TW202307873A - transparent conductive film - Google Patents

Abstract

The purpose of the present invention is to provide a transparent conductive film that has excellent input stability and suitable-input strength. A transparent conductive film according to the present invention has a transparent conductive membrane of an indium-tin complex oxide laminated on at least one surface of a transparent plastic film base material, and exhibits an input initial load of more than 15g but not more than 25g and a voltage loss time of 0.00-0.40 msec. Preferably, the transparent conductive film has a film bending resistance (BR) of 0.38-0.90 N·cm, and has an average (AVSp), of maximum peak height Sp in an electrically conductive surface, satisfying formula (2-1). Formula (2-1): 4.7*BR-3.6 ≤ AVSp < 4.7*BR-1.8 (in the formula, BR represents the film bending resistance (N·cm), and AVSp represents the average maximum peak height ([mu]m)).

Description

transparent conductive film

The present invention relates to a transparent conductive film in which a transparent conductive film of indium-tin composite oxide is laminated on a transparent plastic film substrate.

A transparent conductive film in which a transparent and low-resistance film is laminated on a transparent plastic substrate is widely used in applications utilizing its conductivity, for example, as flat-panel displays such as liquid crystal displays and electroluminescence (EL) displays. , transparent electrodes of touch panels, etc., and are widely used in the fields of electric appliances and electronics.

The resistive film type touch panel is a combination of a fixed electrode coated with a transparent conductive film on a glass or plastic substrate, and a movable electrode (which can be called a thin film electrode) coated with a transparent conductive film on a plastic film. It is used by being superimposed on the upper side of the display body. When the thin-film electrode is pressed with a finger or a pen (referred to as input), the fixed electrode and the transparent conductive film of the thin-film electrode come into contact with each other, and the input position is recognized.

Patent Document 1 discloses a transparent conductive laminate for a touch panel in which at least one surface layer of a polymer film substantially mainly includes a transparent conductive film of crystalline indium oxide. To improve note durability by crystallizing indium oxide. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2004-071171

[Problem to be solved by the invention]

In the touch panel, even if input is continuously performed with a pen, characteristics such as cracking, peeling, and abrasion do not occur in the transparent conductive film (pen sliding durability) are required. In addition, in touch panels, an appropriate range of input strength (adaptive input strength) is required. For example, when pressing the film electrode with a finger, pen, etc., so that the transparent conductive film of the fixed electrode and the film electrode contacts each other, there is a situation where the hand or sleeve accidentally touches the touch panel. Touch the touch panel by mistake with a pen etc. while feeling hesitant on the screen. It is desirable that the number of inputs due to such accidental touch on the touch panel be small (wrong input prevention). However, if the erroneous input prevention property is improved, the comfortable input property tends to decrease. Comfortable input performance means that when inputting with a pen, finger, etc. on a resistive film touch panel, input can be performed even if no force is applied consciously. Both prevention of wrong input and comfortable input are required.

In addition, in terms of touch panels, excellent input stability is required, that is, stable input to the touch panel is required from when the touch panel is touched with a pen or the like to when it is released. For example, it is required to be able to reduce the blurring of characters that occurs when continuously inputting characters (fast writing performance), and to prevent blurring of the swiping strokes of characters (swiping stroke input performance). In the technique of Patent Document 1, the pen sliding durability cannot be improved without crystallizing indium oxide. In addition, conventional transparent conductive film systems including Patent Document 1 are insufficient in terms of input strength (wrong input prevention, comfortable input), input stability (fast writing, swiping stroke input), and the like.

Accordingly, an object of the present invention is to provide a transparent conductive film excellent in adaptive input strength and input stability. In addition, a preferable object of the present invention is to provide a transparent conductive film further having pen sliding durability. [Means to solve the problem]

The present invention is made in view of the above-mentioned situation, and the transparent conductive film of the present invention that can solve the above-mentioned problems includes the following configurations. [1] A transparent conductive film, which is a transparent conductive film with a transparent conductive film of indium-tin composite oxide on at least one area layer on a transparent plastic film substrate, and the input load obtained by test method 1 It is more than 15g and less than 25g, and the voltage loss time obtained by the test method 2 is not less than 0.00 milliseconds and not more than 0.40 milliseconds. [Test method 1] Form an indium-tin composite oxide conductive film (tin oxide content: 10% by mass) with a thickness of 20 nm on one side of a glass substrate, and place dots of epoxy resin on the surface of the film at a pitch of 4 mm. The spacers (60 μm in length×60 μm in width×5 μm in height) were formed in a square lattice shape as a panel board. On the conductive film side of this panel board, an adhesive rectangular frame with a thickness of 105 μm and an inner circumference of 190 mm×135 mm was interposed, and transparent conductive films were stacked so that the conductive films faced each other to prepare an evaluation panel. From the transparent conductive film side of the evaluation panel, continuously press the center of the 4-point grid of dot-shaped spacers with a polyacetal pen whose tip is hemispherical with a radius of 0.8 mm, and set the pressure at which the resistance value starts to stabilize as the input start load . [Test method 2] Connect the above-mentioned evaluation panel to a constant voltage power supply of 6V, and use a pen with a hemispherical tip with a radius of 0.8mm from the side of the transparent conductive film to press the dot shape with a load of 50gf at intervals of 5 times/second. The center of the 4-point grid of the interstitial. Starting from the time when the pen started to separate from the transparent conductive film and the voltage began to decrease from 6V, the time until the voltage reached 5V was measured, and it was defined as the voltage loss time. [2] The transparent conductive film as in [1], wherein the rigidity (BR) of the film obtained by test method 3 is 0.38N. 0.90N above cm. cm or less, the average (AVSp) of the maximum peak height Sp of the conductive surface obtained by test method 4 satisfies the following formula (2-1) and formula (2-2), and the contact area ratio obtained by test method 5 (CA) satisfies the following formula (2-3). 4.7×BR-3.6≦AVSp<4.7×BR-1.8. ． ． Formula (2-1) 0.005≦AVSp≦12.000. ． ． Formula (2-2) CA≧32.6×BR+17.2. ． ． Formula (2-3) (In the formula, the stiffness and softness of the BR series film (N.cm), the average maximum mountain height of the AVSp series (μm), and the contact area ratio of the CA series (%)) [Test method 3] Make the transparent conductive film toward Put a 20 mm x 250 mm transparent conductive film test piece on a horizontal platform, make the test piece protrude from the end point of the horizontal platform by a length of 230 mm, and determine the rigidity (BR) based on the following formula. Rigidity (BR(N.cm))=g×a×b×L ⁴ /(8×δ×10 ¹¹ ) (where g is 9.81 (gravitational acceleration; m/s ² ), a is 20( The length of the short side of the test piece; mm), b represents the specific gravity of the test piece (g/cm ³ ), L is 230 (the length of the long side of the test piece exposed outside the horizontal platform; mm), δ represents the test piece The difference between the height of the front end and the height of the horizontal platform (cm) [Test method 4] On the conductive surface of the transparent conductive film, three points are determined at intervals of 1 cm in the MD direction, and at intervals of 1 cm from the center, on the Determining 2 points symmetrically in the TD direction, a total of 5 measurement points, measuring the maximum peak height Sp (according to ISO 25178) based on the surface roughness at each place, and taking the average value as the average maximum peak height (AVSp) (μm) . [Test method 5] For the conductive surface of the transparent conductive film, measure the average height Rc (μm), the maximum peak height Rp (μm), and the average length Rsm (μm) based on the line roughness, and satisfy the formula (X1) and the formula At least one of (X2) and the place of formula (X3) measured the arithmetic mean height Ra (micrometer) based on the line roughness. Also, the average height Rc (μm), the maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) were measured using a three-dimensional surface shape measuring device VertScan (manufactured by Ryoka System Co., Ltd., R5500H-M100 (Measurement conditions: wave mode, measurement wavelength 560nm, objective lens 50 times)) to determine. The maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) are determined in accordance with the provisions of JIS B 0601-2001. The measurement length of arithmetic mean height Ra (micrometer) shall be 100 micrometers or more and 200 micrometers or less. Rp-Rc-Ra≦0.20． ． ． Formula (X1) (Rp-Rc)/Ra≦5.0. ． ． Formula (X2) Rsm≦30. ． ． Formula (X3) changes the objective lens of the VertScan 3D surface shape measurement device to 10 times, and uses the particle analysis of the same measurement device to achieve "arithmetic mean height Ra(μm)-15×10 ^-3 ( μm)-average height Rc(μm)”, slice in the plane direction and calculate the sum of the cross-sectional areas. The value obtained by dividing the sum of the cross-sectional areas by the area of the measurement field of view was multiplied by 100 as the contact area ratio (CA) (%). [3] The transparent conductive film according to [2], wherein the maximum value MXSp of the maximum peak height Sp obtained by the aforementioned test method 4 is more than 1.0 times and not more than 1.4 times the aforementioned average maximum peak height AVSp, and is determined by the aforementioned test method. The minimum value MNSp of the maximum mountain height Sp obtained by the method 4 is 0.6 to 1.0 times the above-mentioned average maximum mountain height AVSp. [4] The transparent conductive film according to any one of [1] to [3], wherein the transparent conductive film has a thickness of not less than 10 nm and not more than 100 nm. [5] The transparent conductive film according to any one of [1] to [4], wherein the concentration of tin oxide contained in the transparent conductive film is not less than 0.5% by mass and not more than 40% by mass. [6] The transparent conductive film according to any one of [1] to [5], wherein there is a curable resin layer between the transparent conductive film and the transparent plastic film substrate, and further between the transparent plastic substrate and the aforementioned The transparent conductive film is on the opposite side and has a functional layer. [7] The transparent conductive film according to any one of [1] to [6], which has an easy-adhesive layer on at least one side of the transparent plastic film substrate. [8] The transparent conductive film according to [7], wherein the easy-adhesive layer is disposed at least one of between the transparent plastic film substrate and the curable resin layer, or between the transparent plastic substrate and the functional layer. [9] The transparent conductive film according to any one of [1] to [8], wherein the ON resistance specified by Test Method 6 is 10 kΩ or less. [Test method 6] An indium-tin composite oxide conductive film with a thickness of 20 nm (tin oxide content: 10 mass %)) and a transparent conductive film to make an evaluation panel. On the transparent conductive film side of the evaluation panel, a pen with a hemispherical polyacetal pen with a radius of 0.8 mm was used to slide while applying a load of 2.5 N (50,000 times of back and forth, sliding distance 30 mm, sliding speed 180 mm/ Second). After sliding, the sliding part was pressed with a pen load of 0.8N, and the resistance (ON resistance) at the time of electrical connection was measured. [10] The transparent conductive film according to any one of [1] to [9], wherein in the adhesion test according to JIS K5600-5-6:1999 on the surface of the transparent conductive film, the residue of the transparent conductive film The area rate is above 95%. [Effect of Invention]

According to the present invention, it is possible to provide a transparent conductive film excellent in adaptive input strength and input stability. In addition, according to the present invention, in a preferable case, it is possible to provide a transparent conductive film further having pen sliding durability.

[Mode for Carrying Out the Invention]

1. Transparent conductive film The transparent conductive film of the present invention is a transparent conductive film in which a transparent conductive film of indium-tin composite oxide is layered on at least one area of a transparent plastic film substrate. By having a transparent conductive film on the surface, it can be widely used in applications that utilize its conductivity, for example, it can be used as a transparent electrode of a liquid crystal display, an electroluminescent (EL) display, etc., a transparent electrode of a touch panel, etc. Widely used in electrical and electronic fields. The specific layer configuration of the transparent conductive thin film can be appropriately set, and for example, configurations shown in schematic side views such as FIG. 1 , FIG. 2 , FIG. 3 , and FIG. 4 can be exemplified.

