WO2023013734A1 - 積層体 - Google Patents

積層体 Download PDF

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Publication number
WO2023013734A1
WO2023013734A1 PCT/JP2022/029990 JP2022029990W WO2023013734A1 WO 2023013734 A1 WO2023013734 A1 WO 2023013734A1 JP 2022029990 W JP2022029990 W JP 2022029990W WO 2023013734 A1 WO2023013734 A1 WO 2023013734A1
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WO
WIPO (PCT)
Prior art keywords
transparent conductive
conductive layer
layer
thickness direction
laminate
Prior art date
Application number
PCT/JP2022/029990
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English (en)
French (fr)
Japanese (ja)
Inventor
望 藤野
泰介 鴉田
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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Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020237010086A priority Critical patent/KR102665515B1/ko
Priority to JP2022573371A priority patent/JP7377383B2/ja
Priority to CN202280006988.5A priority patent/CN116348293B/zh
Publication of WO2023013734A1 publication Critical patent/WO2023013734A1/ja
Priority to JP2023169714A priority patent/JP2024009841A/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields

Definitions

  • the present invention relates to laminates.
  • a laminate that includes an underlayer and a crystalline transparent conductive layer adjacent to the underlayer is known (see, for example, Patent Document 1 below).
  • one side of the transparent conductive layer in the thickness direction has a first ridge.
  • One surface in the thickness direction of the underlayer has a second ridge. The second ridges of the underlayer overlap the first ridges of the transparent conductive layer when projected in the thickness direction.
  • a second bump corresponding to the shape of the particles is formed on the base layer by applying a resin composition containing particles. Also, a thin film is formed on one side of the base layer in the thickness direction to form the first bumps following the above-described second bumps on the transparent conductive layer.
  • the transparent conductive layer is made crystalline by heating the amorphous transparent conductive layer.
  • the laminate of Patent Document 1 due to the above-described second bumps, it is difficult to align the crystal orientation in the crystallization of the amorphous transparent conductive layer, that is, the crystal growth is inhibited.
  • the transparency of the crystallized transparent conductive layer is low. Therefore, there is a problem that the transparency of the laminate including the transparent conductive layer described above is low.
  • the present invention provides a laminate that has a transparent conductive layer that has excellent adhesion to other layers and that has excellent transparency.
  • the present invention (1) is a laminate comprising an underlying layer and a crystalline transparent conductive layer adjacent to one side of the underlying layer in the thickness direction, wherein one side of the transparent conductive layer in the thickness direction is: A first ridge having a height of 3 nm or more may be provided, and one surface of the underlayer may have a second ridge having a height of 3 nm or more, and the second ridge may have a height of 3 nm or more when projected in the thickness direction. , wherein the transparent conductive layer does not overlap the first ridge, and wherein the transparent conductive layer comprises a stack containing a noble gas having an atomic number greater than argon.
  • the present invention (2) includes the laminate according to (1), wherein the base layer contains a resin.
  • the present invention (3) includes a grain boundary having an edge extending to one surface of the transparent conductive layer, and a ridge starting point from which the first ridge rises is located at or near the edge, or (2) includes the laminate.
  • the present invention (4) further comprises a substrate layer arranged on the opposite side of the base layer to the transparent conductive layer in the thickness direction, wherein the substrate layer contains a resin, (1) to (3)
  • the laminate according to any one of the above is included.
  • the laminate of the present invention has a transparent conductive layer with excellent adhesion to other layers, and has excellent transparency.
  • FIG. 1 is a cross-sectional view of one embodiment of a laminate of the present invention
  • FIG. It is a modified example of the laminate.
  • It is a modified example of the laminate.
  • 1 is an image processing diagram of a TEM photograph of Example 1.
  • FIG. 5 is an image processing diagram in which auxiliary lines are added to FIG. 4;
  • FIG. 4 is a graph showing the relationship between the amount of introduced oxygen and the specific resistance in the reactive sputtering of the first step.
  • FIG. 11 is a schematic cross-sectional view of a conventional example.
  • the laminate 1 extends in the planar direction.
  • the plane direction is perpendicular to the thickness direction.
  • the laminate 1 has, for example, a substantially rectangular shape in plan view. Planar view means viewing in the thickness direction.
  • the laminate 1 has a sheet shape.
  • a sheet includes a film. Sheets and films are not distinguished.
  • the laminate 1 includes a base layer 2, a base layer 3, and a transparent conductive layer 4 in order toward one side in the thickness direction.
