WO2017126466A1 - Film conducteur transparent - Google Patents

Film conducteur transparent Download PDF

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Publication number
WO2017126466A1
WO2017126466A1 PCT/JP2017/001204 JP2017001204W WO2017126466A1 WO 2017126466 A1 WO2017126466 A1 WO 2017126466A1 JP 2017001204 W JP2017001204 W JP 2017001204W WO 2017126466 A1 WO2017126466 A1 WO 2017126466A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive film
film
indium
composite oxide
Prior art date
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PCT/JP2017/001204
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English (en)
Japanese (ja)
Inventor
央 多々見
沼田　幸裕
Original Assignee
東洋紡株式会社
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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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to CN202110288510.3A priority Critical patent/CN112918034B/zh
Priority to CN201780004143.1A priority patent/CN108292183B/zh
Priority to JP2017505680A priority patent/JP6137433B1/ja
Publication of WO2017126466A1 publication Critical patent/WO2017126466A1/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/025—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00—Compounds of tin
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent

Definitions

  • the present invention relates to a transparent conductive film in which a transparent conductive film of crystalline indium-tin composite oxide is laminated on a transparent plastic film substrate, in particular, pen sliding durability when used in a resistive film type touch panel, and
  • the present invention relates to a transparent conductive film excellent in flexibility.
  • a transparent conductive film obtained by laminating a transparent thin film with low resistance on a transparent plastic substrate is used for applications utilizing the conductivity, for example, a flat panel display such as a liquid crystal display or an electroluminescence (EL) display, As a transparent electrode of a touch panel, it is widely used for applications in the electric / electronic field.
  • a flat panel display such as a liquid crystal display or an electroluminescence (EL) display
  • EL electroluminescence
  • a resistive touch panel is a combination of a fixed electrode with a transparent conductive thin film coated on a glass or plastic substrate and a movable electrode (film electrode) with a transparent conductive thin film coated on a plastic film. It is used by overlapping. Pressing the film electrode with a finger or a pen to bring the fixed electrode and the transparent conductive thin film of the film electrode into contact with each other is an input for recognizing the position of the touch panel. Compared to a finger, a pen often has a stronger force on the touch panel. If the touch panel is strongly input with a pen, the transparent conductive thin film on the film electrode side may be broken, such as cracking or peeling.
  • the transparent conductive thin film of the film electrode may be cracked when the film electrode is bent in the touch panel manufacturing process or when it is input to the end of the touch panel. This cracking of the transparent conductive thin film is a phenomenon that occurs because the flexibility of the transparent conductive thin film is poor.
  • a transparent conductive film having both excellent pen sliding durability and flexibility is desired.
  • the transparent conductive thin film on the film electrode side crystalline As a means for improving pen sliding durability, there is a method of making the transparent conductive thin film on the film electrode side crystalline (for example, see Patent Document 1).
  • the conventional transparent conductive film realizes a transparent conductive film excellent in pen sliding durability by controlling the crystallinity of the indium-tin composite oxide.
  • the conventional transparent conductive film was insufficient when the below-described flexibility test was performed.
  • An object of the present invention is to provide a transparent conductive film having excellent pen sliding durability and excellent flexibility when used in a touch panel in view of the above-described conventional problems.
  • the transparent conductive film of this invention which was able to solve said subject consists of the following structures. 1.
  • (1) The bending diameter by the flexibility test described below is 15.2 mm or less (flexibility test)
  • the transparent conductive film heated at 165 ° C. for 75 minutes is cut into a 20 mm ⁇ 80 mm rectangular shape. Next, connect the short sides of the rectangle with a tester and observe the resistance.
  • the transparent conductive film is bent with the transparent conductive film outside, and the bending diameter (mm) of the transparent conductive film when the resistance value of the tester starts to increase is recorded.
  • the present invention it is possible to provide a transparent conductive film having both excellent pen sliding durability and flexibility.
  • the obtained transparent conductive film is extremely useful for applications such as a resistive touch panel.
  • the transparent conductive film of the present invention is a transparent conductive film in which a transparent conductive film of indium-tin composite oxide is laminated on at least one surface on a transparent plastic film substrate, and the following (1) and ( It is preferable to satisfy the condition of 2).
