WO2013115310A1 - Base with transparent conductive film and touch panel - Google Patents
Base with transparent conductive film and touch panel Download PDFInfo
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- WO2013115310A1 WO2013115310A1 PCT/JP2013/052190 JP2013052190W WO2013115310A1 WO 2013115310 A1 WO2013115310 A1 WO 2013115310A1 JP 2013052190 W JP2013052190 W JP 2013052190W WO 2013115310 A1 WO2013115310 A1 WO 2013115310A1
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- conductive film
- transparent conductive
- resin
- substrate
- primer layer
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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
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0443—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a single layer of sensing electrodes
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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
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04112—Electrode mesh in capacitive digitiser: electrode for touch sensing is formed of a mesh of very fine, normally metallic, interconnected lines that are almost invisible to see. This provides a quite large but transparent electrode surface, without need for ITO or similar transparent conductive material
Definitions
- the present invention relates to a transparent electrode such as various flat panel displays and touch panels, a substrate with a transparent conductive film that can be used for an antistatic layer, an electromagnetic wave shielding layer, and the like, and a touch panel using the substrate as an electrode.
- a metal oxide film obtained by sputtering a metal oxide such as indium tin oxide (ITO) or a conductive film made of a conductive polymer is widely known.
- the metal oxide film is fragile and easily broken by physical stress such as bending. Therefore, it is difficult to apply to a product group on the premise that physical stress is applied. Further, in order to impart high conductivity, it is necessary to increase the processing temperature for vapor deposition and annealing. Therefore, application to a plastic substrate is difficult. Furthermore, it is difficult to adhere to plastic substrates such as polycarbonate. Therefore, it is difficult to appropriately form on a plastic substrate.
- a conductive film made of a conductive polymer is inferior in transparency and conductivity as compared with a metal oxide film, and is difficult to apply to transmission applications.
- Patent Document 1 a transparent conductive film formed from metal nanowires has been proposed.
- Patent Document 1 exhibits high conductivity and transparency equivalent to or higher than that of a metal oxide film when metal nanowires are in contact with each other in the film, and has the above disadvantages of the metal oxide film. There is nothing.
- the transparent conductive film of Patent Document 1 has a problem that the adhesiveness deteriorates with time even if the initial adhesiveness with the transparent substrate is good.
- a transparent conductive film using metal nanowires and a substrate with a transparent conductive film excellent in adhesion over time of a transparent substrate, and a touch panel configured using the substrate as an electrode are provided.
- the present inventors have found that the interposition of a primer layer having a wetting tension of a predetermined value or more in between can improve the adhesion with time of a transparent conductive film containing metal nanowires to a transparent substrate, and completed the present invention. . Thereby, the stable continuous use of electronic devices, such as a touch panel, is realizable.
- the substrate with a transparent conductive film of the present invention is obtained by laminating a transparent conductive film containing metal nanowires on a transparent substrate via a primer layer having a surface wetting tension of 30 mN / m or more as defined in JIS K6768: 1999.
- the touch panel of the present invention is characterized by using the substrate with a transparent conductive film of the present invention as an electrode.
- a primer layer can be comprised including the resin part containing the hardened
- the resin content can be 90% by weight or more in the primer layer.
- An ionizing radiation curable resin can be used as the curable resin, and an ionizing radiation curable organic-inorganic hybrid resin can be used as the ionizing radiation curable resin.
- the resin component in the primer layer can further contain a thermoplastic resin together with a cured product of the curable resin.
- the content ratio in the resin component can be set to 50% by weight or more and 90% by weight or less of a cured curable resin, and from 10% to 50% by weight of a thermoplastic resin.
- a primer layer can also be comprised including particle
- the primer layer may contain low refractive index fine particles having an average particle diameter of 1 nm to 200 nm.
- the primer layer having a wetting tension of a predetermined value or more is interposed between the transparent conductive film using the metal nanowire and the transparent substrate. Not only the initial adhesiveness but also the temporal adhesion can be improved. Since the touchscreen of this invention uses the base material with a transparent conductive film of this invention for an electrode, it can implement
- FIG. 1 is a cross-sectional view showing an example of a substrate with a transparent conductive film of the present invention.
- the substrate 4 with a transparent conductive film of this example is configured by laminating a transparent conductive film 3 on a transparent substrate 1 via a primer layer 2.
- the transparent substrate 1 examples include plastic films (for example, various films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, and acrylic) and glass.
- plastic films for example, various films such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, polypropylene, polystyrene, triacetyl cellulose, and acrylic
- plastic films a polyethylene terephthalate film that has been stretched, in particular biaxially stretched, is preferred because of its excellent mechanical strength and dimensional stability.
- the thickness of the transparent substrate 1 varies depending on the use, but is generally about 25 to 500 ⁇ m, preferably 50 to 200 ⁇ m.
- the transparent conductive film 3 includes at least metal nanowires. Any metal nanowire can be used, and its production means is not particularly limited, and known means such as a liquid phase method and a gas phase method can be used.
- a method for producing Ag nanowires the above-mentioned Patent Document 1, as a method for producing Au nanowires, JP 2006-233252A, as a method for producing Cu nanowires, JP 2002-266007, as a method for producing Co nanowires are special. Examples thereof include the method described in Japanese Unexamined Patent Publication No. 2004-149871.
