CN101510457A - Flexible transparent conductive film, flexible functional element, and methods for manufacturing them - Google Patents

Abstract

In a flexible transparent conductive film which consists essentially of a base film and a transparent conductive layer formed by coating the base film with a transparent conductive layer forming coating fluid, the base film is constituted of a plastic film having been provided with gas barrier function, and the transparent conductive layer is chiefly composed of conductive fine oxide particles and a binder matrix, and has been subjected to compressing. Also disclosed is a flexible functional device which has the above flexible transparent conductive film and formed thereon any functional device selected from a liquid-crystal display device, an organic electroluminescent device, a dispersion-type inorganic electroluminescent device and an electronic paper device. The flexible transparent conductive film and the flexible functional device have gas barrier function and a superior flexibility, and are utilizable in thin-gauge equipments such as cards.

Description

Flexible transparent conductive film and flexible functional element and their manufacture method

Technical field

The present invention relates to a kind of flexible transparent conductive film that on base film surface, has a transparency conducting layer and use this transparent conductive film and the flexible functional element of the liquid crystal display cells that obtains, organic electroluminescent device, inorganic decentralization type electroluminescence element, electronic paper elements etc., relate in particular to a kind of have choke function and the good flexual flexible transparent conductive film and the improvement of flexible functional element.

Background technology

In recent years, in the electronic equipment with various displays headed by the liquid crystal or mobile phone etc., the trend of compactization is quickened, and accompanies therewith, is carrying out being replaced by plastic film the research of the glass substrate that in the past always used energetically.Because plastic film is light and be better than pliability, if so can be with thickness thin plastic film applications about several nanometers on as substrates such as liquid crystal display cells, organic electroluminescent device (being designated hereinafter simply as " organic EL "), inorganic decentralization type electroluminescence element (being designated hereinafter simply as " inorganic dispersion-type EL element "), electronic paper elements, then can access extremely light weight and soft flexible functional element.

And, usually as the flexible transparent conductive film that is used for the above-mentioned functions element, well-known is to adopt the physical vaporous deposition of sputtering method or ion plating method etc. to form the plastic film of the transparency conducting layer (being designated hereinafter simply as " sputtering ITO layer ") of indium tin oxide (being designated hereinafter simply as " ITO ")

(being designated hereinafter simply as " sputtering ITO film ").

Above-mentioned sputtering ITO film is on the transparent plastic film of PETG (PET), PEN (PEN) etc., by physical vaporous depositions such as sputters, reach the film that mode about 10～50nm has formed the ITO individual course of inorganic constituents with thickness, thus, can access sheet resistance value and be the low-resistance transparency conducting layer about 100～500 Ω/ (ohm-sq, below identical).

But, because the film that above-mentioned sputtering ITO layer is an inorganic constituents is extremely crisp, so have the problem that is easy to generate microfissure (crack).Therefore, when the sputtering ITO film with the thickness less than 50 μ m (as 25 μ m) of basement membrane is used for above-mentioned flexible functional element, the pliability of basement membrane (flexibility) is too high, in the process of handling or after finally forming functional element, the conductivity that is easy to produce the crack on the sputtering ITO layer and significantly damages film, therefore, present present situation is in fact can't be applied to require to have in the high flexual flexible functional element.

For this reason, for example in the invention of the flat 04-237909 communique of TOHKEMY, the flat 05-036314 communique of TOHKEMY, TOHKEMY 2001-321717 number, TOHKEMY 2002-36411 communique, the record of TOHKEMY 2002-42558 communique, proposed on base film surface to adopt transparency conducting layer to form the method that forms transparency conducting layer with coating fluid, replaced adopting the physical vaporous deposition of sputter etc. to form the said method of ITO layer with this.Be method as described below specifically, promptly, to be that the transparency conducting layer of principal component forms and to coat on the basement membrane with coating fluid with electroconductive oxide particulate and binding agent, and make it dry and the formation coating layer, then, after compressing (calendering) and handle by metallic roll, above-mentioned binding agent composition is solidified, make the method for transparent conductive film thus with transparency conducting layer.And, in the method, handle by the calendering of adopting metallic roll, can improve the packed density of the electrically conductive microparticle in the transparency conducting layer, thereby have electricity (conduction) characteristic that can increase substantially film and the advantage of optical characteristics.

Further, in the invention of TOHKEMY 2006-202738 communique, TOHKEMY 2006-202739 communique, the record of WO2007/039969 communique, propose a kind of transparency conducting layer that adopted and formed the transparent conductive film of using coating fluid, though this film has used at fitted the extremely thin basement membrane of lining form of the basement membrane side of transparent conductive film, but the transparent conductive film that operability is good, wherein, described lining form have can with little adhesive linkage of the interface peel of basement membrane.

But, in the flexible functional element of the liquid crystal display cells that has obtained having adopted above-mentioned transparent conductive film, organic electroluminescent device, inorganic decentralization type electroluminescence element, electronic paper elements etc., in most cases also require its have as to the choke function of steam or oxygen etc. (but in inorganic decentralization type electroluminescence element, when having used in the fluorophor particle under the situation of damp proof coating product, special requirement choke function not).Therefore, studying the commercially available gas barrier property plastic film that to have given the choke function and pasting above-mentioned transparent conductive film, thereby making it to possess the method for choke function by adhesive phase.

But, on transparent conductive film, paste the method for gas barrier property plastic film owing to increased the thickness of gas barrier property plastic film and the thickness of adhesive phase, so the final thickness of functional element increases accordingly, problem with pliability deterioration of functional element, further, when the slim equipment that functional element is assembled into card (IC-card, credit card, prepaid card etc.) etc., exist the problem of the requirement that the thickness that can't satisfy element will approach as far as possible.

Summary of the invention

The present invention is conceived to the problems referred to above and finishes, and its purpose is, provides to have choke function and good flexual flexible transparent conductive film and flexible functional element, and the manufacture method of these flexible transparent conductive films and flexible functional element is provided simultaneously.

So, the inventor etc. are in order to address the above problem, to give the plastic film of choke function directly as basement membrane, replace the gas barrier property plastic film is pasted the said method of transparent conductive film with this, further go up coating transparency conducting layer formation coating fluid at the above-mentioned plastic film (basement membrane) of having given the choke function, and compress processing, thereby directly form the good transparency conducting layer of pliability, its found that with originally anticipation differently, can obtain having choke function and good flexual flexible transparent conductive film simply.The present invention finishes according to this scientific discovery.

Promptly, flexible transparent conductive film of the present invention has been coated with transparency conducting layer and has formed the transparency conducting layer that forms with coating fluid and constitute by basement membrane with on this basement membrane, it is characterized in that, constitute above-mentioned basement membrane by the plastic film of having given the choke function, simultaneously, above-mentioned transparency conducting layer is a principal component with electroconductive oxide particulate and adhesive stroma, and has been implemented the compression processing.

In addition, the manufacture method of flexible transparent conductive film of the present invention, it is characterized in that, on the basement membrane that constitutes by the plastic film of having given the choke function, coating is that the transparency conducting layer of principal component forms and to form coating layer with coating fluid with electroconductive oxide particulate, adhesive and solvent, after the basement membrane enforcement compression processing that is formed with above-mentioned coating layer, coating layer is solidified form transparency conducting layer, make the flexible transparent conductive film that constitutes by above-mentioned basement membrane and transparency conducting layer thus.

Secondly, flexible functional element of the present invention, it is characterized in that, on above-mentioned flexible transparent conductive film, be formed with any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements, simultaneously, when under the situation that is pasted with lining form on the basement membrane, removing described lining form with the interface peel of basement membrane.

In addition, the manufacture method of flexible functional element of the present invention, it is characterized in that, on above-mentioned flexible transparent conductive film, form any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements, when under the situation that is pasted with lining form on the basement membrane, removing described lining form with the interface peel of basement membrane.

And, according to flexible transparent conductive film of the present invention, because the plastic film that will give the choke function directly is used as the basement membrane of transparent conductive film, and go up the formation of employing transparency conducting layer at the described plastic film (basement membrane) of having given the choke function and directly formed the good transparency conducting layer of pliability, so have choke function and good pliability with coating fluid.

In addition, according to flexible functional element of the present invention, owing on having choke function and good flexual above-mentioned flexible transparent conductive film, be formed with any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements, and the THICKNESS CONTROL of flexible functional element is in thin scope, so have good pliability, be easy to be assembled in the slim device as card etc., and can contribute the further slimming of device.

Embodiment

Below, describe the present invention in detail.

At first, as the flexible functional element that can be suitable for flexible transparent conductive film of the present invention, can enumerate aforesaid liquid crystal display cells, organic EL, inorganic dispersion-type EL element, electronic paper elements etc.

In above-mentioned any functional element, employed transparent conductive film is all required to have the choke function (oxygen barrier, water-vapor barrier etc.), as in water-vapor barrier, require the moisture-vapor transmission (WVRT:Water Vapor Transmission Rate) must be at 0.1g/m ²/ below day degree, preferably at 0.01g/m ²/ day following (still, need not to carry out the damp proof of said elements in the inorganic dispersion-type EL element of having used the encapsulated fluorophor particle of implementing damp proof coating) adopted the method that the gas barrier property plastic film is pasted each functional element by bonding agent usually.On the one hand, the slimming of functional element, lightweight, give pliability and become more and more important problem, require to make as far as possible element thin.

