gelation primary drying film increases, the result produces the clay membrane of fold etc. sometimes.Such situation by the stretching clay membrane, flattens fold, makes the clay membrane planarization, can obtain the more level and smooth clay membrane in dry rear surface.As the method for stretching clay membrane, have for example and shift onto method on the clay membrane and 2 such methods that stretch of tension clay membrane such as roller.The stretching of clay membrane can be carried out on the member of surface smoothing, also carries out on the latticed iron wire that can use when making paper etc., also can with under the such support state of contact of level and smooth member not carry out.

Behind the primary drying, additive is separated out on the surface of clay membrane, and this additive of separating out is the mist cause of increased, in this situation, because, remove the additive of separating out by aforesaid liquid, so play effect of the present invention if as mentioned above at the surface configuration aforesaid liquid of primary drying film.

Again, in disposing the primary drying film of aforesaid liquid as described above, either party of clay or additive absorbs aforesaid liquid, whole primary drying film or the near surface part swelling of the primary drying film of aforesaid liquid contact at least.In such state, owing to not only smoothness being improved because of the surperficial swelling surface-area of primary drying film becomes, and soften for gel on the surface of primary drying film, easily owing to external force is out of shape, so if the surface of primary drying film is temporarily contacted with the level and smooth member of surface smoothing, then the surface of primary drying film is being followed the surface of level and smooth member and is being out of shape, the surface smoothingization of primary drying film, thus the smoothness on the surface of the clay membrane that obtains can be improved.For example, be configured in by the primary drying film that will dispose aforesaid liquid on the glass substrate or resin molding of surface smoothing, can access the clay membrane of surface smoothingization.Further, by disposing same glass substrate and resin molding from it,, can make the two sides smoothing of clay membrane with level and smooth member clamping clay membrane.

The level and smooth member that is used for smoothing is so long as surface smoothing, and just there is no particular limitation, can use the such resin substrate of glass substrate, silicon substrate, Polyethylene Terephthalates (PET) film etc.Further, the surface of these level and smooth members can peel off that facilitation is handled and hydrophobic processing treatment, these two kinds of processing be applicable to the same of the support that uses when the above-mentioned primary drying film of manufacturing so that clay membrane is peeled off after smoothing easily.

Further, the primary drying film is contacted when carrying out smoothing with level and smooth member, can apply external force energetically.For example, can be configured on the level and smooth resin molding by the primary drying film that will dispose behind the aforesaid liquid, the roller that rolling surface is level and smooth carries out smoothing thereon.Can apply external force by pressing machine etc., the primary drying film is carried out smoothing by being pressed on the level and smooth member.At this moment, roller can directly contact with the primary drying film with press assembly, wants to prevent that the primary drying film from adhering to roller and press assembly etc. when going up, and can clip the level and smooth resin molding of implementing to peel off facilitation processing etc. as required etc., applies external force.

By the primary drying film that disposes aforesaid liquid being carried out drying again, can obtain obtaining the clay membrane of above-mentioned effect of the present invention.Drying can or with under the member state of contact not carried out on member arbitrarily, but in order finally to obtain the clay membrane of surface smoothing, preferably carries out on the above-mentioned level and smooth member of the surface smoothing of the surface smoothingization that is used to make clay membrane.The exsiccant method limits especially again, but it is desirable to for example centrifugation, filtration, vacuum-drying, freeze vacuum-drying, inert gas atmosphere places down and heating vaporization.Perhaps, also can make up several different methods in these methods.Perhaps, also can only be placed in the atmosphere.At this moment, the smoothness on surface is descended, preferably in dry atmosphere foreign matter try one's best carry out again in few puridryer or the dust free chamber dry.

When dry again, because clay membrane produces volumetric shrinkage, so the stress that is accompanied by above-mentioned volumetric shrinkage is on clay membrane.Especially, when whole film expanded, the stress that is accompanied by above-mentioned volumetric shrinkage played a role strongly.Therefore, on above-mentioned level and smooth member, carry out again in the dry situation, identical with the situation of making the primary drying film sometimes when the clay film strength is unable to bear this stress, at drying process medium clay soil film generation crackle.Take place for fear of above-mentioned situation, it is desirable to above-mentioned level and smooth member and have flexibility, under the variable state of above-mentioned level and smooth member, carry out drying again, peel off clay membrane from above-mentioned level and smooth member then.Above-mentioned level and smooth member as having flexibility it is desirable to resin system film.

According to the manufacture method of such clay membrane of the present invention, can make clay crystalline layer height orientation ground lamination, additive is embedded between clay seam fifty-fifty, homogeneity is good, gas that sneak into causes the few clay membrane of defective.The clay membrane that the result obtains is owing to fine and close laminar structure has the physical strength that the independent film of can be used as is utilized, and linear expansivity is little.And, when using the clay of non-coloring of synthesis of clay etc., the spectral response curve of Yin Pingtan, non-coloring, the spot that can make transmitance or mist can not be with the such clay membranes of Visual Confirmation on a large scale.

It is difficult giving the physical strength definition can be used as the independent film utilization, but the tensile strength of clay membrane it is desirable to more than 10MPa, and better is more than 15MPa, and better is more than 20MPa, it would be desirable more than 25MPa.If more than 10MPa, we can say the intensity of degree with the enough hand processing of energy, if more than 25MPa, we can say to have full intensity.

The clay membrane that obtains by manufacture method of the present invention is because remove the gaseous constituent that argillaceous liquid contains fully, so inner bubble (space) etc. seldom.Therefore, it also is according to the thermotolerance of additive and difference, but by the clay membrane that manufacture method of the present invention obtains for example apace (for example is, the rate of rise in temperature of per minute more than 15 ℃) be heated to 300 ℃ kept 1 hour after, even at length observe the film surface, do not see superficial expansion yet, can under the hot conditions more than 300 ℃, use good heat stability.

Further, in transparent clay membrane, cross over whole visible region and have high transparent, little, the non-coloring of mist, and spot is few in the face of the transparency.The reduction of removing especially mist of the gaseous constituent that argillaceous liquid contains has bigger influence.Mist is descended be very important problem when being applicable to the such optical applications of indicating meter again.

In the present invention, even the operation that the gaseous constituent in the argillaceous liquid is reduced by importing then during the situation of clay thickness (for example, thick than 15 μ m), also can make mist (blur level) after the firm film forming below 5%.Mist it is desirable to below 3%, and better is below 2%, further it is desirable to less than 1%.Again, can make mist in 24 ℃, the environment of 1 air pressure, humidity 45% through the time change below 2%.Mist through the time change and it is desirable to below 1%, better is below 0.5%.Again, can make total light transmittance at the transmittance of the directional light more than 85%, in the wavelength region more than 400nm, below the 800nm measured of UV, visible light optical splitter at the clay membrane more than 85%, below 95%.

If mist surpasses 5%, it is low then probably can to produce the transparency, can not get the problem of desired optical characteristics.Again, the mist of the glass substrate that surface smoothing, mist are low and optical film material etc. is generally in 0.5% front and back, even it is transparent especially also about 0.2%, because the surface of resulting clay membrane was uneven roughly by these substrates or level and smooth member defined when these were used as support or level and smooth member, so the mist of the clay membrane that obtains is also most of from 0.5%, even well be lower limit also with about 0.2%.Again, if mist through the time change to surpass 2%, then probably can produce following bad situation, promptly the transparency of clay membrane descends with the passing of time, can not get desired optical characteristics.

In addition, the upper limit of transmittance is by the specific refractory power decision of film.We consider, and are general, because the specific refractory power great majority of clay are in about 1.5 front and back, so even add the low additive of specific refractory power, be the upper limit with about 95% also with the transmittance of the directional light of the clay membrane of the manufacture method manufacturing of clay membrane of the present invention.Certainly, if give on the surface of clay membrane low-refraction for example antireflection film, utilize the anti-laminated reflective film of the interference of light or impose film that anti glare anti static coatings handles etc. and carry out lamination etc., then can further improve transmitance.

Manufacture method according to clay membrane of the present invention, the effect that utilize the ratio of this additive few, viscosity crystalline layer height ground orientation and lamination, additive embeds fifty-fifty at interlayer, near the clay membrane of absolute value below 20ppm of the average linear expansivity can obtaining from 40 ℃ to 250 ℃.Linear expansivity it is desirable to below 15ppm, and better is below 10ppm, and better is below 7ppm, it is desirable to especially it would be desirable below 3ppm below 5ppm.

So little linear expansivity, by before the film that constitutes of resin or before the nano composite material body in, it is the minimum value that can not arrive, especially in transparent film the value that arrives scarcely ever, even nano composite material body in the past contains clay, based on resin, clay crystalline layer is not orientated densely and to heavens yet, lamination yet.We can say because most electronics is made of little inorganic substance of linear expansivity etc., so as the substrate that such electronics is installed, clay membrane of the present invention has very suitable characteristic.Again, when such clay membrane is used for sealing member etc., because the surface is uneven little, so obtain further to suppress the effect of the leakage of gas etc.

