WO2011108494A1

WO2011108494A1 - Conductive laminate film and touch panel using the same

Info

Publication number: WO2011108494A1
Application number: PCT/JP2011/054523
Authority: WO
Inventors: 正之関口; 貴志蔵田; 正洋田端; 謙太朗平石; 亮田村
Original assignee: Jsr株式会社
Priority date: 2010-03-01
Filing date: 2011-02-28
Publication date: 2011-09-09
Also published as: TW201134665A; JPWO2011108494A1

Abstract

Disclosed is a conductive laminate film formed by laminating a film (I) configured from a transparent resin, and a transparent conductive layer (III). The conductive laminate film has positions with multiple protrusions; the surface on the side of the transparent conductive layer (III) has multiple protrusions, and the surface is curved. The disclosed conductive laminate film does not have background reflections caused by reflected light, and the occurrence of interference fringes is suppressed. Even when used as a touch panel, streak lines due to the shape of the conductive laminate film imparted in order to suppress interference fringes are not visible on the screen; high contrast and low glare are achieved along with a clear display. Disclosed is a conductive laminate film which, especially when used as a touch panel, has a high visibility and excellent durability due to improved slip properties; also disclosed is a touch panel.

Description

Conductive laminated film and touch panel using the same

The present invention relates to a conductive laminated film and a touch panel using the same. Specifically, the present invention relates to a conductive laminated film suitable for use in a touch panel that is provided on a liquid crystal display and can be used as an input means, and a touch panel using the same.

In electronic devices such as personal digital assistants (PDAs), notebook PCs, OA devices, medical devices, or car navigation systems, touch panels that have input means on these displays are widely used.

In the transparent conductive film type touch panel, a transparent base film is provided with a thin film of metal oxide such as indium tin oxide and tin antimonic acid or metal such as gold, palladium, aluminum and silver as a transparent conductive film on one side of the transparent base film. Since these metal oxides or metal thin films have a large light reflection, a touch panel having these thin films as a conductive film has a significantly reduced contrast of a liquid crystal display, resulting in a screen that is extremely difficult to see.

As a method for solving such a problem, in Patent Document 1, two transparent conductive films (a laminated film of glass and ITO) facing each other through a first quarter-wave plate and a spacer in order from the liquid crystal display side. It has been proposed to arrange a second quarter-wave plate and a polarizing plate to increase visibility.

However, in the touch panel having the above configuration, the contrast of the liquid crystal display is still insufficient, and since the touch panel has a multilayer structure, optical characteristics such as light transmittance and viewing angle compensation are insufficient.

On the other hand, Patent Document 2 has an attempt to suppress the generation of interference fringes (hereinafter also referred to as “Newton rings”) by making the transparent resistive film a special shape. However, this method cannot suppress the surface reflected light and cannot obtain high contrast, visibility, and durability.

Further, in the above method, streaky lines derived from a special shape are recognized on the touch panel screen, and improvement is demanded as the screen becomes higher in definition.

For this reason, there has been a strong demand for the appearance of an excellent touch panel having excellent optical characteristics, high visibility, suppression of interference fringes, and higher durability.

Japanese Patent Laid-Open No. 10-48625 JP 2005-18726 A

In the present invention, the generation of interference fringes is suppressed, and in particular, when a streaky line derived from the shape of the conductive laminated film provided to suppress the interference fringes is used as a touch panel, the contrast is not recognized. The object is to provide a conductive laminated film and a touch panel that are high in durability, low in glare, and particularly excellent in durability when used as a touch panel.

The present invention for solving the above-mentioned problems is a conductive laminated film in which a transparent conductive layer (III) is laminated on a film (I) made of a transparent resin, and a plurality of surface portions on the transparent conductive layer (III) side are provided. It is an electroconductive laminated film characterized by having a convex part and having a part including a plurality of convex parts whose surface is formed by a curved surface.

In the conductive laminated film, it is preferable that the plurality of convex portions are formed in a bowl shape and the convex portions meander.

In the conductive laminated film, it is preferable that the plurality of protrusions are formed in a bowl shape and the height of the protrusions varies in the extending direction of the protrusions.

In the conductive laminated film, it is preferable that there is no regularity in the change in the position where the plurality of protrusions are provided and the height of the plurality of protrusions.

The conductive laminated film preferably has a resin layer (II) made of a curable resin composition between the film (I) and the transparent conductive layer (III).

In the conductive laminated film, in the resin layer (II), a plurality of convex portions are formed in a ridge shape on the surface portion on the transparent conductive layer (III) side, and in a plane perpendicular to the length direction of the ridge. In the cross section, it is preferable that the line representing the surface on which the convex portion is formed is a wavy curve.

In the conductive laminated film, the wavy curve is preferably a wavy curve having a regular period.

In the conductive laminated film, it is preferable that the plurality of convex portions formed in a bowl shape meander in the length direction.

In the conductive laminated film, it is preferable that the plurality of convex portions formed in a bowl shape meander at regular intervals along the length direction.

In the conductive laminated film, in the resin layer (II), the maximum height of the protrusions is preferably 0.1 to 10 μm, and the period of wrinkles formed by the protrusions is preferably in the range of 100 to 5000 μm. .

In the conductive laminated film, it is preferable that the convex portions exist in a sea-island shape when viewed in the vertical direction from the film surface.

In the conductive laminated film, the highest height among the heights of the respective convex portions required as the height difference between the highest point of the convex portion and the lowest point of the valley portion adjacent to the convex portion. The maximum height dH of a certain convex portion is 0.1 to 10 μm, and the film surface between the highest point of the convex portion having the maximum height and the lowest point of the valley adjacent to the convex portion It is preferable that the distance dL in the inward direction and the dH satisfy the following formula (1).

In the conductive laminated film, the film (I) is preferably a film obtained by stretching.

In the conductive laminated film, the film (I) is preferably a retardation film having an in-plane retardation in the range of 128 to 148 nm with respect to transmitted light having a wavelength of 550 nm.

In the conductive laminated film, the resin layer (II) is preferably formed of a UV curable resin composition.

In the conductive laminated film, the film (I) preferably contains at least one of a cyclic olefin resin and a polycarbonate resin.

In the conductive laminated film, the film (I) includes a cyclic olefin resin, and the cyclic olefin resin (co) polymerizes at least one monomer represented by the following formula (1). Is preferably obtained.

(In the formula (1), R ¹ to R ⁴ represent any of the following (i) to (iii), x represents an integer of 0 to 3, and y represents 0 or 1.
(I) each independently a hydrogen atom, a halogen atom, or a monovalent organic group optionally containing oxygen, nitrogen, sulfur or silicon, (ii) R ¹ and R ² , R ³ and R ⁴ are (Iii) R ¹ and R ² , R ³ and R ⁴ , and R ² and R ³ are each bonded to a monocyclic or polycyclic carbocyclic or heterocyclic ring. )
In the conductive laminated film, the transparent conductive layer (III) is preferably formed of crystalline ITO.

Another invention is a touch panel having the conductive laminated film.

Moreover, it is a touch panel having the conductive laminated film, and a conductive laminated film in which a transparent conductive layer, a retardation film, and a polarizing plate are laminated in this order.

According to the present invention, there is no reflection due to reflection of light, generation of interference fringes is suppressed, and in particular, streaky lines derived from the shape of the conductive laminated film provided to suppress interference fringes are connected to the touch panel. Even when it is used, it is not recognized on the screen, has high contrast, little glare, can achieve clear display, especially when it is used as a touch panel, it has improved durability and excellent visibility. A laminated film and a touch panel can be provided.

FIG. 1 shows a cross-sectional view perpendicular to the ridge direction and an oblique observation view of the ridge-like surface in a conductive laminated film having convex portions formed in a ridge shape. FIG. 2 shows a cross-sectional observation view perpendicular to the wrinkle direction in the conductive laminated film having convex portions formed in a wrinkle shape. FIG. 3 shows an observation view from above of the conductive laminated film having convex portions formed in a bowl shape. FIG. 4 shows an observation image diagram of a conductive laminated film having convex portions formed in a sea-island shape. FIG. 5 is an enlarged partial sectional view of the touch panel according to the eighteenth embodiment of the present invention. FIG. 6 shows an enlarged partial cross-sectional view of the touch panel according to Embodiment 19 of the present invention. FIG. 7 shows a cross-sectional view perpendicular to the ridge direction and an oblique observation view of the ridge-like surface in a conductive laminated film having a ridge-like projection provided with a resin layer (II). FIG. 8 shows a cross-sectional observation view perpendicular to the wrinkle direction in a conductive laminated film having a ridge-like convex portion provided with a resin layer (II). FIG. 9 shows an observation view from above of a conductive laminated film having a convex portion formed in a bowl shape and provided with a resin layer (II). FIG. 10 is an enlarged partial sectional view of the touch panel according to the seventh embodiment of the present invention. FIG. 11 is an enlarged partial sectional view of the touch panel according to the eighth embodiment of the present invention.

Hereinafter, the present invention will be specifically described.

Conductive laminated film The conductive laminated film of the present invention is a conductive laminated film in which a transparent conductive layer (III) is laminated on a film (I) made of a transparent resin, and the surface on the transparent conductive layer (III) side. The portion has a plurality of convex portions, and has a portion including a plurality of convex portions whose surface is formed by a curved surface.

<Convex>
The conductive laminated film of the present invention has at least a film (I) made of a transparent resin and a transparent conductive layer (III) laminated thereon, and has a convex portion on the surface portion on the transparent conductive layer (III) side. .

In the conductive laminated film, a convex portion is provided on the surface portion of the film (I), and the transparent conductive layer (III) is laminated thereon with a substantially uniform thickness, whereby the surface portion on the transparent conductive layer (III) side. A convex portion may be formed on the surface of the transparent conductive layer (III) without providing the convex portion on the film (I) and providing the convex portion on the transparent conductive layer (III). It may be formed, and the convex part may be formed in the surface part by the side of transparent conductive layer (III) by providing a convex part in both film (I) and transparent conductive layer (III). When the resin layer (II) is provided between the film (I) and the transparent conductive layer (III), by providing a convex portion on the resin layer (II), the transparent conductive layer (III) side A convex portion may be formed on the surface portion.

The conductive laminated film of the present invention has a convex part on the surface part on the transparent conductive layer (III) side, and has a part including a plurality of convex parts whose surface is formed by a curved surface, that is, transparent. In the surface portion on the conductive layer (III) side, the surface of at least one of the portions including the plurality of convex portions is formed with a curved surface, thereby ensuring anti-Newton ring property and improving clearness, Prevention etc. can be achieved.

In the present invention, “the surface is formed with a curved surface and has a portion including a plurality of convex portions” means that the surface having the plurality of convex portions is formed in an arbitrary cross section of the portion including the plurality of convex portions. It means that the representing line is a smooth curve having no cusps. Therefore, even if the surface of each convex part is formed with a curved surface, if the two convex parts are joined at an angle, the cross section including the two convex parts has Since a cusp appears at the connection point of the two convex portions, the portion including the two convex portions does not mean that the surface is formed of a curved surface.

It is preferable that the convex portion has no regularity in the change in the position where the plural convex portions are provided and the height of the plural convex portions. If the convex part has such regularity, for example, primary reflected light and secondary reflected light interfere with each other, and Newton's ring is likely to appear. Here, the regularity means that, for example, the convex portions are formed with a certain distance, and the heights of adjacent convex portions are periodically changed.

The plurality of convex portions provided on the surface portion on the side of the bowl-shaped transparent conductive layer (III) are preferably formed in a bowl shape. In a cross section obtained by cutting a convex portion formed in a bowl shape with a plane orthogonal to the length direction, a line indicating a surface on which the convex portion is formed is preferably a wavy curve. Moreover, it is preferable that the convex part formed in bowl shape meanders in the length direction.

The convex portion formed in a bowl shape will be further described with reference to the drawings. FIG. 1 is a diagram in which a film (I) having convex portions formed in a bowl shape is cut from a plane perpendicular to the length direction of the convex portions and observed obliquely from above. In FIG. 1, the plurality of convex portions are linearly provided in parallel to form a ridge. In FIG. 1, the ridgeline of each convex part was shown with the dotted line. Here, the “ridge line” is an ideal line drawn by connecting the vertices of one convex part in all cross sections orthogonal to the length direction of the convex part.

In this cross section, the line indicating the surface on which the convex portion is formed is a wavy curve. By drawing such a curve, when the conductive laminated film is used as a touch panel, a streak-like line due to the hook shape is not recognized, and it is possible to cope with higher definition of the screen. Furthermore, it is preferable that the slipperiness when used as a touch panel is improved, the touch is improved, the resistance value change when the touch panel is used for a long time can be suppressed, and the durability can be further improved. By doing so, it is possible to provide a conductive laminated film and a touch panel that can suppress generation of interference fringes, have high contrast, have less glare, achieve a clear display, have excellent durability, and high visibility. .

The pitch (P) of the curve indicating the surface on which the convex portions on this surface are formed is determined by a plurality of convex portions. Here, the pitch is the length in the plane direction from the apex of the wavy curve to the adjacent apex. As shown in FIG. 1, the height of the convex portion is obtained as a height difference between the highest point of the convex portion and the lowest point of the valley adjacent to the convex portion.

The P of the wavy curve appearing in the cross section is preferably in the range of 50 to 5000 μm, more preferably 100 to 1000 μm. When P is less than 50 μm, glare may occur, and when it exceeds 5000 μm, anti-Newton ring properties may not be sufficiently exhibited.

Further, the maximum height of the convex portion formed in a bowl shape is usually set in the range of 0.1 to 10 μm, preferably 0.5 to 3 μm. If it is smaller than 0.1 μm, the anti-Newton ring property does not appear, and if it is larger than 10 μm, a bumpy feeling is felt at the time of input when assembled as a touch panel. Here, the maximum height of the convex portion is the largest height among the heights of the plurality of convex portions.

When laminating the film (I) having a convex portion formed in a bowl shape with another film or sheet, for example, when using liquid crystal for the lower display device, as a countermeasure against moire, Visibility is improved by laminating the length direction of the convex portions formed in a shape at an angle of 10 to 45 °. Therefore, when a quarter-wave retardation film is used as the base film, it is desirable that the convex portions are laminated so that the length direction of the convex portion is an angle of 10 to 80 ° with respect to the slow axis.