So, foothold of the present invention is, the gas barrier property plastic film (given the plastic film of choke function) soft when approaching is directly as basement membrane, and go up by transparency conducting layer at the plastic film (basement membrane) of having given the choke function and to form when directly forming the good transparency conducting layer of pliability with coating fluid, resulting transparent conductive film can be taken into account giving and good pliability of choke function, thereby can solve above-mentioned problem.

At this, as mentioned above, in flexible transparent conductive film of the present invention, go up by rubbing method (promptly adopting transparency conducting layer to form the method that forms transparency conducting layer with coating fluid) formation by being the transparency conducting layer of principal component with electroconductive oxide particulate and adhesive stroma at the plastic film (basement membrane) of having given the choke function.

In addition, as the method for giving the choke function to plastic film, be widely used in the method for implementing the choke coating on the plastic film.For example, as the gas barrier property plastic film that is used for packing timber or liquid crystal display cells, known evaporation is arranged on film the film of silica (with reference to the special public clear 58-12953 communique of JP), evaporation the film of aluminium (with reference to the clear 58-217344 communique of TOHKEMY), but its water-vapor barrier is 1g/m ²About/sky.But maximization and the height along with OLED display or LCD becomes more meticulous in recent years, requires film substrate must have higher gas barrier property, and requires it to have the 0.1g/m of being lower than when representing with water-vapor barrier ²The performance in/sky.For corresponding to this, inquired into by adopting the plasma that glow discharge produces under the low pressure condition to come film forming sputtering method or CVD method to carry out film forming, further also proposed to make and had organic membrane stacked mutually and the technology (with reference to WO2000/026973 communique, TOHKEMY 2003-191370 communique) of the choke film of the structure of inoranic membrane by vacuum vapour deposition or near the plasma discharging method atmospheric pressure.In addition, as having 0.001g/m ²The film of/day following water-vapor barrier has also proposed to be laminated with the gas-barrier films duplexer (with reference to TOHKEMY 2007-277631 communique) of two-layer above ceramic layer.

And, the plastic film (basement membrane) of having given the choke function of the present invention can use the commercially available gas barrier property plastic film that obtains by the whole bag of tricks of putting down in writing in the special public clear 53-12953 communique of above-mentioned JP, the clear 58-217344 communique of TOHKEMY, WO2000/026973 communique, TOHKEMY 2003-191370 communique, the TOHKEMY 2007-277631 communique.And according to the difference of the kind of functional element, needed gas barrier properties is also different, and in organic EL or liquid crystal cell, water-vapor barrier requires at 0.01g/m ²Below/the sky, preferably require at 0.001g/m ²/ day.But because it is on the high side usually to have a film of high resistant airway dysfunction, therefore, can or allow that the life-span is waited according to the environment for use of the device of the kind of employed functional element, use, device carries out suitable selection.

Then, to be used for the above-mentioned thickness of having given the plastic film (basement membrane) of choke function of the present invention be 3～50 μ m, be preferably 6～25 μ m.If the basement membrane thickening, then its rigidity uprises usually, and the pliability of flexible functional element is impaired.On the one hand, if the basement membrane attenuation though can improve the pliability of flexible functional element, brings difficulty to processing ease in manufacturing process, cause productive deterioration sometimes.Especially, when the thin thickness of basement membrane during to less than 3 μ m, thereby the operability that exists the general film that is difficult to be circulated usually, basement membrane self become extremely difficult make described later by support film (lining form) thereby the lining that carries out becomes difficulty and because the inscape that the intensity of basement membrane self reduces the element that comprises gas barrier layer or transparency conducting layer of flexible functional element produces problems such as damage, thereby not preferred.

In addition, the material of above-mentioned basement membrane (having given the plastic film of choke function) then has no particular limits so long as have the transparency or light transmission and can form the material of transparency conducting layer thereon, can use various plastic films.Can use the plastic film of PETG (PET), PEN (PEN), nylon, polyether sulfone (PES), Merlon (PC), polyethylene (PE), polypropylene (PP), urethanes, fluororesin etc. specifically, wherein, from inexpensive and good strength, have viewpoints such as the transparency and flexibility concurrently, preferred PET film.

In addition, as above-mentioned basement membrane (having given the plastic film of choke function), also can use fiber by inorganic and/or organic (plastics) (contain needle-like, bar-shaped, must the shape particulate) or the film strengthened of sheet particulate (containing tabular).Even the extremely thin film of film by these fibers or the reinforcement of sheet particulate also can have good intensity.

In addition, in order to improve and to be adherence force between the transparency conducting layer of principal component with electroconductive oxide particulate and adhesive stroma, can form the easily adhesion processing of face enforcement in advance of using coating fluid to the transparency conducting layer that will be coated with of above-mentioned basement membrane (having given the plastic film of choke function), specifically, can implement plasma treatment, Corona discharge Treatment, short wavelength ultraviolet treatment with irradiation etc. in advance.

At this, as the plastic film of having given the choke function, when the plastic film of said gas-blocking coating had been implemented in use, forming transparency conducting layer on any of above-mentioned plastic film could.For example; when the gas barrier layer of the plastic film of having implemented the choke coating is formed with transparency conducting layer; become the said gas-blocking layer and be sandwiched in structure between plastic film and the transparency conducting layer; gas barrier layer can not be exposed to outside (because being protected by plastic film and transparency conducting layer), so be difficult to produce the deterioration of the gas barrier layer that is caused by scar or medicine.But, the formation of the transparency conducting layer on the gas barrier layer of the plastic film of having implemented the choke coating, formation than the transparency conducting layer on plastic film, be difficult to guarantee adherence force, also might nesa coating form gas barrier layer is produced bad influence, suitably select so be necessary kind or its behaviour in service of the device that is suitable for according to flexible transparent conductive film with coating fluid.

In addition, also can paste many plastic films of having given the choke function and constitute basement membrane, further strengthen the choke function of basement membrane thus.For example, be 0.1g/m if paste two water-vapor barriers ²The gas barrier property plastic film in/sky then can access 0.05g/m ²The water-vapor barrier in/sky.But, given the plastic film of choke function if paste, the gross thickness of basement membrane thickening correspondingly then, thus can reduce pliability.Therefore, whether constitute above-mentioned basement membrane by the high performance single plastic film of having given the choke function, perhaps paste many inexpensive gas barrier property plastic films (having given the plastic film of choke function) and constitute basement membrane, can wait suitably according to the thickness of the functional element of cost or use and according to desired pliability and select.

In addition, on the face that does not form transparency conducting layer of above-mentioned basement membrane (having given the plastic film of choke function), also can implement hard surface coating processing, Anti Glare Coatings processing, antireflection (low reflection) coating processing.The outmost surface that finally becomes flexible functional element of the present invention (having formed the element of functional element on the transparency conducting layer of flexible transparent conductive film) owing to the above-mentioned face that does not form transparency conducting layer is exposed externally, so handle if on this face, implement hard surface coating, then can improve marresistance, for example can prevent the reduction etc. of the Presentation Function of the reduction of the gas barrier properties that causes because of choke coating damaged or above-mentioned flexible functional element effectively.Equally, Anti Glare Coatings is handled, anti-reflection coating is handled if implement, and then can be controlled at the external light reflection on the outmost surface of above-mentioned flexible functional element, so can further improve display performance.

But, because basement membrane (having given the plastic film of choke function) has the thin thickness of aforesaid 3～50 μ m, therefore, when operability in the manufacturing process that considers flexible transparent conductive film and flexible functional element and productivity, preferably adopt support film (lining form) to come lining (reinforcement) basement membrane.Preferred this support film (lining form) with the bonding plane of basement membrane on have the little adhesive linkage that can peel off after bonding.In addition, be common situation though be far from being, when the raw material of support film (lining form) itself have little cementability, because support film (lining form) is with the effect of little adhesive linkage, so need not to go up the little adhesive linkage of formation in support film (lining form).

At this, the thickness of above-mentioned support film (lining form) is more than the 50 μ m, is preferably more than the 75 μ m, more elects as more than the 100 μ m.If the thickness less than 50 μ m of support film (lining form), then the rigidity of film reduces, bring obstacle for the operation in the manufacturing process of various flexible functional elements, further, cause the problem of base material bending (curling) easily, or (when the stacked printing as the luminescent coating in dispersion-type EL element etc.) is easy to generate problem when forming the functional element layer.On the other hand, the thickness of support film (lining form) is preferably below the 200 μ m.The thickness of support film (lining form) is if surpass 200 μ m, and then film is not only hard but also heavy, becomes the unworkable while, and is taking cost into account also not preferred.

