KR102040461B1 - The conductive film - Google Patents
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- KR102040461B1 KR102040461B1 KR1020150088575A KR20150088575A KR102040461B1 KR 102040461 B1 KR102040461 B1 KR 102040461B1 KR 1020150088575 A KR1020150088575 A KR 1020150088575A KR 20150088575 A KR20150088575 A KR 20150088575A KR 102040461 B1 KR102040461 B1 KR 102040461B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
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Abstract
The present application relates to a conductive film, a manufacturing method of the conductive film and its use.
The present application can provide a conductive film, a method for producing a conductive film, and a use thereof, which can improve visibility problems due to a pattern crushing phenomenon even after a heat treatment step.
Description
The present application relates to a conductive film, a manufacturing method of the conductive film and its use.
Operating system's input device that enables the user to enter data easily by touching the screen (hand) with a hand or an object is called Touch Screen Panel (TSP). (Resistive), capacitive, and the like.
Currently, the most widely used methods are resistive and capacitive, and the resistive method detects a point when a potential difference occurs at a pressed point when a finger or a pen is touched. Principle, also called pressure-sensitive.
In addition, the capacitive method uses a capacitance in a human body to detect a portion of the current change direction.
Indium-Tin Oxide (ITO) film, which is commonly used in the structure of the resistive and capacitive touch screen panels, is formed by depositing a transparent conductive film made of an indium tin compound, which is a metal conductive material, in a physical or chemical manner. The transparent electrode (electric circuit, pattern) is to be formed on the base substrate.
In particular, in the capacitive type, visibility of transparent electrodes (electric circuits, patterns) becomes a problem. In order to improve the visibility problem, an optical control layer is formed on a lower surface on which a conductive layer such as an ITO layer is formed to minimize reflectance between the etched (patterned forming process) and the unetched surface. .
In addition, the conductive film forms a layer such as a transparent under coating layer under the conductive layer in addition to the optical control layer, thereby improving adhesion and transmittance between the conductive layer and the base layer. The undercoating layer may be formed by a wet coating or a vacuum stuttering method. However, since the formation process of each layer needs to be performed separately, the manufacturing process is complicated and the cost is high.
In addition, despite the above-mentioned efforts to improve visibility, the phenomenon of pressing of the base portion where ITO is not patterned may occur in the post-heat treatment process of the ITO layer, and thus there is still a problem in that visibility is lowered.
The present application provides a conductive film that improves the problem of lowering visibility due to the bending phenomenon of the conductive film.
The present application also provides the use of a conductive film, for example a touch panel comprising a conductive film.
The present application has been made to solve the above problems, a base film; A first resin layer formed on one surface of the base film; A second resin layer formed on a surface on which the first resin layer of the base film is not formed; And an amorphous or non-patterned conductive layer, wherein the first resin layer is formed on the side opposite to the surface in contact with the base film. The conductive film may form, for example, a curved structure in which the conductive layer direction is concave when heat treated at 150 ° C. for 1 hour.
In one example, the radius of curvature of the curved structure may be in the range of 1 mm to 1,000 mm.
In one example, the thickness of the first resin layer may be in the range of 0.3 μm to 1.3 μm.
In one example, the thickness of the second resin layer may be in the range of 0.9 μm to 1.7 μm.
The ratio (T1 / T2) of the thickness T1 of the first resin layer and the thickness T2 of the second resin layer may be in the range of 0.75 to 1.30, for example.
In one example, the absolute value of the difference between the refractive index (based on the wavelength 550nm) of the first resin layer and the refractive index (based on the 550nm wavelength) of the base film may be 0.3 or less.
The conductive film of the present application may further include a conductive layer on the first resin layer, for example.
The present application also provides a substrate film; A first resin layer formed on one surface of the base film; A second resin layer formed on a surface on which the first resin layer of the base film is not formed; And a crystalline or patterned conductive layer formed on the opposite side of the surface where the first resin layer is in contact with the base film, and relates to a conductive film forming a curved structure in which the conductive layer direction is concave. The conductive film, for example, the radius of curvature of the curved structure may be in the range of 1 mm to 1,000 mm.
The present application also relates to a touch panel comprising a conductive film.
The present application can provide a conductive film excellent in visibility and its use by preventing the visibility problem caused by the bending phenomenon that may occur by heat treatment or the like.
1 (a) and 1 (b) are schematic views of known conductive films.
2 is a schematic view of the conductive film of the present application.
Hereinafter, the present application will be described in more detail with reference to examples, but the present invention is only an embodiment limited to the gist of the present application. On the other hand, the present application is not limited to the process conditions presented in the following examples, it is apparent to those skilled in the art that can be arbitrarily selected within the range of conditions necessary to achieve the purpose of the present application. .
The present application relates to a conductive film and its use.
