WO2016194488A1

WO2016194488A1 - Layered-product roll, optical unit, organic el display device, and processes for producing transparent electroconductive film and optical unit

Info

Publication number: WO2016194488A1
Application number: PCT/JP2016/062026
Authority: WO
Inventors: 武田　健太郎; 直樹津野; 豪彦安藤; 明憲西村; 貴巳疋田
Original assignee: 日東電工株式会社
Priority date: 2015-05-29
Filing date: 2016-04-14
Publication date: 2016-12-08

Abstract

A layered-product roll which is a continuous layered product wound into a roll, wherein the layered product comprises a transparent electroconductive film comprising a polycycloolefin film and a transparent electroconductive layer, and the polycycloolefin film has a slow axis, the direction of which lies within ±2º based on the longitudinal direction of the continuous layered product, throughout the whole continuous layered product excluding the edge parts on both sides which each have a width of 5% of the overall width of the continuous layered product.

Description

Laminated roll, optical unit, organic EL display device, transparent conductive film, and optical unit manufacturing method

The present invention relates to a transparent conductive film including a polycycloolefin film and a transparent conductive layer and a method for producing the same, a roll of a laminate including such a transparent conductive film, an optical unit including such a transparent conductive film, and The present invention relates to a manufacturing method thereof and an organic EL display device including such an optical unit.

A transparent conductive film based on a polycycloolefin film is conventionally known (Patent Document 1). Since the polycycloolefin film is optically isotropic, it is suitable for use in combination with a film that controls the phase of light, such as a polarizing film or a retardation film.

On the other hand, an organic EL display device integrated with a touch sensor using a transparent conductive film is known as disclosed in Patent Document 2, for example. In this known organic EL display device, as shown in FIG. 1, a touch panel laminate 916 is provided on the viewing side of the organic EL display panel 901, and a polarization having a circular polarization function on the viewing side of the touch panel laminate 916. A functional laminate 920 is provided. The polarization functional laminate 920 includes a polarizing film 921 and a retardation film 923, and the polarizing film 921 is provided on the viewing side of the retardation film 923. The touch panel laminate 916 has a structure in which a dielectric layer 915 and pattern electrodes 912-1 and 912-2 provided on both surfaces of the dielectric layer 915 are laminated. Further, a window 902 is arranged on the viewing side with respect to the polarization functional laminate 920.

In this organic EL display device, a typical example of the retardation film 923 is a ¼ wavelength retardation film. In this case, light incident from the viewing side becomes linearly polarized light by the polarizing film 921, and the linearly polarized light is The circularly polarized light is converted into circularly polarized light by the quarter-wave retardation film, and the light incident on the inside is internally reflected so that the circularly polarized light is in reverse phase. It is converted into linearly polarized light that is orthogonal to the polarization direction and is prevented from being emitted to the viewing side by the polarizing film 921. Therefore, by using an optically isotropic dielectric layer as the dielectric layer 915, the change in the phase of light when the light passes through the dielectric layer 915 is prevented, and the internal antireflection function deteriorates. It is conceivable to prevent the occurrence of a hue shift or a hue shift. Therefore, it is conceivable to use an optically isotropic material such as a polycycloolefin film as the dielectric layer 915.

JP 2014-229279 A JP 2012-133312 A

However, the polycycloolefin film is not completely optically isotropic and has a slight optical anisotropy. The anisotropy of this polycycloolefin film is slight and has not been recognized as a problem until now. However, the deterioration of the visibility due to this slight anisotropy becomes a problem in response to the recent strict demand for the visibility of the display device.

In the width direction of the polycycloolefin film original fabric, the present inventors have a slow axis direction parallel to the MD direction at the center, but the slow phase with respect to the MD direction increases from the center to the end in the width direction. We have discovered a phenomenon that has not been recognized so far, in which the axial displacement increases and the in-plane phase difference also increases. In other words, when several films are cut out in the width direction from the original polycycloolefin film, there arises a problem that the optical properties of the respective cut out films vary, and in the case where one large film is cut out. However, the optical properties deteriorate at the edge of the cut film. In addition, for example, in a known touch sensor integrated organic EL display device as described above, visibility such as a hue shift may be deteriorated. The present inventors have discovered such a problem that has not been recognized so far.

Accordingly, the present invention aims to suppress variations in the direction of the slow axis and in-plane retardation of the transparent conductive film, and to suppress deterioration of optical characteristics such as hue shift in the organic EL display device. I will.

One aspect of the present invention is a roll of a laminate in which a long body of a laminate is wound into a roll, and the laminate includes a transparent conductive film including a polycycloolefin film and a transparent conductive layer. And the direction of the slow axis of the polycycloolefin film is the longitudinal direction of the long body of the laminate, except for the ends on both sides of the width of 5% with respect to the full width of the long body of the laminate. Provides a roll in the range of ± 2 °.

Another aspect of the present invention includes a transparent conductive film including a polycycloolefin film and a transparent conductive layer, and a retardation film, and the variation in the angle of the slow axis of the polycycloolefin film is 4 °. The in-plane retardation of the polycycloolefin film measured with light having a wavelength of 550 nm at 23 ° C. is in the range of 3 to 8 nm, and the variation thereof is in the range of 1.5 nm. The in-plane retardation of the retardation film cancels out the in-plane retardation of the polycycloolefin film so that the entire in-plane retardation of the retardation film and the transparent conductive film becomes a desired value. An optical unit is provided.

In one embodiment of the present aspect, the retardation film may include a quarter wavelength retardation film, and the desired value may be about a quarter wavelength.

In one embodiment of this aspect, the retardation film includes a viewing angle compensation retardation film and a quarter-wave retardation film in order from the transparent conductive film side, and the desired value is about 1 / There can be four wavelengths.

In these cases, the direction of the slow axis of the quarter-wave retardation film can be in the range of 0 ° ± 3 ° with respect to the direction of the slow axis of the polycycloolefin film.

In these cases, the direction of the slow axis of the quarter-wave retardation film can be within a range of 90 ° ± 3 ° with respect to the direction of the slow axis of the polycycloolefin film.

In one embodiment of this aspect, the transparent conductive layer may be formed of indium tin oxide (ITO).

In one embodiment of this aspect, the optical unit further includes a polarizing functional laminate, the polarizing functional laminate includes a polarizing film and the retardation film, and the retardation film is the transparent conductive film. It is arrange | positioned at the said transparent conductive layer side, The said polarizing film shall be arrange | positioned on the opposite side to the said transparent conductive film with respect to the said retardation film.

In this case, the polarization functional laminate may have a function of generating circularly polarized light.

Another aspect of the present invention includes the above-described optical unit and an organic EL display panel, wherein the optical unit is disposed on the viewing side with respect to the organic EL display panel, and the optical unit is the transparent conductive material. An organic EL display device is provided in which a conductive film is disposed between the polarizing film and the organic EL display panel.

Still another embodiment of the present invention includes a step of unwinding the polycycloolefin film from a roll of a polycycloolefin film in which a long body of a polycycloolefin film is wound into a roll, and the unfolded polycycloolefin film Is heated and wound at a heating temperature of 140 to 160 ° C. while being wound by a winding roll, and a transparent conductive layer is formed on the heated polycycloolefin film to produce a transparent conductive film. And a step for producing a transparent conductive film.

In one embodiment of this aspect, the heating temperature may be 145 to 155 ° C.

In this case, the heating temperature may be 148 to 153 ° C.

Yet another embodiment of the present invention is a method for producing the optical unit, wherein the polarizing functional laminate and the transparent conductive film produced by the production method are bonded together to produce the optical unit. The manufacturing method of this is provided.

According to the present invention, it is possible to suppress the variation of the direction of the slow axis and the in-plane retardation of the transparent conductive film, and it is possible to suppress the deterioration of optical characteristics such as hue shift in the organic EL display device.

Hereinafter, according to the present invention, a transparent conductive film including a polycycloolefin film and a transparent conductive layer and a method for producing the same, a roll of a laminate including such a transparent conductive film, and an optical including such a transparent conductive film An embodiment of a unit, a manufacturing method thereof, and an organic EL display device including such an optical unit will be described in detail with reference to the drawings.

It is sectional drawing which shows the conventional organic EL display apparatus. It is sectional drawing of the transparent conductive film by one Embodiment of this invention. It is the elements on larger scale which show the structure of the 2nd cured resin layer in FIG. It is sectional drawing which shows the organic electroluminescent display apparatus by one Embodiment of this invention. It is a figure which shows an example of the change of the front phase difference before and behind the heating winding process of the width direction of a polycycloolefin film. It is a figure which shows an example of the change of the direction of a slow axis before and behind the heating winding process of the width direction of a polycycloolefin film. It is a figure which shows the reflective hue of the optical unit of an Example and a comparative example. It is a figure which shows the measurement result of the reflectance of Example A10 and A11 and Comparative Example A5 and A6.

[Laminate roll]
The roll of the laminated body of this invention is a roll of the laminated body by which the elongate body of the laminated body was wound by roll shape.

The laminate used for the roll of the laminate of the present invention includes a transparent conductive film.

The transparent conductive film used for the roll of the laminate of the present invention includes a polycycloolefin film and a transparent conductive layer.

The direction of the slow axis of the polycycloolefin film used for the roll of the laminate of the present invention is the entire length of the laminate except for the ends on both sides of the width of 5% with respect to the entire width of the laminate. It is within a range of ± 2 °, preferably ± 1.5 ° with respect to the longitudinal direction of the body.

[Optical unit]
The optical unit of the present invention includes a transparent conductive film including a polycycloolefin film and a transparent conductive layer, and a retardation film. The retardation film is disposed on the transparent conductive layer side of the transparent conductive film.

The angle variation of the slow axis of the polycycloolefin film used in the optical unit of the present invention is in the range of 4 °. The in-plane retardation of the polycycloolefin film measured with light having a wavelength of 550 nm at 23 ° C. is in the range of 3 to 8 nm, and the variation thereof is in the range of 1.5 nm.