  • the laminate 1 includes a base layer 2, a base layer 3 arranged on one side 21 in the thickness direction of the base layer 2, and one side 31 in the thickness direction of the base layer 3. and a transparent conductive layer 4 . Two layers that are adjacent in the thickness direction are adjacent.
  • the base layer 2 is arranged on the side opposite to the transparent conductive layer 4 with respect to the base layer 3 in the thickness direction.
  • the base material layer 2 has a sheet shape.
  • the substrate layer 2 is preferably transparent.
  • Materials for the base material layer 2 include, for example, resins, ceramics, and metals.
  • resins include polyester resins, acrylic resins, olefin resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, polystyrene resins, and norbornene resins.
  • the resin is preferably a polyester resin.
  • Polyester resins include, for example, polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate, preferably PET.
  • Ceramics include glass.
  • Metals include, for example, silver, tin, chromium, and zirconium.
  • a preferred material for the base material layer 2 is a resin.
  • the base material layer 2 preferably contains a resin. If the base layer 2 contains a resin, the coefficient of linear expansion of the base layer 2 can be brought close to (matched with) the coefficient of linear expansion of the base layer 3 in this embodiment (described later) in which the base layer 3 contains a resin, Therefore, the thermal contraction rate of the base material 30 (described later) and the laminate 1 can be reduced.
  • the thickness of the base material layer 2 is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, and is, for example, 500 ⁇ m or less, preferably 200 ⁇ m or less, more preferably 100 ⁇ m or less.
  • One surface 21 in the thickness direction of the base material layer 2 may have a third bump with a height of 3 nm or more.
  • the height of the third protrusion is obtained in the same manner as the height of the first protrusion 42 which will be described later.
  • the position and number of the above-described third protrusions in plan view are not limited.
  • the total light transmittance of the substrate layer 2 is, for example, 75% or higher, preferably 85% or higher, and more preferably 90% or higher.
  • the upper limit of the total light transmittance of the base material layer 2 is not limited, and is, for example, 100% or less.
  • the total light transmittance of the base material layer 2 is obtained based on JIS K 7375-2008.
  • the base layer 3 is adjacent to one side of the base layer 2 in the thickness direction. Specifically, the base layer 3 contacts one surface 21 of the base material layer 2 in the thickness direction. Underlayer 3 is preferably transparent. Examples of the underlayer 3 include an optical adjustment layer and a hard coat layer. The underlying layer 3 is a single layer or multiple layers.
  • the base layer 2 and the base layer 3 can be referred to as a base material 30. That is, the substrate 30 includes the substrate layer 2 and the base layer 3 in order toward one side in the thickness direction. Substrate 30 is preferably transparent. Therefore, the base material 30 can be called a transparent base material.
  • the base layer 3 contains resin, and may further contain particles, for example.
  • resins examples include acrylic resins, urethane resins, melamine resins, alkyd resins, and silicone resins.
  • Particles include, for example, inorganic particles and organic particles.
  • Inorganic particles include, for example, metal oxide particles and carbonate particles.
  • Metal oxide particles include, for example, silica particles, zirconium oxide, titanium oxide, zinc oxide, and tin oxide.
  • Carbonate particles include, for example, calcium carbonate particles.
  • Examples of organic particles include crosslinked acrylic particles. The median diameter of the particles is, for example, 1 nm or more, preferably 5 nm or more, more preferably 10 nm or more, and for example, 100 nm or less, preferably 40 nm or less.
  • the base layer 3 preferably does not contain particles and contains resin. If the raw material of the resin is a curable resin, the underlying layer 3 is a cured film.
  • one surface 31 in the thickness direction of the underlayer 3 does not have the second protrusion 32 (see FIG. 2) with a height of 3 nm or more.
  • one surface 31 in the thickness direction of the underlayer 3 is a flat surface. It should be noted that the flat surface allows the presence of bumps with a height of less than 3 nm.
  • the crystal orientation in the transparent conductive layer 4 described below is well aligned, and as a result, The total light transmittance of the transparent conductive layer 4 can be increased.
  • the thickness of the underlayer 3 is, for example, 5 nm or more, preferably 10 nm or more, more preferably 30 nm or more, and for example, 10,000 nm or less, preferably 5,000 nm or less.
  • the total light transmittance of the underlying layer 3 is, for example, 75% or higher, preferably 85% or higher, and more preferably 90% or higher.
  • the upper limit of the total light transmittance of the underlying layer 3 is not limited, and is, for example, 100% or less.
  • the total light transmittance of the underlying layer 3 is obtained based on JIS K 7375-2008.
  • the surface direction of the base material 30 includes the direction of heat shrinkage after the base material 30 is heated.