  • the flexibility test method is as follows. The transparent conductive film heated at 165 ° C. for 75 minutes is cut into a 20 mm ⁇ 80 mm rectangular shape. Next, connect the short sides of the rectangle with a tester and observe the resistance. The transparent conductive film is bent with the transparent conductive film outside, and the bending diameter of the transparent conductive film when the resistance value of the tester begins to increase is recorded.
  • the feature of the transparent conductive film of the present invention is that it has excellent pen sliding durability and flexibility. Pen sliding durability and flexibility are contradictory properties.
  • pen sliding durability will be described.
  • a transparent conductive film of indium-tin composite oxide having excellent pen sliding durability has high crystallinity of the transparent conductive film.
  • the crystallinity will be described.
  • High crystallinity indicates that the ratio of the crystalline part is high. Since the transparent conductive film having high crystallinity has a high ratio of hard crystalline parts, the transparent conductive film becomes hard and the pen sliding durability is excellent.
  • a transparent conductive film of indium-tin composite oxide having excellent flexibility has low crystallinity of the transparent conductive film. Since the transparent conductive film with low crystallinity has a high ratio of soft amorphous parts, the transparent conductive film becomes soft and thus has excellent flexibility. As described above, it can be seen that pen sliding durability and flexibility are contradictory properties. As a result of the study, the inventors have invented that both pen sliding durability and flexibility can be achieved by controlling the crystallinity of the transparent conductive film. Next, a transparent conductive film having a transparent conductive film that achieves both pen sliding durability and flexibility will be described.
  • the flexibility test can evaluate not only the flexibility of the transparent conductive film but also the crystallinity of the transparent conductive film of indium-tin composite oxide.
  • the larger the bending diameter the higher the crystallinity of the transparent conductive film of the indium-tin composite oxide.
  • the flexibility test is particularly suitable for comparing the crystallinity of the transparent conductive film of indium-tin composite oxide with a large number of crystalline parts. It is desirable that the bending diameter is 15.2 mm or less. More preferably, it is 15.0 mm or less. If the bending diameter is 15.2 mm or less, the crystallinity of the indium-tin composite oxide is not too high, so that it is particularly excellent in flexibility.
  • the higher the ⁇ b the higher the crystallinity of the transparent conductive film of indium-tin composite oxide.
  • the ⁇ b test is particularly suitable for comparing the crystallinity of a transparent conductive film of indium-tin composite oxide with a small number of crystalline parts.
  • ⁇ b is preferably 0.60 or more. More preferably, it is 0.65 or more. More preferably, it is 0.68 or more. If ⁇ b is 0.60 or more, the crystallinity of the indium-tin composite oxide is not too low, which is excellent in pen sliding durability.
  • the transparent conductive film has appropriate crystallinity, and both pen sliding durability and flexibility are compatible.
  • the crystal grain size of the indium-tin composite oxide transparent conductive film in the present invention is preferably 10 nm or more. More preferably, it is 30 nm or more. A crystal grain size of 10 nm or more is preferable because it tends to be hard as crystal grains and easily satisfies pen sliding durability.
  • the crystal grain size of the transparent conductive film of indium-tin composite oxide is preferably 1000 nm or less. More preferably, it is 500 nm or less. A crystal grain size of 1000 nm or less is preferred because flexibility is maintained.
  • the transparent conductive film in the present invention is made of an indium-tin composite oxide and preferably contains 0.5% by mass to 9.5% by mass of tin oxide.
  • Tin oxide in the indium-tin composite oxide corresponds to an impurity for indium oxide.
  • the inclusion of tin oxide impurities increases the melting point of the indium-tin composite oxide. That is, the inclusion of tin oxide impurities acts in the direction of inhibiting crystallization.
  • the surface resistance of the transparent conductive film is preferably at a practical level. More preferably, the content of tin oxide is 1% by mass or more, and particularly preferably 2% by mass or more.
  • the content of tin oxide is 9.5% by mass or less, crystallization is likely to occur when adjusting to a semi-crystalline state described later, and the pen sliding durability is good, which is preferable.
  • the content of tin oxide is more preferably 8% by mass or less, further preferably 6% by mass or less, and particularly preferably 4% by mass or less.