In addition, there is no particular limitation to the material of above-mentioned support film (lining form), can use various plastic films.Specifically, can use the plastic film of Merlon (PC), PETG (PET), PEN (PEN), nylon, polyether sulfone (PES), polyethylene (PE), polypropylene (PP), urethanes, fluororesin, polyimides (PI) etc., wherein, from inexpensive and good strength, have viewpoint such as flexibility concurrently, preferred PET film.In addition, the transparency of support film (lining form) and the desired transparency of flexible functional element do not have direct relation, but see through this support film sometimes and carry out characteristic check (brightness, outward appearance, display performance etc.) as the element of goods, so the film that preferably clear is good, also preferred PET film on this point.

And, above-mentioned support film (lining form) with the state of basement membrane adhesion under, through the manufacturing process of flexible transparent conductive film and flexible functional element, be stripped from from basement membrane at last.Therefore, preferred above-mentioned little adhesive linkage has suitable fissility.As so little adhesive linkage, can enumerate acrylic compounds or silicon class, wherein, because the excellent heat resistance of the little adhesive linkage of silicon class is therefore preferred.In addition, the desired fissility of above-mentioned little adhesive linkage is specifically in 180 ° of disbonded tests [draw speed=300mm/ minute], with the peel strength (per unit length in the stripping portion is peeled off needed power) of basement membrane be 1～40g/cm, be preferably 2～20g/cm, more preferably the scope of 2～10g/cm.When peel strength deficiency 1g/cm,, in the manufacturing process of flexible transparent conductive film or flexible functional element, also cause easily sometimes and peel off, so not preferred even support film (lining form) and basement membrane are pasted.On the one hand, if above-mentioned peel strength surpasses 40g/cm, then support film (lining form) and basement membrane are difficult to peel off, and make the deterioration from the operation of support film stripping process that produces flexible functional element sometimes, because of the danger raising attached to phenomenons such as base film surfaces of the deterioration (be full of cracks etc.) of peeling off the stretching that causes element or transparency conducting layer by force, the little adhesive linkage of part.

But,, to implement heating treatment step (for example about 120～140 ℃) to flexible transparent conductive film sometimes and make according to the kind of flexible functional element.Therefore,, also be necessary to keep above-mentioned peel strength, require the material of above-mentioned little adhesive linkage to have thermal endurance for this reason after heating treatment step.Further, when making flexible transparent conductive film, when adopting the ultraviolet curing operation, require the material of little adhesive linkage must have ultra-violet resistance.

And, flexible transparent conductive film enforcement heating treatment step is being made under the situation of flexible functional element, front and back in this heating treatment step, the size changing rate of vertical (MD) of above-mentioned flexible transparent conductive film and horizontal (TM) is all below 0.3%, preferably below 0.15%, further preferably below 0.1%.At this, in plastic film, the size changing rate that is accompanied by heat treated typically refers to shrinkage.The size changing rate (shrinkage) of vertical (MD) but of flexible transparent conductive film and horizontal (TM) does not all preferably surpass 0.3%.It the reasons are as follows,, when flexible transparent conductive film for example is used for flexible dispersion-type EL element, stacks gradually luminescent coating, dielectric layer, backplate layer etc. on flexible transparent conductive film that is.At this moment, every each layer of formation, form with slurry by the pattern printing, be dried, be heated curing, but if arbitrary size changing rate of vertical (MD) of flexible transparent conductive film and horizontal (TM) surpasses 0.3%, then each layer is heating and curing and causes change in size (contraction) when handling, produce the printing skew, therefore, the size of this skew might surpass the permissible range in the dispersion-type EL element manufacturing.

As the method that reduces above-mentioned size changing rate, can consider to use in advance method, use or make above-mentioned basement membrane in advance or the basement membrane of supported film phase contrast carries out the method for thermal contraction, carries out the method for thermal contraction etc. together with the flexible transparent conductive layer by the method for the basement membrane of low thermal shrinkage type support film (lining form) lining through the basement membrane of the low thermal shrinkage type of overheat contraction.

Then, the formation of transparency conducting layer of the present invention can be carried out as described below.At first, the adhesive ingredients that is made of electroconductive oxide particulate and adhesive stroma is scattered in the solvent, thereby forming, the preparation transparency conducting layer uses coating fluid, and this coating fluid of coating/drying forms coating layer on the plastic film (basement membrane) of having given the choke function, then this coating layer is compressed processing together with basement membrane, then, the adhesive ingredients of the coating layer of handling through overcompression is solidified, thereby form above-mentioned transparency conducting layer.

Form the coating process of using coating fluid as above-mentioned transparency conducting layer, can use the method in common of silk screen printing, scraper coating, the coating of line rod, spraying, print roll coating, intaglio printing, ink jet printing etc., but be not limited thereto.

And, with transparency conducting layer form with coating fluid be coated with, the dry and above-mentioned coating layer that obtains, constitute by electroconductive oxide particulate and uncured adhesive ingredients, so, when carrying out above-mentioned compression and handle, not only the packed density of the electrically conductive microparticle in the transparency conducting layer significantly rises, and reduces scattering of light, thereby improve the optical characteristics of film, but also can significantly improve conductivity.Handle as above-mentioned compression, to being formed, transparency conducting layer is coated with the basement membrane that drying forms with coating fluid, by as rolled by hard chrome electroplated metal roller etc. and to get final product, the calendering pressure of the metallic roll of this moment is preferably line pressure: 29.4～490N/mm (30～500kgf/cm) condition, more preferably 98～294N/mm (condition of 100～300kgf/cm).Under the condition of the not enough 29.4N/mm of line pressure (30kgf/cm), it is insufficient to improve effect by the resistance value of rolling the transparency conducting layer of handling, in addition, if line pressure surpasses the condition of 490N/mm (500kgf/cm), when then rolling equipment need maximize, produce the distortion of basement membrane (having given the plastic film of choke function) or support film (lining form) sometimes, thus the perhaps phenomenon that worsens of the destroyed choke function of the gas barrier layer of basement membrane.That is, find even on the gas barrier layer of basement membrane, be applied with compression stress, also can not to cause the reduction of choke function that the transparency or the conductivity of transparency conducting layer are enhanced, and have so far realized the present invention if can carry out rightly handling by the calendering of above-mentioned metallic roll etc.In addition, the calendering pressure (N/mm of per unit area during the calendering of above-mentioned metallic roll is handled ²), be to use nip width (in the contact portion of metallic roll and transparent conductive film line pressure, the width in the zone that transparent conductive film is flattened by metallic roll) removes the value of calculating, nip width depends on the diameter and the line pressure of metallic roll, when being roller diameter about 150mm, then nip width is about 0.7～2mm.

But, used thickness is the thin basement membrane (having given the plastic film of choke function) about 3～50 μ m in the present invention, but come under the situation of phase contrast having pasted support film (lining form) on this basement membrane, handle even extremely thin basement membrane is implemented above-mentioned calendering, also can prevent the distortion of basement membrane or the generation of fold effectively.Further, in the calendering processing of being undertaken by hard chrome electroplated metal roller, this metallic roll is the concavo-convex minimum mirror roller on surface, so can make the surface of the transparency conducting layer that obtains after above-mentioned calendering is handled extremely level and smooth.This be because, even form on the coating layer that obtains with coating fluid and have convex portion being coated with nesa coating, also can be in the calendering of being undertaken by above-mentioned metallic roll be handled level and smooth this convex portion physically.And, if the surface smoothing of transparency conducting layer is good, then in above-mentioned various functional elements, have the effect that prevents interelectrode short circuit or element generation of defects, very desirable.

In addition, the coating that transparency conducting layer forms with coating fluid both can be comprehensive coating (whole printing), also can be the pattern printing.In addition, the thickness of above-mentioned transparency conducting layer is generally [transmitance (transmitance that does not contain the only transparency conducting layer of basement membrane) that is scaled transparency conducting layer is equivalent to about 92～96%] about 0.5～1 μ m, thickness (3～50 μ m) than basement membrane (having given the plastic film of choke function) is thin, therefore, even have pattern by pattern printing transparent conductive layer, the pressure in the time of also can applying above-mentioned compression equably and handle.

And, transparency conducting layer of the present invention, be that the adhesive ingredients of having implemented the coating layer that above-mentioned compression handles is cured and obtains, this curing can form the kind of using coating fluid according to transparency conducting layer, suitably selects heat treated (dry solidification, hot curing), ultraviolet irradiation processing (ultraviolet curing) etc. to get final product.

Then, form the electroconductive oxide particulate of using coating fluid as being used for transparency conducting layer of the present invention, be with indium oxide, tin oxide, in the zinc oxide any one is above to be the particulate of principal component, for example, can exemplify indium tin oxide (ITO) particulate, indium-zinc oxide (IZO) particulate, indium-tungsten oxide (IWO) particulate, indium-titanium oxide (ITiO) particulate, indium Zirconium oxide particulate, tin-antimony oxide (ATO) particulate, fluorine tin-oxide (FTO) particulate, aluminium zinc oxide (AZO) particulate, gallium zinc oxide (GZO) particulate etc., if but have the transparency and conductivity, be not limited to this.But, wherein because the characteristic of ITO particulate is the highest, so preferred.