- the metal constituting the metal nanowire examples include elemental metals, alloys, and metal oxides. At least one cross-sectional dimension of the metal nanowire is preferably 200 nm or less from the viewpoint of transparency, and preferably 10 nm or more from the viewpoint of conductivity. In addition, the metal nanowire preferably has an aspect ratio of 10 or more, more preferably 50 or more, and even more preferably 100 or more, from the viewpoint of conductivity.
- the transparent conductive film 3 further includes a resin component that binds the metal nanowire together with the metal nanowire.
- a resin component the resin component illustrated in the explanation column of the primer layer 2 described later can be used.
- the content ratio of metal nanowires in the total solid content forming the transparent conductive film 3 is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more.
- the content is preferably 90% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.
- the refractive index of the transparent conductive film 3 is usually about 1.45 or more and 1.52 or less.
- a primer layer 2 is interposed between the transparent substrate 1 and the transparent conductive film 3.
- the primer layer 2 has a surface wetting tension (JIS K6768: 1999) adjusted to 30 mN / m or more, preferably 32 mN / m or more.
- the primer layer 2 is preferably composed of a resin component.
- the resin content in the primer layer 2 is preferably 90% by weight or more, more preferably 95% by weight or more.
- the resin content is reduced, it is difficult to adjust the surface wetting tension to 30 mN / m or more while maintaining the coating layer strength of the primer layer 2 to be high to some extent.
- the primer layer 2 is formed so that the resin content is 90% by weight or more, the surface wetting tension of the primer layer 2 can be easily adjusted.
- the resin component referred to in this example includes a cured product of a curable resin and a thermoplastic resin.
- the cured product in this example refers to curing of a polymerization initiator, a polymerization accelerator (such as an ultraviolet sensitizer), and a curing agent necessary for curing the curable resin together with a curable resin as a curing main agent. It is used in the concept including auxiliary agents.
- the resin component constituting the primer layer 2 includes at least a cured product of a curable resin.
- the primer layer 2 is formed including the cured product of the curable resin, it is easy to adjust the surface wetting tension to a predetermined value or more compared to the case where the primer layer 2 is formed only by the thermoplastic resin without including the primer layer 2. .
- curable resins examples include polyester resins, acrylic resins, acrylic urethane resins, urethane resins, epoxy resins, polycarbonate resins, melamine resins, phenol resins, silicone resins, acrylate resins (polyester acrylate resins). Resin (polyurethane acrylate resin, epoxy acrylate resin, etc.), etc., such as resin (thermosetting resin, ionizing radiation curable resin) capable of forming a cured product (cured film) by heat or ionizing radiation. A curable resin can also be used. Among these, an ionizing radiation curable resin is preferable from the viewpoint of improving the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3 and capable of forming a cured product having excellent surface hardness.
- ionizing radiation curable resin those which are cross-linked and cured by irradiation with ionizing radiation (ultraviolet rays or electron beams) are used.
- ionizing radiation ultraviolet rays or electron beams
- photocationically polymerizable resin examples include epoxy resins such as bisphenol epoxy resins, novolac epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins, and vinyl ether resins.
- Examples of the photopolymerizable prepolymer include polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, and melamine (meth) acrylate ( And (meth) acrylates.
- photopolymerizable monomer examples include styrene monomers such as styrene and ⁇ -methylstyrene, (meth) acrylates such as methyl (meth) acrylate and butyl (meth) acrylate, and unsaturated carboxylic acids such as (meth) acrylamide.
- Substituted amino alcohol esters of unsaturated acids such as acid amides, (meth) acrylic acid-2- (N, N-diethylamino) ethyl, (meth) acrylic acid-2- (N, N-dibenzylamino) ethyl, Ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, isocyanuric acid triacrylate (eg, tris- (2-hydroxyethyl) -isocyanuric acid ester (meth) acrylate), 3 -Phenoxy- -In polyfunctional compounds such as propanoyl acrylate, 1,6-bis (3-acryloxy-2-hydroxypropyl) -hexyl ether, and in molecules such as trimethylolpropane trithioglycolate, pentaerythritol tetrathioglycolate Examples include poly
- the ionizing radiation curable resin is a curing aid such as a photopolymerization initiator or an ultraviolet sensitizer when cured by ultraviolet irradiation. It is preferable to contain an agent.
- Photopolymerization initiators include photo radical polymerization initiators such as acetophenones, benzophenones, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, ⁇ -acyloxime esters, thioxanthones, onium salts, sulfonate esters, organometallics
- photocationic polymerization initiators such as complexes.
- Examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
- an ionizing radiation curable organic-inorganic hybrid resin from the viewpoint of further improving the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3.
- ionizing radiation curable organic-inorganic hybrid resins are organic and inorganic. The mixture is intimately mixed, and the dispersion state is at or close to the molecular level. By irradiation with ionizing radiation, the inorganic component and the organic component react to form a film.
- Examples of the inorganic component in the organic-inorganic hybrid resin include metal oxides such as silica and titania, and silica is preferable.
- silica examples include reactive silica in which a photosensitive group having photopolymerization reactivity is introduced on the surface.
- the groups represented by the following general formulas (1) and (2), hydrolyzable silyl group, and polymerizable unsaturated group are included in the molecule.
- bonded through the silyloxy group by the hydrolysis reaction of a hydrolyzable silyl group can be used.
- X is selected from NH, an oxygen atom and a sulfur atom
- Y is selected from an oxygen atom and a sulfur atom.