The present application is to improve the visibility problem due to the pattern pressing phenomenon that can occur in the heat treatment for crystallization of the conductive layer in the deposition and patterning of the conductive layer or to improve the durability of the film during the deposition and patterning of the conductive layer and its manufacture It may provide a method.
1 is a schematic view of a conventional conductive film. As shown in (a) and (b) of FIG. 1, a conventional conductive film is curved in the conductive layer direction as shown in (a) of FIG. 1 when undergoing a predetermined heat treatment or (b) of FIG. 1. As described above, the phenomenon in which the pattern portion of the conductive layer is pressed, such as bending in a direction opposite to the conductive layer direction may occur. In addition, the pressing phenomenon of the pattern may cause a visibility problem in which the pattern portion of the conductive layer is visually identified.
However, the conductive film according to the present application by forming a predetermined resin layer on both sides of the base film, by adjusting the thickness range between the resin layer to form a curved structure in the conductive layer direction during heat treatment at a predetermined condition The problem of pattern visibility was improved.
In one example, the present application is a substrate film; A first resin layer formed on one surface of the base film; A second resin layer formed on a surface on which the first resin layer of the base film is not formed; And an amorphous or non-patterned conductive layer, wherein the first resin layer is formed on the side opposite to the surface in contact with the base film. The conductive film is heat treated at a predetermined heat treatment process, for example, at a temperature of 150 ° C. for 1 hour to form a curved structure in which the conductive layer direction is concave.
That is, the conductive film of the present application includes a conductive layer that is not crystallized or patterned, and has a curved structure concave in the conductive layer direction upon heat treatment at the above-described heat treatment process conditions, for example, a temperature of 150 ° C. for 1 hour. It may be to form.
The term "amorphous conductive layer" in the present application is a state before the conductive layer formed by the deposition process is crystallized by a predetermined heat treatment process, for example, the degree of crystallinity (%) is less than 10%, less than 9%, less than 8% , Less than 7%, less than 6%, or less than 5%.
In the present application, the term "non-patterned conductive layer" may mean a conductive layer in a state before the conductive layer formed by the deposition process includes a pattern portion and a non-pattern portion simultaneously through a predetermined patterning process. have.
The material of the conductive layer is not particularly limited, and for example, gold, silver, platinum, palladium, copper, titanium oxide, cadmium oxide, copper iodide, and indium oxide containing tin (ITO: Indium Tin Oxide) and antimony are contained. At least one metal oxide selected from the group consisting of tin oxide, fluorine-containing tin oxide (FTO), and zinc oxide; Carbon nanotubes; Metal nanowires formed of a material such as silver or copper; Alternatively, the present invention may be a conductive polymer such as a polythiophene-based polymer or a polyanilin-based polymer including poly (styrenesulfonate).
For example, the conductive layer may have a refractive index in the range of 1.9 to 2.1 for a 550 nm wavelength.
In addition, the conductive layer may have a thickness ranging from 0.01 to 0.022 μm. When the thickness of the conductive layer is less than 0.01 µm, the conductivity is lowered. When the thickness of the conductive layer is greater than 0.022 µm, transparency may be lowered.
The method of forming the conductive layer may include, for example, a process of depositing the above-described material for forming the conductive layer by sputtering or the like, but is not limited thereto. Methods of forming the conductive layer are known in the art, and can be used in the present application without limitation.
The electroconductive film of this application contains a base film, and includes the 1st resin layer and the 2nd resin layer on both surfaces of the said base film, respectively. The first resin layer and the second resin layer are for distinguishing two resin layers having different physical properties formed on both surfaces of the base film. For example, the resin layer formed on the conductive layer side is called a first resin layer. The resin layer formed on the opposite surface can be called a 2nd resin layer.
The conductive film of the present application includes a base film.
In one example, the base film may be a transparent film, and a known one suitable for a conductive film having transparency and strength in an appropriate range may be adopted.
Specifically, the material of the base film may be polyolefin such as polyethylene or polypropylene; Polyesters such as polyethylene terephthalate and polyethylene naphthalate; Polyamides such as 6-nylon or 6,6-nylon; Polycarbonate; Polyethersulfones; Or norbornene-based resins may be used, but is not limited thereto. The base film may be single or in mixture of 2 or more types. In addition, the base film may be in the form of a single film or in the form of a laminated film.
The base film of the present application may also be one whose surface is modified.
In one example, the base film may be a surface modified using a known treatment method such as chemical treatment, corona discharge treatment, mechanical treatment, ultraviolet (UV) treatment, active plasma treatment or glow discharge treatment.
In addition, the base film may include known additives such as antistatic agents, ultraviolet absorbers, infrared absorbers, plasticizers, lubricants, colorants, antioxidants or flame retardants.
The thickness of the base film may be set in an appropriate thickness range in consideration of the purpose of minimizing the occurrence of wrinkles due to the transparency, thinning and tension during processing. In one example, the base film may have a thickness range of 10 μm to 80 μm, or 20 μm to 60 μm, but is not limited thereto.
