JP6010078B2 - Light transmissive conductive film, method for producing the same, and use thereof - Google Patents

Description

  The present invention relates to a light-transmitting conductive film, a manufacturing method thereof, and an application thereof.

  As a light transmissive conductive film mounted on a touch panel, a light transmissive conductive layer containing indium oxide is disposed on at least one surface of a light transmissive support layer made of polyester or the like, directly or via another layer. Many such light-transmitting conductive films are used.

  When forming a light-transmitting conductive form as a grid-like electrode (so-called patterning), after placing the light-transmitting conductive film, the film is removed only in a predetermined region by chemical treatment, so-called etching. Processing is performed, and as a result, an electrode having a desired shape is formed. Therefore, the light-transmitting conductive film that is difficult to be etched by the etching process or excessively easily etched has a problem that it is difficult to pattern it into a desired shape.

  Thus, a light-transmitting conductive film having excellent characteristics (so-called etching property) that can be easily formed into a desired shape by an etching process is required as a light-transmitting conductive film mounted on a touch panel. It has been.

  Attempts have been made so far to provide a light-transmitting conductive form having excellent etching properties by controlling the crystallinity of a light-transmitting conductive layer containing indium oxide (Patent Document 1 and 2).

JP 2000-129427 A Japanese Patent No. 4269588

The present invention provides a light-transmitting conductive film comprising (A) a light-transmitting support layer containing a polyester resin and (B) a light-transmitting conductive layer containing indium oxide having excellent etching properties. This is the issue.

The inventors of the present invention have made extensive studies, and in the XRD measurement by the thin film method, a transparent conductive film in which the diffraction intensity of polyester and the diffraction intensity of indium oxide have a predetermined relationship can newly solve the above problem. I found it. The present invention has been completed by further various studies based on this new knowledge, and is as follows.
Item 1
(A) a light-transmissive support layer containing a polyester resin; and (B) a light-transmissive conductive layer containing indium oxide,
The light transmissive conductive layer (B) is a light transmissive conductive film disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers. And
_{(Ib α -Ib α-0.025 °} ) / (Ia α -Ia α-0.025 °)
The average value of the function f (α) represented by the formula is 0.08 to 5.00, wherein the light transmissive conductive film (where α is
α _min + n × 0.025 ° (n = 1, 2, 3,...)
(However, α _min is the minimum incident angle at which the peak of (222) plane can be confirmed in the thin film method XRD measurement within the range of 0.100 ° or more)
Is a variable represented by
Satisfying the following formulas (I) and (II):
α ≦ 0.600 ° ・ ・ ・ ・ (I)
f (α) ≧ 0.7 × f (α−0.025 °) (II)
Ia _α is the peak intensity around 2θ = 26 ° derived from the polyester resin in the thin film method XRD measurement at the incident angle α, and Ib _α is the (222) plane derived from indium oxide in the thin film method XRD measurement at the incident angle α. The peak intensity. ).
Item 2
Item 2. The light transmissive conductive film according to Item 1, wherein the thickness of the light transmissive support layer (A) is 20 to 200 µm.
Item 3
The polyester resin is polyethylene terephthalate, the optical transparent conductive film according to claim 1 or 2.
Item 4
Item 4. The light-transmitting conductive film according to any one of Items 1 to 3, wherein the light-transparent conductive layer (B) has a thickness of 15 to 30 nm.
Item 5
Item 5. The light transmissive conductive film according to any one of Items 1 to 4, which can be obtained by heating at 90 to 160 ° C in the air for 10 to 120 minutes.
Item 6
Item 6. The light transmissive conductive film according to any one of Items 1 to 5, wherein the light transmissive conductive layer (B) contains indium tin oxide that can be obtained by adding 3 to 10% of SnO ₂ to indium oxide. . Item 7
Item 7. A touch panel comprising the light transmissive conductive film according to any one of items 1 to 6.

  ADVANTAGE OF THE INVENTION According to this invention, the light-transmitting conductive film containing the light-transmitting conductive layer containing (A) light-transmitting support layer and (B) indium oxide which has the outstanding etching property can be provided.

It is sectional drawing which shows the transparent conductive film of this invention by which the transparent conductive layer (B) is arrange | positioned adjacent to the single side | surface of a transparent support layer (A). It is sectional drawing which shows the light transmissive conductive film of this invention by which the light transmissive conductive layer (B) is arrange | positioned adjacent to both surfaces of a light transmissive support layer (A). A diffraction intensity Ia derived from a polyester resin and a diffraction intensity Ib derived from indium oxide, respectively, measured at three consecutive X-ray incident angles (α−0.025 °, α °, α + 0.025 °) with a difference of 0.025 ° from each other. Is a graph obtained by plotting the diffraction intensity derived from a polyester resin on the horizontal axis and the diffraction intensity derived from indium oxide on the vertical axis. It is an example of the graph of a function f ((alpha)). 1 shows a light transmissive conductive film of the present invention in which an undercoat layer (C) and a light transmissive conductive layer (B) are arranged adjacent to each other in this order on one side of a light transmissive support layer (A). It is sectional drawing. The light-transmitting conductive film of the present invention is shown in which an undercoat layer (C) and a light-transmitting conductive layer (B) are arranged adjacent to each other in this order on both surfaces of the light-transmitting support layer (A). It is sectional drawing. The light of the present invention, wherein a hard coat layer (D), an undercoat layer (C), and a light transmissive conductive layer (B) are arranged adjacent to each other in this order on one side of the light transmissive support layer (A). It is sectional drawing which shows a permeable conductive film. The hard coat layer (D), the undercoat layer (C), and the light transmissive conductive layer (B) are arranged adjacent to each other in this order on one surface of the light transmissive support layer (A), and the other It is sectional drawing which shows the transparent conductive film of this invention by which another hard-coat layer (D) is directly arrange | positioned on the surface. The light of the present invention, wherein the hard coat layer (D), the undercoat layer (C), and the light transmissive conductive layer (B) are arranged adjacent to each other in this order on both surfaces of the light transmissive support layer (A). It is sectional drawing which shows a permeable conductive film.