The transparent conductive film of FIG. 1 is formed on one side of a transparent plastic film substrate 7 with a transparent conductive film 5 interposed therebetween a curable resin layer 6 , and a functional layer 8 is formed on the opposite surface of the transparent plastic film substrate 7 . If the curable resin layer 6 is formed between the transparent conductive film 5 and the transparent plastic film substrate 7 , it can prevent monomers and oligomers from being separated from the transparent plastic film substrate 7 onto the transparent conductive film 5 . The transparent conductive film of the present invention improves the adaptive input strength and input stability by controlling the input start load and voltage loss time described later, and further improves the adaptive input strength and input stability by preventing the precipitation of oligomers. In addition, by preventing the precipitation of monomers and oligomers by using the curable resin layer 6 and the functional layer 8, the transparency and visibility of the transparent conductive film can be further improved. In addition, by having the curable resin layer 6 and/or the functional layer 8, the rigidity and softness of the transparent conductive film described later can be adjusted. Also, depending on the rigidity of the transparent plastic film substrate, the curable resin layer 6 and/or the functional layer 8 are not necessarily required.

In one aspect, the transparent conductive film of the present invention is laminated with an easy-adhesive layer on at least one side of the transparent plastic film substrate. For example, as shown in FIG. 2 , the curable resin layer 6 and the transparent plastic film substrate 7 are bonded with an easy adhesive layer 9 . Alternatively, as shown in FIG. 3 , the functional layer 8 and the transparent plastic film substrate 7 are bonded with an easy-adhesive layer 9 . Alternatively, as shown in FIG. 4 , the curable resin layer 6 and the functional layer 8 are respectively bonded to the transparent plastic film substrate 7 with an easy-adhesive layer 9 . The presence of the easy-adhesive layer 9 can more effectively prevent the hardening resin layer 6 and/or the functional layer 8 from peeling off from the transparent plastic film substrate 7 due to external force.

The transparent conductive film of the present invention is characterized (feature 1) in that the initial input load obtained by Test Method 1 is greater than 15 g and not more than 25 g. Comfortable input performance can be improved by reducing the input start load to a predetermined value or less.

[Test method 1] On one side of the glass substrate, an indium-tin composite oxide conductive film (tin oxide content: 10% by mass) was formed with a thickness of 20 nm, and dot-shaped spacers (60 μm in length) of epoxy resin were placed on the surface of the film at a pitch of 4 mm. × 60 μm in width × 5 μm in height) was formed in a square lattice shape as a panel board. On the conductive film side of this panel board, an adhesive rectangular frame with a thickness of 105 μm and an inner circumference of 190 mm×135 mm was interposed, and transparent conductive films were stacked so that the conductive films faced each other to prepare an evaluation panel. From the transparent conductive film side of the evaluation panel, continuously press the center of the 4-point grid of dot-shaped spacers with a polyacetal pen whose tip is hemispherical with a radius of 0.8 mm, and set the pressure at which the resistance value starts to stabilize as the input start load . Here, the "stable resistance value" means, for example, a state in which the resistance value fluctuates within the range of ±5% of the average value.

In addition, the above-mentioned transparent conductive film is characterized (characteristic 2) in that the voltage loss time obtained by the test method 2 is not less than 0.00 milliseconds and not more than 0.40 milliseconds. By keeping the voltage loss time within a predetermined range, the contact time for electrical stability becomes longer. By setting the input start load within a predetermined range, the prevention of wrong input can be improved, and by setting the voltage loss time within a predetermined range, input stability such as stroke stability and fast writing performance can be improved. Regarding the reason for exerting the effect of this input stability, although it should not be interpreted as being limited to a specific theory, it is considered that the reason is that the contact time for electrical stability can be made longer, and electrical instability can be further reduced. contact status. As a result, the time during which the input is unstable is shortened. For example, when continuously writing characters, blurring of characters can be prevented, and blurring of characters in rapid writing can be reduced. In addition, for example, when writing on the touch panel, the problem that the characters displayed on the touch panel become blurred and are not displayed can be solved. Therefore, it is possible to clearly draw desired characters, pictures, and the like on the resistive film type touch panel. For example, it is also possible to express the strokes of the strokes of a character as if expressed with a writing brush. A transparent conductive film having feature 1 (load at input start) and feature 2 (voltage loss time) is extremely useful in applications such as resistive touch panels.

The voltage loss time is preferably less than 0.39 milliseconds, more preferably less than 0.35 milliseconds, more preferably less than 0.30 milliseconds, and the shorter the better. In addition, the voltage loss time may be longer than 0.01 milliseconds, for example, may be longer than 0.02 milliseconds. That is, the voltage loss time is preferably from 0.01 to 0.39 milliseconds, more preferably from 0.01 to 0.35 milliseconds, and still more preferably from 0.02 to 0.30 milliseconds.

[Test method 2] Connect the above-mentioned evaluation panel to a constant voltage power supply of 6V, and use a pen with a hemispherical tip with a radius of 0.8mm from the transparent conductive film side to press 4 points of the dot-shaped spacer at intervals of 5 times/second with a load of 50gf The center of the grid. The measurement starts when the pen starts to separate from the transparent conductive film and the voltage decreases from 6V, and the time until the voltage reaches 5V is taken as the voltage loss time. For example, FIG. 5 is a conceptual diagram showing the relationship between voltage and time in one aspect of the present invention, the horizontal axis 13 is the time axis, the vertical axis 14 represents the voltage, and the voltage loss time 15 is measured.

The above-mentioned transparent conductive film preferably has an ON resistance defined by Test Method 6 of 10 kΩ or less (feature 3). The smaller the ON resistance, the more the pen sliding durability can be improved. The ON resistance is preferably at most 8 kΩ, more preferably at most 5 kΩ, even more preferably at most 3 kΩ, and most preferably at most 1.0 kΩ. Also, the ON resistance may be, for example, 0.1 kΩ or more, 2 kΩ or more, or 4 kΩ or more. That is, the ON resistance is preferably 0.1 to 10 kΩ, more preferably 0.1 to 8 kΩ, more preferably 0.1 to 5 kΩ, still more preferably 0.1 to 3 kΩ, and most preferably 0.1 to 1 kΩ. In addition, it may be 2 to 10 kΩ, 2 to 8 kΩ, 2 to 5 kΩ, 2 to 3 kΩ, 4 to 10 kΩ, 4 to 8 kΩ, or 4 to 5 kΩ. [Test method 6] A panel board in which an indium-tin composite oxide conductive film (tin oxide content: 10% by mass) with a thickness of 20 nm is formed on one side of a glass substrate so that the conductive films face each other through epoxy beads with a diameter of 30 μm. , and a transparent conductive film to make an evaluation panel. On the transparent conductive film side of the evaluation panel, a pen with a hemispherical polyacetal pen with a radius of 0.8 mm was used to slide while applying a load of 2.5 N (50,000 times of back and forth, sliding distance 30 mm, sliding speed 180 mm/ Second). After sliding, the sliding part was pressed with a pen load of 0.8N, and the resistance (ON resistance) at the time of electrical connection was measured.

The aforementioned transparent conductive film is preferably 0.38N in film rigidity (BR) obtained by test method 3. 0.90N above cm. below cm. By making the film rigidity (BR) more than a predetermined value, the input start load can be made more than a predetermined value. In addition, by making the film stiffness (BR) below a predetermined value, ON resistance can be made below a predetermined value. Also, reducing the film rigidity (BR) is also useful in reducing the input start load. Film rigidity (BR) is better at 0.42N. More than cm, more preferably 0.46N. more than cm. In addition, more preferably 0.80N. cm or less, more preferably 0.70N. Below cm, the best is 0.60N. below cm. That is, the rigidity (BR) of the film is more preferably 0.42-0.80N. cm, more preferably 0.42-0.70N. cm, especially 0.46~0.60N. cm.

[Test method 3] Place a 20mm x 250mm transparent conductive film test piece on a horizontal platform with the transparent conductive film facing upwards, and make the test piece protrude from the end point of the horizontal platform by a length of 230mm, and determine the hardness and softness based on the following formula degree (BR). In addition, when a transparent conductive film is facing down, the value of rigidity and softness will change, so pay attention. Rigidity (BR(N.cm))=g×a×b×L ⁴ /(8×δ×10 ¹¹ ) (where g is 9.81 (gravitational acceleration; m/s ² ), a is 20( The length of the short side of the test piece; mm), b represents the specific gravity of the test piece (g/cm ³ ), L is 230 (the length of the long side of the test piece exposed outside the horizontal platform; mm), δ represents the test piece The difference between the height of the front end and the height of the horizontal platform (cm))

In the transparent conductive film, it is preferable that the average (AVSp) of the maximum peak height Sp of the conductive surface obtained by Test Method 4 satisfies the following formula (2-1). The input start load is governed by the two parameters of film stiffness (BR) and average maximum peak height (AVSp). By making the average maximum peak height (AVSp) more than the predetermined value obtained from film stiffness (BR) , it is possible to make the input start load below a predetermined value. In addition, by making the average maximum height (AVSp) below a predetermined value, the input start load can be made above a predetermined value, and the voltage loss time can be adjusted within a more preferable range in some cases. 4.7×BR-3.6≦AVSp<4.7×BR-1.8. ． ． Formula (2-1) (In the formula, the rigidity and softness of the BR series film (N.cm), and the average maximum mountain height of the AVSp series (μm)) [Test method 4] On the conductive surface of the transparent conductive film, 3 points are determined at intervals of 1 cm in the MD direction, and 2 points are symmetrically determined at intervals of 1 cm from the center in the TD direction. A total of 5 measurement points are determined at each The maximum peak height Sp (according to ISO 25178) based on the surface roughness was measured locally, and the average value thereof was defined as the average maximum peak height (AVSp) (μm).

The inequality sign relationship on the left side of the formula (2-1) is more preferably 4.7×BR-3.5≦AVSp, and more preferably 4.7×BR-3.4≦AVSp. The inequality sign relationship on the right side of formula (2-1) is more preferably AVSp<4.7×BR-1.9, and even more preferably AVSp<4.7×BR-2.0. That is, it is more preferably 4.7×BR-3.5≦AVSp<4.7×BR-1.9, and still more preferably 4.7×BR-3.4≦AVSp<4.7×BR-2.0.

In the transparent conductive film, it is preferable that the average maximum peak height (AVSp) satisfies the following formula (2-2). When the average maximum mountain height (AVSp) is more than a predetermined value, the transparent conductive film can be rolled into a roll without hindrance. The average maximum mountain height (AVSp) is more preferably at least 0.010 (μm), and still more preferably at least 0.020 (μm). In addition, by setting the average maximum mountain height (AVSp) below a predetermined value, accidental electrical contact can be prevented more appropriately. 0.005≦AVSp≦12.000. ． ． Formula (2-2) (In the formula, AVSp is the average maximum mountain height (μm)) That is, AVSp is more preferably from 0.010 to 12.000 μm, and still more preferably from 0.020 to 12.000 μm.

