WO2017213043A1 - Film conducteur transparent et écran tactile - Google Patents

Film conducteur transparent et écran tactile Download PDF

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Publication number
WO2017213043A1
WO2017213043A1 PCT/JP2017/020596 JP2017020596W WO2017213043A1 WO 2017213043 A1 WO2017213043 A1 WO 2017213043A1 JP 2017020596 W JP2017020596 W JP 2017020596W WO 2017213043 A1 WO2017213043 A1 WO 2017213043A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive film
film
resin layer
transparent
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PCT/JP2017/020596
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English (en)
Japanese (ja)
Inventor
圭祐 松本
金谷　実
智剛 梨木
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2016221744A external-priority patent/JP6796460B2/ja
Priority claimed from JP2016248125A external-priority patent/JP6789801B2/ja
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020187031335A priority Critical patent/KR102432417B1/ko
Priority to CN201780035711.4A priority patent/CN109313963B/zh
Publication of WO2017213043A1 publication Critical patent/WO2017213043A1/fr

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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
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • 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

Definitions

  • the present invention relates to a transparent conductive film and a touch panel.
  • a transparent electrode made of a transparent conductive layer such as indium-tin composite oxide (ITO) is used.
  • the conductor with a transparent electrode used for touch panels basically uses glass or plastic film as a substrate, but smartphones and tablets that require portability use plastic film from the viewpoint of thinness and weight.
  • a transparent conductive film is preferably used.
  • Patent Document 1 a transparent conductive film having a transparent conductive film patterned on at least one cured resin layer on one surface of a transparent resin film has been proposed.
  • An object of the present invention is to provide a transparent conductive film having excellent moisture and heat resistance and a touch panel provided with the transparent conductive film.
  • the inventors of the present application have found that when a transparent conductive film patterned with a transparent conductive film is placed in a high temperature and high humidity environment, the transparent resin film expands due to moisture absorption. It was found that the transparent conductive film could not follow the expansion and cracks in the transparent conductive film were generated.
  • the inventors of the present application have further studied and found that the object can be achieved by adopting the following configuration, and have completed the present invention.
  • the present invention is a transparent conductive film having a cured resin layer and a transparent conductive film in this order on a transparent resin film
  • the cured resin layer is a cured product film obtained by curing a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more, The thickness of the cured resin layer is 150 nm or less,
  • the cured resin layer has a surface elastic modulus of 4 GPa or more and 12 GPa or less.
  • a cured resin layer is formed using a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more, and the surface elastic modulus of the cured resin layer is 4 GPa or more and 12 GPa or less. And a cured product film having a three-dimensional crosslinked structure can be formed, and the film strength of the cured resin layer is high. Thereby, the water resistance and expansion resistance of the cured resin layer can be improved, and as a result, the moisture and heat resistance of the transparent conductive film when the transparent conductive film is patterned can be improved.
  • the weight average molecular weight of the epoxy resin is less than 1500 or the surface elastic modulus of the cured resin layer is less than 4 GPa, the film strength of the cured resin layer becomes insufficient, and the moisture and heat resistance of the transparent conductive film decreases. There is a risk.
  • the surface elastic modulus of the cured resin layer exceeds 12 GPa, the flexibility of the cured resin layer is lowered, and there is a possibility that whitening or cracking may occur when the transparent conductive film is bent.
  • the gelation time when the mixture of the resin composition and the epoxy resin curing accelerator is heated at 170 ° C. is 50 seconds or less.
  • the gelation time is generally an indicator of the reactivity of the target composition or the like, particularly the curing reactivity, and the shorter the gelling time, the higher the curing reactivity.
  • the curing accelerator contains antimony. Since the curing accelerator containing antimony has high reactivity, the curing reaction of the resin composition can be advanced rapidly and sufficiently, and a stronger cured product film can be efficiently formed.
  • the epoxy resin is a rubber-modified epoxy resin. Thereby, toughness and impact resistance can be suitably imparted to the cured resin layer.
  • the saturation expansion coefficient of the cured resin layer in an atmosphere of 85 ° C. and 85% humidity is 0.5% or less.
  • the transparent conductive film is patterned, and the change rate of the surface resistance value before and after the transparent conductive film is placed in an atmosphere at a temperature of 85 ° C. and a humidity of 85% for 240 hours is preferably 1.5 or less. .
  • the present invention also relates to a touch panel including the transparent conductive film. Since the said touch panel uses the transparent conductive film with high heat-and-moisture resistance, it can exhibit the outstanding durability and a weather resistance.