After making clay membrane, clay and additive are disperseed equably, remove entrained gas fully, the result obtains clay crystalline layer height ground orientation, laminated clay membrane, as the gimmick of confirming whether to obtain such clay membrane, the direct viewing that the laminated condition of infiltration type electron microscope (TEM) was analyzed, reached to the X-ray diffraction spectrographic of X-ray diffraction device is effective.In the past, what carry out widely was, measured by X-ray diffraction, to the oriented layer pressure condition of formed clay membrane on the support of glass substrate etc., contain clay crystalline in the nano composite material body of clay and disperse, peel off state etc. and carry out research evaluation.Generally, the intensity and the position of the main peak (at the bottom reflection peak of minimum 2 θ sides) that the X-ray diffraction spectrum that a diffraction by clay crystalline (001) face obtains is produced, and the rising of the background of the X-ray diffraction spectrographic in low 2 θ zones etc., can know clay crystalline laminated condition (equispaced of layer), dispersion state.

Average interfloor distance in the clay membrane of the ratio less than 30 quality % of additive then is below the 10nm if convert in the position of the above-mentioned main peak in X-ray diffraction spectrum.This average interfloor distance it is desirable to below 7nm, and better is below 5nm, and better is below 4nm, it is desirable to especially it would be desirable below 2nm below 3.5nm.Again, if average interfloor distance then manifests obtaining high gas barrier property below 1.5nm, this gas barrier property is below the measurement range of existing determinator.

The average interfloor distance of this ideal is if be converted into the summit position (values of 2 θ) of an above-mentioned diffraction peak, then using as 1.54 of the K α of general copper

The mensuration of wavelength the time, the thickness of clay crystalline one deck is approximately in the clay membrane that the clay of the clay by montmorillonite family of 1nm, synthetic mica family constitutes, with 2 θ corresponding to the zone more than 0.8, below 9.0.

In addition, the minimum value of above-mentioned average interfloor distance only is equivalent to the minimum value of the average interfloor distance of the composition that is made of clay, but in clay membrane of the present invention, because additive is embedded in interlayer fifty-fifty, so average interfloor distance big than the composition that only constitutes by clay.As the gimmick of confirming it, be benchmark with following, promptly whether the summit position of the above-mentioned main peak in the x ray diffraction spectrum moves to and the comparing in low 2 θ sides of the composition that only is made of clay, and perhaps whether the peak width of above-mentioned main peak expands to and hangs down 2 θ sides.In addition, whether the average interfloor distance in the clay membrane in above-mentioned ideal scope, also can directly measure the interfloor distance of the picture that the photo photography of TEM obtains and confirm.

Again, the clay membrane that obtains of the manufacture method by clay membrane of the present invention generally has high block for hydrogen, oxygen, the such inorganic gas of nitrogen.According to the clay that uses, the kind of additive, gas barrier property presents bigger difference, but with the transmitance definition, then is below 1/2 of film that only is made of the additive that uses.Transmitance only it is desirable to below 1/10 of film that is made of the additive that uses, and better is below 1/100, and better is below 1/1000.According to the composition of clay membrane, also demonstrate the following gas barrier property of measurement range of gas permeation degree determinator general in the present situation (device of モ コ Application company) sometimes.

And clay membrane of the present invention is owing to having the intensity that the independent film of can be used as is utilized, so can be used for various uses.For example, utilize thermotolerance, gas barrier property, flexibility, low linear expansion etc., can be at high temperature on clay membrane, directly form driving loop as the active matrix at the back side of elastic Electronic Paper.Like this,, promptly not be used in to form on the stable on heating glass substrate etc. and driven after the loop, copied at resin molding etc.,, on cost, also had advantage so can reduce the manufacturing process of Electricity paper because can not use former method.If the back side of Electronic Paper does not then generally need the transparency, if but clay membrane is transparent, and the substrate of frontal plane side or the choke film that then can be used as the visual side of Electronic Paper use.In addition, there is no particular limitation can to use the kind of Electronic Paper of clay membrane of the present invention, but for example Electronic Paper of electrophoresis drive-type, electronics powder fluid mode is arranged for example.

Other can apply flexibly the feature as insulativity, also the elastic base plate of clay membrane as circuit can be used widely.When utilizing as the substrate of circuit, for the purpose of broken string that prevents distribution etc., the uneven and linear expansivity of better is substrate surface is littler, and clay membrane of the present invention is more suitable.Especially, conductor part You Tu cloth on substrate or printing conductive printing ink and in the elasticity printed base plate that forms, utilize the thermotolerance and the low linear expansion coefficient of clay membrane, can under higher temperature, burn till, so can make the resistivity of the conductor part that forms by coating or printing lower conductive ink.As the suitable purposes of such elastic base plate and elasticity printed base plate, substrate, copper-clad laminate of RFID label etc. are arranged for example.Further, if transparent clay membrane then also goes for the such needs of solar cell some equipment by light.

Again, and the organic semiconductor of penta benzene or thiophene-based representative general because oxygen or moisture and worsen easily, again,, also be subjected to the influence of oxygen and moisture easily though the amorphous inorganic semiconductor does not arrive the organic semi-conductor degree.Therefore, in the equipment that uses these, must stop the intrusion of oxygen or water vapour fully.Because clay membrane of the present invention has high gas barrier property; even so have the substrate that the electronics of the organic semiconductor of the deterioration sensitivity that oxygen etc. is caused or amorphous inorganic semiconductor uses or the choke film of organic semiconductor or amorphous inorganic semiconductor as protection, also suitable.Again, clay membrane is because at high temperature also keep flexibility, so also can make above-mentioned electronics elastification.

In addition, clay membrane of the present invention is applied in above-mentioned Electronic Paper, elastic base plate, elasticity printed base plate, when having the electronics of organic semiconductor or amorphous inorganic semiconductor, also can directly use clay membrane.Also can be as required add that to clay membrane film with other function (for example, mainly be the water vapor barrier film that is made of inorganic materials, the reinforcement that is made of resin material etc., the protective layer that prevents to be hurt etc., make the smoothing layer of surface smoothingization) etc. uses.

The reinforcement that also can be further constitutes, the protective layer that prevents to be hurt etc., make the film with other function different of smoothing layer etc. of surface smoothingization additional to after the clay membrane with clay with above-mentioned water vapor barrier film, by resin material etc.; surface configuration liquid at clay membrane makes it to expand; it is carried out drying again, the smoothness of clay membrane part is improved.For example, after the film that be stained with also can for the one side of clay membrane to constitute etc.,, carry out again dry by will in liquid or by spraying liquid on the clay face, making it swelling by the film immersion that clay and resin molding constitute by resin.Certainly, in the composite membrane that is formed by clay membrane and the film laminated multi-layer except that clay with other function, if the outermost layer of the one side of composite membrane is a clay membrane at least, then available above-mentioned gimmick improves.

Below, clay membrane of the present invention and manufacture method thereof are described in more detail.

There is no particular limitation to the kind of employed clay among the present invention, and natural clay, synthesis of clay can.For example, it is desirable to mica, vermiculite, polynite, iron polynite, beidellite, saponite, hectorite, rich magnesium montmorillonite, nontronite, magadiite, hydrotalcite, kaolinite and halloysite.Especially in transparent clay membrane, it is desirable to synthesis of clay.As synthesis of clay, it is desirable to synthetic saponite, synthetic li-montmorillonite, synthetic rich magnesium montmorillonite, synthetic mica, synthetic hydrotalcite, synthetic kaolinite etc., from aspects such as dispersivenesses, better is the clay that belongs to montmorillonite family.From the viewpoint of gas barrier property, it is desirable to belong to the big natural montmorillonite of the aspect ratio of clay crystalline layer or the clay of mica family.Further, from the viewpoint of gas barrier property, the clay of the synthetic montmorillonite family of high aspect ratio, synthetic mica, hydrotalcite are also desirable.

Again, also can use the hydrophobicity clay that obtains through following processing,, handle, improve the dispersiveness in organic solvent even with salt with such organic ion such as ammonium salt, microcosmic salt, imidazole salts, carboxylic acid.This processing is the processing that mineral ion that hydrophilic clay is possessed is exchanged into organic ion.Further, also can use the hydrophobicity clay that obtains through following processing, promptly the hydroxyl of the above-mentioned octahedra thin slice that the integrant as layer structure of most clay mineral is had by chemical reaction convert other to hydrophobic substituting group (for example, hydroxyl is substituted by the processing of other organic group by combining) with silane coupling agent dehydration arbitrarily, thereby water tolerance is further improved, perhaps be controlled at the dispersiveness in the organic solvent.Especially, from aspects such as the easy degree of the carrying out of above-mentioned processing or dispersivenesses, make the clay hydrophobization that belongs to montmorillonite family and the organic montmorillonite that obtains suits with above-mentioned processing.