The electroconductive film of this application contains a 1st resin layer and a 2nd resin layer on both surfaces of a base film. The said 2nd resin layer is formed in the surface in which the 1st resin layer of a base film is not formed. The term "resin layer" in the present application means a layer containing 15% or more of a resin component, and may mean a layer having appropriate rigidity and having a predetermined refractive index.
In the conductive film of the present application, the thermal expansion coefficient and the bending phenomenon according to the physical properties of the first resin layer and the second resin layer may be determined. In one example, the first resin layer may serve to lower the thermal expansion coefficient of the conductive film to 20 ppm / ° C. or less by controlling the thickness range while adding inorganic particles to a predetermined content.
The first resin layer may contain, for example, inorganic particles. As described above, the inorganic particles may be used to adjust the refractive index to a range similar to that of the base film and to impart proper rigidity to the first resin layer.
In one example, the inorganic particles may be exemplified by ZnO, TiO 2 , CeO 2 , SiO 2 , SnO 2 , ZrO 2 , MgO or Ta 2 O 5 , but are not limited thereto.
The inorganic particles may be included in the first resin layer in an appropriate ratio in consideration of the rigidity of the first resin layer, the desired refractive index, and the like.
In one example, the first resin layer may include the inorganic particles in the range of 40% by weight, 50% by weight, or 60% by weight or more. Within the weight range as described above, the first resin layer may provide a conductive film having the desired refractive index and rigidity and ultimately improving pattern visibility. The content of the inorganic particles may be, for example, a value calculated using a thermogravimetric analyzer (TGA). The upper limit of the inorganic particle content range is not particularly limited, but may be, for example, 99 wt% or less, 95 wt% or less, or 90 wt% or less.
The first resin layer may exhibit an index of refraction similar to that of the base film by including the inorganic particles within the above range.
In one example, the absolute value of the difference between the refractive index (based on 550 nm wavelength) of the first resin layer and the refractive index (based on 550 nm wavelength) of the base film may be 0.3 or less. It is possible to achieve the desired optical properties of the conductive film within the above refractive index difference. In another example, the absolute value of the difference between the refractive index (based on the 550 nm wavelength) of the first resin layer and the refractive index (based on the 550 nm wavelength) of the base film may be 0.2 or less or 0.1 or less.
Specifically, the first resin layer may have a refractive index measured at a wavelength of 550 nm in the range of 1.5 to 1.8. In another example, the first resin layer may have a refractive index measured at a wavelength of 550 nm in the range of 1.5 to 1.7 or 1.6 to 1.7.
The thickness of the first resin layer may be in the range of 0.3 μm to 1.3 μm, for example. The thickness of the first resin layer is a factor that allows the conductive film according to the present application to form a curved structure concave in the conductive layer direction together with the thickness of the second resin layer to be described later. Appropriate values can be set in consideration of the thickness of the strata. Specifically, the thickness of the first resin layer may be in the range of 0.4 μm to 1.3 μm, 0.5 μm to 1.3 μm, or 0.8 μm to 1.3 μm.
For example, the second resin layer of the present application has a predetermined thickness range difference and a thermal expansion coefficient difference from the first resin layer, thereby imparting overall rigidity to the conductive film, and according to a predetermined heat treatment step. It may serve to prevent the conductive film from bending in the direction.
In one example, the ratio T1 / T2 of the thickness T1 of the first resin layer and the thickness T2 of the second resin layer may be in the range of 0.75 to 1.30. The pattern part pressing phenomenon of a conductive film can be improved within such a thickness ratio range. In another example, the ratio T1 / T2 may be in the range of 0.8 to 1.2 or 0.9 to 1.1, preferably low heat of the conductive film when the ratio T1 / T2 is in the range of 0.9 to 1.1. Pressing of the pattern can be minimized due to the expansion coefficient. When the ratio (T1 / T2) of the thickness T1 of the first resin layer and the thickness T2 of the second resin layer is less than 0.75 or more than 1.30, the conductive film has the visibility of the pattern after the above-described heat treatment step. Problems may arise.
The thickness of the second resin layer may be appropriately set in a range that can satisfy the thickness ratio with the first resin layer, and may be, for example, in the range of 0.9 μm to 1.7 μm.
In another example, the thickness of the second resin layer may be in the range of 0.9 μm to 1.6 μm, 0.9 μm to 1.5 μm, or 0.9 μm to 1.4 μm.
The first resin layer and the second resin layer may be, for example, a coating layer formed by polymerization of a radically polymerizable compound.
In one example, the first resin layer and the second resin layer may comprise polymerized units of radically polymerizable compounds, such as monofunctional or polyfunctional (meth) acrylate compounds. The term "monofunctional or polyfunctional (meth) acrylate compound" refers to (meth) acrylate monomers, oligomers or mixtures thereof containing one or more polymerizable functional groups, such as acryloyl or methacryloyl groups. It may mean. In addition, the "(meth) acrylate" may mean an acrylate or methacrylate.
