CN101374766B - Clay film and method for producing same - Google Patents

Abstract

The present invention provides a transparent clay film and a method for producing the same. The transparent clay film is uniformly dispersed with clay or additives, and defects such as cracks and cracks are hardly generated, and the haze is difficult to change over time even if it is placed in the atmosphere. change to increase. Synthetic soapstone as clay and water as a solvent were mixed to obtain a clay dispersion. Also, sodium polyacrylate as an additive and water as a solvent were mixed to obtain an additive-containing liquid. Next, the clay dispersion and the additive-containing liquid are mixed to obtain a uniform clay-containing liquid. And, under vacuum, the clay-containing liquid is degassed. The degassed clay-containing liquid was applied to a flat portion on the surface of a polypropylene tray. And, after drying, the formed clay film was peeled off from the platter.

Description

Clay membrane and method of manufacture thereof

Technical field

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

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 through 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 ZX 21 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, hopes 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 accomplish 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 gas barrier property is high, can be used as the gas-barrier material use of prevention from the entering of the oxygen of outside and 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 move purposes.See from such viewpoint, hope 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, computingmachine, 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 polyethylene terephthalate, polycarbonate, the substrate that gathers the resin formation of 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, 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 at the high temperature more than 300 ℃; 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.Gather imide resin and have 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.See from such viewpoint, hope 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 characteristic 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 through 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 up 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 the 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.

Through such thin slice, perhaps combine these thin slices through lamination, 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 (like magadiite) that stratiform is gathered silicic acid.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 through tetrahedron thin slice and octahedra thin slice with the clay crystalline clay mineral that combines lamination to form as the unit layer of mineral at 1: 1, famous is kaolinite, halloysite.And with the clay crystalline clay mineral that combines lamination (be tetrahedron thin slice-octahedra thin slice-tetrahedron thin slice) form as unit layer at 2: 1 pyrophyllite, talcum, smectite family clay, vermiculite, mica clay mineral etc. are arranged through tetrahedron thin slice and octahedra thin slice.It is said; Especially the clay (for example polynite, saponite, hectorite, rich magnesium smectite etc.) that belongs to smectite 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,, then, also there is the transmitance of gas to become the example about part, but almost do not have gas barrier property to improve the above example of one digit number through adding clay if try to get gas barrier property.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 degree (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 internals 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 through Dispersion of Clay liquid is spread out on the sheet glass, standing and drying formed the consistent film of particulate orientation, formed the to take the bearing sample (with reference to non-patent literature 3) of adjustment X-ray diffraction method through this film.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 on the substrate surface of being made by the material of glass etc., to form, and 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 method for manufacture (referenced patent document 1) of the transparent clay membrane that constitutes; A kind of method of manufacture of layered clay mineral film (referenced patent document 2); This method of manufacture is utilized the reaction between layered clay mineral and phosphoric acid or the phosphate; Through implementing to promote the thermal treatment of this reaction, the integrated structure orientation that layered clay mineral is had is fixing; A kind of smectite that contains is that the epithelium of the complex compound of the above metal of clay mineral and divalent is handled use compsn (referenced 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.

As the transparent film that uses clay, there is aqueous dispersions with synthetic saponite or synthetic li-montmorillonite to be coated on the film as the example of the phasic difference film of liquid-crystal display etc. again.This transparent film is bigger poor through 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 (referenced 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 to be the film of main body with the clay hardly, 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 and a kind ofly gather that imines and hydrophobicity clay constitute, HS and have water-proof transparent clay film by transparent again.This hydrophobicity clay is thereby that the mineral ion that the hydrophilic clay that is dispersed in the smectite family in the water has 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 degree increases as a result, and becoming is transparent state (haze 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 through 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 through the method that is described below.That is, this method is the adjustment clay dispersion, obtains the dispersion liquid of homogeneous; Level leaves standstill this dispersion liquid; Make clay particle deposition, use various solid-liquid separating method (for example spinning, 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 (referenced 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 (referenced patent document 7) of clay membrane through use; Through using the clay slip of the solid ratio that improves argillaceous liquid, can make clay membrane (referenced patent document 8) at short notice; Also have through using synthesis of clay, can make the transparent clay membrane in the visible region of the non-coloring that is main body with the clay.

And, confirm with clay to be to lead and make closely and the to heavens clay membrane of orientation of clay crystalline layer, with few the comparing of ratio of former clay; Possess jointly and be characterised in that (1) has high heat resistance, (2) have high gas barrier property to the inorganic gas of oxygen or hydrogen etc.; (3) pore-free in the film, (4) have flexibility, and (5) have resistance; (6) linear expansivity is low; (7) have flame retardant resistance, (8) have insulativity, find to be suitable for use in the material that constitutes above-mentioned sealing member or the 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, in clay dispersion, produces inhomogenous aggregate, 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 is condensed into granular clay or additive and makes scattering of light, the problem of generation mist degree increase etc.; Even so want that the kind of additive or addition are also restricted sometimes through adding the rerum natura of additive raising clay membrane.