FIG. 2 is an observation view of a cross section orthogonal to the length direction of the convex portion formed in a bowl shape. The curved part drawn by the top of the convex part in this cross section and the curved part drawn by the valley part sandwiched between the two convex parts are rounded curves having radii of curvature (Rt) and (Rb), respectively. This curve may be a sinusoid. Each roundness of the curved line is appropriately adjusted in terms of touch panel feel, ease of striped lines, interference fringe prevention effect, and durability performance. This roundness can be adjusted, for example, by adjusting the respective curvature radii. In this case, the curvature radii (Rt) and (Rb) are preferably not less than half and not more than 30 times the pitch (P). More preferably, the pitch (P) is not less than 10 times and particularly preferably not less than 3 times and not more than 10 times the pitch (P). In addition, it is preferable that the curvature radii (Rt) and (Rb) are the same from the viewpoint of ease of production, and it is preferable that the curvature radius (Rt) is larger than (Rb) from the viewpoint of improving the touch on the touch panel. Moreover, the length (L) of the film plane direction in FIG. 2 of the straight line part which connects the curved part which the top part of the convex part in the said cross section draws, and the curved part of the valley part pinched | interposed into two convex parts is pitch ( P) is preferably 1/3 or less, more preferably 1/5 or less, and particularly preferably 1/10 or less.

It is preferable that the convex portion formed in a bowl shape meanders. Here, “meandering” means that the convex portion formed in a bowl shape draws a wavy curve along the length direction on a plane parallel to the plane of the conductive laminated film of the present invention. Say. The wave shape may be a regular wave shape or a non-regular wave shape.

FIG. 3 shows an observation view from above of the conductive laminated film in which convex portions formed in a bowl shape meander at a pitch (Pl). In FIG. 3, the plurality of convex portions have the same wave shape, are provided with the same period, and form a ridge. The pitch (Pl) is the length in the planar direction from the apex of the wavy curve to the apex.

In the conductive laminated film of the present invention, it is preferable that the ridge line of the convex portion draws a wavy curve on the plane of the conductive laminated film. As described above, the “ridge line” is a notional line drawn by connecting the vertices of one convex portion in all cross sections orthogonal to the length direction of the convex portion. In FIG. 1, the ridge line of the convex portion is a straight line, whereas in FIG. 3, which is one embodiment of the present invention, the ridge line of each convex portion formed in a bowl shape is regular on a plane parallel to the film plane. Meandering. By making the saddle shape like this, the streak line becomes harder to be recognized, the smoothness when used as a touch panel is improved and the touch is improved, and the resistance value change when the touch panel is used for a long time This is preferable because the durability can be further improved.

When the pitch of the regular curve in the film plane at this time is (Pl) and the width of the curve is (W), the pitch (Pl) is preferably 1 to 30 times, more preferably the pitch (P). Is not less than 2 times and not more than 20 times, particularly preferably not less than 3 times and not more than 10 times, and the width (W) of the curve is preferably not less than 1/2 times and not more than 30 times, more preferably not less than 1 time of the pitch (P). 20 times or less, particularly preferably 3 times or more and 10 times or less. When the ratio of the pitch (Pl) to the pitch (P) in the regular curve in the film plane direction and the ratio of the width (W) of the curve to the pitch (P) is less than the lower limit of the above range, the touch panel is used. A feeling of glare may occur, and if the upper limit of the above range is exceeded, the effect of making the ridge line a curve may be diminished.

It is also preferable to vary the height of each convex portion formed in a bowl shape. In that case, the height variation width is within a range of ± 50%, more preferably ± 30%, and particularly preferably ± 10% with respect to the average height of one convex portion. If it does so, since durability performance when it is set as a touch panel improves, it is preferable.

Also, it is preferable that the curve indicating the surface on which the convex portion in the cross section orthogonal to the length direction of the ridge has a height variation within a certain range. The variation range at that time is preferably adjusted to a range of ± 50%, more preferably ± 30%, particularly preferably ± 10% with respect to the average height.

Also, when the ridge line of the convex portion formed in a bowl shape draws a wavy curve on the plane of the film, the amplitude may be appropriately adjusted so that the amplitude has a variation within a certain range. In this case, the variation range is preferably adjusted to a range of ± 50%, more preferably ± 30%, and particularly preferably ± 10% with respect to the average amplitude.

By adjusting the variation within the range, desired characteristics can be obtained in appearance and durability.

It is also preferable that the plurality of convex portions formed in a bowl shape are intermittently formed in the length direction of the bowl. In this case, the length of the convex portion is preferably in the range of 1 to 10 times, more preferably 1 to 5 times, and particularly preferably 2 to 4 times the pitch of the ridges. In this case, it is particularly important that the intermittent portion, which is a portion where the ridge-shaped convex portion is not formed, has the curved shape described in the sea-island structure described later. By doing so, in addition to a good appearance, a further durability performance can be obtained.

Sea Island Shape A plurality of convex portions provided on the surface portion on the transparent conductive layer (III) side may be provided in a sea island shape. The sea island shape will be further described with reference to the drawings. (1) to (4) in FIG. 4 show image views of a conductive laminated film having a convex portion formed on one side as a sea-island shape as an example of a sea-island shape according to the present invention, as observed from the top and cross-sectional directions. . The important point here is that any shape does not have a locally acute angle portion, but has a curved shape. By doing so, desired characteristics can be obtained in appearance and durability. Such a curved shape change can be formed, for example, by stretching a film.

4 (1) to (4), a top view is shown on the left side, and a cross-sectional view of the dotted line shown in the top view is shown on the right side. In the top views of FIGS. 4 (1) to (4), the convex portion does not appear with a contour line, but is represented with an ideal contour line in order to visually represent the convex portion. In the cross-sectional views of FIGS. 4 (1) to 4 (4), the two opposing arrows indicate the height of the convex portion.

In FIG. 4 (1), convex portions having a rectangular planar shape are arranged in multiple rows in the long side direction, and the convex portions are half of the long sides between two adjacent rows. They are arranged so as to be shifted by the length. In the cross-sectional view, the film surface has a wavy curve.

In FIG. 4 (2), convex portions having a rhombus in the planar shape are arranged. In the cross-sectional view, the film surface has a wavy curve.

In FIG. 4 (3), convex portions having an elliptical planar shape are arranged. In the cross-sectional view, the film surface draws a rounded curve in the portion where the convex portion is provided, and is linear in the portion where the convex portion is not provided.

In FIG. 4 (4), the convex portions having a rectangular planar shape are arranged in rows and columns. In the cross-sectional view, the film surface has a wavy curve.

Even in the case where the convex portion is formed in any shape such as a bowl shape or a sea island shape, the maximum height dH of the convex portion is preferably 0.1 to 10 μm, and the maximum height of the convex portion having the maximum height is preferably It is preferable that the distances dL and dH in the film in-plane direction between the high point and the lowest point of the valley adjacent to the convex portion satisfy the following formula (1).

dH is more preferably 0.5 to 5 μm, particularly preferably 1 to 3 μm, and the range of dH / dL is more preferably greater than 0 and not greater than 0.03, particularly preferably greater than 0 and not greater than 0.01. is there. The maximum height dH is the largest height among the heights of the plurality of convex portions. The height of the convex portion is obtained as a difference in height between the highest point of the convex portion and the lowest point of the valley adjacent to the convex portion. When there are a plurality of combinations of two points on the film surface giving dH, dL is determined by two points at which dL is the minimum value.

When the convex portion satisfies the above conditions, the generation of interference fringes is suppressed, and particularly when the streaky line derived from the shape of the conductive laminated film provided to suppress the interference fringes is used as the touch panel In addition, it is not recognized on the screen, has high contrast, little glare, and when it is used as a touch panel, it has excellent durability because it has improved sliding properties, and a highly visible conductive laminate film and touch panel can be obtained. it can.

<Film made of transparent resin (I)>
The film (I) made of a transparent resin may be any film as long as it has transparency and can be used as a base film for a conductive laminated film, and a film containing a known transparent resin can be used. In the present invention, it is preferable to use a film containing a cyclic olefin resin and / or a polycarbonate resin as the film (I) made of a transparent resin. When the film (I) made of a transparent resin contains a cyclic olefin resin and / or a polycarbonate resin, it may be formed of one kind of cyclic olefin resin or polycarbonate resin, and two or more kinds of cyclic olefin resins. Resin composition containing two or more polycarbonate resins, or one or more cyclic olefin-based resins and one or more polycarbonate resins, or a resin composition containing other resin components It may be formed from an object. In the present invention, the film (I) made of a transparent resin is more preferably a film made of a resin or a resin composition in which the resin component is only one or more cyclic olefin resins, or only one or more polycarbonate resins. Preferably, the film is made of only one or more cyclic olefin-based resins. When the film (I) made of a transparent resin is a film made of a cyclic olefin resin or a polycarbonate resin, in addition to being excellent in transparency, it can be suitably used as a retardation film, suppressing reflected light and improving visibility. Improvements can be made.

The film (I) made of the transparent resin according to the present invention may be a film showing no retardation or a retardation film. When the film (I) is a retardation film, it is desirable that the in-plane retardation with respect to transmitted light with a wavelength of 550 nm is 128 to 148 nm, preferably 133 to 143 nm, and preferably a 1 / 4λ retardation film. Particularly preferred. Here, the phase difference is defined by the product (Δnd) of the refractive index difference (Δn) of birefringent light and the thickness (d). When the film (I) made of a transparent resin has such a phase difference, reflected light can be effectively prevented, and a high-contrast touch panel is obtained, which is preferable.

The retardation film is preferably obtained by stretching a film obtained from a cyclic olefin resin or a polycarbonate resin, and obtained by stretching a film obtained from a cyclic olefin resin. More preferably.

Cyclic olefin-based resin The cyclic olefin-based resin that can constitute the transparent resin film (I) includes a monomer containing at least one cyclic olefin-based compound having a norbornene skeleton, or a copolymer together with the cyclic olefin-based compound. A monomer composition containing a polymerizable monomer is preferably a ring-opening (co) polymerization or addition (co) polymerization, and a double bond in the main chain of the obtained (co) polymer A hydrogenated product is more preferably used.

The cyclic olefin-based resin is a resin obtained by (co) polymerizing a monomer containing at least one compound represented by the following formula (1) (hereinafter also referred to as “specific monomer”). It is preferable.

(In the formula (1), R ¹ ~ R ⁴ are each independently a hydrogen atom, a halogen atom, or an oxygen, nitrogen, represents an organic group which may monovalent that contain sulfur or silicon, and R ¹ R ² , R ³ and R ⁴ may be independently bonded to each other to form an alkylidene group. R ¹ and R ² , R ³ and R ⁴ , R ² and R ³ And each independently may be bonded to each other to form a monocyclic or polycyclic carbocyclic or heterocyclic ring, x represents an integer of 0 to 3, and y represents 0 or 1.)
As the cyclic olefin resin suitably used in the present invention, the following (co) polymers (i) to (iii) are preferable.
(I) A ring-opening (co) polymer of a specific monomer and, if necessary, a copolymerizable monomer (hereinafter also referred to as “specific ring-opening (co) polymer”).
(Ii) Hydrogenated (co) polymers of specific ring-opening (co) polymers.
(Iii) Addition (co) polymer of a specific monomer and, if necessary, a copolymerizable monomer.

Among these, in the present invention, among the (co) polymers of (ii) above, that is, in the main chain of the (co) polymer obtained by ring-opening (co) polymerizing a monomer containing a specific monomer. A resin in which the double bond is hydrogenated is preferable. Examples of such a cyclic olefin-based resin include resins having a structural unit represented by the following formula (1 ′).

(Wherein ^{(1 '), R 1 ~} R 4, x and y are respectively similar to the R ¹ ~ R ^4, x and y of the above formula (1).)
(Specific monomer)
A specific monomer may be used individually by 1 type, or may be used together 2 or more types.

Among these specific monomers, R ¹ and R ^{3 in} the above formula (1) are preferably a hydrogen atom or 1 to 10 carbon atoms, more preferably 1 to 4, more preferably 1 to 2 represents a hydrocarbon group, R ² and R ⁴ represent a hydrogen atom; or a monovalent organic group which may contain an oxygen atom, a nitrogen atom, a sulfur atom or a silicon atom, and R ² and R ⁴ At least one represents a hydrogen atom or a monovalent organic group having a polarity other than a hydrocarbon group, x represents an integer of 0 to 3, y represents an integer of 0 to 3, more preferably x + y = 0 to 4, more preferably 0 to 2, particularly preferably x = 0 and y = 1. Use of a monomer containing such a specific monomer is preferable in that the obtained cyclic olefin-based resin has a high glass transition temperature and excellent mechanical strength.

Examples of the monovalent organic group having the polarity include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These monovalent organic groups having polarity may be bonded via a linking group such as a methylene group. In addition, a hydrocarbon group or the like in which a divalent organic group having polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group is also exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and an allyloxycarbonyl group are more preferable.

Further, in the above formula (1), when at least one of R ² and R ⁴ contains a monomer representing a monovalent organic group having a polarity represented by the formula: — (CH ₂ ) _n COOR The obtained cyclic olefin-based resin is preferable in that it has a high glass transition temperature, low hygroscopicity, and excellent adhesion to various materials. In the formula, R represents a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, desirably an alkyl group. Further, n is usually an integer of 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the resulting cyclic olefin resin is higher, and a specific monomer in which n is 0. Is preferred because of its easy synthesis.

In the above formula (1), R ¹ or R ³ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and further preferably a methyl group. In particular, it is obtained that such an alkyl group is bonded to the same carbon atom as the carbon atom to which the monovalent organic group having the polarity represented by the above formula: — (CH ₂ ) _n COOR is bonded. This is preferable in that the hygroscopicity of the cyclic olefin resin can be lowered.

(Copolymerizable monomer)
The cyclic olefin resin used in the present invention may be obtained by copolymerizing a copolymerizable monomer together with a cyclic olefin compound such as a specific monomer.

Specific examples of the copolymerizable monomer in the ring-opening (co) polymer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms in the cycloolefin is preferably 4-20, and more preferably 5-12. These may be used alone or in combination of two or more.

The copolymerizable monomer in the addition (co) polymer is preferably a compound having a reactive unsaturated double bond, specifically, an olefinic compound such as ethylene, propylene, and butene; And vinyl unsaturated hydrocarbon compounds such as α-methylstyrene and vinylcyclopentene; and (meth) acrylates such as methyl methacrylate.