1. Light transmissive conductive film The light transmissive conductive film of the present invention comprises:
(A) a light-transmissive support layer containing a polyester resin; and (B) a light-transmissive conductive layer containing indium oxide,
The light transmissive conductive layer (B) is a light transmissive conductive film disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers. And
_{(Ib α -Ib α-0.025 °} ) / (Ia α -Ia α-0.025 °)
The average value of the function f (α) represented by the formula is 0.08 to 5.00, wherein the light transmissive conductive film (where α is
α _min + n × 0.025 ° (n = 1, 2, 3,...)
(However, α _min is the minimum incident angle at which the peak of (222) plane can be confirmed in the thin film method XRD measurement within the range of 0.100 ° or more)
Is a variable represented by
Satisfying the following formulas (I) and (II):
α ≦ 0.600 ° ・ ・ ・ ・ (I)
f (α) ≧ 0.7 × f (α−0.025 °) (II)
Ia _α is the peak intensity around 2θ = 26 ° derived from the polyester resin in the thin film method XRD measurement at the incident angle α, and Ib _α is the (222) plane derived from indium oxide in the thin film method XRD measurement at the incident angle α. The peak intensity. )
It is.

  In the present invention, “light-transmitting” means having a property of transmitting light (translucent). “Light transmissivity” includes transparency. “Light transmissivity” means, for example, the property that the total light transmittance is 80% or more, preferably 85% or more, more preferably 87% or more. In the present invention, the total light transmittance is measured based on JIS-K-7105 using a haze meter (trade name: NDH-2000 manufactured by Nippon Denshoku Co., Ltd. or equivalent).

  In this specification, when mentioning the relative positional relationship between two layers among a plurality of layers arranged on one surface of the light transmissive support layer (A), the light transmissive support layer (A) is used as a reference. One layer having a large distance from the light transmissive support layer (A) is referred to as “upper layer” or “located above”, and the other layer having a small distance from the light transmissive support layer (A). May be referred to as “lower layer” or “located below”.

  In FIG. 1, the one aspect | mode of the transparent electroconductive film of this invention is shown. In this embodiment, the light transmissive conductive layer (B) is disposed adjacent to each other on one side of the light transmissive support layer (A). Such a light-transmitting conductive film is sometimes referred to as a “single-sided light-transmitting conductive film”.

  FIG. 2 shows another embodiment of the light transmissive conductive film of the present invention. In this embodiment, the light transmissive conductive layers (B) are disposed adjacent to each other on both surfaces of the light transmissive support layer (A). Such a light-transmitting conductive film is sometimes referred to as a “double-sided light-transmitting conductive film”.

1.1 Light transmissive support layer (A)
In the present invention, the light transmissive support layer refers to a light transmissive conductive film containing a light transmissive conductive layer, which plays a role of supporting the layer containing the light transmissive conductive layer. Although it does not specifically limit as a light transmissive support layer (A), For example, in the light transmissive conductive film for touch panels, what is normally used as a light transmissive support layer can be used.

The light transmissive support layer (A) contains a polyester resin. As the polyester resin is not particularly limited, good Mashiku is polyethylene terephthalate (PET), like polyethylene naphthalate (PEN) and the like. The polyester resin, in particular PE T is preferred. The light transmissive support layer (A) may contain two or more kinds of polyester resins.

The light transmissive support layer (A) may further contain other components. The light transmissive support layer (A) may further contain two or more other components in addition to the one or more polyester resins.

  The thickness of the light transmissive support layer (A) is not particularly limited, but is preferably 20 to 200 μm, more preferably 25 to 200 μm, more preferably 30 to 190 μm, and more preferably 50 to 150 μm. Further preferred. The thickness of the light-transmitting support layer is measured using a thickness measuring device (DIGIMICRO MF501 + MFC-101 manufactured by Nikon Corporation or equivalent).

1.2 Light transmissive conductive layer (B)
The light transmissive conductive layer (B) contains indium oxide, and may contain tin oxide and / or zinc oxide as a dopant. As the light-transmissive conductive layer (B), indium tin oxide (ITO) is preferable.

  The material of the light transmissive conductive layer (B) is not particularly limited, and examples thereof include indium oxide, zinc oxide, tin oxide, and titanium oxide. The light transmissive conductive layer (B) is preferably a light transmissive conductive layer containing indium oxide doped with a dopant in terms of achieving both transparency and conductivity. The light transmissive conductive layer (B) may be a light transmissive conductive layer made of indium oxide doped with a dopant. Although it does not specifically limit as a dopant, For example, a tin oxide, a zinc oxide, those mixtures, etc. are mentioned.

In the case of using indium oxide doped with tin oxide as the material of the light transmissive conductive layer (B), indium oxide (III) (In ₂ O ₃ ) doped with tin oxide (IV) (SnO ₂ ) (Tin-doped indium oxide; ITO) is preferable. In this case, the addition amount of SnO ₂ is not particularly limited, and examples thereof include 1 to 15% by weight, preferably 2 to 10% by weight, and more preferably 3 to 8% by weight. Moreover, you may use as a raw material of a transparent conductive layer (B) what added the other dopant to indium tin oxide in the range which the total amount of a dopant does not exceed the numerical range of the left. Although it does not specifically limit as another dopant in the left, For example, selenium etc. are mentioned.

