JP4005001B2 - Functional film for transfer having functional layer, object provided with functional layer, and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a functional film for transfer having a functional layer comprising a compressed layer of functional fine particles on a support, an object provided with the functional layer, and a method for producing an object provided with the functional layer. .
[0002]
In the present invention, the functional film includes both a functional film and a functional sheet. Moreover, what a support body is a metal is also contained in the functional film of this invention.
[0003]
The functional layer is a layer having a function, and the function means a function performed through a physical and / or chemical phenomenon. Functional layers include conductive layer, ultraviolet shielding layer, infrared shielding layer, magnetic layer, ferromagnetic layer, dielectric layer, ferroelectric layer, electrochromic layer, electroluminescence layer, insulating layer, light absorption layer, light selection Layers having various functions such as an absorption layer, a reflection layer, an antireflection layer, a catalyst layer, and a photocatalyst layer are included.
[0004]
In particular, the present invention relates to a functional film for transfer having a transparent conductive layer, an object provided with the transparent conductive layer, and a method for producing an object provided with the transparent conductive layer. The transparent conductive layer can be used as a transparent electrode such as a plasma display panel electrode, an electroluminescence panel electrode, an electrochromic element electrode, a liquid crystal electrode, a transparent surface heating element, and a touch panel, and can be used as a transparent electromagnetic wave shielding layer. it can.
[0005]
[Prior art]
Conventionally, functional layers made of various functional materials have been used for physical vapor deposition (PVD) methods such as vacuum deposition, laser ablation, sputtering, ion plating, and chemicals such as thermal CVD, photo CVD, and plasma CVD. Manufactured by chemical vapor deposition (CVD). These generally require a large-scale apparatus, and some are not suitable for forming a large-area film.
[0006]
For example, the transparent conductive layer is as follows. Currently, the transparent conductive layer is mainly produced by a sputtering method. There are various types of sputtering methods. For example, an inert gas ion generated by direct current or high frequency discharge in vacuum is accelerated and collided with the target surface, and atoms constituting the target are knocked out from the surface and deposited on the substrate surface. This is a method of forming a film.
[0007]
The sputtering method is excellent in that a conductive layer having a low surface electrical resistance can be formed even if the surface has a relatively large area. However, there is a drawback that the apparatus is large and the film forming speed is slow. If the area of the conductive layer is further increased in the future, the apparatus will further increase. This causes a problem that technically the control accuracy must be increased, and a problem that the manufacturing cost increases from another viewpoint. Further, in order to compensate for the slow deposition rate, the number of targets is increased to increase the speed, but this is also a factor that increases the size of the apparatus.
[0008]
Attempts have also been made to produce a transparent conductive layer by a coating method. In the conventional coating method, a conductive paint in which conductive fine particles are dispersed in a binder solution is applied on a substrate, dried and cured, and a conductive layer is formed. The coating method has an advantage that a conductive layer having a large area can be easily formed, the apparatus is simple, the productivity is high, and the conductive layer can be manufactured at a lower cost than the sputtering method. In the coating method, when conductive fine particles come into contact with each other, an electric path is formed and conductivity is expressed. However, the conductive layer produced by the conventional coating method has a drawback that contact is insufficient, and the resulting conductive layer has a high electric resistance value (inferior in conductivity), and its application is limited.
[0009]
As a coating method not using a binder resin, for example, JP-A-8-199096 discloses a binder comprising a tin-doped indium oxide (ITO) powder, a solvent, a coupling agent, a metal organic acid salt or an inorganic acid salt. A method is disclosed in which a conductive layer-forming coating material not included is applied to a glass plate and baked at a temperature of 300 ° C. or higher. In this method, since no binder is used, the electric resistance value of the conductive layer is lowered.
[0010]
It is also known to form a film by coating using a sol-gel method. The coating method using the sol-gel method is also suitable for forming a large-area film.
[0011]
However, in any of the above coating methods, if the support is flexible like a film, a functional layer with a large area can be easily formed, but the support is flexible like a plate. In the case where the film thickness is poor, the coating is difficult compared to the case of the flexible support, and in particular, it is difficult to control the film thickness uniformly. That is, in the case of a flexible film, the coater portion can be installed and the film can be moved and applied, and the film thickness can be easily controlled. On the other hand, in the case of a plate material with poor flexibility, it is possible to apply it by moving the plate material if it is a small area, but if the plate material is large, if the plate material is moved, the accuracy of the film thickness may be increased due to shaking or the like. It tends to get worse. There is also a method of moving the coater, but if the flatness of the plate material is poor, the accuracy of the film thickness is deteriorated.
[0012]
Japanese Patent Application Laid-Open No. 6-103839 discloses a method for producing a transparent conductive substrate by transfer.
[0013]
[Patent Document 1]
JP-A-8-199096
[Patent Document 2]
JP-A-6-103839
[Patent Document 3]
WO01 / 87590
[0014]
[Problems to be solved by the invention]
Therefore, the present inventor, in WO 01/87590, a functional layer capable of expressing various functions by a coating method for imparting a functional layer having a uniform thickness to an object having poor flexibility such as a plate material, For example, the functional film for transfer which has a transparent conductive layer with a low electrical resistance value, the object provided with the functional layer, and the method of manufacturing the object provided with the functional layer were proposed.
[0015]
The present inventor further studied and used an adhesive layer having an excellent adhesive ability even after high-temperature treatment, and baked after transfer to obtain a functional layer having a higher function, for example, a lower electric resistance value. It has been found that a transparent conductive layer can be formed on an object surface.
[0016]
An object of the present invention is to provide a functional film for transfer for imparting a functional layer having a higher function of a uniform thickness to the surface of a poorly flexible object such as a plate material, The object is to provide a method for producing an applied object and an object provided with a functional layer.
[0017]
In particular, an object of the present invention is to provide a conductive film for transfer for providing a transparent conductive layer having a lower electric resistance value with a uniform thickness on the surface of an object having poor flexibility such as a plate, and its transparent An object of the present invention is to provide an object provided with a conductive layer and a method of manufacturing an object provided with a transparent conductive layer.
[0018]
[Means for Solving the Problems]
The present invention has at least a functional layer that can be peeled off from the support on the support, the functional layer is a compressed layer of functional fine particles, and an acrylic monomer ( A functional film for transfer provided with an adhesive layer containing at least M) and a silicone-based resin (S). The support has flexibility.
[0019]
The present invention is the functional film for transfer described above, wherein the adhesive layer further contains an acrylic resin (P).
[0020]
In the present invention, the adhesive layer includes an acrylic resin (P) and an acrylic monomer (M) at a weight ratio P / M = 0/10 to 8/2, and a silicone resin (S). It is the said functional film for transcription | transfer containing by weight ratio S / (P + M) = 0.01 / 100-50,000 / 100 with respect to the sum total (P + M) of acrylic resin (P) and an acrylic monomer (M).
[0021]
The present invention is the functional film for transfer described above, wherein a photopolymerization initiator is further contained in the adhesive layer. The present invention is the functional film for transfer described above, wherein the adhesive layer is cured by irradiation with active energy rays.
[0022]
In the present invention, “peelable” includes the case shown in FIG.
FIG. 1A shows a form of peeling used in a normal sense, in which layers A and B that are in contact with each other are completely peeled from the interface.
FIG. 1B and FIG. 1C show a form of peeling in which the layer A and the layer B in contact with each other are peeled off from the interface, but a part of one layer A remains on the other layer B. When viewed microscopically as described above, even if it cannot be said that the film is completely peeled as shown in FIG. 1 (a), it can be peeled if each layer after peeling substantially forms a layer. In the case of the present invention, the functional fine particle compressed layer includes the case corresponding to the layer A in FIGS. 1 (b) and 1 (c).
[0023]
In the present invention, “the functional layer that can be peeled from the support” or “the functional layer that can be peeled from the support” means that the support and the functional layer are peelable from each other. means. When the functional film for transfer of the present invention is actually used, the support is often peeled off from the functional layer attached on the target object via the adhesive layer.
[0024]
The present invention is the functional film for transfer described above, wherein one or more intermediate layers are provided on a support, and the functional layer is provided on the intermediate layer. The functional film for transfer usually has an intermediate layer between the support and the functional layer.
[0025]
The functional film for transfer of the present invention includes two forms depending on whether the functional layer surface is exposed or not exposed when the functional layer is transferred to the object to be transferred.