(Ring-opening polymerization catalyst)
The ring-opening (co) polymerization reaction is performed in the presence of a metathesis catalyst. As this metathesis catalyst, a known catalyst can be used. For example, (a) at least one selected from W, Mo and Re compounds, and (b) a Deaming periodic table group IA element (for example, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.) or a group IVB element (for example, Ti, Zr, etc.) and at least one selected from those having at least one of the element-carbon bond or the element-hydrogen bond A catalyst composed of a combination. In this case, alcohols, aldehydes, ketones, amines and the like can be suitably contained in the catalyst in order to increase the activity of the catalyst. Further, compounds shown in JP-A-1-132626, page 8, lower right column, line 16 to page 9, upper left column, line 17 may be contained.

(Solvent for polymerization reaction)
Examples of the solvent used in the ring-opening (co) polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include pentane, hexane, heptane, octane, nonane, decane, etc. Alkanes; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedi Halogenated alkanes such as bromide, chlorobenzene, chloroform, tetrachloroethylene, aryl halides; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane; Ether, tetrahydrofuran, include such ethers such as dimethoxyethane, they may be used in combination of two or more types may be used alone. Of these, aromatic hydrocarbons are preferred.

As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

The molecular weight of the resulting ring-opening (co) polymer can be adjusted depending on the polymerization temperature, the type of catalyst, and the type of solvent. For example, ethylene, propene, 1-butene, 1-pentene, 1-hexene Further, α-olefins such as 1-heptene, 1-octene, 1-nonene and 1-decene and a molecular weight regulator such as styrene may be added.

The ring-opening (co) polymer obtained as described above can be used as it is, but (ii) hydrogen obtained by hydrogenating an olefinically unsaturated bond in the molecule of this (co) polymer. The additive (co) polymer is preferable because it is excellent in heat-resistant coloring and light resistance and can improve the durability of the retardation film.

(Hydrogenation catalyst)
For the hydrogenation reaction, a method of hydrogenating a normal olefinically unsaturated bond can be applied. That is, a hydrogenation catalyst is added to a ring-opening (co) polymer solution, and hydrogen gas at atmospheric pressure to 300 atmospheres, preferably 3 to 200 atmospheres, is applied at 0 to 200 ° C., preferably 20 to 180 ° C. Is done by letting

As the hydrogenation catalyst, those used in the usual hydrogenation reaction of olefinic compounds can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. In addition, homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the better the stability to heat and light. When used as the transparent film of the present invention, stable characteristics can be obtained over a long period of time.

In addition, when an aromatic group is present in the ring-opening (co) polymer molecule, the aromatic group is less likely to deteriorate the heat resistance coloring property and light resistance, and conversely optical characteristics such as refractive index and wavelength dispersion. There are cases where advantageous effects are brought about with respect to optical properties such as properties or heat resistance, and a suitable film (I) can be obtained without hydrogenation.

The ring-opening (co) polymer obtained as described above includes known antioxidants such as 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3, 3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and / or UV absorbers such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc. Can be stabilized. Further, additives such as a lubricant can be added for the purpose of improving processability.

The hydrogenated (co) polymer used as the cyclic olefin resin preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less, preferably 1% by weight or less. It is more preferable that

Further, as the cyclic olefin resin, a (co) polymer obtained by cyclizing the ring-opened (co) polymer by Friedel-Craft reaction and then hydrogenating it is also used.

(Addition polymerization catalyst)
As the catalyst for synthesizing the addition (co) polymer, a known catalyst can be used, specifically, at least one selected from the group consisting of a titanium compound, a zirconium compound and a vanadium compound, and an assistant. It is an organoaluminum compound as a catalyst.

(Physical properties of cyclic olefin resin)
The molecular weight of the cyclic olefin resin is an intrinsic viscosity [η] _inh , preferably 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, still more preferably 0.4 to 1.5 dl / g. The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably 8,000 to 100,000, more preferably 10,000 to 80,000, and still more preferably 12 The weight average molecular weight (Mw) is preferably in the range of 20,000 to 300,000, more preferably 30,000 to 250,000, and still more preferably 40,000 to 200,000. Are preferred.

When the intrinsic viscosity [η] _inh , number average molecular weight and weight average molecular weight are within the above ranges, the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin, and the conductive laminated film of the present invention The balance with the stability of optical characteristics when used is good.

The glass transition temperature (Tg) of the cyclic olefin resin is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and further preferably 140 to 200 ° C. This is to stabilize the change in optical properties of the obtained cyclic olefin resin film and prevent thermal deterioration of the resin when heated to near Tg and processed, such as stretching.

The saturated water absorption at 23 ° C. of the cyclic olefin resin is preferably 2% by weight or less, more preferably 0.01 to 2% by weight, and further preferably 0.1 to 1% by weight. If the saturated water absorption is within this range, the optical characteristics are uniform, the adhesiveness between the obtained cyclic olefin resin film and other optical members and adhesives is excellent, and peeling does not occur during use. Moreover, it is excellent in compatibility with an antioxidant and the like, and can be added in a large amount. The saturated water absorption is a value obtained by immersing in 23 ° C. water for 1 week and measuring the increased weight according to ASTM D570.

The cyclic olefin resin has a photoelastic coefficient (C _P ) of 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ) and a stress optical coefficient (C _R ) of 1,000 to 4,000 (× 10 Those satisfying ⁻¹² Pa ⁻¹ ) are preferable. Here, with respect to the photoelastic coefficient (C _P ) and the stress optical coefficient (C _R ), various documents such as Polymer Journal, Vol. 27, No, 9pp 943-950 (1995), Journal of the Japanese Society of Rheology, Vol. .19, No. 2, p93-97 (1991), photoelastic experiment method, Nikkan Kogyo Shimbun, 7th edition of 1975. The former represents the degree of occurrence of phase difference due to stress in the glass state of the polymer, while the latter represents the degree of occurrence of phase difference due to stress in the flow state.

The large photoelastic coefficient (C _P ) means that stress generated from external factors or strain generated from its own frozen strain when a cyclic olefin resin film is used in combination with another optical member or adhesive. For example, when a transparent conductive layer is laminated as in the present invention or when it is used fixed to another optical member, residual strain at the time of bonding is expressed. It means that an unnecessary phase difference is likely to be generated due to a minute stress generated by shrinkage of a material accompanying a temperature change or a humidity change. Therefore, it is better that the photoelastic coefficient (C _P ) is as small as possible.

On the other hand, a large stress optical coefficient (C _R ) means that, for example, a desired retardation can be obtained with a small stretch ratio when imparting retardation to a cyclic olefin-based resin film. There is a great merit that it is easy to obtain a film capable of imparting a phase difference, and that when the same phase difference is desired, the film can be thinned as compared with a film having a small stress optical coefficient (C _R ).

From the above viewpoint, the photoelastic coefficient (C _P ) is preferably 0 to 100 (× 10 ⁻¹² Pa ⁻¹ ), more preferably 0 to 80 (× 10 ⁻¹² Pa ⁻¹ ), and still more preferably 0. To 50 (× 10 ⁻¹² Pa ⁻¹ ), particularly preferably 0 to 30 (× 10 ⁻¹² Pa ⁻¹ ), and most preferably 0 to 20 (× 10 ⁻¹² Pa ⁻¹ ). Minimizes unnecessary phase difference due to stress generated when the transparent conductive layer is laminated, stress generated when the conductive laminated film is fixed to other optical members, and phase change caused by environmental changes during use This is to limit it to the limit.

(Additive)
The cyclic olefin-based resin can be further stabilized by adding known antioxidants, ultraviolet absorbers and the like. Moreover, in order to improve workability, the additive used in conventional resin processings, such as a lubricant, can also be added.

Examples of the antioxidant include pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

Polycarbonate resin The polycarbonate resin that can form the transparent resin film (I) is not particularly limited, and any aromatic homopolycarbonate or copolycarbonate known in the art can be used. . The polycarbonate component may be produced according to any method generally known in the art, such as interfacial polycondensation, homogeneous phase polycondensation, or transesterification. These methods and the associated reactants, polymers, catalysts, solvents and conditions are well known in the art and are described in U.S. Pat. Nos. 2,964,974, 2,970,137, 2,999,835. 2,999,846, 3,028,365, 3,153,008, 3,187,065, 3,215,668, 3,258,414 and No. 5,010,162. Suitable polycarbonates are based, for example, on one or more of the following bisphenols: dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (Hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfoxides, bis (hydroxyphenyl) sulfones, alkylcyclohexylidene bisphenols, α, α-bis (hydroxyphenyl) diisopropylbenzenes , Derivatives in which these nuclei are alkylated or derivatives in which the nuclei are halogenated, and mixtures thereof.

Specific examples of these bisphenols include 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, α, α-bis (4-hydroxyphenyl) diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro- 4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4) -Hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α, α-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3 , 5-dichloro-4-hydroxyphenyl) propane and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane. A particularly preferred bisphenol is 2,2-bis (4-hydroxyphenyl) propane, more commonly known as bisphenol A. The above bisphenols can be reacted with phosgene to produce an aromatic polycarbonate. Suitable polycarbonates are also described in US Pat. No. 4,677,162.

Other resin When the film made of the transparent resin according to the present invention is made of a resin other than the cyclic olefin resin and the polycarbonate resin, examples of the transparent resin include polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, and triacetyl cellulose. , Polyethersulfone, polyimide and the like.

Production of Film (I) Made of Transparent Resin Film (I) made of transparent resin used in the present invention is not particularly limited in its production method, and a transparent resin such as a cyclic olefin resin or a polycarbonate resin is previously used as a film or sheet. After forming into a shape, it can be obtained by stretching. In particular, the film (I) made of a transparent resin obtained by stretching is preferable because it is suitable for a touch panel that requires an antireflection function. When the convex portion is formed on the surface of the transparent conductive layer (III) by providing the convex portion on the film (I), the convex portion provided on the film (I) may be formed after the stretching process. Alternatively, a preliminary convex portion may be made on the film before stretching and the film may be stretched.

The method for forming the transparent resin into a film can be appropriately selected according to the type of the transparent resin or the desired properties of the film, such as a melt molding method and a solvent casting method (solution casting method). The method can be adopted. As a method for forming the film, a solvent casting method is preferable from the viewpoint of good film thickness uniformity and surface smoothness. From the viewpoint of production cost, the melt molding method is preferable. The film thus formed is not particularly limited, but the film thickness is usually 70 to 300 μm, preferably 80 to 250 μm, and the difference between the maximum thickness and the minimum thickness of the film is usually within 3 μm, preferably Is within 2 μm.

When the transparent resin is formed into a film or sheet, it is preferable to form a convex portion on at least one surface thereof. If it does in this way, the film (I) which has a desired convex part can be obtained by extending | stretching this film-like thing or a sheet-like thing. A known method can be used as a method for forming the convex portion. For example, in the melt molding method, when the molten resin is cooled and solidified, a method of transferring by pressing against a metal roll having a concave portion is preferably used. It is done. For metal rolls, for example, the surface of a relatively soft metal such as copper or nickel that is easy to surface is plated, and the surface of the roll is desired after it has been cut into a desired shape by cutting or the like, and the metal roll surface is textured The roll etc. which plated chromium, nickel, etc. so that it may become the shape of this are used suitably. Moreover, it is desirable to apply a known film such as diamond-like carbon to the surface of these metal rolls for the purpose of preventing scratches. Further, for example, in the solvent casting method, a transparent resin solution is cast on a base material made of stainless steel having a recess and a plastic base material such as polyethylene terephthalate, and the solvent is removed by drying. The method is preferably used. At this time, the amount of residual solvent in the resin film is preferably 20% or less, more preferably 10% or less, particularly preferably 5% or less. By setting the residual solvent amount within this range, the amount depends on the solvent during stretching. It is preferable because foaming can be suppressed.

After forming the transparent resin into a film or sheet, it is also preferable to form a protrusion on at least one surface of the film or sheet using, for example, an embossing roll or the like. Even if it does in this way, the film (I) which has a desired convex part can be obtained by extending | stretching the film-form thing or sheet-like thing which has this convex part. As the embossing roll, a known material or the above-described metal roll is appropriately used.

The film (I) made of a transparent resin used in the present invention can be produced by using a film-like product obtained by molding the transparent resin as described above as a raw film, and stretching the film. Specifically, the raw film can be produced by stretching by a known uniaxial stretching method, biaxial stretching method, oblique stretching method or the like. That is, the horizontal uniaxial stretching method by the tenter method, the inter-roll compression stretching method, the longitudinal uniaxial stretching method using rolls with different circumferences, or the biaxial stretching method combining horizontal uniaxial and longitudinal uniaxial, An oblique stretching method in which the optical axis is slanted in the film plane without contrasting the moving speed and the shape of the guide roll, a stretching method by an inflation method, and the like can be used. Among these, horizontal uniaxial stretching and vertical uniaxial stretching are preferable from the viewpoint of production cost, oblique stretching is preferable from the surface where the optical axis can be adjusted obliquely, and biaxial stretching is preferably used from the viewpoint of easy control of the film surface shape.

The stretching speed at the time of stretching is usually 1 to 5,000% / min, preferably 50 to 1,000% / min, more preferably 100 to 1,000% / min, and further preferably 100 to 500% / min. Here, the stretching speed of 1% / min means a speed at which the length of the film becomes longer by 1% of the original length per minute. In the case of the biaxial stretching method, stretching may be performed in two directions at the same time, or the stretching may be performed in a direction different from the first stretching direction after uniaxial stretching. In these cases, the intersecting angle of the two stretching axes is usually in the range of 120 to 60 degrees, and the stretching speed may be the same or different in each stretching direction.

The stretching temperature is not particularly limited, but is usually Tg ± 40 ° C., preferably Tg−5 to Tg + 40 ° C., more preferably Tg, based on the glass transition temperature (Tg) of the resin constituting the film. ˜Tg + 30 ° C., particularly preferably in the range of Tg + 10 to Tg + 30 ° C. Moreover, when the convex shape is formed only on one side of the film, it is preferable to increase the temperature of the surface on which the convex shape is formed by 5 ° C. or more, and preferably by 10 ° C. or more. Is more preferable. In that case, temperature adjustment is suitably performed by adjusting the temperature distribution setting in the whole thermostat which heats a film, installing a spot heater etc. in a thermostat. When the processing temperature at the time of stretching is within the above range, the film surface shape can be made into a curved convex state, and the occurrence of unevenness can be suppressed while suitably controlling the occurrence of phase difference. To preferred.

The draw ratio is usually 1.01 to 10 times, preferably 1.5 to 5 times, more preferably 2.0 to 3.5 times. When the draw ratio exceeds 10 times, it may be difficult to control the film surface shape and retardation.