In this specification, Re [550] means an in-plane retardation value measured with light having a wavelength of 550 nm at 23 ° C. Re [550] is the formula: Re [550] = when the refractive indices in the slow axis direction and the fast axis direction of the film at a wavelength of 550 nm are nx and ny, respectively, and d (nm) is the thickness of the film. It can be calculated by (nx−ny) × d. The slow axis means the direction in which the in-plane refractive index is maximum.

The in-plane retardation of the retardation film used in the optical unit of the present invention cancels out the almost constant in-plane retardation with little variation of the polycycloolefin film, and the entire retardation film and the transparent conductive film. The in-plane phase difference is set to a desired value.

The retardation film used in the optical unit of the present invention includes a quarter-wave retardation film, and the desired value can be about ¼ wavelength. The retardation film used in the optical unit of the present invention includes a viewing angle compensation retardation film and a quarter-wave retardation film in order from the transparent conductive film side, and the desired value is about ¼ wavelength. It can be. Here, the desired value of approximately ¼ wavelength means that the desired value is ideally ¼ wavelength at all wavelengths in the visible light region. The in-plane retardation at a wavelength of 550 nm is preferably 130 to 150 nm, and more preferably 140 to 146 nm.

The direction of the slow axis of the quarter-wave retardation film is substantially parallel to the direction of the slow axis of the polycycloolefin film, that is, within a range of ± 2 ° with respect to the direction of the slow axis of the polycycloolefin film. can do. With such a configuration, the in-plane retardation of the polycycloolefin film can be easily canceled by the retardation film.

The optical unit further includes a polarizing functional laminate, the polarizing functional laminate includes a polarizing film and the retardation film, the retardation film is disposed on the transparent conductive layer side of the transparent conductive film, and the polarizing film has a retardation. The film may be disposed on the opposite side of the transparent conductive film.

The polarizing functional laminate can have a function of generating circularly polarized light.

[Method for producing transparent conductive film]
The method for producing a transparent conductive film of the present invention includes a step of unwinding the polycycloolefin film from a roll of a polycycloolefin film in which a long body of a laminate including a polycycloolefin film is wound in a roll shape, The polycycloolefin film thus obtained is heated and wound at a heating temperature of 140 to 160 ° C. while being wound with a winding roll, and a transparent conductive layer is formed on the heated and wound polycycloolefin film. Producing a transparent conductive film.

In this way, while winding the long body of the laminate including the polycycloolefin film with a winding roll, that is, while giving a constant tension to the polycycloolefin film, the glass transition temperature (Tg) of the polycycloolefin film is By performing the heating and winding process at a temperature close to 165 ° C., the direction of the slow axis can be aligned with the MD direction.

The heating temperature is more preferably 145 to 155 ° C, and still more preferably 148 to 153 ° C.

[Manufacturing method of optical unit]
In the method for producing an optical unit of the present invention, a polarizing functional laminate including a retardation film and a polarizing film and a transparent conductive film produced by the production method are bonded together to produce an optical unit.

<Polarizing film>
For the polarizing film used in the optical unit of the present invention, it is possible to use a polyvinyl alcohol-based resin oriented with iodine and stretched by a stretching process such as air stretching (dry stretching) or boric acid water stretching process.

As a method for producing a polarizing film, typically, as described in JP-A-2004-341515, a production method (single layer stretching method) including a step of dyeing a single layer of a PVA resin and a step of stretching. ) JP-A-51-069644, JP-A-2000-338329, JP-A-2001-343521, International Publication No. 2010/100917, JP-A-2012-073563, JP-A-2011-2816. The manufacturing method including the process of extending | stretching the PVA-type resin layer and the extending | stretching resin base material in the state of a laminated body, and the process of dyeing | staining as described in (1). With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

The production method including the step of stretching in the state of the laminate and the step of dyeing is as described in JP-A-51-069644, JP-A-2000-338329, and JP-A-2001-343521. There is an aerial stretching (dry stretching) method. And the process of extending | stretching in boric-acid aqueous solution like the international publication 2010/100917 and Unexamined-Japanese-Patent No. 2012-073563 in the point which can be extended | stretched at high magnification and can improve polarization | polarized-light performance. A production method including the step of performing air-assisted auxiliary stretching before stretching in a boric acid aqueous solution as described in JP 2012-073563 A is particularly preferable. Also, as described in JP 2011-2816 A, a method of stretching a PVA resin layer and a stretching resin base material in a laminated state, then excessively dyeing the PVA resin layer, and then decoloring (Over-staining and decoloring method) is also preferable. The polarizing film used in the optical layered body of the present invention is composed of a polyvinyl alcohol resin in which iodine is oriented as described above, and a polarizing film stretched in a two-stage stretching process consisting of air-assisted stretching and boric acid-water stretching, can do. Further, the polarizing film used in the optical laminate of the present invention is made of a polyvinyl alcohol resin in which iodine is oriented as described above, and excessively dyes the laminate of the stretched PVA resin layer and the stretching resin substrate. And it can be set as the polarizing film produced by decoloring after that.

<Phase difference film>
The retardation film used for the optical unit of the present invention includes a single-layer or multilayer retardation film.

<Phase difference film>
As the retardation film used in the optical unit of the present invention, one obtained by stretching a polymer film or one obtained by aligning and fixing a liquid crystal material can be used. In the present specification, the retardation film refers to a film having birefringence in the plane and / or in the thickness direction, thereby realizing a predetermined function.

Examples of the retardation film include an antireflection retardation film (see JP 2012-133303 [0221], [0222] [0228]) and a viewing angle compensation retardation film (JP 2012-133303 [0225]). , [0226]), and a tilted alignment phase difference film for viewing angle compensation (see Japanese Unexamined Patent Application Publication No. 2012-133303 [0227]).

The retardation film is not particularly limited as long as it has substantially the above-mentioned function. For example, the retardation value, the arrangement angle, the three-dimensional birefringence, and whether it is a single layer or a multilayer are not particularly limited. Can be used.

The in-plane birefringence Δn which is nx-ny of the retardation film of the present invention is 0.001 to 0.2, preferably 0.002 to 0.15.

The retardation film preferably has an in-plane retardation value (Re [550]) measured with light having a wavelength of 550 nm and an in-plane retardation value (Re [450] measured with light having a wavelength of 450 nm at 23 ° C. ]). In the retardation film having such a wavelength dispersion characteristic, when the ratio is within this range, the longer the wavelength, the more the phase difference appears, and an ideal retardation characteristic can be obtained at each wavelength in the visible region. For example, when used in an organic EL display, a retardation film having such wavelength dependency as a quarter wavelength plate is prepared, and a circularly polarizing plate or the like can be prepared by bonding with a polarizing plate, It is possible to realize a neutral polarizing plate and a display device with less hue wavelength dependency. On the other hand, when the ratio is out of this range, the wavelength dependency of the reflected hue becomes large, and coloring problems occur in the polarizing plate and the display device.

The ratio of Re [550] and Re [450] (Re [450] / Re [550]) of the retardation film is 0.8 or more and less than 1.0, more preferably 0.8 to 0.98. .

The retardation film preferably has an in-plane retardation value (Re [550]) measured with light having a wavelength of 550 nm and an in-plane retardation value (Re [650] measured with light having a wavelength of 650 nm at 23 ° C. ]) Smaller than. A retardation film having such a wavelength dispersion characteristic has a constant retardation value in a red region. For example, when used in a liquid crystal display device, a phenomenon in which light leaks depending on a viewing angle or a display image is red. It is possible to improve a taste-taking phenomenon (also referred to as a red-ish phenomenon).

The ratio of Re [650] to Re [550] (Re [550] / Re [650]) of the retardation film is 0.8 or more and less than 1.0, preferably 0.8 to 097. By setting Re [550] / Re [650] in the above range, for example, when the retardation film is used in an organic EL display, even better display characteristics can be obtained.

Re [450], Re [550], and Re [650] can be measured using the product name “AxoScan” manufactured by Axometrics.

In this specification, NZ refers to the ratio of nx-nz, which is birefringence in the thickness direction, and nx-ny, which is in-plane birefringence (also referred to as Nz coefficient).

NZ of the retardation film of the present invention is −10 to 1.5, preferably −8 to 1.4, more preferably −6 to 1.3.

For example, when normal longitudinal stretching is performed, width shrinkage occurs because the width direction is not fixed with respect to stretching in the longitudinal direction of the film. For this reason, molecules are more aligned in a uniaxial direction, and the refractive index relationship is, for example, nx> ny = nz. In this case, the folding strength in the longitudinal direction of the film, which is the stretching direction, becomes strong, but the folding strength in the width direction becomes very weak. In order to solve this, a state in which a force for regulating the width is generated in an angular direction intersecting the stretching direction (for example, in the case of lateral uniaxial stretching, in a direction perpendicular to the width direction of the film which is the stretching direction). By applying stretching, the molecules can be oriented not only in the stretching direction but also in the angular direction intersecting with the stretching direction. The refractive index relationship can be nx> ny> nz. Thus, the folding strength in the stretching direction and the folding strength in the width direction can be compatible at a high level.

The absolute value of the photoelastic coefficient at 23 ° C. of the retardation film; C (m ² / N) is 0.5 × 10 ⁻¹² to 100 × 10 ⁻¹² (m ² / N), preferably 1 × 10 ^{− 12} to 80 × 10 ⁻¹² (m ² / N). Due to the shrinkage stress of the polarizing film, the heat of the display panel, and the surrounding environment (moisture resistance / heat resistance), the retardation film is forcefully applied, and the resulting change in retardation value can be prevented. A display panel device having excellent display uniformity can be obtained. Preferably, C of the retardation film is 3 × 10 ⁻¹² to 45 × 10 ⁻¹² , particularly preferably 5 × 10 ⁻¹² to 40 × 10 ⁻¹² or less. By setting C in the above range, it is possible to reduce a change or unevenness in the retardation value that occurs when a force is applied to the retardation film. In addition, the photoelastic coefficient and Δn tend to be in a trade-off relationship, and within this photoelastic coefficient range, it is possible to maintain display quality without reducing the phase difference expression.