  The light transmissive conductive layer (B) may be composed of any one of the various materials described above, or may be composed of a plurality of types.

  The light transmissive conductive layer (B) is not particularly limited, but may be a crystalline or amorphous body, or a mixture thereof.

  The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) directly or via one or more other layers.

  The light transmissive conductive layer (B) is crystallized by heat treatment. As the degree of crystallization progresses, the value of the function f (α) can be increased. In other words, the value of the function f (α) can be adjusted by obtaining an average value of the function f (α) in advance before the heat treatment and adjusting the degree of crystallization by performing the heat treatment as necessary. .

  In the light transmissive conductive layer (B), preferably, the peak of the (222) plane is the strongest in comparison with other peaks in the thin film method XRD measurement.

  The thickness of the light transmissive conductive layer (B) is 15 to 30 nm, preferably 16 to 28 nm, and more preferably 17 to 25 nm.

  The thickness of the light transmissive conductive layer (B) is measured as follows. It is measured by observation with a transmission electron microscope. Specifically, the light-transmitting conductive film is thinly cut in a direction perpendicular to the film surface using a microtome or a focus ion beam, and the cross section is observed.

  The method for forming the light transmissive conductive layer (B) may be either wet or dry.

  The method for forming the light transmissive conductive layer (B) is not particularly limited, and examples thereof include an ion plating method, a sputtering method, a vacuum deposition method, a CVD method, and a pulse laser deposition method. As a method for forming the light transmissive conductive layer (B), a sputtering method is preferable.

In order to obtain the light-transmitting conductive film of the present invention in which the diffraction intensity of the polyester resin and the diffraction intensity of indium oxide have a predetermined relationship in the XRD measurement of the incident angle α by the thin film method, the sputtering method is not particularly limited. In the case of forming the light transmissive conductive layer (B) by, for example, oxygen partial pressure, average surface roughness (Ra) of the underlying layer, partial pressure of water introduction, film formation temperature, and light transmissive conductive layer (B ) May be adjusted as appropriate.

1.3 Function f (α)
The light transmissive conductive film of the present invention is characterized in that the average value of the function f (α) is 0.08 to 5.00.

The function f (α) is
_{(Ib α -Ib α-0.025 °} ) / (Ia α -Ia α-0.025 °)
It is represented by

However,
Ia _α is the peak intensity around 2θ = 26 ° derived from the polyester resin in the thin film method XRD measurement at the incident angle α, and Ib _α is the (222) plane derived from indium oxide in the thin film method XRD measurement at the incident angle α. The peak intensity.

Ia _{α-0.025 °} is a peak intensity around 2θ = 26 ° derived from a polyester resin in a thin film method XRD measurement with an X-ray incident angle 0.025 ° smaller than the incident angle α, and Ib _{α-0.025 °} is the peak intensity of the (222) plane derived from indium oxide in the XRD measurement of the X-ray incident angle 0.025 ° smaller than the incident angle α.

That is, the function f (α) is obtained as follows. From two X-ray diffraction patterns measured at two X-ray incident angles with a difference of 0.025 °, diffraction intensity derived from two polyester resins and diffraction intensity derived from two indium oxides are obtained. The horizontal axis diffraction intensity derived from the polyester resin, and the diffraction intensity from indium oxide as the vertical axis, the diffraction of the diffraction intensity and from indium oxide-derived polyester resin were measured in the two X-ray incidence angle of 0.025 ° difference Plot two coordinates determined from intensity. The function f (α) is the slope of the straight line connecting the two points (FIG. 3).

Where α is
α _min + n × 0.025 ° (n = 1, 2, 3,...)
(However, α _min is the minimum incident angle at which the peak of (222) plane can be confirmed in the thin film method XRD measurement within the range of 0.100 ° or more)
Is a variable represented by
The following formulas (I) and (II) are satisfied.
α ≦ 0.600 ° ・ ・ ・ ・ (I)
f (α) ≧ 0.7 × f (α−0.025 °) (II)
Thus, the average value of the function f (α) means that when α is α _min + 1 × 0.025 °, α _min + 2 × 0.025 °, α _min + 3 × 0.025 °,. f (α) is the average value of each numerical value.

The minimum value of α is a value obtained by adding 1 × 0.025 ° to the minimum incident angle α _{min at} which the peak of the (222) plane can be confirmed in the thin film method XRD measurement within a range of 0.100 ° or more. is there.

  In the present invention, “the peak of (222) plane can be confirmed” means that the peak can be confirmed by a general method, that is, the peak can be confirmed when the background is subtracted by background processing. . For example, in a diffraction pattern in which 2θ is 28 ° to 34 °, the diffraction intensity derived from the (222) plane is obtained when the background processing is performed based on the profiles of 28 ° to 29 ° and 32 ° to 34 °. The stronger is applicable. In the above range, when diffraction from other substances appears, the base range may be changed as appropriate so as to avoid the diffraction, and background processing may be performed. More specifically, “(222) plane peak can be confirmed” means that the diffraction intensity of the (222) plane is higher than that of the diffraction pattern before and after the diffraction pattern in the above. Yes. In the above, for example, a comparison with a tendency of a diffraction pattern of 2.0 ° in the front-back direction may be performed. In the above, the comparison is preferably made with the tendency of the diffraction pattern of 1.5 ° before and after, more preferably with the tendency of the diffraction pattern of 1 ° before and after.