The stretched film may be cooled as it is, but is allowed to stand in a temperature atmosphere of Tg-20 ° C. to Tg for at least 10 seconds or more, preferably 30 seconds to 60 minutes, more preferably 1 minute to 60 minutes. As a result, a stable retardation film with little change in retardation characteristics with time can be obtained. Further, it is also suitably performed to contact a roll adjusted to a temperature range of preferably Tg-20 ° C to Tg + 10 ° C, more preferably Tg-10 ° C to Tg + 5 ° C. By doing so, it is preferable from the point that the curved convex shape of the film surface can be formed more uniformly.

Further, the linear expansion coefficient of the film (I) comprising the transparent resin of the present invention after stretching is preferably 1 × 10 ⁻⁴ (1 / ° C.) or less, more preferably in the temperature range of 20 ° C. to 100 ° C. Is 9 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 8 × 10 ⁻⁵ (1 / ° C.) or less, and particularly preferably 7 × 10 ⁻⁵ (1 / ° C.) or less. Further, the difference in linear expansion coefficient between the stretching direction and the direction perpendicular thereto is preferably 5 × 10 ⁻⁵ (1 / ° C.) or less, more preferably 3 × 10 ⁻⁵ (1 / ° C.) or less, and further preferably 1 × 10 ⁻⁵ (1 / ° C.) or less. By setting the linear expansion coefficient within the above range, when the film (I) is used in the conductive laminated film of the present invention, a change in phase difference caused by a change in stress caused by the influence of temperature and humidity during use In addition, changes in resistance value of the transparent conductive film can be suppressed, and long-term characteristics can be stabilized. Moreover, when the conductive laminated film of the present invention using the film (I) is used as a touch panel, deformation due to a change in the external environment can be suppressed and generation of interference fringes can be further suppressed.

In the film stretched as described above, molecules are oriented by stretching and a phase difference is imparted to transmitted light. This phase difference is determined by the retardation value, stretching ratio, stretching temperature, stretching of the film before stretching. It can control by the thickness of the film after orientation.

The total light transmittance of the film (I) made of the transparent resin used in the present invention is preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more, since the visibility of the touch panel is improved. is there.

Surface Treatment The film (I) made of the transparent resin according to the present invention is subjected to a surface treatment for the purpose of improving the adhesion with the resin layer (II) and the transparent conductive layer (III) made of a curable resin composition. There may be. Examples of the surface treatment include plasma treatment, corona treatment, alkali treatment, and coating treatment. In particular, by using corona treatment, the adhesion between the transparent resin film (I) and the resin layer (II) can be strengthened.

The corona treatment conditions, is preferably 1 ~ 1000W / m ² / min as an irradiation amount of corona discharge electron, and more preferably in the ^{10 ~ 100W / m 2 / min} . If the irradiation amount is lower than this, a sufficient surface modification effect may not be obtained, and if the irradiation amount is higher than this, the treatment effect reaches the inside of the retardation film, and the film itself is There is a risk of deterioration.

Moreover, when forming the said resin layer (II) on the film (I) which consists of a transparent resin which carried out the corona treatment, you may use the film (I) immediately after a corona treatment, but use it after carrying out static elimination. This is preferable in terms of preventing foreign matter adhesion.

<Resin layer (II) made of curable resin composition>
Between the film (I) made of the transparent resin and the transparent conductive layer (III), it is made of a curable resin composition for the purpose of improving the surface hardness, adhesion, etc. and adjusting the smoothness of the surface protrusions. It is preferable to provide the resin layer (II).

As described above, when the resin layer (II) is provided between the film (I) and the transparent conductive layer (III), by providing a convex portion on the surface portion of the resin layer (II), A convex portion may be formed on the surface portion on the conductive layer (III) side. If it does in this way, the conductive laminated film of this invention can achieve the anti-Newton ring property ensuring, the improvement of a clear feeling, and prevention of glare.

The convex portion provided on the surface portion of the resin layer (II) can be formed in a bowl shape or a sea island shape as described above. By laminating the transparent conductive layer (III) with a substantially uniform thickness on the resin layer (II) provided with such convex portions, the above-mentioned bowl-like shape is formed on the surface portion on the transparent conductive layer (III) side. Or the electroconductive laminated film which has the convex part formed in sea island shape can be obtained.

Hereinafter, the resin layer (II) having convex portions provided in a bowl shape of the resin layer (II) will be described.

The convex part of the resin layer (II) is formed in a bowl shape, and in the cross section obtained by cutting along a plane perpendicular to the length direction of the bottle, the line indicating the surface on which the convex part is formed is a wavy curve. Preferably there is. It is preferable that the plurality of convex portions forming the ridge meander in the length direction of the ridge.

The wavy curve is preferably a wavy curve having a regular period (pitch: hereinafter also referred to as P), and the plurality of convex portions forming the wrinkles are regularly formed along the length direction of the wrinkles. It is also preferable to meander at a regular cycle (pitch: hereinafter also referred to as Pl).

The P of the wavy curve appearing in the cross section is preferably in the range of 100 to 5000 μm, more preferably in the range of 200 to 1000 μm. When P is less than 100 μm, glare may occur, and when it exceeds 5000 μm, anti-Newton ring properties may not be sufficiently exhibited.

Further, the maximum height of the convex portion formed in a bowl shape is usually set in the range of 0.1 to 10 μm, preferably 0.5 to 3 μm. If it is less than 0.1 μm, the anti-Newton ring property does not appear, and if it exceeds 10 μm, a feeling of bumpiness is felt at the time of input when assembled as a touch panel.

It is preferable that the plurality of convex portions forming the ridge meander with the Pl. Here, “meandering” means that the convex portion formed in a bowl shape draws a wavy curve along the length direction on a plane parallel to the plane of the conductive laminated film of the present invention. Say.

The bowl-shaped convex part is preferably formed by continuously transferring the shape onto a film (I) made of a transparent resin by a transfer roll having a concave part capable of forming such a convex part. When laminating the resin layer (II) having a ridge-shaped convex part with another film or sheet, for example, when using a liquid crystal in the lower display device, the length of the ridge with respect to the polarization axis as a countermeasure against moire Visibility is improved by laminating the directions at an angle of 10 to 45 °. Therefore, when a ¼λ retardation film is used as the base film, it is desirable that the longitudinal direction of the ridge is laminated at an angle of 10 to 80 ° with respect to the slow axis.

The convex portion formed in a bowl shape will be further described with reference to the drawings. FIG. 7 shows a laminated film in which a resin layer (II) having convex portions provided in a bowl shape is formed on one side of a film (I) made of a transparent resin by a UV curable resin composition. It is the figure cut from the surface orthogonal to the direction and observed from diagonally upward. The pitch (P) of the ridges is determined by a plurality of convex portions of the resin layer (II).

In this cross section, the line indicating the surface on which the convex portion is formed is preferably a wavy curve having a regular period. Thus, by drawing a curved line, when a touch panel is used, a streak-like line caused by a bowl shape is not recognized, and it is possible to cope with higher definition of the screen. Furthermore, it is preferable that the sliding property when used as a touch panel is improved, the touch is improved, the resistance value change when the touch panel is used for a long time can be suppressed, and the durability performance can be further improved. By doing so, it is possible to provide a conductive laminated film and a touch panel that can suppress generation of interference fringes, have high contrast, have less glare, achieve a clear display, have excellent durability, and high visibility. .

FIG. 8 is an observation view of a cross section orthogonal to the length direction of the convex portion formed in a bowl shape. The curved part drawn by the convex part in this cross section and the curved part drawn by the valley part sandwiched between the two convex parts are rounded curves having curvature radii (Rt) and (Rb), respectively. This curve may be a sinusoid. A sine curve is preferable from the viewpoint of ease of making the mold. In addition, the touch of the touch panel and the ease of eliminating the streak lines, the interference fringe prevention effect and the durability performance can be adjusted by adjusting the respective curvature radii. In that case, the curvature radii (Rt) and (Rb) are each preferably not less than half and not more than 30 times of the pitch (P), more preferably not less than 1 and not more than 10 times, particularly preferably not less than 1 time of the pitch (P). Is not less than 3 times and not more than 10 times the pitch (P). Moreover, although it is preferable to make the curvature radii (Rt) and (Rb) the same, it is preferably used from the viewpoint of ease of production, but from the aspect of improving the touch on the touch panel, making the curvature radius (Rt) larger than (Rb). preferable. Moreover, the length (L) of the film plane direction in FIG. 8 of the straight line part which connects the curved part which the convex part in the said cross section draws, and the curved part of the valley part pinched | interposed into two convex parts is pitch (P). Is preferably 1/3 or less, more preferably 1/5 or less, particularly preferably 1/10 or less.

FIG. 9 shows an observation view from above of the resin layer (II) having convex portions formed in a bowl shape, which is a preferred example. In the conductive laminated film of the present invention, it is preferable that the ridge line of the convex portion formed in a bowl shape draws a wavy curve having a regular period (pitch) on the plane of the conductive laminated film. In FIG. 7, the ridge line of the convex portion is a straight line, whereas in FIG. 9, the convex portion is meandering regularly on a plane parallel to the film plane. By making the ridge-shaped projections in this way, the streak-like lines are less likely to be recognized, the slipperiness when used as a touch panel is improved and the touch is improved, and when the touch panel is used for a long time The resistance value change can be suppressed, and the durability performance can be further improved, which is preferable.

When the pitch of the regular curve in the film plane at this time is (Pl) and the width of the curve is (W), the pitch (Pl) is preferably 1 to 30 times, more preferably the pitch (P). Is not less than 2 times and not more than 20 times, particularly preferably not less than 3 times and not more than 10 times, and the width (W) of the curve is preferably not less than 1/2 times and not more than 30 times, more preferably not less than 1 time of the pitch (P). 20 times or less, particularly preferably 3 times or more and 10 times or less are used. If the regular curve in the film plane direction is less than the range, glare may occur when the touch panel is used, and if it exceeds the range, the effect of the curve may be reduced.

(Curable resin composition)
The curable resin composition is preferably a UV curable resin composition from the viewpoint that the other layers have low influence, can be cured efficiently, and the curing conditions are easily controlled. The UV curable resin composition preferably comprises (A) a polyfunctional monomer having 3 or more acryloyl groups (hereinafter also referred to as “(A) component”), (B) acrylic acid in a glycidyl (meth) acrylate polymer. A polymer obtained by addition reaction (hereinafter also referred to as “component (B)”) and (C) optionally other acrylic oligomer (hereinafter also referred to as “component (C)”) are blended in a specific amount. In particular, the component (A) is a component that can impart hardness of the transparent conductive layer (III), adhesion to the film (I) made of a transparent resin, and the like. The component (B) is a component that can impart further improvement in the hardness of the transparent conductive layer, curability, reduction of curling during curing, and the like. (C) component is an arbitrary component which can provide toughness etc.

The surface tension of the component (A) is suitably in the range of 37 mN / m or less, more preferably 30 mN / m or more, from the viewpoint that sufficient hardness and adhesion can be obtained. The surface tension is measured by a vertical plate method using a Kyowa CBVP surface tension meter.

Specific examples of the component (A) include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, triacrylate of glycerin propylene glycol adduct, triacrylate of trimethylolpropane propylene glycol adduct, and the like. Of these, trimethylolpropane triacrylate and ditrimethylolpropane tetraacrylate are preferred because the cured coating film has high hardness.

The blending amount of the component (A) in the curable resin composition is suitably 40 to 60% by weight (however, the total of the components (A) to (C) is 100% by weight), 50 to 60% by weight is preferred.

The component (B) is a polymer acrylate obtained by adding an acrylic acid to a glycidyl (meth) acrylate polymer as described above. The amount of acrylic acid added to the epoxy group is suitably about 1: 1 to 1: 0.8 because unreacted epoxy adversely affects the stability of the composition, and 1: 1 to 1: 0.9. The degree is preferred.

Examples of the glycidyl (meth) acrylate polymer include homopolymers of glycidyl (meth) acrylate, copolymers of glycidyl (meth) acrylate and various α, β-unsaturated monomers not containing a carboxyl group, and the like. Can be mentioned. Examples of the α, β-unsaturated monomer not containing a carboxyl group include various (meth) acrylic acid esters, styrene, vinyl acetate, acrylonitrile and the like. When a glycidyl (meth) acrylate polymer is obtained by copolymerizing glycidyl (meth) acrylate and an α, β-unsaturated monomer not containing a carboxyl group, crosslinking occurs during the reaction. Therefore, high viscosity and gelation can be effectively prevented. The molecular weight of the glycidyl (meth) acrylate polymer is about 5,000 to 100,000 in terms of weight average molecular weight from the viewpoint of reducing curling at the time of curing and preventing gelation at the time of the acrylic addition reaction. About 1,000 is preferable. The weight average molecular weight is obtained in terms of polystyrene by gel permeation chromatography (GPC). (B) 70 weight% or more is suitable for the usage-amount of the glycidyl (meth) acrylate in a component in consideration of the hardness of a transparent conductive layer, the transferability of a polymer, etc., and 75 weight% or more is preferable.

A known copolymerization method can be applied to the production of the component (B). The glycidyl (meth) acrylate polymer is prepared by charging this monomer, a polymerization initiator, and, if necessary, a chain transfer agent and a solvent into a reaction vessel under conditions of 80 to 90 ° C. and 3 to 6 hours under a nitrogen stream. It is appropriate to do in The glycidyl (meth) acrylate polymer thus obtained and acrylic acid can be subjected to a ring-opening esterification reaction to obtain the component (B). This reaction is usually carried out in an oxygen stream in order to prevent the polymerization of acrylic acid itself, and the reaction temperature is suitably 100 to 120 ° C. and the reaction time is about 5 to 8 hours.

The blending amount of the component (B) in the cured resin composition is suitably 10 to 60% by weight (however, the total of the components (A) to (C) is 100% by weight), and 20 ~ 50% by weight is preferred.

Specific examples of the component (C) include polyfunctional polyester acrylate, polyfunctional urethane acrylate, and epoxy acrylate. Of these, polyfunctional urethane acrylates are preferred from the viewpoints of scratch resistance and toughness of the cured coating film. For example, (a) a urethane reaction product of (meth) acrylate having a hydroxyl group and an isocyanate compound having two or more isocyanate groups in the molecule, and (b) an isocyanate compound having two or more isocyanate groups in the molecule. Examples include a reaction product obtained by reacting a polyol, polyester or polyamide-based diol to synthesize an adduct, and then adding a (meth) acrylate having a hydroxyl group to the remaining isocyanate group (for example, JP-A-2002-275392). Issue).