As the retardation film of the present invention, a retardation film exhibiting reverse dispersion wavelength dependency (reverse dispersion wavelength characteristic) with a single film can be suitably used. As the phase film exhibiting the reverse dispersibility, a resin containing a polycarbonate resin described in the trade name “Pure Ace WR” or Japanese Patent No. 4938151 or an oligofluorene described in Japanese Patent Application No. 2013-214986 can be used. .

In one embodiment, the retardation film of the present invention is produced by orienting a polymer film by stretching.

As the method for stretching the polymer film, any appropriate stretching method can be adopted depending on the purpose. Examples of the stretching method suitable for the present invention include a transverse uniaxial stretching method, a longitudinal and transverse simultaneous biaxial stretching method, and a longitudinal and transverse sequential biaxial stretching method. As a means for stretching, any suitable stretching machine such as a tenter stretching machine or a biaxial stretching machine can be used. Preferably, the stretching machine includes a temperature control unit. When extending | stretching by heating, the internal temperature of a extending | stretching machine may be changed continuously and may be changed continuously. The process may be divided once or twice or more. The stretching direction is preferably stretched in the film width direction (TD direction) or in an oblique direction.

In the oblique stretching, an unstretched resin film is sent out in the longitudinal direction, and an oblique stretching process of stretching in a direction that forms an angle within the specific range with respect to the width direction is continuously performed. Thereby, it is possible to obtain a long retardation film in which the angle (orientation angle θ) formed by the width direction of the film and the slow axis falls within the specific range.

As a method of obliquely stretching, the film is continuously stretched in a direction that forms an angle of the specific range with respect to the width direction of the unstretched resin film, and a slow axis is set in the specific range with respect to the width direction of the film. If it can form in the direction which makes an angle, it will not restrict | limit in particular. It is possible to adopt any appropriate method from the conventionally known stretching methods such as JP-A-2005-319660, JP-A-2007-30466, JP-A-2014-194482, JP-A-2014-199483, and JP-A-2014-199483. it can.

The temperature at which the unstretched resin film is stretched (stretching temperature) can be appropriately selected depending on the purpose. Preferably, the stretching is performed in the range of Tg−20 ° C. to Tg + 30 ° C. with respect to the glass transition temperature (Tg) of the polymer film. By selecting such conditions, the retardation value is likely to be uniform, and the film is less likely to be crystallized (white turbid). Specifically, the stretching temperature is 90 ° C. to 210 ° C., more preferably 100 ° C. to 200 ° C., and particularly preferably 100 ° C. to 180 ° C. The glass transition temperature can be obtained by a DSC method according to JIS K 7121 (1987).

Any appropriate means can be adopted as means for controlling the stretching temperature. Examples of the temperature control means include an air circulation type thermostatic oven in which hot air or cold air circulates, a heater using microwaves or far infrared rays, a roll heated for temperature adjustment, a heat pipe roll, a metal belt, and the like. .

Magnification ratio (stretch ratio) for stretching the unstretched resin film can be appropriately selected according to the purpose. The draw ratio is preferably more than 1 and 6 times or less, more preferably more than 1.5 times and 4 times or less.

The feeding speed during stretching is not particularly limited, but is preferably 0.5 m / min to 30 m / min, more preferably 1 m / min to 20 m / min from the viewpoint of mechanical accuracy and stability. If it is said extending | stretching conditions, not only the target optical characteristic can be acquired, but the phase difference film excellent in optical uniformity can be obtained.

Also. As another embodiment, using a polycycloolefin film or a polycarbonate film, the angle formed by the absorption axis of the polarizing plate and the slow axis of the half-wave plate is 15 °, and the absorption axis of the polarizing plate is 1 / A retardation film laminated with a single sheet of acrylic adhesive may be used so that the angle formed by the slow axis of the four-wavelength plate is 75 °.

In another embodiment, the retardation film of the present invention may be a laminate of retardation layers prepared by aligning and fixing a liquid crystal material. Each retardation layer may be an alignment solidified layer of a liquid crystal compound. By using a liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be remarkably increased as compared with a non-liquid crystal material, and thus the thickness of the retardation layer for obtaining a desired in-plane retardation. Can be significantly reduced. As a result, it is possible to further reduce the thickness of the circularly polarizing plate (finally, an organic EL display device). In the present specification, the “alignment solidified layer” refers to a layer in which a liquid crystal compound is aligned in a predetermined direction in the layer and the alignment state is fixed. In the present embodiment, typically, the rod-like liquid crystal compounds are aligned in a state aligned in the slow axis direction of the retardation layer (homogeneous alignment), or are slow in the normal direction to the in-plane direction. There are orientations in which the axes are aligned (homeotropic orientation). Examples of the liquid crystal compound include a liquid crystal compound (nematic liquid crystal) whose liquid crystal phase is a nematic phase. As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The liquid crystal compound may exhibit liquid crystallinity either lyotropic or thermotropic. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.

When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the alignment state of the liquid crystal monomer can be fixed by polymerizing or crosslinking the liquid crystal monomer. After aligning the liquid crystal monomers, for example, if the liquid crystal monomers are polymerized or cross-linked, the alignment state can be fixed thereby. Here, a polymer is formed by polymerization and a three-dimensional network structure is formed by crosslinking, but these are non-liquid crystalline. Therefore, in the formed retardation layer, for example, a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change specific to the liquid crystal compound does not occur. As a result, the retardation layer is an extremely stable retardation layer that is not affected by temperature changes.

The temperature range in which the liquid crystal monomer exhibits liquid crystal properties varies depending on its type. Specifically, the temperature range is preferably 40 ° C. to 120 ° C., more preferably 50 ° C. to 100 ° C., and most preferably 60 ° C. to 90 ° C.

Any appropriate liquid crystal monomer can be adopted as the liquid crystal monomer. For example, the polymerizable mesogenic compounds described in JP-T-2002-533742 (WO00 / 37585), EP358208 (US521118), EP66137 (US4388453), WO93 / 22397, EP0266172, DE195504224, DE44081171, and GB2280445 can be used. Specific examples of such a polymerizable mesogenic compound include, for example, trade name LC242 of BASF, trade name E7 of Merck, and trade name LC-Silicon-CC3767 of Wacker-Chem. As the liquid crystal monomer, for example, a nematic liquid crystal monomer is preferable.

The alignment solidified layer of the liquid crystal compound is subjected to an alignment treatment on the surface of a predetermined substrate, and a coating liquid containing the liquid crystal compound is applied to the surface to align the liquid crystal compound in a direction corresponding to the alignment treatment, It can be formed by fixing the alignment state. In one embodiment, the substrate is any suitable resin film, and the alignment solidified layer formed on the substrate can be transferred to the surface of the polarizing film. At this time, the angle between the absorption axis of the polarizing film and the slow axis of the liquid crystal alignment solidified layer is set to 15 °. The retardation of the liquid crystal alignment solidified layer is λ / 2 (about 270 nm) for a wavelength of 550 nm. Further, as described above, a liquid crystal alignment solidified layer having a wavelength of λ / 4 (about 140 nm) with respect to a wavelength of 550 nm is formed on a transferable substrate, and 1 / of the laminate of the polarizing film and the half-wave plate. The two-wavelength plate is laminated so that the angle formed by the absorption axis of the polarizing film and the slow axis of the quarter-wave plate is 75 °.

Any appropriate alignment treatment can be adopted as the alignment treatment. Specifically, a mechanical alignment process, a physical alignment process, and a chemical alignment process are mentioned. Specific examples of the mechanical alignment treatment include rubbing treatment and stretching treatment. Specific examples of the physical alignment process include a magnetic field alignment process and an electric field alignment process. Specific examples of the chemical alignment treatment include oblique vapor deposition and photo-alignment treatment. Arbitrary appropriate conditions may be employ | adopted for the process conditions of various orientation processes according to the objective.

The alignment of the liquid crystal compound is performed by processing at a temperature showing a liquid crystal phase according to the type of the liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound takes a liquid crystal state, and the liquid crystal compound is oriented according to the orientation treatment direction of the substrate surface.

In one embodiment, the alignment state is fixed by cooling the liquid crystal compound aligned as described above. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the alignment state is fixed by subjecting the liquid crystal compound aligned as described above to a polymerization treatment or a crosslinking treatment.

Specific examples of the liquid crystal compound and details of the method of forming the alignment solidified layer are described in JP-A No. 2006-163343. The description in this publication is incorporated herein by reference.

[Protective film]
For the protective film of the transparent resin material used in the optical unit of the present invention, cycloolefin resins such as norbornene resins, olefin resins such as polyethylene and polypropylene, polyester resins, (meth) acrylic resins, and the like can be used. .

The thickness of the protective film used in the optical laminate of the present invention is 10 to 50 μm, preferably 15 to 45 μm, and a surface treatment layer such as an antiglare layer or an antireflection layer can be appropriately provided.

The permeation humidity of the protective film used in the optical layered body of the present invention is 200 g / m ² or less, preferably 170 g / m ² or less, more preferably 130 g / m ² or less, and particularly preferably 90 g / m ² or less.