  • the heating temperature can be selected according to the heat resistance of the substrate 30 .
  • the thermal contraction rate after heating the substrate 30 at 160° C. for 1 hour is, for example, 0.01% or more, preferably 0.05% or more, and is, for example, 2% or less, preferably 1.
  • the surface direction of the base material 30 includes the direction in which it is 0% or less, more preferably 0.5% or less. If the thermal contraction rate of the base material 30 is equal to or more than the above-described lower limit and equal to or less than the upper limit, cracks in the transparent conductive layer 4 are suppressed, and the first protrusions 42 described later can be formed.
  • Transparent conductive layer 4 The transparent conductive layer 4 is adjacent to one side of the base layer 3 in the thickness direction. Specifically, the transparent conductive layer 4 contacts one surface 31 of the base layer 3 in the thickness direction. The transparent conductive layer 4 forms one surface of the laminate 1 in the thickness direction. The transparent conductive layer 4 has a sheet shape extending in the plane direction. In this embodiment, the transparent conductive layer 4 is a single layer.
  • the transparent conductive layer 4 preferably has a height of 4 nm or more, more preferably 5 nm or more, more preferably 7 nm or more, still more preferably 10 nm or more, and particularly preferably a height of 10 nm or more. height of 15 nm or more and, for example, a height of 50 nm or less, preferably a height of 30 nm or less, more preferably a height of 20 nm or less.
  • the transparent conductive layer 4 is provided with the first protrusions 42 having a height equal to or higher than the lower limit and equal to or lower than the upper limit, so that the transparent conductive layer 4 is excellent in adhesion to another layer 5 described later.
  • the number of first protrusions 42 may be singular or plural, and preferably plural from the viewpoint of improving adhesion.
  • the number of second protrusions 32 (see FIG. 2) per unit length is 0 because of the above. Therefore, the number of first ridges 42 per unit length is greater than the number of second ridges 32 (see FIG. 2) per unit length.
  • the adhesive strength of the one surface 41 in the thickness direction of the transparent conductive layer 4 is reliable.
  • the total light transmittance of the transparent conductive layer 4 can be reliably increased.
  • the number of first protrusions 42 per unit length is, for example, 1/ ⁇ m or more, preferably 2/ ⁇ m or more, more preferably 3/ ⁇ m or more, and still more preferably 4 5/ ⁇ m or more, particularly preferably 5/ ⁇ m or more, and most preferably 8/ ⁇ m or more. It is 20 pieces/ ⁇ m or less.
  • the number of first protrusions 42 per unit length is counted by observing the cross section of the transparent conductive layer 4 with a TEM, as will be described in the examples below.
  • the average height of the first protrusions 42 is, for example, 3 nm or more, preferably 4 nm or more, more preferably 5 nm or more, even more preferably 6 nm or more, particularly preferably 7 nm or more, and most preferably 8 nm or more. Also, for example, it is 40 nm or less, preferably 20 nm or less, more preferably 15 nm or less, and still more preferably 10 nm or less.
  • the average height of the first ridges 42 is described in a later example.
  • the transparent conductive layer 4 is provided with the first protrusions 42 whose average height is equal to or more than the lower limit and equal to or less than the upper limit described above.
  • one surface 41 in the thickness direction of the transparent conductive layer 4 further includes a flat portion 43, for example.
  • the flat portion 43 is located outside the raised start portion 431 .
  • the uplift starting portion 431 is a portion where the first uplift 42 starts uplifting from the flat portion 43 .
  • the height of the first protrusion 42 is determined by making it hang down along the thickness direction from one end portion 432 located on one side in the thickness direction to the line segment connecting the two rise start portions 431 in a cross-sectional view. is the length from the one end 432 to the drooping point when obtaining The height of the first protrusion 42 is obtained by, for example, observing a TEM photograph (cross-sectional observation).
  • the transparent conductive layer 4 is crystalline.
  • the transparent conductive layer 4 does not contain amorphous regions.
  • the transparent conductive layer 4 consists only of crystalline regions.
  • the transparent conductive layer 4 is crystalline or amorphous is determined, for example, by the following test.
  • the transparent conductive layer 4 is immersed in a 5% by mass hydrochloric acid aqueous solution for 15 minutes, then washed with water and dried. is 10 k ⁇ or less, the transparent conductive layer 4 is crystalline, and when the resistance between the two terminals exceeds 10 k ⁇ , the transparent conductive layer 4 is amorphous.
  • the total light transmittance of the transparent conductive layer 4 can be increased.
  • the transparent conductive layer 4 has grain boundaries 44 .