As the ammonium salt in the salt with organic ion, the quaternary ammonium salt of ammonium salt with alkyl, phenmethyl, polyoxyethylene groups, oxyethylene group, oxypropylene group etc., dimethyl two (stearyl) ammonium salt, trimethylammonium stearyl ammonium salt etc. is arranged for example.Again, the thermotolerance height of microcosmic salt, imidazole salts etc. also is difficult to present at high temperature and decomposes or painted etc., and this is as you know.Therefore, if use the hydrophobicity clay of handling through microcosmic salt or imidazole salts etc., then can obtain the clay membrane of excellent heat resistance.The hydrophobicity clay is because low with the affinity of water, so the affinity of clay membrane that obtains and water is also low, it has excellent water-resistance as a result.

In addition, the clay among the present invention comprise these hydrophilic clay and hydrophobicity clay the two.In the hydrophobicity clay, be defined as the part of clay with the organic ion of the surface bonding of above-mentioned tetrahedron thin slice or octahedra thin slice.The existence of the organic ion in the hydrophobicity clay, though owing to make clay crystalline interfloor distance increase some, so produced the such shortcoming of gas barrier property decline, but owing to combine securely with the surface of tetrahedron thin slice and octahedra thin slice, so it is generally less to the influence of the transparency of clay membrane or dimensional stability etc., also have from the such advantage this respect of the unexistent water tolerance of possess hydrophilic property clay, also suit.Again, the hydrophobicity clay generally the mineral ion of the basic metal etc. of the interlayer by will being present in hydrophilic clay be exchanged into organic ion and obtain.Therefore, if use the hydrophobicity clay that has carried out sufficient ion-exchange, then can obtain the clay membrane of alkali metal containing hardly on the principle.Therefore, think to be used in to detest on the alkali-metal electronics and suit.

There is no particular limitation to the kind of the additive that uses among the present invention, but (in order to ensure the homogeneity of the inside of the smoothness on surface or clay membrane) is to have flexibility, elasticity or flowability so generally it is desirable to additive itself because the stress that the main effect of additive is the volumetric shrinkage when improving the flexibility of clay membrane or intensity and relaxing the solvent of removing argillaceous liquid to be caused.It is solid that the form of additive itself need not, so long as dissolve equably or be dispersed in the solvent, also can be liquid or colloidal sol, the such material of gel.When making transparent clay membrane, it is desirable to additive also is transparent or painted few material.

As such material, it is desirable to the polymkeric substance that main chain mainly comprises carbon, silicon especially.Certainly, also can be to have in clay membrane with other monomers or polymer polymerizing and change into the monomer of the polymerizability of polymkeric substance.Can also contain and play and the synergistic organic ion of clay bonded.

Shown in such additive is specific as follows.When making clay dissolving or dispersive solvent be water, to it is desirable to additive also be possess hydrophilic property, the dispersiveness in water or the high material of solvability.For example, ε-Ji Neixianan, dextrin, starch, cellulose-based resin, cellulosic fibre, Keratin sulfate, agar, wheat-flour, gluten, Synolac, urethane resin, Resins, epoxy, fluoro-resin, acrylic resin, methacrylic resin, phenolic resin, polyamide resin, vibrin, polyimide resin, polyvinyl resin, polyoxyethylene glycol, polyacrylamide, polyethylene oxide, protein, thymus nucleic acid, Yeast Nucleic Acid, polyamino acid, multivalence phenol, benzoic acids compounds suit.Perhaps, can use the such aqueous dispersion material of latex or latex.In addition, because these dispersiveness or solvability height in water, so water tolerance is generally low.Therefore can add salt or other reactive monomer, polymkeric substance or oligopolymer etc., make the additive water fast.Just, when using the material of the such aqueous dispersion of latex or latex, also can be by the heat treated after the film forming etc., improve the water tolerance of film.

In addition, the hydrophobicity clay that uses organic montmorillonite etc. is as clay, when making solvent outside the water as solvent, or during the such mixed solvent of the hydrophilic solvent that makes water and other, need not to use dispersiveness possess hydrophilic property, in water or the high additive of solvability.At this moment, if the low additive of dispersiveness in water or solvability, the clay membrane that then obtains also is hydrophobicity, and the result can obtain the high clay membrane of water tolerance.

As such additive, it is that resin, aliphatic polycarbonate resin, aromatic polyester resin, aliphatic polyester based resin, aliphatic poly olefine resin, annular ethylene series resin, polyamide-based resin, polyphenylene ether are that resin, thermoplastic poly imines are that resin, poly-acetal are that resin, polysulfones are the thermoplastic resin of resin, amorphism fluorine resin etc. that phenylethylene resin series, acrylic resin, aromatic copolycarbonate are for example arranged for example.

Also can use the poly-imide resin of Resins, epoxy, thermohardening type modification poly (phenylene ether) resin, thermohardening type, urea resin, allyl resin, silicone resin, benzo oxazine resin, phenolic resin, unsaturated polyester resin, span to come the contract heat-curing resin of imines cyanate resin, Synolac, furane resin, melantine, urethane resin, aniline resin etc. of acid anhydrides again.

Other also can use light-cured resin, and Resins, epoxy that for example comprises potentiality light cationic polymerization initiators etc. is arranged for example.In addition, when above-mentioned light-cured resin is solidified, can be in light-struck heating simultaneously.Again, in the present invention, can use solidifying agent, curing catalysts etc. when using thermosetting resin and light-cured resin, these are so long as be generally used for thermosetting resin and the solidified of light-cured resin, and just there is no particular limitation.As the object lesson of solidifying agent, polyfunctional amine, polymeric amide, acid anhydrides, phenolic resin are arranged for example, as the object lesson of curing catalysts, imidazoles is arranged for example.These solidifying agent, curing catalysts can independent a kind of uses, perhaps mix more than 2 kinds and use.Again, above-mentioned resin may be used alone, can also be two or more kinds in combination.

Above-mentioned material mainly is the resin that main chain is made of carbon atom, but main chain is made of not necessarily carbon atom, for example can be the resin that main chain is made of Siliciumatom, also can be the resin (for example polysiloxane) that main chain mainly is made of silicon and oxygen.

Further, the employed salt that contains such organic ion such as ammonium salt, microcosmic salt, imidazole salts of the processing of above-mentioned clay also can be used as the additive use.Such salt because with the bonding force height of clay, so suitable as additive.Especially, in 1 molecule, contain the additive at above-mentioned organic salt position more than 2 owing to making the crosslinked bonding force that improves between the clay crystallizing layer between the clay crystallizing layer, so can improve the water tolerance or the gas barrier property of clay membrane.As such additive that contains the above-mentioned organic salt position more than 2, the molecule that for example has chain that constitutes by Siliciumatom by the unit more than 2 that contains above-mentioned organic salt position or the chain (for example polysilane or polysiloxane etc.) that constitutes by Siliciumatom and Sauerstoffatom be formed by connecting for example.Further, the molecule that has the such position with polymerizability in the unit that contains above-mentioned organic salt position and vinyl or epoxy group(ing) in 1 molecule is arranged for example.

In addition, additive is not defined as the material that helps to improve the clay film strength, when for example desiring to give flame retardant resistance, can add the such inorganic combustion inhibitor of ANTIMONY TRIOXIDE SB 203 99.8 PCT, when desiring to give plasticity, can add the such softening agent of dimethyl phthalate.Just, when making transparent clay membrane, it is desirable to above-mentioned additive also is transparent or painted few material.

Again, there is no particular limitation to the solvent types used among the present invention, but can make water or organic solvent.Also can use a spot of ethanamide of dissolving, N, the water of the organism of dinethylformamide, ethanol, methyl alcohol etc. or salt etc. again.The purpose of adding organism, salt etc. for a change the Dispersion of Clay in the argillaceous liquid, change argillaceous liquid viscosity, change clay membrane the easy degree of exsiccant, improve the homogeneity of clay membrane etc.

For the hydrophobicity clay is disperseed fully, the high polar solvent of interpolation methyl alcohol etc. is effective.Especially, when main solvent is the little solvent of the polarity of toluene etc., it is desirable in main solvent, add the so high polar solvent of a spot of methyl alcohol.The addition of the high polar solvent that methyl alcohol is such it is desirable to more than 0.1 quality % of main solvent, below the 20 quality %, and better is more than the 0.5 quality %, below the 15 quality %.