  • FIG. 1 is a cross-sectional view showing an example of the transparent conductive film of the present embodiment.
  • the transparent conductive film in FIG. 1 has a transparent conductive film 3 on one side of a transparent resin film 1 with a cured resin layer 2 interposed therebetween.
  • the transparent conductive film 3 is patterned.
  • the patterning of the transparent conductive film 3 is indicated by having a pattern part a having the transparent conductive film 3 and a non-pattern part b not having the transparent conductive film 3.
  • the non-pattern part b has the cured resin layer 2.
  • the transparent resin film 1 is not particularly limited, but various plastic films having transparency are used.
  • the materials include polyester resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, polycycloolefin resin, (meth) acrylic resin, poly Examples thereof include a vinyl chloride resin, a polyvinylidene chloride resin, a polystyrene resin, a polyvinyl alcohol resin, a polyarylate resin, and a polyphenylene sulfide resin. Of these, polyester resins, polycarbonate resins, and polyolefin resins are particularly preferable.
  • the thickness of the transparent resin film 1 is not particularly limited, it may be in the range of 5 ⁇ m to 200 ⁇ m, may be in the range of 20 ⁇ m to 130 ⁇ m, and may be in the range of 40 ⁇ m to 130 ⁇ m. .
  • the thicker the transparent resin film 1, the higher the hygroscopicity and the easier the expansion but by adopting the following specific cured resin layer, the transparent conductive film of the transparent conductive film can be used even if the transparent resin film has a thickness in the above range. Cracks can be prevented and the desired electrical characteristics can be exhibited.
  • the transparent resin film 1 is subjected to etching or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. on the surface in advance, and the cured resin layer 2 provided thereon You may make it improve the adhesiveness with respect to the transparent resin film 1.
  • etching or undercoating treatment such as sputtering, corona discharge, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc.
  • the cured resin layer 2 is a cured product film obtained by curing a resin composition containing an epoxy resin having a weight average molecular weight of 1500 or more (hereinafter also referred to as “high molecular weight epoxy resin” for convenience).
  • the high molecular weight epoxy resin is preferably the main component of the resin composition.
  • the main component means a component having the maximum content among the components contained in the resin composition, and the content is preferably 20% by weight or more, and 40% by weight or more based on the total amount of the resin composition. More preferred.
  • the high molecular weight epoxy resin those generally used can be used, and one or more epoxy groups such as a glycidyl group, an alicyclic epoxy group, and an aliphatic epoxy group are preferably included in the molecule.
  • one or more epoxy groups such as a glycidyl group, an alicyclic epoxy group, and an aliphatic epoxy group are preferably included in the molecule.
  • epichlorohydrin-bisphenol A type epoxy resin epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, phenol novolac type epoxy resin, water Bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid-glycidyl ether ester type epoxy resin, III-aminophenol type epoxy resin, diamino Diphenylmethane epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanur Epoxy resins such as glycidyl ethers of polyhydric alcohols such as silicate, polyalkylene glycol diglycidyl ether,
  • the high molecular weight epoxy resin a hydrogenated bisphenol A type epoxy resin or a hydrogenated bisphenol F type epoxy resin having a weight average molecular weight of 1500 or more is preferable from the viewpoint of the strength, flexibility, and weather resistance of the resulting cured film. .
  • an epoxy resin having a weight average molecular weight of less than 1500 (hereinafter, also referred to as “low molecular weight epoxy resin” for convenience) among the above listed epoxy resins can be used.
  • an alicyclic epoxy resin is preferable.
  • the alicyclic epoxy resin known ones can be suitably used.
  • a low molecular weight epoxy resin may be used independently and may use 2 or more types together.
  • the weight average molecular weight of the high molecular weight epoxy resin may be 1500 or more, preferably 1700 or more, and more preferably 1800 or more.
  • the upper limit of the weight average molecular weight is preferably 5000, more preferably 2000, from the viewpoint of suppressing embrittlement due to excessive curing of the resulting cured resin layer.
  • the weight average molecular weight is a value measured by GPC (gel permeation chromatography, HLC-8320 GPC manufactured by TOSOH) and calculated in terms of polystyrene.
  • the measurement conditions are as follows. Column: SHODEX GPC KF-802.5 / GPC KF-G, column size: 6.0 mm inner diameter ⁇ 150 mm, solvent: tetrahydrofuran (THF), solution concentration: 0.05 wt%, flow rate: 1 mL / min, detector: differential Refractometer (RI), column temperature: 40 ° C., injection amount: 2 mL
  • the high molecular weight epoxy resin is preferably a rubber-modified epoxy resin.