In one example, the monofunctional (meth) acrylate compound can be an alkyl (meth) acrylate.
Specifically, the alkyl (meth) acrylate may be an alkyl (meth) acrylate having an alkyl group having 1 to 20 carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl ( Meta) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2 Ethylbutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (Meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, octadecyl (meth) acrylate or isobonyl (meth) Acryl Although the agent or the like can be illustrated, without being limited thereto.
As said polyfunctional (meth) acrylate compound, 1, 4- butanediol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, neopentylglycol di (meth) acrylate, for example , Polyethylene glycol di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentylglycol di (meth) acrylate, dicyclopentanyl ) Di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxy ethyl isocyanurate, allylated Cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylic , Tricyclodecane dimethanol (meth) acrylate, neopentylglycol modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate or 9,9-bis [4- (2- Difunctional (meth) acrylates such as acryloyloxyethoxy) phenyl] fluorene and the like; Trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide Trifunctional (meth) acrylates such as modified trimethylolpropane tri (meth) acrylate, trifunctional urethane (meth) acrylate or tris (meth) acryloxyethyl isocyanurate; Tetrafunctional (meth) acrylates such as diglycerin tetra (meth) acrylate or pentaerythritol tetra (meth) acrylate; 5-functional (meth) acrylates, such as propionic acid modified dipentaerythritol penta (meth) acrylate; Reactant of dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate or urethane (meth) acrylate (ex. Isocyanate monomer or trimethylolpropane tri (meth) acrylate Hexafunctional (meth) acrylates, such as), etc. can be used.
Moreover, as a polyfunctional (meth) acrylate, it is a compound called in the industry what is called a photopolymerizable oligomer, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, or polyether ( Meth) acrylate etc. can also be used.
The present application may form the first resin layer and the second resin layer by selecting one kind or two or more types from the radical polymerizable compounds as described above.
In one example, the method of forming the first resin layer may include, for example, coating the first resin layer-forming composition on a base film using a known coating method and then curing.
Specifically, the first resin layer is, for example, a well-known coating on a base film with a composition for forming a first resin layer containing the aforementioned monofunctional or polyfunctional (meth) acrylate compound, inorganic particles, an initiator and a solvent. Method, specifically, by coating using a method such as gravure coating, microgravure coating, slot die coating, spin coating, spray coating, roll coating, bar coating or dip coating, and then hardening.
As the initiator included in the composition for forming the first resin layer, for example, a benzoin-based, hydroxy ketone-based, amino-ketone-based or phosphine oxide-based photoinitiator may be used as a radical photoinitiator.
Specifically, as the radical photoinitiator, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, 2, 2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenylketone , 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) Ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthra Quinone, 2-methyl thioxanthone, 2-ethyl thioxanthone, 2-chloro thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal, p Dimethylamino Benzoic acid ester, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] or 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like can be used. May be, but is not limited thereto.
The amount of the initiator may be adjusted within a range suitable for polymerizing a monofunctional or polyfunctional (meth) acrylate compound included in the first resin layer-forming composition, for example, in the range of 0.05 to 3 parts by weight. As may be included in the composition for forming a first resin layer, but is not limited thereto.
As a solvent contained in the composition for forming a first resin layer, for example, water, an organic solvent or a mixture thereof can be used.
As the organic solvent, for example, an alcohol solvent, a halogen-containing hydrocarbon solvent, a ketone solvent, a cellosolve solvent, an amide solvent, or the like can be used.
More specifically, the alcohol solvent is methanol, ethanol, isopropyl alcohol, n-butanol or diacetone alcohol, and the like. The halogen-containing hydrocarbon solvent is chloroform, dichloromethane or ethylene dichloride, and the ketone solvent is acetaldehyde, acetone, methylethyl, or the like. Ketone or methyl isobutyl ketone and the like, the cellosolve solvents are methyl cellosolve or isopropyl cellosolve and the like, and the amide solvents may be dimethylformamide, formamide or acetamide.
The composition for forming the first resin layer may include, for example, 40% by weight or more, 50% by weight or 60% by weight or more of the inorganic particles relative to the total solids. The upper limit of the inorganic particle content range is not particularly limited, but may be, for example, 99 wt% or less, 95 wt% or less, or 90 wt% or less. By including the inorganic particles in the above range, the first resin layer can exhibit a refractive index similar to that of the base film, and can also have appropriate rigidity.