[Transparent conductive film]
FIG. 2 is a schematic cross-sectional view of a transparent conductive film according to an embodiment of the present invention. The transparent conductive film in FIG. 2 includes a substrate laminate 1 and a transparent conductive layer 13. The base laminate 1 includes a polycycloolefin film 10, a first cured resin layer 11 formed on the first main surface S1 of the polycycloolefin film 10, and a first main surface S1 of the polycycloolefin film 10. Includes a second cured resin layer 12 formed on the opposite second main surface S2 side. An optical adjustment layer 16 is provided between the first cured resin layer 11 and the transparent conductive layer 13. As shown in FIG. 3, the second cured resin layer 12 includes a plurality of spherical particles 14 and a binder resin layer 15 that fixes the spherical particles to the surface of the polycycloolefin film 10. Since the 2nd cured resin layer 12 has the convex part 12a on the surface, when a transparent conductive film is wound up by the roll to roll manufacturing method, it can suppress that transparent conductive films block. it can. Moreover, although the base-material laminated body 1 can be comprised only by the polycycloolefin film 10 or the polycycloolefin film 10, and the 1st cured resin layer or the 2nd cured resin layer, the said transparent conductive layer 13 is formed. It is preferable that the 1st cured resin layer 11 of the side, the polycycloolefin film 10, and the 2nd cured resin layer 12 are included in this order.

[Transparent conductive layer]
The transparent conductive layer is preferably a layer formed of a metal oxide. As the metal oxide, metal oxidation of at least one metal selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten A thing is used suitably. The metal oxide may further contain a metal atom shown in the above group, if necessary. Of these, indium-tin composite oxide (ITO) and indium zinc composite oxide are preferable. In addition, indium oxide (In 2 O 3) doped with tetravalent metal ions or divalent metal ions is used. Such an indium composite oxide layer has a high transmittance of 80% or more in the visible light region (380 nm to 780 nm) and a low surface resistance per unit area (300 Ω / □ or less: ohms per square). It has characteristics.

The surface resistance value of the indium composite oxide layer is preferably 300Ω / □ or less, and more preferably 270Ω / □ or less. Such a transparent conductive film having a small surface resistance value is formed at 120 ° C. to 200 ° C. after an amorphous layer of indium composite oxide is formed on the cured resin layer by, for example, sputtering or vacuum deposition. It can be obtained by heat-treating for about 30 to 90 minutes to change the amorphous layer into a crystalline layer. The conversion means is not particularly limited, and an air circulation oven, an IR heater, or the like is used.

(Definition of crystalline)
A transparent conductive film having a transparent conductive layer formed on a substrate laminate is dipped in hydrochloric acid having a concentration of 5% by weight at 20 ° C. for 15 minutes, then washed with water and dried, and a resistance between terminals of 15 mm is measured with a tester. When measurement is performed and the inter-terminal resistance does not exceed 10 kΩ, it is assumed that the conversion of the ITO film to the crystalline state is completed.

The thickness of the transparent conductive layer is preferably 15 to 50 nm, more preferably 20 to 40 nm, and still more preferably 25 to 35 nm. When the thickness of the transparent conductive layer is less than 15 nm, the electrical resistance of the film surface increases and it becomes difficult to form a continuous film. Further, when the thickness of the transparent conductive layer exceeds 50 nm, the transparency may be lowered. The transparent conductive layer may have a structure in which a plurality of transparent conductive layers having different compositions are laminated.

The arithmetic average surface roughness Ra in the field of view of 452 μm × 595 μm on the surface of the transparent conductive layer is preferably greater than 0 nm and less than or equal to 10 nm, more preferably greater than 0 nm and less than or equal to 9 nm, from the viewpoint of improving transparency. Preferably, it is larger than 0 nm and 7 nm or less. The difference between the arithmetic average surface roughness Ra in the 452 μm × 595 μm visual field of the surface of the second cured resin layer and the arithmetic average surface roughness Ra in the 452 μm × 595 μm visual field of the surface of the transparent conductive layer is 5 nm or more. Is preferably 10 nm or more, more preferably 15 nm or more.

The transparent conductive layer may include a metal nanowire or a metal mesh.

(Metal nanowires)
A metal nanowire is a conductive material having a metal material, a needle shape or a thread shape, and a diameter of nanometer. The metal nanowire may be linear or curved. If a transparent conductive layer composed of metal nanowires is used, the metal nanowires can be formed into a mesh shape, so that even with a small amount of metal nanowires, a good electrical conduction path can be formed, and transparent with low electrical resistance. A conductive film can be obtained. Furthermore, when the metal nanowire has a mesh shape, an opening is formed in the mesh space, and a transparent conductive film having high light transmittance can be obtained.

As the metal constituting the metal nanowire, any appropriate metal can be used as long as it is a highly conductive metal. As a metal which comprises the said metal nanowire, silver, gold | metal | money, copper, nickel etc. are mentioned, for example. Moreover, you may use the material which performed the plating process (for example, gold plating process) to these metals. Among these, silver, copper, or gold is preferable from the viewpoint of conductivity, and silver is more preferable.

(Metal mesh)
The transparent conductive layer including a metal mesh is formed by forming fine metal wires in a lattice pattern on the substrate laminate. It is possible to use the same metal as that constituting the metal nanowire. The transparent conductive layer containing a metal mesh can be formed by any appropriate method. For example, the transparent conductive layer is formed by applying a photosensitive composition containing silver salt (a composition for forming a transparent conductive layer) onto the substrate laminate, and then performing an exposure process and a development process to form a fine metal wire in a predetermined pattern. It can obtain by forming.

[Hardened resin layer]
The cycloolefin resin itself tends to be very easily damaged. Since the polycycloolefin film 10 is easily scratched in each step such as formation of the transparent conductive layer, patterning of the transparent conductive layer, or mounting on the electronic device, the cured resin layer is formed on both sides of the polycycloolefin film 10 as a first resin layer. It is preferable to form a cured resin layer and a second cured resin layer.

The cured resin layer is a layer obtained by curing a curable resin. For the curable resin, any of a resin that uses thermal curing, active energy ray curing, or both in combination as a curing mechanism may be employed. You may use a crosslinking agent, an initiator, a sensitizer, etc. with curable resin as needed. The thicknesses of the first cured resin layer and the second cured resin layer are preferably independently 0.5 μm to 5 μm, more preferably 0.7 μm to 3 μm, and most preferably 0.8 μm to 2 μm. is there. The first cured resin layer and the second cured resin layer are prepared by applying a resin composition containing each curable resin and a crosslinking agent, an initiator, a sensitizer, and the like to be added as necessary on the transparent resin film. In the case where contains a solvent, the solvent is dried and cured by application of heat, active energy rays or both. For the heat, known means such as an air circulation oven or an IR heater can be used, but it is not limited to these methods. Examples of active energy rays include, but are not limited to, ultraviolet rays, electron beams, and gamma rays. As the curable resin, an acrylic resin or an epoxy resin is preferable, and an acrylic resin is more preferable.

The first cured resin layer 11 or the second cured resin layer 12 preferably includes a plurality of spherical particles 14 and a binder resin layer 15 that fixes the spherical particles to the surface of the polycycloolefin film 10. In particular, it is more preferable that the second cured resin layer 12 includes the plurality of spherical particles 14 and the binder resin layer 15. FIG. 3 is a partially enlarged view showing the configuration of the second cured resin layer 12 in FIG. The second cured resin layer 12 includes a plurality of spherical particles 14 and a binder resin layer 15 that fixes the spherical particles 14 to the surface of the polycycloolefin film 10. The mode particle diameter of the spherical particles 14 is described as w, and the thickness of the binder resin layer 15 is described as d. The portion where the spherical particles 14 are present on the outer surface of the second cured resin layer 12, that is, the surface not in contact with the polycycloolefin film 10, has a convex shape protruding by the difference wd. The portion where the spherical particles 14 are not present has a substantially planar shape. A part of the binder resin layer 15 is thinly formed on the upper surface of each spherical particle 14. Here, the “moderate particle diameter” refers to a particle diameter showing a maximum value of the particle distribution. “Binder resin layer thickness” refers to the thickness of a flat portion where spherical particles do not exist. In the second cured resin layer 12, the relationship between the mode particle diameter w of the spherical particles 14 and the thickness d of the binder resin layer 15 is preferably such that wd is greater than 0 and 1.2 μm or less. .1 μm to 1.0 μm is more preferable, and 0.3 μm to 0.9 μm is more preferable. Thereby, the antiblocking property which can endure a roll to roll manufacturing method can be implement | achieved more reliably, suppressing the influence on a haze.

The arithmetic average surface roughness Ra of the surface of the first cured resin layer is preferably greater than 0 nm and less than or equal to 10 nm, more preferably greater than 0 nm and less than or equal to 9 nm, and greater than 0 nm from the viewpoint of improving transparency. More preferably, it is 7 nm or less.

The arithmetic average surface roughness Ra of the surface of the second cured resin layer is preferably greater than 5 nm and less than or equal to 100 nm, more preferably greater than 7 nm and less than or equal to 70 nm, and even more preferably greater than 10 nm and less than or equal to 60 nm. . When the arithmetic average surface roughness Ra is within the above range, the anti-blocking property that can withstand the roll-to-roll manufacturing method can be improved.

The arithmetic average surface roughness Ra on the second cured resin layer side is preferably rougher than the arithmetic average surface roughness Ra on the first cured resin layer side. Thereby, while having anti-blocking property which can be equal to a roll-to-roll manufacturing method, the white haze (haze) by the side of a transparent conductive layer can be reduced. Further, the difference between the arithmetic average surface roughness Ra in the visual field of 452 μm × 595 μm on the surface of the second cured resin layer and the arithmetic average surface roughness Ra in the visual field of 452 μm × 595 μm of the surface of the first cured resin layer is 5 nm or more. It is preferably 10 nm or more, more preferably 15 nm or more.

As the spherical particles, those having transparency such as various metal oxides, glass and plastics can be used without any particular limitation. For example, inorganic particles such as silica, alumina, titania, zirconia, calcium oxide, polymethyl methacrylate, polystyrene, polyurethane, acrylic resin, acryl-styrene copolymer, benzoguanamine, melamine, polycarbonate, and other cross-linked or uncrosslinked polymers. Examples include crosslinked organic particles and silicone particles. The particles can be used by appropriately selecting one type or two or more types, but organic particles are preferable. As the organic particles, acrylic resins are preferable from the viewpoints of sphericity and heat resistance.