  • the rubber component for modifying the epoxy resin is not particularly limited. Butadiene rubber, acrylonitrile butadiene rubber, styrene butadiene rubber, butyl rubber, nitrile rubber, natural rubber, isoprene rubber, chloroprene rubber, ethylene-propylene rubber, urethane rubber, silicone Examples thereof include rubber, fluororubber, ethylene-vinyl acetate rubber, epichlorohydrin rubber and the like. Of these, butadiene rubber is preferable in terms of toughness and chemical resistance.
  • the rubber-modified epoxy resin may be used alone or in combination of two or more.
  • a conventionally known method can be adopted as a method for preparing the rubber-modified epoxy resin. For example, a carboxyl group is introduced into the terminal of the polymer main chain of the rubber component, and this carboxyl group and the epoxy group of the epoxy resin are converted into a phosphorus catalyst And a method of reacting in the presence of a catalyst such as an amine catalyst.
  • the resin composition preferably contains a curing accelerator.
  • a curing accelerator is not particularly limited, and examples thereof include organic metal salts of organic acids such as octanoic acid, stearic acid, acetylacetonate, naphthenic acid and salicylic acid, such as zinc, copper, iron and antimony; metal chelates and the like.
  • a hardening accelerator contains antimony.
  • the antimony-containing curing accelerator can rapidly and sufficiently advance the curing reaction of the resin composition and can efficiently form a stronger cured product film.
  • a hardening accelerator can be used individually or in combination of 2 or more types.
  • the content of the curing accelerator is not particularly limited, but is preferably 0.005 to 5 parts by weight, more preferably 0 with respect to the total amount (100 parts by weight) of the epoxy group-containing compound contained in the resin composition. 0.01 to 4 parts by weight, more preferably 0.01 to 1 part by weight. If the content of the curing accelerator is below the lower limit, the curing acceleration effect may be insufficient. On the other hand, when content of a hardening accelerator exceeds the said upper limit, hardened
  • the gelation time when the mixture of the resin composition and the epoxy resin curing accelerator is heated at 170 ° C. is preferably 50 seconds or shorter, and more preferably 20 seconds or shorter.
  • the gelation time of the resin composition to which the curing accelerator is added is preferably 50 seconds or less, the curing reaction of the resin composition can be rapidly and sufficiently advanced to form a stronger cured product film.
  • the gelation time is preferably short, it is preferably 10 seconds or longer from the viewpoint of the stability and handling properties of the mixture.
  • an acrylic resin, a urethane resin, an amide resin, a silicone resin, or the like may be appropriately added to the resin composition.
  • various additives can also be added to the resin composition.
  • a leveling agent, a pigment, a filler, a dispersant, a plasticizer, an ultraviolet absorber, a surfactant, an antioxidant, a thixotropic agent, and the like can be used.
  • the surface elastic modulus of the cured resin layer may be 4 GPa or more and 12 GPa or less. Furthermore, the surface elastic modulus is preferably 4.5 GPa or more, and more preferably 5 GPa or more. The surface elastic modulus is preferably 10 GPa or less, and more preferably 9 GPa or less.
  • the surface elastic modulus of the cured resin layer is less than the above lower limit, the film strength of the cured resin layer becomes insufficient, and the heat and moisture resistance of the transparent conductive film may be lowered.
  • the surface elastic modulus of the cured resin layer exceeds the above upper limit, the flexibility of the cured resin layer is lowered, and whitening or cracking may occur when the transparent conductive film is folded.
  • the saturation expansion coefficient of the cured resin layer in an atmosphere of 85 ° C. and 85% humidity is preferably 0.5% or less, and more preferably 0.4% or less.
  • the saturation expansion coefficient can be obtained by using a thermomechanical measurement apparatus (TMA) and by putting a film in an atmosphere at a temperature of 85 ° C. and a humidity of 85% and obtaining a dimensional change when the film is saturated.
  • the cured resin layer 2 is provided between the transparent resin film 1 and the transparent conductive film 3 and does not have a function as a conductor layer. That is, the cured resin layer 2 is provided as a dielectric layer so that it can be insulated between the patterned transparent conductive films 3. Therefore, the cured resin layer 2 usually has a surface resistance of 1 ⁇ 10 6 ⁇ / ⁇ or more, preferably 1 ⁇ 10 7 ⁇ / ⁇ or more, and more preferably 1 ⁇ 10 8 ⁇ / ⁇ or more. There is no particular upper limit on the surface resistance of the cured resin layer 2. Generally, the upper limit of the surface resistance of the cured resin layer 2 is about 1 ⁇ 10 13 ⁇ / ⁇ , which is a measurement limit, but may exceed 1 ⁇ 10 13 ⁇ / ⁇ .