It is preferable that the contact area ratio (CA) obtained by the test method 5 satisfy the following formula (2-3) in the said transparent conductive film. By making the contact area ratio (CA) more than a predetermined value, the voltage loss time can be made less than a predetermined value. The reason is considered to be that the larger the contact area ratio (CA), the higher the stability of the electrical contact between the conductive layers. Therefore, when the pen, finger, etc. leave the transparent conductive film of the resistive film touch panel, it is possible to strive to become an electrical contact. The time before sexual contact becomes erratic in the area of contact. In addition, in the formula (2-3), the contact area ratio (CA) becomes larger as the rigidity (BR) increases, the reason is: the larger the rigidity (BR), the pen, finger, etc. leave the resistive film The faster the speed of the transparent conductive film of the touch panel, it is necessary to use a transparent conductive film with a large contact area ratio (CA). CA≧32.6×BR+17.2. ． ． Formula (2-3) (In the formula, the rigidity and softness of the BR series film (N.cm), the contact area ratio of the CA series (%))

[Test method 5] For the conductive surface of the transparent conductive film, measure the average height Rc (μm), the maximum peak height Rp (μm), and the average length Rsm (μm) based on the line roughness, and satisfy the formula (X1) and the formula At least one of (X2) and the place of formula (X3) measured the arithmetic mean height Ra (micrometer) based on the line roughness. Also, the average height Rc (μm), the maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) were measured using a three-dimensional surface shape measuring device VertScan (manufactured by Ryoka System Co., Ltd., R5500H-M100 (Measurement conditions: wave mode, measurement wavelength 560nm, objective lens 50 times)) to determine. The maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) are determined in accordance with the provisions of JIS B 0601-2001. The measurement length of arithmetic mean height Ra (micrometer) shall be 100 micrometers or more and 200 micrometers or less. Rp-Rc-Ra≦0.20． ． ． Formula (X1) (Rp-Rc)/Ra≦5.0. ． ． Formula (X2) Rsm≦30. ． ． Formula (X3) Change the objective lens of VertScan, the above-mentioned 3D surface shape measurement device, to 10 times, and use the particle analysis of the same measurement device to achieve the "arithmetic mean height Ra (μm)-15×10 ^-3 (μm)-average height Rc (μm)", cut in the plane direction, and calculate the sum of the cross-sectional areas. The value obtained by dividing the sum of the cross-sectional areas by the area of the measurement field of view was multiplied by 100 as the contact area ratio (CA) (%).

In the aforementioned test method 5, "arithmetic mean height Ra (μm) - 15×10 ^-3 (μm)" is considered for the following reasons. Most of the transparent conductive film in contact with the transparent conductive glass are protrusions of the average height of the transparent conductive film. Because it is difficult to accurately calculate the contact area with the protrusions of this average height, a height slightly smaller than the above-mentioned average height of protrusions (= height 15×10 ^-3 (μm) lower than the average height of the transparent conductive film) is used. The cross-sectional area of the transparent conductive film side of the transparent conductive film at the place is used as a proxy index (also, this height is the height based on the average height Rc (μm) descending from the average plane). Here, if the arithmetic mean roughness Ra of JIS B 0601-2001 is used as the average protrusion height of the transparent conductive film, it is affected by the number of coarse protrusions located on the transparent conductive film side of the transparent conductive film, but the height is very high , the arithmetic average roughness Ra becomes larger than the actual average protrusion height of the transparent conductive film, which is unfavorable. Therefore, in order to eliminate the influence of coarse protrusions, the arithmetic mean roughness Ra (μm) is measured at a place satisfying at least one of formula (X1) and formula (X2) and formula (X3).

The relationship between CA and BR shown in formula (2-3) is more preferably CA≧32.6×BR+17.5, and still more preferably CA≧32.6×BR+18.0.

It is preferable that the maximum value MXSp of the maximum peak height Sp obtained by the aforementioned test method 4 is more than 1.0 times and less than 1.4 times (more preferably more than 1.0 times and 1.40 times) the aforementioned average maximum peak height AVSp. the following). By making the maximum value MXSp below a predetermined value, the in-plane distribution of the high protrusions of the transparent conductive film becomes uniform, and the input operation of the touch panel can be performed with the same input load no matter where it is, which is preferable. More preferably, it is 1.3 times or less. More preferably, it is 1.2 times or less.

The minimum value MnSp of the maximum peak height Sp obtained by the above-mentioned test method 4 of the above-mentioned transparent conductive film is preferably 0.6 to 1.0 times (more preferably 0.60 to 1.0 times) the above-mentioned average maximum peak height AVSp. By making the minimum value MNSp more than a predetermined value, the in-plane distribution of the high protrusions of the transparent conductive film becomes uniform, and it is possible to perform input on the touch panel with the same input load at any place, which is preferable. More preferably, it is at least 0.7 times, and even more preferably at least 0.8 times. In addition, by setting both the maximum value MXSp and the minimum value MNSp within predetermined ranges, it is possible to make the variation of the input start load less than ±5% of the average value. Furthermore, it is also possible to prevent the input start load from varying among products.

The total light transmittance of the aforementioned transparent conductive film is, for example, not less than 70% and not more than 95%, preferably not less than 80% and not more than 95%, more preferably not less than 85% and not more than 90%.

2. Transparent conductive film The transparent conductive film of the transparent conductive film contains an indium-tin composite oxide. The concentration of tin oxide contained in the transparent conductive film is preferably from 0.5 mass % to 40 mass %. When 0.5% by mass or more of tin oxide is contained, the surface resistance of the transparent conductive film is preferably at a practical level. Moreover, by making the tin oxide concentration 40 mass % or less, the tin oxide concentration contained in the transparent conductive film of a transparent conductive thin film can be made close to the tin oxide concentration contained in the transparent conductive glass substrate for touch panels. The closer the tin oxide concentration of the transparent conductive film and the transparent conductive film of the glass substrate is, the easier the electrical contact between the two transparent conductive films is, and the better the input strength and input stability are. The tin oxide concentration of the transparent conductive film is more preferably at most 25% by mass, more preferably at most 20% by mass, most preferably at most 18% by mass, more preferably at least 1% by mass, even more preferably at least 2% by mass. That is, the tin oxide concentration is more preferably 1 to 25% by mass, still more preferably 1 to 20% by mass, and most preferably 2 to 18% by mass.

Moreover, generally, the tin oxide concentration contained in the transparent conductive glass substrate for touch panels is 10 mass %. The difference between the tin oxide concentration of the transparent conductive film and the tin oxide concentration of the glass substrate is, for example, 30 mass % or less, preferably 20 mass % or less, more preferably 10 mass % or less.

The crystallinity of the transparent conductive film may be any of 0% to 100%, preferably 10% to 100%, more preferably 50% to 100%. The higher the degree of crystallinity, the more excellent the pen gliding property.

The surface resistance of the transparent conductive film is, for example, not less than 50Ω/□ and not more than 900Ω/□, preferably not less than 50Ω/□ and not more than 700Ω/□, more preferably not less than 70Ω/□ and not more than 500Ω/□.

The thickness of the transparent conductive film is preferably not less than 10 nm and not more than 100 nm. If the thickness of the transparent conductive film is more than 10nm, the overall transparent conductive film is attached to the transparent plastic film substrate or the hardened resin layer described later, the film quality of the transparent conductive film is stable, and the surface resistance value is easily stabilized within the preferred range. . In addition, it is also effective for reducing the ON resistance specified in Test Method 6. More preferably, the thickness of the transparent conductive film is not less than 13 nm, and more preferably not less than 16 nm. In addition, when the thickness of the transparent conductive film is 100 nm or less, the crystal grain size and the degree of crystallization of the transparent conductive film become moderate, and the total light transmittance becomes a practical level, which is preferable. More preferably, it is 50 nm or less, still more preferably, it is 30 nm or less, and most preferably, it is 25 nm or less. That is, the thickness of the transparent conductive film is more preferably from 13 to 50 nm, still more preferably from 16 to 30 nm, particularly preferably from 16 to 25 nm.

In an adhesion test based on JIS K5600-5-6:1999 on the surface of the transparent conductive film, the residual area ratio of the transparent conductive film is preferably at least 95%, more preferably at least 99%, and most preferably at least 99.5%. . When the remaining area ratio of the transparent conductive film in the adhesion test is within the above range, the transparent conductive film-based transparent plastic film substrate, the layer in contact with the transparent conductive film such as the curable resin layer described later, and the transparent conductive film Adhere to the touch panel, even if the touch panel is continuously input with a pen, cracking, peeling, abrasion, etc. can still be suppressed on the transparent conductive film, and even if a force greater than that assumed in normal use is applied, the transparent A conductive film is preferable since cracking, peeling, etc. are suppressed.

The formation method of the aforementioned transparent conductive film is not particularly limited, for example, preferably on at least one side of the transparent plastic film substrate 7 (hereinafter referred to as the film to be processed) that can be formed with a curable resin layer 6 on the surface, by A method of forming a transparent conductive film of an indium-tin composite oxide by a sputtering method. In order to produce a transparent conductive film with high productivity, it is preferable to use a so-called roll sputtering device that supplies the film to be processed from a film roll, and rolls it into a roll shape after film formation.

FIG. 6 is an apparatus schematic diagram showing an example of a film forming unit in a roll sputtering apparatus. In this illustrated example, the film 1 to be processed sent out from a film roll not shown in the figure runs while partially contacting the surface of the center roll 2 . An indium-tin sputtering target 4 is placed in a mask (chimney) 3 having an opening facing the contact portion between the film to be processed 1 and the center roll 2, and deposited on the surface of the film to be processed 1 traveling on the center roll 2. Indium-tin composite oxide thin films are laminated. In addition, the temperature of the center roll 2 can be controlled by an unillustrated temperature controller.

As the target, it is preferable to use a sintered target of indium-tin composite oxide. In order to improve production efficiency, a plurality of sintering targets of indium-tin composite oxide may be provided in the flow direction of the thin film.

In forming a film-forming gas environment, it is preferable to flow oxygen, an inert gas (such as argon gas) or the like while using a mass flow controller as needed. By adding oxygen, the surface resistance and total light transmittance of the transparent conductive film can be adjusted more appropriately. The flow ratio (volume ratio) of oxygen and inert gas (oxygen/inert gas) is, for example, 0.005 or more, preferably 0.010 or more, more preferably 0.020 or more, such as 0.15 or less, preferably 0.1 or less, more preferably 0.07 or less, more preferably 0.05 or less. That is, the flow ratio (volume ratio) of oxygen and inert gas (oxygen/inert gas) is, for example, 0.005-0.15, preferably 0.010-0.1, more preferably 0.020-0.07, and still more preferably 0.020-0.05. In addition, in the film-forming gas environment, it is also possible to flow a gas containing hydrogen atoms while using a mass flow controller as needed (if it is a gas containing hydrogen atoms such as hydrogen, ammonia, hydrogen+argon mixed gas, etc., there is no Special restrictions. However, water is excluded.).

The central value (intermediate value between the maximum value and the minimum value) of the partial pressure ratio (water pressure/inert gas partial pressure) of water in the film-forming gas environment to the inert gas is, for example, 7.00×10 ^-3 or less, preferably 5.00×10 ^-3 or less, more preferably 3.00×10 ^-3 or less. The less water in the film-forming gas environment, the more appropriate the film quality of the transparent conductive film, the easier the surface resistance value becomes a better value, and the higher the reliability of crystallization. However, it is conceivable to control the moisture content with the goal of reaching the degree of vacuum, but it is preferable to measure the moisture content (hydraulic pressure) during film formation for the following two reasons. First, if a film is formed on a plastic film by sputtering, the film is heated and moisture is released from the film. The attainment of vacuum does not reflect the effect of this amount of released moisture. Second, the influence of moisture in the center of the roll when forming a film unwound from a film roll is not reflected in the degree of vacuum attainment. If the film roll is held in a vacuum chamber, the water in the outer layer of the roll is easily detached, but the water in the inner layer of the roll is difficult to detach. When the measurement reaches the vacuum degree, the advance of the film roll is stopped, but when the film is formed, the film is advanced, and the inner part of the film roll containing a lot of water is rolled out one after another, so the moisture content in the film-forming gas environment increases. Increased by more than the amount of water measured to reach the vacuum degree.