  • the surface resistance of the transparent conductive film of the present invention is preferably 50 to 900 ⁇ / ⁇ .
  • the thickness of the transparent conductive film is preferably 10 nm or more and 30 nm or less.
  • the thickness of the transparent conductive film is 10 nm or more, the transparent conductive film is not too amorphous, and it is easy to give appropriate crystallinity to make a semi-crystalline state described later, and as a result, pen sliding durability is maintained.
  • the thickness of the transparent conductive film is 13 nm or more, more preferably 16 nm or more.
  • the thickness of the transparent conductive film is 30 nm or less because the crystallinity of the transparent conductive film does not become too high, the semi-crystalline state is easily maintained, and the flexibility is maintained. More preferably, it is 26 nm or less, More preferably, it is 22 nm or less.
  • the manufacturing method for obtaining the transparent conductive film of this invention can be illustrated preferably.
  • a sputtering method is preferably used as a method of forming a transparent conductive film of crystalline indium-tin composite oxide on at least one surface on the transparent plastic film substrate.
  • the ratio of the moisture pressure to the inert gas in the film formation atmosphere during sputtering is precisely controlled so that the difference between the maximum value and the minimum value from the start of film formation to the end of film formation is 2.0 ⁇ 10 ⁇ 4 or less.
  • FIG. 5 shows a schematic diagram of an example of a sputtering apparatus suitably used in the present invention, in which the traveling film 101 travels while partially contacting the surface of the center roll 102.
  • An indium-tin sputtering target 104 is installed through the chimney 103, and a thin film of indium-tin composite oxide is deposited and laminated on the surface of the film 101 running on the center roll.
  • the center roll 102 is temperature controlled by a temperature controller (not shown).
  • the inert gas include helium, neon, argon, krypton, and xenon.
  • the central value (middle value between the maximum value and the minimum value) of the ratio of the moisture pressure to the inert gas in the film formation atmosphere during sputtering is 4.0 ⁇ 10 ⁇ 4 to 2.9 ⁇ 10 ⁇ 3 . It is desirable.
  • the central value of the ratio of moisture pressure to inert gas depends somewhat on the content of tin oxide in the transparent conductive film of indium-tin composite oxide and the thickness of the transparent conductive film. When the amount of tin oxide added in the transparent conductive film of indium-tin composite oxide is large or the transparent conductive film is thin, the center value of the ratio of the moisture pressure to the inert gas is set lower in the above range. It is desirable to do.
  • the central value of the ratio of the moisture pressure to the inert gas is within the above range. It is desirable to set it higher. Moreover, in order to make the surface resistance and total light transmittance of a transparent conductive film into a practical level, it is desirable to add oxygen gas at the time of sputtering.
  • the crystallinity of the transparent conductive film decreases when the amount of water in the film formation atmosphere is large. Therefore, the amount of moisture in the film formation atmosphere is an important factor.
  • the amount of water when forming an indium-tin composite oxide on a plastic film it is desirable to actually observe the amount of water during film formation. It is not preferable to use the ultimate vacuum to control the amount of moisture in the film formation atmosphere as follows.
  • the first reason why it is not preferable is that when a film is formed on a plastic film by sputtering, the film is heated, and moisture is released from the film. The amount of water increases when the degree is measured.
  • the second point is for a device that puts a large amount of transparent plastic film.
  • the film is fed in the form of a film roll.
  • water tends to escape from the outer layer portion of the roll, but water does not easily escape from the inner layer portion of the roll.
  • the film roll is stopped, but the film roll travels during film formation, so the inner layer portion of the film roll containing a lot of water is unwound, so moisture in the film formation atmosphere
  • the amount increases and exceeds the amount of water when the ultimate vacuum is measured.
  • in controlling the amount of moisture in the film-forming atmosphere it can be preferably handled by observing the ratio of the water pressure to the inert gas in the film-forming atmosphere during sputtering.