- X is an oxygen atom
- Y is a sulfur atom.
- hydrolyzable silyl groups include carboxylylate silyl groups such as alkoxylyl groups and acetoxysilyl groups, halogenated silyl groups such as chlorosilyl groups, aminosilyl groups, oxime silyl groups, and hydridosilyl groups.
- the polymerizable unsaturated group include acryloyloxy group, methacryloyloxy group, vinyl group, propenyl group, butadienyl group, styryl group, ethynyl group, cinnamoyl group, malate group, and acrylamide group.
- reactive silica those having an average particle diameter of preferably 1 nm or more, preferably 100 nm or less, more preferably 10 nm or less are used. By using reactive silica having an average particle diameter in a predetermined range, it is easy to maintain transparency when the primer layer 2 is formed.
- the content of the inorganic component in the organic-inorganic hybrid resin is preferably 10% by weight or more, more preferably 20% by weight, preferably 65% by weight or less, more preferably 40% by weight or less.
- the organic component in the organic-inorganic hybrid resin is a compound having a polymerizable unsaturated group polymerizable with the inorganic component (preferably reactive silica) (for example, having two or more polymerizable unsaturated groups in the molecule). And polyunsaturated organic compounds or unit price unsaturated organic compounds having one polymerizable unsaturated group in the molecule).
- polyunsaturated organic compound examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, glycerol tri (meth) acrylate, and 1,4-butanediol di (meth) acrylate.
- Examples of monounsaturated organic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) ) Acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-ethoxy
- the resin component constituting the primer layer 2 preferably further includes a thermoplastic resin together with a cured product of the curable resin.
- a thermoplastic resin in the resin component constituting the primer layer 2, the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3 can be made more than when the primer layer 2 is formed only by a cured product of a curable resin. It can be made even better.
- the thermoplastic resin include cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, polypropylene resin, polyamide resin, polyimide resin, and fluorine resin. Among these, it is preferable to use a thermoplastic resin having a glass transition temperature of 70 ° C. or less from the viewpoint of improving the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3.
- the weight ratio between the two is preferably 50 wt% to 90 wt% and the latter is 10 wt%. % To 50% by weight, more preferably 60% to 80% by weight for the former and 20% to 40% by weight for the latter. By setting it as such a weight ratio, while making it easy to make adhesiveness with time easy, it can prevent that the intensity
- the resin component constituting the primer layer 2 may be composed only of a resin having a hydrophilic group, or may be composed of a mixture of a resin having no hydrophilic group and a resin having a hydrophilic group. Moreover, you may comprise with what mixed the particle
- examples of the hydrophilic group herein include at least polyalkylene oxide, hydroxyl group, carboxyl group, sulfonyl group, phosphate, amino group, isocyanate group, glycidyl group, alkoxysilyl group, ammonium salt, various metal salts, and the like. 1 type or more is mentioned. By setting it as such a structure, it becomes easy to adjust the wetting tension on the surface of a primer layer more than predetermined value.
- the primer layer 2 preferably contains particles together with the resin component. By including particles in the primer layer 2, the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3 can be made better. In particular, when the cured layer of the organic-inorganic hybrid resin is included in the primer layer 2, when the organic-inorganic hybrid resin is cured, the primer layer 2 has an effect of pushing up the particles to the surface of the primer layer 2. can do.
- the particles include inorganic particles (for example, silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide, etc.) and resin particles (for example, acrylic resin particles, silicone resin). Particles, nylon resin particles, styrene resin particles, polyethylene resin particles, benzoguanamine resin particles, urethane resin particles, etc.).
- inorganic particles for example, silica, alumina, talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium dioxide, zirconium oxide, etc.
- resin particles for example, acrylic resin particles, silicone resin.
- the average particle diameter of the particles is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less.
- the average particle diameter By setting the average particle diameter to 3 ⁇ m or more, the temporal adhesion between the transparent substrate 1 and the transparent conductive film 3 can be made better.
- the thickness By setting the thickness to 10 ⁇ m or less, it is possible to prevent a decrease in transparency.
- the average particle diameter in this case means what was calculated by the Coulter counter method.
- the particles having an average particle diameter of preferably 3 ⁇ m or more and 10 ⁇ m or less are preferably contained in an amount of 0.02 parts by weight or more and 1 part by weight or less with respect to 100 parts by weight of the resin in the primer layer 2, more preferably 0 0.03 parts by weight or more and 0.5 parts by weight or less.
- the refractive index of the primer layer 2 is preferably adjusted so that the difference from the transparent conductive film 3 is within 0.05.
- the pattern can be made inconspicuous when the transparent conductive film 3 is patterned by etching.
- the primer layer 2 contains low refractive index fine particles.
- the low refractive index fine particles preferably have an average particle diameter of 1 nm or more and 200 nm or less from the viewpoints of particle aggregation prevention and transparency.
- the average particle diameter in this case means what was calculated by the dynamic light scattering method.
- low refractive index fine particles examples include magnesium fluoride, silsesquioxane, silica, polystyrene, calcium fluoride, cryolite and the like.
- these low refractive index fine particles those having a hollow structure or mesoporous structure are preferred in that they have a lower refractive index.
- Such low refractive index fine particles are preferably contained in an amount of 0.5 to 700 parts by weight with respect to 100 parts by weight of the resin content in the primer layer 2.