In the film roll for forming a transparent conductive film, the height difference between the most convex and the most concave at the end surface of the roll is preferably 10 mm or less, more preferably 8 mm or less, and more preferably 4 mm or less. If it is 10 mm or less, water and organic components from the end faces of the film will hardly be released when the film roll is put into a sputtering device, so the film quality of the transparent conductive film will be improved.

It is desirable to pass the treated film through a bombardment step before forming the transparent conductive film. The bombardment step refers to applying a voltage to discharge in a state where only an inert gas such as argon or a mixed gas of a reactive gas such as oxygen and an inert gas flows in, so as to generate plasma. Specifically, it is desirable to bombard the thin film by RF sputtering with a SUS target or the like. The film is exposed to the plasma through the bombardment step, so water and organic components are released from the film. When the transparent conductive film is formed, the water and organic components released from the film are reduced, and the film quality of the transparent conductive film is improved. In addition, since the layer in contact with the transparent conductive film is activated by the bombardment step, the adhesiveness of the transparent conductive film is improved, and the pen sliding durability is further improved.

The aforementioned film to be processed 1 is preferably coated with a protective film having a low water absorption rate on the surface opposite to the surface on which the transparent conductive film is formed. By affixing the protective film, it becomes difficult to release gas such as water from the film 1 to be processed, and the film quality of the transparent conductive film is improved. As a base material of the said protective film, olefins, such as polyethylene, a polypropylene, and cycloolefin, are mentioned, for example.

During film formation, the film 1 to be processed is cooled to, for example, below 0°C, preferably below -5°C. By cooling the film 1 to be processed, the release of impurities such as water and organic gas from the film can be suppressed, and the film quality of the transparent conductive film can be appropriately adjusted. The temperature of the film during film formation can be substituted by the set temperature of a temperature controller that adjusts the temperature of the center roll that advances into contact with the film.

The sputtering device is preferably equipped with an exhaust device such as a rotary pump, a turbomolecular pump, or a cryopump. With the exhaust device, the moisture content in the film-forming gas environment can be controlled.

Preferably, after forming a transparent conductive film laminated with indium-tin composite oxide on the film to be processed, heating is applied for 0.1 hour to 12 hours at 80°C to 200°C in an oxygen-containing gas atmosphere deal with. By setting it as 80 degreeC or more, the crystallinity of a transparent conductive film can be improved, and pen sliding durability can be improved further. By setting it as 200 degrees C or less, the flatness of a transparent plastic film can be ensured.

3. Transparent plastic film substrate The transparent plastic film substrate used in the present invention refers to melt-extruding or solution-extruding organic polymers to form a film, and stretching, cooling, and heat-fixing in the longitudinal direction and/or width direction as required. film. Examples of the aforementioned organic polymer include polyolefins such as polyethylene and polypropylene; polyethylene terephthalate, polyethylene 2,6-terephthalate, and polytrimethylene terephthalate. , polybutylene terephthalate and other polyesters; nylon 6, nylon 4, nylon 66, nylon 12 and other polyamides; polyimide, polyamide imide, polyether, polyether ether Ketone, polycarbonate, polyarylate, cellulose propionate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyetherimide, polyphenylene sulfide, polyphenylene ether, polystyrene, para Positional polystyrene, norbornene-based polymers, etc.

Among these organic polymers, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene 2,6-terephthalate, para Polystyrene, norbornene-based polymers, polycarbonate, polyarylate, etc. In addition, these organic polymers can also be copolymerized with a small amount of monomers of other organic polymers and blended with other organic polymers.

Surface activation treatments such as corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, electron beam irradiation treatment, and ozone treatment may be applied to the transparent plastic film substrate within a range not impairing the object of the present invention.

The thickness of the transparent plastic film substrate is preferably in the range of not less than 125 μm and not more than 280 μm, more preferably not less than 150 μm and not more than 250 μm. The thicker the transparent plastic film substrate is, the easier the rigidity (BR) of the film becomes, and the easier it is for the average maximum mountain height (AVSp) to satisfy the right side of formula (2-1). In addition, if the thickness of the transparent plastic film substrate is 125 μm or more, the mechanical strength can be maintained, so especially when used in a touch panel, the prevention of wrong input becomes better. In addition, when used in a touch panel, It is preferable because the deformation to pen input is small and the pen sliding durability is excellent. On the other hand, when the thickness is 280 μm or less, when used for a touch panel, an appropriate input strength and excellent input stability can be maintained, which is preferable.

4. Hardened resin layer The curable resin layer is, for example, formed between the transparent plastic film substrate and the transparent conductive film, and becomes the base layer of the transparent conductive film. In addition, it is preferable that monomers and oligomers generated from the transparent plastic film substrate can be prevented from being precipitated onto the transparent conductive film, so that the comfortable input of the touch panel will not be hindered. In addition, the transparent conductive film can be strongly adhered to the curable resin layer by the easy-adhesive layer, and the force applied to the transparent conductive film can be dispersed, so the transparent conductive film can be suppressed in the pen sliding durability test. Cracks, peeling, abrasion, etc. are therefore preferred.

The resin of the curable resin layer is not particularly limited as long as it is a resin that is cured by heating, application of energy such as ultraviolet irradiation, electron beam irradiation, and a curing agent. For example, silicone-based resins, Acrylic resin, methacrylic resin, epoxy resin, melamine resin, polyester resin, urethane resin, etc. These may be used alone or in combination of two or more. From the viewpoint of productivity, it is preferable to use an ultraviolet curable resin as a main component.

As the ultraviolet curable resin, for example, polyfunctional acrylate resin such as acrylic acid or methacrylate ester of polyol; The synthesized polyfunctional urethane acrylate resin, etc. If necessary, monofunctional monomers such as vinylpyrrolidone, methyl methacrylate, styrene, and the like can be added to these polyfunctional resins and copolymerized.

The curable resin layer preferably contains a curing reaction initiator at least before curing. The hardening reaction initiator can be selected according to the hardening type of the curable resin, and examples thereof include radical polymerization initiators such as thermal polymerization initiators and photopolymerization initiators, curing agents, etc., preferably photopolymerization starter. The amount of the curing reaction initiator is, for example, 1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the curable resin.

As the photopolymerization initiator, known compounds that absorb ultraviolet rays and generate radicals can be used without particular limitation, and examples thereof include various benzoins, phenyl ketones, and benzophenones.

The curable resin layer preferably contains particles. Concavities and convexities can be formed on the surface of the curable resin layer by the particles. Therefore, if particles are included, the contact area ratio CA will basically decrease from 100%, and on the other hand, the control of the average maximum peak height AVSp becomes easy. In addition, there are cases where the rigidity BR decreases due to the increase of the particle amount, and the rigidity BR can also be adjusted by the particle amount. In addition, various properties such as pen sliding durability, Newton ring resistance, and film winding properties can be more effectively exhibited by particles. In addition, when the amount of particles with relatively large particle diameters (for example, particle A described later) is small and the amount of particles with relatively small particle diameters (for example, particle B described later that is used in combination with particle A) is large, the same method as adding There is a tendency that the contact area ratio CA becomes larger and the average maximum peak height AVSp becomes larger compared with particles of a particle size.

Examples of the aforementioned particles include inorganic particles, organic particles, and the like, and are preferably inorganic particles. Examples of inorganic particles include silicon oxide particles and the like. Examples of organic particles include particles made of polyester resin, polyolefin resin, polystyrene resin, polyamide resin, and the like. Particles may be one kind, or two or more kinds.

The number average particle size of the aforementioned particles is, for example, 0.01 to 10 μm, preferably 0.03 to 5 μm, more preferably 0.05 to 3 μm, and most preferably 0.05 to 1.8 μm. The larger the average particle diameter, the larger the average maximum peak height AVSp of the transparent conductive layer can be. In addition, the average maximum peak height can be increased by increasing the average particle diameter, and by increasing the resin concentration (solid content concentration) in the coating solution of the curable resin described later, the hardened The thickness of the type resin layer is reduced to make it larger.

In addition, the standard deviation of the aforementioned particle diameter is, for example, 20% or less of the average particle diameter, preferably 10% or less of the average particle diameter, more preferably 5% or less of the average particle diameter. The smaller the standard deviation of the particle diameter, the larger the contact area ratio CA of the transparent conductive film can be made.

In one aspect, it is preferable to use a particle B having a number average particle diameter of 0.01 μm or more and less than 1.0 μm, and in another aspect, it is preferable to use a number average particle diameter of 0.4 μm or more and 1.8 μm in combination. The following particles A having a larger number average particle diameter than the particles B, and particles B having a number average particle diameter of 0.01 μm or more and less than 1.0 μm. The average particle diameter of the particles B is preferably 0.05 μm or more. When the average maximum peak height AVSp becomes large (for example, becomes 0.6 μm or more), the contact area ratio CA may become too small, but the contact area ratio can be appropriately adjusted by using both particles A and B. Also, if the average maximum mountain height AVSp becomes more than the right side (4.7×BR-1.8) of formula (2-1), even if two kinds of particles A and B are used, the contact area ratio CA will become too small, so the average The maximum mountain height AVSp is smaller than the right side of formula (2-1).

When one type of particle B is included, the amount of particle B in the curable resin layer is 0.1 mass % to 25 mass %, preferably 0.5 mass % or more, relative to 100 mass % of the solid content of the cured resin layer. 18% by mass or less. In addition, when two types of particles A and B are included, the amount of particles A in the curable resin layer is, for example, 0.1% by mass to 5% by mass relative to 100% by mass of the solid content of the cured resin layer. The amount of particle B in the curable resin layer is relative to 100% by mass of the solid content of the cured resin layer, preferably more than the amount of particle A, for example, more than 5% by mass and 30% by mass or less, preferably 6% by mass % or more and 15% by mass or less.

By adjusting the size and amount of the particles in the above manner, the average maximum peak height AVSp of the transparent conductive layer can satisfy the formula (2-1), and at the same time, the contact area ratio CV will not become too small. In addition, the rigidity BR of the film can also be adjusted. Therefore, the input start load can be controlled within an appropriate range, the voltage loss time can be shortened, and the adaptive input strength and input stability can be achieved.

The thickness of the curable resin layer is preferably in the range of 0.1 μm to 15 μm. More preferably, it is in the range of 0.5 μm to 10 μm, particularly preferably in the range of 1 μm to 8 μm. When the thickness of the curable resin layer is 0.1 μm or more, sufficient protrusions can be formed, which is preferable. On the other hand, productivity is more favorable when it is 15 micrometers or less. In addition, when the curable resin layer is thick, the rigidity BR of the transparent conductive film tends to increase.

The curable resin layer may contain a resin that is incompatible with the curable resin (hereinafter, may be simply referred to as an incompatible resin). By dispersing the immiscible resin in the curable resin layer, unevenness can be formed on the surface of the curable resin layer, and the surface roughness of a wide area can be improved. Examples of incompatible resins include polyester resins, polyolefin resins, polystyrene resins, and polyamide resins.