The composition for forming a first resin layer of the present application may further contain known additives, for example, surfactants, plasticizers, surface lubricants, leveling agents, antioxidants, corrosion inhibitors, light stabilizers, ultraviolet absorbers, and polymerization inhibitors, in addition to the aforementioned components. Or a silane coupling agent or the like. The content of the components may be added in an appropriate amount within a range that does not harm the physical properties of the conductive film, for example, may be included in the range of 0.01 to 2 parts by weight relative to 100 parts by weight of the composition for forming the first resin layer.
The method of curing the first resin layer is not particularly limited, and for example, the monofunctional or polyfunctional (meth) acrylate compound can be cured by appropriately irradiating a condition such as UV light or the like that can be polymerized by an initiator. It can be used, but is not limited thereto.
The first resin layer cured by the coating may have a thickness in the range of 0.3 μm to 1.3 μm. Within the thickness range as described above, the desired rigidity of the first resin layer may be achieved, and inorganic particles may be included in a predetermined range to exhibit a refractive index difference of 0.3 or less with the base film at a wavelength of 550 nm.
Further, the method for forming the second resin layer may be formed by, for example, applying a composition for forming the second resin layer containing the monofunctional or polyfunctional (meth) acrylate compound and the initiator described above and then curing the same. The specific application and curing method may be the same as mentioned in the method for forming the first resin layer.
As described above, the first resin layer and the second resin layer may have appropriate rigidity, and may serve to lower the thermal expansion coefficient of the conductive film.
In one example, the conductive film of the present application may have a thermal expansion coefficient of 20 ppm / ° C. or less. Since the lower the thermal expansion coefficient of the conductive film means that the deformation caused by the heat treatment process is reduced, the lower limit is not particularly limited, for example, 1 ppm / ℃ or more, 2 ppm / ℃ or more, 3 ppm / ℃ or more, 4 ppm / ℃ Or at least 5 ppm / ° C. The thermal expansion coefficient is calculated by linear thermal expansion coefficient of the average thermal expansion coefficient measured while cooling and heating at a rate of 10 ℃ / min in a temperature range of 25 ℃ to 150 ℃ using a thermo mechanical analyzer (TMA), for example Can be a value.
In the conductive film of the present application, after forming a first resin layer and a second resin layer having a predetermined thickness and thermal expansion coefficient difference on both surfaces of the base film as described above, after the predetermined heat treatment step, amorphous or non-patterned A curved structure concave in the direction of the conductive layer can be formed.
In one example, the radius of curvature of the concave curved structure of the conductive film may be in the range of 1 mm to 1,000 mm.
The conductive film of the present application may further include an undercoat layer. The undercoating layer may be located, for example, between the first resin layer and the amorphous or unpatterned conductive layer.
The undercoating layer is, for example, positioned between the conductive layer and the first resin layer, and has a predetermined refractive index, and may serve to reduce the reflectance of the conductive film.
For example, the undercoating layer may have a refractive index of 550 nm in a range of 1.4 to 1.7, but is not limited thereto. The range may vary depending on the refractive indices of the conductive layer and the first resin layer.
The undercoating layer may be, for example, an organic layer, an inorganic layer, or an organic-inorganic composite layer formed of an organic material, an inorganic material, or a composite thereof.
As the organic material, for example, a resin made of an organic material capable of thermal or UV curing may be used, and specifically, an acrylic, epoxy, urethane, thiourethane, alkyd resin, or siloxane polymer may be exemplified.
The inorganic materials include CaF 2 , BaF 2 , SiO 2 , LaF 3 , CeF 3 , Al 2 O 3 , silicon oxynitride, aluminum oxynitride, and the like.
In addition, the organic-inorganic composite is acrylic, epoxy, including high refractive particles of a single composition or composite composition, such as TiO 2 , Nb 2 O 5 , Ta 2 O 5 , Sb 2 O 5 , ZrO 2 , ZnO or ZnS One or more selected from the group consisting of urethane-based, thiourethane-based, melamine, alkyd resins, siloxane-based polymers and organosilane compounds represented by the following general formula (1) can be used. In this case, when the organosilane compound is used, the refractive index may be adjusted and crosslinked by mixing with the high refractive particles.
[Formula 1]
(R 1 ) m -Si-X (4-m)
Wherein R 1 may be the same as or different from each other, and alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynylaryl, Halogen, substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, acryloxy , Methacryloxy, epoxy or vinyl group,
X may be the same or different from each other, and hydrogen, halogen, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R 2 ) 2 , wherein R 2 is H, or 1 to C 12 alkyl), wherein oxygen or —NR 2 (wherein R 2 is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R 1 and Si to form — (R 1 ) m —O—Si—X ( 4-m) or (R 1 ) m -NR 2 -Si-X (4-m) , where m is an integer from 1 to 3.