In addition, we know if clay crystalline layer closely and to heavens is orientated through the ratio that increases the clay membrane medium clay soil always, then are difficult to from clay membrane, remove gaseous constituent remaining in the clay membrane.That is, sneak into bubble (space) that the gaseous constituent of argillaceous liquid causes when being included in the clay membrane, the problem below existing, 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 degree 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, on support, form membranaceously, 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 receive 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 up of clay and additive is if be placed in the atmosphere for a long time, and then mist degree increases sometimes, and clay membrane is fuzzy, and the transparency descends.This mist degree 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 degree 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, the problem below producing 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; Through 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, the problem below existing: 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 method of manufacture 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 the high and mist degree of a kind of transmittance is little is placed on that mist degree in the atmosphere also is difficult in time and the transparent clay membrane and the method for manufacture 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: the open communique of Japan's patent is put down into 6 years No. 95290

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

Patent documentation 3: the open communique of Japan's patent 2002 No. 30255

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

Patent documentation 5: the open communique of Japan's patent 2006 No. 37079

Patent documentation 6: the open communique of Japan's patent 2005 No. 104133

Patent documentation 7: the open communique of Japan's patent 2005 No. 313604

Patent documentation 8: the open communique of Japan's patent 2006 No. 265088

Non-patent literature 1: must rattan klatch compile " the plain face と of clay science ヘ reception-clay glamour-(to the true qualities and the glamour of the invitation-clay of clay science) ", Japan, three publication altogether, p.6 (2000)

Non-patent literature 2: the clear volume of discal patch, " Port リ マ one is a Na ノ コ Application Port ヅ ッ ト Zhi Pin development (product development of polymer system nano composite material) ", and Japan, publish in the border, and p.25～90 (2004)

Non-Patent Document 3: Whitewater Haruo, "Clay Minerals Science - Clay Science Fundamental - (clay mineralogy - Clay scientific basis -)", Japan, Asakura Shoten, 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 said problem, the present invention by following constitute form.Promptly; The method of manufacture of clay membrane of the present invention is characterized in that, has: argillaceous liquid adjustment operation; Respectively modulation make clay dispersion in solvent clay dispersion and additive is dispersed or dissolved in contain additive liquid in the solvent; Said clay dispersion and said is contained additive liquid mixes, make the said additive in the total amount of said clay and said 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, removes said solvent then, carries out drying.

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

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

Further; It is desirable to said argillaceous liquid is located at than is placed under the high temperature of normal temperature and under reduced pressure; The gas that said argillaceous liquid is contained reduces; Better is through under temperature higher than normal temperature and decompression, stirring said argillaceous liquid, the gas minimizing that said argillaceous liquid is contained.

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

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

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

Further, in the method for manufacture of clay membrane of the present invention, it is desirable to said clay and be affinity for water high, be dispersed in hydrophilic clay in the water easily.Again, said clay can be high to the affinity of organic solvent, 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 said organic ion and contain at least a in ammonium ion, phosphorus (Off ォ ス Off ォ ニ ゥ system) ion, the imidazol ion the affinity of organic solvent and the dispersed hydrophobicity clay that improves through the mineral ion that hydrophilic clay is had.In addition, it is also desirable the hydroxyl of the octahedra thin slice of the integrant of clay to be transformed into other hydrophobic substituent hydrophobicity clays.

Further, in the method for manufacture 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 method of manufacture manufacturing of aforesaid clay membrane of the present invention, and lamellated clay crystallization forms in the film thickness direction laminated.And, it is desirable to from 40 ℃ to 250 ℃ average coefficient of linear expansion below 20ppm.It is desirable in addition from 30 ℃ to 250 ℃ average coefficient of linear expansion below 10ppm.In addition, it is desirable to tensile strength more than 10MPa.

Again, it is desirable to, the mist degree 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 degree, better is mist degree further it is desirable to mist degree less than 1% below 2%.Further, the mist degree 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 up of the clay membrane of the method for manufacture 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 up of the clay membrane of the method for manufacture 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 up of the clay membrane of the method for manufacture 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 up of the clay membrane of the method for manufacture 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 method for manufacture 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 up 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 gets into the additive between the unit layer of clay is many and open greatlyyer between the clay crystalline layer, upsets clay crystalline orientation further, receives 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 through 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 characteristic 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, through 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 it is generally comparatively difficult only to obtain can be used as the 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 through 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 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 sometimes increases and produces cohesion, transparent deficiency in transparent clay membrane.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, and the result finds to access the righttest method of manufacture of the clay membrane that is dispersed with clay and additive equably.Promptly; The method of manufacture of clay membrane of the present invention is characterized in that, has: (a) argillaceous liquid adjustment 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 above-mentioned is contained additive liquid mix, 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.