The curable resin layer is formed by making the curable resin before curing into a liquid state, applying it to the lamination object (transparent plastic film substrate, easy-adhesive layer, etc.) and curing it. The coating may contain, in addition to the aforementioned curable resin, a hardening reaction initiator (a thermal polymerization initiator, a photopolymerization initiator, a radical polymerization initiator, a hardener, etc., preferably a photopolymerization initiator agent), particles, resins incompatible with hardening resins, solvents, etc. In addition, other well-known additives, such as a silicone-based leveling agent, etc., may be added to this coating liquid as needed. The solvent used is not particularly limited, for example, alcohol-based solvents such as ethanol and isopropanol; ester-based solvents such as ethyl acetate and butyl acetate; ether-based solvents such as dibutyl ether and ethylene glycol monoethyl ether ; Such as methyl isobutyl ketone, cyclohexanone and other ketone solvents; such as toluene, xylene, solvent naphtha and other aromatic hydrocarbon solvents, used alone or in combination.

The concentration of the curable resin in the coating solution (referred to as solid content concentration) can be appropriately selected in consideration of the viscosity and the like according to the coating method. The solid content concentration is, for example, not less than 35% by mass and not more than 58% by mass, preferably not less than 42% by mass and not more than 55% by mass. When the solid content concentration is high and the thickness of the curable resin layer is thin (for example, 4.0 μm or less), the average maximum peak height of the curable resin layer becomes higher according to the relationship of formula (2-1), and the contact area ratio CA becomes smaller Propensity. Also, when the solid content concentration exceeds 58% by mass (for example, when it exceeds 58% by mass and is about 65% by mass or less), the thickness of the curable resin layer is 4.0 μm or less. In this case, if the particle size of the particles A is set to be 0.80 μm or less, and the amount of the particles A is 4% by mass or less with respect to the solid content of the cured resin layer 100% by mass, it is easy to realize the formula (2-1). The average maximum mountain height and contact area ratio CA are within the appropriate range.

There are no particular limitations on the method of applying the coating liquid to the layered object, and for example, known methods such as bar coating, gravure coating, and reverse coating can be used. The applied coating liquid solvent is evaporated and removed in the subsequent drying step. When an incompatible resin (polyester resin, etc.) is dissolved in the coating liquid, in this drying step, the incompatible resin becomes particles and precipitates in the ultraviolet curable resin. After the coating film is dried, a curable resin layer can be formed by performing an appropriate treatment (for example, ultraviolet irradiation) according to the type of curing.

The coating surface to be laminated may be treated, if necessary, to improve the adhesion of the curable resin layer before coating the coating liquid. As the treatment for improving the adhesion, it can be mentioned: the discharge treatment method of irradiating glow or corona discharge for increasing carbonyl, carboxyl, and hydroxyl groups; for increasing polar groups such as amine groups, hydroxyl groups, and carbonyl groups, it is carried out with acid or alkali. Chemical treatment method, etc.

As mentioned above, in order to make the average maximum mountain height AVSp and the contact area ratio CA within the predetermined range, it is necessary to adjust various factors. It is adjusted by using the following relationship. That is, basically, if the particle size is large, if the solid content concentration is high, or if the thickness of the resin layer is thin, the absolute value of the average maximum peak height AVSp tends to increase. The average maximum mountain height AVSp that satisfies the formula (2-1) changes with the rigidity and softness BP, the smaller the rigidity and softness BP, the smaller the average maximum mountain height AVSp. In addition, basically, as the average maximum mountain height AVSp becomes higher, the contact area ratio CA becomes smaller. However, if two types of average particle diameters are used to add to the resin layer, and the particle addition amount of large particles is reduced, the average maximum peak height AVSp increases and the contact area ratio CV increases. In the case of using particles of two sizes, the smaller the amount of large particles added, the greater the influence of the average particle diameter of small particles on the contact area ratio CA.

5. Functional layer Except that the functional layer is formed on the opposite side of the transparent plastic film substrate, it is preferably the same as the aforementioned hardening resin layer. The description of the aforementioned hardening resin layer is applicable to the functional layer except for the size and amount of particles. If the functional layer is laminated on the transparent plastic film substrate, the precipitation of monomers and oligomers from the transparent plastic film substrate can be prevented, and the decrease in visibility of the transparent conductive film can be suppressed. In addition, the rigidity BR of the transparent conductive film can be adjusted. Moreover, since it becomes difficult to generate|occur|produce scratches by inputting with a pen etc. by having a functional layer in a transparent plastic film base material, it is preferable.

When mixing particles (particles C) into the functional layer, the number average particle size of the particles C is, for example, 0.01 μm to 10 μm, preferably 0.1 μm to 7 μm, more preferably 1 μm to 5 μm. The particle C is preferably 0.1 to 60 parts by mass, more preferably 0.3 to 40 parts by mass, and still more preferably 0.5 to 30 parts by mass per 100 parts by mass of the hardening resin in the functional layer. servings or less. The rigidity BR of the transparent conductive film can be adjusted by the amount of the particles C. In addition, surface protrusions can be formed on the functional layer by the particles C, and film winding properties can also be maintained.

In an adhesion test based on JIS K5600-5-6:1999 on the surface of the functional layer, the residual area ratio of the functional layer is preferably at least 95%, more preferably at least 99%, and most preferably at least 99.5%. Since the residual area ratio of the functional layer in the adhesion test is within the above range, the transparent conductive film is a transparent plastic film substrate and the functional layer is in close contact. Even if the touch panel is continuously input with a pen, the function can still be controlled. The layer suppresses appearance defects such as cracking, peeling, and abrasion, and it is preferable to suppress cracking, peeling, etc. of the functional layer even if a force greater than that assumed in normal use is applied.

In the case where the transparent conductive film has a functional layer and a cured resin layer, the thicknesses of the functional layer and the cured resin layer are preferably the same. In addition, it is preferable that the absolute value of the thickness difference between the functional layer and the cured resin layer has the following relation. 0.1μm≦｜Thickness of cured resin layer - thickness of functional layer｜≦3μm In some cases, the rigidity BR of the transparent conductive film can be adjusted by setting a thickness difference between the functional layer and the cured resin layer. In addition, various characteristics such as pen sliding durability can be more effectively exhibited. In addition, the adaptive input strength can be further improved. In addition, the particle mass per unit volume of the cured resin layer and the particle mass per unit volume of the functional layer are preferably different.

6. Easy adhesive layer The easy-adhesive layer is preferably formed of a composition containing a urethane resin, a crosslinking agent, and a polyester resin. The crosslinking agent is preferably a blocked isocyanate, more preferably a trifunctional or higher blocked isocyanate, particularly preferably a tetrafunctional or higher blocked isocyanate. The thickness of the easily-adhesive layer is preferably from 0.001 μm to 2.00 μm.

This application is an applicant claiming the right of priority based on Japanese Patent Application No. 2021-103501 filed on June 22, 2021. This application incorporates the entire contents of the specification of Japanese Patent Application No. 2021-103501 filed on June 22, 2021 as a reference. [Example]

Hereinafter, the present invention will be described in further detail by examples, but the present invention is not limited to these examples at all. In addition, various measurement evaluations in Examples were performed by the following methods.

1. Measurement evaluation (1) Average particle size of silicon oxide particles Particles in the cross section of the transparent conductive film were observed with a scanning electron microscope (VE-8800, manufactured by Keyence Corporation), 50 particles were randomly picked out, and the respective particle diameters were observed. Next, for the observed 50 particles, the particle diameters are grouped into intervals of 0.020 μm, the total number of particles contained in each interval is calculated, and the following histogram is made: the vertical axis is the number of particles, and the horizontal axis is the interval of 0.020 μm Scale particle size. Among the particles whose particle size is within ±30% of the absolute value of the center value of the particle size interval of the maximum value of the peak of the normal distribution obtained from the histogram, the average number of observed particle sizes is defined as the average particle size . For example, when there are two peaks in the normal distribution state in the histogram, it means that two kinds of particles are added, and the two kinds of average particle diameters are calculated by the same method as above.

(2) Thickness of curable resin layer, thickness of functional layer The thickness of the curable resin layer was measured by observing the cross-section of the transparent conductive film with a scanning electron microscope (manufactured by Keyence, VE-8800), observing arbitrary 5 points, and taking the average value as the thickness. The same method is used for the thickness of the functional layer.

(3) Content of tin oxide contained in the transparent conductive film Cut out a sample (approximately 15 cm ² ), put it into a quartz Erlenmeyer flask, add 20 ml of 6 mol/l hydrochloric acid, and seal it with a film (film seal) so that the acid does not volatilize Lose. It was left to stand for 9 days while shaking occasionally at room temperature to dissolve the transparent conductive film. The remaining film was taken out, and hydrochloric acid in which the transparent conductive film was dissolved was used as a measurement solution. In and Sn in the solution were determined by the calibration curve method using an ICP emission analyzer (manufacturer name: Rigaku, device type: CIROS-120 EOP). The measurement wavelength of each element is a wavelength with no interference and high sensitivity. In addition, standard solutions were used by diluting commercially available In and Sn standard solutions.

(4) Thickness of transparent conductive film The thin film sample piece on which the transparent conductive film was laminated was cut out to a size of 1 mm×10 mm, and embedded in epoxy resin for electron microscopy. This was fixed to the sample holder of the ultramicrotome, and a thin section of cross-section parallel to the short side of the buried sample piece was prepared. Next, a portion of the sliced thin film without obvious damage was photographed using a transmission electron microscope (manufactured by JEOL, JEM-2010) at an accelerating voltage of 200 kV under bright field at an observation magnification of 10,000 times. The film thickness was obtained from the photograph.

(5) Crystallinity of transparent conductive film The film sample piece on which the transparent conductive film was laminated was cut out to a size of 1 mm×10 mm, and the conductive film was stuck on the top surface of a suitable resin block with the conductive film facing outward. After trimming, an ultra-thin section almost parallel to the surface of the film is made using a general ultramicrotome technique. This section was observed with a transmission electron microscope (JEOL, JEM-2010), and a surface portion of the conductive film without obvious damage was selected, and photographed at an accelerating voltage of 200 kV and a direct magnification of 40,000 times. As the crystallinity evaluation of the transparent conductive film, the ratio of crystal grains observed under a transmission electron microscope, that is, the degree of crystallinity was observed.

(6) Total light transmittance (%) The total light transmittance was measured using NDH-2000 manufactured by Nippon Denshoku Industries Co., Ltd. in accordance with JIS-K7361-1:1997. (7) Surface resistance Based on JIS-K7194:1994, it measured by the 4-terminal method. As a measuring machine, Lotesta AX MCP-T370 manufactured by Mitsubishi Chemical Analytech Co., Ltd. was used.

(8) Adhesion test Implemented in accordance with JIS K5600-5-6:1999. The results in the following tables represent the adhesiveness by the remaining area ratio (%). The maximum value of the remaining area ratio is 100%. The closer the residual area ratio in the adhesion test in the table is to 100%, the smaller the peeled area is.