The maximum value of α is a maximum value satisfying f (α) ≧ 0.7 × f (α−0.025 °) or 0.600 ° whichever is smaller. However, when both are the same, the value is set to the maximum value of α. The respective coordinates determined from the diffraction intensity and the diffraction intensity from indium oxide derived from the polyester resin obtained from each of the X-ray diffraction pattern measured for each angle of incidence within the range, the horizontal diffraction intensity derived from the polyester resin Each point plotted with the vertical axis and the diffraction intensity derived from indium oxide as the vertical axis is almost linear (FIG. 3).

  In FIG. 4, the points surrounded by the dotted line frame satisfy the above formulas (I) and (II), and the point plotted fourth from the left is plotted third from the left. On the other hand, this is an example when the relationship of f (α) ≧ 0.7 × f (α−0.025 °) is not satisfied.

  In all the calculations above, the calculation is made to 3 digits after the decimal point and rounded off to 3 digits after the decimal point.

  X-ray diffraction is measured by a thin film method using a Rigaku Corporation thin film evaluation data horizontal X-ray diffractometer SmartLab or equivalent. A parallel beam optical arrangement is used, and a CuKα ray (wavelength: 1.5418Å) is used as a light source at a power of 40 kV and 30 mA. The incident side slit system uses a solar slit of 5.0 °, a height control slit of 10 mm, and an incident slit of 0.1 mm, and the light receiving side slit has a parallel slit analyzer (PSA) of 0.114 deg. Is used. The detector uses a scintillation counter. The sample stage uses a porous adsorption sample holder to adsorb and fix the sample to such an extent that the sample does not become uneven. If the curl is strong and cannot be fixed by suction, the end of the sample is supplementarily fixed with adhesive tape or the like and fixed by suction. The step interval and the measurement speed are appropriately adjusted so that the X-ray diffraction pattern can be recognized. As an example, the step interval and measurement speed are preferably 0.02 ° step interval and 1.5 ° / min measurement speed. The measurement range is 20 ° to 35 °.

  The measurement is performed in the range of the incident angle of X-rays of 0.1 to 0.6 ° in units of 0.025 ° in order from the low angle side. Since the intensity of the diffraction line varies depending on the fixed state of the sample, the sample remains fixed on the sample stage until a series of measurements is completed. The obtained X-ray diffraction pattern does not need to be monochromatic, and each peak intensity may be a value obtained by subtracting the background. The sample used is one that has been heat-treated at 150 ° C. for 1 hour in an air atmosphere by a blow dryer or the like.

  In the present invention, the thickness of each layer is determined by observation with a transmission electron microscope. Specifically, the light-transmitting conductive film is thinly cut in a direction perpendicular to the film surface using a microtome or a focus ion beam, and the cross section is observed.

1.4 Undercoat layer (C)
The light transmissive conductive film of the present invention further contains an undercoat layer (C), and at least one light transmissive conductive layer (B) is light transmissive supported via at least the undercoat layer (C). It may be arranged on the surface of the layer (A).

  The light transmissive conductive layer (B) may be disposed adjacent to the undercoat layer (C).

  In FIG. 5, the one aspect | mode of the single-sided transparent electroconductive film of this invention is shown. In this embodiment, the undercoat layer (C) and the light transmissive conductive layer (B) are disposed adjacent to each other in this order on one surface of the light transmissive support layer (A).

  In FIG. 6, the one aspect | mode of the double-sided transparent electroconductive film of this invention is shown. In this embodiment, the undercoat layer (C) and the light transmissive conductive layer (B) are disposed adjacent to each other in this order on both surfaces of the light transmissive support layer (A).

  Although the material of an undercoat layer (C) is not specifically limited, For example, you may have a dielectric property. The material for the undercoat layer (C) is not particularly limited. For example, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon alkoxide, alkylsiloxane and its condensate, polysiloxane, silsesquioxane, Examples include polysilazane and niobium oxide (V). The undercoat layer (C) may be composed of any one of them, or may be composed of a plurality of types.

As the undercoat layer (C), a layer containing SiO _x (x = 1.0 to 2.0) is preferable. The undercoat layer (C) may be a layer made of SiO _x (x = 1.0 to 2.0).

One layer of the undercoat layer (C) may be disposed. Alternatively, two or more layers may be arranged adjacent to each other or separated from each other via other layers. Two or more undercoat layers (C) are preferably disposed adjacent to each other. For example, when three layers are arranged adjacent to each other, an undercoat layer (d-2) made of SiO ₂ is interposed between them, and both are made of SiO _x (x = 1.0 to 2.0) so as to sandwich it. It is preferable to dispose the undercoat layers (d-1) and (d-3).

  Although it does not specifically limit as thickness per one layer of an undercoat layer (C), For example, 5-50 nm etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the undercoat layers (C) adjacent to each other may be within the above range.

The thickness of the undercoat layer (C) is measured as follows. Obtained by observation with a transmission electron microscope. Specifically, the light-transmitting conductive film is thinly cut perpendicularly to the film surface using a microtome or a focused ion beam, and the cross section is observed.
In addition, the undercoat layer (C) has a small amount of adhesion per unit area, such as to provide adhesion between the lower layer and the upper layer of the undercoat layer. Some of them cannot be confirmed. In such a case, the thickness of the undercoat layer (C) is determined based on a calibration curve prepared in advance by measuring the intensity based on the substance constituting the undercoat layer using a fluorescent X-ray analysis (XRF) apparatus. The amount of adhesion is calculated using the bulk density.

  The refractive index of the undercoat layer (C) is not particularly limited as long as the light-transmitting conductive film of the present invention can be used as a light-transmitting conductive film for a touch panel, but is preferably 1.4 to 1.5, for example.