Examples of the organosilane include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxy Silane, phenyldimethoxysilane, phenyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triphenylmethoxysilane, Triphenylethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, diphenylmethylmethoxysilane, diphenylmethylethoxysilane, dimethylethoxysilane, dimethylethoxysilane, diphenylmethoxysilane, diphenyl Ethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-aminophenylsilane, allyltrimethoxysilane, n- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-amine Propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyldiisopropylethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxy Silane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, n-phenylaminopropyltrimethoxysilane, vinylmethyldiethoxysilane, vinyltriethoxysilane or vinyltrimethoxysilane.
In the organic-inorganic composite, the metal alkoxide may include a single or two or more compounds represented by the following Chemical Formula 2.
[Formula 2]
M- (R 3 ) z
In Formula 2, M represents at least one metal selected from the group consisting of aluminum, zirconium and titanium, R 3 may be the same or different from each other, halogen, alkyl having 1 to 12 carbon atoms, alkoxy, acyloxy, or It is a hydroxyl group, z is an integer of 3 or 4.
As the undercoat layer, when an organic-inorganic composite layer is used, the content of the organic material may be 1 to 99.99% by weight, specifically 5% by weight or more. In addition, the content of the inorganic material may be used in 0.01 to 99% by weight, specifically, less than 95% by weight may be used.
The undercoat layer may have a single layer or a multilayer structure of two or more layers.
In one example, the undercoat layer may be a single layer or a multi-layer structure formed by a wet coating such as a conventional coating method, for example, spin coating, dip coating or spray coating.
In another example, the undercoating layer may be a single layer or a multilayer structure formed by depositing the above-described organic, inorganic or organic-inorganic composite.
The present application also relates to a conductive film comprising a crystalline or patterned conductive layer.
In the present application, the term "crystalline conductive layer" refers to a conductive layer having a crystallization degree (%) of 75% or more, 80% or more, 85% or more or 90% or more by a predetermined heat treatment process. Can mean.
In the present application, the term “patterned conductive layer” may mean a conductive layer in a state in which the conductive layer simultaneously includes a pattern portion and a non-pattern portion through a predetermined patterning process.
In one example, the present application is a substrate film; A first resin layer formed on one surface of the base film; A second resin layer formed on a surface on which the first resin layer of the base film is not formed; And a crystalline or patterned conductive layer, which is formed on the side opposite to the surface of the first resin layer in contact with the base film, and relates to a conductive film forming a curved structure in which the conductive layer direction is concave.
The conductive film including the crystalline or patterned conductive layer may include, for example, the undercoat described above.
Specifically, as shown in FIG. 2, the conductive film of the present application includes the
The conductive film including the crystalline or patterned conductive layer of the present application may be after undergoing a predetermined heat treatment step.
In one example, the heat treatment process may be to crystallize the material of the conductive layer, or to improve durability of the film by performing additional heat treatment after patterning the conductive layer.
Specifically, the heat treatment process may be performed for a time of 10 minutes to 100 minutes at a temperature of 100 ℃ to 200 ℃.
The conductive film according to the present application forms a concave curved structure having a predetermined radius of curvature in the conductive layer direction after the heat treatment process as described above, thereby improving the visibility problem of the pattern.
In one example, the radius of curvature of the curved structure of the conductive film may be in the range of 1 mm to 1,000 mm.
The present application also relates to a touch panel comprising a conductive film. The conductive film of the present application may be useful as an upper substrate and / or a lower substrate of a touch panel, particularly a resistive touch panel. In the resistive touch panel, a pair of conductive films are arranged to be aligned through a spacer. When the upper panel is pressed with a finger or a pen, the conductive film is bent, and the conductive layer of the upper substrate and the lower substrate contacts each other. It can be a structure which detects a position by energizing.
The conductive film according to the present application may implement a touch panel that may be improved in visibility, excellent in transparency, and manufactured at an economical cost.
The touch panel as described above may be mounted on a display device such as an LCD, a PDP, an LED, an OLED, or an E-paper, for example, but is not limited thereto.
Hereinafter, the conductive film according to the present application will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are only examples according to the present application, but are not intended to limit the technical spirit of the present application. Self-explanatory to those of ordinary skill in the field.
Physical properties of the conductive film according to the present application were measured by the following method.
1. Measurement of thermal expansion coefficient of conductive film
The average thermal expansion coefficient measured while cooling and raising the conductive film at a rate of 10 ° C./min in a temperature range of 25 ° C. to 150 ° C. using a TMA (thermo mechanical analyzer) was calculated as a linear thermal expansion coefficient.
2. Curvature radius measurement experiment
When the conductive film subjected to the predetermined heat treatment was cut into 10 cm ｘ 10 cm and placed on the plane, the maximum value (H 1 ) of the distance from each corner or one side of the plane and the length of the string (S 1 ) of the film were measured. The radius of curvature R value was obtained by the following general formula (1).