(9) Rigidity (BR) (Test method 3) A test piece of 20 mm×250 mm was taken from the transparent conductive film, and the test piece was arranged on a horizontal table with a smooth surface so that the transparent conductive film faced upward. Only the 20mm x 20mm part of the test piece is placed on the horizontal platform so that the 20mm x 230mm part protrudes horizontally from the end point of the horizontal platform. Also, a weight was placed on a portion of 20 mm×20 mm of the test piece, and the weight and size of the weight were selected so that no gap was formed between the test piece and the horizontal table. Next, the difference (=δ) between the height of the horizontal platform and the height of the front end of the film was read using a scale. The stiffness was calculated by substituting the numerical value into the following formula. Rigidity BR(N.cm)=g×a×b×L ⁴ /(8×δ×10 ¹¹ ) (where g is 9.81 (gravitational acceleration; m/s ² ), a is 20 (test piece The length of the short side of the test piece; mm), b represents the specific gravity of the test piece (g/cm ³ ), L is 230 (the length of the long side of the test piece exposed outside the horizontal platform; mm), δ represents the front end of the test piece Difference (cm) between the height and the height of the horizontal platform) The above-mentioned specific gravity b was measured by the following method. Cut the transparent conductive film into a square of 5.0 cm square, use a micrometer, measure the total thickness of 10 points with 3 significant figures, and change the place, and calculate the average value of the thickness (t: μm). The weight (w: g) of the sample cut into a square of 5.0 cm square was measured with 4 significant figures using an automatic loading scale, and the specific gravity was calculated|required from the following formula. Also, the specific gravity is simplified to 2 significant figures. Specific gravity b(g/cm ³ )=w/(5.0×5.0×t×10 ^-4 )

(10) Maximum mountain height (Sp), average maximum mountain height AVSp (μm) (test method 4) The maximum peak height (Sp) (ISO; surface roughness) at 5 points was measured from the conductive surface of the transparent conductive film, and the arithmetic mean thereof was defined as the average maximum peak height (AVSp). The 5-point selection method first selects any point A. Next, 1 point was selected at 1 cm upstream and downstream with respect to A and the length (MD) direction of the film, and 2 points were totaled. Next, 1 point was selected at 1 cm on the left and right with respect to A and the width (TD) direction of the film, and 2 points were totaled. The maximum mountain height (Sp) (ISO; surface roughness) is specified in ISO 25178, using a 3-dimensional surface shape measurement device VertScan (manufactured by Ryoka System Co., Ltd., R5500H-M100 (measurement conditions: wave mode, measurement wavelength 560nm, objective lens 10 times)) to find out. In addition, values smaller than 1 nm are rounded for simplification.

(11) The displacement rate of the upper side of the maximum mountain height (MXSp/AVSp), the displacement rate of the lower side of the maximum mountain height (MNSp/AVSp) The ratio of the maximum value MXSp of the maximum mountain height Sp obtained by the aforementioned test method 4 to the average value AVSp is defined as the maximum mountain height upper side displacement rate (MXSp/AVSp). In addition, the ratio (MNSp/AVSp) of the minimum value MNSp of the maximum mountain height Sp obtained by the above-mentioned test method 4 to the average value AVSp is defined as the maximum mountain height lower side displacement rate.

(12) Contact area ratio CA (%), average height Rc (μm), maximum peak height Rp (μm), average length Rsm (μm), arithmetic mean height Ra (μm) (test method 5) for transparent conductive films On the conductive surface, measure the average height Rc (μm) based on the line roughness, the maximum peak height Rp (μm), and the average length Rsm (μm), and satisfy at least one of the formula (X1) and the formula (X2) and the formula ( In the case of X3), the arithmetic mean height Ra (μm) based on the line roughness was measured. Also, the average height Rc (μm), the maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) were measured using a three-dimensional surface shape measuring device VertScan (manufactured by Ryoka System Co., Ltd., R5500H-M100 (Measurement conditions: wave mode, measurement wavelength 560nm, objective lens 50 times)) to determine. In addition, the determination of the maximum mountain height Rp (μm), the average length Rsm (μm), and the arithmetic mean height Ra (μm) complies with the provisions of JIS B 0601-2001. The measurement length of arithmetic mean height Ra (micrometer) shall be 100 micrometers or more and 200 micrometers or less. Rp-Rc-Ra≦0.20． ． ． Formula (X1) (Rp-Rc)/Ra≦5.0. ． ． Formula (X2) changes the objective lens of the VertScan 3D surface shape measurement device to 10 times, and uses the particle analysis of the same measurement device to achieve "arithmetic mean height Ra(μm)-15×10 ^-3 ( μm)-average height Rc(μm)”, cut in the plane direction and calculate the sum of the cross-sectional area. The value obtained by dividing the sum of the cross-sectional areas by the area of the measurement field of view was multiplied by 100 as the contact area ratio (CA) (%).

(13) Input start load measurement (test method 1) As shown in Figure 6, the hardened resin layer of the laminated film (film to be processed) 1 on the center roll 2 is sputtered, and the target 4 in the mask 3 is sputtered. A transparent conductive film is formed. The target 4 is a sintered target of indium-tin composite oxide or an indium oxide sintered target not containing tin oxide. Electric power is applied at a power density of 3W/cm ² , and a transparent conductive film is formed by DC magnetron sputtering. Film thickness is controlled by varying the speed at which the film passes over the target. An indium-tin composite oxide conductive film (tin oxide content: 10% by mass) with a thickness of 20 nm was formed on one side of a glass substrate (size: 232 mm×151 mm) by sputtering. Specifically, a glass substrate (size: 232 mm×151 mm) having a thickness of 1.1 mm was put into a vacuum chamber, and the vacuum was evacuated to 1.5×10 ^-4 Pa. Next, after oxygen was introduced, argon was introduced to make the total pressure 0.6 Pa. The flow ratio of oxygen to argon was set at 0.033. Using a sintered target of indium-tin composite oxide (tin oxide content: 10% by mass), input power at a power density of 3W/cm ² , and form a 20nm-thick layer on one side of a glass substrate by DC magnetron sputtering. Indium-tin composite oxide conductive film (tin oxide content: 10% by mass). The film-formed glass substrate was heated at 230° C. for 1 hour in air. On the surface of the conductive film formed on one side of the glass substrate, dot-shaped spacers (60 μm in length x 60 μm in width x height) of epoxy resin (manufactured by Toyobo Co., Ltd., product name: CR-102C-23) were placed at a pitch of 4 mm. 5 μm) formed in a square grid (ITO glass substrate). Starting from any one of the four corners of the ITO glass substrate, a double-sided tape (thickness: 105 μm, width 6 mm) was attached to the transparent conductive film side to form a rectangle of 190 mm×135 mm. On the double-sided tape attached to the ITO glass substrate, the transparent conductive film (size: 220 mm x 135 mm) obtained in the example or comparative example was stuck, and the conductive films were laminated so that they faced each other. At this time, one short side of the transparent conductive film protruded from the ITO glass substrate (evaluation panel). The ITO glass substrate and the transparent conductive film of the obtained evaluation panel were connected by a testing machine. From the side of the transparent conductive film, a pen made of polyacetal (manufactured by Toray Plastic Seiko Co., Ltd., trade name: TPS (registered trademark) POM (NC), tip shape: 0.8mmR) is continuously applied to the test machine. The load value at which the measured resistance value is stable is set as the input start load. The position 12 where the load is applied with a pen, as shown in the partial enlarged view of FIG. 7 , is the central area of four dot-shaped spacers 11 arranged in a grid on the surface of the ITO glass substrate 10 . In addition, the input start load was measured at any 3 points more than 50 mm away from the double-sided tape, and an average value was obtained. The first digit after the decimal point is rounded off. In addition, another evaluation panel was produced in the same manner as above, and the input start load was obtained. When the first decimal place is rounded off, when the two input start loads match, it is evaluated that the input start load is stable, and one value is shown in Table 6. On the other hand, when the two input start loads do not match, the two results are shown in Table 6.

(14) Determination of voltage loss time (test method 2) Connect the evaluation panel created by the load measurement at the input start to a constant voltage power supply. Next, a recorder (manufactured by Keyence Corporation, GR-7000) capable of measuring the voltage of the ITO glass substrate and the transparent conductive film was connected. Here, the recorder is used to observe the temporal change of the voltage. Next, 6V was applied to the constant voltage power supply, and the voltage measurement was started with the recorder in units of 0.02 milliseconds. Next, from the side of the transparent conductive film, use a pen made of polyacetal (manufactured by Toray Plastic Seiko Co., Ltd., trade name: TPS (registered trademark) POM (NC), tip shape: 0.8mmR) five times per second. A load of 50 g is applied at a pace. The position where the load is applied with a pen is near the center of the evaluation panel, the center area of 4 dot-shaped gaps arranged in a grid. The time-change data of the voltage when the load was applied to the transparent conductive film with a pen was taken out from the recorder. Starting from the time when the pen started to separate from the transparent conductive film and the voltage began to decrease from 6V, the time until the voltage reached 5V was measured and recorded as the voltage loss time (see FIG. 5 ).

(15) Suitability input strength test (wrong input prevention, comfortable input) A resistive film type touch panel was produced using the transparent conductive thin film obtained in the Example and the comparative example. Using a polyacetal pen (manufactured by Toray Plastic Seiko Co., Ltd., trade name: TPS (registered trademark) POM (NC), tip shape: 0.8 mmR), the input strength was investigated. (prevention of wrong input) ○...There is little input when touching the touch panel while feeling hesitant. ×...There are many inputs when touching the touch panel while feeling hesitant. (comfortable input) ○...Enable input even without consciously exerting pressure. △... Behavior is unstable. ×...If you do not apply force consciously, you may not be able to input.

(16) Input stability (swipe stroke stability, fast writing) The resistive film type touch panel was produced using the transparent conductive thin film obtained in the Example and the comparative example. Input stability was checked using a polyacetal pen. (Swipe stroke stability) ○...When inputting characters, it is difficult to blur the strokes of the Na-shaped strokes. ×...When inputting characters, the strokes of the Na-shape tend to become blurred. (quick writing characteristics) ○...When continuously inputting characters, blurring of characters is less likely to occur. ×... When continuously inputting characters, blurring of the characters tends to occur.

(17) Pen sliding durability (test method 6) A transparent conductive film is used as a panel plate on one side, and an indium-tin composite oxide film (oxidized Tin content: 10% by mass), as the panel board on the other side. For the production of the other panel panel, specifically, a glass substrate (size: 5 cm x 6 cm) with a thickness of 1.1 mm was put into a vacuum chamber, and the vacuum was evacuated to 1.5 x 10 ^-4 Pa. Next, after oxygen was introduced, argon was introduced to make the total pressure 0.6 Pa. The flow ratio of oxygen to argon was set at 0.033. Using a sintered target of indium-tin composite oxide (tin oxide content: 10% by mass), input power at a power density of 3W/cm ² , and form a 20nm-thick layer on one side of a glass substrate by DC magnetron sputtering. Indium-tin composite oxide conductive film (tin oxide content: 10% by mass). The film-formed glass substrate was heated at 230° C. for 1 hour in air. On the surface of the conductive film formed on one side of the glass substrate, as shown in FIG. 8, beads (30 μm in diameter) of epoxy resin (manufactured by Toyobo Co., Ltd., product name: CR-102C-23) were placed at a pitch of 4 mm. Formed in a square lattice shape (ITO glass substrate). The transparent conductive film (size: 5 cm x 6 cm) and the ITO glass substrate obtained in Examples or Comparative Examples were stacked so that the transparent conductive films faced each other. When overlapping, as shown in Figure 9, make the longitudinal direction of transparent conductive film 20 and ITO glass substrate 10 orthogonal, make respective terminal point 16 align simultaneously, make the longitudinal direction one-side end 18 of transparent conductive film 20 , and the one-side end 17 in the longitudinal direction of the ITO glass substrate 10 protrude from the overlapping surface 19, and the protruding parts 17 and 18 are respectively connected to a testing machine. Next, a load of 2.5 N was applied to a polyacetal pen (manufactured by Toray Plastic Seiko Co., Ltd., trade name: TPS (registered trademark) POM (NC), tip shape: 0.8mmR), and the touch panel was subjected to 50,000 strokes. back-and-forth linear sliding test. The sliding distance at this time was set to 30 mm, and the sliding speed was set to 180 mm/sec. The sliding position 21 is, as shown in the partially enlarged view of FIG. 8 , between dot-shaped spacers 11 arranged in a grid on the surface of the ITO glass substrate 10 . After the sliding durability test, the ON resistance (resistance value when the movable electrode (thin film electrode) and the fixed electrode are in contact) when the sliding portion was pressed with a pen load of 0.8N was measured. Ideally, the ON resistance is 10kΩ or less.