  • the crystallinity of the transparent conductive film in the present invention is not too high and not too low (such crystallinity is referred to as semicrystalline or semicrystalline). It is very difficult to make the transparent conductive film stable and semi-crystalline. This is because the state stopped in the middle of the phase change from amorphous to crystalline is semicrystalline. Therefore, it is very sensitive to the amount of moisture in the film-forming atmosphere, which is a parameter related to crystallinity. If the amount of water in the film-forming atmosphere is small, almost perfect crystallinity (high crystallinity) is obtained. In addition, if the amount of moisture in the film-forming atmosphere is too large, it becomes amorphous (low crystallinity).
  • the moisture pressure against the inert gas in the film formation atmosphere during sputtering is reduced.
  • the ratio is desirably precisely controlled so that the difference between the maximum value and the minimum value from the start of film formation to the end of film formation is 2.0 ⁇ 10 ⁇ 4 or less.
  • the ratio of the moisture pressure to the inert gas in the film formation atmosphere during sputtering is precisely controlled so that the difference between the maximum value and the minimum value from the start of film formation to the end of film formation is 2.0 ⁇ 10 ⁇ 4 or less.
  • the following [1], [2], and [3] can be preferably adopted.
  • Water is introduced into the deposition atmosphere with a mass flow controller, and the gas analyzer continuously observes the ratio of moisture pressure to inert gas in the deposition atmosphere during sputtering.
  • the gas analyzer continuously observes the ratio of moisture pressure to inert gas in the deposition atmosphere during sputtering.
  • a hydrogen atom-containing gas (hydrogen, ammonia, hydrogen + argon mixed gas or any other gas containing hydrogen atoms) is introduced into the film formation atmosphere with a mass flow controller, and the gas analyzer
  • the ratio of moisture pressure to inert gas in the deposition atmosphere during sputtering is continuously observed, and the observation result of the moisture pressure is fed back to the mass flow controller so that the ratio of moisture pressure to inert gas in the deposition atmosphere during sputtering is Precise control can be preferably employed so that the difference between the maximum value and the minimum value of the value is 2.0 ⁇ 10 ⁇ 4 or less.
  • the hydrogen atom-containing gas is separated and combined with oxygen in the film formation atmosphere to become water. Therefore, the addition of the hydrogen atom-containing gas has the same effect as the addition of water.
  • the temperature of the center roll in contact with the transparent plastic film may be lowered.
  • the temperature of the temperature controller that controls the temperature of the center roll in contact with the transparent plastic film is substituted.
  • the amount of moisture in the film-forming atmosphere changes every moment, so constantly monitor the amount of moisture and respond quickly if you detect changes in the amount of moisture. It is preferable to adjust the water content to the desired level. Since the above [1] and [2] use a mass flow, it is possible to adjust to the target moisture amount by quickly responding after detecting the change in the moisture amount. In the above [3], since a temperature controller having a high response speed to temperature is used, it is possible to adjust to the target moisture amount by quickly responding after detecting a change in the moisture amount.
  • the transparent conductive film is formed on the transparent plastic film by setting the film temperature during sputtering to 80 ° C. or less. It is desirable to form a film. When the temperature is 80 ° C. or lower, it is possible to prevent generation of a large amount of impurity gas such as water and organic gas from the film, and there is no possibility of causing a problem that the film slides with respect to the center roll.
  • the central value of the ratio of moisture pressure to inert gas in the film forming atmosphere during sputtering is preferably 4.0 ⁇ 10 ⁇ 4 to 2.9 ⁇ 10 ⁇ 3 . It is preferable that the central value of the ratio of the moisture pressure to the inert gas is 4.0 ⁇ 10 ⁇ 4 or more because the crystallinity of the transparent conductive film does not become too high and the flexibility is maintained.
  • the central value of the ratio of the moisture pressure to the inert gas is 2.9 ⁇ 10 ⁇ 3 or less, the crystallinity of the transparent conductive film is not particularly low, and the pen sliding durability is preferably maintained.
  • the central value of the ratio of the moisture pressure to the inert gas also depends on the amount of tin oxide added to the transparent conductive film of indium-tin composite oxide and the thickness of the transparent conductive film.
  • the amount of tin oxide added in the transparent conductive film of indium-tin composite oxide is large or the transparent conductive film is thin, the center value of the ratio of the moisture pressure to the inert gas is set lower in the above range. It is desirable to do.
  • the central value of the ratio of moisture pressure to inert gas is within the above range. It is desirable to set it higher.