If in hydrophobicity Dispersion of Clay liquid, add a spot of methyl alcohol, then invade methyl alcohol between the clay crystallizing layer of Ning Ju hydrophobicity clay, make interlayer every expansion.And,, can be distributed near the clay crystalline unit layer if add adequate time and shearing force.Thus, greatly promoted the clay crystalline to disperse, the condensation product of clay does not almost have, and therefore most clay is peeled off near unit layer, can obtain additive and clay blended argillaceous liquid very equably.And, make clay membrane by promote dispersive argillaceous liquid by such interpolation methyl alcohol etc., play such effect, promptly especially in transparent clay membrane, reduce mist significantly.

Again, when using the hydrophobicity clay of the above-mentioned processing of process, can use aromatic hydrocarbons (for example toluene, dimethylbenzene), ethers (for example ethyl ether, tetrahydrofuran (THF)), ketone (for example acetone, ethyl methyl ketone), aliphatic hydrocarbon (for example octane), alcohols (for example methyl alcohol, ethanol, Virahol), halohydrocarbon (for example chloroform, methylene dichloride, 1 as solvent, the 2-ethylene dichloride), N, dinethylformamide, N-Methyl pyrrolidone, dioctyl phthalate (DOP), methyl-sulphoxide, methyl Cellosolve etc.

The kind of the organic solvent of dispersing hydrophobic clay is owing to depend on the kind of the organo-functional group that makes the clay crystalline surface that hydrophobicity manifests significantly, so need to select suitable material.Again, also to note final in argillaceous liquid solvability, the dispersiveness of blended additive select, it is desirable to select the solvability of Dispersion of Clay and additive, dispersed all good organic solvent.Just, the solvent of clay dispersion may not be with the kind sample with the solvent that contains additive liquid, and clay and additive all keep good dispersion state when obtaining argillaceous liquid as long as mix, and just there is no particular limitation.

Below, by embodiment, the present invention is carried out more specific description.

Embodiment 1

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

10.2g clay and 594ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 25 ℃ of strong down vibrations 2 hours.Also have, 1.8g sodium polyacrylate and 594ml pure water are put into the plastic seal container together with rotor, after 25 ℃ of strong down vibrations 2 hours, stirred 7 minutes with the rotating speed of homogenizer with 10000rpm again, what obtain homogeneous contains additive liquid.At this moment, contain the heating of additive liquid, temperature rises to about 60 ℃, and the viscosity of liquid reduces.

Then, with this clay dispersion with contain additive liquid and put into the plastic seal container, after 25 ℃ of strong down vibrations 2 hours, stirred 20 minutes with the rotating speed of homogenizer again, obtain the argillaceous liquid of homogeneous with 10000rpm together with rotor.At this moment, the heating of argillaceous liquid, temperature rises to about 90 ℃, and the viscosity of argillaceous liquid reduces.And, about 90 ℃ argillaceous liquid is put into vacuum degasser, under the decompression below the 0.08MPa, carry out 20 minutes the degassing.

Then, this argillaceous liquid is coated on flat in the surface of the tray that polypropylene makes.The little bamboo clappers in the ground of stainless steel is used in the coating of argillaceous liquid, utilizes the roll adjustment plate as guiding, forms the argillaceous liquid film of thickness homogeneous.This tray is put in the forced blowing type baking box, under 60 ℃ temperature condition, heated about 6 hours, make it dry.The clay membrane that produces is peeled off from tray, obtained the clay membrane that thickness is about the homogeneous of 22 μ m.The clay membrane that obtains has the physical strength that the independent film of can be used as is utilized.Again, the transparency height, flexibility is good.

In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, in order to confirm the transparency of clay membrane, ultraviolet-visible pectrophotometer " UV-3101PC " with Shimadzu Scisakusho Ltd's manufacturing, after measuring the transmitance in the wavelength region that wavelength 200nm is above, 800nm is following, have transmitance (with reference to Fig. 1) more than 85% in scope, do not observe painted from 312nm to 800nm.Further, the total light transmittance of the clay membrane that the nephelometer made from Japanese electric look Industrial Co., Ltd " NDH2000 " is measured is 91.7%, and mist (turbidity) is 2.3%.

Then, in order to confirm the dimensional stability of this clay membrane, " TMA/SS220 " that make with エ ス ア イ ア イ Na ノ テ Network ノ ジ one Co., Ltd. measures linear expansivity.Sample is wide to be 3mm, loads to be 2g, is cooled to 31 ℃ after being heated to 233 ℃ with the temperature rise rate of 5 ℃/min, is heated to 300 ℃ with the temperature rise rate of 5 ℃/min at once afterwards, measures linear expansivity.As a result, the average linear expansivity from 40 ℃ to 250 ℃ temperature range is 5.4ppm, and the value of linear expansivity is roughly certain in the said temperature scope.

In order to confirm that this clay membrane is clay crystalline layer height orientation and lamination densely, carry out the analysis of X-ray diffraction with the X-ray diffraction device " RINT-2500 " of the リ ガ of Co., Ltd. Network.The X ray wavelength that uses is 1.54056 of Cu/K α

In the X-ray diffraction spectrum that obtains (with reference to figure 2), 7.44 position in 2 θ (being converted into interfloor distance is 1.19nm) observes clear and definite main peak, can know in the clay membrane clay crystalline layer height ground lamination and densely the orientation.

Again, use Hitachi to make the TEM " HF-2000 " that Co., Ltd. of institute makes, take after the electron micrograph of section of clay membrane, can know be clay crystalline layer with the average interfloor distance orientation of about 1.2nm the structure of the homogeneous of lamination (with reference to Fig. 3) densely.

Again, in order to confirm the gas barrier property of this clay membrane, the gas permeation amount determining device made from Japanese beam split Co., Ltd. " Gaspcrm-100 " is measured the transmission coefficient of oxygen.As a result, confirm that the transmission coefficient of the oxygen in the room temperature is less than 3.2 * 10 ^-11Cm ²s ^-1CmHg ^-1, can understand to demonstrate high gas barrier properties.

Embodiment 2

When making clay membrane, change the amount of the argillaceous liquid that pours into the polypropylene tray the samely, make 3 clay membranes that thickness is different with embodiment 1.The thickness of the clay membrane that obtains is respectively 13 μ m, 19 μ m and 24 μ m.

After embodiment 1 measures transmitance the samely, the scope from 326nm to 800nm of the scope from 344nm to 800nm of the scope from 278nm to 800nm of thickness 13 μ μ m, thickness 19 μ m, thickness 24 μ μ m all has the transmitance more than 85%, does not all observe painted.Again, the shape of the ultraviolet-visible absorption spectroscopy of any is all about the same with the clay membrane of embodiment 1.

Again, after embodiment 1 measured total light transmittance the samely, thickness 13 μ m's was 91.7%, and thickness 19 μ m's is 90.9%, and thickness 24 μ m's is 91.6%.Again, measure mist (turbidity) afterwards with embodiment 1, thickness 13 μ m's is 1.9% the samely, and thickness 19 μ m's is 3.4%, and thickness 24 μ m's is 2.9%.

Embodiment 3

With embodiment 1 the same operation, the argillaceous liquid that obtains outgasing.In the brazen tray of B4 model, put surface enforcement into and peel off the level and smooth PET film that the thickness of facilitation processing is 50 μ m (great achievement ラ ミ ネ one -Co., Ltd. makes), with adhesive tape fixedly the PET film around after, cross in the enforcement of this PET film and to peel off coating argillaceous liquid on the face that facilitation handles, obtain the clay membrane of the homogeneous of the about 22 μ m of thickness the samely with embodiment 1.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.

In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, after embodiment 1 measures transmitance, have transmitance more than 85% the samely, do not observe painted in scope from 264nm to 800nm.Again, the clay membrane of the shape of ultraviolet-visible absorption spectroscopy and embodiment 1 is about the same.Again, measure total light transmittance with embodiment 1, be 92.0% the samely, measures mist (turbidity), is 1.6%.

In atmosphere under 300 ℃ with this clay membrane heating 1 hour, similarly measure transmitance, have transmitance more than 85% from the scope of 385nm to 800nm, do not observe painted.The shape of ultraviolet-visible absorption spectroscopy is preceding about the same with heating.Again, equally measuring total light transmittance is 91.1%, measures mist (turbidity), is 1.9%, confirms to have high thermotolerance.

Comparative example 1

To and contain additive liquid with the clay dispersion of embodiment 1 the same manufacturing and put into the plastic seal container, after 25 ℃ of strong down vibrations 2 hours, stir 20 minutes with the rotating speed of homogenizer again, obtain the argillaceous liquid of homogeneous with 10000rpm together with rotor.