  • the grain boundary 44 includes one end edge 441 reaching one surface 41 of the transparent conductive layer 4 in the thickness direction.
  • the grain boundaries 44 described above advance from each of the two one edges 441 to the other side in the thickness direction, and are connected at an intermediate portion in the thickness direction.
  • the grain boundary 44 extends from the one edge 441 toward the other side in the thickness direction and reaches the other side of the transparent conductive layer 4 in the thickness direction, that is, the other edge 442 that reaches the one side 31 of the underlying layer 3 in the thickness direction.
  • the grain boundary 44 does not include the other edge 442 and one grain boundary 44 includes two one edges 441 .
  • the one surface 41 of the transparent conductive layer 4 can easily form the first protrusion 42 .
  • the above-described protuberance start portion 431 is positioned, for example, at the above-described one end edge 441 and/or is positioned near the above-described one end edge 441 .
  • the one end edge 441 corresponding to the first protrusion 42A is, for example, an endless shape in plan view. There is a beginning 431A.
  • the two swelling start portions 431B of the first swelling 42B located on the right side of FIG. located nearby.
  • the neighborhood is, for example, two distances within 15 nm, preferably within 10 nm.
  • the remaining raised starter 431 B is located at one edge 441 .
  • the protuberance starting portion 431 is positioned at and/or near one edge 441 of the grain boundary 44 , a large number of the first protuberances 42 are reliably formed on the one surface 41 of the transparent conductive layer 4 . Therefore, the adhesiveness of the one surface 41 of the transparent conductive layer 4 is excellent.
  • Examples of materials for the transparent conductive layer 4 include metal oxides.
  • the metal oxide contains at least one metal selected from the group consisting of In, Sn, Zn, Ga, Sb, Nb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd and W .
  • the material of the transparent conductive layer 4 is preferably indium zinc composite oxide (IZO), indium gallium zinc composite oxide (IGZO), indium gallium composite oxide (IGO), indium tin composite oxide. (ITO) and antimony tin composite oxide (ATO), preferably indium tin composite oxide (ITO) from the viewpoint of increasing the total light transmittance.
  • the content of tin oxide (SnO 2 ) in the indium tin composite oxide is, for example, 0.5% by mass or more, preferably 3% by mass or more, more preferably 6% by mass or more. , less than 50% by mass, preferably 25% by mass or less, more preferably 15% by mass or less.
  • the transparent conductive layer 4 contains a rare gas having an atomic number greater than that of argon.
  • transparent conductive layer 4 contains a noble gas with an atomic number greater than argon and does not contain argon.
  • the transparent conductive layer 4 is suppressed from taking in a large amount of sputtering gas. Therefore, the crystallinity of the transparent conductive layer 4 is enhanced, and as a result, the total light transmittance of the transparent conductive layer 4 is sufficiently increased. Furthermore, the specific resistance (described later) of the transparent conductive layer 4 is lowered as the crystallinity of the transparent conductive layer 4 is improved.
  • the material of the transparent conductive layer 4 is a metal oxide containing a noble gas with an atomic number greater than that of argon. That is, the material of the transparent conductive layer 4 is a composition in which a metal oxide is mixed with a rare gas having an atomic number greater than that of argon.
  • Rare gases with atomic numbers greater than argon include, for example, krypton, xenon, and radon. These can be used alone or in combination.
  • the noble gas having an atomic number greater than that of argon is preferably krypton and xenon, and more preferably krypton (Kr) from the viewpoint of obtaining low cost and excellent electrical conductivity.
  • the method of identifying noble gases with atomic numbers greater than argon is not limited.
  • Rutherford Backscattering Spectrometry, secondary ion mass spectrometry, laser resonance ionization mass spectrometry, and/or X-ray fluorescence spectroscopy reveal noble gases with atomic numbers higher than argon in the transparent conductive layer 4. identified.
  • the content of the rare gas having an atomic number greater than that of argon in the transparent conductive layer 4 is, for example, 0.0001 atom % or more, preferably 0.001 atom % or more, and, for example, 1.0 atom % or less, or more. preferably 0.7 atom% or less, more preferably 0.5 atom% or less, even more preferably 0.3 atom% or less, particularly preferably 0.2 atom% or less, most preferably 0.15 atom% or less be. If the content of the noble gas having an atomic number greater than that of argon in the transparent conductive layer 4 is within the above range, the total light transmittance of the transparent conductive layer 4 can be increased.
  • the thickness of the transparent conductive layer 4 is, for example, 15 nm or more, preferably 35 nm or more, more preferably 50 nm or more, even more preferably 75 nm or more, even more preferably 100 nm or more, particularly preferably 120 nm or more.