  • the method for forming a transparent conductive film of crystalline indium-tin composite oxide on at least one surface of a transparent plastic film substrate it is desirable to introduce oxygen gas during sputtering. Introducing oxygen gas at the time of sputtering is preferable because there is no problem due to lack of oxygen in the transparent conductive film of indium-tin composite oxide, the surface resistance of the transparent conductive film is low, and the total light transmittance is high. Therefore, it is desirable to introduce oxygen gas at the time of sputtering in order to bring the surface resistance and total light transmittance of the transparent conductive film to a practical level.
  • the total light transmittance of the transparent conductive film of the present invention is preferably 70 to 95%.
  • the transparent conductive film of the present invention comprises an indium-tin composite oxide transparent conductive film formed on a transparent plastic film substrate and then laminated at 80 to 200 ° C. in an oxygen-containing atmosphere. It is desirable that the heat treatment is performed for 12 hours. When the temperature is 80 ° C. or higher, it is preferable to easily increase the crystallinity so as to obtain a semi-crystalline state and to improve pen sliding durability. When it is 200 ° C. or lower, the flatness of the transparent plastic film is secured, which is preferable.
  • the transparent plastic film substrate used in the present invention is a film obtained by subjecting an organic polymer to melt extrusion or solution extrusion into a film, and stretching, cooling, and heat setting in the longitudinal direction and / or the width direction as necessary.
  • Organic polymers include polyethylene, polypropylene, polyethylene terephthalate, polyethylene-2,6-naphthalate, polypropylene terephthalate, nylon 6, nylon 4, nylon 66, nylon 12, polyimide, polyamideimide, polyethersulfane, poly Ether ether ketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene oxide, polystyrene Syndiotactic polystyrene, and norbornene-based polymer and the like.
  • organic polymers polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, syndiotactic polystyrene, norbornene polymer, polycarbonate, polyarylate, and the like are preferable. These organic polymers may be copolymerized with a small amount of other organic polymer monomers or blended with other organic polymers.
  • the thickness of the transparent plastic film substrate used in the present invention is preferably in the range of 10 to 300 ⁇ m, particularly preferably in the range of 70 to 260 ⁇ m.
  • the thickness of the plastic film is 10 ⁇ m or more, the mechanical strength is maintained, and deformation with respect to pen input particularly when used for a touch panel is small, which is preferable from the viewpoint of durability.
  • the thickness is 300 ⁇ m or less, it is preferable that a load for positioning by pen input is not particularly required when used for a touch panel.
  • the transparent plastic film substrate used in the present invention has a surface activity such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, ozone treatment, etc., as long as the object of the present invention is not impaired.
  • the treatment may be performed.
  • the first point is that the adhesion between the transparent conductive thin film and the curable resin layer is increased, so that the transparent conductive film can be prevented from being peeled off by the sliding of the pen, and the pen sliding durability is improved.
  • the second point is that the true contact area when the transparent conductive thin film comes into contact with the glass is reduced by sliding the pen, and the sliding property between the glass surface and the transparent conductive film is improved, so that the pen sliding durability is improved. It is. Details of the curable resin layer are described below.
  • the curable resin preferably used in the present invention is not particularly limited as long as it is a resin that is cured by application of energy such as heating, ultraviolet irradiation, electron beam irradiation, etc., and silicone resin, acrylic resin, methacrylic resin, epoxy resin , Melamine resin, polyester resin, urethane resin and the like. From the viewpoint of productivity, it is preferable to use an ultraviolet curable resin as a main component.
  • Examples of such ultraviolet curable resins are synthesized from polyfunctional acrylate resins such as acrylic acid or methacrylic acid ester of polyhydric alcohol, diisocyanate, polyhydric alcohol and hydroxyalkyl ester of acrylic acid or methacrylic acid.
  • polyfunctional acrylate resins such as acrylic acid or methacrylic acid ester of polyhydric alcohol, diisocyanate, polyhydric alcohol and hydroxyalkyl ester of acrylic acid or methacrylic acid.
  • a polyfunctional urethane acrylate resin can be used.
  • a monofunctional monomer such as vinyl pyrrolidone, methyl methacrylate, styrene or the like can be added to these polyfunctional resins for copolymerization.