2. Laminated film In the field of the embodiment, a laminated film including the following transparent plastic film substrate, cured resin layer, and functional layer was used. (1) Substrate (transparent plastic film substrate): a biaxially aligned transparent PET film (manufactured by Toyobo Co., Ltd., A4380, the thickness of which is described in Table 1) having an easy-adhesive layer on both sides.

(2) Curing type resin layer: Described in Table 1 in 100 parts by mass (solid content) of acrylic resin (manufactured by Dainichi Seika Co., Ltd., SEIKABEAM (registered trademark) EXF-01J) containing a photopolymerization initiator Silicon oxide particles (particles A, particles B) having the number average particle diameters listed in Table 1 were blended in an amount of . In addition, the addition amount of the particle|grains described in Table 1 represents the quantity with respect to 100 mass % of solid content of resin. A mixed solvent of toluene/methyl ethyl ketone (MEK) (8/2: mass ratio) was added so that the solid content concentration became the value shown in Table 1, and stirred to uniformly disperse it to prepare a coating liquid (coating liquid A) . The prepared coating solution A was coated on one side of the transparent plastic film substrate using a Myer bar so that the thickness of the coating film became the value described in Table 1. After drying at 80° C. for 1 minute, the coating film was cured by irradiating ultraviolet rays (light intensity: 300 mJ/cm ² ) using an ultraviolet irradiation device (manufactured by Eyegraphics, Inc., UB042-5AM-W type).

(3) Functional layer: the amount described in Table 2 in 100 parts by mass (solid content) of acrylic resin (manufactured by Dainichi Seika Co., Ltd., SEIKABEAM (registered trademark) EXF-01J) containing a photopolymerization initiator Silicon oxide particles (particles C) having a number average particle diameter described in Table 2 were blended. In addition, the addition amount of the particle|grains described in Table 2 represents the quantity with respect to 100 mass % of solid content of resin. A mixed solvent of toluene/MEK (8/2: mass ratio) was added as a solvent so that the solid content concentration became the value shown in Table 2, and stirred to uniformly disperse it to prepare a coating liquid (coating liquid C). The prepared coating solution C was applied to the surface of the transparent plastic film substrate opposite to the above-mentioned curable resin layer using a Mel bar so that the thickness of the coating film became the value described in Table 2. After drying at 80° C. for 1 minute, the coating film was cured by irradiating ultraviolet rays (light intensity: 300 mJ/cm ² ) using an ultraviolet irradiation device (manufactured by Eyegraphics, Inc., UB042-5AM-W type).

Examples 1-8 The laminated film was put into a vacuum chamber, and the vacuum was evacuated to 1.5×10 ^-4 Pa. Next, after oxygen was introduced, argon was introduced to make the total pressure 0.6 Pa. Table 3 shows the flow ratios of oxygen and argon. As shown in FIG. 6 , the hardened resin layer of the laminated film (film to be processed) 1 on the center roll 2 is sputtered to form a transparent conductive film from the target 4 in the mask 3 . The target 4 is a sintered target of indium-tin composite oxide or an indium oxide sintered target not containing tin oxide. Electric power is applied at a power density of 3W/cm ² , and a transparent conductive film is formed by DC magnetron sputtering. Film thickness is controlled by varying the speed at which the film passes over the target. In addition, the partial pressure ratio of water to inert gas in the film-forming gas environment during sputtering was measured using a gas analyzer (manufactured by Inficon, Transpector XPR3), and is shown in Table 3. The ratio of this moisture is as recorded in Table 3, depending on whether there is a bombardment step, whether there is a protective film, the unevenness of the end surface of the film roll, and the adjustment of the temperature of the temperature medium of the temperature control machine that controls the temperature of the center roll that the film contacts and travels. Make adjustments. In the aforementioned bombardment step, SUS (stainless steel) was used as a target, and RF sputtering was performed at 0.5 W/cm ² . The amount of gas introduced into RF sputtering was the same as the amount of gas introduced into the vacuum apparatus described in the examples. When using a protective film, a polyethylene film with a thickness of 65 μm is used. An acrylic adhesive is applied to one side of the protective film. A protective film is attached to the surface of the laminated film opposite to the surface on which the transparent conductive film is formed. The temperature of the above-mentioned warm medium is the value described in Table 3, which corresponds to the temperature in the middle of the maximum value and the minimum value of the temperature from the start of film formation to the end of film formation. The heat treatment shown in Table 3 was applied to the film laminated with the transparent conductive film to obtain a transparent conductive film. For the obtained transparent conductive film, the film thickness, crystallinity, total light transmittance (%), surface resistance (Ω/□), adhesion to the transparent conductive film, and adhesion to the functional layer of the transparent conductive film were evaluated. sex. The results are shown in Table 4.

For the obtained transparent conductive film, stiffness (BR), average maximum peak height (AVSp), contact area ratio (CA), maximum peak height upper side displacement rate (MXSp/AVSp), maximum peak height lower side displacement rate ( MNSp/AVSp). The results are shown in Table 5.

For the obtained transparent conductive film, the load at the start of input, the voltage loss time, the suitability input strength test (wrong input prevention, comfortable input), input stability (swipe-shaped stroke stability, fast writing property), and pen were investigated. Sliding durability. The results are shown in Table 6.

Comparative Examples 1-8 Except having used the laminated film produced under the conditions shown in Table 1-Table 2, and having formed a transparent conductive film under the condition of Table 3, it carried out similarly to Examples 1-8, and produced the transparent conductive film. Various characteristics of the obtained thin film are shown in Table 4 - Table 6.

[Table 1] Substrate Hardened resin layer Thickness (μm) With or without hardened resin layer Amount of particle A added (wt%) Particle B addition amount (wt%) Particle A Particle size (μm) Particle B Particle size (μm) Solid content concentration (%) Thickness (μm) Example 1 188 have 5 9 1.00 0.30 47 6.0 Example 2 188 have none 1 - 0.10 45 5.0 Example 3 125 have none 15 - 0.05 45 6.0 Example 4 250 have 4 4 0.40 0.20 50 3.0 Example 5 250 have 3 11 1.80 0.70 55 5.0 Example 6 188 have none 10 - 0.40 55 15.0 Example 7 188 have 3 5 0.70 0.40 60 4.0 Example 8 188 have none 9 - 0.10 55 15.0 Comparative example 1 188 have none 27 - 0.60 45 5.0 Comparative example 2 100 have none 40 - 0.10 45 15.0 Comparative example 3 300 none - - - - - - - Comparative example 4 250 have 4 11 2.00 0.70 58 5.0 Comparative Example 5 188 have - 30 - 0.60 65 4.0 Comparative example 6 188 have none 35 - 0.10 45 9.0 Comparative Example 7 188 have 5 9 1.00 0.40 60 4.0 Comparative Example 8 250 none - - - - - - -

[Table 2] functional layer With or without functional layer Particle C Addition Amount (Wt%) Particle C Particle size (μm) Solid content concentration (%) Thickness (μm) Example 1 have 15.0 3.00 50 3.0 Example 2 have 15.0 3.00 50 3.0 Example 3 have 20.0 3.00 50 4.0 Example 4 have 1.0 3.00 50 3.0 Example 5 have 5.0 3.00 50 6.0 Example 6 have 1.0 3.00 50 11.0 Example 7 have 15.0 3.00 50 6.0 Example 8 have 1.0 3.00 50 11.0 Comparative example 1 have 28.0 3.00 50 6.0 Comparative example 2 have 27.0 3.00 55 10.0 Comparative example 3 have 1.0 3.00 50 4.0 Comparative example 4 have 7.0 3.00 50 9.0 Comparative Example 5 have 15.0 3.00 50 1.0 Comparative Example 6 have 15.0 3.00 43 5.0 Comparative Example 7 have 10.0 3.00 60 2.0 Comparative Example 8 none - - - -

[table 3] Film forming conditions of transparent conductive film Oxygen/Ar flow ratio Water/Ar partial pressure ratio (×10 ^-3 ) Roll temperature (℃) bombardment step protective film Concave-convex height difference on the end surface of film roll (mm) Tin oxide content (wt%) heat treatment Example 1 0.049 1.40 -12 have have 2 3 150°C 60 minutes Example 2 0.049 1.40 -12 have have 2 3 150°C 60 minutes Example 3 0.049 1.40 -12 have have 2 3 150°C 60 minutes Example 4 0.041 1.40 -12 have have 2 36 150°C 60 minutes Example 5 0.046 1.30 -12 have have 2 10 150°C 60 minutes Example 6 0.041 6.90 0 have have 9 36 150°C 60 minutes Example 7 0.042 0.55 -12 have have 5 1 165°C 75 minutes Example 8 0.008 0.80 -12 have have 2 36 150°C 60 minutes Comparative example 1 0.041 1.40 -12 have have 2 36 150°C 60 minutes Comparative example 2 0.049 1.10 -12 have have 2 3 150°C 60 minutes Comparative example 3 0.049 1.70 -12 have have 2 3 150°C 60 minutes Comparative example 4 0.049 1.80 -12 have have 2 3 150°C 60 minutes Comparative Example 5 0.049 8.20 2 none none 11 36 150°C 60 minutes Comparative example 6 0.008 0.80 -12 have have 2 0 80°C 20 minutes Comparative Example 7 0.049 1.40 -12 have have 2 3 150°C 60 minutes Comparative Example 8 0.049 1.70 -12 have have 2 45 150°C 60 minutes

[Table 4] Transparent Conductive Film(1) Thickness of transparent conductive film (nm) Crystallinity (%) Total light transmittance (%) Surface resistance (Ω/□) Adhesion test of transparent conductive layer (%) Adhesion test of functional layer (%) Example 1 twenty three 100 87 450 100 100 Example 2 twenty three 100 87 450 100 100 Example 3 twenty three 100 87 450 100 100 Example 4 twenty two 0 86 480 100 100 Example 5 twenty one 0 86.9 250 100 100 Example 6 90 0 81 110 100 100 Example 7 13 70 87.5 570 100 100 Example 8 80 0 82 125 100 100 Comparative example 1 twenty three 0 87 450 100 100 Comparative example 2 twenty three 100 87 450 100 100 Comparative example 3 twenty three 100 87 450 10 100 Comparative example 4 twenty three 100 87 450 100 100 Comparative Example 5 8 0 88 1200 100 100 Comparative Example 6 110 100 68 1700 100 100 Comparative Example 7 twenty three 100 87 450 100 100 Comparative Example 8 twenty three 0 87 600 10 -