[0026]
The functional film for transfer of the first form in which the functional layer surface is not exposed is described below:
In the film of the first form, an intermediate layer that can be peeled from the support is formed on the support, a compressed layer of the functional fine particles is formed on the peelable intermediate layer, and the peelable intermediate layer Is the functional film for transfer, which can be peeled off from the support together with the compressed layer of the functional fine particles. When the functional layer is transferred to the transfer target object using the functional film of the first form, the functional layer is transferred onto the surface of the target object, and the peelable intermediate layer exists on the functional layer. An intermediate | middle layer may lose | disappear at the time of baking and may contain the component which does not lose | disappear also by baking. For example, in the case where the intermediate layer is a resin composed only of an organic component, it disappears upon firing, but in the case of a resin containing Si (silicon), a siloxane bond is formed by firing, and a hard coat can be obtained. In the functional film for transfer according to the first aspect, the intermediate layer that can be peeled off from the support is not particularly limited as long as it is configured to have the above-described function during transfer.
[0027]
The functional film for transfer of the second form in which the functional layer surface is exposed is described below:
In the film of the second form, an underlayer is formed on the support, the compressed layer of functional fine particles is formed on the underlayer, and the compressed layer of functional fine particles can be peeled from the underlayer. The functional film for transfer described above.
[0028]
The underlayer is a layer that is not substantially peeled from the support during transfer. In other words, in the film of the second form, an intermediate layer that is not peeled from the support is formed on the support, and a compressed layer of the functional fine particles is formed on the intermediate layer that is not peeled. The compressed layer of fine particles is the above-mentioned functional film for transfer that can be peeled off from the support and the intermediate layer that is not peeled off.
[0029]
When the functional layer is transferred to the transfer target object using the functional film of the second form, the functional layer is transferred to the surface of the target object, and the functional layer surface is exposed.
In the functional film for transfer according to the second embodiment, the base layer, that is, the intermediate layer that is not peeled off, may be a resin layer mainly composed of a resin.
[0030]
In the present invention, the compressed layer of the functional fine particles is obtained by compressing a functional fine particle-containing layer formed by applying and drying a liquid in which the functional fine particles are dispersed on a support or an intermediate layer. The functional film for transfer described above. In the present invention, the compressed layer of the functional fine particles is 44 N / mm. ² It is the said functional film for transcription | transfer obtained by compressing with the above compression force.
[0031]
In producing the functional film for transfer, the dispersion of functional fine particles may contain a small amount of resin, but it is particularly preferable that no resin is contained. When the dispersion of functional fine particles contains a resin, the content of the resin is preferably less than 25 when expressed in volume and the volume of the functional fine particles is 100.
[0032]
In the present invention, the functional fine particles are conductive fine particles, and the functional fine particle compression layer is the transfer functional film as a conductive layer, that is, the transfer conductive film. It is also preferable that the functional fine particle compression layer is a transparent conductive layer.
[0033]
In the present invention, any one of the functional films for transfer described above is attached to the surface of the target object to which the functional layer is to be applied via the adhesive layer of the film, and the adhesive layer is cured after the application. It is an object provided with a functional layer, obtained by peeling off the support and then firing. When the functional film for second form transfer is used, an object having the functional layer surface exposed directly can be obtained. In the present invention, the functional layer may be patterned.
[0034]
Further, in the present invention, any one of the functional films for transfer described above is attached to the surface of the target object to which the functional layer is to be applied via the adhesive layer of the film, and the adhesive layer is cured after the application. The substrate is peeled off and then fired, and the object is provided with a functional layer.
[0035]
In addition, the present invention is a method in which the conductive film for transfer is attached to the surface of a target object to which a conductive layer is to be applied via the adhesive layer of the film, and the adhesive layer is cured after being attached, Is an object provided with a conductive layer, which is obtained by peeling and then baking.
[0036]
Furthermore, the present invention is a method in which the conductive film for transfer is attached to the surface of a target object to which a conductive layer is to be applied via the adhesive layer of the film, and the adhesive layer is cured after the application, Is a method of manufacturing an object provided with a conductive layer, characterized in that the substrate is peeled off and then fired.
[0037]
Furthermore, the present invention also relates to an object having an adhesive layer on the surface, a functional fine particle compressed layer on the adhesive layer, and the compressed layer being fired. In the present invention, the adhesive layer is the object having silicon dioxide as a main component. The object provided with this functional layer can be formed using the functional film for transfer of the present invention provided with an adhesive layer as described above.
[0038]
Moreover, the object provided with the functional layer can also be formed using the functional film for transfer in which the adhesive bond layer is not provided as a modification.
[0039]
That is, the present invention has at least a functional layer that can be peeled from the support on the support, and the functional layer prepares a functional film for transfer which is a compressed layer of functional fine particles,
An adhesive layer including at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the functional layer is to be applied,
The transfer functional film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, It is an object provided with a functional layer obtained by peeling and then firing.
[0040]
Furthermore, the present invention provides a functional film for transfer having at least a functional layer that can be peeled off from the support on the support, and the functional layer is a compressed layer of functional fine particles.
An adhesive layer including at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the functional layer is to be applied,
The transfer functional film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, It is a method for producing an object provided with a functional layer, characterized by peeling and then firing.
[0041]
Further, the present invention has at least a conductive layer that can be peeled off from the support on the support, and the conductive layer prepares a conductive film for transfer that is a compressed layer of conductive fine particles,
An adhesive layer containing at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the conductive layer is to be applied,
The transfer conductive film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, It is an object provided with a conductive layer, which is obtained by peeling and then firing.
[0042]
Furthermore, the present invention provides at least a conductive layer that can be peeled from the support on the support, and the conductive layer prepares a conductive film for transfer that is a compressed layer of conductive fine particles,
An adhesive layer containing at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the conductive layer is to be applied,
The transfer conductive film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, It is a method for producing an object provided with a conductive layer, characterized by peeling and then baking.
[0043]
DETAILED DESCRIPTION OF THE INVENTION
First, the functional film for transfer of the present invention will be described.
2 and 3 show examples of the layer structure of the functional film for transfer according to the first and second aspects of the present invention (hereinafter also simply referred to as a functional film).
[0044]
FIG. 2 is a cross-sectional view showing an example of a layer structure of a functional film in which a functional layer (4) is formed on a support (1) and an adhesive layer (5) is formed on the functional layer (4). It is.
[0045]
FIG. 3 is a cross-sectional view showing a layer structure example of a functional film in which a resin layer (3), a functional layer (4), and an adhesive layer (5) are formed in this order on a support (1). . The resin layer (3) is a peelable intermediate layer in the first form and a base layer in the second form, that is, a non-peeled intermediate layer. In the case of the first embodiment, the surface of the support (1) on the resin layer (3) side is peeled off and peeled between the support (1) and the resin layer (3) during transfer. In the case of the second form, the adhesiveness between the support (1) and the resin layer (3) is high, and peeling occurs between the resin layer (3) and the functional layer (4) during transfer.
[0046]
In the present invention, the functional layer (4) is not particularly limited, and includes a conductive layer, an ultraviolet shielding layer, an infrared shielding layer, a magnetic layer, a ferromagnetic layer, a dielectric layer, a ferroelectric layer, and an electrochromic layer. And layers having various functions such as an electroluminescence layer, an insulating layer, a light absorption layer, a light selective absorption layer, a reflection layer, an antireflection layer, a catalyst layer, and a photocatalyst layer. Therefore, in the present invention, functional fine particles that should constitute the target layer are used. The functional fine particles are not particularly limited, and mainly inorganic fine particles having a cohesive force are used. In the present invention, in the production of any functional film, by applying the coating / compression molding method described below, a functional coating film having sufficient mechanical strength can be obtained, and a large amount of binder resin can be obtained. The adverse effect of the binder resin in the conventional coating method used can be eliminated. As a result, the intended function is further improved.
[0047]
For example, in the production of a transparent conductive layer, tin oxide, indium oxide, zinc oxide, cadmium oxide, antimony-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), aluminum-doped zinc oxide Conductive inorganic fine particles such as (AZO) are used. ITO is preferable in that it provides better conductivity. Or what coated inorganic material, such as ATO and ITO, on the surface of fine particles which have transparency, such as barium sulfate, can also be used. The particle diameter of these fine particles varies depending on the degree of scattering required depending on the application of the conductive film, and cannot be generally described depending on the shape of the particles, but is generally 10 μm or less, preferably 1.0 μm or less, 5 nm to 100 nm is more preferable.