  • the ultraviolet curable resin is usually used by adding a photopolymerization initiator.
  • a photopolymerization initiator known compounds that absorb ultraviolet rays and generate radicals can be used without particular limitation. Examples of such photopolymerization initiators include various benzoins, phenyl ketones, and benzophenones. And the like.
  • the addition amount of the photopolymerization initiator is usually preferably 1 to 5 parts by mass per 100 parts by mass of the ultraviolet curable resin.
  • a resin that is incompatible with the curable resin in addition to the curable resin, which is the main component, in the curable resin layer.
  • phase separation occurs in the curable resin and the incompatible resin can be dispersed in the form of particles.
  • the dispersed particles of the incompatible resin irregularities can be formed on the surface of the curable resin, and the surface roughness in a wide region can be improved.
  • examples of the incompatible resin include a polyester resin, a polyolefin resin, a polystyrene resin, and a polyamide resin.
  • the blending ratio thereof Is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, and particularly preferably 0.5 to 5 parts by mass per 100 parts by mass of the ultraviolet curable resin.
  • the blending amount of the polyester resin is 0.1 parts by mass or more per 100 parts by mass of the ultraviolet curable resin, the convex portions formed on the surface of the curable resin layer are not too small, and the surface roughness can be effectively imparted. This is preferable because a further improvement effect of pen sliding durability is obtained.
  • the blending amount of the polyester resin is 20 parts by mass or less per 100 parts by mass of the ultraviolet curable resin, it is preferable that the strength of the curable resin layer is maintained and chemical resistance is also maintained.
  • the polyester resin has a difference in refractive index from that of the ultraviolet curable resin, the haze value of the curable resin layer tends to increase and the transparency tends to decrease, which may be less preferable.
  • it can be preferably used as an antiglare film having a high haze value and an antiglare function by actively utilizing the deterioration of transparency caused by dispersed particles of a high molecular weight polyester resin.
  • the UV curable resin, photopolymerization initiator and high molecular weight polyester resin are dissolved in a common solvent to prepare a coating solution.
  • the solvent to be used is not particularly limited, and examples thereof include alcohol solvents such as ethyl alcohol and isopropyl alcohol, ester solvents such as ethyl acetate and butyl acetate, dibutyl ether, and ethylene glycol monoethyl ether.
  • Ether solvents, ketone solvents such as methyl isobutyl ketone and cyclohexanone
  • aromatic hydrocarbon solvents such as toluene, xylene and solvent naphtha can be used alone or in combination.
  • the concentration of the resin component in the coating solution can be appropriately selected in consideration of the viscosity according to the coating method.
  • the ratio of the total amount of the ultraviolet curable resin, the photopolymerization initiator and the high molecular weight polyester resin in the coating solution is usually 20 to 80% by mass.
  • the prepared coating solution is coated on a transparent plastic film substrate.
  • the coating method is not particularly limited, and conventionally known methods such as a bar coating method, a gravure coating method, and a reverse coating method can be used.
  • the solvent of the coated coating solution is removed by evaporation in the next drying step.
  • the high molecular weight polyester resin that has been uniformly dissolved in the coating solution becomes fine particles and precipitates in the ultraviolet curable resin.
  • the plastic film is irradiated with ultraviolet rays, whereby the ultraviolet curable resin is crosslinked and cured to form a curable resin layer.
  • fine particles of the high molecular weight polyester resin are fixed in the hard coat layer, and protrusions are formed on the surface of the curable resin layer to improve the surface roughness in a wide region.
  • the thickness of the curable resin layer is preferably in the range of 0.1 to 15 ⁇ m. More preferably, it is in the range of 0.5 to 10 ⁇ m, and particularly preferably in the range of 1 to 8 ⁇ m. When the thickness of the curable resin layer is 0.1 ⁇ m or more, sufficient protrusions are preferably formed. On the other hand, if it is 15 micrometers or less, productivity is good and preferable.
