KR20190105586A - Film laminate for touch panel - Google Patents

Abstract

The present invention provides a technique for preventing cracks in the conductive layer even when the conductive layer is directly formed on the film that can be deformed under a high temperature and high humidity environment. The film laminated body for touch panels of this invention is a film laminated body for touch panels provided with the film base material with an electrically conductive layer, and the low moisture permeability base material laminated | stacked on one side of the film base material with an electrically conductive layer, The film base material with an electrically conductive layer is It has a film base material containing a resin film, and the conductive layer directly provided in at least one surface of the said film base material, and the water vapor transmission rate at 40 degreeC and 92% RH of this low moisture-permeable base material is 1.0 g / (m <^2> day) or less. .

Description

Film laminate for touch panel

The present invention relates to a film laminate for touch panels.

In recent years, smart devices represented by smart phones, and also display devices such as digital signage, window displays, and the like, have increased in use under strong external light. As a result, problems such as reflection of external light and reflection of the background by a touch panel part used in the display device itself or the display device, a glass substrate, a metal wiring, or the like have arisen. In particular, the organic electroluminescent (EL) display device, which has been put to practical use in recent years, has a highly reflective metal layer, which tends to cause problems such as reflection of external light and reflection of the background. In view of this, it is known to prevent these problems by providing a circularly polarizing plate having a retardation film (typically? / 4 plate) on the viewing side as an antireflection film.

Also, as represented by smartphones in recent years, there has been a surge in touch panel input display devices in which the image display device also serves as a touch panel input device. In particular, a so-called inner touch panel type input display device in which a touch sensor is incorporated between a display cell (eg, a liquid crystal cell, an organic EL cell) and a polarizing plate has been put into practical use. In such an inner touch panel type input display device, a transparent conductive layer functioning as a touch panel electrode is formed on an isotropic substrate, and is introduced by being laminated on a retardation film (typically λ / 4 plate) as a conductive layer with an isotropic substrate. . Although it is preferable to form a transparent conductive layer directly in a retardation film from a thinning viewpoint of a display apparatus, the optical characteristic of a retardation film is large from the desired characteristic in the high temperature environment in sputtering at the time of forming a transparent conductive layer, and post-processing. It is because the base material for sputtering must be used because it will come out.

Japanese Laid-Open Patent Publication No. 2005-189645 Japanese Laid-Open Patent Publication No. 2006-171235

In response to the above demands, a technique has been developed in which a transparent conductive layer is directly formed on a retardation film (laminated without interposing an adhesive layer). However, according to the studies by the present inventors, when the transparent conductive layer is directly formed on the retardation film, the retardation film is deformed (for example, the retardation film whose orientation is controlled by stretching is contracted or expanded) under high temperature and high humidity environment, while the transparent conductive It can be seen that there is a problem of environmental durability that the layer does not follow the deformation and cracks occur (eg, FIG. 5).

The present invention has been made to solve the above problems, and its object is to provide a technique for preventing cracks in the conductive layer even when the conductive layer is directly formed on the film that can be deformed under high temperature and high humidity environment. will be.

According to this invention, the film laminated body for touch panels provided with the film base material with an electrically conductive layer and the low moisture-permeable base material laminated | stacked on one side of the said film base material with an electrically conductive layer is provided. In the film laminated body for touch panels of this invention, the said film base material with a conductive layer has a film base material containing a resin film, and the conductive layer directly provided in at least one surface of the said film base material, and 40 degreeC of the said low moisture-permeable base material , 92% RH, and the water vapor transmission rate is 1.0 g / (m ² · day) or less.

In one embodiment, the said low moisture-permeable base material is equipped with a support base material and the inorganic thin film provided in the one side of this support base material.

In one embodiment, the said inorganic thin film contains at least 1 sort (s) of inorganic compound chosen from the group which consists of an oxide, nitride, hydride, and its composite compound.

In one embodiment, the said film base material is 85 degreeC and 85% R.H. Shrink in at least one direction under the environment.

In one embodiment, the in-plane phase difference Re (550) of the said resin film is 100 nm-180 nm.

In one embodiment, the said film base material further contains the functional layer provided in at least one surface of the said resin film, and the said conductive layer is provided directly on the said functional layer of the said film base material.

In one embodiment, the said film laminated body further contains a polarizing plate.

In one embodiment, the said polarizing plate, the said film base material with a conductive layer, and the said low moisture-permeable base material are laminated | stacked in this order from the visual recognition side through an adhesive layer.

In one embodiment, 40 degreeC of either or both of the contact bonding layer interposed between the said polarizing plate and the said film base material with a conductive layer, and the contact bonding layer interposed between the said film film with a conductive layer and the said low moisture-permeable base material. , 92% RH is less than 100g / (m ^{2 ·} day).

In one embodiment, the said polarizing plate contains a polarizer and retardation film.

 According to this invention, a crack can be prevented from generate | occur | producing in a conductive layer by controlling the water vapor transmission rate of the peripheral member of the film base material with a conductive layer in which the conductive layer was directly formed in the film base material.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic sectional drawing of the film laminated body for touch panels in one Embodiment of this invention.
It is a schematic sectional drawing of the film laminated body for touch panels in other embodiment of this invention.
It is a schematic sectional drawing of the film laminated body for touch panels in another embodiment of this invention.
It is a schematic sectional drawing of the film laminated body for touch panels in another embodiment of this invention.
(A) is a micrograph of the cleavage type crack of the conductive layer resulting from expansion of a film, (b) is a micrograph of the buckling type crack of the conductive layer resulting from shrinkage of a film to be.

EMBODIMENT OF THE INVENTION Hereinafter, although preferred embodiment of this invention is described, this invention is not limited to these embodiment.

(Definitions of terms and symbols)

Definitions of terms and symbols in the present specification are as follows.

(1) refractive index (nx, ny, nz)

'nx' is the refractive index of the direction in which the in-plane refractive index is maximum (that is, the slow axis direction), 'ny' is the refractive index of the direction orthogonal to the slow axis in the plane (ie, the fast axis direction), and 'nz' is Refractive index in the thickness direction.

(2) In-plane phase difference (Re)

"Re ((lambda))" is an in-plane retardation of the film measured with light having a wavelength of λ nm at 23 ° C. For example, 'Re (450)' is an in-plane retardation of a film measured with light having a wavelength of 450 nm at 23 ° C. Re ((lambda)) is calculated | required by Formula: Re = (nx-ny) xd, when making thickness of a film d (nm).

(3) phase difference (Rth) in thickness direction

"Rth ((lambda))" is a phase difference of the thickness direction of the film measured with the light of wavelength (lambda) nm at 23 degreeC. For example, "Rth (450)" is a phase difference in the thickness direction of the film measured with the light of wavelength 450nm at 23 degreeC. Rth (λ) is obtained by the formula: Rth = (nx−nz) × d when the film thickness is d (nm).

(4) Nz coefficient

Nz coefficient is calculated | required by Nz = Rth / Re.

(5) angle

When referring to angles herein, unless otherwise specified, the angles include angles in both clockwise and counterclockwise directions.