Through 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 degree 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 degree 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 degree are that the method JIS K 7136 that asks according to the mist degree of the optical TP JIS K 7105 of the TP 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 method of manufacture through 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 flowability of clay dispersion more significantly descends, 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 through 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 through 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, through being higher than under the temperature of normal temperature the mixed clay dispersion liquid and containing additive liquid and obtain argillaceous 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 in solvent, to add clay or additive, 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; The mixed clay dispersion liquid is 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 with containing additive liquid being higher than under the temperature of normal temperature the mixed clay dispersion 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, obtain the argillaceous liquid of clay and additive that is scattered here and there more equably, so can suppress the generation of condensation prod through being higher than each liquid of adjustment under the temperature of normal temperature; 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.

Through 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 is made up of clay and additive, clay dispersion, contain at least a of additive liquid, argillaceous liquid, the use said vesse is modulated 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 through powerful whipping force and degassing ability, even and under the state of the gelation that surpasses the fluidity boundary, also can stir, so very suitable to the argillaceous liquid that is used to obtain high solid formation 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 solid form branchs concentration high, outgas for HV 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 method of manufacture 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 the 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 through 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, in the high clay membrane of clay ratio, is substantially necessary operation.

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 such as described above thick, its thicker more difficultly during film forming is removed the gaseous constituent of sneaking into argillaceous liquid from clay membrane inside, and this gaseous constituent remains in the inside of clay membrane more easily.This expression thickness is thick more, then owing to remain in the defective that the bubble etc. of the inside of clay membrane causes, takes place more easily that the transparency that for example scattering of light etc. causes descends and the breakage of the clay membrane during heating.

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 through spinning from argillaceous liquid the method for divided gas flow composition, it is desirable to especially carry out the method for vacuum outgas through 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 through 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 because the inner entrap bubble of argillaceous liquid 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 stated, 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 through stirring, the partial solid rising that forms branch concentration of argillaceous liquid can not take place, and prevent 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 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 through argillaceous liquid is configured in, and be to get into outgas in the waiting situation of operation of groove (tank) under the state of thick tunicle to compare at argillaceous liquid, can more effectively make the gaseous constituent minimizing.

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 through improving solid formation, can shorten the time that drying 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 through 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 property of clay membrane.

Again, improve viscosity, according to circumstances, can manifest significantly, can make mobile decline thus, so can remove the restriction of the support of above-mentioned that kind through 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, does not have special qualification, can use known solid-liquid separation techniques such as spinning, 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 through 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 stated, be difficult to remove the gaseous constituent that remains in the argillaceous liquid, therefore importantly must, the gaseous constituent that argillaceous liquid is contained concentrate again after reducing fully if concentrated argillaceous liquid.Again, not only concentrated but also when outgasing, and importantly must accomplish the degassing before carrying out concentrating.

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

When using the for example heating vaporization in these methods, for example be advisable to use smooth tray to be coated with argillaceous liquid above that 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 up of polyethylene terephthalate (PET), the such resin of Vestolen PP 7052 arranged for example.The substrate that also can have brass, copper, stainless steel, the such metal of aluminium to constitute for example again.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 up 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, the problem below existing was split at drying process medium clay soil film sometimes, and 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; Remain in the inner stress of clay membrane so can relax, suppress clay membrane and crackle occurs.

As long as support has flexibility, easy deformation; There is not special qualification; 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 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 Vestolen PP 7052 of hydrophobicity, tetrafluoroethylene etc.Handle as peeling off facilitation; For example uviolizing processing, electron rays radiation treatment, ion beam irradiation processing, corona discharge process, plasma treatment (remote plasma treatment is for example arranged for example; The flame plasma processing), physical treatment (, making contact area reduce) for example to the treat mechanically 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 through the physical stimulation that receives 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 through the above-mentioned facilitation processing of peeling off, but, have fluororesin-coated for example and method titanium oxide 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 property decline of clay membrane.Concerning transparent film, the light diffuse-reflectance is to make the mist degree cause of increased further.

In the clay membrane that is made up 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 up 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 through 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 through absorbing airborne moisture.Therefore, under the environment of clay membrane at controlling moisture that firm drying is finished, keep a little while, this is effective to the internal stress of removing the clay membrane that is made up of hydrophilic clay.

As stated, through 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 yld 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 through cylinder according to the present invention.

When removing the solvent of argillaceous liquid, be advisable to use forced blowing type baking box etc. through 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 righttest time of drying.Because specific heat of water is big, dry spended time 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 adjustment 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 method for manufacture 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, 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 degree 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 through rough increase; Mist degree increases, and clay membrane blurs and transparency decline, so be the important problem that should solve.

Such problem; Can be through 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 degree is descended owing to can make the surface smoothingization of clay membrane through such method again.

The method of 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) does not have special qualification; 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 vapor atmosphere held primary drying film in the high density of aforesaid liquid.

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 through 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 film smoothing effectively and suppress the increase through the mist degree that causes after a while.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, carry on the latticed iron wire that it is desirable to use when making paper etc. and put the primary drying film, the configuration aforesaid liquid.Like this, because unnecessary aforesaid liquid flows away from the surface of primary drying film easily, so a part or the whole redispersion that can suppress the primary drying film are in aforesaid liquid and swelling excessively.