- the primer layer 2 of this example does not contain excessive leveling agents (silicone type, fluorine type, acrylic type, etc.).
- leveling agent silicone type, fluorine type, acrylic type, etc.
- the thickness of the primer layer 2 is not particularly limited and can be adjusted depending on the particles used. For example, when the primer layer 2 contains particles having an average particle diameter of 3 ⁇ m or more and 10 ⁇ m or less, the thickness of the primer layer 2 is usually about 2 ⁇ m or more and 9 ⁇ m or less. In addition, when the primer layer 2 includes low refractive index fine particles having an average particle diameter of 1 nm or more and 200 nm or less, the thickness of the primer layer 2 in the case of not having a high refractive index layer described later is usually about 0.5 ⁇ m or more and 3 ⁇ m or less. The thickness of the primer layer 2 in the case of having a high refractive index layer to be described later is usually about 10 nm to 100 nm.
- An overcoat layer for protecting the conductive film 3 may be provided on the transparent conductive film 3.
- the overcoat layer may be a resin film formed from various resins or an inorganic film formed from an inorganic substance.
- a high refractive index layer may be provided between the transparent substrate 1 and the primer layer 3.
- the refractive index of the high refractive index layer is preferably about 0.2 to 0.3 higher than the refractive index of the primer layer 2.
- the high refractive index layer is formed from a binder resin and high refractive index fine particles.
- the binder resin the same resin as that of the primer layer 2 can be used.
- the high refractive index fine particles preferably have an average particle diameter of 1 nm or more and 200 nm or less from the viewpoints of particle aggregation prevention and transparency.
- the average particle diameter in this case means what was calculated by the dynamic light scattering method.
- the high refractive index fine particles preferably have a refractive index of 1.6 or more, and examples thereof include oxide particles selected from titanium, aluminum, cerium, yttrium, zirconium, niobium, and antimony. Such high refractive index fine particles are preferably contained in an amount of 5 to 300 parts by weight with respect to 100 parts by weight of the binder resin in the high refractive index layer.
- the thickness of the high refractive index layer is preferably 10 nm or more and 100 nm or less.
- the transparent conductive film 3, the primer layer 2 and the high refractive index layer of this example are coated with a composition (coating liquid) containing each film and the resin component constituting each layer, dried, and irradiated with ionizing radiation as necessary. And can be formed by forming a coating film.
- the surface of the transparent conductive film 3 may be subjected to pressure treatment.
- pressure treatment By subjecting the surface of the transparent conductive film 3 to pressure treatment, the transparent conductive film 3 that has been made uneven by the metal nanowires protruding from the surface can be planarized.
- the pressure treatment include means for passing the substrate 4 with a transparent conductive film through a hot roll having an outer peripheral surface formed on a smooth surface or pressing the substrate 4 with a hot press having a pressure surface formed on a smooth surface.
- the substrate 4 with a transparent conductive film of this example can be used for various flat panel displays, transparent electrodes such as touch panels, antistatic layers, electromagnetic wave shielding layers, and the like.
- transparent electrodes such as touch panels, antistatic layers, electromagnetic wave shielding layers, and the like.
- touch panels include resistive touch panels and capacitive touch panels.
- a resistive touch panel has an upper electrode having a transparent conductive layer on one side of a transparent substrate, a lower electrode having a transparent conductive layer on one side of the transparent substrate, and a transparent conductive layer between the upper electrode and the lower electrode. It consists of a basic structure that is arranged with a spacer so as to face each other. In such a resistive film type touch panel, the above-mentioned substrate 4 with a transparent conductive film can be used as an upper electrode or a lower electrode.
- the capacitive touch panel can be divided into a surface type and a projected type.
- the surface mold has a basic configuration in which a transparent conductive film and a protective layer are provided on one surface of a substrate, and electrodes disposed at four corners.
- the substrate 4 with a transparent conductive film described above can be used as a substrate and a transparent conductive film that constitute such a surface-type capacitive touch panel.
- the projection type is a conductive element group formed along a second direction intersecting the X-axis trace, which is a conductive element group formed along a predetermined first direction on a transparent substrate.
- the basic configuration includes a Y-axis trace, an insulating layer disposed at least at the intersection of the X-axis trace and the Y-axis trace, and a connection wiring to an external lead-out line.
- the touch panel of the present invention is configured to have the above-described substrate 4 with a transparent conductive film on a transparent substrate in such a projected capacitive touch panel.
- a primer layer coating solution a having the following formulation was applied, dried and irradiated with ultraviolet rays to form a primer layer having a thickness of 3 ⁇ m.
- the wetting tension on the surface of the primer layer was 32 mN / m.
- the said transparent conductive layer coating liquid was apply
- Example 2 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the amount of the acrylic resin particles added to the primer layer coating liquid a was changed to 0.05 part.
- the wetting tension on the surface of the primer layer was 32 mN / m.
- Example 3 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution b.
- the wetting tension on the primer layer surface was 33 mN / m.
- Example 4 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution c. The wetting tension on the primer layer surface was 33 mN / m.
- Example 5 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution d.
- the wetting tension on the surface of the primer layer was 32 mN / m.
- Example 1 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution e.
- the wetting tension on the primer layer surface was 22.6 mN / m or less.