  • the thickness of the transparent conductive layer 4 is, for example, 500 nm or less, preferably 300 nm or less, more preferably 200 nm or less.
  • the thickness of the transparent conductive layer 4 is measured, for example, by observing a TEM photograph (cross-sectional observation).
  • the total light transmittance of the transparent conductive layer 4 is, for example, 75% or higher, preferably 80% or higher, more preferably 85% or higher, still more preferably 90% or higher.
  • the upper limit of the total light transmittance of the transparent conductive layer 4 is not limited, and is, for example, 100% or less.
  • the total light transmittance of the transparent conductive layer 4 is obtained based on JIS K 7375-2008.
  • the specific resistance of one surface 41 in the thickness direction of the transparent conductive layer 4 is, for example, 5.0 ⁇ 10 ⁇ 4 ⁇ cm or less, preferably 3 ⁇ 10 ⁇ 4 ⁇ cm or less, more preferably 2.5. ⁇ 10 ⁇ 4 ⁇ cm or less, more preferably 2.3 ⁇ 10 ⁇ 4 ⁇ cm or less, particularly preferably 2.0 ⁇ 10 ⁇ 4 ⁇ cm or less, particularly preferably 1.8 ⁇ 10 ⁇ 4 ⁇ cm or less, most preferably 1.5 ⁇ 10 ⁇ 4 ⁇ cm or less, and for example, 0.1 ⁇ 10 ⁇ 4 ⁇ cm or more, preferably 0.5 ⁇ 10 ⁇ 4 ⁇ cm or more, more preferably 1.0 ⁇ 10 ⁇ 4 ⁇ cm or more, still more preferably 1.01 ⁇ 10 ⁇ 4 ⁇ cm or more, even more preferably 1.05 ⁇ 10 ⁇ 4 ⁇ cm or more, particularly preferably 1.10 ⁇ 10 ⁇ 4 ⁇ cm or more.
  • a specific resistance is measured by the four-probe method
  • each layer is laid down in a roll-to-roll process.
  • a long base material layer 2 is prepared.
  • a resin composition containing the resin described above is applied to one surface 21 of the base material layer 2 .
  • the resin composition contains a curable resin
  • the curable resin is cured by heat or ultraviolet irradiation.
  • the base layer 3 containing resin is formed.
  • the resin composition contains a resin but does not contain particles, so the above-described second bumps 32 (see FIG. 2) are not formed on one surface 31 of the base layer 3 in the thickness direction.
  • the heat shrinkage rate in the longitudinal direction (MD direction) of the base material 30 when heated at 160° C. for 1 hour is not limited, and is, for example, 0.1% or more, preferably 0.2% or more. and is, for example, 2.0% or less, preferably 1.0% or less.
  • the thermal shrinkage rate in the width direction (the direction orthogonal to the longitudinal direction and the thickness direction) (TD direction) of the base material 30 when heated at 160 ° C. for 1 hour is not limited, for example, -0.2% or more, Preferably 0.00% or more, more preferably 0.01% or more, still more preferably 0.05% or more, and for example, 1.0% or less, preferably 0.5% or less be.
  • the transparent conductive layer 4 is formed on one surface 31 of the base layer 3 in the thickness direction.
  • the method of forming the transparent conductive layer 4 includes, for example, a first step and a second step.
  • an amorphous transparent conductive layer 40 is formed on one side 31 of the underlying layer 3 in the thickness direction.
  • an amorphous transparent conductive layer 40 is formed on one surface 31 of the underlying layer 3 in the thickness direction by sputtering, preferably reactive sputtering.
  • a sputtering apparatus is used for sputtering.
  • the sputtering device includes a film-forming roll.
  • a film-forming roll is equipped with a cooling device.
  • the cooling device can cool the film forming roll.
  • the film-forming roll can cool the base layer 3 (including the base material 30).
  • the above metal oxide (sintered body) is used as a target.
  • the surface temperature of the film-forming roll corresponds to the film-forming temperature in sputtering.
  • the film formation temperature is, for example, 10.0° C. or lower, preferably 0.0° C. or lower, more preferably ⁇ 2.5° C. or lower, further preferably ⁇ 5.0° C. or lower, further preferably ⁇ 7. 0° C. or lower, and for example, -50° C. or higher, preferably -20° C. or higher, more preferably -10° C. or higher.
  • the base layer 3 (including the base material 30) can be sufficiently cooled, so that the grain boundary 44 does not include the other edge 442 and is one grain boundary. 44 is obtained a transparent conductive layer 4 comprising two one-sided edges 441 . Therefore, the first protrusion 42 can be reliably formed on the one surface 41 of the transparent conductive layer 4 .