This argillaceous liquid is not outgased, the same with embodiment 3, be coated on the surface of PET film, obtain the clay membrane of the homogeneous of the about 17 μ m of thickness.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.There are many visual identifiable bubbles on the surface of confirming clay membrane, touches and can clearly feel uneven with finger.Again, measure total light transmittance with embodiment 1, be 91.8% the samely, measures mist (turbidity), is 5.1%.

Comparative example 2

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

5.1g clay and 594ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 25 ℃ of strong down vibrations 2 hours.In this clay dispersion, directly add the 0.9g sodium polyacrylate,, obtain argillaceous liquid 25 ℃ of following thermal agitations 2 hours.Use the argillaceous liquid that obtains like this, carry out follow-up operation the samely, obtain the clay membrane of the homogeneous of the about 17 μ m of thickness with embodiment 3.

The clay membrane that obtains has the physical strength that the independent film of can be used as is used.In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.After embodiment 1 measures transmitance the samely, do not have the wavelength region may (with reference to figure 1) of the transmitance more than 85% again.Again, measure total light transmittance with embodiment 1 is 91.8% the samely, measures mist (turbidity), is 7.0%.

Comparative example 3

When making clay membrane, change the amount of the argillaceous liquid that pours into tray the samely, make 2 clay membranes that thickness is different with comparative example 2.The thickness of the clay membrane that obtains is respectively 15 μ m and 16 μ m.

After embodiment 1 measured transmitance the samely, any clay membrane did not all have the wavelength region may of the transmitance more than 85%.Again, measure total light transmittance with embodiment 1, thickness 15 μ m's is 92.0% the samely, and thickness 16 μ m's is 91.7%.Again, measure mist (turbidity) with embodiment 1, thickness 15 μ m's is 7.7% the samely, and thickness 16 μ m's is 6.5%.

Comparative example 4

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

1.8g sodium polyacrylate and 594ml pure water are put into the plastic seal container together with rotor,, obtain containing additive liquid 25 ℃ of strong down vibrations 2 hours.Contain in the additive liquid at this and to add the 5.1g clay, 25 ℃ of following thermal agitations 2 hours, clay fully disperseed, and observes many bigger clay aggregates, can not obtain being suitable for making the argillaceous liquid of clay membrane.

Comparative example 5

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

4.0g clay and 196ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 22 ℃ of strong down vibrations 2 hours.Also have, 2g sodium polyacrylate and 198ml pure water are put into the plastic seal container together with rotor, after 22 ℃ of strong down vibrations 2 hours, stirred 7 minutes with the rotating speed of homogenizer with 10000rpm again, what obtain homogeneous contains additive liquid.

Then, with this clay dispersion with contain additive liquid and put into the plastic seal container together with rotor.Clay dispersion is that mass ratio is 3 pairs 7 with the ratio that contains the amount of additive liquid.After 22 ℃ of following thermal agitations 2 hours, stirred 20 minutes with the rotating speed of homogenizer again with 10000rpm, obtain the argillaceous liquid of the content of clay less than the homogeneous of 50 quality %.

Use this argillaceous liquid to need not to outgas, the same with embodiment 3, obtain the clay membrane of the homogeneous of thick about 20 μ m.In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, measure total light transmittance with embodiment 1 is 91.8% the samely, and measuring mist (turbidity) is 6.3%.

Embodiment 4

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium carboxy methyl cellulose (manufacturing of ア Le De リ Star チ Co., Ltd.) as additive.

1.0g clay and 89ml pure water are put into the plastic seal container together with rotor,, obtain clay dispersion 25 ℃ of strong down vibrations 2 hours.Also have, 0.18g sodium carboxy methyl cellulose and 30ml pure water are put into the plastic seal container together with rotor, after 25 ℃ of down strong vibrations 2 hours, stirred 10 minutes with the rotating speed of homogenizer again, obtain containing additive liquid with 10000rpm.

Then, with this clay dispersion with contain additive liquid and mix, after vibrating strongly 2 hours, stirred 10 minutes with the rotating speed of homogenizer again, obtain the argillaceous liquid of solid formation branch concentration 1 quality % with 10000rpm.And, stir de-gassing vessel AR-100 (シ of Co., Ltd. Application キ-manufacturing) with this argillaceous liquid stirring 5 minutes with possessing limit rotation-revolution type around the container of axle revolution limit rotation.Afterwards, with the degassing pattern degassing 2 minutes, this degassing pattern be with stop from then the centrifugal force that only carries out revolution motion remove and sneak into bubble.The argillaceous liquid that obtains is put into the dispotray of plastics, make the following thin liquid film shape of the about 5mm of thickness, under the decompression below the 0.08MPa, carry out vacuum outgas 10 minutes.

On the sheet brass of B6 model, be equipped with in the tray that the guiding of the teflon (registered trademark) of thickness 1mm is made and put into the identical PET film that uses with embodiment 3, the argillaceous liquid (thickness 3mm) of coating 20.1g on the face that is being coated with polyorganosiloxane resin of PET film.And, make the liquid level of argillaceous liquid of coating level and smooth with glass stick.

This tray of containing argillaceous liquid is put in the baking oven, under 60 ℃ temperature condition, heated about 5 hours, make it dry.After the drying, the clay membrane that obtains is peeled off from the PET film, obtained the transparent clay film that thickness is about the homogeneous of 14 μ m.

Again, the total light transmittance of measuring clay membrane with embodiment 1 is 91.3% the samely, and measuring mist (turbidity) is 3.5%.

Embodiment 5

Use natural montmorillonite (the Network ニ ピ ア F that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

27.4g clay and 658ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 25 ℃ of strong down vibrations 2 hours.Also have, 1.44g sodium polyacrylate and 142ml pure water are put into the plastic seal container together with rotor, after 25 ℃ of strong down vibrations 2 hours, stirred 7 minutes with the rotating speed of homogenizer with 10000rpm again, what obtain homogeneous contains additive liquid.At this moment, contain the heating of additive liquid, temperature rises to about 60 ℃, and the viscosity of liquid reduces.

Then, with this clay dispersion with contain additive liquid and put into the plastic seal container, after 25 ℃ of strong down vibrations 2 hours, stirred 20 minutes with the rotating speed of homogenizer again, obtain the argillaceous liquid of homogeneous with 10000rpm together with rotor.At this moment, the heating of argillaceous liquid, temperature rises to about 90 ℃, and the viscosity of argillaceous liquid reduces.And, about 90 ℃ argillaceous liquid is put into vacuum degasser at once, under the decompression below the 0.08MPa, carry out 20 minutes the degassing.

Then, this argillaceous liquid is coated on the flat in the surface of brazen tray, coating argillaceous liquid uses the little bamboo clappers in ground of stainless steel, utilizes the roll adjustment plate as guiding, forms the argillaceous film of thickness homogeneous.This tray is put in the forced blowing type baking box, and heating is about 6 hours under 60 ℃ temperature condition, makes it dry.The clay membrane that generates is peeled off from tray, obtained the clay membrane that thickness is about the homogeneous of 40 μ m.The clay membrane that obtains use so can be used as independent film, and flexibility is good owing to have sufficient mechanical.

In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.

Comparative example 6

Use natural montmorillonite (the Network ニ ピ ア F that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use sodium polyacrylate (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

27.4g clay and 658ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 25 ℃ of strong down vibrations 2 hours.In this clay dispersion, add the 1.44g sodium polyacrylate,, produce many bigger clay aggregates, can not obtain being suitable for making the argillaceous liquid of clay membrane 25 ℃ of following thermal agitations 2 hours.

Embodiment 6

Use natural montmorillonite (the Network ニ ピ ア F that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use ε-Ji Neixianan (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

27.4g clay and 600ml pure water are put into the plastic seal container together with rotor,, obtain the clay dispersion of homogeneous 25 ℃ of strong down vibrations 2 hours.Again, 1.44g ε-Ji Neixianan and 58ml pure water are put into the plastic seal container together with rotor, stir with agitator, what obtain homogeneous contains additive liquid.

Then, with this clay dispersion with contain additive liquid and put into the plastic seal container, after 25 ℃ of strong down vibrations 1 hour, stirred 20 minutes with the rotating speed of homogenizer again, obtain the argillaceous liquid of homogeneous with 10000rpm together with rotor.At this moment, the heating of argillaceous liquid, temperature rises to about 90 ℃, and the viscosity of argillaceous liquid reduces.And, about 90 ℃ argillaceous liquid is put into vacuum degasser, under the decompression below the 0.08MPa, carry out 40 minutes the degassing.Begin the degassing, after about 15 minutes, almost do not observe from argillaceous liquid and produce bubble.