A. Overall structure of the film laminated body for touch panels

1-4 is schematic sectional drawing of the film laminated body for touch panels by one Embodiment of this invention (Hereinafter, it may only be called a "film laminated body."). The film laminated body 100a shown in FIG. 1 is the film base material 10 with the conductive layer 12 which has the film base material 11 and the conductive layer 12 directly provided in the one surface, and the electroconductivity of the film base material 10 with a conductive layer. The low moisture-permeable base material 20 laminated | stacked through the adhesive layer 30 on the surface of the layer 12 side is provided. The low moisture-permeable base material 20 includes a support base material 21 and an inorganic thin film 22 provided on one side of the support base material 21. The film laminated body 100b shown in FIG. 2 is the film base material 10 with a conductive layer which has the film base material 11 and the conductive layer 12 directly provided in the one surface, and the film of the film base material 10 with a conductive layer. The low moisture-permeable base material 20 laminated | stacked on the surface by the side of the base material 11 via the adhesive layer 30 is provided. The film laminated body 100c shown in FIG. 3 consists of the film base material 10 with a conductive layer which has the film base material 11 and the conductive layers 12a and 12b directly provided on both surfaces, and the film base material 10 with a conductive layer. The low moisture-permeable base material 20 laminated | stacked on the surface by the side of the conductive layer 12a via the adhesive layer 30 is provided. In these embodiments, the film base material 11 is comprised by the resin film 13 which may be a retardation film. In addition, although not shown in figure, you may interpose an anchor coat layer between the support base material 21 and the inorganic thin film 22 of the low moisture-permeable base material 20 as needed.

The film laminated body of this invention may further contain the polarizing plate which is an arbitrary component. For example, the film laminate 100d shown in FIG. 4 further includes a polarizing plate 40. The polarizing plate 40 is laminated | stacked on the visual recognition side of the film base material 10 with a conductive layer through the contact bonding layer 30b. That is, in the film laminated body 100d, the polarizing plate 40, the contact bonding layer 30b, the film base material 10 with a conductive layer, the contact bonding layer 30a, and the low moisture permeability base material 20 are laminated | stacked in this order from the visual recognition side. . In this embodiment, the film base material 11 is comprised by the resin film 13 which may be a retardation film, and the functional layer 14 provided in the surface of the display cell (for example, liquid crystal cell, organic electroluminescent cell) side, The conductive layer 12 is directly provided on the surface of the functional layer 14 side of the film base material 11. According to such a structure, the film laminated body 100d can be preferably applied to what is called an inner touch panel type input display apparatus in which a touch sensor is integrated between a display cell and a polarizer.

Unlike the above-described example, the functional layer may be provided only on the viewing side of the film base material, or may be provided on both sides of the film base material.

As mentioned above, in this invention, the conductive layer is directly provided in at least one surface of a film base material. In the present specification, 'directly installed' refers to being laminated without interposing an adhesive layer.

Preferably the total thickness (total thickness of the film base material with an electrically conductive layer, a low moisture-permeable base material, and the adhesive layer interposed between them) from the film base material with an electrically conductive layer in the said film laminated body is 25 micrometers-300 micrometers More preferably, they are 50 micrometers-200 micrometers. According to the embodiment of the present invention, remarkable thinning can be realized in that the conductive layer is directly provided on the film substrate surface.

In one embodiment, the film laminated body of this invention is elongate. The elongate film laminate may, for example, be wound onto a roll and stored and / or transported.

The above embodiments may be appropriately combined, and modifications apparent in the art may be added to the components in the above embodiments, and the configurations in the above embodiments may be replaced with an optically equivalent configuration. You may also

Hereinafter, the component of a film laminated body is demonstrated.

B. Film base with conductive layer

B-1. Film substrate

The film substrate includes any suitable resin film. In one embodiment, 85 ° C., 85% R.H. A resin film (e.g., a resin film having a strain rate of less than 0.01%) that does not substantially cause deformation under the environment can be used. In the case of using such a resin film, generation of cracks in the conductive layer can be prevented. In another embodiment, 85 ° C., 85% R.H. A resin film that deforms in at least one direction under the environment can be used. When using such a resin film, the effect of this invention can be exhibited more preferably. The deformation is typically contraction or expansion. When a resin film is a stretched film, there exists a tendency which shrinkage | contraction in the direction parallel to a extending | stretching direction, and expansion in the direction orthogonal to a extending | stretching direction tend to arise. 85 ° C., 85% R.H. Strain rate (shrinkage rate [(original dimension-dimension after exposure) / original dimension × 100) or expansion rate [(dimension-original dimension after exposure) / original dimension in at least one direction of the resin film after 4 hours exposure in an environment X100]) is generally at least 0.01%, for example 0.03% to 1%, and for example 0.05% to 0.5%.

Glass transition temperature (Tg) of a resin film becomes like this. Preferably it is 150 degreeC or more, More preferably, it is 155 degreeC or more, More preferably, it is 158 degreeC or more, More preferably, it is 160 degreeC or more, Especially preferably, it is 163 degreeC or more to be. On the other hand, the said glass transition temperature becomes like this. Preferably it is 180 degrees C or less, More preferably, it is 175 degrees C or less, More preferably, it is 170 degrees C or less. If the glass transition temperature is too low, undesired changes in optical properties may occur in the high temperature environment of sputtering for forming the conductive layer and subsequent post-treatment. When glass transition temperature is too high, molding stability may worsen and transparency may be impaired. In addition, glass transition temperature is calculated | required according to JISK7121 (1987).

The absolute value of the photoelastic coefficient of the resin film is preferably 20 × 10 ^-12 (m ² / N) or less, and more preferably 1.0 × 10 ^-12 (m ² / N) to 15 × 10 ^-12 (m ² / N), and more preferably 2.0 x 10 ^-12 (m ² / N) to 12 x 10 ^-12 (m ² / N). If the absolute value of a photoelastic coefficient is such a range, the color change before and after sputtering can be suppressed.

The resin film may be optically isotropic. Or a resin film has birefringence and may be optically anisotropic. The optically anisotropic resin film may be a retardation film capable of exhibiting an optical compensation function. By forming a conductive layer directly on the film base material containing such a resin film (retardation film), there is no need to separately install the base material for sputtering, so that a further layer of the film laminate (image display device) can be made thinner. do. In addition, in this specification, "optically isotropic" means that in-plane phase difference Re (550) is 0 nm-10 nm, and phase difference Rth (550) of thickness direction is -10 nm-+10 nm.

In the case of imparting an optical compensation function to the resin film (that is, when the resin film is a retardation film), the in-plane retardation Re (550) is, for example, 100 nm to 180 nm, preferably 120 nm to 160 nm, and more. Preferably they are 135 nm-155 nm. That is, the resin film can function as a so-called λ / 4 plate. Hereinafter, the optical characteristic of the resin film in the case where a resin film is a retardation film is demonstrated.

The resin film preferably satisfies the relationship of Re (450) <Re (550) <Re (650). That is, the resin film shows the wavelength dependence of reverse dispersion whose retardation value becomes large according to the wavelength of the measurement light. Re (450) / Re (550) of the resin film is preferably 0.8 or more and less than 1.0, more preferably 0.8 to 0.95. Re (550) / Re (650) is preferably 0.8 or more and less than 1.0, more preferably 0.8 to 0.97.

Resin films typically exhibit a relationship of nx> ny in refractive index characteristics and have a slow axis. The angle between the slow axis of the resin film and the absorption axis of the polarizer is, for example, 35 ° to 55 °, preferably 38 ° to 52 °, more preferably 42 ° to 48 °, and still more preferably about 45 °. If the said angle is such a range, the film laminated body which has very excellent circular polarization characteristic (as a result very excellent antireflection characteristic) can be obtained by making a resin film into (lambda) / 4 plate.