The kind of aforesaid liquid does not have special qualification so long as that make the clay swelling or additive dissolving or dispersive are got final product, and 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, through 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 through the stretching clay membrane, flattens fold, makes the clay membrane planarization, can obtain the more level and smooth clay membrane in surface, dry back.As the method for stretching clay membrane, have for example and shift onto on the clay membrane method 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, carries out on the latticed iron wire that also can when making paper, use 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 degree cause of increased; In this situation; Because, remove the additive of separating out through aforesaid liquid, so play effect of the present invention if as stated 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 because of the surperficial swelling surface-area of primary drying film becomes smoothness being improved, 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 through 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, through 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.

Be used for the level and smooth member of smoothing so long as surface smoothing does not just have special qualification, can use such resin substrate of glass substrate, silicon substrate, Polyethylene Terephthalates (PET) film etc.Further, the surface of these level and smooth members can be peeled off facilitation and 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 through the primary drying film that will dispose behind the aforesaid liquid, the roller that rolling surface is level and smooth above that carries out smoothing.Can apply external force through 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 last times such as roller and press assembly, can clip as required the level and smooth resin molding of implementing to peel off facilitation processing etc. etc., applies external force.

Through 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 on the above-mentioned level and smooth member of the surface smoothing of the surface smoothingization that is used to make clay membrane, carries out.The exsiccant method limits especially again, but it is desirable to for example spinning, filtration, vacuum-drying, freezes vacuum-drying, inert gas atmosphere held 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 method for manufacture 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 degree can not be with the such clay membrane 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 ability, if more than 25MPa, we can say to have full intensity.

The clay membrane that obtains through method of manufacture of the present invention is because remove the gaseous constituent that argillaceous liquid contains, so inner bubble (space) etc. seldom fully.Therefore; Also be according to the thermotolerance of additive and difference, but through the clay membrane that method of manufacture of the present invention obtains be for example apace (for example, 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 degree, and spot is few in the face of the transparency.The reduction of removing especially mist degree of the gaseous constituent that argillaceous liquid contains has bigger influence.Mist degree 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 through importing then during the situation of clay thickness (for example, thick than 15 μ m), also can make mist degree (turbidity) after the firm film forming below 5%.Mist degree it is desirable to below 3%, and better is below 2%, further it is desirable to less than 1%.Again, can make mist degree in 24 ℃, the environment of 1 air pressure, humidity 45% through the time change below 2%.Mist degree 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 spectroscope at the clay membrane more than 85%, below 95%.

If mist degree surpasses 5%, it is low then probably can to produce the transparency, can not get the problem of desired optical characteristics.Again; The mist degree of the glass substrate that surface smoothing, mist degree 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, thus the mist degree of the clay membrane that obtains also great majority from 0.5%, even good be lower limit also with about 0.2%.Again, if mist degree through the time change to surpass 2%, bad situation below then probably can producing, 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, use the transmittance of directional light of clay membrane of the method for manufacture manufacturing of clay membrane of the present invention also to be the upper limit with about 95%.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.

Method of manufacture 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 below 5ppm, it would be desirable below 3ppm.

So little linear expansivity; By before the film that constitutes of resin, or before the nano composite material body in; Being the minimum value that can not arrive, especially is the value that arrives scarcely ever in transparent film, even former nano composite material body contains clay; Be main body with the resin, clay crystalline layer is not orientated densely and to heavens yet, lamination yet.We can say because most electronics is made up 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, and 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 through 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 through 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 below 3.5nm, it would be desirable below 2nm.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 when the mensuration of using as the wavelength of the K α of general copper ; The thickness of clay crystalline one deck is approximately in the clay membrane that the clay of the clay by smectite family, the synthetic mica family of 1nm constitutes, with 2 θ corresponding to the zone more than 0.8, below 9.0.

In addition; The minimum value of the average interfloor distance of the compsn that the minimum value of above-mentioned average interfloor distance only is equivalent to be made up 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 compsn 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 XRD X spectrum moves to and the comparing in low 2 θ sides of the compsn that only is made up 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 method for manufacture through 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 up of the additive that uses.Transmitance only it is desirable to below 1/10 of film that is made up 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 property 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 Electronic 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 substrate or the choke film of frontal plane side that then can be used as the visual side of Electronic Paper uses.In addition, the kind that can use the Electronic Paper of clay membrane of the present invention does not have special qualification, but the for example Electronic Paper of electrophoresis drive-type, electronics powder fluid mode is arranged for example.

Other can apply flexibly the characteristic as insulativity, also can the elastic base plate of clay membrane as circuit be used widely.When utilizing as the substrate of circuit, from the purpose of the 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 on substrate is by coating or printing conductive printing ink and in the elasticity printed base plate that forms; Utilize the hear resistance and the low linear expansion coefficient of clay mambrane; 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 through light.