[0048]
By applying this manufacturing method, excellent conductivity can be obtained. In the present invention, the transparent means that visible light is transmitted. Regarding the degree of light scattering, the required level varies depending on the use of the conductive layer. In the present invention, those having scattering, which is generally referred to as translucent, are also included.
[0049]
In the production of a ferromagnetic layer, γ-Fe ₂ O _Three , Fe _Three O _Four Mainly composed of iron oxide magnetic powders such as Co-FeOx and Ba ferrite and ferromagnetic metal elements such as α-Fe, Fe-Co, Fe-Ni, Fe-Co-Ni, Co, and Co-Ni Ferromagnetic alloy powder or the like is used. By applying this production method, the saturation magnetic flux density of the magnetic coating film is improved.
[0050]
In the production of dielectric layers and ferroelectric layers, magnesium titanate, barium titanate, strontium titanate, lead titanate, lead zirconate titanate (PZT), lead zirconate, lanthanum added Dielectric or ferroelectric fine particles such as lead zirconate titanate (PLZT), magnesium silicate, and lead-containing perovskite compounds are used. Application of this manufacturing method can improve dielectric properties or ferroelectric properties.
[0051]
In the production of metal oxide layers that exhibit various functions, iron oxide (Fe ₂ O _Three ), Silicon oxide (SiO ₂ ), Aluminum oxide (Al ₂ O _Three ), Titanium dioxide (TiO ₂ ), Titanium oxide (TiO), zinc oxide (ZnO), zirconium oxide (ZrO) ₂ ), Tungsten oxide (WO _Three ) And other metal oxide fine particles are used. By applying this manufacturing method, the filling degree of the metal oxide in the film is increased, so that each function is improved. For example, SiO on which a catalyst is supported ₂ , Al ₂ O _Three When is used, a porous catalyst layer having practical strength can be obtained. TiO ₂ When is used, the photocatalytic function can be improved. In addition, WO _Three When is used, an improvement in the coloring effect in the electrochromic display element can be obtained.
[0052]
In the production of the electroluminescence layer, zinc sulfide (ZnS) fine particles are used. By applying this manufacturing method, an inexpensive electroluminescent layer can be manufactured by a coating method.
[0053]
In the present invention, a liquid in which functional fine particles selected from the above-mentioned various functional fine particles are dispersed is used as a functional coating depending on the purpose. This functional coating is applied and dried on a support or an intermediate layer provided on the support to form a functional fine particle-containing layer. Thereafter, the functional fine particle-containing layer is compressed to form a compressed layer of functional fine particles to obtain a functional layer.
[0054]
The liquid in which functional fine particles such as conductive fine particles are dispersed is not particularly limited, and various known liquids can be used. For example, as liquid, saturated hydrocarbons such as hexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol, butanol, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diisobutyl ketone, etc. Ketones, esters such as ethyl acetate and butyl acetate, ethers such as tetrahydrofuran, dioxane and diethyl ether, amides such as N, N-dimethylformamide, N-methylpyrrolidone (NMP) and N, N-dimethylacetamide And halogenated hydrocarbons such as ethylene chloride and chlorobenzene. Among these, polar liquids are preferable, and those having an affinity for water, such as alcohols such as methanol and ethanol, and amides such as NMP, have good dispersibility without using a dispersant. It is preferable. These liquids can be used singly or as a mixture of two or more. Moreover, a dispersing agent can also be used according to the kind of liquid.
[0055]
Water can also be used as the liquid. When water is used, the resin layer surface needs to be hydrophilic. Since the resin film and the resin layer are usually hydrophobic, water is easily repelled, and it is difficult to obtain a uniform film. In such a case, it is necessary to mix alcohol with water, or to make the surface of the resin layer hydrophilic by corona treatment or the like.
[0056]
The amount of the liquid to be used is not particularly limited, and the fine particle dispersion may have a viscosity suitable for coating. For example, the amount of the liquid is about 100 to 100,000 parts by weight with respect to 100 parts by weight of the fine particles. It is preferable to select appropriately according to the kind of the fine particles and the liquid.
[0057]
The dispersion of the fine particles in the liquid may be performed by a known dispersion method. For example, it is dispersed by a sand grinder mill method. In dispersing, it is also preferable to use media such as zirconia beads in order to loosen the aggregation of the fine particles. Also, care should be taken not to mix impurities such as dust during dispersion.
[0058]
The fine particle dispersion preferably contains no resin. That is, it is preferable that the resin amount = 0. In the conductive layer, if no resin is used, the contact between the conductive fine particles is not hindered by the resin, and the volume filling rate of the fine particles is increased. Therefore, the conductivity between the conductive fine particles is ensured, and the electric resistance value of the obtained conductive layer is low. It is possible to include a resin as long as it does not impair the filling property. For example, the upper limit of the content of the resin in the dispersion is expressed by the volume before dispersion, and the conductive When the volume of the fine particles is 100, the volume is less than 25.
[0059]
WO _Three Fine particles and TiO ₂ Even in a functional layer using fine particles or the like, if the resin is not used, the contact between the fine particles is not hindered by the resin, so that each function can be improved. It is possible to include a resin as long as the contact between the fine particles is not hindered and does not impair each function, but the amount is, for example, about 80 or less when the volume of each fine particle is 100. Volume.
[0060]
Thus, it is preferable not to use a resin in the functional layer at the time of compression (that is, in the fine particle dispersion), and even if it is used, a small amount is preferable. The amount of the resin to be used may be appropriately determined because it can be changed to some extent according to the purpose of the functional layer.
[0061]
Various additives may be blended in the fine particle dispersion within a range satisfying performance required for each function such as conductivity and catalytic action. For example, additives such as ultraviolet absorbers, surfactants, and dispersants.
[0062]
As the support (1), a flexible resin film that does not break even when the compression force in the compression step is increased is suitable. The resin film is lightweight and easy to handle. In the present invention, in the production of the functional film for transfer, since there is no pressurization step at high temperature and no baking step, a resin film can be used as a support.
[0063]
Examples of the resin film include polyester films such as polyethylene terephthalate (PET), polyolefin films such as polyethylene and polypropylene, polycarbonate films, acrylic films, norbornene films (manufactured by JSR Corporation, Arton, etc.), and the like. In addition to the resin film, cloth, paper, or the like can be used as the support.
[0064]
In the case of the functional film having the layer structure of FIG. 2, the formed functional layer (4) is formed on the surface of the support (1) on the side where the functional layer (4) is to be formed. In order to obtain a state in which the film can be peeled off, a peeling treatment is preferably performed. For example, a silicone release agent or the like may be applied to the support surface.
[0065]
In the case of the first form functional film having the layer structure of FIG. 3, the resin layer (3) is formed in order to peel off between the support (1) and the resin layer (3) at the time of transfer. Depending on the compatibility between the resin material and the support (1), the surface of the support (1) on the resin layer (3) side may be subjected to a peeling treatment.
[0066]
In the case of the second form functional film having the layer structure shown in FIG. 3, the resin layer (3) is compared with the functional layer (4) because it is peeled off during the transfer. It is preferable to have a high hardness such as a pencil hardness of 2H or more and 4H or less. Further, it is preferable that the adhesion between the support (1) and the resin layer (3) is high. For the resin layer (3) in the second embodiment, a relatively hard resin can be used, and examples of such a resin include an acrylic resin, a urethane resin, a vinyl chloride resin, and a silicone resin. Use one that provides hardness. The resin layer can also contain fine particles such as silica for adjusting the hardness of the resin layer. After compression, the resin layer may be cured with heat, ultraviolet light, or the like.
[0067]
The resin of the resin layer (3) in the functional films of the first and second forms is preferably one that does not dissolve in the liquid in which the functional fine particles are dispersed. In the conductive layer, when the resin layer is dissolved, the solution containing the resin comes around the conductive fine particles due to capillarity, and the filling rate of the fine particles is reduced. As a result, the electric resistance value of the obtained conductive layer Rises.
[0068]
The functional fine particle dispersion is applied onto the resin layer (3) or the support (1) and dried to form a functional fine particle-containing layer such as a conductive fine particle-containing layer.