In addition, the average grain diameter of above-mentioned electroconductive oxide particulate is preferably 1～500nm, more preferably 5～100nm.If the not enough 1nm of average grain diameter, then transparency conducting layer formation becomes difficult with the manufacturing of coating fluid, and the resistance value of resulting transparency conducting layer uprises sometimes.On the one hand, if surpass 500nm, then transparency conducting layer forms and precipitates easily with electroconductive oxide particulate in the coating fluid, so operate the very difficult while, is difficult to reach simultaneously high permeability and low-resistance value sometimes in transparency conducting layer.In addition, the average grain diameter of above-mentioned electroconductive oxide particulate is represented the value with TEM (TEM) observation.

In addition, thus transparency conducting layer forms the effect that adhesive ingredients with coating fluid has the bonding force of the effect of the conductivity that the electroconductive oxide particulate is bonded to each other improve film and intensity or basement membrane that raising becomes substrate and transparency conducting layer.Further, in the manufacturing process of functional element, in order to prevent because of wait the deterioration of the transparency conducting layer that the organic solvent that contains in the employed various printing slurries when forming various functional membrane causes, the effect that also has the solvent resistance of giving by stacked printing.And, as above-mentioned adhesive ingredients, can use organic and/or inorganic bond, can wait and carry out suitable selection according to being coated with film formation condition that transparency conducting layer forms basement membrane with coating fluid, transparency conducting layer, to satisfy above-mentioned functions.

In addition, as above-mentioned organic bond, but be not the heat property resin that can not use acrylic resin or mylar etc., but preferably has solvent resistance usually, therefore, must use crosslinkable resin, can from thermosetting resin, normal temperature cure resin, uv curing resin, electron ray curing resin etc., select.For example, can enumerate epoxy resin, fluororesin etc. as thermosetting resin; Can enumerate the epoxy resin of two property at night or polyurethane resin etc. as the normal temperature cure resin; Can enumerate resin that contains various oligomer, homopolymers, light trigger etc. as uv curing resin; Can enumerate resin that contains various oligomer, homopolymers etc. as the electron ray curing resin, but be not limited to these resins.

In addition, as above-mentioned inorganic bond, can enumerate with Ludox, alumina sol, zirconia sol, titanium oxide sol etc. is the adhesive of principal component.For example, can utilize as above-mentioned Ludox and in silicic acid tetraalkyl ester, added water or acid catalyst is hydrolyzed and carried out the polymer of dehydration polycondensation or make the commercially available polymer that silicic acid tetraalkyl ester solution further is hydrolyzed and the polycondensation of dewatering forms that is aggregated to 4～5 aggressiveness etc.But, the polycondensation if transition is dewatered, then solution viscosity rises, and final curing is so the degree of the polycondensation of will dewatering is adjusted at below the upper limit viscosity that can coat on the basement membrane (having given the plastic film of choke function).As long as the degree of the extent control of polycondensation below above-mentioned upper limit viscosity gets final product and have no particular limits though will dewater, when considering film-strength, weatherability etc., then preferable weight-average molecular weight is about 500～50000.And, when the hydrating polymer of this alkyl silicate (Ludox) forms the coating with coating fluid, dried heating at transparency conducting layer, dehydration polycondensation reaction (cross-linking reaction) almost finishes, and becomes hard esters of silicon acis adhesive stroma (is the adhesive stroma of principal component with the silica).Above-mentioned dehydration polycondensation reaction be after finishing from the drying of film (coating layer) immediately, behind the process certain hour, the electroconductive oxide particulate firmly is consolidated into irremovable each other degree, therefore, when using inorganic bond, after transparency conducting layer forms coating with coating fluid, drying, preferably carry out above-mentioned compression as far as possible apace and handle.

In addition,, also can use the mixed adhesive of organic and inorganic as adhesive, for example can enumerate with organo-functional group modified above-mentioned Ludox a part adhesive or be the adhesive of principal component with the various coupling agents of silane coupling agent etc.In addition, used the transparency conducting layer of the mixed adhesive of inorganic bond or organic and inorganic must have outstanding solvent resistance, but must carry out suitable selection, can not reduce and as flexibility of bonding force between the basement membrane of substrate or transparency conducting layer etc.

Then, when the proportion of hypothesis electroconductive oxide particulate and adhesive ingredients is respectively about 7.2 (proportion of ITO) and about 1.2 (proportion of common organic binder resin), the ratio that the transparency conducting layer that the present invention uses forms with electroconductive oxide particulate in the coating fluid and adhesive ingredients is expressed as electroconductive oxide particulate: adhesive ingredients=85:15～97:3 with weight ratio, more elects 87:13～95:5 as.Its reason is, when the calendering of carrying out coating layer is in the present invention handled, if adhesive ingredients is more than the ratio of 85:15, then the resistance of transparency conducting layer becomes too high sometimes, on the contrary, if adhesive ingredients is less than the ratio of 97:3, when then the intensity of transparency conducting layer reduces, can't obtain and become the sufficient adhesive between the basement membrane of substrate sometimes.

In addition, the transparency conducting layer that uses among the present invention forms and can prepare by following method with coating fluid.At first, the electroconductive oxide particulate with after solvent and dispersant are as required mixed, is carried out dispersion treatment, obtain the electroconductive oxide particle dispersion liquid.As above-mentioned dispersant, can enumerate the various surfactants of the various coupling agents of silane coupling agent coupling agent etc., various macromolecule dispersing agent, anion system/nonionic system/cation system etc.These dispersants can carry out suitable selection according to the kind or the decentralized approach of employed electroconductive oxide particulate.In addition, even do not use dispersant fully, also can and select suitable process for dispersing to obtain good dispersity sometimes according to the combination between employed electroconductive oxide particulate and the solvent.The use of dispersant might cause the resistance value of film (transparency conducting layer) or the deterioration of weatherability, does not use coating fluid so preferably do not use the transparency conducting layer of dispersant to form.Can adopt the method in common of ultrasonic Treatment, homogenizer, paint shaker, bead mill etc. as dispersion treatment.

In resulting above-mentioned electroconductive oxide particle dispersion liquid, add adhesive ingredients, further carry out the composition adjustment of electroconductive oxide particle concentration, solvent composition etc., obtain transparency conducting layer formation coating fluid thus.At this, adhesive ingredients is added in the dispersion liquid of electroconductive oxide particulate, but also can before the dispersion step of above-mentioned electroconductive oxide particulate, add in advance, have no particular limits.The concentration of electroconductive oxide particulate can be carried out suitable setting according to employed coating process.

Then, form the solvent of using coating fluid, have no particular limits, can carry out suitable selection according to the material of coating process, film forming condition, basement membrane as the transparency conducting layer that uses among the present invention.For example can enumerate the alcohols solvent of water, methyl alcohol (MA), ethanol (EA), 1-propyl alcohol (NPA), isopropyl alcohol (IPA), butanols, amylalcohol, phenmethylol, diacetone alcohol (DAA) etc.; The ketones solvent of acetone, methylethylketone (MEK), methyl propyl ketone, methylisobutylketone (MIBK), cyclohexanone, isophorone etc.; Ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, hydroxy methyl acetate, hydroxyl ethyl acetate, the glycolic acid butyl ester, Methoxy Methyl Acetate, the Methoxy acetic acid ethyl ester, the Methoxy acetic acid butyl ester, the ethyoxyl methyl acetate, the ethyoxyl ethyl acetate, the 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxy-propionic acid methyl esters, the 3-ethoxyl ethyl propionate, the 2 hydroxy propanoic acid methyl esters, the 2 hydroxy propanoic acid ethyl ester, the 2 hydroxy propanoic acid propyl ester, 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-methoxy propyl propyl propionate, 2-ethoxy-propionic acid methyl esters, the 2-ethoxyl ethyl propionate, 2-oxygen-2 Methylpropionic acid methyl esters, 2-oxygen-2 Methylpropionic acid ethyl ester, 2-methoxyl group-2 Methylpropionic acid methyl esters, 2-ethyoxyl-2 Methylpropionic acid ethyl ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-ketobutyric acid methyl esters, the esters solvent of 2-ketobutyric acid ethyl ester etc.; Glycol monoethyl ether (MCS), ethylene glycol monoethyl ether (ECS), glycol isopropyl ether (IPC), ethylene glycol monobutyl ether (BCS), ethylene glycol monomethyl ether acetate, the ethylene glycol monobutyl ether acetic acid esters, methyl proxitol (PGM), propylene glycol ethylether (PE), methyl proxitol acetate (PGM-AC), propylene glycol ethylether acetic acid esters (PE-AC), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol single-butyl ether, the diethylene glycol monomethyl ether acetic acid esters, the TC acetic acid esters, diethylene glycol single-butyl ether acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, the diethylene glycol dibutyl ethers, dipropylene glycol monomethyl ether, DPG list ether, the diol, derivatives of DPG single-butyl ether etc.; The benzene derivative of toluene, dimethylbenzene, trimethylbenzene, detergent alkylate etc.; Formamide (FA), N-methylformamide, dimethyl formamide (DMF), dimethylacetylamide, dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP), gamma-butyrolacton, ethylene glycol, diethylene glycol, propylene glycol, DPG, 1,3-butanediol, pentanediol, 1,3-ethohexadiol, oxolane (THF), chloroform, Mineral spirits, terpineol etc., but be not limited to this.