  The method of disposing the undercoat layer (C) may be either wet or dry, and is not particularly limited. Examples of the wet include a sol-gel method, a fine particle dispersion, and a method of applying a colloid solution.

  As a method of disposing the undercoat layer (C), as a dry method, for example, a method of laminating on an adjacent layer by sputtering, ion plating, vacuum vapor deposition, chemical vapor deposition, and pulsed laser deposition Etc.

1.5 Hard coat layer (D)
The light transmissive conductive film of the present invention may further contain a hard coat layer (D).

  When the light-transmitting conductive film of the present invention contains a hard coat layer (D), at least one light-transmitting conductive layer (B) is at least a light-transmitting support layer through the hard coat layer (D). It is arrange | positioned on the surface of (A).

  In FIG. 7, the one aspect | mode of the single-sided transparent electroconductive film of this invention containing a hard-coat layer (D) is shown. In this embodiment, the hard coat layer (D), the undercoat layer (C), and the light transmissive conductive layer (B) are arranged adjacent to each other in this order on one surface of the light transmissive support layer (A). Yes.

  FIG. 8 shows another embodiment of the single-sided light-transmitting conductive film of the present invention containing the hard coat layer (D). In this embodiment, the hard coat layer (D), the undercoat layer (C), and the light transmissive conductive layer (B) are arranged adjacent to each other in this order on one surface of the light transmissive support layer (A). In addition, another hard coat layer (D) is directly disposed on the other surface of the light transmissive support layer (A).

  In FIG. 9, the one aspect | mode of the double-sided transparent electroconductive film of this invention containing a hard-coat layer (D) is shown. In this embodiment, the hard coat layer (D), the undercoat layer (C), and the light transmissive conductive layer (B) are arranged adjacent to each other in this order on both sides of the light transmissive support layer (A). Yes.

  Although it does not specifically limit as a hard-coat layer (D), For example, what is normally used as a hard-coat layer in the transparent conductive film for touchscreens can be used.

  The material of the hard coat layer (D) is not particularly limited, and examples thereof include acrylic resins, silicone resins, urethane resins, melamine resins, and alkyd resins. The hard coat layer may contain a filler containing silicon, niobium, zirconia, or the like in addition to the exemplified materials.

  Although the thickness per one layer of a hard-coat layer (D) is not specifically limited, For example, 0.1-3 micrometers, 0.2-2 micrometers, 0.3-1 micrometer etc. are mentioned. When two or more layers are disposed adjacent to each other, the total thickness of all the hard coat layers (D) adjacent to each other may be within the above range. In the example list shown on the left, the following are more preferable than the above. The thickness of the hard coat layer (D) is measured as follows. Obtained by observation with a transmission electron microscope. Specifically, the light-transmitting conductive film is thinly cut perpendicularly to the film surface using a microtome or a focused ion beam, and the cross section is observed.

  The method of disposing the hard coat layer (D) is not particularly limited, and examples thereof include a method of applying to a film and curing with heat, a method of curing with active energy rays such as ultraviolet rays and electron beams, and the like. From the viewpoint of productivity, a method of curing with ultraviolet rays is preferable.

  The light-transmitting conductive film of the present invention preferably does not contain the hard coat layer (D) or has a thickness of about 0.3 to 1 μm even if it is contained.

1.6 Other layers (E)
The light transmissive conductive film of the present invention has an undercoat layer (C) and a hard coat layer (D) on at least one surface of the light transmissive support layer (A) in addition to the light transmissive conductive layer (B). And at least one other layer selected from the group consisting of at least one other layer (E) different from them may be further disposed.

  Although it does not specifically limit as another layer (E), For example, an adhesive layer etc. are mentioned.

  The adhesive layer is a layer that is disposed between two layers so as to be adjacent to each other and to adhere the two layers to each other. Although it does not specifically limit as a contact bonding layer, For example, what is normally used as a contact bonding layer in the transparent conductive film for touchscreens can be used. The adhesive layer may be composed of any one of these, or may be composed of a plurality of types.

  Further, an inorganic layer containing copper, nickel, silver, chromium, or the like may be formed on the light transmissive conductive layer. At this time, XRD measurement may not be possible due to the presence of the inorganic layer. In this case, the inorganic layer is removed with an acid aqueous solution or an alkaline aqueous solution containing sulfate, chloride, ammonium salt or hydroxide. Then, XRD measurement may be performed after washing as appropriate.

1.7 Use of the light-transmitting conductive film of the present invention The light-transmitting conductive film of the present invention is excellent in etching property, and thus the light-transmitting conductive layer (B) can be easily patterned.

  Therefore, the light transmissive conductive film of the present invention is suitable for an application to be used after patterning the light transmissive conductive layer (B).

  The patterning method is not particularly limited, but is performed, for example, as follows. First, a resist (a protective film for protecting the layer from the etching solution) is applied to the region to be left on the light-transmitting conductive layer. The application means may be performed by screen printing depending on the type of the resist. If a photoresist is used, it is performed as follows. Apply the photoresist to the area you want to leave on the light-transmitting conductive layer using a spin coater or slit coater, etc., and partially irradiate light or an electron beam to change the solubility of the photoresist only in that area. Thereafter, the portion having relatively low solubility is removed (this is called development). In this way, the resist is present only in the region to be left on the light-transmitting conductive layer. Subsequently, an etching solution is allowed to act on the light-transmitting conductive layer to selectively dissolve a region of the light-transmitting conductive layer that is not protected by the resist, and finally, the dissolved matter is removed to thereby remove the pattern. Form.

  The shape of the pattern formed by patterning is not particularly limited, but is usually striped or diamond-shaped. A lattice-like pattern can be formed by superimposing two light-transmitting conductive films patterned in stripes so that the stripe directions are orthogonal to each other.