  • the thickness of the cured resin layer 2 is not particularly limited, but is 150 nm or less, preferably about 20 to 100 nm from the viewpoints of heat and humidity resistance, the effect of preventing oligomer generation from the transparent resin film 1 and optical characteristics. More preferably, it is 30 to 50 nm. When two or more cured resin layers 2 are provided, the thickness of each layer is about 20 to 60 nm, preferably 25 to 55 nm.
  • the refractive index of the cured resin layer 2 is preferably such that the difference between the refractive index of the transparent conductive film 3 and the refractive index of the cured resin layer is 0.1 or more.
  • the difference between the refractive index of the transparent conductive film 3 and the refractive index of the cured resin layer is preferably from 0.1 to 0.9, and more preferably from 0.1 to 0.6.
  • the refractive index of the cured resin layer 2 is usually 1.3 to 2.5, more preferably 1.38 to 2.3, and further preferably 1.4 to 2.3.
  • the transparent conductive film 3 preferably has a refractive index difference of 0.1 or more from the cured resin layer 2.
  • the refractive index of the transparent conductive film 3 is usually about 1.95 to 2.05.
  • the method for forming the cured resin layer is not particularly limited, but is preferably by coating.
  • a resin composition containing the above components is uniformly dissolved and dispersed in a solvent to prepare a coating solution.
  • the solvent is not particularly limited.
  • aromatic solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone
  • ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, ethylene glycol di
  • the solid concentration of the coating solution is preferably 0.5% to 2.5% by weight, more preferably 1.0% to 2.0% by weight, and particularly preferably 1.5% to 1.9% by weight. preferable.
  • the cured resin layer is formed by applying the above coating solution on a transparent resin film and curing it.
  • the coating solution may be performed directly on the transparent resin film 1 or may be performed on an undercoat layer or the like formed on the transparent resin film 1.
  • the application method of the coating solution can be appropriately selected according to the state of the coating solution and the painting process.
  • dip coating method air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method It can be applied by a die coating method or an extrusion coating method.
  • a cured resin layer can be formed by heating and curing the obtained coating film.
  • a heating method heating by a hot air dryer, an infrared dryer, a vacuum dryer, a microwave heating dryer or the like can be employed.
  • the heating temperature is, for example, 100 to 200 ° C., preferably 120 to 180 ° C.
  • the heating time is, for example, 0.5 to 10 minutes, and preferably 1 to 5 minutes.
  • the constituent material of the transparent conductive film 3 is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten.
  • a metal oxide of at least one metal is used.
  • the metal oxide may further contain a metal atom shown in the above group, if necessary.
  • indium oxide containing tin oxide and tin oxide containing antimony are preferably used.
  • the thickness of the transparent conductive film 3 is not particularly limited, but it is preferably 10 nm or more in order to obtain a continuous film having good surface resistance of 1 ⁇ 10 3 ⁇ / ⁇ or less.
  • the film thickness is preferably 15 to 35 nm, more preferably in the range of 20 to 30 nm, since transparency is lowered when the film thickness becomes too thick.
  • the thickness is less than 15 nm, the surface electrical resistance increases and it becomes difficult to form a continuous film. Moreover, when it exceeds 35 nm, transparency will fall.
  • the method for forming the transparent conductive film 3 is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness. In addition, after forming the transparent conductive film 3, it can be crystallized by performing an annealing treatment within a range of 100 to 150 ° C., if necessary. For this reason, it is preferable that the transparent resin film 1 has a heat resistance of 100 ° C. or higher, more preferably 150 ° C. or higher. In the present embodiment, the transparent conductive film 3 is patterned by etching.
  • the annealing treatment of the transparent conductive film 3 is preferably performed after the transparent conductive film 3 is patterned. Furthermore, when the cured resin layer 2 is etched, it is preferable that the transparent conductive film 3 is annealed after the cured resin layer 2 is etched.
  • the transparent conductive film 3 may be patterned on the cured resin layer 2.
  • the patterning can form various patterns according to the application to which the transparent conductive film is applied.
  • the pattern part and the non-pattern part are formed by patterning the transparent conductive film 3
  • examples of the shape of the pattern part include a stripe shape.
  • FIG. 5 relates to a top view of the transparent conductive film of the present embodiment, and is an example in the case where the transparent conductive film 3 is formed in a stripe shape, and the pattern portion a and the non-pattern portion b of the transparent conductive film 3 are in a stripe shape. Is formed.