[Formula 1]
R = H 1 + R x cos (S 1 / 2R)
[ Example One]
First Preparation of resin layer forming composition (A1)
Radical polymerizable acrylate (Dipentaerythritol hexaacrylate, DPHA), inorganic particles (ZrO 2 ) and initiator (Irgacure184) are mixed at a ratio of 40: 60: 3, and solvent (Methyl isobutyl ketone (MIBK)) is added to the inorganic to total solids. A first resin layer-forming composition (A1) having a particle content of 60 wt% and a refractive index of about 1.65 was prepared.
2nd Preparation of resin layer forming composition (A2)
Radical polymerizable acrylate (Dipentaerythritol hexaacrylate, DPHA) and initiator (Irgacure184) are mixed in a ratio of 100: 3, and a solvent (Methyl isobutyl ketone, MIBK) is added to the composition for forming a second resin layer having a refractive index of about 1.52 (A2). ) Was prepared.
Preparation of Conductive Film
The first resin layer-forming composition (A1) was coated on one surface of a 50-micrometer-thick PET substrate film (UH-13 PET, refractive index of about 1.65), on which both surfaces were released, and irradiated with ultraviolet light to give a first thickness of about 0.9 μm. A resin layer was formed, and the second resin layer-forming composition (A2) was coated on the surface on which the first resin layer of the PET base film (UH-13 PET) was not formed. The second resin layer of was formed. Subsequently, after coating the composition (A3) for forming an epoxy resin and a propylene glycol monomethyl ether (PGME) undercoating layer on the first resin layer, it was irradiated with ultraviolet rays to have a refractive index of 1.5 (550 nm standard) and a thickness of about A 30 nm undercoat layer was formed. In addition, ITO was deposited on the undercoat layer by vacuum sputtering to form a conductive layer. Thereafter, the ITO conductive layer is patterned, and an Ag photosensitive curing process is performed at 150 ° C. for 1 hour, thereby sequentially conducting a conductive film including a second resin layer / base film / first resin layer / undercoat layer / conductive layer. Was prepared. Physical properties and pattern visibility evaluation results of the conductive film of Example 1 are shown in Table 1 below.
[ Example 2]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 1.2 μm. Physical properties and pattern visibility evaluation results of the conductive film of Example 2 are shown in Table 1 below.
[ Example 3]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 1.2 μm and the thickness of the second resin layer was 1.3 μm. Physical properties and pattern visibility evaluation results of the conductive film of Example 3 are shown in Table 1 below.
[ Comparative example One]
A conductive film was prepared in the same manner as in Example 1 except that the thickness of the first resin layer was 0.6 μm. Physical properties and pattern visibility evaluation results of the conductive film of Comparative Example 1 are shown in Table 1 below.
[ Comparative example 2]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 0.6 μm and the thickness of the second resin layer was 1.3 μm. Physical properties and pattern visibility results of the conductive film of Comparative Example 2 are shown in Table 1 below.
[ Comparative example 3]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 0.9 μm and the thickness of the second resin layer was 1.3 μm. Physical properties and pattern visibility results of the conductive film of Comparative Example 3 are shown in Table 1 below.
[ Comparative example 4]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 0.6 μm and the thickness of the second resin layer was 1.7 μm. Physical properties and pattern visibility results of the conductive film of Comparative Example 4 are shown in Table 1 below.
[ Comparative example 5]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 0.9 μm and the thickness of the second resin layer was 1.7 μm. Physical properties and pattern visibility results of the conductive film of Comparative Example 5 are shown in Table 1 below.
[ Comparative example 6]
A conductive film was produced in the same manner as in Example 1 except that the thickness of the first resin layer was 1.2 μm and the thickness of the second resin layer was 1.7 μm. Physical properties and pattern visibility results of the conductive film of Comparative Example 6 are shown in Table 1 below.
[ Experimental Example ]-Pattern Visibility Assessment
The pattern visibility of the conductive films prepared according to Examples and Comparative Examples was visually evaluated, but the following criteria were evaluated.
1.0: Pattern visibility is very good
1.5: excellent pattern visibility
2.0: Good pattern visibility
2.5: Poor pattern visibility
3.0: Very poor pattern visibility
As shown in Table 1, in the case of the conductive film according to the embodiment of the present application, the ratio of the thickness range of the first resin layer and the second resin layer satisfies the range of 0.75 to 1.30, and in the conductive layer direction after the heat treatment step By forming a concave curved structure, the pattern visibility is excellent. On the other hand, in the case of the conductive film of the comparative example, the ratio of the thickness range of the first resin layer and the second resin layer is outside the range of 0.75 to 1.30 to form a concave curved structure in the opposite direction of the conductive layer direction, thereby pattern visibility It can be confirmed that this is degraded.