  • Sputtering gases include noble gases with higher atomic numbers than argon.
  • Noble gases having atomic numbers greater than argon include, for example, krypton, xenon, and radon, preferably krypton (Kr).
  • the sputtering gas preferably does not contain argon.
  • a sputtering gas may be mixed with a reactive gas.
  • Reactive gases include, for example, oxygen.
  • the ratio of the introduction amount of the reactive gas to the total introduction amount of the sputtering gas and the reactive gas is, for example, 0.1 flow % or more, preferably 0.5 flow % or more, and, for example, 5 flow % or less. , preferably 3 flow % or less.
  • the amorphous transparent conductive layer 40 formed in the first step may not have the first protrusions 42 or may already have the first protrusions 42 .
  • the amorphous transparent conductive layer 40 is crystallized to form the crystalline transparent conductive layer 4 . Specifically, in the second step, the amorphous transparent conductive layer 40 is heated.
  • the heating temperature is, for example, 80° C. or higher, preferably 110° C. or higher, more preferably 130° C. or higher, particularly preferably 150° C. or higher, and for example, 200° C. or lower, preferably It is 180° C. or lower, more preferably 175° C. or lower, still more preferably 170° C. or lower.
  • the heating time is, for example, 1 minute or longer, preferably 3 minutes or longer, more preferably 5 minutes or longer, and is, for example, 5 hours or shorter, preferably 3 hours or shorter, more preferably 2 hours or shorter. be. Heating is performed, for example, under an air atmosphere.
  • the laminate 1 having the substrate layer 2, the base layer 3, and the transparent conductive layer 4 in order toward one side in the thickness direction is manufactured.
  • the heat shrinkage rate in the longitudinal direction (MD direction) of the laminate 1 when heated at 160 ° C. for 1 hour is not limited, and is, for example, 0.1% or more, preferably 0.2% or more. and is, for example, 2.0% or less, preferably 1.0% or less.
  • the thermal shrinkage rate in the width direction (direction perpendicular to the longitudinal direction and thickness direction) (TD direction) of the laminate 1 when heated at 160 ° C. for 1 hour for example, -0.2% or more, Preferably 0.00% or more, more preferably 0.01% or more, still more preferably 0.05% or more, and for example, 1.0% or less, preferably 0.5% or less be.
  • the first bumps 42 can be reliably formed on the one surface 41 of the transparent conductive layer 4 if the thermal contraction rate in each of the MD direction and the TD direction is equal to or higher than the above lower limit.
  • the total light transmittance of the laminate 1 is, for example, 75% or more, preferably 80% or more, more preferably 85% or more, preferably 86% or more, more preferably 87% or more, and For example, 100% or less.
  • the upper limit of the total light transmittance of the laminate 1 is not limited.
  • the total light transmittance of the laminate 1 is measured using a haze meter.
  • another layer 5 is arranged on one side of the laminate 1 in the thickness direction, that is, on one side 41 of the transparent conductive layer 4 in the thickness direction.
  • the coating layer 51 is formed by coating.
  • Other layers 51 include, for example, a light-modulating coating layer, a metal paste layer, and the like.
  • the other layer 5 is adjacent to one surface 41 of the transparent conductive layer 4 in the thickness direction.
  • the other layer 5 is, for example, a light control layer (voltage-driven light control coating such as PDLC, PNLC, SPD, or current-driven light control coating such as electrochromic (EC)), silver, It is a functional member such as a metal paste containing copper, titanium, or the like.
  • the laminate 1 is used for articles, for example.
  • the laminate 1 is an optical laminate, and the above-described articles include optical articles. More specifically, examples of articles include touch sensors, electromagnetic wave shields, light control elements, photoelectric conversion elements, heat ray control members, light-transmitting antenna members, light-transmitting heater members, image display devices, and lighting.
  • the base layer 3 does not have the second bumps 32 (see FIG. 2). Therefore, the crystal orientation of the crystalline transparent conductive layer 4 can be properly aligned. Therefore, the total light transmittance of the transparent conductive layer 4 can be increased. Therefore, since the laminate 1 includes the above-described transparent conductive layer 4, the total light transmittance is high.
  • one surface 41 in the thickness direction of the transparent conductive layer 4 is provided with a first protrusion 42 . Therefore, the transparent conductive layer 4 has excellent adhesion to the other layer 5 due to the anchor effect based on the first protrusions 42 .