The content of the spherical particles in the first cured resin layer is preferably 0.0000 to 0.0020 parts by weight, preferably 0.0000 to 0.0015 parts by weight based on 100 parts by weight of the solid content of the resin composition. More preferably, it is 0.0000 to 0.0010 parts by weight. The content of the spherical particles in the second cured resin layer is preferably 0.0010 to 0.0300 parts by weight with respect to 100 parts by weight of the solid content of the resin composition, preferably 0.0015 to 0.00. The amount is more preferably 0200 parts by weight, still more preferably 0.0020 to 0.0150 parts by weight. When the content of the spherical particles in the first cured resin layer or the second cured resin layer is in the above range, the arithmetic average surface roughness Ra on both sides can be adjusted separately. Sufficient base bulges are easily formed to impart lubricity, and the haze of the transparent conductive film due to light scattering by the spherical particles is reduced, and the visibility tends to increase.

As the material of the binder resin used for the binder resin layer, any material can be selected as long as it can fix spherical particles. For example, the binder resin is obtained by curing a curable resin composition with ultraviolet rays or an electron beam. The curable resin composition preferably contains a polyfunctional acrylate polymer such as pentaerythritol and dipentaerythritol, a polymer obtained by addition-reacting acrylic acid to a glycidyl acrylate polymer, and a polymerization initiator.

[Optical adjustment layer]
As shown in FIG. 2, the transparent conductive film may further include one or more optical adjustment layers 16 between the first cured resin layer 11 and the transparent conductive layer 13. When the transmittance of the transparent conductive film is increased or when the transparent conductive layer 13 is patterned, the transmittance difference or the reflectance difference is reduced between the pattern part where the pattern remains and the opening part where the pattern does not remain, Used to obtain a transparent conductive film with excellent visibility.

The optical adjustment layer is formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material. As a material for forming the optical adjustment layer, NaF, Na3AlF6, LiF, MgF2, CaF2, SiO2, LaF3, CeF3, Al2O3, TiO2, Ta2O5, ZrO2, ZnO, ZnS, SiOx (x is 1.5 or more and less than 2), etc. And organic substances such as acrylic resin, urethane resin, melamine resin, alkyd resin, and siloxane polymer. In particular, it is preferable to use a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organic silane condensate as the organic substance. The optical adjustment layer can be formed using the above materials by a coating method such as a gravure coating method or a bar coating method, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the optical adjustment layer is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, and even more preferably 20 nm to 130 nm. If the thickness of the optical adjustment layer is too small, it is difficult to form a continuous film. On the other hand, when the thickness of the optical adjustment layer is excessively large, the transparency of the transparent conductive film tends to decrease, or cracks tend to occur in the optical adjustment layer.

The optical adjustment layer may have nanoparticles having an average particle diameter of 1 nm to 500 nm. The content of the nanoparticles in the optical adjustment layer is preferably 0.1% by weight to 90% by weight. As described above, the average particle diameter of the nanoparticles used in the optical adjustment layer is preferably in the range of 1 nm to 500 nm, and more preferably 5 nm to 300 nm. Further, the content of the nanoparticles in the optical adjustment layer is more preferably 10% by weight to 80% by weight, and further preferably 20% by weight to 70% by weight. By containing nanoparticles in the optical adjustment layer, the refractive index of the optical adjustment layer itself can be easily adjusted.

Examples of the inorganic oxide forming the nano fine particles include fine particles such as silicon oxide (silica), hollow nano silica, titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and niobium oxide. Among these, fine particles of silicon oxide (silica), titanium oxide, aluminum oxide, zinc oxide, tin oxide, zirconium oxide, and niobium oxide are preferable. These may be used alone or in combination of two or more.

[Polycycloolefin film]
The polycycloolefin film, which is a film substrate that supports the metal wiring layer, may be a single layer or multiple layers. The thickness of the polycycloolefin film is preferably 20 μm to 200 μm from the viewpoint of transparency and handleability.

The polycycloolefin film has a plurality of protrusions on both sides on which the metal wiring layer is formed. By providing a plurality of protrusions on the surface of the polycycloolefin film, the polycycloolefin film is provided with slipperiness and wear resistance, and the metal wiring layer is continuously formed while maintaining high quality. The film formation rate can be increased to improve productivity.

The protrusion has an outer diameter D exceeding 0 and not more than 3 μm, preferably 0.1 μm to 2 μm, in a plan view of the surface of the polycycloolefin film on which the metal wiring layer is formed. The outer diameter of the protrusion can be measured, for example, by observing an image of the surface on the side where the metal wiring layer of the polycycloolefin film is formed at a predetermined magnification. When the outer diameter D is 3 μm or less, it is possible to reliably prevent the metal wiring from being disconnected near the boundary between the surface of the polycycloolefin film and the surface of the protrusion.

The height of the protrusion is preferably more than 0 and 3 μm or less, more preferably 0.1 μm to 2 μm, based on the flat surface of the polycycloolefin film.

The shape of the protrusion is substantially dome-shaped in this embodiment, and the cross section in the plane direction of the polycycloolefin film is substantially circular, and the cross section in the thickness direction is substantially semicircular. However, the protrusions in the present invention can provide slipperiness and abrasion resistance to the polycycloolefin film, and can form a high-quality metal wiring layer continuously and at a high speed. Other shapes may be used.

Examples of means for providing protrusions on the polycycloolefin film include a method in which a lubricant is dispersed inside the polycycloolefin film, and a method in which a binder in which a plurality of particles are dispersed is applied to the film surface. .

Polycycloolefin film can be obtained from, for example, Nippon Zeon Co., Ltd.

(Metal wiring layer)
The metal wiring layer is formed in a pattern, for example, in a mesh shape to impart translucency. The mesh pattern of the metal wiring layer is not particularly limited, and is, for example, a square lattice, a rhombus lattice, or a polygonal lattice.

The material for forming the metal wiring layer is not limited as long as it has electrical conductivity, but is preferably silver, copper, or an alloy thereof, and more preferably copper.

The line width of the metal wiring layer is more than 5 μm and less than 8 μm, preferably more than 5.5 μm and 7 μm or less. If it is the range of such a line | wire width, the disconnection resulting from the protrusion of a film base material can be prevented. When the line width is 5 μm or less, the network pattern of the metal wiring layer becomes difficult to be visually recognized, but the frequency of the metal wiring breaks due to the protrusions of the film base, and the quality and reliability are high when mass-produced. Lower. On the other hand, when the line width is 8 μm or more, the mesh pattern of the metal wiring layer is remarkably visually recognized.

The thickness of the metal wiring layer is 0.1 μm or more and less than 0.5 μm, preferably more than 0.1 μm and 0.4 μm or less, and more preferably 0.15 μm to 0.35 μm. By reducing the thickness of the metal wiring layer to, for example, less than 2 μm, the mesh pattern is further prevented from being visually recognized. In such a configuration, when external light is incident on the touch sensor from an oblique direction, the side surface of the metal wiring layer does not shine and is difficult to be visually recognized.

The metal wiring layer is characterized in that it has a flat shape, and the ratio of the line width to the thickness (line width / thickness) is preferably 10 or more and less than 80, and more preferably 15-50. A touch sensor satisfying such a relationship is excellent in productivity, does not cause disconnection of the metal wiring, and is difficult to visually recognize the mesh pattern of the metal wiring layer.

Sectional area of the metal wiring layer, in order to obtain the electrical conductivity required for a touch panel sensor, preferably 0.5 [mu] m ² ~ 4 [mu] m ^2, more preferably from 0.5μm ^² ~ 3.2μm ^2, particularly preferably Is 0.5 μm ² to 2.5 μm ² .

The pitch interval of the metal wiring layers is preferably 200 μm to 800 μm, and more preferably 350 μm to 650 μm, in order to obtain sufficient translucency. The aperture ratio of the metal wiring layer is preferably 95% to 99%, more preferably 96% to 99%.

As a method of forming the metal wiring layer, for example, after forming a metal layer on the entire surface of the film substrate, a predetermined resist pattern (resist pattern) is stacked on the metal layer, and etching is performed. A method of removing the resist after removing the metal layer in the unnecessary region is used so that a network-like metal wiring layer is formed. The metal layer can be formed by, for example, a sputtering method, a plating method, or a combination thereof.

[Organic EL display device]
The organic EL display device of the present invention includes the above-described optical unit and an organic EL display panel, the optical unit is arranged on the viewing side with respect to the organic EL display panel, the optical unit is a transparent conductive film is polarized It arrange | positions so that it may be located between a film | membrane and an organic electroluminescence display panel.

Although it is optional, a window can be arranged on the viewing side with respect to the organic EL display device laminate.

FIG. 4 is a cross-sectional view showing one embodiment of an organic EL display device according to the present invention. The organic EL display device 100 includes an optical unit 110 and an organic EL display panel 101. An optical unit 110 is arranged on the viewing side with respect to the organic EL display panel 101.

Although it is optional, a transparent window 102 can be arranged on the viewing side with respect to the optical unit 110.

The optical unit 110 includes a transparent conductive film 116, a polarizing film 121, and a retardation film 123.

The polarizing film 121 is disposed on the side opposite to the transparent conductive film 116 with respect to the retardation film 123. In this case, the polarizing film 121 and the retardation film 123 constitute the polarizing functional laminate 120. The polarization functional laminate 120 generates, for example, circularly polarized light and compensates the viewing angle in order to prevent light incident on the inside from the viewing side of the polarizing film 121 from being internally reflected and emitted to the viewing side. It is for doing.

Although it is optional, a protective film can be adhered to one side or both sides of the polarizing film 121.

The optical unit 110 is disposed so that the transparent conductive film 116 is positioned between the polarizing film 121 and the organic EL display panel 101.