[0069]
The application of the fine particle dispersion is not particularly limited and can be performed by a known method. For example, it can be performed by a coating method such as a reverse roll method, a direct roll method, a blade method, a knife method, an extrusion nozzle method, a curtain method, a gravure roll method, a bar coat method, a dip method, a kiss coat method, or a squeeze method. Moreover, it is also possible to make a dispersion liquid adhere on a resin layer or a support body by spraying, spraying, etc.
[0070]
The drying temperature depends on the type of liquid used for dispersion, but is preferably about 10 to 150 ° C. If it is less than 10 ° C, condensation of moisture in the air tends to occur, and if it exceeds 150 ° C, the resin film support is deformed. Also, care should be taken so that impurities do not adhere to the surface of the fine particles during drying.
[0071]
The thickness of the functional fine particle-containing layer such as the conductive fine particle-containing layer after coating and drying depends on the compression conditions in the next step and the use of each functional film such as the final conductive film. do it.
[0072]
Thus, when functional fine particles such as conductive fine particles are dispersed in a liquid, applied, and dried, a uniform film can be easily formed. When the fine particle dispersion is applied and dried, the fine particles form a film even if no binder is present in the dispersion. The reason for forming a film without the presence of a binder is not necessarily clear, but when the liquid is reduced after drying, fine particles gather together due to capillary force. Furthermore, the fact that it is a fine particle has a large specific surface area and a strong cohesive force, so it is thought that it may become a film. However, the strength of the film at this stage is weak. In addition, the conductive layer has a high resistance value and a large variation in resistance value.
[0073]
Next, the formed functional fine particle-containing layer such as the conductive fine particle-containing layer is compressed to obtain a compressed layer (4) of functional fine particles such as the conductive fine particles. By compressing, the strength of the film is improved. That is, by compressing, the contact points between functional fine particles such as conductive fine particles increase and the contact surface increases. For this reason, the coating film strength increases. Since the fine particles originally have a property of easily agglomerating, they become a strong film by being compressed.
[0074]
In the conductive layer, the coating strength increases and the electrical resistance decreases. In the catalyst layer, the coating film strength is increased, and the resin layer is not used or the amount of the resin is small, so that the catalyst layer becomes a porous layer. Therefore, a higher catalytic function can be obtained. Also in other functional layers, a high-strength film in which fine particles are connected to each other can be obtained, and since no resin is used or the amount of resin is small, the filling amount of fine particles per unit volume is increased. Therefore, higher functions can be obtained.
[0075]
Compression is 44 N / mm ² It is preferable to carry out with the above compressive force. 44 N / mm ² If the pressure is less than 1, the functional fine particle-containing layer such as the conductive fine particle-containing layer cannot be sufficiently compressed. For example, it is difficult to obtain a conductive layer having excellent conductivity. 135 N / mm ² The above compressive force is more preferable, 180 N / mm ² The compression force of is more preferable. The higher the compression force, the better the coating strength and the better the adhesion with the support. In the conductive layer, a layer having higher conductivity is obtained, the strength of the conductive layer is improved, and the adhesion between the conductive layer and the resin layer is strengthened. The higher the compression force, the higher the pressure resistance of the device, so generally 1000 N / mm ² The compression force up to is appropriate.
[0076]
Moreover, it is preferable to perform compression at the temperature which the said support body does not deform | transform. For example, when the said support body is a resin film, it becomes the temperature range below the glass transition temperature (secondary transition temperature) of the said resin.
[0077]
The compression is not particularly limited and can be performed by a sheet press, a roll press, or the like, but is preferably performed using a roll press machine. Roll press is a method in which a film to be compressed is sandwiched between rolls and compressed, and the roll is rotated. A roll press is uniformly high pressure, and is more suitable for productivity than a sheet press.
[0078]
The roll temperature of the roll press machine is preferably room temperature (an environment in which humans can easily work) from the viewpoint of productivity. In the compressed atmosphere (hot press) in which the heated atmosphere or the roll is heated, there is a problem that the resin film stretches when the compression pressure is increased. When the compression pressure is weakened so that the resin film of the support does not stretch under heating, the mechanical strength of the coating film decreases. In the conductive layer, the mechanical strength of the coating film decreases and the electrical resistance increases. It is also preferable to adjust the temperature so that the roll temperature does not rise due to heat generation when continuously compressed by a roll press.
[0079]
When there is a reason for wanting to minimize moisture adhesion on the surface of fine particles, a heated atmosphere may be used to reduce the relative humidity of the atmosphere, but the temperature range is within the range where the film does not easily stretch. It is. Generally, it is a temperature range below the glass transition temperature (secondary transition temperature). In consideration of fluctuations in humidity, the temperature may be a little higher than the required temperature.
[0080]
The glass transition temperature of the resin film is obtained by measuring dynamic viscoelasticity, and indicates a temperature at which the dynamic loss of main dispersion reaches a peak. For example, when looking at a PET film, its glass transition temperature is around 110 ° C.
[0081]
The roll of the roll press machine is preferably a metal roll because a strong pressure is applied. Also, if the roll surface is soft, fine particles may be transferred to the roll during compression, so that the roll surface is hard chrome, ceramic sprayed film, a film obtained by ion plating such as TiN, DLC (diamond-like carbon), etc. It is preferable to treat with a hard film.
[0082]
In this way, a compressed layer (4) of functional fine particles such as conductive fine particles is formed. The thickness of the functional fine particle compressed layer such as conductive fine particles may be about 0.1 to 10 μm, although it depends on the application. Moreover, in order to obtain a thick compressed layer of about 10 μm, a series of operations of applying a dispersion of fine particles, drying, and compression may be repeated. Furthermore, in the present invention, it is of course possible to form each functional layer such as a conductive layer on both sides of the support.
[0083]
In the functional films of the first and second embodiments of the present invention, the functional fine particle compressed layer (4) may be composed of at least two different functional fine particle compressed layers.
[0084]
Depending on the purpose and application of the multilayer functional layer, a multilayer structure may be formed by combining a plurality of functional layers having different functions. By combining a plurality of functional layers, for example, multilayer functional layers for solar cells, electroluminescent elements, electrochromic elements and the like can be obtained.
[0085]
Specifically, for solar cells, a multilayer structure including a transparent conductive layer, a transparent insulator layer, a chalcopallite structure semiconductor layer composed of Group I, Group III, and Group IV, and a metal electrode is sequentially exemplified.
For the distributed direct current operation electroluminescent element, a multilayer structure of a transparent conductive layer, an EL light emitting layer, and a back electrode is exemplified in order.
Examples of the transmissive electrochromic device include a multilayer structure of a transparent conductive layer, a first color developing layer, a dielectric layer, a second color developing layer, and a transparent conductive layer in this order.
In addition to these, various multilayer structures according to various applications are conceivable.
[0086]
The multilayer structure can be obtained by repeatedly performing a series of operations of applying a dispersion of the corresponding functional fine particles, drying, and compressing. All of the layers constituting the multilayer functional layer are not necessarily compressed layers. For example, in the case of a solar cell, the transparent conductive layer, the transparent insulator layer, and the semiconductor layer may be formed by compression, and the metal electrode may be formed by vapor deposition.
[0087]
In the functional film for transfer according to the first and second embodiments of the present invention, an adhesive layer (5) is formed on the functional layer (4). The adhesive layer (5) is formed from an adhesive composition containing at least the acrylic monomer (M) and the silicone resin (S). The adhesive composition preferably contains an acrylic resin (P) for good initial tackiness.
[0088]
Since the adhesive layer contains the acrylic resin (P) and the acrylic monomer (M), an adhesive layer having a tacky feeling can be obtained simply by applying the adhesive composition solution and drying it. The adhesive film can be reliably attached to the surface of the object to be transferred. And after bonding, an adhesive layer is hardened by active energy ray irradiation, such as an ultraviolet-ray, a hard hardened layer is obtained, and the support body of the functional film for transcription | transfer can be peeled easily. The acrylic resin (P) preferably has a glass transition temperature Tg of 30 ° C. or higher. Even after the acrylic resin component in the cured layer disappears by baking at a high temperature after peeling of the support, the adhesive layer contains the silicone resin (S). ₂ With the adhesive layer mainly composed of, it is possible to maintain reliable adhesion of the functional layer to the surface of the object to be transferred. In this case, the adhesive layer after firing is not necessarily a complete layer, and may be present sparsely between the functional layer and the object, for example.