  • one surface 31 in the thickness direction of the base layer 3 has a second protrusion 32 with a height of 3 nm or more. That is, in the laminate of the present invention, one surface of the underlayer in the thickness direction may be provided with a second bump having a height of 3 nm or more. Does not overlap the first ridge.
  • the second protrusions 32 described above do not overlap the first protrusions 42 of the transparent conductive layer 4 when projected in the thickness direction.
  • the number of first protrusions 42 per unit length is greater than the number of second protrusions 32 per unit length, for example.
  • the adhesive strength of the one surface 41 in the thickness direction of the transparent conductive layer 4 is surely improved, The total light transmittance of the transparent conductive layer 4 can be reliably increased.
  • the number of second protrusions 32 per unit length is, for example, 25/ ⁇ m or less, preferably 20/ ⁇ m or less, more preferably 10/ ⁇ m or less, still more preferably 5
  • the number of particles per micrometer is less than or equal to 0 per micrometer, or more than 1 per micrometer.
  • the ratio of the number of second protrusions 32 per unit length to the number of first protrusions 42 per unit length is, for example, 0.9 or less, preferably 0.5 or less, more preferably 0.3 or less. , more preferably 0.2 or less, particularly preferably 0.1 or less.
  • the ratio of the number of second protrusions 32 per unit length to the number of first protrusions 42 per unit length is, for example, 0.0001 or more.
  • the value obtained by subtracting the number per unit length of the second protrusions 32 from the number per unit length of the first protrusions 42 is, for example, 1/ ⁇ m or more, preferably 2/ ⁇ m or more, more preferably 5/ ⁇ m or more, more preferably 7/ ⁇ m or more, particularly preferably 10/ ⁇ m or more.
  • the value obtained by subtracting the number of second bumps 32 per unit length from the number of first bumps 42 per unit length is, for example, 30 pieces/ ⁇ m or less.
  • the method of providing the above-described second protrusions 32 on the underlying layer 3 is not particularly limited.
  • the crystallization of the first protrusion 42 causes the transparent conductive layer 4 to In the other surface of the thickness direction adjacent to the second protrusion 32 and its vicinity, the crystal orientation is difficult to align, that is, the crystal growth is inhibited, and the total light transmittance of the transparent conductive layer 4 decreases.
  • the second protrusions 32 do not overlap the first protrusions 42 of the transparent conductive layer 4 when projected in the thickness direction. Therefore, the total light transmittance of the transparent conductive layer 4 can be increased, and the total light transmittance of the laminate 1 can be increased.
  • one embodiment is preferred.
  • one surface 31 of the underlayer 3 does not have the second bumps 32, so that the crystal orientation in the transparent conductive layer 4 can be further adjusted. Therefore, the total light transmittance of the transparent conductive layer 4 can be increased, and the total light transmittance of the laminate 1 can be increased.
  • the laminate 1 does not include the base layer 2, but includes the underlying layer 3 and the transparent conductive layer 4. That is, in this modified example, the laminate 1 includes only the base layer 3 and the transparent conductive layer 4 .
  • the base layer 3 does not contain resin and is made of an inorganic substance.
  • inorganic substances include metal materials and ceramic materials.
  • Metal materials include, for example, silver, tin, chromium, and zirconium.
  • ceramic materials include glass.
  • the underlayer 3 of the modified example and the underlayer 3 of one embodiment the underlayer 3 of one embodiment is preferable. Since the base layer 3 of one embodiment contains a resin, the coefficient of thermal shrinkage is high, and compressive stress is applied to the laminate 1 including the base layer 3 and the transparent conductive layer 4 described above.
  • the transparent conductive layer 4 in which the grain boundary 44 does not include the other edge 442 and the one grain boundary 44 includes two one edge 441, and the first ridge 42 can be preferably formed, As a result, the total light transmittance can be increased.
  • Examples and comparative examples are shown below to describe the present invention more specifically.
  • the present invention is not limited to Examples and Comparative Examples.
  • specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( content ratio), physical properties, parameters, etc. can.
  • Example 1 An ultraviolet curable resin was applied to one surface 21 in the thickness direction of the substrate layer 2 made of a long PET film (thickness: 50 ⁇ m, manufactured by Toray Industries, Inc.) to form a coating film.
  • the ultraviolet curable resin composition contains an acrylic resin.
  • the coating film was cured by ultraviolet irradiation to form the underlayer 3 .
  • the thickness of the underlying layer 3 was 2 ⁇ m.
  • an amorphous transparent conductive layer 40 was formed on one surface 31 of the base layer 3 in the thickness direction by a reactive sputtering method (first step).
  • a DC magnetron sputtering apparatus was used in the reactive sputtering method.
  • Sputtering conditions in this example are as follows.