The transparent conductive film 116 includes a polycycloolefin film 115 and a transparent conductive layer 112.

The variation in the angle of the slow axis of the polycycloolefin film 115 is in the range of 4 °, and the in-plane retardation of the polycycloolefin film 115 measured with light having a wavelength of 550 nm at 23 ° C. is in the range of 3 to 8 nm. And the variation is in the range of 1.5 nm. The in-plane retardation of the retardation film 123 cancels out the in-plane retardation of the polycycloolefin film 115 so that the entire in-plane retardation of the retardation film 123 and the transparent conductive film 116 becomes a desired value. Has been.

In the present embodiment, the in-plane retardation of the retardation film 123 cancels out the in-plane retardation within a substantially constant range of 3 to 8 nm with almost no variation of the polycycloolefin film 115, and the retardation film 123. Since the in-plane retardation of the entire transparent conductive film 116 is set to about ¼ wavelength, the reflected hue is good.

Although optional, the retardation film 123 includes a ¼ wavelength retardation film, and the desired value is about ¼ wavelength.

Although optional, the retardation film 123 includes a viewing angle compensation retardation film and a quarter-wave retardation film in order from the transparent conductive film 116 side, and the desired value is about ¼ wavelength.

Although optional, the direction of the slow axis of the quarter-wave retardation film is within a range of ± 3 ° with respect to the direction of the slow axis of the polycycloolefin film 115. With such a configuration, the in-plane retardation of the polycycloolefin film 115 can be easily canceled by the retardation film 123, and the reflectance of light incident from the surface on the polarizing film side of the optical unit is reduced. be able to.

Although it is optional, the direction of the slow axis of the quarter-wave retardation film is in the range of 90 ° ± 3 ° with respect to the direction of the slow axis of the polycycloolefin film 115. Therefore, the in-plane retardation of the polycycloolefin film 115 can be easily canceled by the retardation film 123, and the reflectance of light incident from the surface on the polarizing film side of the optical unit can be reduced.

A transparent conductive film comprising the polycycloolefin film of the present invention and a transparent conductive layer and a method for producing the same, a roll of a laminate comprising such a transparent conductive film, an optical unit comprising such a transparent conductive film and its A manufacturing method and an organic EL display device including such an optical unit will be further described using the following examples. In addition, the transparent conductive film containing the polycycloolefin film of this invention and a transparent conductive layer, its manufacturing method, the roll of the laminated body containing such a transparent conductive film, and the optical unit containing such a transparent conductive film And the manufacturing method and the organic EL display device including such an optical unit are not limited only to these examples.

[Example A1]
[Transparent conductive film]
(Formation of cured resin layer)
Acrylic spherical particles (trade name, manufactured by Soken Chemical Co., Ltd.) having 100 parts by weight of an ultraviolet curable resin composition (trade name “UNIDIC (registered trademark) RS29-120” manufactured by DIC) and a mode particle diameter of 1.9 μm. A curable resin composition containing spherical particles containing 0.002 part by weight of “MX-180TA”) was prepared. The prepared spherical particle-containing curable resin composition is applied to one surface of a long polycycloolefin film having a thickness of 50 μm and a width of 1550 mm (trade name “ZEONOR (registered trademark)” manufactured by Nippon Zeon Co., Ltd.). Formed.

Next, the coating layer was irradiated with ultraviolet rays from the side on which the coating layer was formed, and a second cured resin layer was formed so as to have a thickness of 1.0 μm. A first cured resin layer was formed on the other surface of the polycycloolefin film by the same method as described above except that spherical particles were not included so that the thickness became 1.0 μm.

Further, an organic-inorganic hybrid resin (trade name: OPSTAR Z7412 (registered trademark, manufactured by JSR Corporation) composed of zirconium oxide particles having an average particle diameter of 30 nm and an acrylic resin binder as an optical adjustment layer on the first cured resin layer. ), Solid content: 20%, solvent: 80%) to form a base laminate, and a roll of the base laminate wound in a roll shape was produced.

(Heating process)
Next, the roll-to-roll method is used to roll up the obtained substrate laminate from the roll of the substrate laminate into an air circulation oven and wind it up at 150 ° C. for 3 minutes while winding it with a take-up roll. The process was implemented and the roll of the base material laminated body which was wound by roll shape and was heat-up processed was produced.

(Formation of transparent conductive layer)
Next, the obtained base material laminate fed out from the roll of the base material laminate that has been heated and rolled up is put into a take-up type sputtering device, and the surface of the first cured resin layer has a thickness of 27 nm. A crystalline indium tin oxide layer was formed. Thereafter, the polycycloolefin film on which the amorphous layer of indium / tin oxide is formed is put into an air circulation oven by a roll-to-roll method, and subjected to a heat treatment at 130 ° C. for 90 minutes to obtain a transparent conductive layer. Was converted from amorphous to crystalline to form a transparent conductive film having a transparent conductive layer having a surface resistance of 100 Ω / □, and a roll of transparent conductive film wound into a roll was produced.

[Retardation film]
Polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. 9,9- [4- (2-hydroxyethoxy) phenyl] fluorene (BHEPF), isosorbide (ISB), diethylene glycol (DEG), diphenyl carbonate (DPC), and magnesium acetate tetrahydrate in a molar ratio of BHEPF / ISB / DEG / DPC / magnesium acetate = 0.438 / 0.537 / 0.025 / 1.005 / 1.00 × 10 ⁻⁵ . After sufficiently replacing the inside of the reactor with nitrogen (oxygen concentration 0.0005 to 0.001 vol%), heating was performed with a heating medium, and stirring was started when the internal temperature reached 100 ° C. After 40 minutes from the start of temperature increase, the internal temperature was reached to 220 ° C., and control was performed so as to maintain this temperature. The phenol vapor produced as a by-product with the polymerization reaction was led to a reflux condenser at 100 ° C., and a monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the phenol vapor not condensed was led to a condenser at 45 ° C. and recovered.

Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Subsequently, the temperature increase and pressure reduction in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Thereafter, polymerization was allowed to proceed until a predetermined stirring power was obtained. When a predetermined power is reached, nitrogen is introduced into the reactor, the pressure is restored, the reaction solution is withdrawn in the form of strands, pelletized with a rotary cutter, and BHEPF / ISB / DEG = 43.8 / 53.7 / A polycarbonate resin A having a copolymer composition of 2.5 [mol%] was obtained. This polycarbonate resin had a reduced viscosity of 0.430 dL / g and a glass transition temperature of 145 ° C.

The obtained polycarbonate resin was vacuum-dried at 80 ° C. for 5 hours, and then a single screw extruder (manufactured by Isuzu Chemical Industries, screw diameter 25 mm, cylinder setting temperature: 240 ° C.), T-die (width 900 mm, setting temperature: 240). ° C), a chill roll (set temperature: 120 to 130 ° C), and a film forming apparatus equipped with a winder, a 150 μm thick polycarbonate resin film was produced.

A sample having a width of 250 mm and a length of 250 mm was cut out from the polycarbonate resin film obtained as described above. Then, this sample was stretched uniaxially at a fixed end at a stretching temperature of 145.6 ° C. and a stretching ratio of 2.4 times with a batch type biaxial stretching apparatus (Browner Co., Ltd., trade name “KARO-IV”), and a thickness of 70 μm. A retardation film was prepared.

[Polarizing film]
A long polyvinyl alcohol film is immersed in the following five baths [1] to [5] through a plurality of sets of rolls having different peripheral speeds while sequentially applying tension in the longitudinal direction of the film, and the final draw ratio is the film. The original length was stretched to 6.0 times. This film was dried in an oven at 50 ° C. for 4 minutes to obtain a polarizing film having a thickness of 12 μm.
[1] Swelling bath: pure water at 30 ° C. [2] Dyeing bath: iodine concentration within the range of 0.02 to 0.2% by weight and potassium iodide concentration of 0.14 to 100 parts by weight of water It was made into the range of 1.4 weight%. The concentration ratio of iodine and potassium iodide is 1 to 7. The film was immersed in an aqueous solution containing 30 ° C. for an arbitrary time so that the final transmittance of the polarizing film was 41 to 47%.
[3] First crosslinking bath: 40 ° C. aqueous solution containing 3% by weight of potassium iodide and 3% by weight of boric acid.
[4] Second crosslinking bath: 60 ° C. aqueous solution containing 5% by weight of potassium iodide and 4% by weight of boric acid.
[5] Washing bath: 25 ° C. aqueous solution containing 3% by weight of potassium iodide

[Polarized functional laminate]
Hard-coated triacetylcellulose protective film (Konica Minolta, trade name “KC2UA”, thickness 25 μm), hard-coated triacetylcellulose protective film (Konica Minolta, Konica Minolta) Product name “KC2UA”, thickness 25 μm) was prepared. The polarizing film and retardation film obtained as described above were cut out to 150 mm × 300 mm, respectively. The retardation film was cut out so that the slow axis forms an angle of 45 ° with respect to the short side or the long side. And said 2 protective film was bonded together on both surfaces of the polarizing film through the polyvinyl alcohol-type adhesive agent, respectively. Further, the slow axis of the retardation film and the absorption axis of the polarizing film form an angle of 45 ° on the side of the protective film on which the protective film is attached to both sides of the polarizing film and the surface treatment is not performed. The retardation film was bonded through an acrylic pressure-sensitive adhesive layer. Next, the produced polarizing functional laminate was trimmed to a size of 70 mm × 120 mm to produce a polarizing functional laminate that functions as a circularly polarizing plate.

[Optical unit]
A 70 mm × 120 mm transparent conductive film was cut out from the long transparent conductive film obtained as described above. At that time, the transparent conductive film is such that the center point of the transparent conductive film substantially coincides with the center in the width direction of the long transparent conductive film and the longitudinal direction is parallel to the MD direction. Was cut out. The surface of the cut out transparent conductive film on the side of the transparent conductive layer and the surface of the polarizing functional laminate obtained as described above on the side of the retardation film, the direction of the slow axis of the retardation film and the transparent conductivity The optical unit was produced by bonding together with an acrylic pressure-sensitive adhesive layer so that the MD direction of the film was parallel.