- Photopolymerizable prepolymer (beam set 575) 10 parts ⁇ Photopolymerizable monomer (polyethylene glycol diacrylate) 5 parts (component: polyethylene glycol diacrylate) (NK Ester A-1000: Shin-Nakamura Chemical Co., Ltd., 100% solid content) ⁇ Silicon-based leveling agent 0.02 parts (polyether-modified dimethylpolysiloxane) (BYK331: Big Chemie, solid content 100%) ⁇ Photopolymerization initiator (Irgacure 651) 0.5 part ⁇ Dilute solvent 23 parts
- Example 2 A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution f.
- the wetting tension on the primer layer surface was 22.6 mN / m or less.
- the substrates with a transparent conductive film of Examples 1 to 5 were excellent in initial adhesion and temporal adhesion of the transparent conductive film because the wetting tension on the surface of the primer layer was 30 mN / m or more.
- the substrate with a transparent conductive film in each of Examples 1, 2 and 4 was compared with Examples 3 and 5 in that an ionizing radiation curable resin (ionizing radiation curable organic-inorganic hybrid resin was used in the primer layer). Including) and a thermoplastic resin, the adhesion with time was extremely excellent.
- the substrates with a transparent conductive film of Examples 1 and 2 are particles having an average particle diameter in the range of 3 to 10 ⁇ m, together with ionizing radiation curable organic-inorganic hybrid resin and thermoplastic resin, as compared with Example 4.
- the adhesion over time was even better.
- the substrates with transparent conductive films of Comparative Examples 1 and 2 had a wetting tension on the primer layer surface of less than 30 mN / m. As a result, although the initial adhesion of the transparent conductive film was excellent, the adhesion over time was not satisfactory.
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Abstract
Description
本発明のタッチパネルは、本発明の透明導電膜付き基材を電極に用いて構成したことを特徴とする。 The substrate with a transparent conductive film of the present invention is obtained by laminating a transparent conductive film containing metal nanowires on a transparent substrate via a primer layer having a surface wetting tension of 30 mN / m or more as defined in JIS K6768: 1999. Features.
The touch panel of the present invention is characterized by using the substrate with a transparent conductive film of the present invention as an electrode.
(1)プライマー層を、硬化型樹脂の硬化物を含む樹脂分を含めて構成することができる。この場合、樹脂分の含有割合をプライマー層中の90重量%以上とすることができる。
(2)硬化型樹脂として、電離放射線硬化型樹脂を用いることができ、電離放射線硬化型樹脂として、電離放射線硬化型有機無機ハイブリッド樹脂を用いることができる。 The present invention includes the following aspects.
(1) A primer layer can be comprised including the resin part containing the hardened | cured material of curable resin. In this case, the resin content can be 90% by weight or more in the primer layer.
(2) An ionizing radiation curable resin can be used as the curable resin, and an ionizing radiation curable organic-inorganic hybrid resin can be used as the ionizing radiation curable resin.
(4)プライマー層を、樹脂分とともに、さらに粒子を含めて構成することもできる。この場合、平均粒子径が3μm以上10μm以下の粒子を用いることができる。また粒子の含有量を、樹脂分100重量部に対して、0.02重量部以上1重量部以下とすることができる。 (3) The resin component in the primer layer can further contain a thermoplastic resin together with a cured product of the curable resin. In this case, the content ratio in the resin component can be set to 50% by weight or more and 90% by weight or less of a cured curable resin, and from 10% to 50% by weight of a thermoplastic resin.
(4) A primer layer can also be comprised including particle | grains with a resin part. In this case, particles having an average particle diameter of 3 μm or more and 10 μm or less can be used. Moreover, content of particle | grains can be 0.02 weight part or more and 1 weight part or less with respect to 100 weight part of resin parts.
本発明のタッチパネルは、本発明の透明導電膜付き基材を電極に用いるので、安定した連続使用を実現することができる。 In the substrate with a transparent conductive film of the present invention, the primer layer having a wetting tension of a predetermined value or more is interposed between the transparent conductive film using the metal nanowire and the transparent substrate. Not only the initial adhesiveness but also the temporal adhesion can be improved.
Since the touchscreen of this invention uses the base material with a transparent conductive film of this invention for an electrode, it can implement | achieve the stable continuous use.
光重合開始剤としては、アセトフェノン類、ベンゾフェノン類、ミヒラーケトン、ベンゾイン、ベンジルメチルケタール、ベンゾイルベンゾエート、α-アシルオキシムエステル、チオキサンソン類などの光ラジカル重合開始剤や、オニウム塩類、スルホン酸エステル、有機金属錯体などの光カチオン重合開始剤が挙げられる。紫外線増感剤としては、n-ブチルアミン、トリエチルアミン、トリ-n-ブチルホスフィンなどが挙げられる。 In addition to the above-mentioned photocationic polymerizable resin, photopolymerizable prepolymer or photopolymerizable monomer, the ionizing radiation curable resin is a curing aid such as a photopolymerization initiator or an ultraviolet sensitizer when cured by ultraviolet irradiation. It is preferable to contain an agent.
Photopolymerization initiators include photo radical polymerization initiators such as acetophenones, benzophenones, Michler's ketone, benzoin, benzylmethyl ketal, benzoylbenzoate, α-acyloxime esters, thioxanthones, onium salts, sulfonate esters, organometallics Examples include photocationic polymerization initiators such as complexes. Examples of the ultraviolet sensitizer include n-butylamine, triethylamine, and tri-n-butylphosphine.