  • a sintered body of indium oxide and tin oxide was used as a target.
  • the tin oxide concentration in the sintered body was 10% by mass.
  • a DC power supply was used to apply voltage to the target.
  • the horizontal magnetic field strength on the target was set to 90 mT.
  • the film formation temperature was -8°C.
  • the film formation temperature is the surface temperature of the film formation roll, which is the same as the temperature of the substrate 30 . Further, after evacuating the film formation chamber to a final vacuum of 0.6 ⁇ 10 ⁇ 4 Pa in the DC magnetron sputtering apparatus, Kr as a sputtering gas and a reactive gas were introduced into the film formation chamber.
  • the ratio of the introduced amount of oxygen to the total introduced amount of Kr and oxygen introduced into the film forming chamber is about 2.6 flow rate %.
  • the oxygen introduction amount is within the region R of the resistivity-oxygen introduction amount curve, and the resistivity of the amorphous transparent conductive layer 40 is 6.3 ⁇ 10 ⁇ 4 ⁇ cm. adjusted to be The specific resistance-oxygen introduction amount curve shown in FIG. The dependence of the specific resistance of the layer 40 on the amount of introduced oxygen was investigated in advance.
  • the amorphous transparent conductive layer 40 was crystallized by heating in a hot air oven (second step).
  • the heating temperature was 160° C., and the heating time was 1 hour.
  • the thickness of the crystalline transparent conductive layer 4 was 145 nm.
  • a laminate 1 having a substrate layer 2, a base layer 3, and a crystalline transparent conductive layer 4 in order on one side in the thickness direction was manufactured (see FIG. 1).
  • Comparative example 1 A laminate 1 was produced in the same manner as in Example 1. However, the sputtering gas was changed from Kr to Ar, the atmospheric pressure in the deposition chamber was changed from 0.2 Pa to 0.4 Pa, and the ratio of the amount of introduced oxygen to the total amount of Ar and oxygen introduced into the deposition chamber was changed to Changed to about 1.6% flow rate.
  • Comparative example 2 A laminate 1 was produced in the same manner as in Comparative Example 1. However, an ultraviolet curable resin composition containing an acrylic resin and silica particles with a median diameter of 20 nm was used (see FIG. 7).
  • the cross section of each of the underlying layer 3 and the transparent conductive layer 4 was subjected to FE-TEM observation. The presence of each of the ridges 32 was confirmed.
  • the number of first protrusions 42 existing within a length of 1 ⁇ m on one surface 41 in the thickness direction of the transparent conductive layer 4 was counted. The observation magnification was set so that the existence and height of the first protrusion 42 and the second protrusion 32 could be observed.
  • the apparatus and measurement conditions are as follows.
  • FIB device Hitachi FB2200, acceleration voltage: 10 kV FE-TEM device; JEM-2800 manufactured by JEOL, acceleration voltage: 200 kV
  • Example 1 As a result, in both Example 1 and Comparative Example 1, the first bumps 42 were observed, but the second bumps 32 were not observed.
  • FIG. 4 shows an image processing diagram of the TEM photograph of Example 1. As shown in FIG. FIG. 5 shows a diagram in which the grain boundaries 44 in FIG. 4 are drawn with dashed lines.
  • the height of the highest protrusion was 15 nm.
  • the average height of the first bumps 42 obtained by selecting 10 arbitrary first bumps 42 was 7 nm. That is, the average height of the first bumps 42 was determined as the average height of arbitrary ten first bumps 42 .
  • Example 1 the number of first bumps 42 per unit length of the first bumps 42 in Example 1 and Comparative Example 1 was counted by TEM image (cross-sectional observation). As a result, in Example 1, the number was 10/ ⁇ m, and in Comparative Example 2, the number was 7/ ⁇ m.
  • the transparent conductive layer 4 in Comparative Examples 1 and 2 did not contain Kr atoms by confirming that there was no peak in the vicinity of the scanning angle of 28.2° in the X-ray spectrum. .
  • Thermal shrinkage rate of base material 30 and laminate 1 The thermal shrinkage rate was measured after heating the substrate 30 of Example 1 at 160° C. for 1 hour. As a result, the thermal contraction rate of the substrate 30 in the MD direction was 0.5%, and that of the laminate 1 in the TD direction was 0.1%.
  • the thermal shrinkage rate was measured after heating the laminate 1 of Example 1 at 160°C for 1 hour. As a result, the heat shrinkage rate of the laminate 1 in the MD direction was 0.4%, and that in the TD direction of the laminate 1 was 0.2%.
  • the laminate is used for optical articles.

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