The substrate laminate, the retardation film, and the optical unit obtained after the heating and winding process were subjected to various evaluations as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A2]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end in the width direction of the long transparent conductive film, the conditions were the same as in Example A1. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A3]
The same as Example A1 except that the temperature of the heating and winding process was set to 140 ° C. and that the stretching temperature of the retardation film was set to 145.4 ° C. in order to obtain a retardation film having a different in-plane retardation. Under the conditions, a substrate laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows.
Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A4]
Except for the point where the transparent conductive film was cut out so that the center point of the transparent conductive film was positioned at about 50 mm from the end in the width direction of the long transparent conductive film, the conditions were the same as in Example A3. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A5]
The same as Example A1 except that the temperature of the heating and winding process was set to 145 ° C. and that the stretching temperature of the retardation film was set to 145.4 ° C. in order to obtain a retardation film having a different in-plane retardation. Under the conditions, a substrate laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A6]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end in the width direction of the long transparent conductive film, the same conditions as in Example A5 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A7]
Except for the point that the temperature of the heating and winding process was 155 ° C., a substrate laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Example A1, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A8]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was located at a position of about 50 mm from the end in the width direction of the long transparent conductive film, the same conditions as in Example A7 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A9]
Except for the point where the transparent conductive film was cut out so that the center point of the transparent conductive film was located at a position of about 100 mm from the end in the width direction of the long transparent conductive film, the conditions were the same as in Example A1. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A10]
In the production of the optical unit, except that the transparent conductive film and the polarizing functional laminate are bonded so that the slow axis direction of the retardation film and the MD direction of the transparent conductive film form an angle of 3 °, A base material laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Example A1, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A11]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end of the long transparent conductive film in the width direction, the same conditions as in Example A10 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A12]
In the production of the optical unit, the surface where the transparent conductive film and the polarizing functional laminate are bonded so that the slow axis direction of the retardation film and the MD direction of the transparent conductive film form an angle of 90 °; In order to obtain a retardation film having different internal retardation, the substrate laminate, the retardation film, and the optical unit were prepared under the same conditions as in Example A1, except that the stretching temperature of the retardation film was 146.1 ° C. Manufacture and production were performed, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example A13]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was located at a position of about 50 mm from the end of the long transparent conductive film in the width direction, the same conditions as in Example A12 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example B1]
In order to obtain a retardation film having a different in-plane retardation from the point that a lot different from Example A1 was used as the long polycycloolefin film used for the production of the transparent conductive film, the retardation film A base laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Example A1 except that the stretching temperature was 146.1 ° C., and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example B2]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end in the width direction of the long transparent conductive film, the base was the same as in Example B1. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example B3]
Except for the point that the temperature of the heating and winding process was 140 ° C., a substrate laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Example B1, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example B4]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end in the width direction of the long transparent conductive film, the conditions were the same as in Example B3. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Example C]
A base laminate is manufactured under the same conditions as in Example A1, except that the long polycycloolefin film used for manufacturing the base laminate is a different lot from Examples A1 and B1. And the heat hoisting process was performed, and various evaluations before and after the heat hoisting process were performed as follows. The characteristics of the substrate laminate before and after the heating and winding process are shown in FIGS.

[Comparative Example A1]
A transparent conductive film, a retardation film, and an optical unit are manufactured and produced under the same conditions as in Example A1, except that the heating and winding process is not performed and the stretching temperature of the retardation film is 145.0 ° C. Various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Comparative Example A2]
Except for the point where the transparent conductive film was cut out so that the center point of the transparent conductive film was located at a position of about 50 mm from the end in the width direction of the long transparent conductive film, the conditions were the same as in Comparative Example A1. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Comparative Example A3]
Except for the point that the temperature of the heating and winding process was 130 ° C., a substrate laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Comparative Example A1, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example A4]
Except for the point where the transparent conductive film was cut out so that the center point of the transparent conductive film was located at a position of about 50 mm from the end of the long transparent conductive film in the width direction, the same conditions as in Comparative Example A3 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example A5]
In the production of the optical unit, except that the transparent conductive film and the polarizing functional laminate are bonded together so that the slow axis direction of the retardation film and the MD direction of the transparent conductive film form an angle of 5 °, A base material laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Example A1, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example A6]
Except that the transparent conductive film was cut out so that the center point of the transparent conductive film was about 50 mm from the end of the long transparent conductive film in the width direction, the same conditions as in Comparative Example A5 were used. A material laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example B1]
Manufacture and manufacture a transparent conductive film, retardation film, and optical unit under the same conditions as in Example B1 except that the heating and winding process is not performed and the stretching temperature of the retardation film is 145.0 ° C. Various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Comparative Example B2]
Except for the point where the transparent conductive film is cut out so that the center point of the transparent conductive film is about 50 mm from the widthwise end of the long transparent conductive film, it functions under the same conditions as in Comparative Example B1 A laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Comparative Example B3]
A functional laminate, a retardation film, and an optical unit were manufactured and produced under the same conditions as in Comparative Example B1, except that the heating and winding process was performed at 150 ° C. as in Examples B1 and B2. Evaluation was performed. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example B4]
A functional laminate, a retardation film, and an optical unit were produced and produced under the same conditions as in Examples B1 to B4 except that the temperature of the heating and winding process was 130 ° C., and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example B5]
Except for the point where the transparent conductive film is cut out so that the center point of the transparent conductive film is about 50 mm from the widthwise end of the long transparent conductive film, it functions under the same conditions as in Comparative Example B4 A laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Comparative Example B6]
The same as Comparative Example B1 except that the temperature of the heating roll-up treatment was 165 ° C. and that the stretching temperature of the retardation film was 146.4 ° C. in order to obtain a retardation film having a different in-plane retardation. A functional laminate, a retardation film, and an optical unit were manufactured and produced under conditions, and various evaluations were performed as follows. Table 1 shows the characteristics of the obtained substrate laminate, retardation film, and optical unit after the heating and winding process.

[Comparative Example B7]
Except for the point where the transparent conductive film is cut out so that the center point of the transparent conductive film is about 50 mm from the widthwise end of the long transparent conductive film, it functions under the same conditions as in Comparative Example B6 A laminate, a retardation film, and an optical unit were manufactured and produced, and various evaluations were performed as follows. Table 1 shows the properties of the obtained substrate laminate, retardation film, and optical unit.

[Evaluation]
(Measurement of thickness)
The thickness of the polarizing film, the retardation film, and the protective film was measured using a dial gauge (manufactured by Mitutoyo Corporation).

(Measurement of in-plane phase difference and slow axis direction)
The in-plane retardation and slow axis direction of the substrate laminate and the in-plane retardation of the retardation film were measured in a 23 ° C. room using [Axometrics product name “AxoScan”]. Here, in the measurement of the in-plane retardation and the slow axis direction of the obtained substrate laminate, the influence of the first and second cured resin layers and the optical adjustment layer in the substrate laminate can be ignored. The measured in-plane retardation and slow axis direction of the substrate laminate can be regarded as the in-plane retardation and slow axis direction of the polycycloolefin film. For the base material laminates of Examples A1 to A4, B1 to B2, and Comparative Examples A1 to A4 and B1 to B3, the obtained long base material laminates were cut into a size of 70 mm × 120 mm. Cut out so that the center point of the cut base laminate is 50 mm from the center or end in the width direction of the long base laminate, and the longitudinal direction is parallel to the MD direction. A sample was prepared. And the direction with respect to the slow axis of a base-material laminated body measured the angle with respect to the longitudinal direction of a sample, ie, MD direction. Moreover, about the base-material laminated body of Example C, the base material laminated body of the roll of the obtained base material laminated body before the heating roll-up process and the obtained base material of the roll of the base-material laminated body which was heat-rolled-up processed With respect to the laminate, the in-plane phase difference and the direction of the slow axis were measured at intervals of 50 nm from the end in the width direction without cutting out.

(Measurement of reflectance and hue of optical unit)
Sample obtained by attaching a reflective plate (product name “Therapy DMS-X42” manufactured by Toray Film Processing Co., Ltd.) with aluminum deposited on PET using acrylic adhesive (thickness: 23 μm) on the transparent conductive film side of the obtained optical unit It was. Reflectance and reflection hue (a *, b *) near the center point of the surface of the optical unit on the polarizing film side, reflection spectral spectrum is spectrocolorimeter [product name “CM-2600d” manufactured by Konica Minolta Sensing Co., Ltd.] ] Was measured in a room at 23 ° C. The light source used was a value of D65, and was measured by an SCI (Specular Component Included) method (including specular reflection light).

Table 1 shows the measurement results. Moreover, the change of the direction of the slow axis before and behind the heating winding process over the width direction of the polycycloolefin film of Example C, and the change of a phase difference are shown to FIG. Here, as described above, in the measurement of the in-plane retardation and the direction of the slow axis of the obtained substrate laminate, the first and second cured resin layers and the optical adjustment layer in the substrate laminate were measured. Since the influence is negligible, the measured in-plane retardation and slow axis direction of the substrate laminate can be regarded as the in-plane retardation and slow axis direction of the polycycloolefin film. 7A and 7B show the measurement results of the reflection hues of Examples A1 to A13 and Comparative Examples A1 to A6, Examples B1 to B4, and Comparative Examples B1 to B7. 7A and 7B, the reflection hue (a *, b *) = (− 0.59, −2.15) of the retardation film used in the comparative example is shown as a target value. Moreover, the measurement result of the reflectance of Examples A10 and A11 and Comparative Examples A5 and A6 is shown in FIG.