Again, and the organic semiconductor of penta benzene or thiophene-based representative general because oxygen or moisture and worsen easily, again,, also receive 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 responsive organic semiconductor of deterioration 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 uses 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 up of inorganic materials, the reinforcement that is made up of resin material etc., the resist that prevents to be hurt etc., make the smoothing layer of surface smoothingization) etc. uses.

The reinforcement that also can be further constitutes, the resist 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. by resin, through the film immersion that will constitute by clay and resin molding in liquid, or make it swelling through spraying liquid on the clay face, carry out drying again.Certainly, in the composite package 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 package is a clay membrane at least, then available above-mentioned gimmick improves.

Below, clay membrane of the present invention and method of manufacture thereof are carried out further detailed explanation.

Kind to employed clay among the present invention does not have special qualification, and natural clay, synthesis of clay can.For example, it is desirable to mica, vermiculite, polynite, iron polynite, beidellite, saponite, hectorite, rich magnesium smectite, 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 smectite, synthetic mica, synthetic hydrotalcite, synthetic kaolinite etc., from aspects such as dispersivenesses, better is the clay that belongs to smectite 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, see that the clay of the synthetic smectite family of high aspect ratio, synthetic mica, hydrotalcite are also desirable from the viewpoint of gas barrier property.

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; The hydrophobic substituting group that the hydroxyl of the above-mentioned octahedra thin slice that promptly integrant as layer structure of most clay mineral is had through chemical reaction converts other to (for example; Hydroxyl is substituted by the processing of other organic group through combining with the dehydration of silane coupling agent arbitrarily), thus 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 smectite 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, ethenoxy group, oxypropylene group etc., dimethyl-two (stearyl) ammonium salt, trimethylammonium stearyl ammonium salt etc. is arranged for example.Again, the thermotolerance of microcosmic salt, imidazole salts etc. is high, also is difficult to appear 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 it is produced gas barrier property such shortcoming that descends, but owing to combine securely, so generally less to the influence of the transparency of clay membrane or dimensional stability etc. with the surface of tetrahedron thin slice and octahedra thin slice; 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 through will being present in hydrophilic clay be exchanged into organic ion and obtain.Therefore, if use the hydrophobicity clay that has carried out sufficient IX, 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.

Kind to the additive that uses among the present invention does not have special qualification; 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, epoxy resin, fluoro-resin, vinyl resin, methacrylic resin, phenolic resin, polyamide resin, vibrin, polyimide resin, polyvinyl resin, polyoxyethylene glycol, SEPIGEL 305, 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 solvabilities in water are high, 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 through 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 when making the such mixed solvent of water and other hydrophilic solvent, 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 resin, to gather ethylidene ether be 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 epoxy resin, thermohardening type modification poly (phenylene ether) resin, thermohardening type to gather imide resin, urea resin, allyl resin, silicone resin, benzo oxazine resin, phenolic resin, unsaturated polyester resin, span and 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 epoxy resin 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 when using thermosetting resin and light-cured resin, use solidifying agent, curing catalysts etc., these just do not have special qualification so long as be generally used for thermosetting resin and the solidified of light-cured resin.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 can use separately, also can mix use more than 2 kinds.

Above-mentioned material mainly is the resin that main chain is made up of carbon atom, but main chain is made up of not necessarily carbon atom, for example can be the resin that main chain is made up of Siliciumatom, also can be the resin (for example ZGK 5) that main chain mainly is made up 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 is because of high with the bonding force of clay, so suitable to additive.Especially, the additive that in 1 molecule, contains above-mentioned organic salt position more than 2 is 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 Siliciumatom the unit more than 2 that contains above-mentioned organic salt position or the chain (for example polysilane or ZGK 5 etc.) that constitutes Siliciumatom and Sauerstoffatom be formed by connecting for example.Further, the molecule that in 1 molecule, has the such position with polymerizability in the unit that contains above-mentioned organic salt position and vinyl or epoxy group(ing) 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, the solvent types of using among the present invention is not had special qualification, 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 property 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 the hydrophobicity clay of cohesion, make interlayer at a distance from enlarging.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 prod 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 through promote dispersive argillaceous liquid by such interpolation methyl alcohol etc., play such effect, promptly especially in transparent clay membrane, reduce mist degree significantly.

Again; When using the hydrophobicity clay of the above-mentioned processing of process; Can use aromatic hydrocarbons (for example toluene, YLENE), ethers (for example ethyl ether, 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, DOP, methyl-sulphoxide, methyl Cellosolve etc.

The kind of the organic solvent of dispersing hydrophobic property clay is owing to depend on the kind of the organo-functional group that makes the clay crystalline surface that hydrophobicity manifests, so need to select suitable material significantly.Again, also to note final in argillaceous liquid solvability, the dispersiveness of blended additive select, it is desirable to select solvability, all good organic solvent of dispersiveness of Dispersion of Clay property and additive.Just, the solvent of clay dispersion may not be with kind appearance 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 do not have special qualification.

Below, through embodiment, the present invention is explained more specifically.