The resin film represents any suitable refractive index ellipsoid as long as it has a relationship of nx> ny. Preferably, the refractive index ellipsoid of a resin film shows the relationship of nx> ny≥nz or nx> nz> ny. In addition, "ny = nz" here includes not only the case where ny and nz are exactly the same, but also the case where it is substantially the same. Therefore, there may be a case where ny <nz is provided within a range that does not impair the effects of the present invention. Nz coefficient becomes like this. Preferably it is 0.2-2.0, More preferably, it is 0.2-1.5, More preferably, it is 0.2-1.0. By satisfying such a relationship, a very good reflection color can be achieved when the film laminate is used for an image display device.

The thickness of the resin film can be set to any suitable value. When the resin film functions as a retardation film such as λ / 4 plate, the thickness can be set so that a desired in-plane retardation can be obtained. Specifically, the thickness of a resin film is 10 micrometers-200 micrometers, Especially, the thickness as retardation film becomes like this. Preferably it is 10 micrometers-80 micrometers, More preferably, it is 10 micrometers-60 micrometers, Most preferably Is 30 µm to 50 µm.

The resin film contains any suitable resin that can satisfy the above characteristics. Examples of the resin include polycarbonate resins, polyvinyl acetal resins, cycloolefin resins, acrylic resins, cellulose ester resins, and the like. Preferably it is polycarbonate resin. Polycarbonate resin is relatively easy to synthesize a copolymer using a plurality of monomers, molecular design for adjusting the balance of various physical properties is possible. In addition, heat resistance, stretchability, mechanical properties and the like are also relatively good. In the present invention, the polycarbonate resin generally refers to a resin having a carbonate bond in the structural unit, and includes, for example, a polyester carbonate resin. Polyester carbonate resin means resin which has a carbonate bond and an ester bond as a structural unit which comprises the said resin.

It is preferable that a polycarbonate resin contains the structural unit represented by following General formula (1) or (2) at least.

[Formula 1]

[Formula 2]

(In formula (1) and (2), R <^1> -R <^3> is a C1-C4 alkylene group which may respectively independently have a direct bond and a substituent, R <^4> -R <^9> is a hydrogen atom and a substituent each independently. An alkyl group having 1 to 10 carbon atoms, an aryl group having 4 to 10 carbon atoms which may have a substituent, an acyl group having 1 to 10 carbon atoms which may have a substituent, an alkoxy group having 1 to 10 carbon atoms, A C1-C10 aryloxy group which may have a substituent, an amino group which may have a substituent, a C1-C10 vinyl group which may have a substituent, a C1-C10 ethynyl group which may have a substituent, and a substituent A sulfur atom, a silicon atom having a substituent, a halogen atom, a nitro group or a cyano group, provided that R ⁴ to R ⁹ may be the same as or different from each other, and at least two adjacent groups in R ⁴ to R ⁹ To form a ring.)

The said structural unit can express reverse wavelength dispersibility efficiently even if there is little content in resin. Moreover, since the resin containing the said structural unit is also excellent in heat resistance, and high birefringence can be obtained by extending | stretching, it has a characteristic suitable as said retardation film.

Content in resin of the structural unit represented by the said General formula (1) or (2) is 100 weight% of the total amount of the weight of all the structural units and the coupling group which comprise polycarbonate resin, in order to acquire the optimal wavelength dispersion characteristic as retardation film. When it is set as 1 weight% or more, 50 weight% or less is preferable, 3 weight% or more and 40 weight% or less are more preferable, 5 weight% or more and 30 weight% or less are especially preferable.

As a preferable structure among the structural units represented by the said General formula (1) and (2), the structure which has a frame | skeleton illustrated to the following [A] group specifically is mentioned.

[A]

[Formula A1]

[Formula A2]

[Formula A3]

[Formula A4]

[Formula A5]

[Formula A6]

Also in the said [A] group, the performance of the diester structural unit of (A1) and (A2) is high, and (A1) is especially preferable. The specific diester structural unit has better thermal stability than the structural unit derived from the dihydroxy compound represented by the general formula (1), and tends to exhibit good characteristics also for optical properties such as expression of reverse wavelength dispersion and photoelastic coefficient. There is this. In addition, when a polycarbonate resin contains the structural unit of diester, such resin is called polyester carbonate resin.

The polycarbonate resin can contain a structural unit represented by the general formula (1) or (2) together with other structural units, thereby designing a resin that satisfies the various physical properties required for the retardation film. In particular, in order to give high heat resistance which is important physical property, it is preferable to contain the structural unit represented by following General formula (3).

[Formula 3]

(In formula (3), R <^10> -R <^15> represents a hydrogen atom, a C1-C12 alkyl group, an aryl group, a C1-C12 alkoxy group, or a halogen atom each independently.)

The structural unit represented by the formula (3) is a component having a high glass transition temperature, and despite the aromatic structure, the photoelastic coefficient is relatively low, and satisfies the characteristics required for the resin film.

Content in resin of the structural unit represented by the said General formula (3) contains 1 weight% or more and 30 weight% or less when the weight total amount of all the structural units and the coupling group which comprise a polycarbonate resin are 100 weight%. It is preferable, 2 weight% or more and 20 weight% or less are more preferable, 3 weight% or more and 15 weight% or less are especially preferable. Within this range, the resin does not drop excessively while providing sufficient heat resistance, and a resin excellent in workability can be obtained.

The structural unit represented by the said General formula (3) can be introduce | transduced in resin by superposing | polymerizing the dihydroxy compound containing this structural unit. As the dihydroxy compound, physical properties are good, and 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane is also used from the viewpoint of availability. Particularly preferred.

It is preferable that a polycarbonate resin further contains the structural unit represented by following General formula (4).

[Formula 4]

The structural unit represented by the formula (4) has the characteristics of high birefringence expression when the resin is drawn and low photoelastic coefficient. Examples of the dihydroxy compound into which the structural unit represented by the general formula (4) can be introduced include isosorbide (ISB), isomannide, and isoide, which are related to stereoisomers. It is most preferable to use ISB from a viewpoint.

The polycarbonate resin may contain other structural units in addition to the structural units described above depending on the required physical properties. Examples of the monomer containing other structural units include aliphatic dihydroxy compounds, alicyclic dihydroxy compounds, dihydroxy compounds containing acetal rings, oxyalkylene glycols, dihydroxy compounds containing aromatic components, Diester compounds and the like. 1,4-cyclohexanedimethanol (hereinafter sometimes abbreviated as CHDM) or tricyclodecane dimethanol (hereinafter abbreviated as TCDDM) from the viewpoint of good balance of various physical properties and availability. And hydroxy compounds such as spiroglycol (hereinafter sometimes abbreviated as SPG) are preferably used.

The polycarbonate resin includes heat stabilizers, antioxidants, catalyst deactivators, ultraviolet absorbers, light stabilizers, mold release agents, dyes, impact modifiers, antistatic agents, lubricants, lubricants, plasticizers, and the like, which are commonly used within the scope of not impairing the object of the present invention. A compatibilizer, a nucleating agent, a flame retardant, an inorganic filler, a foaming agent, etc. may be included.

Polycarbonate resins are aromatic polycarbonates, aliphatic polycarbonates, aromatic polyesters, aliphatic polyesters, polyamides, polystyrenes, polyolefins, acrylics, amorphous polyolefins, ABS, The polymer alloy formed by kneading with one kind or two or more kinds of synthetic resins such as AS, polylactic acid, polybutylene succinate and rubber or the like may be used.

The additives and modifiers may be prepared by mixing the above components with resin by a mixer such as a tumbler, a V-type blender, a Nauta mixer, a bandari mixer, a kneading roll, an extruder, or the like. Especially, kneading by an extruder, especially a twin screw extruder, is preferable from a viewpoint of dispersibility improvement.