熱可塑性樹脂としては、セルロース系樹脂、アセタール系樹脂、ビニル系樹脂、ポリエチレン系樹脂、ポリスチレン系樹脂、ポリプロピレン系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、フッ素系樹脂などが挙げられる。これらの中でも、透明基材1と透明導電膜3の経時密着性をより良好にする観点から、ガラス転移温度が70℃以下の熱可塑性樹脂を用いることが好ましい。 The resin component constituting the
Examples of the thermoplastic resin include cellulose resin, acetal resin, vinyl resin, polyethylene resin, polystyrene resin, polypropylene resin, polyamide resin, polyimide resin, and fluorine resin. Among these, it is preferable to use a thermoplastic resin having a glass transition temperature of 70 ° C. or less from the viewpoint of improving the temporal adhesion between the
このような抵抗膜式タッチパネルにおいて、上部電極ないしは下部電極として、上述した透明導電膜付き基材4を用いることができる。 A resistive touch panel has an upper electrode having a transparent conductive layer on one side of a transparent substrate, a lower electrode having a transparent conductive layer on one side of the transparent substrate, and a transparent conductive layer between the upper electrode and the lower electrode. It consists of a basic structure that is arranged with a spacer so as to face each other.
In such a resistive film type touch panel, the above-mentioned
表面型は、基板の一方の面に透明導電膜、保護層を備え、さらに4隅に配置された電極を具備した基本構成からなっている。
このような表面型の静電容量式タッチパネルを構成する基板および透明導電膜として、上述した透明導電膜付き基材4を用いることができる。 The capacitive touch panel can be divided into a surface type and a projected type.
The surface mold has a basic configuration in which a transparent conductive film and a protective layer are provided on one surface of a substrate, and electrodes disposed at four corners.
The
本発明のタッチパネルは、このような投影型の静電容量式タッチパネルにおいて、透明基板上に、上述した透明導電膜付き基材4を有するように構成する。 The projection type is a conductive element group formed along a second direction intersecting the X-axis trace, which is a conductive element group formed along a predetermined first direction on a transparent substrate. The basic configuration includes a Y-axis trace, an insulating layer disposed at least at the intersection of the X-axis trace and the Y-axis trace, and a connection wiring to an external lead-out line.
The touch panel of the present invention is configured to have the above-described
金属ナノワイヤとして、論文「Materials Chemistry and Physics vol.114 p333-338 “Preparation of Ag nanorodswith high yield by polyol process”」に準じて作製した銀ナノワイヤを用いた。この銀ナノワイヤは、短径側の平均径が50nm、アスペクト比が約100である。
次に、IPAを分散媒として銀ナノワイヤを3.0%で分散した分散液を作製した。次に、シリコーン樹脂(三菱化学社:MS51)28.53部をIPA53.82部に溶解し、母液を作製した。次に、母液に分散液15.0質量部加えてよく混合した後、0.1H硝酸を2.65部加えてよく混合し、25℃の恒温雰囲気下で1時間撹拌混合し、銀ナノワイヤを3%含む固形分15%の透明導電膜用塗布液を調製した。 1. Preparation of Coating Solution for Transparent Conductive Film Silver nanowires prepared according to the paper “Materials Chemistry and Physics vol. 114 p333-338“ Preparation of Ag nanorods with high yield by polyol process ”” were used as metal nanowires. This silver nanowire has an average diameter on the short side of 50 nm and an aspect ratio of about 100.
Next, a dispersion liquid in which silver nanowires were dispersed at 3.0% using IPA as a dispersion medium was prepared. Next, 28.53 parts of a silicone resin (Mitsubishi Chemical Corporation: MS51) was dissolved in 53.82 parts of IPA to prepare a mother liquor. Next, 15.0 parts by mass of the dispersion was added to the mother liquor and mixed well, then 2.65 parts of 0.1H nitric acid was added and mixed well, and the mixture was stirred and mixed in a constant temperature atmosphere at 25 ° C. for 1 hour. A coating solution for transparent conductive film having a solid content of 15% containing 3% was prepared.
[実施例1]
厚み125μmの透明ポリエステルフィルム(コスモシャインA4350:東洋紡績社)の一方の面に、下記処方のプライマー層塗布液aを塗布、乾燥、紫外線照射し、厚み3μmのプライマー層を形成した。プライマー層表面のぬれ張力は32mN/mであった。次いで、プライマー層上に、上記透明導電層塗布液を塗布、乾燥し、厚み0.3μmの透明導電膜を形成し、透明導電膜付き基材を得た。 2. Preparation of substrate with transparent conductive film [Example 1]
On one surface of a 125 μm thick transparent polyester film (Cosmo Shine A4350: Toyobo Co., Ltd.), a primer layer coating solution a having the following formulation was applied, dried and irradiated with ultraviolet rays to form a primer layer having a thickness of 3 μm. The wetting tension on the surface of the primer layer was 32 mN / m. Subsequently, the said transparent conductive layer coating liquid was apply | coated and dried on the primer layer, the 0.3-micrometer-thick transparent conductive film was formed, and the base material with a transparent conductive film was obtained.