[table 5] Rigidity BR Average maximum mountain height AVSp (μm) Contact area ratio CA (%) Maximum mountain height upper side displacement rate MXSp/AvSp Displacement rate MNSp/AVSp at the lower side of the maximum mountain height Rigidity BR (N･cm) Formula (2-1) left side (A1) Formula (2-1) right side (A2) Formula (2-3) right side (A3) Example 1 0.65 -0.545 1.255 38.4 1.236 41.3 1.24 0.76 Example 2 0.61 -0.733 1.067 37.1 0.053 92.1 1.13 0.83 Example 3 0.39 -1.767 0.033 29.9 0.030 94.9 1.10 0.87 Example 4 0.87 0.489 2.289 45.6 0.510 63.7 1.18 0.80 Example 5 0.89 0.583 2.383 46.2 2.350 48.0 1.32 0.64 Example 6 0.83 0.301 2.101 44.3 0.521 52.0 1.19 0.81 Example 7 0.57 -0.921 0.879 35.8 0.852 55.3 1.21 0.79 Example 8 0.78 0.066 1.866 42.6 0.077 88.2 1.19 0.77 Comparative example 1 0.58 -0.869 0.931 36.1 0.694 35.3 1.20 0.81 Comparative example 2 0.35 -1.941 -0.141 28.7 0.257 77.4 1.17 0.82 Comparative example 3 0.95 0.865 2.665 48.2 0.004 100.0 1.25 0.75 Comparative example 4 0.89 0.583 2.383 46.2 2.598 44.2 1.35 0.63 Comparative Example 5 0.66 -0.498 1.302 38.7 0.743 34.8 1.43 0.58 Comparative example 6 0.80 0.160 1.960 43.3 0.149 82.1 1.14 0.84 Comparative Example 7 0.63 -0.639 1.161 37.7 1.425 34.4 1.27 0.72 Comparative Example 8 0.91 0.677 2.477 46.9 0.004 100.0 1.25 0.75

[Table 6] Enter the starting load (g) Voltage loss time (ms) Wrong entry prevention comfort input Na stroke stability fast writing Pen sliding durability (resistance･(kΩ) Example 1 16 0.38 ○ ○ ○ ○ 0.1 Example 2 twenty one 0.12 ○ ○ ○ ○ 0.1 Example 3 16 0.07 ○ ○ ○ ○ 0.1 Example 4 25 0.27 ○ ○ ○ ○ 9 Example 5 16 0.39 ○ ○ ○ ○ 8 Example 6 twenty three 0.39 ○ ○ ○ ○ 2 Example 7 16 0.25 ○ ○ ○ ○ 0.3 Example 8 25 0.14 ○ ○ ○ ○ 3 Comparative example 1 17 0.43 ○ ○ x x 8 Comparative example 2 15 0.15 x ○ ○ ○ 0.8 Comparative example 3 37 0.13 ○ x ○ ○ ∞ Comparative example 4 15 0.45 x ○ x x 0.1 Comparative Example 5 18, 20 have variation 0.41 ○ △ x x 15 Comparative Example 6 26 0.18 ○ x ○ ○ 0.1 Comparative Example 7 14 0.42 x ○ x x 0.1 Comparative Example 8 34 0.07 ○ x ○ ○ ∞ [Possibility of industrial use]

The transparent conductive film can be widely used in the fields of electrical appliances and electronics as flat-panel displays such as liquid crystal displays and electroluminescence (EL) displays, transparent electrodes of touch panels, and the like.

1: Treated film 2: Center roll 3: mask 4: target 5: Transparent conductive film 6: Hardened resin layer 7: Transparent plastic film substrate 8: Functional layer 9: Easy adhesive layer 10: ITO glass substrate 11: Point gap 12: The position where the load is applied with a pen 13: time 14: Voltage 15: Voltage loss time 16: Endpoint 17,18: beyond the part 19: Overlapping faces 20: Transparent conductive film 21: Position for sliding

Fig. 1 is a schematic side view showing an example of the transparent conductive film of the present invention. Fig. 2 is a schematic side view showing another example of the transparent conductive film of the present invention. Fig. 3 is a schematic side view showing still another example of the transparent conductive film of the present invention. Fig. 4 is a schematic side view showing another example of the transparent conductive film of the present invention. FIG. 5 is a conceptual diagram showing the relationship between voltage and time in one aspect of the present invention. Fig. 6 is a schematic diagram of an apparatus showing an example of the film forming method of the present invention. Fig. 7 is a schematic plan partial enlarged view for explaining the method of measuring the input start load in the present invention. Fig. 8 is a schematic plan partial enlarged view for explaining the pen sliding durability measurement method in the present invention. Fig. 9 is a schematic plan view for explaining the pen sliding durability measurement method in the present invention.

none.

Claims (10)

A transparent conductive film, which is a transparent conductive film with at least one area layer of a transparent conductive film of indium-tin composite oxide on a transparent plastic film substrate, The initial input load calculated by test method 1 is greater than 15g and less than 25g, The voltage loss time obtained by test method 2 is 0.00 milliseconds to 0.40 milliseconds, [Test method 1] On one side of the glass substrate, an indium-tin composite oxide conductive film (tin oxide content: 10% by mass) was formed with a thickness of 20 nm, and dot-shaped spacers (60 μm in length) of epoxy resin were placed on the surface of the film at a pitch of 4 mm. × 60 μm in width × 5 μm in height) is formed into a square grid as a panel plate, and a rectangular frame with a thickness of 105 μm and an inner circumference of 190 mm × 135 mm with adhesion is sandwiched on the conductive film side of the panel plate. The evaluation panel was made by stacking transparent conductive films facing each other. From the transparent conductive film side of the evaluation panel, the center of the 4-dot grid of dot-shaped spacers was continuously pressed with a polyacetal pen whose tip was hemispherical with a radius of 0.8 mm. , set the pressure when the resistance value starts to stabilize as the input load, [Test method 2] Connect this evaluation panel to a constant voltage power supply of 6V, and use a hemispherical pen with a tip of 0.8 mm in radius from the transparent conductive film side to press 4 points of the dot-shaped spacer at intervals of 5 times/second with a load of 50 gf At the center of the grid, the pen starts to separate from the transparent conductive film and the voltage starts to decrease from 6V as a starting point, and the time until the voltage reaches 5V is measured, and is defined as the voltage loss time. Such as the transparent conductive film of claim 1, wherein the rigidity (BR) of the film obtained by test method 3 is 0.38N. 0.90N above cm. cm or less, the average (AVSp) of the maximum peak height Sp of the conductive surface obtained by test method 4 satisfies the following formula (2-1) and formula (2-2), and the contact area ratio obtained by test method 5 (CA) satisfies the following formula (2-3): 4.7×BR-3.6≦AVSp<4.7×BR-1.8. ． ． Formula (2-1) 0.005≦AVSp≦12.000. ． ． Formula (2-2) CA≧32.6×BR+17.2. ． ． Formula (2-3) (In the formula, the stiffness and softness of the BR series film (N.cm), the average maximum mountain height of the AVSp series (μm), and the contact area ratio of the CA series (%)) [Test method 3] Make the transparent conductive film toward Put the 20mm×250mm transparent conductive film test piece on the horizontal platform, make the test piece protrude from the end point of the horizontal platform by a length of 230mm, and determine the rigidity (BR) based on the following formula, the rigidity (BR) (N.cm))=g×a×b×L ⁴ /(8×δ×10 ¹¹ ) (In the formula, g is 9.81 (gravity acceleration; m/s ² ), a is 20 (the short side of the test piece length of the test piece; mm), b represents the specific gravity of the test piece (g/cm ³ ), L is 230 (the length of the long side of the test piece exposed outside the horizontal platform; mm), and δ represents the height of the front end of the test piece and the water level Difference in platform height (cm)) [Test method 4] On the conductive surface of the transparent conductive film, three points are determined at intervals of 1 cm in the MD direction, and symmetrically arranged at intervals of 1 cm from the center in the TD direction Determine 2 points, a total of 5 measurement points, measure the maximum peak height Sp (according to ISO 25178) based on surface roughness at each place, and set the average value as the average maximum peak height (AVSp) (μm), [Test method 5 ] For the conductive surface of the transparent conductive film, the average height Rc (μm), the maximum peak height Rp (μm), and the average length Rsm (μm) based on the line roughness are measured, and the formula (X1) and formula (X2) are satisfied At least one of the formula (X3) place, measure the arithmetic mean height Ra (μm) based on the line roughness, and the average height Rc (μm), the maximum height Rp (μm), the average length Rsm (μm), and The arithmetic mean height Ra (μm) is determined using a 3-dimensional surface shape measurement device VertScan (manufactured by Ryoka System Co., Ltd., R5500H-M100 (measurement conditions: wave mode, measurement wavelength 560nm, objective lens 50 times)), and the maximum mountain height Rp (μm ), the average length Rsm (μm), and the arithmetic mean height Ra (μm) are determined in accordance with the provisions of JIS B 0601-2001. Ra≦0.20． ． ． Formula (X1) (Rp-Rc)/Ra≦5.0. ． ． Formula (X2) Rsm≦30. ． ． Formula (X3) Change the objective lens of the VertScan 3D surface shape measurement device to 10 times, and use the particle analysis of the same measurement device to achieve "arithmetic mean height Ra(μm)-15×10 ^-3 ( μm)-average height Rc(μm)", slice in the plane direction, find the sum of the cross-sectional area, and set the following value as the contact area ratio (CA) (%): The sum of the areas divided by the area of the measured field of view was multiplied by 100. The transparent conductive film according to claim 2, wherein the maximum value MXSp of the maximum peak height Sp obtained by the test method 4 is more than 1.0 times and not more than 1.4 times the average maximum peak height AVSp, and The minimum value MNSp of the maximum mountain height Sp obtained by this test method 4 is 0.6 times or more and 1.0 times or less of the average maximum mountain height AVSp. The transparent conductive film according to any one of claims 1 to 3, wherein the thickness of the transparent conductive film is not less than 10 nm and not more than 100 nm. The transparent conductive film according to any one of claims 1 to 3, wherein the concentration of tin oxide contained in the transparent conductive film is not less than 0.5% by mass and not more than 40% by mass. The transparent conductive film according to any one of claims 1 to 3, wherein there is a cured resin layer between the transparent conductive film and the transparent plastic film substrate, Further, there is a functional layer on the side opposite to the transparent conductive film of the transparent plastic substrate. The transparent conductive film according to any one of claims 1 to 3, wherein at least one side of the transparent plastic film substrate has an easy-adhesive layer. The transparent conductive film according to claim 7, wherein the easy-adhesive layer is arranged at least one of between the transparent plastic film substrate and the cured resin layer, or between the transparent plastic substrate and the functional layer. The transparent conductive film according to any one of claims 1 to 3, wherein the ON resistance specified by test method 6 is 10kΩ or less, [Test method 6] A panel board in which an indium-tin composite oxide conductive film (tin oxide content: 10% by mass) with a thickness of 20 nm is formed on one side of a glass substrate so that the conductive films face each other through epoxy beads with a diameter of 30 μm. , and a transparent conductive film to make an evaluation panel, on the side of the transparent conductive film of the evaluation panel, use a pen with a hemispherical polyacetal pen with a radius of 0.8mm to slide while applying a load of 2.5N (the number of times of reciprocation is 5 Ten thousand times, sliding distance 30mm, sliding speed 180mm/sec), after sliding, press the sliding part with a pen load of 0.8N, and measure the resistance (ON resistance) at the time of electrical connection. The transparent conductive film according to any one of claims 1 to 3, wherein in the adhesion test according to JIS K5600-5-6:1999 on the surface of the transparent conductive film, the residual area ratio of the transparent conductive film is 95% above.

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