Then, the flexible functional element that flexible transparent conductive film of the present invention is suitable for is described.As such flexible functional element, can enumerate aforesaid liquid crystal display cells, organic EL, inorganic dispersion-type EL element, electronic paper elements etc.

At this, above-mentioned liquid crystal display cells is meant the electronic display elements of the non-light emitting-type in the display that is widely used in mobile phone, PDA (personal digital assistant) and PC (PC) etc., simple matrix mode and active matrix mode are arranged, consider preferred active matrix-style from the aspect of picture quality and answer speed.Its basic structure is to clip liquid crystal with transparency electrode (corresponding to transparency conducting layer of the present invention), and the structure that the liquid crystal molecule orientation is shown with driving voltage, actual element is on the basis of above-mentioned transparency electrode, and further stacked colour filter, phase-contrast film, polarization film wait and use.In addition, in order to ensure the exhibit stabilization of liquid crystal display cells, must prevent that steam to the sneaking into of liquid crystal, for example requiring moisture-vapor transmission=0.01g/m ²Below/the sky.

In addition, above-mentioned organic EL is different from liquid crystal display cells, and it is a self-emission device, can obtain high brightness under low voltage drive, so be hopeful to use as the display unit of display etc.Its structure is, forms positive hole injecting layer (hole injecting layer) that the electroconductive polymer by polythiofuran derivative etc. constitutes, organic luminous layer (the low mulecular luminescence layer that forms by evaporation or the polymeric luminescence layer that forms by coating), negative electrode layer (to the metal level of the magnesium that the electronics injection is good, work function is low (Mg) of luminescent layer, calcium (Ca), aluminium (Al) etc.), choke the coating layer encapsulation process of metal or glass (or by) on as the transparency conducting layer of anode electrode layer successively.The said gas-blocking coating layer is necessary for the deterioration that prevents organic EL, for example, to steam, requires moisture-vapor transmission=10 ^-5G/m ²Very high gas barrier properties below about/sky.

In addition, above-mentioned inorganic dispersion-type EL element is to apply strong AC field on the layer of fluorophor particle and come luminous self-emission device containing, and is used for backlight liquid crystal display such as mobile phone, remote controller etc. all the time.In addition, as new purposes in recent years, for example as the light source of the keyboard input part (remote input units) of the various device of the personal digital assistant device of mobile phone, remote controller, PDA, portable PC etc. and assembled.When being applied to above-mentioned remote input units, requiring to make element thin and soft as far as possible, thereby guarantee the good operation sense of button durability and keyboard operation.Its basic structure is; on transparency conducting layer as transparency electrode; at least successively be formed with the structure of luminescent coating, dielectric layer, backplate layer by silk screen printing, in the device of reality, also be formed with the collecting electrodes of silver etc. or insulating protective layer etc. usually.

In addition, above-mentioned electronic paper elements is the electronic display elements of self non-luminous non-light emitting-type, even have the storage effect of cutting off the electricity supply and also keeping its demonstration same as before, remains as the display that is used for display text.Its display mode can enumerate by electrophoresis make electrophoresis mode that colored particles flows in interelectrode liquid, by make have dichromatic particle in electric field, rotate carry out the painted ball mode of reversing, for example cholesteryl liquid crystal is clipped in the liquid crystal mode that shows between the transparency electrode, make colored particles (last toner) or electronics powder fluid (Quick Response Liquid Powder; Quick liquid powder) in air, move the powder class mode that shows, based on electrochemical oxidation/reduction carry out color development the electroluminescence mode, separate out/dissolution of metals the electro-deposition mode that shows by the change in color that produces with this etc. by electrochemical oxidation/reduction.In addition, in the electronic paper elements of variety of way,, must prevent steam, though according to the difference of mode and difference for example requires moisture-vapor transmission=0.01～0.1g/m to the sneaking into of display layer in order to ensure its stability ²/ day.

And, any kind of flexible functional element in above-mentioned liquid crystal display cells, organic EL, inorganic dispersion-type EL element, the electronic paper elements, all can on the transparency conducting layer of flexible transparent conductive film of the present invention, form various functional elements respectively and obtain, thereby can reach the problem of the desired slimming of functional element, lightweight, pliability (flexibility).

As mentioned above, though the thin basement membrane of flexible functional elements of the present invention such as liquid crystal display cells, organic EL, inorganic dispersion-type EL element, electronic paper elements, but use as transparent electrode material owing to will have the flexible transparent conductive film of choke function, so have good pliability, for example can easily be assembled in the various slim equipment that comprises card etc., and, can also the further slimming of these equipment be contributed.

Below, specify embodiments of the invention, but the present invention is not limited to the technology contents of these embodiment.

[embodiment 1]

In as the 24g methyl isopropyl ketone (MIBK) of solvent and 36g cyclohexanone, mix the granular ITO particulate that the 36g average grain diameter is 0.03 μ m [trade name: SUFP-HX, Sumitomo Metal Industries mine (strain) are made], after carrying out dispersion treatment, add 3.8g urethane acrylate class uv curing resin adhesive and 0.2g light trigger [trade name: Darocure 1173, Chiba Japan (strain) company make], carry out good stirring, be dispersed with the transparency conducting layer formation coating fluid (A liquid) that the average mark shot directly is the ITO particulate of 125nm thereby prepared.

Then, before making transparent conductive film, will give the plastic film [trade name: the formation of GX-P-F film, letterpress (strain) company manufacturing (being designated hereinafter simply as the GX film), GX film: the moisture-vapor transmission=0.04g/m of the PET film of thickness 12 μ m/aluminium oxide gas barrier layer/esters of silicon acis polyvinyl alcohol mixing coating layer, GX film of the about 13 μ m of thickness of choke function earlier ²/ sky, visible light transmitance=88.5%, haze value=2.3%] as the basement membrane of transparent conductive film, on the face that is formed with said gas-blocking layer (constituting) of this basement membrane by aluminium oxide gas barrier layer and esters of silicon acis polyvinyl alcohol mixing coating layer, by the little adhesive linkage of thermal endurance silicon, paste the support film (lining form) that the PET film by thickness 100 μ m constitutes.

Then, in above-mentioned basement membrane and opposite sides support film (promptly, do not form the PET pellicular front of gas barrier layer) implement Corona discharge Treatment after, (the line footpath: 0.10mm) mode is coated with transparency conducting layer formation coating fluid (A liquid) with the coating of line bar type on this treated side, and after under 60 ℃ dry one minute, by implementing diameter that hard chrome electroplates is that the metallic roll of 100mm is rolled processing (line pressure: 200kgf/cm=196N/mm, nip width: 0.9mm), further, by high-pressure mercury-vapor lamp carry out adhesive ingredients curing (in the nitrogen, 100mW/cm ²* 2 seconds), on basement membrane, form the transparency conducting layer that constitutes by ITO particulate of filling densely and adhesive stroma (thickness: about 0.5 μ m), thereby obtain the electrically conducting transparent layer film (basement membrane thickness that has transparency conducting layer: about 13.5 μ m) of embodiment 1.

In addition, the transparent conductive film of embodiment 1 has the formation of [support film (lining form)]/[basement membrane that is made of the GX film]/[transparency conducting layer], the thickness of the basement membrane that is made of the GX film is about 13.5 μ m as described above, extremely thin and soft, in addition, the transparency of each constituent material of GX film of having given the choke function is high, thus in the transparent conductive film of embodiment 1, because of the absorption that has caused visible light of basement membrane minimum.

And, with the result that the moisture-vapor transmission of the transparent conductive film of embodiment 1 is measured together with support film, moisture-vapor transmission=0.04g/m ²/ day, can confirm in the forming process of transparency conducting layer less than the deterioration that causes moisture-vapor transmission because of Corona discharge Treatment or calendering processing etc.At this, above-mentioned support film is made of the PET film that does not have the choke function, its moisture-vapor transmission is big more than tens times than the moisture-vapor transmission of the GX film of having given the choke function, so, can think the transparent conductive film measured together with support film moisture-vapor transmission and the moisture-vapor transmission of peeling off above-mentioned support film resulting [being formed with the GX film of transparency conducting layer] from transparent conductive film much at one.In addition, a series of mensuration of moisture-vapor transmission are MOCON (the モ コ Application) method (experimental situations: 40 ℃ * 95%RH) carry out according to JIS K 7129B method.

In addition, the peel strength between [support film (lining form)] of the transparent conductive film of embodiment 1 and [basement membrane that is made of the GX film] is 5.0g/cm.At this, above-mentioned peel strength is 180 ° of peel strengths [with the draw speeds of basement membrane with 300mm/ minute, the intensity when implementing 180 ° disengaging (peeling off)].

In addition, the membrane property of above-mentioned transparency conducting layer is respectively the visible light transmitance: haze value 3.7%, sheet resistance value: 1000 Ω/ 95.3%.In addition, about sheet resistance value, the tendency that temporary transient decline is arranged after just having finished is solidified in the influence of the ultraviolet irradiation when being subjected to adhesive curing, so, measure after one day at the formation transparency conducting layer.Further, the transmitance of above-mentioned transparency conducting layer and haze value only are the value of transparency conducting layer, are calculated by following calculating formula 1 and 2 respectively.