The molecular weight of the polycarbonate resin can be expressed by the reduced viscosity. The reduced viscosity is measured using methylene chloride as the solvent, precisely preparing the polycarbonate resin concentration to 0.6 g / dL, and using a Uberod viscous tube at a temperature of 20.0 ° C ± 0.1 ° C. The lower limit of the reduced viscosity is usually preferably 0.25 dL / g or more, more preferably 0.30 dL / g or more, and particularly preferably 0.32 dL / g or more. The upper limit of the reduced viscosity is usually preferably 0.50 dL / g or less, more preferably 0.45 dL / g or less, and particularly preferably 0.40 dL / g or less. If the reduced viscosity is smaller than the lower limit, there may be a problem that the mechanical strength of the molded article becomes small. On the other hand, when a reduced viscosity is larger than the said upper limit, the fluidity | liquidity at the time of shaping | molding falls, and the problem that productivity and moldability fall may arise.

It is preferable that melt viscosity in a measurement temperature of 240 degreeC and a shear rate of 91.2 sec ^-1 of polycarbonate resin is 3000 Pa * s or more and 7000 Pa * s or less. 4000 Pa * s or more is more preferable, and, as for the minimum of melt viscosity, 4500 Pa * s or more is especially preferable. The upper limit of the melt viscosity is more preferably 6500 Pa · s or less, and particularly preferably 6000 Pa · s or less.

The resin film is required to have high heat resistance, and in general, as the heat resistance (glass transition temperature) is increased, the resin tends to become soft, but by melting the resin at least in the melt viscosity range as described above, it is possible to melt the resin. Processing also becomes possible.

It is preferable that the polycarbonate resin has a refractive index of 1.49 or more and 1.56 or less in sodium d-ray (589 nm). More preferably, the refractive index is 1.50 or more and 1.55 or less.

In order to give the resin film the optical characteristic requested | required as a retardation film, it is necessary to introduce an aromatic structure in resin. However, the aromatic structure causes a decrease in transmittance of the resin film by increasing the refractive index. Moreover, in general, the aromatic structure has a high photoelastic coefficient and degrades the overall optical properties. It is preferable to select the structural unit which expresses the characteristic requested | required efficiently to the said polycarbonate resin, and to suppress content of the aromatic structure in resin to the minimum.

The said resin film is obtained by film-forming resin, such as said polycarbonate resin, for example. Arbitrary suitable shaping | molding methods can be employ | adopted as a method of forming a film. Specific examples include compression molding, transfer molding, injection molding, extrusion, blow molding, powder molding, FRP molding, cast coating (for example, casting), calender molding, and hot press. Especially, the extrusion molding method or the cast coating method which raises the smoothness of the film obtained and can obtain favorable optical uniformity is preferable. In the cast coating method, there is a possibility that problems due to the remaining solvent may occur. Particularly preferably, the extrusion molding method, particularly the melt extrusion molding method using a T die, is preferable from the viewpoint of the productivity of the film and the ease of post-stretching treatment. Molding conditions can be appropriately set according to the composition and type of resin used, characteristics desired as a retardation film, and the like.

The resin film obtained by film molding is further extended as needed.

As the stretching, any suitable stretching method and stretching conditions (eg, stretching temperature, stretching ratio, stretching direction) may be adopted. Specifically, various stretching methods such as free end stretching, fixed end stretching, free end contraction, and fixed end contraction may be used alone, or may be used simultaneously or sequentially. The stretching direction can also be performed in various directions and dimensions, such as the longitudinal direction, the width direction, the thickness direction, and the inclination direction.

By appropriately selecting the stretching method and the stretching conditions, a retardation film having the desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) can be obtained.

In one embodiment, a retardation film is produced by uniaxial stretching or fixed-end uniaxial stretching of a resin film. As a specific example of fixed end uniaxial stretching, the method of extending | stretching in a width direction (horizontal direction) is mentioned, running a resin film in a longitudinal direction. The draw ratio is preferably 1.1 to 3.5 times.

In another embodiment, the retardation film can be produced by continuously obliquely stretching the long resin film in a predetermined angular direction with respect to the longitudinal direction. By adopting oblique stretching, a long stretched film having an orientation angle (slow axis in a predetermined angular direction) of a predetermined angle with respect to the longitudinal direction of the film is obtained, and roll-to-roll is possible, for example, when laminating with a polarizer. The process can be simplified. In addition, the production efficiency can be remarkably improved by the synergistic effect that the conductive layer can be formed directly on the resin film (retardation film). In addition, the predetermined angle may be an angle formed by the absorption axis of the polarizer and the slow axis of the retardation film in the film stack. As described above, the angle is preferably 35 ° to 55 °, more preferably 38 ° to 52 °, still more preferably 42 ° to 48 °, and particularly preferably about 45 °.

As a drawing machine used for diagonal drawing, the tenter type drawing machine which can add the feed force, the tension force, or the pulling force of a different speed left and right in the horizontal and / or longitudinal direction, for example is mentioned. Although a tenter type drawing machine includes a horizontal uniaxial drawing machine, a simultaneous biaxial drawing machine, and the like, any suitable drawing machine can be used as long as the elongated resin film can be continuously obliquely drawn.

By appropriately controlling the left and right speeds in the stretching machine, a retardation film (substantially long retardation film) having the desired in-plane retardation and having a slow axis in the desired direction can be obtained.

As the diagonal stretching method, for example, Japanese Laid-Open Patent Publication No. 50-83482, Japanese Laid-Open Patent Publication No. 2-113920, Japanese Laid-Open Patent Publication No. 3-182701, Japanese Laid-Open Patent Publication No. 2000-9912, Japanese Laid-Open Patent Publication The method described in 2002-86554, Unexamined-Japanese-Patent No. 2002-22944, etc. are mentioned.

The stretching temperature of the film may vary depending on the in-plane retardation value and thickness desired for the retardation film, the kind of resin used, the thickness of the film used, the stretching ratio and the like. Specifically, the stretching temperature is preferably Tg-30 ° C to Tg + 30 ° C, more preferably Tg-15 ° C to Tg + 15 ° C, and most preferably Tg-10 ° C to Tg + 10 ° C. By extending | stretching at such temperature, the retardation film which has a suitable characteristic in this invention can be obtained. In addition, Tg is the glass transition temperature of the constituent material of a film.

If necessary, a functional layer may be provided on the surface of the resin film. The functional layer may be provided on one side of the resin film or may be provided on both sides. The functional layer may have a single layer structure or a multilayer structure of two or more layers.

Examples of the functional layer include a hard coat layer, an antiglare treatment layer and an antireflection layer, an index matching layer, an antiblocking layer, an oligomer prevention layer, and the like. Since these layer forming materials are well-known in the art, the detailed description is abbreviate | omitted.

The functional layer can be formed directly on the surface of the resin film by, for example, a gravure coating method, a coating method such as a bar coating method, a vacuum deposition method, a sputtering method, an ion plating method, or the like using a material capable of forming each layer.

In one embodiment, the antiglare layer, the antireflection layer, or the index matching layer is formed on the side of the side where the conductive layer of the resin film is provided, and the hard coat layer or the antiblocking layer can be formed on either side or both sides. have.

The thickness of the functional layer (total thickness in the case of a multi-layer structure) may be, for example, 10 nm to 5 mu m, preferably 20 nm to 4 mu m.

B-2. Conductive layer

The conductive layer is typically a transparent conductive layer. The total light transmittance of the conductive layer is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.