  • the width of the pattern portion a is larger than the width of the non-pattern portion b, but is not limited to this range.
  • the rate of change of the surface resistance value of the transparent conductive film before and after the patterned transparent conductive film is placed in an atmosphere of 85 ° C. and 85% humidity for 240 hours is preferably 1.5 or less, and 1.3 or less. It is more preferable that As a result, even when the transparent conductive film is placed in a harsh environment, the desired electrical characteristics can be exhibited, and thereby various applications can be developed.
  • a hard coat layer, an easy-adhesion layer, an anti-blocking layer, and the like may be provided on the surface of the transparent resin film 1 opposite to the surface on which the transparent conductive film 3 is formed, as necessary.
  • the manufacturing method of the transparent conductive film of this embodiment will not be restrict
  • a transparent conductive film having a transparent conductive film on at least one cured resin layer from the transparent resin film side on one side or both sides of the transparent resin film It can be manufactured by etching and patterning. In the etching, the transparent conductive film is covered with a mask for forming a pattern, and the transparent conductive film is etched with an etching solution.
  • indium oxide containing tin oxide and tin oxide containing antimony are suitably used, so that an acid is suitably used as the etching solution.
  • the acid include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, phosphoric acid, organic acids such as acetic acid, mixtures thereof, and aqueous solutions thereof.
  • a transparent pressure-sensitive adhesive layer is disposed on one side of the transparent conductive film of the present embodiment so that the patterned transparent conductive film 3 is disposed on one side of the transparent conductive film on which the transparent substrate 5 is bonded.
  • the transparent substrate 5 can be bonded via 4. 4 shows a transparent conductive film having a structure in which a transparent substrate 5 is bonded to a transparent resin film 1 (a surface on which a transparent conductive film 3 is not provided) of the transparent conductive film of FIG. It is a film.
  • the transparent substrate 5 may have a composite structure in which at least two transparent substrate films are bonded together with a transparent adhesive layer.
  • patterning of the said transparent conductive film 3 can also be given with respect to the transparent conductive film made into this structure.
  • the thickness of the transparent substrate 5 is usually preferably 90 to 300 ⁇ m, more preferably 100 to 250 ⁇ m.
  • the thickness of each substrate film is 10 to 200 ⁇ m, more preferably 20 to 150 ⁇ m, and the transparent substrate 5 includes a transparent adhesive layer on these substrate films. The total thickness is controlled so as to fall within the above range.
  • a base film the thing similar to the above-mentioned transparent resin film 1 is mentioned.
  • the transparent conductive film (for example, the transparent resin film 1) and the transparent substrate 5 are bonded together by providing the pressure-sensitive adhesive layer 4 on the transparent substrate 5 side and bonding the transparent resin film 1 to the adhesive layer 4.
  • the pressure-sensitive adhesive layer 4 may be provided on the transparent resin film 1 side, and the transparent substrate 5 may be bonded thereto.
  • the latter method is more advantageous in terms of productivity because the pressure-sensitive adhesive layer 4 can be continuously formed with the transparent resin film 1 in a roll shape.
  • the transparent substrate 5 can also be laminated on the transparent resin film 1 by sequentially bonding a plurality of substrate films with an adhesive layer.
  • the thing similar to the following transparent adhesive layer 4 can be used for the transparent adhesive layer used for lamination
  • the transparent conductive films can be bonded to each other by appropriately selecting a laminated surface of the transparent conductive films on which the pressure-sensitive adhesive layer 4 is stacked.
  • the pressure-sensitive adhesive layer 4 can be used without particular limitation as long as it has transparency. Specifically, for example, acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyvinyl ethers, vinyl acetate / vinyl chloride copolymers, modified polyolefins, epoxy systems, fluorine systems, natural rubbers, rubbers such as synthetic rubbers, etc. Those having the above polymer as a base polymer can be appropriately selected and used.
  • an acrylic pressure-sensitive adhesive is preferably used from the viewpoint that it is excellent in optical transparency, exhibits adhesive properties such as appropriate wettability, cohesiveness and adhesiveness, and is excellent in weather resistance and heat resistance.
  • the adhesive primer is not particularly limited as long as it can improve the anchoring force of the adhesive.
  • a silane coupling agent having a reactive functional group such as amino group, vinyl group, epoxy group, mercapto group, chloro group and hydrolyzable alkoxysilyl group in the same molecule, the same molecule Titanate coupling agent having hydrolyzable hydrophilic group and organic functional group containing titanium in the inside, and aluminum having hydrolyzable hydrophilic group and organic functional group containing aluminum in the same molecule
  • a resin having an organic reactive group such as a so-called coupling agent such as an nate coupling agent, an epoxy resin, an isocyanate resin, a urethane resin, or an ester urethane resin can be used. From the viewpoint of easy industrial handling, a layer containing a silane coupling agent is particularly preferred.