[calculating formula 1]

The transmitance of transparency conducting layer (%)=[(together with transparency conducting layer and the transmitance measured by the basement membrane of support film phase contrast)/(by the transmitance of the basement membrane of support film phase contrast)] * 100

[calculating formula 2]

The haze value of transparency conducting layer (%)=(together with transparency conducting layer and the haze value measured by the basement membrane of support film phase contrast)-(by the haze value of the basement membrane of support film phase contrast)

In addition, the sheet resistance of transparency conducting layer is that the sheet resistance meter ロ レ ス AP (MCP-T400) that adopts Mitsubishi Chemical's (strain) company to make measures.Haze value and visible light transmitance then adopt the haze meter (NDH5000) of Japanese electric look (strain) company manufacturing, and measure according to JIS K7136.

Then, transparent conductive film at embodiment 1 (is called " first transparent conductive film ", in addition, this basement membrane is called " first basement membrane ", transparency conducting layer is called " first transparency conducting layer ") transparency conducting layer (first transparency conducting layer) go up to form the display layer (bed thickness 40 μ m) of the electrophoresis mode that constitutes by the microcapsules that contain white particles and black particle, further on formed above-mentioned display layer, the transparent conductive film of pasting another embodiment 1 (is called " second transparent conductive film ", in addition, this basement membrane is called " second basement membrane ", transparency conducting layer is called " second transparency conducting layer ") transparency conducting layer (second transparency conducting layer) side.

Then, with above-mentioned display layer is the center, end at first transparent conductive film of its both sides and each transparency conducting layer of second transparent conductive film (first transparency conducting layer and second transparency conducting layer), after adopting conductive silver slurry to form respectively to apply voltage with the Ag lead-in wire, peel off each support film (lining form) of first transparent conductive film and second transparent conductive film respectively, thereby obtain flexible functional element (the electronic paper elements) (component thickness: about 67 μ m) of embodiment 1.

In addition, in electronic paper elements, be preferably on an electrode, to use transparency conducting layer originally when improving contrast etc. when considering, on another electrode, then use the black conductive film of carbon pastes coated film etc.At this moment, the basement membrane of painting black conducting film need not to have the transparency, so basement membrane can use metal evaporation plastic film of the metal forming of stainless steel etc. or aluminium etc. etc.But in various embodiments of the present invention and comparative example, for convenience, all use transparency conducting layer two electrode both sides that are used for electronic paper elements is applied voltage.

And the above-mentioned flexible functional element (electronic paper elements) of the about 67 μ m of the thickness of embodiment 1 has the formation of [first basement membrane with about 13 μ m of thickness of choke function]/[first transparency conducting layer of the about 0.5 μ m of thickness]/[display layer (thickness: 40 μ m)]/[second transparency conducting layer of the about 0.5 μ m of thickness]/[second basement membrane with about 13 μ m of thickness of choke function].

In addition; in this flexible functional element (electronic paper elements); in order to prevent short circuit between the electrode or electric shock etc., at above-mentioned transparency conducting layer (first transparency conducting layer and second transparency conducting layer) or apply voltage and be formed with the insulating protective layer that has adopted insulation paste on the Ag lead-in wire.But it is not the part that relates to essence of the present invention, and the Therefore, omited is to its explanation.In addition, in the manufacturing process of the flexible functional element of embodiment 1, each basement membrane with the interface of support film (lining form) on can be stripped from simply.This is because the peel strength between [support film (lining form)] of the transparent conductive film of embodiment 1 and [basement membrane that is made of the GX film] is the cause of aforesaid 5.0g/cm.

And the direct voltage that voltage applies 10V between with the Ag lead-in wire that applies at the flexible functional element (electronic paper elements) of embodiment 1 carries out the counter-rotating of polarity repeatedly, and its result has repeated the demonstration of black and white.

[embodiment 2]

Before making transparent conductive film, plastic film [trade name: GX film with the about 13 μ m of two embodiment, 1 employed thickness, letterpress (strain) company makes] gas barrier layer (constituting) by aluminium oxide gas barrier layer and esters of silicon acis polyvinyl alcohol mixing coating layer, paste mutually with bonding agent, thereby make the function intensified film of the choke [formation of film: the PET film of the PET film of thickness 12 μ m/aluminium oxide gas barrier layer/esters of silicon acis polyvinyl alcohol mixing coating layer/bond layer (about 8 μ m)/esters of silicon acis polyvinyl alcohol mixing coating layer/aluminium oxide gas barrier layer/thickness 12 μ m, the moisture-vapor transmission of film is lower than 0.01g/m ²/ day (that is moisture-vapor transmission＜the 0.01g/m of film, ²/ sky), visible light transmitance=87.2%, haze value=4.5%], with the basement membrane of the function intensified film of this choke as transparent conductive film, and on the side's of this basement membrane (the function intensified film of choke) PET pellicular front, paste the support film (lining form) that the PET film by thickness 125 μ m constitutes by the little adhesive linkage of thermal endurance silicon.

Then, after the easy adhesion that the face (being the opposing party's PET pellicular front) with opposition side above-mentioned support film basement membrane implements to be undertaken by corona discharge is handled, on this treated side, form in addition with coating fluid (A liquid) with line bar type coating method coating transparency conducting layer, operate in the same manner with embodiment 1, thereby on basement membrane, form the transparency conducting layer (thickness: about 0.5 μ m), obtain the transparent conductive film (basement membrane thickness that has transparency conducting layer: about 34.5 μ m) of embodiment 2 that constitutes by ITO particulate of filling densely and adhesive stroma.

In addition, the transparent conductive film of embodiment 2 has the formation of [support film (lining form)]/[having pasted the basement membrane of two GX films]/[transparency conducting layer], the thickness of the basement membrane that is made of two GX films is about 34 μ m as described above, thin and extremely soft, in addition, the transparency of each constituent material of the function intensified film of choke of having pasted the GX film is high, so in the transparent conductive film of embodiment 2, the visible light that causes because of the existence of basement membrane absorbs minimum.

And, with the result that the moisture-vapor transmission of the transparent conductive film of embodiment 2 is measured together with support film, its moisture-vapor transmission＜0.01g/m ²/ day, can confirm in the forming process of transparency conducting layer, not caused the deterioration of moisture-vapor transmission because of Corona discharge Treatment or calendering processing etc.At this, above-mentioned support film is made of the PET film that does not have the choke function, its moisture-vapor transmission is big more than tens times than the moisture-vapor transmission of the basement membrane of having pasted two GX films of giving the choke function, so, can think the transparent conductive film measured together with support film moisture-vapor transmission and the moisture-vapor transmission of having peeled off resulting [basement membrane that is formed with transparency conducting layer and constitutes] after the above-mentioned support film from transparent conductive film by two GX films much at one.

In addition, [support film (lining form)] of the transparent conductive film of embodiment 2 and the peel strength between [having pasted the basement membrane of two GX films] are 4.0g/cm.At this, above-mentioned peel strength is represented 180 ° of peel strengths [with the draw speed of basement membrane with 300mm/ minute, the intensity when implementing 180 ° disengaging (peeling off)] similarly to Example 1.

In addition, the membrane property of above-mentioned transparency conducting layer is respectively the visible light transmitance: haze value 3.5%, sheet resistance value: 1050 Ω/ 95.1%.In addition, about sheet resistance value, the tendency that temporary transient decline is arranged after just having begun is solidified in the influence of the ultraviolet irradiation when being subjected to adhesive curing, so, measure after one day at the formation transparency conducting layer.Further, the transmitance of above-mentioned transparency conducting layer and haze value only are the value of transparency conducting layer, with embodiment 1 in the same manner, calculate by aforementioned calculation formula 1 and 2 respectively.

Then, use the transparent conductive film of embodiment 2,, obtain flexible functional element (the electronic paper elements) (component thickness: about 109 μ m) of embodiment 2 with the method roughly the same with embodiment 1.In addition, the above-mentioned flexible functional element (electronic paper elements) of the about 109 μ m of the thickness of embodiment 2 has the formation of [first basement membrane with about 34 μ m of thickness of choke function]/[first transparency conducting layer of the about 0.5 μ m of thickness]/[display layer (thickness: 40 μ m)]/[second transparency conducting layer of the about 0.5 μ m of thickness]/[second basement membrane with about 34 μ m of thickness of choke function].In addition, in the manufacturing process of the flexible functional element of embodiment 2, each basement membrane also with the interface of support film (lining form) on can be stripped from simply.

And the direct voltage that voltage applies 10V between with the Ag lead-in wire that applies at the flexible functional element (electronic paper elements) of embodiment 2 carries out the counter-rotating of polarity repeatedly, and its result has repeated white black demonstration.