[0089]
In order to obtain good initial tackiness, hardness after curing, and excellent adhesion performance after firing, the adhesive layer comprises an acrylic resin (P) and an acrylic monomer (M) as a solid content. Weight ratio S with respect to the total (P + M) of the acrylic resin (P) and the acrylic monomer (M), containing the silicone resin (S) as a solid content, including the weight ratio P / M = 0/10 to 8/2 /(P+M)=0.01/100 to 50,000 / 100 is preferable. Since the acrylic monomer (M) is liquid at room temperature, when the acrylic resin (P) is not included, the initial tackiness is only borne by the silicone resin (S). When the acrylic resin (P) that is solid at room temperature is included, initial tackiness by the acrylic resin (P) is obtained. In order to obtain initial tackiness by the acrylic resin (P), it is preferable that P / M = 2/8 to 8/2. When P / M is larger than 8/2, the initial tackiness tends to decrease, and when P / M is smaller than 2/8, the viscosity of the adhesive composition solution becomes too low, which causes inconvenience when pasting. May occur. Further, when S / (P + M) is smaller than 0.01 / 100, the adhesion performance after firing tends to be lowered, and when S / (P + M) is larger than 50,000 / 100, initial tackiness is reduced. There is a tendency. More preferably, the adhesive layer includes an acrylic resin (P) and an acrylic monomer (M) at a weight ratio P / M = 2/8 to 8/2, and the silicone resin (S) is acrylic. It is included at a weight ratio S / (P + M) = 0.5 / 100 to 100/100 with respect to the total (P + M) of the resin (P) and the acrylic monomer (M).
[0090]
A publicly known thing can be used as acrylic resin (P), for example, acrylic resin 103B, 1BR-305 (all are the Taisei Kako Co., Ltd. product) etc. are mentioned. As the acrylic monomer (M), known ones can be used. For example, trifunctional or higher acrylics such as KAYARAD GPO-303, KAYARAD TMPTA, and KAYARAD THE-330 (all manufactured by Nippon Kayaku Co., Ltd.). Based monomers.
[0091]
As the silicone resin (S), various known ones such as straight silicone, silicone acrylic, and silicone epoxy can be used. For example, Fresella N (manufactured by Matsushita Electric Works), TSR-144 (GE Toshiba Silicone ( Etc.). The silicone resin is liquid in the varnish state, but becomes a solid when the solvent volatilizes. Silicone resin is generally non-volatile, and when fired, it becomes a silicon dioxide-like substance having organic residues in silicon dioxide or part of Si. Silicone monomers are liquid and volatile and therefore volatilize during firing. Therefore, a silicone resin is used in the present invention.
[0092]
Moreover, when there exists a request | requirement of improving the adhesiveness of the target object and adhesive layer which should provide a functional layer at the time of transcription | transfer, you may add a silicone monomer with a silicone resin to an adhesive bond layer.
[0093]
The adhesive layer usually further contains a photopolymerization initiator. Various photopolymerization initiators can be used, and examples thereof include KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.). The amount of the photopolymerization initiator may be about 0.01 to 20% by weight based on the total weight (P + M) of the acrylic resin (P) and the acrylic monomer (M). When the adhesive layer is cured by irradiation with active energy rays such as ultraviolet rays, productivity when the functional film for transfer is adhered to the target object is increased. Moreover, you may use the well-known thing which added the photoinitiator to the acrylic monomer as a photoinitiator. As what added the photoinitiator to the acryl-type monomer, UV curable resin SD-318 (made by Dainippon Ink Chemical Co., Ltd.), XNR5535 (made by Nagase ChemteX Corporation) etc. are mentioned, for example. .
[0094]
In the adhesive, additives such as an ultraviolet absorber and an infrared absorber may be included as necessary.
[0095]
A release film may be provided on the adhesive layer (5) of the functional film for transfer of the present invention to protect the adhesive layer surface until use.
[0096]
Formation of the adhesive layer (5) can be carried out by applying an adhesive composition solution onto the functional layer (4). In addition, an adhesive layer is formed on a separate release support prepared separately, and this adhesive layer on the release support comes into contact with the functional layer (4) on the support (1). The adhesive layer (5) may be provided on the functional layer (4) by laminating and adhering (adhering) as described above. In this case, simultaneously with the formation of the adhesive layer (5), a peeling support is provided on the adhesive layer, and the adhesive layer surface is protected until use. A part of the adhesive is impregnated in the functional layer (4). Although the thickness of the adhesive layer depends on the tackiness of the adhesive, etc., it may be about 0.1 μm to 100 μm before firing, and more preferably 1 μm to 20 μm.
[0097]
In the present invention, it is also preferable to heat-treat the functional fine particle compression layer after forming the functional fine particle compression layer and before forming the adhesive layer. By the heat treatment, the internal stress at the time of forming the compressed layer remaining in the resin layer is relieved, and the corrosion resistance of the functional film to various substances and various solvents is improved.
[0098]
What is necessary is just to select the conditions of heat processing suitably. The heat treatment temperature is preferably 50 ° C. or higher and more preferably 80 ° C. or higher for relaxing internal stress. The upper limit of the heat treatment temperature is usually 130 ° C., for example, when a resin film is used as the support. The heat treatment time is also usually in the range of 1 minute to 100 hours, preferably 10 minutes to 50 hours, more preferably 30 minutes to 25 hours. The atmosphere during the heat treatment may be any of vacuum, reduced pressure, air, nitrogen gas, and inert gas such as argon.
[0099]
Next, the object provided with the functional layer of the present invention and the manufacturing method thereof will be described. FIG. 4 shows an example of the layer structure of the object of the present invention provided with the functional layer (4) of the functional film of the first and second embodiments described above.
[0100]
FIG. 4 is a cross-sectional view showing a layer configuration example in which the functional layer (4) is provided on the surface of the target object (6) via the adhesive layer (5). That is, FIG. 4 shows an example in which the functional layer (4) is transferred using the functional film shown in FIG. 2 or the second form functional film shown in FIG.
[0101]
In order to obtain an object provided with the functional layer of the present invention, first, the functional layer (4) of the functional film described above is transferred from the support (1) onto the target object (6). In other words, the functional film is attached to the surface of the target object (6) via the adhesive layer (5) of the functional film so that the support (1) is on the outside, and after bonding, the adhesive layer (5 ) Is preferably cured by ultraviolet irradiation, and then the support (1) of the functional film is peeled off. After the transfer, it is fired to obtain a functional layer that exhibits higher functions. During the transfer, an adhesive similar to that used for the adhesive layer (5) may be applied to the surface of the target object (6) in advance.
[0102]
FIG. 5 is a diagram for explaining peeling at the time of transfer. In FIG. 5, (a) shows the state which stuck the functional film of the 1st form or the 2nd form shown in FIG. 3 on the transfer target object (6) surface. In the present invention, the terms “releasable” and “not peelable” are used to represent the behavior when transferred onto a target object as described below. Therefore, it does not mean absolute bonding strength.
[0103]
The relationship among the layers in the present invention will be described with reference to FIG. Regarding the adhesion between the resin layer (3) and the functional layer (4), some of the functional fine particles of the functional layer (4) in contact with the resin layer (3) are embedded in the resin layer (3) by compression. It is considered that the functional layer (4) is in close contact with the resin layer (3). Therefore, the higher the compression pressure, the higher the adhesion of both layers (3) (4), and the higher the pressure of the resin layer (3), the higher the adhesion of both layers (3) (4). . The adhesion force varies depending on the type, shape, particle size, etc. of the functional fine particles, and also varies depending on the presence and type of the resin contained in the functional fine particle layer during compression.
[0104]
In FIG. 5, the interface between the support (1) and the resin layer (3) (referred to as interface I), the interface between the resin layer (3) and the functional layer (4) (referred to as interface II), the functional layer. There is an interface (referred to as interface III) between (4) and the adhesive layer (5), and an interface (referred to as interface IV) between the adhesive layer (5) and the target object (6). In the present invention, the invention of the first embodiment can be achieved by making the adhesion at the interface I lower than the adhesion at any other interface. Moreover, the invention of the second embodiment is achieved by making the adhesion at the interface II lower than the adhesion at any other interface.