  • the pressure-sensitive adhesive layer 4 can contain a cross-linking agent according to the base polymer.
  • the pressure-sensitive adhesive layer 4 may be made of, for example, a natural or synthetic resin, a glass fiber or glass bead, a filler made of metal powder or other inorganic powder, a pigment, a colorant, an antioxidant, or the like. These appropriate additives can also be blended. Moreover, it can also be set as the adhesive layer 4 to which light diffusivity was provided by containing transparent fine particles.
  • the transparent fine particles include, for example, conductive inorganic fine particles such as silica, calcium oxide, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, and antimony oxide having an average particle size of 0.5 to 20 ⁇ m.
  • conductive inorganic fine particles such as silica, calcium oxide, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide, and antimony oxide having an average particle size of 0.5 to 20 ⁇ m.
  • suitable ones such as crosslinked or uncrosslinked organic fine particles made of a suitable polymer such as polymethyl methacrylate and polyurethane can be used.
  • the pressure-sensitive adhesive layer 4 is usually used as a pressure-sensitive adhesive solution having a solid content concentration of about 10 to 50% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent.
  • a solvent an organic solvent such as toluene or ethyl acetate or an adhesive such as water can be appropriately selected and used.
  • the cushioning effect cannot be expected when the thickness of the pressure-sensitive adhesive layer 4 is less than 1 ⁇ m, it is difficult to improve the scratch resistance of the transparent conductive film 3, pen input durability and surface pressure durability for touch panels. Tend to be. On the other hand, if it is too thick, the transparency is impaired, and it is difficult to obtain good results in terms of the formation of the pressure-sensitive adhesive layer 4, the bonding workability of the transparent substrate 5, and the cost.
  • the transparent substrate 5 bonded via the pressure-sensitive adhesive layer 4 gives good mechanical strength to the transparent resin film 1 and, in addition to pen input durability and surface pressure durability, in particular, curl. It contributes to the prevention of such occurrences.
  • a release film S for example, a transition prevention layer and / or a release layer is provided on the surface of the polyester film that adheres to at least the pressure-sensitive adhesive layer 4. It is preferable to use a laminated polyester film or the like.
  • the total thickness of the release film S is preferably 30 ⁇ m or more, and more preferably in the range of 60 to 100 ⁇ m. This is to suppress deformation (dentation) of the pressure-sensitive adhesive layer 4 that is assumed to be generated by foreign matter or the like that has entered between the rolls when the pressure-sensitive adhesive layer 4 is formed and stored in a roll state.
  • the transparent conductive film of the present embodiment can be suitably applied to, for example, an optical method, an ultrasonic method, a capacitance method, a resistance film method, or the like. In particular, it is suitable for a capacitive touch panel.
  • the transparent conductive film of the present embodiment includes, for example, an electrophoresis method, a twist ball method, a thermal rewritable method, an optical writing liquid crystal method, a polymer dispersed liquid crystal method, a guest / host liquid crystal method, a toner display method, and a chromism. It can be suitably used for flexible display elements such as a method and an electric field deposition method.
  • FIG. 2 shows a case where there are two cured resin layers 2.
  • the cured resin layers 21 and 22 are provided in this order from the transparent resin film 1 side.
  • it is a case where it has the cured resin layers 21 and 22 in the non-pattern part b.
  • the cured resin layer 22 above the first layer may be patterned or may not be patterned.
  • an inorganic material can be suitably used in the present embodiment.
  • NaF 1.3
  • Na 3 AlF 6 (1.35)
  • LiF (1.36 LiF (1.36)
  • MgF 2 (1.38)
  • CaF 2 1.4
  • BaF 2 (1. 3)
  • inorganic substances such as SiO 2 (1.46), LaF 3 (1.55), CeF 3 (1.63), Al 2 O 3 (1.63) Is the refractive index of Of these, SiO 2 , MgF 2 , A1 2 O 3 and the like are preferably used.
  • SiO 2 is suitable.
  • a composite oxide containing about 10 to 40 parts by weight of cerium oxide and about 0 to 20 parts by weight of tin oxide with respect to indium oxide can be used.
  • the cured resin layer formed of an inorganic material can be formed as a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method, or by a wet method (coating method).
  • a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method, or by a wet method (coating method).
  • SiO 2 is preferable as described above.
  • a SiO 2 film can be formed by applying silica sol or the like.