The conductive layer can be patterned as needed. The conductive portion and the insulating portion can be formed by patterning. As a result, an electrode can be formed. The electrode may function as a touch sensor electrode that senses contact with the touch panel. The shape of the pattern is preferably a pattern that works well as a touch panel (for example, a capacitive touch panel). As a specific example, Japanese Patent Application Publication No. 2011-511357, Japanese Patent Application Publication No. 2010-164938, Japanese Patent Application Publication No. 2008-310550, Japanese Patent Application Publication No. 2003-511799, Japanese Patent Application Publication No. 2010- The pattern of 541109 is mentioned.

The density of the conductive layer is preferably ^{1.0g / cm 3 ~10.5g / cm 3} , more preferably from ^{1.3g / cm 3 ~8.0g / cm 3} .

The surface resistance of the conductive layer is preferably 0.1? /?-1000? / ?, more preferably 0.5? /?-500? / ?, and still more preferably 1? /?-250? / ?.

Representative examples of the conductive layer include a conductive layer containing a metal oxide. Examples of the metal oxides include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimony composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Especially, it is preferable that it is indium-tin composite oxide (ITO).

The thickness of the conductive layer is preferably 0.01 µm to 0.06 µm, more preferably 0.01 µm to 0.045 µm. If it is such a range, the electrically conductive layer excellent in electroconductivity and light transmittance can be obtained.

The conductive layer can typically be formed by sputtering on the surface of the film substrate.

C. Low moisture permeability base material

The water vapor transmission rate (water vapor transmission rate) at 40 ° C and 92% RH of the low-moisture-permeable substrate is 1.0 g / (m 2 · day) or less, preferably 0.2 g / (m 2 · day) or less, and more preferably 0.1 g / (M 2 · day) or less, more preferably 0.05 g / (m 2 · day) or less. If the moisture permeability is in such a range, deformation of the film substrate due to moisture absorption, for example, shrinkage can be preferably suppressed, and as a result, cracks can be prevented from occurring in the conductive layer due to the deformation. It is preferable that the water vapor transmission rate ideally does not transmit water vapor at all (that is, 0 g / (m 2 · day)).

The total light transmittance of the low-moisture-permeable substrate is preferably 70% or more, more preferably 75% or more, and even more preferably 80% or more in terms of optical properties.

As a low moisture-permeable base material, arbitrary appropriate structures can be employ | adopted as long as it has the said desired characteristic. In one embodiment, the low-moisture-permeable base material is equipped with a support base material and the inorganic thin film provided in the one side of this support base material. The inorganic thin film may be directly provided on the supporting substrate. Or you may provide it on a support base material through an anchor coat layer.

The support substrate is preferably transparent. The support substrate preferably has a total light transmittance of visible light (for example, light having a wavelength of 550 nm) of 85% or more, more preferably 90% or more, and still more preferably 95% or more.

In one embodiment, the support base material is optically isotropic. If it is such a structure, when a film laminated body is applied to an image display apparatus, the bad influence on the display characteristic of the said image display apparatus can be prevented.

The average refractive index of a support base material becomes like this. Preferably it is less than 1.7, More preferably, it is 1.59 or less, More preferably, it is 1.4-1.55. If the average refractive index is in such a range, back reflection can be suppressed, and it has the advantage that a high light transmittance can be achieved.

As a material which comprises a support base material, arbitrary appropriate materials which can satisfy the said characteristic can be used. As a specific example, resin which has cyclic structures, such as resin which does not have conjugated systems, such as norbornene-type resin and an olefin resin, lactone ring, glutarimide ring, etc. in an acryl-type main chain, polyester resin, polycarbonate resin is mentioned, for example. have. If it is such a material, when the support base material is formed, expression of retardation according to the orientation of a molecular chain can be suppressed small.

Preferably the thickness of a support base material is 10 micrometers-50 micrometers, More preferably, they are 20 micrometers-35 micrometers.

The inorganic thin film is formed of any suitable inorganic compound. The inorganic thin film preferably contains at least one inorganic compound selected from the group consisting of oxides, nitrides, hydrides and composite compounds thereof. Specifically, the inorganic compound may be a complex compound of an oxide, a nitride, and / or a hydride as well as an oxide, nitride, or hydride alone. Transparency can be further excellent by using such a compound. The inorganic compound forming the inorganic thin film may have any suitable structure. Specifically, it may have a complete crystal structure or may have an amorphous structure.

As elements constituting the inorganic compound, carbon (C), silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), zinc (Zn), tin (Sn), nickel (Ni), sodium (Na), boron (B), titanium (Ti), lead (Pb), zirconium (Zr), yttrium (Y), hydrocarbons and oxides, carbides, nitrides and mixtures thereof. . These may be used alone or in combination of two or more kinds. Among these, carbon, silicon, and aluminum are used preferably. Specific examples of the inorganic compound include diamond-like carbon (DLC), silicon nitride (SiNx), silicon oxide (SiOy), aluminum oxide (AlOz), aluminum nitride, and the like. As x value of SiNx, Preferably it is 0.3-2. As y value of SiOy, Preferably it is 1.3-2.5. As z value of AlOz, Preferably it is 0.7-2.3. Silicon oxide and aluminum oxide are particularly preferred. This is because the high gas barrier property can be stably maintained.

The thickness of the inorganic thin film is preferably 0.1 nm to 5000 nm, more preferably 0.5 nm to 1000 nm, still more preferably 10 nm to 1000 nm, particularly preferably 30 nm to 500 nm, particularly preferably 50 nm. -200 nm. If it is such a range, the inorganic thin film which has sufficient barrier property, does not produce a crack and peeling, and is excellent in transparency can be obtained.

As the inorganic thin film, any suitable configuration may be adopted. Specifically, the inorganic thin film may be formed in a single layer or may be a laminate of a plurality of layers. As a specific example in the case where an inorganic thin film is a laminated body, the 3-layered structure of an inorganic oxide layer / inorganic nitride layer / inorganic oxide layer (for example, SiOy layer / SiNx layer / SiO layer) is mentioned. In addition, there may be mentioned inorganic thin film is another specific example of when a laminate, ZnO, Al, and two-layer configuration of the second oxide layer consisting of the first oxide layer / SiO ₂ containing SiO _2. In this configuration, the first oxide layer is disposed on the supporting substrate side.

As described above, the first oxide layer contains ZnO, Al, and SiO ₂ . The first oxide layer preferably contains Al in an amount of 2.5% by weight to 3.5% by weight and SiO ₂ in an amount of 20.0% by weight to 62.4% by weight, based on the total weight. ZnO is preferably a residual amount. By containing ZnO in such a range, the layer excellent in amorphousness, barrier property, bendability, and heat resistance can be formed. By containing Al in such a range, since the 1st oxide layer is typically formed by sputtering, the electrical conductivity of a target can be increased. By containing SiO ₂ in such a range, the refractive index of the first oxide layer can be reduced without causing abnormal discharge and without impairing barrier properties.

The thickness of the first oxide layer is preferably 10 nm to 100 nm, more preferably 10 nm to 60 nm, still more preferably 20 nm to 40 nm. If the thickness is in such a range, there is an advantage that both high light transmittance and excellent barrier properties can be achieved.

The average refractive index of the first oxide layer is preferably 1.59 to 1.80. If the average refractive index is in this range, there is an advantage that high light transmittance can be achieved.

The first oxide layer is preferably transparent. The first oxide layer preferably has a total light transmittance of visible light (for example, light having a wavelength of 550 nm) of 85% or more, more preferably 90% or more, and even more preferably 95% or more.