[embodiment 3]

The average grain diameter of mixing 36g in as the 24g methyl isopropyl ketone (MIBK) of solvent and 36g cyclohexanone is the granular ITO particulate of 0.03 μ m [trade name: SUFP-HX, Sumitomo Metal Industries mine (strain) are made], after carrying out dispersion treatment, add the aqueous thermosetting epoxy resin adhesive of 4.0g, carry out good stirring, be dispersed with the transparency conducting layer formation coating fluid (B liquid) that the average mark shot directly is the ITO particulate of 130nm thereby prepared.

Then, before making transparent conductive film, will give plastic film [manufacturing of company of Dai Nippon Printing's (strain), the trade name: the formation of IB-P-ET-PXB film (being designated hereinafter simply as " IB film "), IB film: the moisture-vapor transmission=0.08g/m of the PET film of thickness 12 μ m/aluminium oxide gas barrier layer/esters of silicon acis polyvinyl alcohol mixing coating layer, IB film of the about 13 μ m of thickness of choke function earlier ²/ sky, visible light transmitance=88.5%, haze value=2.1%] as the basement membrane of transparent conductive film, on the PET pellicular front of the not formation said gas-blocking layer (constituting) of this basement membrane, paste the support film (lining form) that the PET film by thickness 100 μ m constitutes by the little adhesive linkage of thermal endurance silicon by aluminium oxide gas barrier layer and esters of silicon acis polyvinyl alcohol mixing coating layer.

Then, above-mentioned basement membrane with support film opposite sides (promptly being formed with the PET pellicular front of gas barrier layer) on, (the line footpath: mode 0.15mm) is coated with transparency conducting layer and forms with coating fluid (B liquid) with the coating of line bar type, after under 60 ℃ dry one minute, roll processing (line pressure: 200kgf/cm=196N/mm by the metallic roll that implements the diameter 100mm that hard chrome electroplates, nip width: 0.9mm), further, carried out the curing (crosslinked) of adhesive ingredients in 20 minutes by heating down at 100 ℃, on basement membrane, form the transparency conducting layer that constitutes by ITO particulate of filling densely and bonding intermixture (thickness: about 1.0 μ m), thereby obtain the transparent conductive film (basement membrane thickness that has transparency conducting layer: about 14 μ m) of embodiment 3.

In addition, the transparent conductive film of embodiment 3 has the formation of [support film (lining form)]/[basement membrane that is made of the IB film]/[transparency conducting layer], the thickness of the basement membrane that is made of the IB film is about 13 μ m as described above, thin and very soft, in addition, the transparency of each constituent material of IB film of having given the choke function is high, thus in the transparent conductive film of embodiment 3, because of the absorption that has caused visible light of basement membrane minimum.

And, with the result that the moisture-vapor transmission of the transparent conductive film of embodiment 3 is measured together with support film, moisture-vapor transmission=0.08g/m ²/ day, can confirm in the forming process of transparency conducting layer, not handle and wait the deterioration that has caused moisture-vapor transmission because of calendering.At this, above-mentioned support film is made of the PET film that does not have the choke function, because its moisture-vapor transmission is big more than tens times than the moisture-vapor transmission of the IB film of having given the choke function, so, can think the transparent conductive film measured together with support film moisture-vapor transmission and the moisture-vapor transmission of having peeled off support film resulting [being formed with the IB film of transparency conducting layer] from transparent conductive film much at one.

In addition, the peel strength between [support film (lining form)] of embodiment 3 described transparent conductive films and [basement membrane that is made of the IB film] is 4.0g/cm.At this, above-mentioned peel strength is also similarly represented 180 ° of peel strengths with embodiment 1 and 2.

In addition, the membrane property of above-mentioned transparency conducting layer is respectively the visible light transmitance: haze value 4.4%, sheet resistance value: 650 Ω/ 91.0%.In addition, the transmitance of above-mentioned transparency conducting layer and haze value only are the value of transparency conducting layer, with embodiment 1 in the same manner, calculate by aforementioned calculation formula 1 and 2 respectively.

Then, use the transparent conductive film of embodiment 3,, obtain flexible functional element (the electronic paper elements) (component thickness: about 68 μ m) of embodiment 3 with the method roughly the same with embodiment 1.In addition, the above-mentioned flexible functional element (electronic paper elements) of the about 68 μ m of the thickness of embodiment 3 has the formation of [first basement membrane with about 13 μ m of thickness of choke function]/[first transparency conducting layers of the about 1.0 μ m of thickness]/[display layer (thickness: 40 μ m)]/[second transparency conducting layers of the about 1.0 μ m of thickness]/[second basement membrane with about 13 μ m of thickness of choke function].In addition, in the manufacturing process of the flexible functional element of embodiment 3, each basement membrane also with the interface of support film (lining form) on can be stripped from simply.

And the direct voltage that voltage applies 10V between with the Ag lead-in wire that applies at the flexible functional element (electronic paper elements) of embodiment 3 carries out the counter-rotating of polarity repeatedly, and its result has repeated the demonstration of black and white.

[comparative example 1]

The PET film of the basement membrane used thickness 25 μ m of 1 transparent conductive film as a comparative example, the transparency conducting layer that uses among the coating embodiment 1 on this basement membrane by line bar type coating (line footpath 0.10mm) forms with coating fluid (A liquid), after under 60 ℃ dry one minute, roll processing (line pressure: 200kgf/cm=196N/mm, nip width: 0.9mm) by the metallic roll that implements the diameter 100mm that hard chrome electroplates, further, by high-pressure mercury-vapor lamp carry out adhesive ingredients curing (in the nitrogen, 100mW/cm ²* 2 seconds), thus on basement membrane, formed the transparency conducting layer (thickness: about 0.5 μ m) that constitutes by ITO particulate of filling densely and bonding intermixture.

Then, on the face that does not form transparency conducting layer of above-mentioned basement membrane, by bond layer (the about 20 μ m of thickness), paste plastic film [manufacturing of letterpress (strain) company, the trade name: GX film, the formation of GX film: the moisture-vapor transmission=0.05g/m of the PET film of thickness 12 μ m/aluminium oxide gas barrier layer/esters of silicon acis polyvinyl alcohol mixing coating layer, GX film of the about 13 μ m of thickness that given the choke function that use among the embodiment 1 ²/ sky, visible light transmitance=88.5%, haze value=2.3%], thus the transparent conductive film (thickness that has the basement membrane of transparency conducting layer: 58.5 μ m) of comparative example 1 obtained.

In addition, the formation of the transparent conductive film of comparative example 1 has aforesaid [having given the plastic film (GX film) of the about 13 μ m of thickness of choke function]/[bond layers of the about 20 μ m of thickness]/[basement membrane that constitutes by the PET film of thickness 25 μ m]/[transparency conducting layer of the about 0.5 μ m of thickness], its gross thickness is 58.5 μ m, than gross thickness is the embodiment 1 described transparent conductive film of 13.5 μ m, and its pliability is poor.In addition, because the transparency of each constituent material of the basement membrane that is made of PET, bond layer, GX film etc. is high, so in the electrically conducting transparent layer film of comparative example 1, the visible light that causes because of the existence of above-mentioned basement membrane, bond layer, GX film etc. absorbs minimum.

In addition, the membrane property of above-mentioned transparency conducting layer is respectively the visible light transmitance: haze value 3.8%, sheet resistance value: 1000 Ω/ 95.0%.In addition, about sheet resistance value, the influence of the ultraviolet irradiation when being subjected to adhesive curing has the tendency of temporary transient decline after curing has just finished, so measure after one day at the formation transparency conducting layer.Further, similarly to Example 1, the transmitance of above-mentioned transparency conducting layer and haze value only are the value of transparency conducting layer, are calculated by following calculating formula 3 and 4 respectively.

[calculating formula 3]

The transmitance of transparency conducting layer (%)=[(together with transparency conducting layer and be pasted with the transmitance that the basement membrane of GX film is measured)/(being pasted with the transmitance of the basement membrane of GX film)] * 100

[calculating formula 4]

The haze value of transparency conducting layer (%)=(together with transparency conducting layer and be pasted with the haze value that the basement membrane of GX film is measured)-(being pasted with the haze value of the basement membrane of GX film)

In addition, similarly to Example 1, the sheet resistance meter ロ レ ス AP (MCP-T400) that the sheet resistance of transparency conducting layer adopts Mitsubishi Chemical's (strain) company to make measures.Haze value and visible light transmitance also adopt the haze meter (NDH5000) of Japanese electric look (strain) company manufacturing, and measure according to JISK7136.

Then, use the transparent conductive film of comparative example 1,, obtain the flexible functional element (electronic paper elements) of comparative example 1 with the method roughly the same with embodiment 1.

Promptly, transparent conductive film at comparative example 1 (is called " first transparent conductive film ", in addition, this basement membrane is called " first basement membrane ", transparency conducting layer is called " first transparency conducting layer ") transparency conducting layer (first transparency conducting layer) go up to form the display layer (bed thickness 40 μ m) of the electrophoresis mode that constitutes by the microcapsules that contain white particles and black particle, further on formed above-mentioned display layer, the transparent conductive film of pasting another comparative example 1 (is called " second transparent conductive film ", in addition, this basement membrane is called " second basement membrane ", transparency conducting layer is called " second transparency conducting layer ") transparency conducting layer (second transparency conducting layer) side.