Then, this argillaceous liquid is coated on flat in the surface of brazen tray.The little bamboo clappers in the ground of stainless steel is used in the coating of argillaceous liquid, utilizes the roll adjustment plate as guiding, forms the argillaceous film of thickness homogeneous.This tray is put in the forced blowing type baking box, and heating is about 6 hours under 60 ℃ temperature condition, makes it dry.The clay membrane that produces is peeled off from tray, obtained the clay membrane that thickness is about the homogeneous of 30 μ m.The clay membrane that obtains use so can be used as independent film, and flexibility is good owing to have sufficient mechanical.

The rate of rise in temperature about 18 ℃ with per minute is heated to 300 ℃ with this clay membrane, remains on 300 ℃ and observes after 1 hour.So, though clay membrane melanism is not a little observed the expansion that can with the naked eye confirm.After with scanning electron microscope (SEM) section of this clay membrane being observed, the unusual homogeneous (with reference to figure 4) in inside as can be known.

In order to confirm the dimensional stability of this clay membrane, measure linear expansivity with embodiment 1 the samely.Sample is wide to be 3mm, loads to be 5g.Temperature rise rate with 5 ℃/min is heated to 148 ℃, keeps being cooled to 38 ℃ after this temperature 1 hour.And the temperature rise rate with 5 ℃/min is heated to 299 ℃ at once, measures linear expansivity.Its result, the linear expansivity from 40 ℃ to 299 ℃ temperature range is 1.2～8.0ppm/ ℃.

In order to confirm that this clay membrane is a clay crystalline layer height orientation and lamination densely carries out the analysis of X-ray diffraction with embodiment 1 the samely.In the X-ray diffraction spectrum that obtains (with reference to figure 5), 6.48 position in 2 θ (being converted into interfloor distance is 1.36nm) observes clear and definite main peak, expression in the clay membrane clay crystalline layer height ground lamination and be orientated densely.

Again, after embodiment took the electron micrograph of section of clay membrane the samely, clay crystalline layer was lamination (with reference to Fig. 6) densely equally with the average interfloor distance orientation of about 1.2nm as can be known.A little bit smaller a little than by X-ray diffraction analysis of the average interfloor distance of estimating from electron micrograph, this is because the analysis of X-ray diffraction is under atmosphere, and electron micrograph carries out under high vacuum when taking.That is, infer that reason is owing to the moisture of sneaking into clay membrane volatilizees under vacuum, so average interfloor distance dwindles a little.

In order to confirm the gas barrier property of this clay membrane, measure the transmission coefficient of oxygen with embodiment 1 the samely.As a result, confirm that the transmission coefficient of the oxygen in the room temperature is less than 3.2 * 10 ^-11Cm ²s ^-1CmHg ^-1, can understand to demonstrate high gas barrier properties.

Comparative example 7

Obtain argillaceous liquid with embodiment 6 the samely.Will by with homogenizer to stirring and temperature rises to about 90 ℃ argillaceous liquid placed at normal temperatures about 30 minutes, temperature drops to after about 30 ℃, puts vacuum into to take off subtraction unit, outgases under the decompression below the 0.08MPa 40 minutes.Generation from the bubble of argillaceous liquid exists with low frequency during outgasing, but confirms last.

The same with embodiment 6, obtain the clay membrane of the homogeneous of the about 30 μ m of thickness with this argillaceous liquid.The clay membrane that obtains use so can be used as independent film, and flexibility is good owing to have sufficient mechanical.

Lift velocity with the about 18 ℃ temperature of per minute is heated to 300 ℃ with this clay membrane,, observes after 1 hour 300 ℃ of maintenances.So clay membrane is melanism a little, the diameter of observing many point-like (spot) is about the circular expander of 1～5mm.After with SEM the section of this film being observed, observe many tiny spaces (with reference to figure 7).This expression is removed the gaseous constituent that contains at argillaceous liquid when insufficient, sneaks into the inside that bubble (space) that the gaseous constituent of argillaceous liquid causes remains in clay membrane morely, might produce the expansion as above-mentioned circle during heating.

Embodiment 7

Use hydrophobicity hectorite (Le-セ Application イ ト SAN that コ one プ ケ ミ カ Le Co., Ltd. makes) as clay, use ア サ Off レ Star Network ス L451 (manufacturing of the ケ ミ カ of Asahi Chemical Industry Le ズ Co., Ltd.) as additive.

The mixed solvent of 8.5g clay and 62g toluene and 12g methyl alcohol is put into Erlenmeyer flask simultaneously, under about 25 ℃, stirred 2 hours, obtain the clay dispersion of homogeneous by rotor.Again, 4511.5g ア サ Block レ Star Network ス L451 and 16g toluene are put in the Erlenmeyer flask, stirred 1 hour by rotor, what obtain homogeneous contains additive liquid.

Then, with this clay dispersion with contain additive liquid and in another Erlenmeyer flask, mix, under about 25 ℃, stirred 2 hours, obtain the argillaceous liquid of homogeneous by rotor.And, Yi Bian this argillaceous liquid is under reduced pressure stirred, Yi Bian outgased several minutes.

Cover inner face with the used identical brazen tray of embodiment 4 with aluminium foil, do into the part towards the bottom surface of tray of aluminium foil smooth.To put in the tray with the same PET film that embodiment 3 uses and (just, be placed on the aluminium foil) coating argillaceous liquid on the PET film.The rod of glass is used in the coating of argillaceous liquid, by utilizing the roll adjustment plate as guiding, forms the argillaceous overlay film of thickness homogeneous.

This tray is placed on the hot plate, and heating is about 30 minutes under 80 ℃ temperature condition, makes it dry.The clay membrane that produces is peeled off from the PET film, obtained the clay membrane that thickness is about the homogeneous of 57 μ m.The clay membrane that obtains use so can be used as independent film, and flexibility is good owing to have sufficient mechanical.

Again,, after embodiment 1 measures transmitance, have transmitance more than 85% the samely, do not observe painted in scope from 360nm to 800nm in order to confirm the transparency of clay membrane.Again, measure total light transmittance with embodiment 1 is 90.1% the samely, and measuring mist (turbidity) is 1.6%.

In 200 ℃ of following atmosphere,, similarly measure after the transmitance, have transmitance more than 85%, do not observe painted from the scope of 420nm to 800nm with this clay membrane heating 30 minutes.Again, similarly measuring total light transmittance is 91.1%, and measuring mist (turbidity) is 1.7%.

Again, this clay membrane is immersed in 24 ℃ the water after 24 hours, do not have the variation that can with the naked eye confirm, intensity also almost descends, and has high water tolerance as can be known.The water-intake rate of following dipping that changes in weight before and after dipping calculates is about 1.9%.

Comparative example 8

Use hydrophobicity hectorite (Le-セ Application イ ト SAN that コ one プ ケ ミ カ Le Co., Ltd. makes) as clay, use ア サ Off レ Star Network ス L451 (manufacturing of the ケ ミ カ of Asahi Chemical Industry Le ズ Co., Ltd.) as additive.

8.0g clay and 80g toluene are put into Erlenmeyer flask, under about 25 ℃, stirred 2 hours, obtain the clay dispersion of homogeneous by rotor.Again, 1.5g ア サ Block レ Star Network ス L451 and 10g toluene are put in the Erlenmeyer flask, stirred 1 hour by rotor under about 25 ℃, what obtain homogeneous contains additive liquid.

With this argillaceous liquid, the same with embodiment 7, obtain the clay membrane of the homogeneous of the about 84 μ m of thickness.The clay membrane that obtains uses so can be used as independent film, and has flexibility owing to have sufficient mechanical.

In order to confirm the transparency of clay membrane, after embodiment 1 measured transmitance the samely, the result did not have the zone of the transmitance more than 85%, did not observe painted.Again, measure total light transmittance with embodiment 1 is 90.8% the samely, and measuring mist (turbidity) is 23.8%.

Embodiment 8

The same with embodiment 1, adjust the same argillaceous liquid of forming.In the brazen tray of B4 model, put into the PET film (PET film with adhesive tape be not fixed on tray on) identical, coating argillaceous liquid on the face that is being coated with polyorganosiloxane resin of PET film with embodiment 3.The little bamboo clappers in the ground of stainless steel is used in the coating of argillaceous liquid, utilizes the roll adjustment plate as guiding, forms the argillaceous overlay film of thickness homogeneous.

This tray is put in the forced blowing type baking box, and heating is about 6 hours under 60 ℃ temperature condition, under the deformable state of PET film as support, makes it dry.Dry end just, the integrated ground of PET film and clay membrane is crooked, and its part does not contact with the bottom surface of tray, is isolating state.The clay membrane that generates is ined succession after the PET film takes out, in atmosphere, placed 30 minutes, after bending almost disappears, clay membrane is peeled off from the PET film, obtain the clay membrane that thickness is about the homogeneous of 22 μ m.

The clay membrane that obtains has the physical strength that the independent film of can be used as is used.The transparency height is flexible good again.Again, whole film is not observed crackle or fissured generation.