(Evaluation)
The following was found from FIG. The in-plane retardation increased from the center to the end in the width direction of the polycycloolefin film before the heating and winding process. The minimum value of the in-plane retardation was 1.30 nm, and the maximum value was 2.86 nm. On the other hand, in the polycycloolefin film after the heat winding process, the in-plane retardation value increases to 3.99 nm and the maximum value to 5.11 nm across the width direction. The variation in the in-plane retardation was suppressed from 1.55 nm before the heating winding process to 1.12 nm.

Moreover, although the direction of the slow axis is parallel to the MD direction in the central part in the width direction of the polycycloolefin film before the heating and winding process, the slow axis with respect to the MD direction is increased from the central part to the end part in the width direction. The deviation of the direction of became larger. The direction of the slow axis with respect to the MD direction was an angle range of −7.27 to + 7.08 °, and greatly exceeded the angle range of ± 2 °. On the other hand, in the polycycloolefin film after the heat hoisting treatment, the direction of the slow axis with respect to the MD direction is an angle range of −1.26 to + 0.67 °, and ± 1, 5 ° with respect to the MD direction. It was within the angle range. That is, by the heating and winding process, the direction of the slow axis of the polycycloolefin film was aligned with the MD direction, and variations in the direction of the slow axis could be suppressed.

Table 1 shows the following. In Examples A1 to A9 and B1 to B4, the slow axis direction of the polycycloolefin film is in the range of ± 2 ° with respect to the MD direction of the transparent conductive film, and is almost aligned in the MD direction. In Comparative Examples A2, A4, B2, and B5 where the ends were cut off, the direction of the slow axis of the polycycloolefin film with respect to the MD direction of the transparent conductive film was 2.7 ° or more and exceeded ± 2 °. That is, in the polycycloolefin film of each example, the direction of the slow axis was aligned with the MD direction, and variation in the direction of the slow axis could be suppressed.

And in Examples A2, A4, A6, A8 and Comparative Example A4, Examples B2, B4 and Comparative Example B5, the temperature of the heating and winding process is 165 ° C. which is the glass transition temperature (Tg) of the polycycloolefin film. As it approached, it was found that the direction of the slow axis was closer to the MD direction, and variations in the direction of the slow axis were suppressed.

In Comparative Examples B6 and B7, the in-plane retardation of the polycycloolefin film was 9.5 nm or more. That is, when the temperature of the heat hoisting treatment reached 165 ° C., which is the Tg of the polycycloolefin film, the in-plane retardation of the polycycloolefin film exceeded 8 nm.

Accordingly, the temperature of the heat hoisting process is 140 to 155 ° C. in Examples A1 to A9 and B1 to B4, 130 ° C. in Comparative Examples A4 and B5, and 165 ° C. in Comparative Examples B6 and B7. From the above, it was found that the temperature of the heat hoisting treatment is preferably 140 to 160 ° C, more preferably 145 to 155 ° C, and even more preferably 148 to 153 ° C.

Further, the in-plane retardation of the polycycloolein films of Examples A1 to A9 and B1 to B4 is the in-plane position of Comparative Examples A1 to A4 and B1 to B2 of the long polycycloolefin film without heating and winding up processing. Although larger than the phase difference, in each of Examples A1, A2 and A9, Examples A3 and A4, Examples A5 and A6, Examples A7 and A8, Examples B1 and B2, and Examples B3 and B4 The variation in the in-plane retardation of the long polycycloolefin film was within a range of 1 nm and the in-plane retardation was almost constant regardless of the position in the polycycloolefin film.

As can be seen from FIGS. 7A and 7B, the reflection hues of Examples A1 to A9, A12 to A13, and B1 to B4 are close to the reflection hues of the target values, and Examples A2, A4 and A9, The reflection hue of Example B2 was close to the reflection hue of the target value compared to the reflection hues of Comparative Examples A2 and A4 and Comparative Examples B2, B5, and B7. In addition, the reflection hues of Examples B1 to B4 are closer to the reflection hue of the target value than the reflection hue of Comparative Example B3.

That is, in the optical unit of each example, the in-plane retardation of the polycycloolefin film is increased by the heating and winding process, but the slow axis direction of the polycycloolefin film is aligned in the MD direction, and the in-plane retardation is It was almost constant regardless of the position in the polycycloolefin film. And, the in-plane retardation of the retardation film cancels out the almost constant in-plane retardation with little variation of the polycycloolefin film, and the entire in-plane retardation of the retardation film and the transparent conductive film is Since the wavelength was about ¼, the reflection hue of the optical unit was good.

In addition, considering that light is incident on the polarizing film itself from the air and that the reflectance is about 5% on the surface of the polarizing film, as shown in FIG. 8, the position of the transparent conductive film relative to the MD direction can be seen. Reflection of optical units of Examples A10 and A11 in which the direction of the slow axis of the retardation film is 3 ° (the direction of the slow axis of the retardation film is 3 °, 3.5 ° with respect to the slow axis of the polycycloolefin film) The rate is 5 ° in the direction of the slow axis of the retardation film with respect to the MD direction of the transparent conductive film (5 °, 5.5 ° in the direction of the slow axis of the retardation film with respect to the slow axis of the polycycloolefin film). It can be seen that the reflectances of the comparative examples A5 and A6 in FIG. The reflectances of Examples A1 to A9, A12 to A13, and B1 to B4 in which the direction of the slow axis of the retardation film with respect to the MD direction of the transparent conductive film is 0 ° or 90 ° are higher than those of Examples A10 and A11. Since it was small, in the optical unit of each Example, the reflectance could be suppressed.

As mentioned above, although this invention was demonstrated with reference to drawings about specific embodiment, many changes are possible for this invention besides the structure shown and described. Therefore, the present invention is not limited to the configurations shown and described, and the scope should be defined only by the appended claims and their equivalents.

DESCRIPTION OF SYMBOLS 1 Base material laminated body 10 Polycycloolefin film 11 1st cured resin layer 12 2nd cured resin layer 12a (The 2nd cured resin layer surface) convex part 13 Transparent conductive layer 14 Spherical particle 16 Optical adjustment layer S1 (Polycycloolefin First main surface S2 (of the film) Second main surface (of the polycycloolefin film) w Most frequent particle diameter of spherical field particles d Binder resin layer thickness 100 Organic EL display device 101 Organic EL display panel 102 Window 110 Optical unit 112 Transparent Conductive layer 115 Polycycloolefin film 116 Transparent conductive film 120 Polarizing functional laminate 121 Polarizing film 123 Phase difference film 900 Organic EL display device 901 Organic EL display panels 912-1 and 912-2 Pattern electrode 915 Dielectric layer 920 Polarizing function Laminated body 921 Polarizing film 923 Retardation layer

Claims

It is a roll of a laminate in which the long body of the laminate is wound in a roll shape,
The laminate includes a transparent conductive film including a polycycloolefin film and a transparent conductive layer,
The slow axis direction of the polycycloolefin film is relative to the longitudinal direction of the long body of the laminate, except for the ends on both sides of the width of 5% with respect to the full width of the long body of the laminate. Roll within the range of ± 2 °.
A transparent conductive film comprising a polycycloolefin film and a transparent conductive layer;
Retardation film,
Including
The variation in the direction of the slow axis of the polycycloolefin film is within an angular range of 4 °,
The in-plane retardation of the polycycloolefin film measured with light having a wavelength of 550 nm at 23 ° C. is in the range of 3 to 8 nm, and the variation thereof is in the range of 1.5 nm.
The in-plane retardation of the retardation film cancels out the in-plane retardation of the polycycloolefin film so that the entire in-plane retardation of the retardation film and the transparent conductive film becomes a desired value. Optical unit.
3. The optical unit according to claim 2, wherein the retardation film includes a ¼ wavelength retardation film, and the desired value is about ¼ wavelength.
The retardation film includes a viewing angle compensation retardation film and a quarter-wave retardation film in order from the transparent conductive film side, and the desired value is about ¼ wavelength. Optical unit.
5. The optical unit according to claim 3, wherein a direction of a slow axis of the ¼ wavelength retardation film is in a range of 0 ° ± 3 ° with respect to a direction of a slow axis of the polycycloolefin film. .
5. The optical unit according to claim 3, wherein a direction of a slow axis of the ¼ wavelength retardation film is in a range of 90 ° ± 3 ° with respect to a direction of a slow axis of the polycycloolefin film. .
The optical unit according to any one of claims 2 to 6, wherein the transparent conductive layer is made of indium tin oxide (ITO).
The optical unit further includes a polarization functional laminate,
The polarizing functional laminate includes a polarizing film and the retardation film,
The retardation film is disposed on the transparent conductive layer side of the transparent conductive film,
The optical unit according to any one of claims 2 to 7, wherein the polarizing film is disposed on the side opposite to the transparent conductive film with respect to the retardation film.
The optical unit according to claim 8, wherein the polarization functional laminate has a function of generating circularly polarized light.
An optical unit according to claim 9,
An organic EL display panel;
Including
The optical unit is disposed on the viewing side with respect to the organic EL display panel,
The organic EL display device in which the optical unit is disposed such that the transparent conductive film is positioned between the polarizing film and the organic EL display panel.
Paying out the polycycloolefin film from the roll of the polycycloolefin film in which the long body of the polycycloolefin film is wound in a roll;
A step of heating and winding the unrolled polycycloolefin film at a heating temperature of 140 to 160 ° C. while winding it with a winding roll;
Forming a transparent conductive layer on the heat-rolled polycycloolefin film to produce a transparent conductive film;
The manufacturing method of the transparent conductive film containing this.
The method for producing a transparent conductive film according to claim 11, wherein the heating temperature is 145 to 155 ° C.
The method for producing a transparent conductive film according to claim 11, wherein the heating temperature is 148 to 153 ° C.
A method for producing the optical unit according to claim 8, wherein the polarizing functional laminate and the transparent conductive film produced by the production method according to any one of claims 11 to 13 are bonded together to form the optical unit. An optical unit manufacturing method for generating a unit.