Polyfunctional urethane acrylate is a urethane reaction product composed of (meth) acrylate having a hydroxyl group and a polyvalent isocyanate compound having two or more isocyanate groups. As the (meth) acrylate having a hydroxyl group, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate and the like are preferable.

The blending amount of the component (C) in the cured resin composition is suitably 0 to 50% by weight (however, the total of the components (A) to (C) is 100% by weight).

As a method used for curing the curable resin composition, heat, active energy rays, or the like is preferably used. As the active energy ray, for example, any of ultraviolet rays and electron beams may be used. When the resin composition is cured with an electron beam or the like, a photopolymerization initiator is not required. However, when cured with ultraviolet rays, the photopolymerization initiator is usually 1 to 15 weights per 100 parts by weight of the resin composition. About parts can be contained. As the photopolymerization initiator, various known ones such as Darocur 1173, Irgacure 651, Irgacure 184, Irgacure 907, Irgacure 754 (all manufactured by Ciba Specialty Chemicals) and benzophenone can be used. If necessary, various additives other than those described above, for example, a polymerization inhibitor, an antioxidant, an ultraviolet absorber, an antistatic agent, a light stabilizer, a solvent, an antifoaming agent, and a leveling agent may be blended.

(Physical properties of laminated film consisting of film (I) / resin layer (II))
The conductive laminated film of the present invention has a film (I) made of a transparent resin and a transparent conductive layer (III), and optionally has a resin layer (II), but on the film (I) made of a transparent resin. The laminated film obtained by forming the resin layer (II) preferably has the following physical properties.

(1) Haze is also called haze value and represents the degree of haze and the degree of diffusion. For example, using a commercially available Suga Test Machine Co., Ltd. HGM-2DP, etc., it conforms to JIS K-7136. The haze (%) can be measured. The haze of the title film is preferably 1% or less. When the haze is outside the above range, white blur occurs and the visibility of the touch panel decreases.

(2) When the total light transmittance (%) is measured according to JIS K-7361 using, for example, a commercially available Suga Test Instruments Co., Ltd. HGM-2DP, the touch panel visibility is improved. Therefore, 80% or more is preferable, 83% or more is more preferable, and 85% or more is more preferable.

(3) When the transmitted light b * (%) is measured in accordance with JIS Z-8722 using, for example, a commercially available color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., the visibility of the touch panel is low. From the viewpoint of improvement, 0 to 10% is preferable, 0 to 5% is more preferable, and 0 to 2% is more preferable.

(4) The pencil hardness is preferably HB or higher when measured by JIS K5600-5-4 using NP manufactured by Toyo Seiki Co., Ltd. If it is less than HB, the transparent conductive film may be damaged during ITO film formation.

(5) For anti-glare properties, when a fluorescent lamp (total luminous flux 3520 lm) is projected on the title film and the degree of blurring of the fluorescent lamp outline is visually evaluated, it is preferable that the fluorescent lamp outline is not known at all.

(6) It is preferable that the luminance unevenness of the pixel is hardly recognized when the screen of the mobile tool SL-6000N manufactured by Sharp is displayed in green, and then the mark film is placed and evaluated by visual observation.

(7) The anti-Newton ring property is determined by placing the film on a smooth glass plate (thickness 3 mm, material: soda glass) so that the resin layer adheres and pressing it with a finger to see if Newton rings occur. It is preferable that no Newton ring is generated.

(8) The heat shrinkage rate (%) is determined by allowing the title film to stand for 60 minutes in a forced circulation dryer heated to 150 ° C., and using the dimension measurement microscope 176-812 made by Mitutoyo before and after heating. When measuring the change and calculating the heat shrinkage rate, it is preferably 1.5% or less, more preferably 1.3% or less, and even more preferably 1.0% or less. If the heat shrinkage rate exceeds 1.5%, the touch panel may be deformed.

(9) The retardation is not particularly limited, but when the transparent resin film (I) is a retardation film, “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments The phase difference (nm) measured for transmitted light having a wavelength of 550 nm is preferably 128 to 148 nm, and more preferably 133 to 143 nm. If the phase difference deviates from the above, the contrast and visibility of the liquid crystal display may be lowered.

<Transparent conductive layer (III)>
The conductive laminated film of the present invention is formed by laminating a transparent conductive layer (III) on a film (I) made of a transparent resin, or comprising the above-described curable resin composition on a film (I). A resin layer (II) or the like is appropriately formed, and a transparent conductive layer (III) is further laminated thereon.

The transparent conductive layer (III) constituting the conductive laminated film of the present invention is not particularly limited as long as it is a layer having transparency in the visible light region and having conductivity. A layer obtained from an inorganic / organic composite material dispersed with indium oxide containing indium oxide (indium tin oxide, hereinafter also referred to as ITO), indium oxide containing titanium oxide, tin oxide, titanium oxide, polythiophene, inorganic nanoparticles, etc. Is mentioned. In the present invention, the transparent conductive layer (III) is preferably a layer made of ITO, and more specifically a layer made of crystalline ITO.

(Formation of transparent conductive layer (III))
As a method for forming the transparent conductive layer (III), any of the conventionally known techniques such as a vacuum deposition method, a sputtering method, and an ion plating method can be used. From the viewpoint of adhesion, it is preferable to form a thin film by a sputtering method. In addition to the above, the thin film material to be used is, for example, metal oxide such as tin oxide containing antimony, gold, silver, platinum, palladium, copper, aluminum, nickel, chromium, titanium, cobalt, tin, or these An alloy or the like may be used. The thickness of the conductive thin film is preferably 30 mm or more, and if it is thinner than this, it may be difficult to form a continuous film having good conductivity with a surface resistance of 1000 Ω / □ or less. On the other hand, if the thickness is too large, the transparency may be lowered. Therefore, the preferred thickness is about 50 to 2000 mm.

When the transparent conductive layer (III) made of ITO is formed by a sputtering method, a conventionally known ITO target is used as a target. As a target material used for forming the ITO film, the weight ratio of indium oxide to tin oxide is preferably 99: 0.5 to 99:20, more preferably 99: 1 to 90:15, and still more preferably 99: 1. It is desirable to use the one of up to 90:10. When the weight ratio is out of the above range, the resistance value increases.

The temperature during the ITO film formation is preferably not more than the glass transition temperature (Tg) of the film (I) made of transparent resin, more preferably “room temperature to Tg of transparent resin”, and “room temperature to Tg of transparent resin— “20 ° C.” is more preferable. When the Tg of the transparent resin constituting the film (I) is exceeded, the film may be deteriorated. In addition, when Tg of resin layer (II) which consists of curable resin compositions is lower than Tg of transparent resin, it is desirable to form into a film at the temperature below Tg of the said resin layer (II).

Also, traces of oxygen in Ar as the atmosphere gas during ITO deposition, preferably the total of Ar and O _2, preferably 0.05 to 20 vol%, more preferably 0.01 to 10% by volume, further When 0.1 to 3% by volume of O ₂ is preferably introduced, the transparency and conductivity of the ITO thin film can be improved.

When an ITO thin film is formed as the transparent conductive layer (III), the ITO is preferably crystalline ITO. The film formation method of the crystalline ITO thin film includes a pulse sputtering method in which the power applied to the target electrode (cathode) is intermittently changed, and a dual cathode pulse sputtering method in which a plurality of cathodes are arranged as a basic configuration in this pulse sputtering method. Is used. These sputtering methods preferably use a magnetron sputtering method in order to cope with a plasma discharge at a better degree of vacuum. Also, in order to have a stable generation of pulse current and freedom of condition setting, a pulse generation unit is used. It is preferable to use a bipolar type or a unipolar type. The crystalline ITO thin film can also be obtained by crystallization by annealing at a temperature level of about 150 ° C. after the film formation. The durability is remarkably improved by using a crystallized ITO film.

<Easily adhesive layer>
The conductive laminated film of the present invention improves adhesion and provides gas barrier properties between the transparent resin film (I) or the resin layer (II) made of a cured resin layer and the transparent conductive layer (III). Therefore, it is also preferable to have an easy-adhesion layer. The easy-adhesion layer may or may not contain metal oxide fine particles, but inclusion of metal oxide fine particles is preferable because adhesion is improved. Usually, a preferable easy-adhesion layer is prepared by preparing a coating liquid comprising a composition containing metal oxide fine particles and polysiloxane, and coating the coating liquid on the film (I) or the resin layer (II), followed by drying. Can be obtained.

(Metal oxide fine particles)
The type of metal oxide fine particles used in the easy adhesion layer is not particularly limited as long as it is an oxide fine particle of a metal element. For example, antimony oxide, zirconium oxide, anatase type titanium oxide, rutile type titanium oxide, brookite type oxidation Titanium, zinc oxide, tantalum oxide, indium oxide, hafnium oxide, tin oxide, niobium oxide, aluminum oxide, cerium oxide, scandium oxide, yttrium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide, samarium oxide, europium oxide, gadolinium oxide, Terbium oxide, dysprosium oxide, holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, calcium oxide, gallium oxide, lithium oxide, strontium oxide, tungsten oxide, oxide Potassium, magnesium oxide, and complexes thereof, and indium - include fine particles such as oxides of the metal 2 or more complex, such as tin oxide.

The primary average particle diameter of the metal oxide fine particles is preferably 0.1 to 100 nm, more preferably 0.1 to 70 nm, and particularly preferably 0.1 to 50 nm. When the primary average particle diameter of the metal oxide fine particles is in the above range, a laminated film having excellent light transmittance can be obtained.

(Polysiloxane)
The polysiloxane used for the easy-adhesion layer is preferably a polyfunctional polysiloxane.

As the polyfunctional polysiloxane, a polysiloxane obtained by subjecting a polyfunctional polysiloxane having a dimethylsiloxane chain and a polydimethylsiloxane to a dealcoholization reaction is preferable. The polyfunctional polysiloxane and the polydimethylsiloxane preferably have an alkoxyl group or a hydroxyl group at the terminal functional group. The polyfunctional polysiloxane and the polydimethylsiloxane are obtained by subjecting dimethylsiloxane and polydimethylsiloxane having different terminal functional groups to a dealcoholization reaction. Polysiloxane is obtained.

<Antireflection layer>
The conductive laminated film of the present invention preferably has an antireflection layer on the lower layer side of the transparent conductive layer (III) for the purpose of improving the transmittance in the visible light region. The antireflection layer usually has a laminated structure of two or more layers including a low refractive index layer such as silicon oxide and magnesium fluoride and a high refractive index layer such as titanium oxide, niobium oxide and tantalum oxide.

As a method for forming a low and high refractive index layer composed of these inorganic oxides, vacuum deposition, sputtering, ion plating (dry process) or ultrafine particles of inorganic oxides such as metal alkoxides and zirconium oxide are used. A publicly known method such as a coating method (wet process) of the coating liquid containing it can be employed.

It is also preferable to apply an organic material mainly composed of a fluoropolymer as the low refractive layer.

<Characteristics of conductive laminated film>
The conductive laminated film of the present invention preferably has the following physical properties.

(3) When the transmitted light b * (%) is measured in accordance with JIS Z-8722 using, for example, a commercially available color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., the visibility of the touch panel is low. In view of improvement, 0 to 12% is preferable, 0 to 7% is more preferable, and 0 to 4% is more preferable.

(7) Anti-Newton ring property: Newton ring occurs when the film is placed on a smooth glass plate (thickness 3 mm, material: soda glass) so that the curved convex surface is in close contact with the finger. When visually evaluating whether to do, it is preferable that a Newton ring does not generate | occur | produce.

(10) The surface resistance (Ω / □) is preferably 200 to 1500 Ω / □, for example, when measured using a commercially available low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation. More preferably, it is ˜1000Ω / □, and more preferably 300˜500Ω / □. If the surface resistance exceeds 1500 Ω / □, it may be difficult to form a continuous film having good conductivity. On the other hand, if it is less than 200 Ω / □, transparency may be lowered and a touch panel may malfunction.

Touch panel In the touch panel of the present invention, the conductive laminated film of the present invention is suitably used as an upper electrode and / or a lower electrode of a 4-wire resistive film system, 5-wire resistive film system, or the like. And the display apparatus which has a touch-panel function is obtained by arrange | positioning this touch panel in the front surface of a liquid crystal display.

The touch panel of the present invention has the above-described conductive laminated film, and preferably has a configuration in which a conductive laminated film is used as a lower electrode and a conductive laminated film (B) described later is used as an upper electrode. . The conductive laminated film and the conductive laminated film (B) are preferably combined through a spacer as necessary so that the respective transparent conductive layers face each other.

The conductive laminated film (B) used as the upper electrode of the touch panel is preferably formed by laminating a transparent conductive layer, a transparent resin film, and, if necessary, a polarizing plate in this order. The transparent resin film constituting the conductive laminated film (B) used as the upper electrode may be a retardation film or a film that does not exhibit retardation, such as a normal PET film. Moreover, the thing similar to a conductive laminated film can also be used as a conductive laminated film (B).

As a transparent conductive layer which comprises a conductive laminated film (B), the thing similar to the transparent conductive layer (III) which comprises the conductive laminated film (A) mentioned above is mentioned, Especially the transparent conductive layer which consists of ITO is mentioned. Preferably, a transparent conductive layer made of crystalline ITO is more preferable. The transparent conductive layer is formed on the transparent resin film via an easy adhesion layer, an antireflection layer, or the like as necessary.

When the transparent resin film constituting the conductive laminated film (B) is a retardation film, it is desirable that the in-plane retardation with respect to transmitted light having a wavelength of 550 nm is 128 to 148 nm, preferably 133 to 143 nm. A / 4λ retardation film is particularly preferable.

The conductive laminated film (B) used in the present invention preferably has a polarizing plate on the side opposite to the transparent conductive layer of the transparent resin film. The polarizing plate constituting the conductive laminated film (B) has a function of polarizing film, that is, splitting incident light into two polarizing components orthogonal to each other, allowing only one of them to pass, and absorbing or dispersing the other components. If it has a film | membrane, it will not specifically limit. Examples of such a polarizing film include polyvinyl alcohol (hereinafter also referred to as “PVA”) / iodine polarizing film; PVA / dye polarizing film obtained by adsorbing and orienting a dichroic dye on a PVA film; PVA film A polyene-based polarizing film in which a polyene is formed by a dehydration reaction of a polyvinyl chloride film, a dehydrochlorination reaction of a polyvinyl chloride film, or the like. And a polarizing film having a functional dye. Of these, PVA / iodine polarizing films are preferred.