The second oxide layer is composed of SiO ₂ (an inevitable impurity may also be included). By forming such a 2nd oxide layer on the surface of a 1st oxide layer, chemical-resistance and transparency as a whole low moisture-permeable base material can be improved significantly, maintaining the favorable characteristic by a 1st oxide layer. In addition, since the second oxide layer can function as a low refractive index layer, good antireflection characteristics can be imparted to the low moisture-permeable substrate.

The thickness of the second oxide layer is preferably 10 nm to 100 nm, more preferably 50 nm to 100 nm, still more preferably 60 nm to 100 nm. If the thickness is in such a range, there is an advantage that both high light transmittance and excellent barrier properties and excellent chemical resistance can be achieved.

The average refractive index of the second oxide layer is preferably 1.44 to 1.50. As a result, the second oxide layer can function well as a low refractive index layer (antireflection layer).

The second oxide layer is preferably transparent. The second oxide layer preferably has a total light transmittance of visible light (for example, light having a wavelength of 550 nm) of 85% or more, more preferably 90% or more, and still more preferably 95% or more.

Arbitrary suitable methods may be employ | adopted as a formation method of an inorganic thin film. As a specific example, a vapor deposition method and a coating method are mentioned. The vapor deposition method is preferable in that a uniform thin film having high barrier property is obtained. Vapor deposition methods include PVD (physical vapor deposition) and CVD (chemical vapor deposition) such as vacuum deposition, ion plating, and sputtering.

The formation method of a said 1st oxide layer and a 2nd oxide layer is demonstrated in detail below. The first oxide layer may be formed on the supporting substrate, typically by sputtering. The first oxide layer may be formed by a sputtering method under an inert gas atmosphere containing oxygen, for example, using a sputtering target containing Al, SiO ₂ and ZnO. As the sputtering method, a magnetron sputtering method, an RF sputtering method, an RF superimposed DC sputtering method, a pulse sputtering method, a dual magnetron sputtering method and the like can be adopted. The heating temperature of a board | substrate is -8 degreeC-200 degreeC, for example. The gas partial pressure of oxygen with respect to the whole atmospheric gas of oxygen and an inert gas is 0.05 or more, for example.

The detail of the AZO film | membrane which comprises a 1st oxide layer and its manufacturing method is described, for example in Unexamined-Japanese-Patent No. 2013-189657. The description of this publication is incorporated herein by reference.

The second oxide layer can typically be formed on the first oxide layer by sputtering. The second oxide layer is, for example, by targeting Si, SiC, SiN or SiO _, and carrying out a sputter using an inert gas containing oxygen (eg, argon, nitrogen, CO, CO _2, and a mixed gas thereof). Can be formed. Since both the first oxide layer and the second oxide layer contain SiO ₂ , the adhesion between the first oxide layer and the second oxide layer is very excellent. In this regard, in order to express a sufficient barrier function at the interface between the first oxide layer and the second oxide layer, the thickness of the first oxide layer is preferably 10 nm or more as described above. This is because the ratio of the so-called incubation layer, which is a growth initial film, can be sufficiently reduced, and an oxide layer having desired physical properties can be formed. The total thickness of the first oxide layer and the second oxide layer is preferably 200 nm or less, and more preferably 140 nm or less.

Arbitrary suitable materials may be employ | adopted as a formation material of an anchor coat layer. Examples of the material include resins, hydrocarbons, metals, metal oxides, and metal nitrides. The formation material and formation method of an anchor coat layer are described, for example in Unexamined-Japanese-Patent No. 2016-105166. The description of this publication is incorporated herein by reference.

A protective layer may be formed on the surface (inorganic thin film side surface or support substrate side surface) of the low moisture-permeable substrate. The protective layer is typically formed of a resin. Resin which forms a protective layer may be solvent property, or may be aqueous. Specific examples include polyester resins, urethane resins, acrylic resins, polyvinyl alcohol resins, ethylene-unsaturated carboxylic acid copolymers, ethylene vinyl alcohol resins, vinyl modified resins, nitrocellulose resins, silicone resins, isocyanate resins, Epoxy resin, oxazoline group containing resin, modified styrene resin, modified silicone resin, and alkyl titanate are mentioned. These may be used alone or in combination. You may add an inorganic particle to a protective layer in order to improve barrier property, abrasion resistance, and slipperiness | lubricacy. Examples of the inorganic particles include silica sol, alumina sol, particulate inorganic filler and layered inorganic filler. These may be used alone or in combination. The inorganic particles may be added by mixing, or may be added by polymerizing the monomers of the resin in the presence of the inorganic particles.

Arbitrary suitable methods may be employ | adopted as a formation method of a protective layer. When using a resin composition, a coating and immersion are mentioned as a formation method, for example. Specific examples of the coating method include a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, a spray and a brush. After application or dipping, a uniform protective layer can be formed by evaporating the solvent by performing any suitable drying treatment on the application layer or the layer formed by dipping. As a drying process, heat drying, such as hot air drying and hot roll drying, and infrared drying are mentioned, for example. Heating temperature is about 80 to 200 degreeC, for example. The formed protective layer may be subjected to crosslinking treatment by energy ray irradiation in order to increase water resistance and durability.

The thickness of the protective layer is preferably 0.05 µm to 10 µm, more preferably 0.1 µm to 3 µm.

When the anchor coat layer, the inorganic thin film, and the optional protective layer are formed as one structural unit layer, one or more layers of structural unit layers may be provided on the low moisture-permeable substrate. When two or more structural unit layers are provided, the number of layers of a structural unit layer becomes like this. Preferably they are 1 layer-10 layers, More preferably, they are 1 layer-5 layers. In this case, each structural unit layer may be same or different.

The low moisture-permeable substrate is typically laminated on a film substrate with a conductive layer via an adhesive layer. At this time, the inorganic thin film side may be laminated so as to face the adhesive layer, or the supporting substrate side may be laminated so as to face the adhesive layer.

D. Polarizer

The polarizing plate typically includes a polarizer and a first protective film provided on one side thereof (viewing side). The polarizing plate may further include the 2nd protective film provided in the other side (the film base material side with a conductive layer) of a polarizer as needed. Moreover, the polarizing plate with a phase difference film (the structure of a 1st protective film / polarizer / 2nd protective film / retardation film) which further contains a retardation film on the opposite side to the polarizer of this 2nd protective film may be sufficient.

Arbitrary suitable polarizers can be employ | adopted as a polarizer. For example, the polarizer may be a polarizer obtained by dyeing and stretching a single-layer resin film represented by (i) a polyvinyl alcohol (PVA) resin film with a dichroic substance such as iodine. For example, the polarizer may be a polarizer obtained by dyeing and stretching a laminate of (ii) a resin substrate and a PVA resin layer (PVA resin film) laminated on the resin substrate with a dichroic substance, or (iii) a resin substrate. It can be a polarizer obtained by dyeing and extending | stretching a laminated body with the PVA system resin layer apply | coated to the said resin base material with a dichroic substance. The detail of the manufacturing method of the polarizer of (iii) is described, for example in Unexamined-Japanese-Patent No. 2012-73580. This publication is incorporated herein by reference in its entirety.

The thickness of the polarizer is preferably 15 µm or less, more preferably 1 µm to 12 µm, still more preferably 3 µm to 10 µm, and particularly preferably 3 µm to 8 µm. If the thickness of a polarizer is such a range, the curl at the time of heating can be suppressed favorably and the external appearance durability at the time of favorable heating will be obtained. Moreover, if the thickness of a polarizer is such a range, it can contribute to thickness reduction of a film laminated body (as a result, an image display apparatus).