Separation distance: + (conductive layer direction),-(opposite conductive layer direction)
100: conductive layer
101: pattern portion
102: non-pattern portion
200: undercoating layer
300: first resin layer
400: base film
500: second resin layer
Claims (13)
A first resin layer formed on the base film;
A second resin layer formed under the base film;
An under coating layer formed on the first resin layer; And
An amorphous or non-patterned conductive layer formed on the undercoat layer,
The first resin layer contains inorganic particles, the proportion of the inorganic particles in the first resin layer is 60% by weight or more,
The first resin layer and the second resin layer include polymerized units of a monofunctional or polyfunctional (meth) acrylate compound,
The ratio T1 / T2 of the thickness T1 of the first resin layer and the thickness T2 of the second resin layer is in the range of 0.75 to 1.30,
The undercoat layer is composed of an organic material or an organic-inorganic composite,
After the heat treatment for 1 hour at 150 ℃ temperature the upper surface of the undercoat layer forms a concave curved structure,
The radius of curvature of the curved structure is in the range of 1 mm to 1,000 mm,
The thermal expansion coefficient of the conductive film is 15 ppm / ° C or less,
The refractive index for the 550 nm wavelength of the undercoating layer is 1.5 to 1.7,
The undercoat layer comprises a conductive film comprising at least one of the following Chemical Formulas 1 and 2:
[Formula 1]
(R 1 ) m -Si-X (4-m)
In Formula 1, R 1 may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynyl having 1 to 12 carbon atoms Aryl, halogen, substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, Acryloxy, methacryloxy, epoxy or vinyl groups,
X may be the same as or different from each other, and hydrogen, halogen, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R 2 ) 2 , wherein R 2 is H, or 1 to C Alkyl of 12), wherein oxygen or —NR 2 (wherein R 2 is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R 1 and Si to form — (R 1 ) m —O—Si—X ( 4-m) or (R 1 ) m -NR 2 -Si-X (4-m) , m is an integer from 1 to 3;
[Formula 2]
M- (R 3 ) z
In Formula 2, M represents at least one metal selected from the group consisting of aluminum, zirconium and titanium, R 3 may be the same or different from each other, halogen, alkyl having 1 to 12 carbon atoms, alkoxy, acyloxy, or It is a hydroxyl group, z is an integer of 3 or 4.
The thickness of a base film is a conductive film in the range of 10 micrometers-80 micrometers.
The thickness of a 1st resin layer is a conductive film in the range of 0.3 micrometer-1.3 micrometers.
The thickness of a 2nd resin layer is a conductive film in the range of 0.9 micrometer-1.7 micrometers.
A first resin layer formed on the base film;
A second resin layer formed under the base film;
An under coating layer formed on the first resin layer; And
A crystalline or patterned conductive layer formed on the undercoat layer,
The first resin layer contains inorganic particles, the proportion of the inorganic particles in the first resin layer is 60% by weight or more,
The first resin layer and the second resin layer include polymerized units of a monofunctional or polyfunctional (meth) acrylate compound,
The ratio T1 / T2 of the thickness T1 of the first resin layer and the thickness T2 of the second resin layer is in the range of 0.75 to 1.30,
The undercoat layer is composed of an organic material or an organic-inorganic composite,
The upper surface of the undercoat layer forms a concave curved structure,
The radius of curvature of the curved structure is in the range of 1 mm to 1,000 mm,
The thermal expansion coefficient of the conductive film is 15 ppm / ° C or less,
The refractive index for the 550 nm wavelength of the undercoating layer is 1.5 to 1.7,
The undercoat layer comprises a conductive film comprising at least one of the following Chemical Formulas 1 and 2:
[Formula 1]
(R 1 ) m -Si-X (4-m)
In Formula 1, R 1 may be the same or different from each other, alkyl, alkenyl, alkynyl, aryl, arylalkyl, alkylaryl, arylalkenyl, alkenylaryl, arylalkynyl, alkynyl having 1 to 12 carbon atoms Aryl, halogen, substituted amino, amide, aldehyde, keto, alkylcarbonyl, carboxy, mercapto, cyano, hydroxy, alkoxy having 1 to 12 carbon atoms, alkoxycarbonyl having 1 to 12 carbon atoms, sulfonic acid, phosphoric acid, Acryloxy, methacryloxy, epoxy or vinyl groups,
X may be the same as or different from each other, hydrogen, halogen, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl, or -N (R 2 ) 2 , wherein R 2 is H, or 1 to C Alkyl of 12), wherein oxygen or —NR 2 (wherein R 2 is H, or alkyl having 1 to 12 carbon atoms) is inserted between the radicals R 1 and Si to form — (R 1 ) m —O—Si—X ( 4-m) or (R 1 ) m -NR 2 -Si-X (4-m) , m is an integer from 1 to 3;
[Formula 2]
M- (R 3 ) z
In Formula 2, M represents one or more metals selected from the group consisting of aluminum, zirconium and titanium, R 3 may be the same or different from each other, halogen, alkyl having 1 to 12 carbon atoms, alkoxy, acyloxy, or It is a hydroxyl group, z is an integer of 3 or 4.
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