  • a film sample piece laminated with a transparent conductive thin film layer was cut into a size of 1 mm ⁇ 10 mm, and attached to the upper surface of an appropriate resin block with the conductive thin film surface facing outward. After trimming this, an ultrathin section approximately parallel to the film surface was prepared by a general ultramicrotome technique. This section was observed with a transmission electron microscope (manufactured by JEOL, JEM-2010), and the surface portion of the conductive thin film without significant damage was selected, and a photograph was taken at an acceleration voltage of 200 kV and a direct magnification of 40000 times. A portion having a circular or polygonal region observed under a transmission electron microscope is defined as a crystal grain of the transparent conductive film.
  • FIGS. 1 to 4 show an example of a method for identifying the longest part when measuring the longest part of crystal grains. That is, the longest part is identified by the length of the straight line that can measure the largest grain size of each crystal grain.
  • Thickness (film thickness) of transparent conductive film A film sample piece laminated with a transparent conductive thin film layer was cut into a size of 1 mm ⁇ 10 mm and embedded in an epoxy resin for an electron microscope. This was fixed to a sample holder of an ultramicrotome, and a cross-sectional thin section parallel to the short side of the embedded sample piece was produced. Next, in a portion where the thin film of this section is not significantly damaged, a transmission electron microscope (manufactured by JEOL, JEM-2010) is used to photograph at an acceleration voltage of 200 kV and a bright field at an observation magnification of 10,000 times. The film thickness was determined from the photograph taken.
  • Pen sliding durability test A transparent conductive film is used as one panel plate, and the other panel plate is an indium-tin composite oxide thin film (containing tin oxide) having a thickness of 20 nm by plasma CVD on a glass substrate.
  • a transparent conductive thin film (Nippon Soda Co., Ltd., S500) comprising 10% by mass) was used.
  • the two panel plates were arranged through epoxy beads having a diameter of 30 ⁇ m so that the transparent conductive thin film faced to prepare a touch panel.
  • a 2.5 N load was applied to a polyacetal pen (tip shape: 0.8 mmR), and a 160,000 reciprocating linear sliding test was performed on the touch panel.
  • the sliding distance at this time was 30 mm, and the sliding speed was 180 mm / second.
  • the ON resistance resistance value when the movable electrode (film electrode) and the fixed electrode were in contact
  • the ON resistance is desirably 10 k ⁇ or less.
  • Flexibility test A transparent conductive film heated at 165 ° C. for 75 minutes is cut into a 20 mm ⁇ 80 mm rectangular shape. Next, connect the short sides of the rectangle with a tester and observe the resistance. The transparent conductive film is bent with the transparent conductive film outside, and the bending diameter (mm) of the transparent conductive film when the resistance value of the tester starts to increase is recorded.
  • the bending diameter is desirably 15.2 mm or less.
  • the transparent plastic film base material used in the Examples and Comparative Examples is a biaxially oriented transparent PET film (A4340, thickness 188 ⁇ m) having easy-adhesion layers on both sides.
  • a curable resin layer 100 parts by mass of a photopolymerization initiator-containing acrylic resin (Daiichi Seika Kogyo Co., Ltd., Seika Beam (registered trademark) EXF-01J), copolymer polyester resin (Toyobo Co., Ltd., Byron 200, weight average) 3 weight parts of molecular weight 18,000) is added, and a solvent mixture of toluene / MEK (8/2: mass ratio) is added as a solvent so that the solid content concentration is 50 mass%, and the mixture is stirred and dissolved uniformly.
  • a photopolymerization initiator-containing acrylic resin (Daiichi Seika Kogyo Co., Ltd., Seika Beam (registered trademark) EXF-01J)
  • a coating solution was prepared (this coating solution is hereinafter referred to as coating solution A).
  • the prepared coating solution was applied using a Mayer bar so that the thickness of the coating film was 5 ⁇ m. After drying at 80 ° C. for 1 minute, the coating film was cured by irradiating with ultraviolet rays (light quantity: 300 mJ / cm 2 ) using an ultraviolet ray irradiation device (UB042-5AM-W type, manufactured by Eye Graphics Co., Ltd.). .