  Although it does not specifically limit as a use used after patterning a light transmissive conductive layer (B), For example, a touch panel, electronic paper, a solar cell, etc. are mentioned. Details of the touch panel are as described in 2.

2. Touch panel of the present invention The touch panel of the present invention includes the light-transmitting conductive film of the present invention, and further includes other members as necessary.

Specific examples of the configuration of the touch panel of the present invention include the following configurations. The protective layer (1) side is used so that the operation screen side faces, and the glass (5) side faces the side opposite to the operation screen.
(1) Protective layer (2) Light transmissive conductive film of the present invention (Y-axis direction)
(3) Insulating layer (4) Light transmissive conductive film of the present invention (X-axis direction)
(5) Glass Although the touch panel of this invention is not specifically limited, For example, it can manufacture by combining said (1)-(5) and another member according to a normal method as needed.

3. Method for producing light-transmitting conductive film of the present invention The method for manufacturing a light-transmitting conductive film of the present invention comprises a light-transmitting conductive layer on at least one surface of the light-transmitting support layer (A). (B) is included, respectively.

  In the method for producing a light transmissive conductive film of the present invention, in addition to the light transmissive conductive layer (B), an undercoat layer (C), a hard coat is formed on at least one surface of the light transmissive support layer (A). A step of arranging at least one layer selected from the group consisting of the layer (D) and at least one other layer (E) different from the layer (D) may be included.

In the above, the process of disposing each layer is as described for each layer. The order in which each layer is arranged is not particularly limited. For example, the light transmissive support layer (A) may be sequentially disposed on at least one surface from the light transmissive support layer (A) side.
Alternatively, for example, another layer may be first disposed on one surface of a layer that is not the light-transmitting support layer (A) (for example, the light-transmitting conductive layer (B)). Alternatively, one composite layer is obtained by arranging two or more layers adjacent to each other on the one hand, or at the same time, two or more layers are similarly disposed adjacent to each other on the other side. Thus, one type of composite layer may be obtained, and these two types of composite layers may be further arranged adjacent to each other.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Example 1
An SiO ₂ layer having a thickness of 20 nm was formed on a PET resin substrate having a thickness of 125 μm, and an indium tin oxide film having a thickness of 16 nm was further formed. Specifically, a SiO ₂ layer is formed by a DC magnetron sputtering method using a sintered body material made of indium oxide: 95% by weight and tin oxide: 5% by weight as a target material, and light-transmitting is formed thereon. A conductive layer was formed. Heat treatment was performed in the air to finally obtain the light-transmitting conductive film of the present invention.

The light transmissive conductive layer was formed as follows. After evacuating the chamber to 3.0 × 10 ⁻⁴ Pa or less, oxygen gas and argon gas are introduced into the chamber so that the partial pressure of oxygen is 4.5 × 10 ⁻³ Pa. Sputtering was performed at a pressure of 0.2 to 0.3 Pa and a film formation temperature of 50 ° C.

  Then, what was heat-processed at 150 degreeC for 60 minutes in air | atmosphere was evaluated by XRD. The average value of the function f (α) was 1.07. Further, the surface roughness (Ra) of the underlayer was 1.4 nm.

  In all Examples and Comparative Examples, XRD measurement by the thin film method and surface roughness (Ra) of the underlayer were performed as follows. X-ray diffraction was measured by a thin film method using a Rigaku Corporation thin film evaluation data horizontal X-ray diffractometer SmartLab. A parallel beam optical arrangement is used, and a CuKα ray (wavelength: 1.5418Å) is used as a light source at a power of 40 kV and 30 mA. The incident side slit system uses a solar slit of 5.0 °, a height control slit of 10 mm, and an incident slit of 0.1 mm, and the light receiving side slit has a parallel slit analyzer (PSA) of 0.114 deg. Was used. The detector used was a scintillation counter. The sample stage used a porous adsorption sample holder, and the sample was adsorbed and fixed to such an extent that the sample was not uneven. The step interval and measurement speed were 0.02 ° step interval, 1.5 ° / min measurement speed, and the measurement range was 20 ° to 35 °.

  The XRD measurement was performed by changing the X-ray incident angle in the range of 0.1 to 0.6 ° in units of 0.025 ° in order from the low angle side. Since the intensity of the diffraction line varies depending on the fixed state of the sample, the sample was kept fixed on the sample stage until a series of measurements was completed. Further, the obtained X-ray diffraction pattern is not monochromatic.

  From the X-ray diffraction pattern, the peak intensity in the vicinity of 2θ = 26 ° derived from PET resin and the peak intensity of the (222) plane derived from indium tin oxide at the incident angle α are obtained, and the average value of the function f (α) of the present invention is obtained. It was.

  The surface roughness (Ra) of the underlayer is 1 μm in a predetermined contact mode using an atomic force microscope (Shimadzu Corporation, SPM-9700) by preparing a sample without forming a light-transmitting conductive layer. It is a value obtained by averaging the absolute deviation from the average line obtained by scanning the square measurement surface with a probe (OMCL-TR800-PSA-1 spring constant 0.15 N / m, manufactured by OLYMPUS).

Example 2
A SiO ₂ layer having a thickness of 20 nm was formed on a 125 μm-thick PET resin substrate, and an indium tin oxide film having a thickness of 22 nm was formed. Other than that was carried out similarly to Example 1, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 2.86.

Example 3
A SiO ₂ layer having a thickness of 20 nm was formed on a 125 μm-thick PET resin substrate, and an indium tin oxide film having a thickness of 28 nm was formed. Other than that was carried out similarly to Example 1, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 4.15.