[0105]
In order to make the adhesion at the interface I lower than the adhesion at the other interface, the adhesion between the support (1) and the resin layer (3) should be lowered. Therefore, in order to peel off between the support (1) and the resin layer (3) at the time of transfer, the surface of the support (1) on the resin layer (3) side may be subjected to a peeling treatment. Moreover, what is necessary is just to improve the adhesiveness of another interface. In order to improve the adhesion between the resin layer (3) and the functional layer (4), a relatively soft resin layer may be used.
[0106]
In order to make the adhesion at the interface II lower than the adhesion at the other interface, the adhesion between the resin layer (3) and the functional layer (4) may be lowered. When the hardness of the resin layer (3) is relatively high, the adhesion between the compression layer and the resin layer becomes low. However, if the resin layer (3) is hard like a hard coat, the adhesion is too low. In general, the resin layer (3) preferably has a relatively high hardness, for example, a pencil hardness of about 2H to 4H. Moreover, what is necessary is just to improve the adhesiveness of another interface. In order to enhance the adhesion between the support (1) and the resin layer (3), the adhesion may be improved by subjecting the surface of the support (1) to easy adhesion (for example, corona treatment).
[0107]
When peeling the support (1), in the case of the functional film of the first form, peeling occurs between the support (1) and the soft resin layer (3) (arrow I in the figure). The adhesion between the functional layer (4) and the soft resin layer (3) is good, and no separation occurs between the functional layer (4) and the resin layer (3). Therefore, as shown in (b), the functional layer (4) is applied to the surface of the target object (6) via the adhesive layer (5), and the resin layer (3) is formed on the functional layer (4). Exists.
[0108]
By baking after this transfer operation, the resin layer (3) disappears when the resin layer (3) is a resin composed only of an organic component. When the resin layer (3) is a resin containing Si (silicon), a siloxane bond is formed by baking, and the resin layer (3) becomes a hard coat.
[0109]
When the support (1) is peeled off, in the case of the functional film of the second form, the adhesion between the functional layer (4) and the hard resin layer (3) is low, and the resin layer (3) and the functional film Peeling occurs between the layers (4) (arrow II in the figure). Therefore, as shown in (c), the functional layer (4) is applied to the surface of the target object (6) via the adhesive layer (5), and the surface of the functional layer (4) is exposed. By firing after this transfer operation, the object (6) provided with the functional layer (4) is obtained. The functional film of the second form is suitable when it is desired to provide a functional layer exposed on the object surface.
[0110]
By selecting the material and hardness of the resin layer (3) mainly, the functional film of the first form or the second form can be produced.
[0111]
The target object (6) is not particularly limited, and includes various objects that do not disappear during firing. For example, a plate-like object or support that is difficult to form a coating layer having a uniform thickness, or an object such as glass, ceramics, or metal that is difficult to directly form a compression layer is included. For example, the CRT surface is required to be subjected to treatments such as antistatic, electromagnetic wave shielding, and antireflection, and the CRT is a specific example of the target object in the present invention.
[0112]
When transferring the functional layer, the object to be transferred may be surface-treated in advance. For example, when the object to be transferred is glass, the surface may be surface-treated with a silane coupling agent or the like.
[0113]
In the present invention, after the functional layer is transferred, the functional layer is baked to obtain a functional layer exhibiting higher functions. The firing may be performed, for example, at about 250 to 2000 ° C., preferably about 350 to 1200 ° C. in an air atmosphere, although depending on the type of functional fine particles. At this time, the heat resistant temperature of the transferred target object is taken into consideration. For example, after baking at a relatively low temperature of about 250 to 600 ° C., baking may be further performed at a higher temperature.
[0114]
By heat treatment at a high temperature, the filling rate of the functional fine particles in the functional layer is increased, and higher function is obtained with sintering.
In the functional film for transfer, a part of the adhesive is impregnated in the functional layer, and the impregnated adhesive is cured by a curing treatment. Organic components such as acrylic components disappear upon firing. On the other hand, the silicone resin component becomes a silicon dioxide-like substance having an organic residue in silicon dioxide or a part of Si by firing. Thus, during firing, the resin undergoes volume shrinkage, and the filling rate of the functional fine particles is increased by the shrinkage force. If the firing temperature is high, neck growth of functional fine particles occurs and the filling rate becomes higher. In the case of the conductive layer, the filling rate of the conductive fine particles increases due to the volume shrinkage of the resin, the contact between the conductive fine particles becomes strong, and the electric resistance value becomes lower than before firing. When the firing temperature is high, neck growth of the conductive fine particles occurs, the filling rate becomes higher, and a lower electric resistance value can be obtained.
[0115]
In addition, since the silicone resin (S) is included in the adhesive layer of the functional film for transfer of the present invention or the adhesive layer previously provided on the surface of the target object, the functional layer and Reliable adhesion to the transfer target object surface can be maintained. That is, the organic component such as the acrylic component in the adhesive layer disappears by firing, but the silicone resin component becomes a silicon dioxide-like substance having an organic residue in silicon dioxide or a part of Si by firing. Silicon dioxide or a silicon dioxide-like substance is substantially an inorganic substance, has a high melting point, is solid even in a considerably high temperature environment, and remains between the functional layer and the target object, so that reliable adhesion can be maintained.
[0116]
Since the functional layer is a compressed layer of functional fine particles, the surface of the functional layer is uneven when viewed microscopically. When the amount of the silicone-based resin in the adhesive layer is small, the adhesive layer after firing can be made extremely thin. For this reason, the convex part of the functional layer surface and the target object can be brought into contact with each other. On the other hand, by increasing the amount of the silicone resin in the adhesive layer, the adhesive layer after baking becomes thick, and for example, diffusion of sodium ions from glass (target object) to the functional layer can be prevented.
[0117]
In the present invention, the adhesive layer may contain inorganic fine particles. For example, there is a case where a titanium oxide layer is formed on an ITO conductive layer by transfer through an adhesive layer and the ITO conductive layer and the titanium oxide layer are electrically connected. In such a case, if one or several kinds of fine particles such as ITO fine particles and titanium oxide fine particles are contained in the adhesive layer, even if the adhesive layer is relatively thick, the ITO conductive layer and the titanium oxide layer Can be obtained.
[0118]
In addition, when the amount of the silicone resin in the adhesive layer is small, the amount of the silicone resin impregnated in the functional layer is small as compared to when the amount is large, and the voids in the functional layer after firing are also large. After firing, the gap may be separately impregnated with resin or the like. In the case of a transparent conductive film, scattering can be reduced by impregnating with a transparent substance after firing, that is, haze is improved.
[0119]
Moreover, it is also preferable to perform an annealing process after baking. The annealing treatment may be performed by placing the target object that has been transferred and baked, for example, under a reduced pressure of 200 to 300 ° C., or in a nitrogen atmosphere or a hydrogen atmosphere of 200 to 700 ° C. By the annealing treatment, an oxygen deficient state is generated, and in the case of the conductive layer, the electric resistance value is further lowered.
[0120]
As described above, an adhesive layer mainly composed of silicon dioxide is provided on the surface, and a compressed layer of functional fine particles is provided on the adhesive layer, and the compressed layer forms a fired object. Can do.
[0121]
Further, as a modification, instead of the functional transfer film provided with the adhesive layer (5) of the present invention, the same functional transfer film may be used except that no adhesive layer is provided. Good. In this case, an adhesive similar to that used for the adhesive layer (5) is applied in advance to the target object surface to which the functional layer is to be applied, and the adhesive layer previously provided on the object surface is applied. Then, the functional layer is transferred and baked.
[0122]
【Example】
EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
[0123]
[Example 1]
As shown in FIG. 3, a conductive film for transfer of the second form having a resin layer (3), a conductive layer (4) and an adhesive layer (5) in this order on a support (1) was prepared.
[0124]
(Formation of hard resin layer)
A 75 μm thick PET film (1) (HSL, manufactured by Teijin DuPont Film) was corona treated so that the contact angle of pure water was 39 °. 100 parts by weight of A solution of FRESSERA N (manufactured by Matsushita Electric Works Co., Ltd.) and 300 parts by weight of solution B were mixed to obtain a coating solution for the resin layer. The coating solution was applied to the corona-treated surface of the PET film (1), dried and cured at 90 ° C. for 24 hours to form a 1 μm thick silicone resin layer (3).