  • Examples 1 to 9 Each example level was carried out under the conditions shown in Table 1 as follows. The film was put into a vacuum chamber and evacuated to 1.5 ⁇ 10 ⁇ 4 Pa. Next, after introducing oxygen, argon was introduced as an inert gas to bring the total pressure to 0.5 Pa. Electric power was applied at a power density of 2 W / cm 2 to a sintered target of indium-tin composite oxide or an indium oxide sintered target not containing tin oxide, and a transparent conductive film was formed by DC magnetron sputtering. The film thickness was controlled by changing the speed at which the film passed over the target.
  • the ratio of the moisture pressure to the inert gas in the film formation atmosphere during sputtering was measured using a gas analyzer (manufactured by Inficon, Transpector XPR3).
  • a gas analyzer manufactured by Inficon, Transpector XPR3
  • the amount of water or hydrogen atom-containing gas introduced or the film travels in contact to adjust the ratio of moisture pressure to inert gas in the film formation atmosphere during sputtering.
  • the temperature of the temperature control medium that controls the temperature of the center roll is adjusted.
  • the temperature of the temperature controller is variably controlled, and the temperature corresponding to the middle between the maximum value and the minimum value from the start of film formation to the end of film formation is shown in Table 1 as a central value.
  • the film on which the transparent conductive film was formed and laminated was subjected to the heat treatment described in Table 1 and then measured. The measurement results are shown in Table 1.
  • the transparent conductive films described in Examples 1 to 9 are excellent in pen sliding durability and flexibility, and have both characteristics. However, Comparative Examples 1 to 9 cannot achieve both pen sliding durability and flexibility.
  • a transparent conductive film excellent in pen sliding durability and flexibility can be produced, which is extremely useful for applications such as a resistive film type touch panel.

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Abstract

L'invention a pour objectif de fournir un film conducteur transparent qui présente une excellente durabilité de glissement du stylo lorsque le film conducteur transparent est utilisé pour un écran tactile tout en gardant une excellente flexibilité, ce qui le rend insensible à l'apparition de fissures, d'une séparation, d'une rupture, etc. Pour ce faire, l'invention concerne un film conducteur transparent dans lequel un film conducteur transparent formé à partir d'un oxyde composite d'indium-étain est laminé sur au moins une surface d'une base de film plastique transparent et qui possède un diamètre de courbure de maximum 15,2 mm tel que déterminé par un test de flexibilité spécifique tout en ayant un ∆ b d'au moins 0,60 tel que déterminé par un test ∆b spécifique.
PCT/JP2017/001204 2016-01-20 2017-01-16 Film conducteur transparent WO2017126466A1 (fr)

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JP2017505680A JP6137433B1 (ja) 2016-01-20 2017-01-16 透明導電性フィルム

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JP2021034204A (ja) * 2019-08-22 2021-03-01 日東電工株式会社 透明導電性フィルム
WO2021200710A1 (fr) * 2020-03-31 2021-10-07 東洋紡株式会社 Film conducteur transparent
CN114007857A (zh) * 2019-06-27 2022-02-01 日东电工株式会社 透明导电性薄膜
WO2023013734A1 (fr) * 2021-08-06 2023-02-09 日東電工株式会社 Stratifié

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JP7160100B2 (ja) * 2019-03-28 2022-10-25 東洋紡株式会社 透明導電性フィルム
JP6999071B1 (ja) * 2020-08-26 2022-02-14 昭和電工株式会社 透明導電基体
CN116848595A (zh) * 2021-09-17 2023-10-03 日东电工株式会社 透明导电性薄膜

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JP2021034204A (ja) * 2019-08-22 2021-03-01 日東電工株式会社 透明導電性フィルム
WO2021200710A1 (fr) * 2020-03-31 2021-10-07 東洋紡株式会社 Film conducteur transparent
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JP2022109930A (ja) * 2020-03-31 2022-07-28 東洋紡株式会社 透明導電性フィルム
JP7272488B2 (ja) 2020-03-31 2023-05-12 東洋紡株式会社 透明導電性フィルム
WO2023013734A1 (fr) * 2021-08-06 2023-02-09 日東電工株式会社 Stratifié
JPWO2023013734A1 (fr) * 2021-08-06 2023-02-09
JP7377383B2 (ja) 2021-08-06 2023-11-09 日東電工株式会社 積層体

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TWI675381B (zh) 2019-10-21
CN108292183B (zh) 2021-03-16

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