Embodiment 1

Use synthetic saponite (the ス メ Network ト Application SA that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use ZX-I (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 ZX-I and 594ml pure water put into the plastic seal container together with rotor, after 25 ℃ of strong down vibrations 2 hours, again with homogenizer with the rotating speed stirring of 10000rpm 7 minutes, 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 together with rotor, after 25 ℃ of strong down vibrations 2 hours, again with homogenizer with the rotating speed stirring of 10000rpm 20 minutes, obtain the argillaceous liquid of homogeneous.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 the flat in the surface of the tray that Vestolen PP 7052 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 uniform in thickness.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, transparency is high, and 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 the transmitance (with reference to Fig. 1) more than 85%, do not observe painted in scope 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 degree (turbidity) is 2.3%.

Then, in order to confirm the dimensional stability of this clay membrane, " TMA/SS220 " that make with ェ ス ァ ィ ァ ィ Na ノ テ Network ノ ヅ 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 ℃ TR 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 that Cu/K α

is in the X-ray diffraction spectrum that obtains (with reference to figure 2); Clear and definite main peak is observed in 7.44 position in 2 θ (being converted into interfloor distance is 1.19nm), 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, the transmission coefficient of confirming 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 Vestolen PP 7052 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 degree (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 タ-Co., Ltd. makes); With bonding band fixedly the PET film on every side 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, transparency is high, and is 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 the 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 degree (turbidity), is 1.6%.

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

Comparative example 1

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

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 degree (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 ZX-I (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 ZX-I,, 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 degree (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 degree (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 ZX-I (Wako Pure Chemical Industries, Ltd.'s manufacturing) as additive.

1.8g ZX-I 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 ZX-I (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 ZX-I and 198ml pure water put into the plastic seal container together with rotor, after 22 ℃ of strong down vibrations 2 hours, again with homogenizer with the rotating speed stirring of 10000rpm 7 minutes, 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 degree (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 ァ Le De リ ッ 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, again with homogenizer with the rotating speed stirring of 10000rpm 10 minutes, obtain the argillaceous liquid of solid formation branch concentration 1 quality %.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 cf-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 thin liquid film shape below 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 ZX 21 (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 degree (turbidity) is 3.5%.

Embodiment 5

Use natural montmorillonite (the Network ニ ピ ァ F that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use ZX-I (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 ZX-I and 142ml pure water put into the plastic seal container together with rotor, after 25 ℃ of strong down vibrations 2 hours, again with homogenizer with the rotating speed stirring of 10000rpm 7 minutes, 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 together with rotor, after 25 ℃ of strong down vibrations 2 hours, again with homogenizer with the rotating speed stirring of 10000rpm 20 minutes, obtain the argillaceous liquid of homogeneous.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 uniform in thickness.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 ァ F that Network ニ ミ ネ Industrial Co., Ltd makes) as clay, use ZX-I (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 ZX-I,, 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 ァ 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 whisking appliance, 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, after 25 ℃ of strong down vibrations 1 hour, again with homogenizer with the rotating speed stirring of 10000rpm 20 minutes, obtain the argillaceous liquid of homogeneous.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 the 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 uniform in thickness.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 PM 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, can know very homogeneous (with reference to figure 4) of inside.

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 ℃ TR 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) observed clear and definite main peak, expression in the clay membrane clay crystalline layer height ground lamination and be orientated densely.

After embodiment takes the electron micrograph of section of clay membrane the samely, can know that clay crystalline layer is lamination (with reference to Fig. 6) densely equally with the average interfloor distance orientation of about 1.2nm again.A little bit smaller a little than through 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, the transmission coefficient of confirming 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 through 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, under the decompression below the 0.08MPa, outgases 40 minutes.Generation from the bubble of argillaceous liquid exists with low frequency during outgasing, but confirms to the end.

The same with embodiment 6, use this argillaceous liquid to obtain the clay membrane of the homogeneous of the about 30 μ m of thickness.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 PM 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 like above-mentioned circle during heating.

Embodiment 7

Use hydrophobicity hectorite (the Le one セ Application タ ィ ト SAN that コ one プ ケ ミ カ Le Co., Ltd. makes) as clay, use ァ サ Off レ ッ 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, stirred 2 hours through rotor down, obtain the clay dispersion of homogeneous at about 25 ℃.Again, 4511.5g ァ サ Block レ ッ Network ス L451 and 16g toluene are put in the Erlenmeyer flask, stirred 1 hour through rotor, what obtain homogeneous contains additive liquid.

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

Cover the 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, through utilizing the roll adjustment plate as guiding, forms the argillaceous overlay film of uniform in thickness.

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 the 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 degree (turbidity) is 1.6%.

In 200 ℃ of following atmosphere,, likewise measure after the transmitance, have the transmitance more than 85%, do not observe painted from the scope of 420nm to 800nm with this clay membrane heating 30 minutes.Again, likewise measuring total light transmittance is 91.1%, and measuring mist degree (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 can know to have high water tolerance.The water-intake rate of following dipping that weight change before and after dipping calculates is about 1.9%.