The manufacturing method of the polarizing film is not particularly limited, and a conventionally known method can be applied. For example, a method of adsorbing iodine ions after stretching a PVA-based film; a method of stretching a PVA-based film after dyeing with a dichroic dye; a method of stretching a PVA-based film and then dyeing with a dichroic dye; And a method of stretching a chromogenic dye on a PVA-based film; a method of stretching a PVA-based film and then printing a dichroic dye. More specifically, iodine is dissolved in a potassium iodide solution to form higher-order iodine ions, the ions are adsorbed on a PVA film and stretched, and then a 1 to 5% by weight boric acid aqueous solution is added at a bath temperature of 30. A method of producing a polarizing film by immersing at ˜40 ° C .; or a PVA film treated with boric acid in the same manner as described above and stretched about 3 to 7 times in a uniaxial direction, and then dichroism of 0.05 to 5 wt% Examples include a method for producing a polarizing film by immersing the dye in an aqueous dye solution at a bath temperature of 30 to 40 ° C. to adsorb the dye, then drying at 80 to 100 ° C. and heat setting.

The thickness of the polarizing film is not particularly limited, but is preferably 10 to 50 μm, and more preferably 15 to 45 μm.

These polarizing films may be used as they are for the production of the polarizing plate of the present invention, but can also be used after being subjected to corona discharge treatment or plasma treatment on the surface in contact with the adhesive layer.

The polarizing plate used in the present invention may be composed only of a polarizing film, but may have a protective film for the purpose of imparting moisture absorption resistance to the polarizing film.

When the conductive laminated film (B) according to the present invention has a polarizing plate, the transparent conductive layer, the retardation film, and the polarizing plate are preferably laminated in this order. Specifically, the retardation film, and It is preferable that a polarizing plate is formed by adhering to a polarizing film with a pressure-sensitive adhesive on the surface opposite to the transparent conductive layer of the conductive laminated film on which the transparent conductive layer is laminated.

As the pressure sensitive adhesive, polyvinyl alcohol pressure sensitive adhesive, acrylic pressure sensitive adhesive, rubber pressure sensitive adhesive, silicone pressure sensitive adhesive and the like are suitable.

In the touch panel of the present invention, a conductive laminated film (B) in which a transparent conductive layer, a 1 / 4λ retardation film and a polarizing plate are integrally laminated in this order is used as an upper electrode, and a 1 / 4λ retardation is used as a corresponding lower electrode. By using the conductive laminated film in which the resin layer (II) and the transparent conductive layer (III) are laminated on the film (I) which is a film, reflected light is suitably suppressed, and visibility is particularly improved. preferable.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following, “part” means “part by weight”.

Various physical properties were measured or evaluated as follows.
<Examples 1 to 12 and Comparative Examples 1 to 4>
(1) Haze Using a Suga Test Instruments Co., Ltd. HGM-2DP, haze (%) was measured based on JIS K-7136.

(2) Total light transmittance Total light transmittance (%) was measured in accordance with JIS K-7361 using Suga Test Instruments Co., Ltd. HGM-2DP.

(3) Transmitted light b *
Using a color difference meter RETS-1200VA manufactured by Otsuka Electronics Co., Ltd., transmitted light b * (%) was measured according to JIS Z-8722.

(4) Pencil hardness Pencil hardness was measured according to JIS K-5600-5-4 using a pencil scratch coating film hardness tester NP manufactured by Toyo Seiki Co., Ltd.

(5) Antiglare property A fluorescent lamp (total light flux: 3520 lm) was projected on the film, and the degree of blurring of the outline of the fluorescent lamp was visually evaluated according to the following criteria.

A: The outline of the fluorescent lamp is not known at all. B: The outline of the fluorescent lamp is slightly understood. C: The outline of the fluorescent lamp is clearly understood. (6) Unevenness of brightness After the screen of Sharp mobile tool SL-6000N is displayed in green, film And visually evaluated according to the following criteria.

A: Pixel brightness unevenness is hardly recognized B: Pixel brightness unevenness is recognizable, but not noticeable C: Pixel brightness unevenness is clearly recognizable (7) Anti-Newton ring property A film is a smooth glass plate (thickness 3 mm, The material-containing resin layer was placed on top of the material (soda glass) and pressed with a finger, and it was visually evaluated whether Newton rings would occur.

A: Newton ring does not occur B: Newton ring slightly occurs C: Newton ring clearly occurs (8) Heat shrinkage rate The film is allowed to stand for 60 minutes in a forced circulation dryer heated to 150 ° C. Then, the dimensional change of the film before and after heating was measured in the longitudinal direction (MD) and the width direction (TD) of the film using a Mitutoyo dimension measuring microscope 176-812, and the thermal shrinkage rate (%) was calculated.

(9) Residual solvent The film was allowed to stand for 30 minutes in a forced circulation dryer heated to 160 ° C., and the weight change before and after heating was examined. The weight reduction rate (%) was defined as the residual solvent (%).

(10) Phase difference (nm) at a wavelength of 550 nm was measured using “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments.

(11) Surface Resistance The surface resistance value (Ω / □) of the transparent conductive layer was measured using a low resistivity meter “Loresta GP” manufactured by Mitsubishi Chemical Corporation.

(12) Contrast evaluation of touch panel In a dark room, the black display screen of the touch panel was viewed from the front, and the color change was visually observed and evaluated according to the following criteria.

A: There is no color change of the touch panel and there is a clear feeling B: No color change of the touch panel C: Some color change of the touch panel is observed D: Color change of the touch panel is large (13) Visual recognition of the touch panel Evaluation of color The color change of the screen when the viewing angle was changed was visually observed.

A: There is no color change of the touch panel and there is a clear feeling B: There is no color change of the touch panel C: Some color change of the touch panel is observed D: A color change of the touch panel is large (14) Anti-touch panel Newton ring property evaluation The surface on the upper electrode side of the touch panel was pressed with a finger so that the electrodes were in contact with each other, and whether or not Newton ring was generated was visually evaluated.

A: Newton's ring does not occur B: Newton's ring slightly occurs C: Newton's ring appears clearly (15) Streaky line evaluation of the touch panel In a bright normal room, the black display screen of the touch panel is It was examined from the oblique direction whether a streak line could be observed visually, and the following criteria were evaluated.

A: The streak line of the touch panel is not observed at all B: The streak line of the touch panel is slightly observed C: The streak line of the touch panel is clearly observed (16) Evaluation of keystroke durability of the touch panel Using a high load keying tester manufactured by Research Laboratory, silicone rubber (curvature radius 8 cm) was used, and the keying durability was evaluated at room temperature at a load of 750 g and a keying speed of 10 Hz. The initial energization voltage was set to 3V, and a current was passed. The number of keystrokes until the voltage dropped to 2/3 (2V) was examined.

A: Number of keystrokes 10 million times or more B: Number of keystrokes 5 million times to less than 10 million times C: Number of keystrokes less than 5 million times (17) Touch panel touch evaluation Touch panel surface is rubbed with a finger and touch evaluation is performed Was performed according to the following criteria.

A: Feeling the surface unevenness of the touch panel is not felt at all B: Feeling of the surface unevenness of the touch panel is slightly felt C: Feeling of the surface unevenness of the touch panel is felt immediately [Synthesis Example 1] (Synthesis of cyclic olefin polymer A)
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene 227.5 parts, bicyclo [2.2.1] hept-2-ene 22.5 parts, 1-hexene (molecular weight regulator) 18 parts, toluene (for ring-opening polymerization reaction) (Solvent) 750 parts were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 60 ° C. Next, 0.62 part of a toluene solution of triethylaluminum (1.5 mol / L) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / L) of 35 mol: 0.3 mol: 1 mol) was added, and the system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening copolymer solution was obtained. The polymerization conversion rate in this polymerization reaction was 97%.

The autoclave was charged with 4,000 parts of the ring-opening copolymer solution thus obtained, and 0.48 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening copolymer solution. And a hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 160 ° C.

After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover a coagulated product, which was dried to obtain a hydrogenated cyclic olefin polymer A.

[Production Example 1] (Production of Cyclic Olefin Polymer Film A-1)
The cyclic olefin polymer A obtained in Synthesis Example 1 was dissolved in toluene so that the solid content concentration was 30%. The solution viscosity at room temperature of the obtained solution was 30,000 mPa · s. To this solution, pentaerythrityltetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added in an amount of 0.1 weight with respect to 100 parts by weight of the cyclic olefin polymer A. The resulting solution was filtered using a metal fiber sintered filter made by Nippon Pole with a pore diameter of 5 μm while controlling the flow rate of the solution so that the differential pressure was within 0.4 MPa. Using an “INVEX Lab Coater” manufactured by Inoue Metal Industry installed in a clean room, a PET film having a thickness of 100 μm (made by Toray Industries, Inc.) treated with an acrylic acid-based surface treatment agent to make it hydrophilic (easy to adhere). Lumirror U94 "). Next, the obtained liquid layer was subjected to a primary drying treatment at 50 ° C., and further subjected to a secondary drying treatment at 90 ° C., and then peeled off from the PET film, whereby a 188 μm-thick cyclic olefin-based weight was obtained. Merged film A-1 was formed. The cyclic olefin polymer film A-1 thus obtained had a residual solvent amount of 0.5% by weight and a light transmittance of 93% or more.

[Production Example 2] (Production of Cyclic Olefin Polymer Film A-2)
The cyclic olefin polymer film A-1 obtained in Production Example 1 was heated to 148 ° C. in a longitudinal stretching furnace provided with a wind direction control plate, and the temperature distribution in the stretching machine furnace was within 148 ± 0.2 ° C. In the controlled layer, the furnace speed was 1.2 m in the longitudinal direction of the film at 4.0 m / min, uniaxial stretching without fixing the film width direction, R0 was 138 nm, R0 variation was ± 5 nm and light A cyclic olefin polymer film A-2 having an axis of 0 ± 2 degrees with respect to the film longitudinal direction was obtained.

[Production Example 3] (Production of polarizing film)
PVA was pre-stretched at a stretch ratio of 3 times in a dyeing bath at a temperature of 30 ° C. consisting of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight, and then boric acid A polarizing film is obtained by post-stretching at a stretch ratio of 2 in a cross-linking bath having a temperature of 55 ° C. consisting of an aqueous solution having a concentration of 5% by weight and a potassium iodide concentration of 8% by weight, followed by drying. It was.

[Preparation Example 1] (Preparation of mixed adhesive)
Water was added to 163-03045 (molecular weight: 22,000, saponification degree: 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd., which is a PVA resin, to prepare an aqueous solution having a solid content concentration of 7% by weight. . On the other hand, 100 parts of WLS-201 (solid content concentration 35% by weight) manufactured by Dainippon Ink & Chemicals, Inc., which is a polyurethane resin, is added to CR- manufactured by Dainippon Ink Industries, Ltd., which is a polyepoxy curing agent. 5 L (100% active ingredient product) 5 parts was blended and diluted with water to prepare an aqueous solution with a solid content of 20% by weight. The obtained polyurethane resin aqueous solution and polyvinyl alcohol resin aqueous solution were mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and a mixed adhesive having a solid content concentration of 15% by weight was obtained. Prepared.

[Production Example 1] (Production of laminated film B-1)
A UV curable resin (Desolite KZ-9136 manufactured by JSR Corporation) was applied to one side of A-1 obtained in Cyclic Olefin Polymer Film Production Example 1 by the gravure reverse method, and then a bowl shape was formed. Laminate film B- having a sinusoidal resin layer having a sine curve with a maximum height of 2 μm and a pitch P of 1000 μm on a base of 2 μm thickness, irradiated with 1 J / cm ² ultraviolet light while being in close contact with the roll 1 was obtained.

Table 1 shows the results of measuring or evaluating various physical properties of the obtained laminated film B-1.

[Production Example 2] (Production of laminated film B-2)
A laminated film B-2 was obtained in the same manner as in Production Example 1 except that A-2 obtained in Cyclic olefin polymer film production example 2 was used instead of the cyclic olefin polymer film A-1. The results of measuring or evaluating various physical properties of the obtained laminated film B-2 are also shown in Table 1.

[Production Example 3] (Production of laminated film B-3)
In Production Example 1, the curvature radius (Rt) of the ridge-shaped convex portion is 10000 μm (10 times the pitch P), and the curvature radius (Rb) of the concave portion is 3000 μm (3 times the pitch P). ), Except that the width (L) of the straight line connecting the curve of the convex part and the curve of the concave part is set to 100 μm (tenth of the pitch P), and a regular curve having a height of 2 μm and a pitch of 1000 μm is obtained. A laminated film B-3 having a bowl-shaped resin layer was obtained. The results of measuring or evaluating various physical properties of the obtained laminated film B-3 are also shown in Table 1.

[Production Example 4] (Production of laminated film B-4)
A laminated film B-4 was obtained in the same manner as in Production Example 3, except that the cyclic olefin polymer film A-2 was used instead of the cyclic olefin polymer film A-1. The results of measuring or evaluating various physical properties of the obtained laminated film B-4 are also shown in Table 1.

[Production Example 5] (Production of laminated film B-5)
In Production Example 1, the shape of the ridge-shaped ridge line draws a regular curve with respect to the shape from above the ridge-shaped resin layer. Specifically, the pitch (Pl) of the regular curve in the film plane is 8000 μm (pitch P has a regular curve with a height of 2 μm and a pitch of P 1000 μm, except that it is a sine curve with a curve width (W) of 5000 μm (5 times the pitch P). A laminated film B-5 having a cage-shaped resin layer was obtained. The results of measuring or evaluating various physical properties of the obtained laminated film B-5 are also shown in Table 1.

[Production Example 6] (Production of laminated film B-6)
Instead of the cyclic olefin polymer film A-1, a cyclic olefin polymer film A-2 was used, and the shape of the cross-section of the bowl-shaped resin layer was the same as in Production Example 3, the same as in Production Example 5. Thus, a laminated film B-6 was obtained. The results of measuring or evaluating various physical properties of the obtained laminated film B-6 are also shown in Table 1.

[Comparative Production Example 1] (Production of laminated film B-7)
A laminated film B-7 was obtained in the same manner as in Production Example 1, except that the shape of the bowl-shaped resin layer was changed to a protrusion having a cross-section with an isosceles triangle height of 2 μm and a pitch of 1000 μm. The results of measuring or evaluating various physical properties of the obtained laminated film B-7 are also shown in Table 1.