Then, with above-mentioned display layer is the center, end at first transparent conductive film of its both sides and each transparency conducting layer of second transparent conductive film (first transparency conducting layer and second transparency conducting layer), adopt conductive silver slurry to form respectively to apply voltage to go between, thereby obtain flexible functional element (the electronic paper elements) (component thickness: about 157 μ m) of comparative example 1 with Ag.

And, the above-mentioned flexible functional element (electronic paper elements) of the about 157 μ m of the thickness of comparative example 1 has the formation of [the GX film with about 13 μ m of thickness of choke function]/[bond layers of the about 20 μ m of thickness]/[first basement membrane that is made of the PET film of the about 25 μ m of thickness]/[first transparency conducting layer of the about 0.5 μ m of thickness]/[display layer (thickness: 40 μ m)]/[second transparency conducting layer of the about 0.5 μ m of thickness] // [second basement membrane that is made of the PET film of thickness 25 μ m]/[bond layers of the about 20 μ m of thickness]/[GX film with about 13 μ m of thickness of choke function], than gross thickness is the embodiment 1 of 67 μ m, gross thickness is each flexible functional element (electronic paper elements) of the embodiment 3 of 68 μ m, and its pliability is poor.

And, with embodiment 1 in the same manner, the direct voltage that voltage applies 10V between with the Ag lead-in wire that applies at the flexible functional element (electronic paper elements) of comparative example 1 carries out the counter-rotating of polarity repeatedly, its result has repeated the demonstration of black and white.

[comparative example 2]

In comparative example 1, on the face that does not form transparency conducting layer of basement membrane, by bond layer (thickness: about 20 μ m), that uses among the stickup embodiment 2 pastes the functional reinforcement film of the choke that forms (the about 34 μ m of thickness) with bonding agent mutually with the GX thin layer, obtains the transparent conductive film (thickness that has the basement membrane of transparency conducting layer: 79.5 μ m) of comparative example 2.

In addition, that the transparent conductive film of comparative example 2 has is aforesaid [reinforcement of the about 34 μ m of thickness the film of choke function (GX film/bond layer/GX film)]/formation of [bond layers of the about 20 μ m of thickness]/[basement membrane that constitutes by the PET film of thickness 25 μ m]/[transparency conducting layer of the about 0.5 μ m of thickness], its gross thickness is 79.5 μ m, than gross thickness is the embodiment 2 described transparent conductive films (basement membrane that has transparency conducting layer) of 34.5 μ m, and its pliability is poor.In addition, because the transparency of each constituent material of the basement membrane that is made of PET, bond layer, GX film etc. is high, so in the transparent conductive film of comparative example 2, the visible light that causes because of the existence of above-mentioned basement membrane, bond layer, GX film etc. absorbs minimum.

Then, use the transparent conductive film of comparative example 2,, obtain flexible functional element (the electronic paper elements) (component thickness: about 199 μ m) of comparative example 2 with the method roughly the same with embodiment 1.In addition, the above-mentioned flexible functional element (electronic paper elements) of the about 199 μ m of the thickness of comparative example 2 has the formation of [film that the choke function of the about 13 μ m of thickness is reinforced (GX film/bond layer/GX film)]/[bond layers of the about 20 μ m of thickness]/[first basement membrane that is made of the PET film of the about 25 μ m of thickness]/[first transparency conducting layer of the about 0.5 μ m of thickness]/[display layer (thickness: 40 μ m)]/[second transparency conducting layer of the about 0.5 μ m of thickness]/[second basement membrane that is made of the about 25 μ mPET films of thickness]/[bond layers of the about 20 μ m of thickness]/[film that the choke function of the about 34 μ m of thickness is reinforced (GX film/bond layer/GX film)], than gross thickness is the embodiment 2 described flexible function element (electronic paper elements) of 109 μ m, and its pliability is poor.

In addition, with embodiment 1 in the same manner, the direct voltage that voltage applies 10V between with the Ag lead-in wire that applies at the flexible functional element (electronic paper elements) of comparative example 2 carries out the counter-rotating of polarity repeatedly, its result has repeated the demonstration of black and white.

[utilizability on the industry]

Send out according to the liquid crystal indicator that has used flexible transparent conductive film of the present invention, organic electroluminescence The flexible functional element of optical element, inorganic decentralization type electroluminescence element, electronic paper elements etc., flexible The thickness of functional element is controlled to be made thinlyyer, has good pliability, can utilize so have In as the card etc. thin display in industry on utilizability.

Claims (21)

1. flexible transparent conductive film has been coated with transparency conducting layer and has formed the transparency conducting layer that forms with coating fluid and constitute by basement membrane with on this basement membrane, it is characterized in that,

Constitute described basement membrane by the plastic film of having given the choke function, described transparency conducting layer is a principal component with electroconductive oxide particulate and adhesive stroma simultaneously, and implements the compression processing.

2. flexible transparent conductive film, constitute by basement membrane, lining form and transparency conducting layer, described lining form is sticking on single surface of described basement membrane in the mode with the interface peel of basement membrane, described transparency conducting layer with the basement membrane of described lining form opposition side on the coating transparency conducting layer form and form with coating fluid, it is characterized in that

Constitute described basement membrane by the plastic film of having given the choke function, described transparency conducting layer is a principal component with electroconductive oxide particulate and adhesive stroma simultaneously, and implements the compression processing.

3. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that, the thickness of described basement membrane is 3～50 μ m.

4. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that, pastes many and has given the plastic film of choke function and constitute described basement membrane, thereby strengthened the choke function of basement membrane.

5. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that, implements the choke coating on plastic film, thereby has given described choke function.

6. flexible transparent conductive film as claimed in claim 5 is characterized in that, is formed with transparency conducting layer on the gas barrier layer of the plastic film of having implemented described choke coating.

7. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that, the electroconductive oxide particulate of above-mentioned transparency conducting layer is being principal component more than in indium oxide, tin oxide, the zinc oxide any one.

8. flexible transparent conductive film as claimed in claim 7 is characterized in that, is that the electroconductive oxide particulate of principal component is the indium tin oxide particulate with described indium oxide.

9. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that the adhesive stroma of described transparency conducting layer is crosslinked, thereby has organic solvent resistance.

10. flexible transparent conductive film as claimed in claim 1 or 2 is characterized in that, it is to handle by the calendering of roller to carry out that described compression is handled.

11. the manufacture method of a flexible transparent conductive film, it is characterized in that, on the basement membrane that constitutes by the plastic film of having given the choke function, coating is that the transparency conducting layer of principal component forms and to form coating layer with coating fluid with electroconductive oxide particulate, adhesive and solvent, after the basement membrane enforcement compression processing that is formed with described coating layer, coating layer is solidified form transparency conducting layer, thereby make the flexible transparent conductive film that constitutes by above-mentioned basement membrane and transparency conducting layer.

12. the manufacture method of a flexible transparent conductive film, it is characterized in that, constitute basement membrane by the plastic film of having given the choke function, and has lining form on the single face of this basement membrane, and on this basement membrane and face described lining form opposition side coating with the electroconductive oxide particulate, adhesive and solvent are that the transparency conducting layer formation of principal component forms coating layer with coating fluid, after the basement membrane enforcement compression processing that is formed with described coating layer, coating layer is solidified form transparency conducting layer, thereby make by above-mentioned basement membrane, being fitted in the lip-deep described lining form of basement membrane list in mode with the interface peel of basement membrane, and be formed on the flexible transparent conductive film that the epilamellar described transparency conducting layer with the lining form opposition side constitutes.

13. the manufacture method as claim 11 or 12 described flexible transparent conductive films is characterized in that, the thickness of described basement membrane is 3～50 μ m.

14. the manufacture method as claim 11 or 12 described flexible transparent conductive films is characterized in that, pastes many and has given the plastic film of choke function and constitute described basement membrane, thereby strengthened the choke function of basement membrane.

15. the manufacture method as claim 11 or 12 described flexible transparent conductive films is characterized in that, implements the choke coating on plastic film, thereby has given described choke function.

16. the manufacture method as claim 11 or 12 described flexible transparent conductive films is characterized in that, above-mentioned compression processing is handled by the calendering of roller and is carried out.

17. the manufacture method of flexible transparent conductive film as claimed in claim 16 is characterized in that, above-mentioned calendering is handled and (is carried out under 30～500kgf/cm) the condition at line pressure: 29.4～490N/mm.

18. a flexible functional element is characterized in that, on the described flexible transparent conductive film of claim 1, forms any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements.

19. flexible functional element, it is characterized in that, on the described flexible transparent conductive film of claim 2 and opposition side lining form, form any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements, removing described lining form with the interface peel of basement membrane simultaneously.

20. the manufacture method of a flexible functional element, it is characterized in that, on the described flexible transparent conductive film of claim 1, form any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements.

21. the manufacture method of a flexible functional element, it is characterized in that, on the described flexible transparent conductive film of claim 2 and opposition side lining form, form any functional element in liquid crystal display cells, organic electroluminescent device, inorganic decentralization type electroluminescence element, the electronic paper elements, and removing described lining form with the interface peel of basement membrane.