・光重合性プレポリマー 140部
(電離放射線硬化型有機無機ハイブリッド樹脂)
(デソライト7503:JSR社、固形分50%、無機成分38%)
・熱可塑性樹脂 70部
(アクリディックA166:DIC社、固形分45%、ガラス転移温度49℃)
・光重合開始剤 2.2部
(イルガキュア651:チバ・ジャパン社)
・アクリル樹脂粒子 0.25部
(平均粒子径:5.8μm、変動係数7.8%)
・希釈溶剤 230部 <Primer layer coating solution a>
・ 140 parts of photopolymerizable prepolymer (ionizing radiation curable organic-inorganic hybrid resin)
(Desolite 7503: JSR Corporation, solid content 50%, inorganic component 38%)
70 parts of thermoplastic resin (Acridic A166: DIC, solid content 45%, glass transition temperature 49 ° C.)
-Photopolymerization initiator 2.2 parts (Irgacure 651: Ciba Japan)
-0.25 parts of acrylic resin particles (average particle size: 5.8 μm, coefficient of variation 7.8%)
・ 230 parts of diluted solvent
プライマー層塗布液aのアクリル樹脂粒子の添加量を0.05部に変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は32mN/mであった。 [Example 2]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the amount of the acrylic resin particles added to the primer layer coating liquid a was changed to 0.05 part. The wetting tension on the surface of the primer layer was 32 mN / m.
プライマー層塗布液aを下記のプライマー層塗布液bに変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は33mN/mであった。 [Example 3]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution b. The wetting tension on the primer layer surface was 33 mN / m.
・光重合性プレポリマー(電離放射線硬化型樹脂) 17部
(ビームセット575:荒川化学工業社、固形分100%)
・光重合性モノマー(イソシアヌル酸トリアクリレート) 3部
(NKエステルA9300:新中村化学工業社、固形分100%)
・光重合開始剤(イルガキュア651) 0.4部
・希釈溶剤 30部 <Primer layer coating solution b>
17 parts of photopolymerizable prepolymer (ionizing radiation curable resin) (beam set 575: Arakawa Chemical Industries, solid content 100%)
Photopolymerizable monomer (isocyanuric acid triacrylate) 3 parts (NK ester A9300: Shin-Nakamura Chemical Co., Ltd., solid content 100%)
-Photopolymerization initiator (Irgacure 651) 0.4 part-Diluting solvent 30 parts
プライマー層塗布液aを下記のプライマー層塗布液cに変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は33mN/mであった。 [Example 4]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution c. The wetting tension on the primer layer surface was 33 mN / m.
・光重合性プレポリマー(ビームセット575) 35部
・熱可塑性樹脂(アクリディックA166) 35部
・光重合開始剤(イルガキュア651) 1部
・希釈溶剤 120部 <Primer layer coating solution c>
・ 35 parts of photopolymerizable prepolymer (beam set 575) 35 parts of thermoplastic resin (Acridic A166) 1 part of photopolymerization initiator (Irgacure 651) 120 parts of diluting solvent
プライマー層塗布液aを下記のプライマー層塗布液dに変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は32mN/mであった。 [Example 5]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution d. The wetting tension on the surface of the primer layer was 32 mN / m.
・光重合性プレポリマー(デソライト7503) 68部
・光重合開始剤(イルガキュア651) 2部
・希釈溶剤 72部 <Primer layer coating solution d>
・ 68 parts of photopolymerizable prepolymer (Desolite 7503) 2 parts of photopolymerization initiator (Irgacure 651) 72 parts of diluting solvent
プライマー層塗布液aを下記のプライマー層塗布液eに変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は22.6mN/m以下であった。 [Comparative Example 1]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution e. The wetting tension on the primer layer surface was 22.6 mN / m or less.
・光重合性プレポリマー(ビームセット575) 10部
・光重合性モノマー(ポリエチレングリコールジアクリレート) 5部
(成分:ポリエチレングリコールジアクリレート)
(NKエステルA-1000:新中村化学工業社、固形分100%)
・シリコーン系レベリング剤 0.02部
(ポリエーテル変性ジメチルポリシロキサン)
(BYK331:ビックケミー社、固形分100%)
・光重合開始剤(イルガキュア651) 0.5部
・希釈溶剤 23部 <Primer layer coating solution e>
・ Photopolymerizable prepolymer (beam set 575) 10 parts ・ Photopolymerizable monomer (polyethylene glycol diacrylate) 5 parts (component: polyethylene glycol diacrylate)
(NK Ester A-1000: Shin-Nakamura Chemical Co., Ltd., 100% solid content)
・ Silicon-based leveling agent 0.02 parts (polyether-modified dimethylpolysiloxane)
(BYK331: Big Chemie, solid content 100%)
・ Photopolymerization initiator (Irgacure 651) 0.5 part ・ Dilute solvent 23 parts
プライマー層塗布液aを下記のプライマー層塗布液fに変更した以外は、実施例1と同様にして透明導電膜付き基材を得た。プライマー層表面のぬれ張力は22.6mN/m以下であった。 [Comparative Example 2]
A substrate with a transparent conductive film was obtained in the same manner as in Example 1 except that the primer layer coating solution a was changed to the following primer layer coating solution f. The wetting tension on the primer layer surface was 22.6 mN / m or less.