Comparative example 8

Use hydrophobicity hectorite (the Le one セ Application タ ィ ト SAN that コ one プ ケ ミ カ Le Co., Ltd. makes) as clay, use ァ サ Off レ ッ 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, stirred 2 hours through rotor down, obtain the clay dispersion of homogeneous at about 25 ℃.Again, 1.5g ァ サ Block レ ッ Network ス L451 and 10g toluene are put in the Erlenmeyer flask, stirred 1 hour through rotors down at 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 degree (turbidity) is 23.8%.

Embodiment 8

The same with embodiment 1, the same argillaceous liquid of forming of adjustment.In the brazen tray of B4 model, put into the PET film identical (the PET film is not fixed on the tray with the bonding band), 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 uniform in thickness.

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.Transparency is high again, and is flexible good.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 the 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 degree (turbidity) is 1.6%.

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, transparency is high, and is flexible good.The total light transmittance of measuring clay membrane with embodiment 1 is 91.5% the samely, and measuring mist degree (turbidity) is 1.8%.Again, the surface roughness meter made of ケ one ェ Le ェ one テ Application コ one Le society " ァ Le Off ァ step IQ " the surface roughness Ra of the clay membrane measured is 39nm.

After processing 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, at 20 ℃ of held diels, 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, transparency is high, and is 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 the 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 degree 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 degree measured the samely, total light transmittance is 91.8% as a result, and mist degree is 1.6%.Again, place after one month, carry out same mensuration, total light transmittance is 91.9% as a result, and mist degree is 1.5%.

Comparative example 9

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, transparency is high, and is flexible good.The total light transmittance of the clay membrane of measuring with embodiment 1 is 91.8% the samely, and mist degree is 7.0%.The surface roughness Ra of the clay membrane of measuring with embodiment 9 again, is 55nm the samely.

This clay membrane is placed on remains in 24 ℃, the dust free chamber of 1 air pressure, humidity 45%, mist degree 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 10

Mist degree in the comparative example 9 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, at 20 ℃ of held diels, 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, transparency is high, and is 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 the 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 degree is 0.83%.The surface roughness Ra of the clay membrane of measuring with embodiment 9 again, 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 degree measured the samely, total light transmittance is 92.0% as a result, and mist degree is 0.86%.Again, place and carry out same mensuration after one month, total light transmittance is 92.1% as a result, and mist degree is 0.84%.

Embodiment 11

Mist degree in the comparative example 9 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,, make it dry at about 20 ℃ of held diels 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, transparency is high, and is 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 the 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 degree is 0.62%.The surface roughness Ra of the clay membrane of measuring with embodiment 1 again, 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 degree measured the samely, total light transmittance is 92.0% as a result, and mist degree is 0.64%.Again, place and carry out same mensuration after one month, total light transmittance is 92.1% as a result, and mist degree is 0.65%.

Utilizability on the industry

The method of manufacture of clay membrane of the present invention can be made a kind of clay membrane, and the clay and the additive of this clay membrane disperse equably, is difficult to crack, defective such as crack, has the intensity that the independent film of can be used as is utilized.Again, clay membrane of the present invention be defectives such as a kind of clay and additive disperse equably, are difficult to crack, crack, clay membrane with intensity that the independent film of can be used as utilizes.Also have, be placed on that mist degree in the atmosphere also is difficult in time and the transparent clay membrane that increases even be that the high and mist degree of a kind of transmittance is little.

Claims (36)