  • the resin in the first embodiment as the material for forming the cured resin layers 21 and 22, the resin in the first embodiment, the above-described inorganic materials, and the like may be used in appropriate combination.
  • FIG. 2 illustrates the case where the cured resin layer 2 has two layers
  • the cured resin layer 2 may have three or more layers. Even when the cured resin layer 2 has three or more layers, the non-pattern part b has at least the first cured resin layer 21 from the transparent resin film 1 side.
  • the cured resin layer above the first layer may be patterned or may not be patterned.
  • FIG. 3 is also a cross-sectional view showing an example of the transparent conductive film of the present embodiment.
  • the transparent conductive film of FIG. 3 is a case where it has the transparent conductive film 3 patterned on both surfaces of the transparent resin film 1 through the cured resin layer 2.
  • the transparent conductive film of FIG. 3 has the transparent conductive film 3 patterned on both sides, only one side may be patterned.
  • the pattern part a and the non-pattern part b of the patterned transparent conductive film 3 on both sides coincide with each other. Can be appropriately patterned on both sides. The same applies to the other drawings.
  • Example 1 (Formation of cured resin layer) 10 parts of Adekafilterra BUR-12A mainly composed of rubber-modified epoxy resin (weight average molecular weight of epoxy resin skeleton part: 2000) and 0.001 part of Adekafilterra BUR-12B, which is an antimony curing accelerator Then, 90 parts of methyl isobutyl ketone was added to the mixture to prepare a coating solution. The gelation time when the mixture was heated at 170 ° C. was 10 seconds. The coating solution is applied to one surface of a transparent resin film made of a polyethylene terephthalate film (hereinafter referred to as PET film) having a thickness of 50 ⁇ m, and the coating film is dried (at 195 ° C. for 1 minute), whereby the thickness is 30 nm. A cured resin layer was formed.
  • PET film polyethylene terephthalate film
  • the gelation time of the mixture was measured according to “JIS C 6521 5.7 Curing time” except that the amount of the mixture was 2 g and the specified temperature was set to 170 ° C. That is, 2 g of the mixture was placed on a hot plate adjusted to 170 ° C., and time measurement was started. Immediately the contact circle motion was repeated with a spatula and the time until gelation was measured. During contact circle movement, the mixture should be kept within a range of 25 mm in diameter, and spatula should not be lifted while the viscosity of the mixture is low. This up-and-down movement was repeated until the time expired. The curing time was from when the mixture was placed on the hot plate until when the thread was broken when the spatula was lifted. The contact circle motion was set to a speed of about 1 second per rotation. The measurement was repeated three times, and the average value was taken as the curing time (gelation time).
  • Example 2 In the formation of the cured resin layer, 10 parts of Adekafilterra CRX-11 mainly composed of rubber-modified epoxy resin (weight average molecular weight of epoxy resin skeleton part: 2000), Adekafilterra BUR-, which is an antimony-based curing accelerator, A transparent conductive film was produced in the same manner as in Example 1 except that a mixture obtained by mixing 0.001 part of 12B was used. The gel time of this mixture was 32 seconds.
  • Example 3 In the formation of the cured resin layer, 10 parts of Adekafil Terra CRX-10 mainly composed of rubber-modified epoxy resin (weight average molecular weight of epoxy resin skeleton part: 2000), Adekafil Terra BU-, which is an antimony-based curing accelerator, A transparent conductive film was produced in the same manner as in Example 1 except that a mixture obtained by mixing 0.001 part of 12B was used. The gel time of this mixture was 28 seconds.
  • Comparative Example 1 In the formation of the cured resin layer, 10 parts of Adekafilterra CRX-6 mainly composed of acrylic-modified epoxy resin (weight average molecular weight of epoxy resin skeleton part: 500), and 0.5 of zinc-based curing accelerator (Adeka Stub) A transparent conductive film was produced in the same manner as in Example 1 except that a partially mixed mixture was used. The gel time of this mixture was 240 seconds.
  • Comparative Example 2 In the formation of the cured resin layer, 10 parts of Adekafilterra CRX-5 mainly composed of acrylic-modified epoxy resin (weight average molecular weight of epoxy resin skeleton part: 500) and 0.5 of zinc-based curing accelerator (Adeka Stub) are used. A transparent conductive film was produced in the same manner as in Example 1 except that a partially mixed mixture was used. The gel time of this mixture was 99 seconds.