[0125]
(Formation of conductive layer)
300 parts by weight of ethanol was added to 100 parts by weight of ITO fine particles SUFP-HX (manufactured by Sumitomo Metal Mining Co., Ltd.) having a primary particle size of 5 to 30 nm, and the media was dispersed as zirconia beads with a disperser. The obtained coating liquid was applied onto the resin layer (3) using a bar coater, and dried by sending hot air of 50 ° C. The obtained film is hereinafter referred to as a pre-compression ITO film. The thickness of the ITO-containing coating film was 1.7 μm.
[0126]
First, a preliminary experiment for confirming the compression pressure was performed.
Room temperature (23 ° C.) without rotating the roll and heating the roll using a roll press machine having a pair of metal rolls having a diameter of 140 mm (the roll surface is hard chrome plated) The ITO film before compression was sandwiched and compressed. At this time, the pressure per unit length in the film width direction was 660 N / mm. Next, when the pressure was released and the length of the compressed portion in the longitudinal direction of the film was examined, it was 1.9 mm. From this result, 347 N / mm per unit area ² It will be compressed with the pressure of.
[0127]
Next, the pre-compression ITO film similar to that used in the preliminary experiment was sandwiched between metal rolls and compressed under the above conditions, and the roll was rotated and compressed at a feed rate of 5 m / min. In this way, a compressed ITO film was obtained. The thickness of the ITO compressed layer, that is, the conductive layer (4) was 1.0 μm.
[0128]
(Formation of adhesive layer)
100 parts by weight of B liquid of Frescera N (manufactured by Matsushita Electric Works) was put into a stainless steel bat and the solvent was evaporated to obtain 17 parts by weight of a silicone resin. To this, 22.5 parts by weight of toluene was added to obtain a silicone resin solution. Acrylic resin 103B (Tg: about 40 ° C., solid concentration: 50 wt%, manufactured by Taisei Kako Co., Ltd.) 98 parts by weight, UV curable resin SD-318 (Dainippon Ink Chemical Co., Ltd.) 50 wt. Part, 2.5 parts by weight of the silicone resin solution, and 183 parts by weight of methyl ethyl ketone were added to obtain an adhesive layer coating solution. The coating solution was coated on the compressed layer (4) of the ITO film and dried to form an adhesive layer (5) having a thickness of 4 μm. When the adhesive layer (5) was touched with a finger, there was a feeling of tack. In this way, a conductive film for transfer was obtained.
[0129]
(Transfer of conductive layer to glass plate)
First, the surface treatment of the object glass plate was performed. To 100 parts by weight of the silane coupling agent KBM503 (manufactured by Shin-Etsu Chemical Co., Ltd.), 0.9 parts by weight of acetic acid (1N) and 21 parts by weight of water were added for hydrolysis. 100 parts by weight of ethanol was added to 1 part by weight of the hydrolyzed silane coupling agent solution to obtain a surface treatment solution. The surface treatment liquid was applied onto a glass plate using a cotton swab and dried. The glass plate was placed in an atmosphere at 110 ° C. for 5 minutes to react the silane coupling agent with the glass. Thereafter, excess silane coupling agent on the glass plate was wiped off with a cloth soaked with ethanol.
[0130]
Next, the obtained conductive film for transfer was attached with a laminator so that the adhesive layer (5) was in contact with the surface-treated glass plate. The adhesive layer (5) was cured by irradiating with ultraviolet rays, and the support PET film (1) was peeled off after curing. The adhesive layer (5) was very strong.
[0131]
(Baking after transfer)
After curing, the glass plate provided with the conductive layer (4) was placed in an atmosphere of 500 ° C. in air for 1 hour to burn the organic content in the adhesive layer (5). Thereafter, the ambient temperature was lowered to 200 ° C. over 2 hours. Next, the glass plate was placed in an atmosphere at 200 ° C. under reduced pressure (0.1 atm), and the temperature was lowered to 50 ° C. over 5 hours. The glass plate was taken out and lowered to room temperature (23 ° C.). Even after curing, the adhesive layer (5) was very strong. Thus, as shown in FIG. 4, the conductive layer (4) was provided on the glass plate (6) via the adhesive layer (5).
[0132]
(Electric resistance)
When the electric resistance of the conductive layer (4) was measured using a non-contact resistance measuring device (MODEL 717B, manufactured by Coper Electronics Co., Ltd.), it was 100Ω / □.
[0133]
[Example 2]
The composition of the adhesive layer coating solution
Acrylic resin 103B: 90 parts by weight
UV curable resin SD-318: 50 parts by weight
The silicone resin solution: 12.5 parts by weight
Methyl ethyl ketone: 181 parts by weight
A transfer conductive film was obtained in the same manner as in Example 1 except that. When the adhesive layer of the obtained conductive film for transfer was touched with a finger, there was a feeling of tack. Using the obtained conductive film for transfer, the conductive layer was transferred to a glass plate and baked in the same manner as in Example 1. Even after curing, the adhesive layer (5) was very strong. The electric resistance of the conductive layer (4) was 100Ω / □.
[0134]
[Example 3]
The composition of the adhesive layer coating solution
Acrylic resin 103B: 80 parts by weight
UV curable resin SD-318: 50 parts by weight
The silicone resin solution: 25 parts by weight
Methyl ethyl ketone: 178 parts by weight
A transfer conductive film was obtained in the same manner as in Example 1 except that. When the adhesive layer of the obtained conductive film for transfer was touched with a finger, there was a feeling of tack. Using the obtained conductive film for transfer, the conductive layer was transferred to a glass plate and baked in the same manner as in Example 1. Even after curing, the adhesive layer (5) was very strong. The electric resistance of the conductive layer (4) was 100Ω / □.
[0135]
[Example 4]
Using the same conductive film for transfer as used in Example 1, the conductive layer was transferred to a glass plate in the same manner as in Example 1. After curing of the adhesive layer (5), the glass plate provided with the conductive layer (4) was placed in an atmosphere of 500 ° C. in air for 1 hour to burn the organic content in the adhesive layer (5). Then, the atmosphere temperature was lowered to 40 ° C. over 3 hours as a nitrogen atmosphere at 500 ° C., the glass plate was taken out, and lowered to room temperature (23 ° C.). Even after curing, the adhesive layer (5) was very strong. The electric resistance of the conductive layer (4) was 100Ω / □.
[0136]
[Comparative Example 1]
A conductive film for transfer was obtained in the same manner as in Example 1 except that the silicone resin solution was not added to the adhesive layer coating solution. When the adhesive layer of the obtained conductive film for transfer was touched with a finger, there was a feeling of tack. Using the obtained conductive film for transfer, the conductive layer was transferred to a glass plate and baked in the same manner as in Example 1. The adhesive layer was very strong before firing, but the adhesive layer disappeared after firing, and the conductive layer was peeled off from the glass plate.
[0137]
[Comparative Example 2]
A conductive film for transfer was obtained in the same manner as in Example 1 except that the compression operation was not performed. Using the obtained conductive film for transfer, the conductive layer was transferred to a glass plate and baked in the same manner as in Example 1. Even after firing, the adhesive layer (5) was very strong. The electric resistance of the conductive layer (4) was 500Ω / □.
[0138]
[Comparative Example 3]
Using the same conductive film for transfer as used in Example 1, the conductive layer was transferred to a glass plate in the same manner as in Example 1. However, baking after transfer was not performed. The adhesive layer (5) was very strong. The electric resistance of the conductive layer (4) was 250Ω / □.
[0139]
[Example 5]
In this example, a conductive layer and a titanium oxide layer are formed on a target glass by using the same transfer conductive film as used in Example 1 and a transfer titanium oxide film obtained as shown below. did. This is an example assuming an electrode for a wet solar cell (Gretzel cell).
[0140]
A transfer titanium oxide film having a resin layer and a titanium oxide compression layer in this order on the support was prepared.
[0141]
(Formation of hard resin layer)
A 75 μm thick PET film (HSL, manufactured by Teijin DuPont Film) was corona treated so that the contact angle of pure water was 39 °. 100 parts by weight of A solution of FRESSERA N (manufactured by Matsushita Electric Works Co., Ltd.) and 300 parts by weight of solution B were mixed to obtain a coating solution for the resin layer. The coating solution was applied on the corona-treated surface of the PET film, dried, and cured at 90 ° C. for 24 hours to form a 1 μm thick silicone resin layer.