In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, after embodiment 1 measured transmitance the samely, the transmitance in wavelength 500nm was 89.3%, had transmitance more than 80% from the scope of 264nm to 800nm.The total light transmittance of measuring clay membrane with embodiment 1 is 92.0% the samely, and measuring mist (turbidity) is 1.6%.

Comparative example 9

Prepare one because the polypropylene system tray of frame and B4 model thick thereby that can easily not be out of shape is arranged on every side.And, will be coated on the flat on the surface of this tray with the same argillaceous liquid of use among the embodiment 8.The little bamboo clappers in the ground of stainless steel is used in the coating of argillaceous liquid, utilizes the roll adjustment plate as guiding, forms the argillaceous overlay film of thickness homogeneous.

This tray is put in the forced blowing type baking box, under 60 ℃ temperature condition, heated about 6 hours, make it dry.Tray is not out of shape during dry the end, and roughly whole clay membranes is attached to the surface of tray, and the part of clay membrane produces the crack.The clay membrane that produces is peeled off from tray, obtained the clay membrane that thickness is about the homogeneous of 22 μ m.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.Just, as mentioned above, the part of clay membrane produces the crack, so a plurality of partial segmentations of clay membrane can not get the clay membrane of B4 model.

In order to confirm the flexibility of clay membrane, bend to the cylindric of radius 6mm, but do not produce new crack.Again, after embodiment 1 measured transmitance the samely, the transmitance in wavelength 500nm was 89.0%, had transmitance more than 85% from the scope of 312nm to 800nm.The total light transmittance of measuring clay membrane with embodiment 1 is 91.7% the samely, and measuring mist (turbidity) is 2.3%.

Embodiment 9

The same with embodiment 8, obtain the clay membrane (primary drying film) of the homogeneous of the about 21 μ m of thickness.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.The total light transmittance of measuring clay membrane with embodiment 1 is 91.5% the samely, and measuring mist (turbidity) is 1.8%.Again, the surface roughness meter made of ケ-エ Le エ-テ Application コ-Le society " ア Le Off ァ step IQ " the surface roughness Ra of the clay membrane measured is 39nm.

After making this clay membrane, be immersed in about 5 seconds in the pure water at once, after pulling out, be clipped in be coated with polyorganosiloxane resin on the surface with above-mentioned the same PET film between.At this moment, the even surface of two PET films contacts with clay membrane.Then, the glass roller of surface smoothing rolls on the PET film, clay membrane is stretched extrude redundant moisture, peels off the PET film of one side then, places diel down at 20 ℃, makes it dry.The exsiccant clay membrane is peeled off from the PET film of another side, obtained the clay membrane that thickness is about the homogeneous of 10 μ m.The transparent clay film that obtains is owing to having the tensile strength of 32MPa, so have the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.

In order to confirm the flexibility of transparent clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, in order to confirm the transparency of clay membrane, after transmitance in the wavelength region more than embodiment 1 is determined at wavelength 190nm, below the 800nm, have transmitance more than 85% the samely, do not observe painted in scope from 312nm to 800nm.Again, the total light transmittance of the transparent clay membrane of measuring with embodiment 1 is 91.7% the samely, and mist is 1.5%.Again, the surface roughness Ra of the same clay membrane of measuring is 35nm.

The clay membrane that this is transparent was placed in the dust free chamber that remains on 1 air pressure, 24 ℃ of temperature, humidity 45% after 1 week, and with above-mentioned total light transmittance and the mist measured the samely, total light transmittance is 91.8% as a result, and mist is 1.6%.Again, place after one month, carry out same mensuration, total light transmittance is 91.9% as a result, and mist is 1.5%.

Comparative example 10

The same with embodiment 8, obtain the clay membrane of the homogeneous of the about 19 μ m of thickness.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.The total light transmittance of the clay membrane of measuring with embodiment 1 is 91.7% the samely, and mist is 2.3%.Again, the surface roughness Ra of the clay membrane of measuring with embodiment 9 is 47nm the samely.

This clay membrane is placed on remains in 24 ℃, the dust free chamber of 1 air pressure, humidity 45%, mist is to increase to 24.3% after 16.8%, one month after 1 week as a result.Again, the surface roughness Ra of the clay membrane of placement after 1 month is 109nm.

Embodiment 10

To be placed on the primary drying film that comparative example 9 is made the samely in the dust free chamber that remains on 1 air pressure, 24 ℃ of temperature, humidity 45% 1 one months.So, obtain mist and increase to the clay membrane that 26.5% thickness is about 23 μ m.Pure water is sprayed on this clay membrane, as clean surface, makes the clay membrane swelling, be clipped in surface coated then and between the PET film of polyorganosiloxane resin.At this moment, the even surface of two PET films contacts with clay membrane.

Then, the samely the glass roller of surface smoothing is rolled on the PET film, clay membrane is stretched extrude redundant moisture, peel off the PET film of one side then, place diel down, make it dry at 24 ℃ with embodiment 9.The exsiccant clay membrane is peeled off from the PET film of another side, obtained the clay membrane that thickness is about the homogeneous of 12 μ m.The tensile strength of the transparent clay membrane that obtains is 22MPa, has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.

In order to confirm the flexibility of transparent clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, in order to confirm the transparency of clay membrane, after transmitance in the wavelength region more than embodiment 1 is determined at wavelength 190nm, below the 800nm, have transmitance more than 85% the samely, do not observe painted in scope from 328nm to 800nm.Again, the total light transmittance of the transparent clay membrane of measuring with embodiment 1 is 91.8% the samely, and mist is 0.63%.Again, the surface roughness Ra of the clay membrane of measuring with embodiment 1 is 23nm the samely.

The clay membrane that this is transparent was placed in the dust free chamber that remains on 1 air pressure, 24 ℃ of temperature, humidity 45% after 1 week, and with above-mentioned total light transmittance and the mist measured the samely, total light transmittance is 91.7% as a result, and mist is 0.68%.Again, place after one month, carry out same mensuration, total light transmittance is 91.9% as a result, and mist is 0.65%.

Comparative example 11

The same with comparative example 2, obtain the clay membrane of the homogeneous of the about 17 μ m of thickness.The clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.The total light transmittance of the clay membrane of measuring with embodiment 1 is 91.8% the samely, and mist is 7.0%.Again, the surface roughness Ra of the clay membrane of measuring with embodiment 9 is 55nm the samely.

This clay membrane is placed on remains in 24 ℃, the dust free chamber of 1 air pressure, humidity 45%, mist is to increase to 27.0% after 21.4%, one month after 1 week as a result.Again, the surface roughness Ra of the clay membrane of placement after 1 month is 122nm.

Embodiment 11

Mist in the comparative example 11 is increased to for primary drying film immersion about 5 seconds in pure water of 27.0%, after pulling out, be clipped in be coated with polyorganosiloxane resin on the surface with above-mentioned the same PET film between.At this moment, the even surface of two PET films contacts with clay membrane.Then, the glass roller of surface smoothing rolls on the PET film, clay membrane is stretched extrude redundant moisture, peels off the PET film of one side then, places diel down at 20 ℃, makes it dry.The exsiccant clay membrane is peeled off from the PET film of another side, obtained the clay membrane that thickness is about the homogeneous of 12 μ m.The tensile strength of the transparent clay membrane that obtains is 35MPa, has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.

In order to confirm the flexibility of transparent clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, in order to confirm the transparency of clay membrane, after transmitance in the wavelength region more than embodiment 1 is determined at wavelength 190nm the samely, below the 800nm, the result has transmitance more than 85% in the scope from 321nm to 800nm, does not observe painted.Again, the total light transmittance of the transparent clay membrane of measuring with embodiment 1 is 92.0% the samely, and mist is 0.83%.Again, the surface roughness Ra of the clay membrane of measuring with embodiment 9 is 32nm the samely.

The clay membrane that this is transparent was placed in the dust free chamber that remains on 1 air pressure, 24 ℃ of temperature, humidity 45% after 1 week, and with above-mentioned total light transmittance and the mist measured the samely, total light transmittance is 92.0% as a result, and mist is 0.86%.Again, place and carry out same mensuration after one month, total light transmittance is 92.1% as a result, and mist is 0.84%.

Embodiment 12

Mist in the comparative example 11 increases on 27.0% the primary drying film and sprays pure water, as clean surface, make the clay membrane swelling after, be clipped in be coated with polyorganosiloxane resin on the surface with above-mentioned the same PET film between.At this moment, the even surface of two PET films contacts with clay membrane.Then, the samely the glass roller of surface smoothing is rolled on the PET film, clay membrane is stretched extrude redundant moisture, peel off the PET film of one side then, place diel down, make it dry at about 20 ℃ with embodiment 1.The exsiccant clay membrane is peeled off from the PET film of another side, obtained the clay membrane that thickness is about the homogeneous of 10 μ m.The tensile strength 31MPa of the transparent clay membrane that obtains has the physical strength that the independent film of can be used as is used.Again, the transparency height, flexible good.