The polarizer preferably exhibits absorption dichroism at any wavelength having a wavelength of 380 nm to 780 nm. The single transmittance of the polarizer is preferably 43.0% to 46.0%, more preferably 44.5% to 46.0%. The polarization degree of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and still more preferably 99.9% or more.

The first protective film is formed of any suitable film that can be used as a protective film of the polarizer. As a specific example of the material used as the main component of the said film, Cellulose resins, such as a triacetyl cellulose (TAC), polyester type, polyvinyl alcohol type, polycarbonate type, polyamide type, polyimide type, polyether sulfone type, poly Transparent resins, such as a sulfone type, a polystyrene type, a polynorbornene type, a polyolefin type, (meth) acrylic type, and an acetate type, etc. are mentioned. Moreover, thermosetting resins, such as a (meth) acrylic-type, a urethane type, a (meth) acrylic-type urethane type, an epoxy type, a silicone type, or ultraviolet curable resin, etc. are mentioned. In addition, glassy polymers, such as a siloxane polymer, are mentioned, for example. Moreover, the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO01 / 37007) can also be used. As a material of this film, the resin composition containing the thermoplastic resin which has a substituted or unsubstituted imide group in the side chain, and the thermoplastic resin which has a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used, for example, isobutene and N- The resin composition which has the alternating copolymer which consists of methyl maleimide, and an acrylonitrile styrene copolymer is mentioned. The polymer film may be, for example, an extrusion molded product of the resin composition.

When a polarizer is a polarizer obtained by dyeing and extending | stretching and extending | stretching the laminated body of said (iii) resin base material and the PVA system resin layer apply | coated to the said resin base material with a dichroic substance, it does not peel off the said resin base material from a polarizer, and is 1st protection It can be used as a film.

The film laminated body of this invention is typically arrange | positioned at the visual recognition side of an image display apparatus, as mentioned later, and the 1st protective film is arrange | positioned at the visual recognition side at that time. Therefore, surface treatment, such as a hard-coat process, an antireflection process, the anti-sticking process, and an antiglare process, may be given to the 1st protective film as needed. In addition, the first protective film is subjected to a treatment (typically providing a (elliptical) circularly polarized function or giving a super high phase difference) to improve the visibility in the case of viewing through polarized sunglasses as necessary. You may be. By performing such a process, even when the display screen is visually recognized through polarizing lenses, such as polarized sunglasses, excellent visibility can be implement | achieved. Therefore, the film laminate of the present invention can be preferably applied to an image display device that can be used outdoors.

The thickness of the first protective film is preferably 10 µm to 200 µm, more preferably 20 µm to 100 µm, still more preferably 25 µm to 95 µm.

The second protective film may be optically isotropic. Alternatively, the second protective film may have birefringence and may be optically anisotropic. The optically anisotropic second protective film may be a retardation film capable of exhibiting an optical compensation function. The material, thickness, and the like of the second protective film are as described with respect to the first protective film. In addition, when the 2nd protective film is a retardation film which can exhibit an optical compensation function, the optical characteristic (refractive index ellipsoid, retardation, etc.) and the axial relationship with a polarizer are described about the retardation film which is an optional component mentioned later. same. Moreover, embodiment which is a retardation film which a 2nd protective film can exhibit an optical compensation function is contained in embodiment in which a polarizing plate contains a retardation film.

The retardation film that can be provided on the side opposite to the polarizer of the second protective film is produced to have a desired index ellipsoid and retardation according to the purpose and the like.

In one embodiment, the retardation film can function as a λ / 2 plate. In this embodiment, the in-plane retardation Re (550) of the retardation film is 180 nm to 320 nm, more preferably 200 nm to 290 nm, still more preferably 230 nm to 280 nm. The retardation film typically has a refractive index ellipsoid of nx> ny = nz or nx> ny> nz, and its Nz coefficient is, for example, 0.9 to 2, preferably 1 to 1.5, and more preferably 1 to 1.3.

The retardation film may exhibit a reverse dispersion wavelength characteristic in which the retardation value becomes larger according to the wavelength of the measurement light, and may exhibit a positive wavelength dispersion characteristic in which the retardation value becomes smaller according to the wavelength of the measurement light, and the retardation value of the measurement light You may exhibit the flat wavelength dispersion characteristic which hardly changes with a wavelength. It is preferable to exhibit flat wavelength dispersion characteristics. By adopting the lambda / 2 plate (retardation film) having a flat wavelength dispersion characteristic, it is possible to realize excellent antireflection characteristics and reflection color in the oblique direction. Re (450) / Re (550) of the retardation film is preferably 0.99 to 1.07, and Re (650) / Re (550) is preferably 0.998 to 1.07.

The retardation film can be produced by film-forming any suitable resin and stretching as necessary. As the resin, preferably a cyclic olefin resin can be used. As the stretching method, the method described in item B-1. Can be used.

In another embodiment, the retardation film may be a positive C plate having a refractive index ellipsoid of nz> nx = ny. Here 'nx = ny' includes not only the case where nx and ny are exactly the same, but also the case where nx and ny are substantially the same. That is, Re is less than 10 nm. The phase difference Rth in the thickness direction of the film is, for example, -20 nm to -200 nm, more preferably -40 nm to -180 nm, and particularly preferably -40 nm to -160 nm.

As a specific example of the said retardation film, the film (homeotropic oriented liquid crystal film) formed from the liquid crystal material fixed (solidified or hardened) in homeotropic orientation is mentioned. When such a film is used, the film laminated body which can contribute to the improvement of the color sense at the time of visual recognition from the inclination direction, and the improvement of reflection prevention property, when using for an image display apparatus can be obtained. In the present specification, the 'homeotropic alignment' refers to an alignment state in which the major axis direction of the liquid crystal material (liquid crystal compound) is 90 ° ± 30 ° with respect to the main surface of the polarizer. In other words, 'homeotropic orientation' includes purely vertical alignment as well as some oblique orientation. Incidentally, the tilt angle in the oblique direction can be obtained, for example, by the procedure described in Journal of Applied Physics, Vol. 38 (1999), P.748.

The liquid crystal material (liquid crystal compound) capable of forming the homeotropic alignment may be a liquid crystal monomer or a liquid crystal polymer. As a typical liquid crystal compound, a nematic liquid crystal compound is mentioned, for example. An overview of the alignment technique of such a liquid crystal compound is described, for example, in Chemical Summary 44 (Surface Modification, Japanese Chemical Society, pp. 156-163).

The detail of the film containing the liquid crystal material fixed by the said homeotropic orientation is described, for example in Unexamined-Japanese-Patent No. 2008-216782. This publication is incorporated herein by reference in its entirety.

The film containing the liquid crystal material fixed in the homeotropic alignment is, for example, coating a liquid crystal composition containing a liquid crystal material (liquid crystal compound) on the substrate, and homeotropic alignment in the state in which they exhibit a liquid crystal phase, It can form by performing hardening process in the state which maintained the orientation. The obtained film is typically peeled from the substrate and transferred to the second protective film.

The thickness of the retardation film may be set to any suitable value depending on the forming material, the purpose, and the like. Specifically, the thickness of the retardation film functioning as a λ / 2 plate is preferably 10 µm to 60 µm, more preferably 30 µm to 50 µm. Moreover, the thickness of the retardation film which is a positive C plate becomes like this. Preferably it is 0.5 micrometer-60 micrometers, More preferably, it is 0.5 micrometer-50 micrometers, Most preferably, it is 0.5 micrometer-40 micrometers.

A polarizing plate can typically be obtained by bonding each layer together through arbitrary appropriate adhesive layers or adhesive bond layers.