[Example 1] (Production of conductive laminated film C-1)
The corrugated resin layer surface of the laminated film B-1 was subjected to a corona discharge treatment of 50 W · min / m ² in the air.

On the surface, a transparent conductive layer was formed by sputtering under the following conditions using a target containing indium and tin under an argon gas inflow to obtain a conductive laminated film C-1. The surface resistance value in the transparent conductive layer of the obtained conductive laminated film C-1 was measured and found to be 550Ω / □. The results of measuring and evaluating various physical properties are shown in Table 2.

(conditions)
Substrate temperature: 50 ° C. or less Target: In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio) oxide Atmosphere: Under argon flow Argon flow rate: 100 to 500 sccm
Output: 1 ~ 1.5Kw
[Example 2] (Production of conductive laminated film C-2)
A conductive laminated film C-2 was obtained in the same manner as in Example 1 except that the laminated film B-2 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Example 3] (Production of conductive laminated film C-3)
A conductive laminated film C-3 was obtained in the same manner as in Example 1 except that the laminated film B-3 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Example 4] (Production of conductive laminated film C-4)
A conductive laminated film C-4 was obtained in the same manner as in Example 1 except that the laminated film B-4 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Example 5] (Production of conductive laminated film C-5)
A conductive laminated film C-5 was obtained in the same manner as in Example 1 except that the laminated film B-5 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Example 6] (Production of conductive laminated film C-6)
A conductive laminated film C-6 was obtained in the same manner as in Example 1 except that the laminated film B-6 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Comparative Example 1] (Production of conductive laminated film C-7)
A conductive laminated film C-7 was obtained in the same manner as in Example 1 except that the laminated film B-7 was used instead of the laminated film B-1. The results of measuring and evaluating various physical properties are also shown in Table 2.

[Comparative Example 2] (Production of conductive laminated film C-8)
Example 1 except that the cyclic olefin polymer film A-1 was used instead of the laminated film B-1 and one side of the cyclic olefin polymer film A-1 was used instead of the surface of the bowl-shaped resin layer. In the same manner, a conductive laminated film C-8 was obtained. The results of measuring and evaluating various physical properties are shown in Table 2.

[Example 7] (Production of touch panel)
The conductive laminated film C-1 obtained in Example 1 was used as the lower electrode, and a film obtained by sputtering ITO on a 188 μm PET film in the same manner as in Example 1 was used as the upper electrode. The two sheets were overlapped with a spacer so that the transparent conductive film surfaces face each other and placed on the liquid crystal display element to obtain the touch panel of the present invention. The configuration is shown in FIG. The obtained touch panel was subjected to contrast and visibility, anti-Newton ring property and streaked lines, and keystroke durability evaluation and hand touch evaluation. The results are shown in Table 3.

[Example 8] (Production of polarizing plate and touch panel)
The mixed adhesive obtained in Preparation Example 1 was applied to the opposite side of the transparent conductive film of the conductive retardation film obtained by sputtering ITO on the cyclic olefin polymer film A-2 in the same manner as in Example 1. The upper electrode was laminated so as to be in contact with the polarizing film. In addition, it bonded together so that the absorption axis of a polarizing film and the optical axis of the phase-difference film in an electroconductive laminated film may make an angle of 45 degrees in that case.

Using the conductive laminated film C-2 obtained in Example 2 as a lower electrode, these two sheets were overlapped via a spacer so that the transparent conductive film faces each other, and placed on a liquid crystal display element. A touch panel of the present invention was obtained. The configuration is shown in FIG.

At this time, the polarization axis of the liquid crystal display element is set to 45 °, the optical axis of the retardation film of the lower electrode is set to 0 °, the axis of the bowl shape is set to 35 °, and the optical axis of the retardation film of the upper electrode is set to The orientation was 90 ° and the optical axis of the polarizing plate was 45 °.

The contrast, anti-Newton ring property and visibility of the obtained touch panel were evaluated. The results are shown in Table 3.

[Example 9] (Production of touch panel)
Various evaluations were performed in the same manner as in Example 7 except that the conductive laminated film C-3 was used. The results are also shown in Table 3.

[Example 10] (Production of polarizing plate and touch panel)
Various evaluations were performed in the same manner as in Example 8 except that the conductive laminated film C-4 was used. The results are also shown in Table 3.

[Example 11] (Production of touch panel)
Various evaluations were performed in the same manner as in Example 7 except that the conductive laminated film C-5 was used. The results are also shown in Table 3.

[Example 12] (Production of polarizing plate and touch panel)
Various evaluations were performed in the same manner as in Example 8 except that the conductive laminated film C-6 was used and the axis of the center line of the regular period in the in-plane direction of the bowl-shaped film was set to the 35 ° direction. The results are also shown in Table 3.

[Comparative Example 3] (Production of touch panel)
A touch panel was obtained in the same manner as in Example 7 except that the conductive laminated film C-7 was used instead of the conductive laminated film C-1. Various evaluations were performed on the obtained touch panel. The results are also shown in Table 3.

[Comparative Example 4] (Production of touch panel)
A touch panel was obtained in the same manner as in Example 7 except that the conductive laminated film C-8 was used instead of the conductive laminated film C-1. Various evaluations were performed on the obtained touch panel. The results are also shown in Table 3.

<Examples 13 to 22 and Comparative Examples 5 to 8>
(1) Surface shape The surface shape of the film was measured using a non-contact three-dimensional surface shape / roughness measuring machine manufactured by Zygo Corporation.

(5) Luminance unevenness (about the occurrence of glare)
The screen of Sharp mobile tool SL-6000N was displayed in green, and then a film was placed thereon. Visual evaluation was performed according to the following criteria.

A: Pixel brightness unevenness is hardly recognized B: Pixel brightness unevenness is recognizable, but not noticeable C: Pixel brightness unevenness is clearly recognizable (6) Anti-Newton ring property (degree of suppression of occurrence of interference fringes)
The film was placed on a smooth glass plate (thickness 3 mm, material: soda glass) so that the particle-containing resin layer was in close contact and pressed with a finger, and it was visually evaluated whether Newton rings were generated.

A: Newton ring does not occur B: Newton ring slightly occurs C: Newton ring clearly occurs (7) Wavelength using “KOBRA-21ADH / PR” manufactured by Oji Scientific Instruments Co., Ltd. The phase difference (R0: nm) at 550 nm was measured.

(8) Surface Resistance Using a low resistivity meter “Loresta GP” manufactured by Mitsubishi Chemical Corporation, the surface resistance value (Ω / □) of the transparent conductive layer was measured.

(9) Contrast evaluation of touch panel In the dark room, the black display screen of the touch panel was viewed from the front, and the color change was visually observed and evaluated according to the following criteria.

A: There is no color change of the touch panel and there is a clear feeling B: No color change of the touch panel C: Some color change of the touch panel is observed D: Color change of the touch panel is large (10) Visual recognition of the touch panel Evaluation of color The color change of the screen when the viewing angle was changed was visually observed.

A: There is no color change of the touch panel and there is a clear feeling B: No color change of the touch panel C: Some color change of the touch panel is observed D: Color change of the touch panel is large (11) Anti-touch panel Newton ring property (degree of suppression of occurrence of interference fringes) evaluation The surface of the upper electrode side of the touch panel was pressed with a finger so that the electrodes were in contact with each other, and whether or not Newton ring was generated was visually evaluated.

A: Newton ring does not occur B: Newton ring slightly occurs C: Newton ring clearly occurs (12) Streaky line evaluation of the touch panel In a bright normal room, the black display screen of the touch panel is It was examined from the oblique direction whether a streak line could be observed visually, and the following criteria were evaluated.

A: The streak line of the touch panel is not observed at all. B: The streak line of the touch panel is slightly observed. C: The streak line of the touch panel is clearly observed. (13) Evaluation of keystroke durability of the touch panel Using a high load keying tester manufactured by Research Laboratory, silicone rubber (curvature radius 8 cm) was used, and the keying durability was evaluated at room temperature at a load of 750 g and a keying speed of 10 Hz. The initial energization voltage was set to 3V, and a current was passed. The number of keystrokes until the voltage dropped to 2/3 (2V) was examined.

A: Number of keystrokes of 10 million times or more B: Number of keystrokes of 5 million to less than 10 million times C: Number of keystrokes of less than 5 million times (14) Touch panel touch evaluation Touch panel surface is rubbed with a finger to evaluate touch characteristics Was performed according to the following criteria.

A: Feeling the surface unevenness of the touch panel is not felt at all B: Feeling of the surface unevenness of the touch panel is slightly felt C: Feeling of the surface unevenness of the touch panel is felt immediately (15) Film thickness measurement The film thickness is measured with a micrometer did.

[Production Example 4] (Production of Cyclic Olefin Resin Film A-1a)
A norbornene resin (manufactured by JSR Corporation: trade name “ARTON D4531”, glass transition temperature 130 ° C.) was used as the cyclic olefin resin. This raw material is dehumidified and dried under nitrogen at a drying temperature of 100 ° C., led to an extruder (GM Engineering Co., Ltd .: GM-65), melted at 260 ° C., and fed in a fixed amount using a gear pump, and a 5 μm leaf disk Foreign matters were removed using a filter, and extrusion was performed from a T die heated by an aluminum casting heater set at 250 ° C. At this time, the opening of the T die was 1.0 mm, and the distance between the T die outlet and the pressure bonding point of the film of the cooling roll 1 was 70 mm. The cooling roll 1 had a bowl-shaped convex part in which prism-shaped convex parts having a vertex angle of 100 degrees and a pitch of 50 μ were continuously engraved in the roll circumferential direction on the surface of a 300 mmφ roll. The melt extruded from the T die was pressed on the cooling roll 1. The temperature of the cooling roll 1 was 120 ° C. so that the shape was well transferred onto the surface of the norbornene resin film. Then, a 300 mmφ cooling roll 2 was provided on the downstream side, and a 300 mmφ peeling roll was further provided on the downstream side. The temperature of each roll was set to 115 ° C. and 100 ° C., the film was peeled from the peeling roll at a film surface temperature of 98 ° C., and prism-shaped convex portions having a vertex angle of 100 ° and a pitch of 50 μm were continuous in the longitudinal direction of the film. A norbornene-based resin film A-1a having a 250 μm-thick convex portion was obtained.

[Production Example 5] (Production of Cyclic Olefin Resin Film A-2a)
Except that the length of the ridge is 1000 μm and the distance between the ridge and the ridge in the length direction of the ridge is 50 μm, the same as in Production Example 1 except that the cooling roll 2 similar to the cooling roll 1 is used. An intermittent ridge shape in which a prism-shaped convex part having a ridge pitch of 50 μm and a length of 1000 μm is continuous in the longitudinal direction of the film at an apex angle of 100 degrees, and the distance between the ridges in the ridge length direction is 50 μm. A norbornene-based resin film A-2a having a thickness of 250 μm was obtained.

[Production Example 6] (Production of Cyclic Olefin Resin Film A-3a)
The width of 1000 μm is the same as that of Production Example 1 except that the cooling roll 3 similar to the cooling roll 1 is used except that the planar shape having a width of 1000 μm, a length of 2000 μm, and a depth of 10 μm has a rectangular recess. A norbornene-based resin film A-3a having a length of 2000 μm, a height of 10 μm, and a spacing of each grid of 100 μm (the shape image is equivalent to FIG. 4 (1)) having a square-shaped convex portion in a sea-island shape. Got.

[Production Example 7] (Production of Cyclic Olefin Resin Film A-4a)
The width is 1000 μm, the length is 2000 μm, and the depth is 10 μm, except that a cooling roll 4 similar to the cooling roll 1 is used, except that the elliptical recess has a sea-island shape. 250 μm-thick norbornene resin film A—having an elliptical convex shape in the shape of a sea island of 1000 μm, length 2000 μm, height 10 μm, intervals 2000 μm and 500 μm (the shape image corresponds to FIG. 4 (3)) 4a was obtained.

[Production Example 8] (Production of Cyclic Olefin Resin Film A-5a)
A 250 μm-thick norbornene-based resin film A− having no projections on the film surface was used in the same manner as in Production Example 1 except that the cooling roll 5 similar to the cooling roll 1 was used except that the surface state was a mirror surface state. 5a was obtained.

[Production Example 9] (Production of Polarizing Film)
PVA was pre-stretched at a stretch ratio of 3 times in a dyeing bath at a temperature of 30 ° C. consisting of an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.5% by weight, and then boric acid 30 μm thick polarized light by post-stretching at a stretch ratio of 2 in a crosslinking bath of 55 ° C. consisting of an aqueous solution having a concentration of 5% by weight and a potassium iodide concentration of 8% by weight, followed by drying. A membrane was obtained.

[Preparation Example 2] (Preparation of mixed adhesive)
Water was added to 163-03045 (molecular weight: 22,000, saponification degree: 88 mol%) manufactured by Wako Pure Chemical Industries, Ltd., which is a PVA resin, to prepare an aqueous solution having a solid content concentration of 7% by weight. . On the other hand, 100 parts of WLS-201 (solid content concentration 35% by weight) manufactured by Dainippon Ink & Chemicals, Inc., which is a polyurethane resin, is added to CR- manufactured by Dainippon Ink Industries, Ltd., which is a polyepoxy curing agent. 5 L (100% active ingredient product) 5 parts was blended and diluted with water to prepare an aqueous solution with a solid content of 20% by weight. The obtained polyurethane resin aqueous solution and polyvinyl alcohol resin aqueous solution were mixed at a weight ratio of 1: 1 (solid content weight ratio of 80:20), and a mixed adhesive having a solid content concentration of 15% by weight was obtained. Prepared.

[Production Example 7] (Production of film B-1b made of transparent resin)
The cyclic olefin-based resin film A-1a obtained in Production Example 4 was heated in a drawing furnace provided with a wind direction control plate so that the opposite surface was 145 ° C., and a far infrared heater was used. A tenter type horizontal so that the stretched speed is 300% / min and the stretch ratio is 2.5 times in the film width direction in a controlled tank heated to 155 ° C. Film B-1b having a thickness of 100 μm made of a cyclic olefin-based resin film having a retardation R0 of 138 nm, a variation of R0 of ± 5 nm, and an optical axis of 0 ± 2 degrees with respect to the film width direction after uniaxial stretching by a stretching machine Got. When the surface shape of the surface preliminarily shaped of the film was examined with a Zygo Corporation non-contact three-dimensional surface shape / roughness measuring machine, it was a ridge shape having a convex part, and dH / dL was the maximum. A line indicating a surface in a cross section perpendicular to the length direction of the ridge was 0.01 and was a wavy curve having a height of 2 μm and a pitch of 130 μm.