  • Comparative Example 3 In the formation of the cured resin layer, 10 parts of Adekafilterra CRX-4 mainly composed of an unmodified epoxy resin (weight average molecular weight: 500) and 0.5 part of a zinc-based curing accelerator (Adeka Stub) A transparent conductive film was produced in the same manner as in Example 1 except that the mixed mixture was used. The gel time of this mixture was 102 seconds.
  • Comparative Example 4 In the formation of the cured resin layer, 10 parts of Adekafilterra CRX-3 mainly composed of an unmodified epoxy resin (weight average molecular weight: 500) and 0.5 part of a zinc-based curing accelerator (Adeka Stub) A transparent conductive film was produced in the same manner as in Example 1 except that the mixed mixture was used. The gel time of this mixture was 67 seconds.
  • Thickness of each layer About what has thickness of 1 micrometer or more, such as a transparent resin film, it measured with the micro gauge type thickness meter by Mitutoyo. The thickness of the cured resin layer, the ITO film, etc. was calculated based on the waveform from the interference spectrum using MCPD2000 (trade name) which is an instantaneous multi-photometry system manufactured by Otsuka Electronics Co., Ltd.
  • the surface resistance value ( ⁇ / ⁇ ) of the obtained crystalline transparent conductive layer was measured by a four-terminal method according to JIS K7194 (1994), and this was determined as the initial surface resistance value R0. did.
  • a surface resistance value R240 was measured after leaving for 240 hours in a thermo-hygrostat (manufactured by Espec Corp., LHL-113) set at 85 ° C. and 85% RH.
  • R240 / R0 was calculated
  • the transparent conductive films of the examples have excellent heat and moisture resistance and can withstand use under high temperature and high humidity conditions.

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Abstract

L'invention concerne : un film conducteur transparent qui présente une excellente résistance à la chaleur humide ; et un écran tactile qui est pourvu de ce film conducteur transparent. Le film conducteur transparent comprend séquentiellement, sur un film de résine transparente, une couche de résine durcie et un film de conducteur transparent dans cet ordre. Ce film conducteur transparent est configuré de manière que : la couche de résine durcie présente une épaisseur égale ou inférieure à 100 nm ; le film de conducteur transparent soit à motifs ; et le rapport de variation de la résistance superficielle du film de conducteur transparent entre avant et après 240 heures dans une atmosphère à une température de 85 °C et à un taux d'humidité de 85 % soit égal ou inférieur à 1,5.
PCT/JP2017/020596 2016-06-10 2017-06-02 Film conducteur transparent et écran tactile WO2017213043A1 (fr)

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CN201780035711.4A CN109313963B (zh) 2016-06-10 2017-06-02 透明导电性薄膜及触摸面板

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JP2016221744A JP6796460B2 (ja) 2016-11-14 2016-11-14 透明導電性フィルムおよびタッチパネル
JP2016248125A JP6789801B2 (ja) 2016-06-10 2016-12-21 透明導電性フィルムおよびタッチパネル
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60150508A (ja) * 1984-01-18 1985-08-08 日本写真印刷株式会社 透明電極基板の製造方法
JPH07106617A (ja) * 1993-09-30 1995-04-21 Canon Inc 透明電極及びその形成方法並びに該透明電極を用いた太陽電池
JPH11149826A (ja) * 1997-11-17 1999-06-02 Sumitomo Bakelite Co Ltd 導電性フィルム
JP2004118144A (ja) * 2002-09-30 2004-04-15 Kimoto & Co Ltd 導電性反射防止フィルム
JP2010269504A (ja) * 2009-05-21 2010-12-02 Toyobo Co Ltd 透明導電性積層フィルム及び透明導電性積層シート並びにタッチパネル
JP2014229392A (ja) * 2013-05-20 2014-12-08 東洋紡株式会社 透明導電性フィルムおよび静電容量式タッチパネル

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60150508A (ja) * 1984-01-18 1985-08-08 日本写真印刷株式会社 透明電極基板の製造方法
JPH07106617A (ja) * 1993-09-30 1995-04-21 Canon Inc 透明電極及びその形成方法並びに該透明電極を用いた太陽電池
JPH11149826A (ja) * 1997-11-17 1999-06-02 Sumitomo Bakelite Co Ltd 導電性フィルム
JP2004118144A (ja) * 2002-09-30 2004-04-15 Kimoto & Co Ltd 導電性反射防止フィルム
JP2010269504A (ja) * 2009-05-21 2010-12-02 Toyobo Co Ltd 透明導電性積層フィルム及び透明導電性積層シート並びにタッチパネル
JP2014229392A (ja) * 2013-05-20 2014-12-08 東洋紡株式会社 透明導電性フィルムおよび静電容量式タッチパネル

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