In order to confirm the flexibility of transparent clay membrane, bend to the cylindric of radius 6mm, do not produce crack etc., do not produce any defective.Again, in order to confirm the transparency of clay membrane, after transmitance in the wavelength region more than embodiment 1 is determined at wavelength 190nm the samely, below the 800nm, the result has transmitance more than 85% in the scope from 305nm to 800nm, does not observe painted.Again, the total light transmittance of the transparent clay membrane of measuring with embodiment 1 is 91.9% the samely, and mist is 0.62%.Again, the surface roughness Ra of the clay membrane of measuring with embodiment 1 is 26nm the samely.

The clay membrane that this is transparent was placed in the dust free chamber that remains on 1 air pressure, 24 ℃ of temperature, humidity 45% after 1 week, and with above-mentioned total light transmittance and the mist measured the samely, total light transmittance is 92.0% as a result, and mist is 0.64%.Again, place and carry out same mensuration after one month, total light transmittance is 92.1% as a result, and mist is 0.65%.

Utilizability on the industry

The manufacture method of clay mambrane of the present invention can be made a kind of clay mambrane, and clay and the additive of this clay mambrane divide equably Loose, be difficult to crack, the defective such as crack, have the intensity that the independent film of can be used as is utilized. Again, clay mambrane of the present invention is The defectives such as a kind of clay and additive disperse equably, be difficult to crack, crack, have strong that the independent film of can be used as utilizes The clay mambrane of degree. Also have, though be a kind of light transmittance height and mist little be placed in the atmosphere that mist also is difficult in time and The transparent clay mambrane that increases.

Claims (32)

1. the manufacture method of a clay membrane is characterized in that, has:

Argillaceous liquid is adjusted operation, respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, above-mentioned clay dispersion and the above-mentioned additive liquid that contains are mixed, make in the total amount of above-mentioned clay and above-mentioned additive, the ratio of above-mentioned additive is above 0 quality %, below the 50 quality %, thereby obtains argillaceous liquid; With

Drying process is configured in this argillaceous liquid after the surface of support, removes above-mentioned solvent, carries out drying.

2. the manufacture method of a clay membrane is characterized in that, has:

Argillaceous liquid is adjusted operation, respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent, above-mentioned clay dispersion and the above-mentioned additive liquid that contains are mixed, make in the total amount of above-mentioned clay and above-mentioned additive, the ratio of above-mentioned additive is above 0 quality %, below the 30 quality %, thereby obtains argillaceous liquid; With

Drying process is configured in this argillaceous liquid after the surface of support, removes above-mentioned solvent, carries out drying.

3. the manufacture method of clay membrane as claimed in claim 1 or 2 is characterized in that, has the degassing process that gas that described argillaceous liquid contained is reduced.

4. as the manufacture method of each the described clay membrane in the claim 1～3, it is characterized in that having the stripping process that the dry thing that obtains by described drying process is peeled off from described support.

5. as the manufacture method of each the described clay membrane in the claim 1～4, it is characterized in that, adjust in the operation, be higher than under the temperature of normal temperature, mix described clay dispersion and the described additive liquid that contains, obtain described argillaceous liquid at described argillaceous liquid.

6. the manufacture method of clay membrane as claimed in claim 3 is characterized in that, described argillaceous liquid is located at the temperature that is higher than normal temperature, places under reduced pressure simultaneously, and the gas that described argillaceous liquid is contained reduces.

7. the manufacture method of clay membrane as claimed in claim 3 is characterized in that, by described argillaceous liquid is located at the temperature that is higher than normal temperature, under reduced pressure stirs simultaneously, and the gas that described argillaceous liquid is contained reduces.

8. the manufacture method of clay membrane as claimed in claim 4 is characterized in that, described support has flexibility, under the deformable state of described support, carry out drying after, described dry thing is peeled off from described support.

9. the manufacture method of clay membrane as claimed in claim 8 is characterized in that, described support is resinous film.

10. the manufacture method of clay membrane as claimed in claim 8 or 9 is characterized in that, described support is implemented to peel off facilitation handle.

11. the manufacture method of clay membrane is characterized in that as claimed in claim 8 or 9, and described support is implemented hydrophobic processing treatment.

12. manufacture method as each described clay membrane among the claim 1-11, it is characterized in that, has drying process again, this again drying process be that surface configuration at the dry thing that obtains by described drying process makes the liquid of described clay swelling or makes described additive dissolving or dispersive liquid, make it again dry.

13. the manufacture method of clay membrane as claimed in claim 12 is characterized in that, by being immersed in the described liquid, described liquid is configured in the surface of described dry thing.

14. the manufacture method of clay membrane as claimed in claim 12 is characterized in that, by spraying described liquid, described liquid is configured in the surface of described dry thing.

15. manufacture method as each the described clay membrane in the claim 12～14, it is characterized in that, contact with the level and smooth member of surface smoothing by the described dry thing that makes near surface part swelling at least at the described liquid of surface configuration, after its surface smoothingization, carry out again dry to described liquid.

16. the manufacture method of clay membrane as claimed in claim 15 is characterized in that, described level and smooth member has flexibility and deformable, makes described liquid dry again under described dry thing and described level and smooth member state of contact.

17. the manufacture method as each described clay membrane in the claim 1～16 is characterized in that, described clay be to water the affinity height, be dispersed in hydrophilic clay in the water easily.

18. the manufacture method as each described clay membrane in the claim 1～16 is characterized in that, described clay be to organic solvent the affinity height, be dispersed in hydrophobicity clay in the organic solvent easily.

19. the manufacture method of clay membrane as claimed in claim 18, it is characterized in that, described hydrophobicity clay is to be replaced as organic ion by the mineral ion that hydrophilic clay is had to improve the affinity of organic solvent and dispersed, and described organic ion contains at least a in ammonium ion, phosphonium ion, the imidazol ion.

20. the manufacture method as each the described clay membrane in the claim 1～19 is characterized in that, the clay membrane that obtains is transparent.

21. a clay membrane is characterized in that, is a kind of clay membrane made from the manufacture method of each the described clay membrane in the claim 1～20, is formed by lamellated clay crystallization lamination on film thickness direction.

22. clay membrane as claimed in claim 21 is characterized in that, from 30 ℃ to 250 ℃ averages coefficient of linear expansion below 10ppm.

23., it is characterized in that mist is below 5% as claim 21 or 22 described clay membranes, total light transmittance is more than 85% simultaneously, the transmittance in the wavelength region more than 400nm, below the 800nm is more than 85%, below 95%.

24., it is characterized in that mist is below 2% as claim 21 or 22 described clay membranes, total light transmittance is more than 85% simultaneously, the transmittance in the wavelength region more than 400nm, below the 800nm is more than 85%, below 95%.

25., it is characterized in that mist is less than 1% as claim 21 or 22 described clay membranes, total light transmittance is more than 85% simultaneously, the transmittance in the wavelength region more than 400nm, below the 800nm is more than 85%, below 95%.

26. each the described clay membrane as in the claim 23～25 is characterized in that, the mist under the environment of 24 ℃, 1 normal atmosphere, humidity 45% through the time change more than-2%, below 2%.

27. each the described clay membrane as in the claim 21～26 is characterized in that, 15 μ m are thick for Film Thickness Ratio.

28. an Electronic Paper is characterized in that, the clay membrane that at least a portion is obtained by the manufacture method by each the described clay membrane in the claim 1～20 or each the described clay membrane in the claim 21～27 constitute.

29. an elastic base plate is characterized in that, the clay membrane that at least a portion is obtained by the manufacture method by each the described clay membrane in the claim 1～20 or each the described clay membrane in the claim 21～27 constitute.

30. an elasticity printed base plate is characterized in that, the clay membrane that at least a portion is obtained by the manufacture method by each the described clay membrane in the claim 1～20 or each the described clay membrane in the claim 21～27 constitute.

31. substrate, it is characterized in that, this substrate is equipped with the electronic installation with non-luminous organic semiconductor or amorphous inorganic semiconductor, have gas barrier property, the clay membrane that its at least a portion is obtained by the manufacture method by each the described clay membrane in the claim 1～20 or each the described clay membrane in the claim 21～27 constitute.

32. choke film; it is characterized in that; thereby this choke film intercepts the electronic installation that gas protection has non-luminous organic semiconductor or amorphous inorganic semiconductor, and the clay membrane that its at least a portion is obtained by the manufacture method by each the described clay membrane in the claim 1～20 or each the described clay membrane in the claim 21～27 constitute.

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