[Production Example 8] (Production of transparent resin film B-2b)
In the same manner as in Production Example 7 except that A-2a obtained in Cyclic Olefin Resin Film Production Example 5 was used in place of Cyclic Olefin Resin Film A-1a, and a thickness of 100 μm made of a cyclic olefin resin film was used. Film B-2b was obtained. R0 of the film is 138 nm, variation of R0 is ± 5 nm, and the optical axis is 0 ± 2 degrees with respect to the film width direction. The surface shape of the surface of the film preliminarily shaped is not contacted by Zygo Corporation When examined with a three-dimensional surface shape / roughness measuring machine, the shape of the ridges has a convex part, the distance between the ridges in the longitudinal direction of the ridges is 50 μm, and dH / dL is 0.02 at the maximum. The line indicating the surface in the cross section perpendicular to the length direction of the ridge was a curve having a height of 2 μm and a pitch of 130 μm.

[Production Example 9] (Production of transparent resin film B-3b)
Instead of the cyclic olefin resin film A-1a, A-3a obtained in the cyclic olefin resin film production example 6 was used, and a longitudinal uniaxial stretching machine using a nip roll was used, and the same procedure as in Production Example 7 was performed. Thus, a film B-3b made of a cyclic olefin resin film and having a thickness of 130 μm was obtained. R0 of the film is 138 nm, variation of R0 is ± 5 nm, and the optical axis is 0 ± 2 degrees with respect to the longitudinal direction of the film. When examined with a three-dimensional surface shape / roughness measuring instrument, the plane shape was 920 μm in width, 5000 μm in length, 1 μm in height, 108 μm in the direction parallel to the stretching direction, and 250 μm in the direction perpendicular thereto. The convex portion has a sea-island shape, dH / dL is 0.02 at the maximum, and the line indicating the convex portion appearing in the longitudinal section has a curved shape having an edge portion having a curvature radius of 15000 μm.

[Production Example 10] (Production of transparent resin film B-4b)
In the same manner as in Production Example 9 except that A-4a obtained in Cyclic Olefin Resin Film Production Example 7 was used instead of Cyclic Olefin Resin Film A-3a, a 130 μm thick cyclic olefin resin film was formed. Film B-4b was obtained. R0 of the film is 138 nm, variation of R0 is ± 5 nm, and the optical axis is 0 ± 2 degrees with respect to the longitudinal direction of the film. When examined with a three-dimensional surface shape / roughness measuring machine, the planar shape with a width of 720 μm, a length of 5000 μm, and a height of 1 μm has an elliptical convex part in a sea-island shape, and dH / dL is 0.01 at the maximum. The line indicating the convex portion appearing in the longitudinal section was a curved shape having an edge portion having a curvature radius of 15000 μm.

[Production Example 11] (Production of transparent resin film B-5b)
Instead of the cyclic olefin-based resin film A-1a, the surface was shaped using a prism surface-shaped film made of a commercially available polycarbonate resin (manufactured by Goyo Paper Industries Co., Ltd., GTL5000F, thickness 240 μm, glass transition temperature 125 ° C.). A film B-5b made of polycarbonate resin and having a thickness of 100 μm was obtained in the same manner as in Production Example 7 except that the surface was 155 ° C. and the opposite surface was 140 ° C. R0 of the film is 140 nm, variation of R0 is ± 7 nm, and the optical axis is ± 3 degrees with respect to the film width direction, and the surface shape of the surface of the film preliminarily shaped is non-contact tertiary When examined by the original surface shape / roughness measuring machine, it is a ridge shape having a convex portion, dH / dL is 0.02 at the maximum, and a line indicating the surface in a cross section orthogonal to the length direction of the ridge is It was a wavy curve with a height of 2 μm and a pitch of 130 μm.

[Production Example 12] (Production of transparent resin film B-6b)
In the same manner as in Production Example 7 except that A-5a obtained in Cyclic Olefin Resin Film Production Example 8 was used in place of Cyclic Olefin Resin Film A-1a, Film B-6b was obtained. R0 of the film is 138 nm, variation of R0 is ± 5 nm, and the optical axis is 0 ± 2 degrees with respect to the film width direction. When examined with a non-contact three-dimensional surface shape / roughness measuring machine, The surface of the film was smooth and dH / dL was approximately 0.

[Example 13] (Production of conductive laminated film C-1c)
The convex surface of the film B-1b was subjected to a corona discharge treatment of 50 W · min / m ² in the atmosphere.

On the surface, a transparent conductive layer was formed by sputtering under the following conditions using a target containing indium and tin under argon gas flow to obtain a conductive laminated film C-1c. The surface resistance value in the transparent conductive layer of the obtained conductive laminated film C-1c was measured and found to be 550Ω / □. Table 4 shows the results of measurement and evaluation of various physical properties.

(conditions)
Substrate temperature: 50 ° C. or less Target: ITO (In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio))
Atmosphere: Argon flow Argon flow: 100-500sccm
Output: 1 ~ 1.5Kw
Transparent conductive layer thickness: 55nm
[Example 14] (Production of conductive laminated film C-2c)
A UV curable resin (Desolite KZ-9136 manufactured by JSR Corporation) was applied to the convex surface of the film B-2b obtained in Film Production Example 8 by the gravure reverse method, and then an ultraviolet ray of 1 J / cm ² was applied. Irradiated to cure. Sputtering was performed on the UV curable resin film of this film under the same conditions as in Example 13 to form a transparent conductive layer, to obtain a conductive laminated film C-2c. Table 4 shows the results of measurement and evaluation of various physical properties.

[Example 15] (Production of conductive laminated film C-3c)
A conductive laminated film C-3c was obtained in the same manner as in Example 13 except that the film B-3b was used instead of the film B-1b. Table 4 shows the results of measurement and evaluation of various physical properties.

[Example 16] (Production of conductive laminated film C-4c)
A conductive laminated film C-4c was obtained in the same manner as in Example 13 except that the film B-4b was used instead of the film B-1b. Table 4 shows the results of measurement and evaluation of various physical properties.

[Example 17] (Production of conductive laminated film C-5c)
A conductive laminated film C-5c was obtained in the same manner as in Example 13 except that the film B-5b was used instead of the film B-1b. Table 4 shows the results of measurement and evaluation of various physical properties.

[Comparative Example 5] (Production of conductive laminated film C-6c)
A conductive laminated film C-6c was obtained in the same manner as in Example 13 except that the cyclic olefin resin film A-1a was used in place of the film B-1b. Table 4 shows the results of measurement and evaluation of various physical properties.

[Comparative Example 6] (Production of conductive laminated film C-7c)
A conductive laminated film C-7c was obtained in the same manner as in Example 13 except that the cyclic olefin resin film A-5a was used in place of the film B-1b. Table 4 shows the results of measurement and evaluation of various physical properties.

[Example 18] (Production of touch panel)
The conductive laminate film C-1c obtained in Example 1 was used as the lower electrode, and a film obtained by sputtering ITO on a 188 μm PET film in the same manner as in Example 13 was used as the upper electrode. The two sheets were overlapped with a spacer so that the transparent conductive film surfaces face each other and placed on the liquid crystal display element to obtain the touch panel of the present invention. The configuration is shown in FIG. The obtained touch panel was subjected to contrast and visibility, anti-Newton ring property and streaked lines, and keystroke durability evaluation and hand touch evaluation. The results are shown in Table 5.

[Example 19] (Production of polarizing plate and touch panel)
The mixed adhesive obtained in Preparation Example 2 was applied to the opposite side of the transparent conductive film of the conductive retardation film formed by sputtering ITO on the film B-6b in the same manner as in Example 13. The upper electrode was laminated so as to be in contact with the polarizing film produced in Example 9. In addition, it bonded together so that the absorption axis of a polarizing film and the optical axis of the phase-difference film in an electroconductive laminated film may make an angle of 45 degrees in that case.

Using the conductive laminated film C-2c obtained in Example 14 as a lower electrode, the two sheets were overlapped with a spacer so that the transparent conductive film faces each other, and placed on a liquid crystal display element. A touch panel of the present invention was obtained. The configuration is shown in FIG.

At this time, the polarization axis of the liquid crystal display element is set to 45 ° direction, the optical axis of the retardation film of the lower electrode is set to 0 ° direction, the axis of the bowl shape is set to 35 ° direction, and the optical axis of the retardation film of the upper electrode is set to The orientation was 90 ° and the optical axis of the polarizing plate was 45 °.

The contrast, anti-Newton ring property and visibility of the obtained touch panel were evaluated. The results are shown in Table 5.

[Example 20] (Production of touch panel)
Various evaluations were performed in the same manner as in Example 18 except that the conductive laminated film C-3c was used instead of the conductive laminated film C-1c. The results are also shown in Table 5.

[Example 21] (Production of polarizing plate and touch panel)
Various evaluations were performed in the same manner as in Example 19 except that the conductive laminated film C-4c was used instead of the conductive laminated film C-2c. The results are also shown in Table 5.

[Example 22] (Production of touch panel)
Various evaluations were performed in the same manner as in Example 18 except that the conductive laminated film C-5c was used instead of the conductive laminated film C-1c. The results are also shown in Table 5.

[Comparative Example 7] (Production of touch panel)
A touch panel was obtained in the same manner as in Example 18 except that the conductive laminated film C-6c was used instead of the conductive laminated film C-1c. Various evaluations were performed on the obtained touch panel. The results are also shown in Table 5.

[Comparative Example 8] (Production of touch panel)
A touch panel was obtained in the same manner as in Example 18 except that the conductive laminated film C-7c was used instead of the conductive laminated film C-1c. Various evaluations were performed on the obtained touch panel. The results are also shown in Table 5.

The conductive laminated film of the present invention can be suitably used as a transparent electrode of a display such as a liquid crystal display or a touch panel, and is particularly suitable for a touch panel application, particularly a touch panel application for a display device. The touch panel of the present invention is useful as a touch panel for various display devices such as liquid crystal display elements. For example, personal digital assistant (PDA), notebook PC, OA equipment, medical equipment, or electronic equipment such as a car navigation system. It can be suitably used as a touch panel.

Claims

A conductive laminated film in which a transparent conductive layer (III) is laminated on a film (I) made of a transparent resin, the surface portion on the transparent conductive layer (III) side has a plurality of convex portions, and the surface The electroconductive laminated film characterized by having the site | part containing a some convex part currently formed in the curved surface.
The conductive laminated film according to claim 1, wherein the plurality of convex portions are formed in a bowl shape, and the convex portions meander.
The conductive laminated film according to claim 1, wherein the plurality of convex portions are formed in a bowl shape, and the height of the convex portions varies in the extending direction of the convex portions.
The conductive laminated film according to any one of claims 1 to 3, wherein there is no regularity in a change in the position where the plurality of protrusions are provided and the height of the plurality of protrusions.
The conductive layer according to any one of claims 1 to 4, wherein a resin layer (II) comprising a curable resin composition is provided between the film (I) and the transparent conductive layer (III). Laminated film.
In the resin layer (II), a plurality of convex portions are formed in a hook shape on the surface portion on the transparent conductive layer (III) side, and the convex portions are formed in a cross section in a plane perpendicular to the length direction of the hook. 6. The conductive laminated film according to claim 5, wherein the line representing the surface is a wavy curve.
The conductive laminated film according to claim 6, wherein the wavy curve is a wavy curve having a regular period.
The conductive laminated film according to claim 6 or 7, wherein the plurality of convex portions formed in a bowl shape meander in the length direction.
The conductive laminated film according to claim 8, wherein the plurality of convex portions formed in a bowl shape meanders at regular intervals along the length direction thereof.
10. The resin layer (II) according to claim 6, wherein the maximum height of the convex portion is 0.1 to 10 μm, and the period of wrinkles formed by the convex portion is in the range of 100 to 5000 μm. The electroconductive laminated film in any one.
2. The conductive laminated film according to claim 1, wherein the convex portions are present in a sea-island shape when viewed in the vertical direction from the film surface.
The conductive laminated film according to claim 11, further comprising a resin layer (II) made of a curable resin composition between the film (I) and the transparent conductive layer (III).
The maximum height dH of the convex portion, which is the highest height among the heights of the convex portions obtained as the height difference between the highest point of the convex portion and the lowest point of the valley adjacent to the convex portion. Is the distance dL in the film in-plane direction between the highest point of the convex part having the maximum height and the lowest point of the valley adjacent to the convex part, and the dH The conductive laminated film according to any one of claims 1 to 12, wherein and satisfy the following formula (1).
The conductive laminated film according to any one of claims 1 to 14, wherein the film (I) is a film obtained by stretching.
The conductive laminated film according to any one of claims 1 to 14, wherein the film (I) is a retardation film having an in-plane retardation in a range of 128 to 148 nm with respect to transmitted light having a wavelength of 550 nm. .
The conductive laminated film according to any one of claims 1 to 15, wherein the film (I) contains at least one of a cyclic olefin resin and a polycarbonate resin.
The film (I) contains a cyclic olefin resin,
17. The conductive laminated film according to claim 16, wherein the cyclic olefin-based resin is obtained by (co) polymerizing at least one monomer represented by the following formula (1).

(In the formula (1), R 1 to R 4 represent any of the following (i) to (iii), x represents an integer of 0 to 3, and y represents 0 or 1.
(I) each independently a hydrogen atom, a halogen atom, or a monovalent organic group optionally containing oxygen, nitrogen, sulfur or silicon, (ii) R 1 and R 2 , R 3 and R 4 are (Iii) R 1 and R 2 , R 3 and R 4 , and R 2 and R 3 are each bonded to a monocyclic or polycyclic carbocyclic or heterocyclic ring. )
The conductive laminated film according to any one of claims 5 to 10 and 12, wherein the resin layer (II) is formed of a UV curable resin composition.
The conductive laminated film according to any one of claims 1 to 18, wherein the transparent conductive layer (III) is formed of crystalline ITO.
A touch panel comprising the conductive laminated film according to any one of claims 1 to 19.
20. A touch panel comprising: the conductive laminated film according to claim 1; and a conductive laminated film in which a transparent conductive layer, a retardation film, and a polarizing plate are laminated in this order.