Comparative Example 1
A SiO ₂ layer of 20 nm was formed on a 125 μm thick PET resin substrate, and indium tin oxide was formed to a thickness of 34 nm. Other than that was carried out similarly to Example 1, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 5.26.

Example 4
A SiO ₂ layer having a thickness of 10 nm was formed on a 125 μm-thick PET resin substrate, and an indium tin oxide film having a thickness of 22 nm was further formed. Specifically, a SiO ₂ layer is formed by a DC magnetron sputtering method using a sintered body material consisting of 95% by weight of indium oxide and 5% by weight of tin oxide as a target agent, and light-transmitting is formed thereon. A conductive layer was formed. Heat treatment was performed in the air to finally obtain the light-transmitting conductive film of the present invention.

The light transmissive conductive layer was formed as follows. After evacuating the chamber to 3.0 × 10 ⁻⁴ Pa or less, the oxygen partial pressure is 4.5 × 10 ⁻³ Pa and the water pressure is 2.0 × 10 ⁻⁴ Pa in the chamber. Oxygen gas, water, and argon gas were introduced, the pressure in the chamber was set to 0.2 to 0.3 Pa, and the film formation temperature was set to 50 ° C. to perform the sputtering treatment. Then, what was heat-processed at 150 degreeC for 60 minutes in air | atmosphere was evaluated by XRD. The average value of the function f (α) was 1.54. Further, Ra of the underlayer was 1.4 nm.

Example 5
The light transmissive conductive layer was formed as follows. After evacuating the chamber to 3.0 × 10 ⁻⁴ Pa or less, the oxygen partial pressure in the chamber becomes 4.5 × 10 ⁻³ Pa and the water pressure becomes 3.0 × 10 ⁻³ Pa. Oxygen gas, water, and argon gas were introduced, the pressure in the chamber was set to 0.2 to 0.3 Pa, and the film formation temperature was set to 50 ° C. to perform the sputtering treatment. Other than that was carried out similarly to Example 4, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 0.25.

Example 6
The film forming temperature of the light transmissive conductive layer was 80 ° C. Other than that was obtained by the manufacturing method similar to Example 5, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 0.87.

Example 7
The substrate was not heated during the formation of the light transmissive conductive layer. Other than that was obtained by the manufacturing method similar to Example 5, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 0.15.

Comparative Example 2
The light transmissive conductive layer was formed as follows. After evacuating the chamber to 3.0 × 10 ⁻⁴ Pa or less, the oxygen partial pressure is 4.5 × 10 ⁻³ Pa and the moisture pressure is 2.0 × 10 ⁻² Pa in the chamber. Oxygen gas, water, and argon gas were introduced, the pressure in the chamber was set to 0.2 to 0.3 Pa, and the film formation temperature was set to 50 ° C. to perform the sputtering treatment. Other than that was obtained by the manufacturing method similar to Example 4, and obtained the transparent electroconductive film of this invention.
As a result of the XRD evaluation, diffraction on the (222) plane derived from indium oxide was not observed.

Example 8
A SiO ₂ layer having a thickness of 20 nm was formed on a PET resin substrate having a thickness of 100 μm, and an indium tin oxide film having a thickness of 22 nm was further formed. Specifically, a SiO ₂ layer is formed by a DC magnetron sputtering method using a sintered body material consisting of 95% by weight of indium oxide and 5% by weight of tin oxide as a target agent, and light-transmitting is formed thereon. A conductive layer was formed. Heat treatment was performed in the air to finally obtain the light-transmitting conductive film of the present invention.

At this time, the sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was set to 0.7 nm. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 1.63.

Example 9
The sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was set to 2.5 nm. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 3.65.

Example 10
The sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was 3.6 nm. In addition, the substrate was not heated during the formation of the light-transmitting conductive layer. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 3.78.

Example 11
The sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was 3.6 nm. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 4.55.

Example 12
The sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was 4.2 nm. Further, as a target material, a sintered body material composed of indium oxide: 91% by weight and tin oxide: 9% by weight was used. Other than that was carried out similarly to Example 10, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 4.77.

Comparative Example 3
The sputtering power during the SiO ₂ film formation was adjusted, and the surface roughness (Ra) of the underlayer was 4.2 nm. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 8.46.

Example 13
Oxygen gas and argon gas were introduced so that the oxygen partial pressure in the chamber was 3.2 × 10 ⁻³ Pa when the light-transmitting conductive layer was formed. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 1.39.

Example 14
Oxygen gas and argon gas were introduced so that the oxygen partial pressure in the chamber was 5.4 × 10 ⁻³ Pa when the light-transmitting conductive layer was formed. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 3.82.

Example 15
As a target material, a sintered body material composed of indium oxide: 92% by weight and tin oxide: 8% by weight was used. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 2.38.

Example 16
The light transmissive conductive layer was formed as follows. After evacuating the chamber to 3.0 × 10 ⁻⁴ Pa or lower, the oxygen partial pressure is 4.5 × 10 ⁻³ Pa and the water pressure is 1.0 × 10 ⁻⁴ Pa in the chamber. Oxygen gas, water, and argon gas were introduced, the pressure in the chamber was set to 0.2 to 0.3 Pa, and the film formation temperature was set to 50 ° C. to perform the sputtering treatment. Other than that was carried out similarly to Example 4, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 1.86.

Example 17
The light transmissive conductive film of the present invention was obtained in the same manner as in Example 16 except that the moisture pressure was 7.0 × 10 ⁻⁴ Pa. As a result of evaluation by XRD, the average value of the function f (α) was 1.02.