・光重合性プレポリマーとレベリング剤の混合物 15部
(ユニディック17-824-9:DIC社、固形分80%)
・光重合開始剤(イルガキュア651) 0.4部
・希釈溶剤 30部 <Primer layer coating solution f>
15 parts of photopolymerizable prepolymer and leveling agent (Unidic 17-824-9: DIC, solid content 80%)
-Photopolymerization initiator (Irgacure 651) 0.4 part-Diluting solvent 30 parts
各例により得られた透明導電膜付き基材について、JIS K5400:1990における碁盤目テープ法に基づき、初期密着性および経時密着性を評価した。その結果、透明導電膜が全く剥離しなかったものを「◎」、10%未満の面積が剥離したものを「○」、ほぼ100%の面積が剥離したものを「×」とした。結果を表1に示す。
なお、経時密着性については、各例により得られた透明導電膜付き基材を、60℃,90%RHの条件で500時間放置した後に評価を行った。 3. Evaluation of Adhesiveness For the substrate with a transparent conductive film obtained in each example, initial adhesiveness and temporal adhesiveness were evaluated based on the cross-cut tape method in JIS K5400: 1990. As a result, the case where the transparent conductive film was not peeled at all was designated as “◎”, the case where less than 10% of the area was peeled off was designated as “◯”, and the case where the nearly 100% area was peeled off was designated as “x”. The results are shown in Table 1.
In addition, about time-dependent adhesiveness, the base material with a transparent conductive film obtained by each example was evaluated after leaving to stand on condition of 60 degreeC and 90% RH for 500 hours.
Claims (10)
- JIS K6768:1999で規定する表面のぬれ張力が30mN/m以上のプライマー層を介して、金属ナノワイヤを含む透明導電膜を透明基材に積層した透明導電膜付き基材。 JIS K6768: A substrate with a transparent conductive film in which a transparent conductive film containing metal nanowires is laminated on a transparent substrate through a primer layer having a surface wetting tension of 30 mN / m or more as defined in 1999.
- 請求項1記載の透明導電膜付き基材において、前記プライマー層は、硬化型樹脂の硬化物を含む樹脂分を含んで構成されていることを特徴とする透明導電膜付き基材。 2. The substrate with a transparent conductive film according to claim 1, wherein the primer layer includes a resin component containing a cured product of a curable resin.
- 請求項2記載の透明導電膜付き基材において、前記硬化型樹脂として、電離放射線硬化型樹脂を用いたことを特徴とする透明導電膜付き基材。 3. The substrate with a transparent conductive film according to claim 2, wherein an ionizing radiation curable resin is used as the curable resin.
- 請求項3記載の透明導電膜付き基材において、前記電離放射線硬化型樹脂として、電離放射線硬化型有機無機ハイブリッド樹脂を用いたことを特徴とする透明導電膜付き基材。 4. The substrate with a transparent conductive film according to claim 3, wherein an ionizing radiation curable organic-inorganic hybrid resin is used as the ionizing radiation curable resin.
- 請求項2~4の何れかに記載の透明導電膜付き基材において、前記樹脂分は、さらに熱可塑性樹脂を含むことを特徴とする透明導電膜付き基材。 5. The substrate with a transparent conductive film according to claim 2, wherein the resin component further contains a thermoplastic resin.
- 請求項5記載の透明導電膜付き基材において、前記樹脂分中での含有割合が、硬化型樹脂の硬化物:50重量%以上90重量%以下、熱可塑性樹脂:10重量%以上50重量%以下であることを特徴とする透明導電膜付き基材。 6. The substrate with a transparent conductive film according to claim 5, wherein a content ratio in the resin component is a cured product of a curable resin: 50% by weight to 90% by weight, and a thermoplastic resin: 10% by weight to 50% by weight. The base material with a transparent conductive film characterized by being the following.
- 請求項2~6の何れかに記載の透明導電膜付き基材において、前記プライマー層は、さらに、平均粒子径が3μm以上10μm以下の粒子を含んで構成されていることを特徴とする透明導電膜付き基材。 7. The substrate with a transparent conductive film according to claim 2, wherein the primer layer further comprises particles having an average particle diameter of 3 μm or more and 10 μm or less. Substrate with film.
- 請求項7記載の透明導電膜付き基材において、前記樹脂分100重量部に対する含有量が、粒子:0.02重量部以上1重量部以下であることを特徴とする透明導電膜付き基材。 8. The substrate with a transparent conductive film according to claim 7, wherein the content with respect to 100 parts by weight of the resin is particles: 0.02 part by weight or more and 1 part by weight or less.
- 請求項2~8の何れかに記載の透明導電膜付き基材において、前記プライマー層は、さらに、平均粒子径が1nm以上200nm以下の低屈折率微粒子を含んで構成されていることを特徴とする透明導電膜付き基材。 9. The substrate with a transparent conductive film according to claim 2, wherein the primer layer further comprises low refractive index fine particles having an average particle diameter of 1 nm to 200 nm. A substrate with a transparent conductive film.
- 請求項1~9の何れかに記載の透明導電膜付き基材を電極に用いて構成したタッチパネル。 A touch panel comprising the substrate with a transparent conductive film according to any one of claims 1 to 9 as an electrode.
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Also Published As
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JPWO2013115310A1 (en) | 2015-05-11 |
JP6087298B2 (en) | 2017-03-01 |
KR20150009950A (en) | 2015-01-27 |
CN104093561A (en) | 2014-10-08 |
JP6243983B2 (en) | 2017-12-06 |
JP2017013512A (en) | 2017-01-19 |
TW201345706A (en) | 2013-11-16 |
KR102021630B1 (en) | 2019-09-16 |
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