[0142]
(Formation of titanium oxide compression layer)
900 parts by weight of ethanol was added to 100 parts by weight of titanium oxide fine particles having a primary particle diameter of 5 to 40 nm, and the media was dispersed as zirconia beads with a disperser. The obtained coating liquid was applied onto the resin layer using a bar coater, and dried by sending hot air of 50 ° C. The thickness of the titanium oxide-containing coating film before compression was 2.6 μm. This titanium oxide-containing coating film was subjected to a pressure of 330 N / mm per unit length in the film width direction (183 N / mm per unit area). ² ) To obtain a titanium oxide compressed layer. The thickness of the titanium oxide compression layer was 1.5 μm. In this way, a transfer titanium oxide film was obtained.
[0143]
(Transfer and firing of conductive layer on glass plate)
Using the same conductive film for transfer as used in Example 1, the conductive layer was transferred to the glass plate (6) in the same manner as in Example 1. After curing of the adhesive layer (5), the glass plate provided with the conductive layer (4) was placed in an atmosphere of 500 ° C. in air for 1 hour to burn the organic content in the adhesive layer (5). Thereafter, the ambient temperature was lowered and the glass plate was taken out. Even after curing, the adhesive layer (5) was very strong.
[0144]
(Adhesive coating solution)
Acrylic resin 103B: 96 parts by weight
UV curable resin SD-318: 50 parts by weight
Same silicone resin solution as used in Example 1: 5 parts by weight
Methyl ethyl ketone: 182 parts by weight
[0145]
(Transfer and calcination of titanium oxide layer on conductive layer)
On the ITO conductive layer (4) on the glass plate (6), an adhesive coating solution having the above composition was applied and dried. Next, the transfer titanium oxide film was attached with a laminator so that the titanium oxide compression layer (14) and the adhesive coating layer (15) were in contact with each other. The adhesive layer (15) was cured by irradiating ultraviolet rays from the glass surface side, and the support PET film was peeled off after curing. After curing, the glass plate (6) provided with the conductive layer (4) and the titanium oxide layer (14) was fired in air at 500 ° C. for 1 hour, and then the ambient temperature was lowered to 200 ° C. over 2 hours. Next, the glass plate was placed in an atmosphere at 200 ° C. under reduced pressure (0.1 atm), and the temperature was lowered to 50 ° C. over 5 hours. The glass plate was taken out and lowered to room temperature (23 ° C.). In this way, the conductive layer (4) was provided on the glass plate (6) via the adhesive layer (5), and further the titanium oxide layer (14) was provided via the adhesive layer (15). . Note that the application of the adhesive coating liquid onto the ITO conductive layer and the transfer of the titanium oxide layer were not performed on the entire surface of the ITO conductive layer, and a part of the surface of the ITO conductive layer was exposed. Refer to FIG.
[0146]
(Measurement of electrical resistance)
This will be described with reference to FIG.
A tester (T) with two terminals was prepared, and one of the terminals was used as an alligator clip (t1). An aluminum foil having a thickness of 20 μm was cut into a rectangle having a width of 1 mm and a length of 15 mm (AL), and bent at a right angle at 1 mm from one end in the longitudinal direction to form a square end (e) having 1 mm sides. 4 mm from the other end in the longitudinal direction of the aluminum foil (AL) was sandwiched between alligator clips (t1). Refer to FIG.
Place the other terminal (t2) of the tester that is not an alligator clip on the exposed part of the ITO conductive layer (4), and sandwich it with the alligator clip (t1) on the titanium oxide layer (14) surface 50 mm away from it. The square end (e) of the aluminum foil (AL) was applied so that the square surface was in contact with the surface of the titanium oxide layer (14), and the electric resistance value was measured. Refer to FIG. The electric resistance was 300 MΩ / □. Therefore, the titanium oxide layer (14) and the ITO conductive layer (4) were in electrical contact.
[0147]
In the said Example, the functional film for transcription | transfer which has a transparent conductive layer was produced using ITO microparticles | fine-particles as an inorganic microparticle, and the example which gave the conductive layer to the glass plate was shown. In the same manner as in the above examples, functional films for transfer having various inorganic functional layers can be produced using inorganic fine particles having various properties. Of course, as the target object, various objects that need to be provided with a functional layer can be selected. For this reason, the above-described embodiment is merely an example in all respects and should not be interpreted in a limited manner. Furthermore, all modifications belonging to the equivalent scope of the claims are within the scope of the present invention.
[0148]
【The invention's effect】
According to the present invention, a functional film for transfer having a functional layer with excellent performance and an adhesive layer having excellent adhesive ability even after high-temperature treatment can be obtained by a simple operation of coating and compression. . According to this invention, the functional layer which has a higher function is reliably formed by baking after transfer to the target object surface using the said functional film for transfer. The present invention is particularly advantageous when a functional layer having a uniform thickness is applied to an object having poor flexibility such as a plate material.
[0149]
The present invention can be applied to the formation of various functional layers on the surface of an object, but is particularly preferably applicable to the formation of a transparent conductive layer.
[Brief description of the drawings]
FIG. 1 is a diagram for explaining a form of peeling.
FIG. 2 is a cross-sectional view showing an example of a functional film for transfer according to the present invention.
FIG. 3 is a cross-sectional view showing an example of a functional film for transfer according to the present invention.
FIG. 4 is a cross-sectional view showing an example of an object provided with a functional layer of the present invention.
FIG. 5 is a view for explaining peeling during transfer using the functional film for transfer of the present invention.
6 is a diagram for explaining measurement of electrical resistance in Example 5. FIG.
[Explanation of symbols]
(1): Support
(3): Resin layer
(4): Functional layer
(5): Adhesive layer
(6): Target object

Claims (12)

The support has at least a functional layer that can be peeled off from the support, the functional layer is a compressed layer of functional fine particles, and an acrylic monomer (M) and silicone are formed on the functional layer. A functional film for transfer provided with an adhesive layer containing at least a resin (S). The functional film for transfer according to claim 1, wherein the adhesive layer further contains an acrylic resin (P). The adhesive layer includes an acrylic resin (P) and an acrylic monomer (M) at a weight ratio P / M = 0/10 to 8/2, and a silicone resin (S) is added to the acrylic resin (S The functional film for transfer according to claim 1 or 2, which is contained at a weight ratio S / (P + M) = 0.01 / 100 to 50,000 / 100 with respect to the total (P + M) of P) and the acrylic monomer (M). The compressed layer of the functional fine particles is obtained by compressing a functional fine particle-containing layer formed by applying and drying a liquid in which the functional fine particles are dispersed on a support or an intermediate layer. The functional film for transfer according to any one of claims 1 to 3. The functional film for transfer according to any one of claims 1 to 4, wherein the compressed layer of the functional fine particles is obtained by compressing with a compressive force of 44 N / mm ² or more. The functional film for transfer according to any one of claims 1 to 5, wherein the functional fine particles are conductive fine particles, and the compressed layer of the functional fine particles is a conductive layer. The functional film for transfer according to any one of claims 1 to 6 is attached to the surface of a target object to which a functional layer is to be applied via an adhesive layer of the film, and the adhesion is performed after the application. An object provided with a functional layer, obtained by curing the agent layer, peeling the support, and then firing. The functional film for transfer according to any one of claims 1 to 6 is attached to the surface of a target object to which a functional layer is to be applied via an adhesive layer of the film, and the adhesion is performed after the application. A method for producing an object provided with a functional layer, wherein the agent layer is cured, the support is peeled off, and then fired. An object having an adhesive layer on the surface, a compressed layer of functional fine particles on the adhesive layer, and the compressed layer being fired. The object according to claim 9, wherein the adhesive layer contains silicon dioxide as a main component. On the support has at least a functional layer that can be peeled from the support, and the functional layer prepares a functional film for transfer which is a compressed layer of functional fine particles,
An adhesive layer including at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the functional layer is to be applied,
The transfer functional film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, An object provided with a functional layer obtained by peeling and then firing. On the support has at least a functional layer that can be peeled from the support, and the functional layer prepares a functional film for transfer which is a compressed layer of functional fine particles,
An adhesive layer including at least an acrylic monomer (M) and a silicone resin (S) is provided in advance on the target object surface to which the functional layer is to be applied,
The transfer functional film is attached to the object surface through an adhesive layer provided in advance on the object surface so that the support is on the outside, and after the application, the adhesive layer is cured, A method for producing an object provided with a functional layer, characterized by peeling and then baking.

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