Example 18
The light-transmitting conductive film of the present invention was obtained in the same manner as in Example 2 except that the sputtering power during the SiO ₂ film formation was adjusted and the surface roughness (Ra) of the underlayer was set to 0.3 nm. As a result of evaluation by XRD, the average value of the function f (α) was 1.40.

Example 19
The light-transmitting conductive film of the present invention was obtained in the same manner as in Example 2 except that the sputtering power during the SiO ₂ film formation was adjusted and the surface roughness (Ra) of the underlayer was 0.5 nm. As a result of evaluation by XRD, the average value of the function f (α) was 1.46.

Example 20
The same as in Example 16 except that the sputtering power during the SiO ₂ film formation was adjusted, the surface roughness (Ra) of the underlayer was set to 2.5 nm, and SiO ₂ was further formed to 20 nm on the PET resin substrate. A light transmissive conductive film of the invention was obtained. As a result of evaluation by XRD, the average value of the function f (α) was 3.65.

Example 21
The light-transmitting conductive film of the present invention was obtained in the same manner as in Example 2 except that the oxygen partial pressure was 4.0 × 10 ⁻³ Pa. As a result of evaluation by XRD, the average value of the function f (α) was 2.33.

Example 22
The light transmissive conductive film of the present invention was obtained in the same manner as in Example 2 except that the oxygen partial pressure was 4.9 × 10 ⁻³ Pa. As a result of evaluation by XRD, the average value of the function f (α) was 2.98.

Comparative Example 4
Oxygen gas and argon gas were introduced so that the oxygen partial pressure in the chamber was 6.6 × 10 ⁻³ Pa when the light-transmitting conductive layer was formed. Other than that was carried out similarly to Example 2, and obtained the transparent electroconductive film of this invention. As a result of evaluation by XRD, the average value of the function f (α) was 6.16.

Comparative Example 5
A SiO ₂ layer having a thickness of 20 nm was formed on a PET resin substrate having a thickness of 125 μm, and an indium tin oxide film having a thickness of 10 nm was formed. Other than that was carried out similarly to Example 1, and obtained the transparent electroconductive film of this invention. As a result of the XRD evaluation, diffraction on the (222) plane derived from indium oxide was not observed.

  Evaluation of the etching characteristics was performed as follows. The light transmissive conductive film was immersed in 20% hydrochloric acid, and the time until the surface resistance could not be measured was determined. For the light-transmitting conductive film, the immersion time was set at intervals of 10 seconds from 10 seconds to 90 seconds, and the time when the surface resistance became impossible to measure was defined as the etching processing completion time.

  When the etching processing completion time is 40 seconds and 50 seconds, “◎”, when 30 seconds, 60 seconds, and 70 seconds, “◯”, when 20 seconds and 80 seconds, “△”, 10 seconds, 90 seconds, and More than that was evaluated as “x”.

  Table 1 shows the average value of the function f (α), the evaluation results of the etching characteristics, and the like for all the examples and comparative examples. Note that “222NG” in the table indicates that diffraction of the (222) plane derived from indium oxide is recognized even when the incident angle is changed in increments of 0.025 ° in the range of 0.100 ° or more. The case where it was not able to be shown is shown.

  From the results in Table 1, the evaluation result of the etching characteristics is “Δ” or better when the average value of the function f (α) is 0.08 to 5.00, and is 0.2 to 4.00. It turns out that it becomes "(circle)" or a better result at one time, and becomes ((double-circle)) when it exists in 1.5-3.00.

  “ITO (%)” indicates the concentration of tin oxide which is an impurity other than indium oxide contained in the target. For example, “5%” indicates that targets of 95% by weight of indium oxide and 5% by weight of tin oxide were used.

  The film thickness of ITO was determined by observation with a transmission electron microscope. Specifically, the light-transmitting conductive film was cut thinly in the direction perpendicular to the film surface using a focused ion beam, and obtained by observing the cross section.

1 Light-transmissive conductive film 11 Light-transmissive support layer (A)
12 Light transmissive conductive layer (B)
13 Undercoat layer (C)
14 Hard coat layer (D)

Claims (4)

(A) a light transmissive support layer containing a polyethylene terephthalate resin; and (B) a light transmissive conductive layer containing indium tin oxide,
The light transmissive conductive layer (B) is disposed on at least one surface of the light transmissive support layer (A) via an undercoat layer or another layer other than the undercoat layer. A sex film,
_{(Ib α -Ib α-0.025 °} ) / (Ia α -Ia α-0.025 °)
The average value of the function f (α) represented by the formula is 0.08 to 5.00, wherein the light transmissive conductive film (where α is
α _min + n × 0.025 ° (n = 1, 2, 3,...)
(However, α _min is the minimum incident angle at which the peak of (222) plane can be confirmed in the thin film method XRD measurement within the range of 0.100 ° or more)
Is a variable represented by
Satisfying the following formulas (I) and (II):
α ≦ 0.600 ° ・ ・ ・ ・ (I)
f (α) ≧ 0.7 × f (α−0.025 °) (II)
Ia _α is a peak intensity around 2θ = 26 ° derived from polyethylene terephthalate in the thin film method XRD measurement at an incident angle α, and Ib _α is a (222) plane derived from indium oxide in the thin film method XRD measurement at an incident angle α. The peak intensity. ). The light transmissive conductive film according to claim 1, wherein the light transmissive support layer (A) has a thickness of 20 to 200 μm. The light-transmitting conductive film according to claim 1 or 2 , wherein the light-transparent conductive layer (B) has a thickness of 15 to 30 nm. Containing a light transmissive conductive film according to any one of claims 1 to 3 touch panel.

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