1. A manufacture method of clay film, is characterized in that, has: In the clay-containing liquid adjustment step, a clay dispersion liquid in which clay is dispersed in a solvent and an additive-containing liquid in which additives are dispersed or dissolved in a solvent are respectively prepared, and the above-mentioned clay dispersion liquid and the above-mentioned additive-containing liquid are mixed so that the above-mentioned clay and the above-mentioned In the total amount of additives, the proportion of the above-mentioned additives is more than 0% by mass and not more than 30% by mass, thereby obtaining a clay-containing liquid; and A drying step, after disposing the clay-containing liquid on the surface of the support, removing the solvent and drying; and In the re-drying step, a liquid for swelling the clay or a liquid for dissolving or dispersing the additive is placed on the surface of the dried product obtained in the drying step to re-dry it. 2. The method for producing a clay film according to claim 1, further comprising a degassing step for reducing gas contained in the clay-containing liquid. 3. The method for producing a clay film according to claim 1 or claim 2, further comprising a peeling step of peeling the dried product obtained in the drying step from the support. 4. The method for producing a clay film according to claim 1 or claim 2, wherein, in the clay-containing liquid adjustment process, the clay dispersion and the clay dispersion are mixed at a temperature higher than normal temperature. additive-containing liquid to obtain the clay-containing liquid. 5. The manufacture method of clay film as claimed in claim 2, is characterized in that, described clay-containing liquid is set at the temperature higher than normal temperature, is placed under reduced pressure simultaneously, makes the gas contained in described clay-containing liquid reduce. 6. The manufacture method of clay film as claimed in claim 2, is characterized in that, by setting described clay-containing liquid at a temperature higher than normal temperature, stirring under reduced pressure simultaneously, make described clay-containing liquid contained Gas reduction. 7. The method for producing a clay film as claimed in claim 3, wherein the support has flexibility, and after drying in a deformable state of the support, the dry product is removed from the support. body stripping. 8. The method for producing a clay film according to claim 7, wherein the support is a resin film. 9. The method for producing a clay film according to claim 7, wherein a peel-facilitating treatment is performed on the support. 10. The method for producing a clay film according to claim 7, wherein the support is subjected to a hydrophobic treatment. 11. The method for producing a clay film according to claim 1, wherein the liquid is arranged on the surface of the dried object by immersing in the liquid. 12. The method for producing a clay film according to claim 1, wherein the liquid is sprayed on the surface of the dried object. 13. The method for producing a clay film as claimed in claim 1, characterized in that, by arranging the liquid on the surface, the dry matter that is partially swollen near the surface is brought into contact with a smooth member with a smooth surface, and the surface of the film is smoothed. After smoothing, the liquid is re-dried. 14. The method for producing a clay film according to claim 13, wherein the smooth member has flexibility and is deformable, and the liquid is re-dried in a state where the dry matter is in contact with the smooth member. . 15. The method for producing a clay film according to claim 1 or claim 2, wherein the clay is a hydrophilic clay that has a high affinity for water and is easily dispersed in water. 16. The method for producing a clay film according to claim 1 or claim 2, wherein the clay is a hydrophobic clay that has a high affinity for organic solvents and is easily dispersed in organic solvents. 17. The method for producing a clay film according to claim 16, wherein the hydrophobic clay improves affinity and dispersion to organic solvents by replacing the inorganic ions that the hydrophilic clay has with organic ions. Preferably, the organic ions contain at least one of ammonium ions, phosphonium ions, and imidazolium ions. 18. The method for producing a clay film as claimed in claim 1 or claim 2, wherein the obtained clay film has a total light transmittance of more than 70%, a haze of less than 5%, and a thickness of more than 400nm and less than 800nm. The light transmittance in the wavelength range is above 75% and below 95%. 19. A clay film, characterized in that it is a clay film produced by the method for producing a clay film according to claim 1 or claim 2, and is formed by laminating layered clay crystals in the film thickness direction. 20. The clay film according to claim 19, wherein the average coefficient of linear expansion from 40°C to 250°C is 20 ppm or less. 21. The clay film of claim 19, wherein the tensile strength is above 10 MPa. 22. The clay film as claimed in claim 19, characterized in that, the haze is below 5%, while the total light transmittance is above 85%, and the light transmittance in the wavelength range of above 400nm and below 800nm is above 85%. Above, below 95%. 23. The clay film as claimed in claim 19, characterized in that, the haze is below 2%, while the total light transmittance is above 85%, and the light transmittance in the wavelength range above 400nm and below 800nm is 85%. Above, below 95%. 24. The clay film as claimed in claim 19, wherein the haze is less than 1%, and the total light transmittance is above 85%, and the light transmittance in the wavelength range above 400nm and below 800nm is 85% Above, below 95%. 25. The clay film according to claim 22, wherein the change over time of the haze in an environment of 24° C., 1 atm, and 45% humidity is not less than -2% and not more than 2%. 26. The clay film of claim 19, wherein the film thickness is greater than 15 [mu]m. 27. An electronic paper characterized in that at least a part thereof is made of a clay film obtained by the method for producing a clay film according to claim 1 or claim 2. 28. An electronic paper, characterized in that at least a part thereof is made of the clay film according to claim 19. 29. An elastic substrate characterized in that at least a part thereof is composed of a clay film obtained by the method for producing a clay film according to claim 1 or claim 2. 30. An elastic substrate characterized in that at least a part thereof is composed of the clay film according to claim 19. 31. An elastic printed circuit board characterized in that at least a part thereof is composed of a clay film obtained by the method for producing a clay film according to claim 1 or claim 2. 32. An elastic printed circuit board characterized in that at least a part thereof is made of the clay film according to claim 19. 33. A substrate, characterized in that, the substrate is equipped with an electronic device having a non-luminescent organic semiconductor or an amorphous inorganic semiconductor, has gas barrier properties, and at least a part of it is made of the clay film according to claim 1 or claim 2 The clay film composition obtained by the manufacturing method. 34. A substrate on which an electronic device having a non-luminescent organic semiconductor or an amorphous inorganic semiconductor is mounted, has gas barrier properties, and at least a part thereof is composed of the clay film according to claim 19. 35. A gas-barrier film, characterized in that the gas-barrier film blocks gas thereby protecting electronic devices with non-luminescent organic semiconductors or amorphous inorganic semiconductors, at least a part of which is made of the clay according to claim 1 or claim 2 Membrane manufacturing method Obtained clay membrane composition. 36. A gas barrier film which blocks gas to protect an electronic device having a non-luminescent organic semiconductor or an amorphous inorganic semiconductor, at least a part of which is composed of the clay film according to claim 19.

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