E. Adhesive Layer

As the adhesive layer, any suitable adhesive layer can be used as long as the effects of the present invention are not impaired. Especially, the adhesive layer whose water vapor transmission rate in 40 degreeC and 92% R.H. is 100 g / (m <2> * day) or less is used preferably. By controlling the moisture permeability of the adhesive layer below the above-mentioned value, deformation of the film substrate due to moisture absorption, for example, shrinkage can be further suppressed, and as a result, cracking in the conductive layer can be more preferably prevented according to the deformation. Here, 'moisture permeability' means water vapor transmission rate (moisture permeability) at 40 ° C. and 92% R.H. of the adhesive layer. In addition, an "adhesive layer" means an adhesive layer or an adhesive layer.

The same adhesive layer may be sufficient as the adhesive layer interposed between the said polarizing plate and the film base material with an electrically conductive layer, and the film base material with an electrically conductive layer, and the low moisture-permeable base material may be sufficient, and a different adhesive layer may be sufficient as it. Preferably, either adhesive layer meets the moisture permeability, and more preferably both adhesive layers meet the moisture permeability.

The water vapor transmission rate at 40 ° C. and 92% RH of the adhesive layer is more preferably 50 g / (m 2 · day) or less, more preferably 40 g / (m 2 · day) or less, still more preferably 30 g / (m 2 · day) Hereinafter, More preferably, it is 20 g / (m <2> * day) or less. It is preferable that the water vapor transmission rate ideally does not transmit water vapor at all (that is, 0 g / (m 2 · day)).

E-1. Adhesive layer

As an adhesive layer, the layer which consists of arbitrary appropriate adhesive compositions can be employ | adopted. As such an adhesive composition, a natural rubber adhesive composition, (alpha) -olefin adhesive composition, a urethane resin adhesive composition, an ethylene-vinyl acetate resin emulsion adhesive composition, an ethylene-vinyl acetate resin hot melt adhesive composition, an epoxy resin adhesive composition, a vinyl chloride resin, for example Solvent adhesive composition, chloroprene rubber adhesive composition, cyanoacrylate adhesive composition, silicone adhesive composition, styrene-butadiene rubber solvent adhesive composition, nitrile rubber adhesive composition, nitrocellulose adhesive composition, reactive hot melt adhesive composition, phenolic resin adhesive Composition, modified silicone adhesive composition, polyester hot melt adhesive composition, polyamide resin hot melt adhesive composition, polyimide adhesive composition, polyurethane resin hot melt adhesive composition, poly Lepin resin hot melt adhesive composition, polyvinyl acetate resin solvent adhesive composition, polystyrene resin solvent adhesive composition, polyvinyl alcohol adhesive composition, polyvinylpyrrolidone resin adhesive composition, polyvinyl butyral adhesive composition, polybenzimidazole adhesive A composition, a polymethacrylate resin solvent adhesive composition, a melamine resin adhesive composition, a urea resin adhesive composition, a resorcinol adhesive composition, etc. are mentioned. Such an adhesive composition can be used individually by 1 type or in mixture of 2 or more types.

The thickness of the adhesive layer may be selected any suitable thickness depending on the purpose and the like. The thickness of the adhesive layer can be, for example, 0.01 to 10 μm, preferably 0.05 to 8 μm.

E-2. Adhesive layer

As an adhesive layer, the layer which consists of arbitrary appropriate adhesive compositions can be employ | adopted. Examples of the pressure-sensitive adhesive composition include a rubber pressure-sensitive adhesive composition, an acrylic pressure-sensitive adhesive composition, a silicone pressure-sensitive adhesive composition, a urethane pressure-sensitive adhesive composition, a vinyl alkyl ether pressure-sensitive adhesive composition, a polyvinyl alcohol pressure-sensitive adhesive composition, a polyvinylpyrrolidone pressure-sensitive adhesive composition, a polyacrylamide pressure-sensitive adhesive composition, Although a cellulose adhesive composition etc. are mentioned, Among these, it is preferable that it is a rubber adhesive composition from a viewpoint of satisfying the said water vapor transmission rate.

The rubber-based pressure-sensitive adhesive composition preferably contains as a base polymer a rubber-based polymer that exhibits rubber elasticity at a temperature range near room temperature. As a specific example of a rubber type polymer, a styrene thermoplastic elastomer, an isobutylene type polymer, etc. are mentioned. These can be used individually or in combination, respectively.

Examples of the styrene-based thermoplastic elastomers include styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-isoprene-styrene block copolymers (SIS), styrene-butadiene-styrene block copolymers (SBS), and styrene-ethylene-propylene Styrene block copolymer (SEPS, SIS hydrogenated), styrene-ethylene-propylene block copolymer (SEP, hydrogenated styrene-isoprene block copolymer), styrene-isobutylene-styrene block copolymer (SIBS), styrene Styrene-type block copolymers, such as butadiene rubber (SBR), etc. are mentioned.

As isobutylene polymer, polyisobutylene (PIB) which is a homopolymer of isobutylene, a copolymer of isobutylene and normal butylene, a copolymer of isobutylene and isoprene (for example, a regular butyl rubber, chlorination) Butyl rubbers such as butyl rubber, brominated butyl rubber and partially crosslinked butyl rubber), and vulcanized products and modified substances thereof (eg, modified with functional groups such as hydroxyl, carboxyl, amino and epoxy groups). Especially, it is preferable to use polyisobutylene (PIB) from a weather resistance viewpoint. Polyisobutylene is excellent in light resistance because it does not contain a double bond in the main chain.

As said polyisobutylene, commercial items, such as OPPANOL by BASF Corporation, can be used, for example.

It is preferable that the weight average molecular weight (Mw) of the said polyisobutylene is 100,000 or more, It is more preferable that it is 300,000 or more, It is further more preferable that it is 600,000 or more, It is especially preferable that it is 700,000 or more. Moreover, the upper limit of a weight average molecular weight is 5 million or less, for example, 3 million or less are preferable, and 2 million or less are more preferable. By setting the weight average molecular weight of the said polyisobutylene to 100,000 or more, it can be set as the rubber-type adhesive composition which is more excellent in durability at the time of high temperature storage.

The content of the rubber polymer in the total solid of the rubber-based adhesive composition is preferably 50% by weight or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, even more preferably 80% by weight or more, 85 It is further more preferable that it is at least weight%, and it is especially preferable that it is 90 weight% or more. The upper limit of the content of the rubber polymer is, for example, 99% by weight or less, and preferably 98% by weight or less. By including the rubber polymer represented by the styrene thermoplastic elastomer and the isobutylene polymer in the above range, excellent low moisture permeability can be obtained.

The rubber-based pressure-sensitive adhesive composition may further include polymers other than the styrene-based thermoplastic elastomer and the isobutylene-based polymer, elastomers, and the like. Specific examples include butyl rubber (IIR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), EPR (binary ethylene-propylene rubber), EPT (tertiary ethylene-propylene rubber), acrylic rubber, urethane rubber, And thermoplastic thermoplastic elastomers such as polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polymer blends of polypropylene and EPT (tertiary ethylene-propylene rubber). These can be used in the range which does not impair the effect of this invention, The compounding quantity can be 0 weight part-10 weight part with respect to a total of 100 weight part of a styrene-type thermoplastic elastomer and / or isobutylene-type polymer.

When polyisobutylene is used as a rubber polymer, it is preferable that an adhesive composition further contains the hydrogen abstraction type photoinitiator. A hydrogen draw type photoinitiator is what irradiates an active energy ray, and does not cleave, it can draw hydrogen rather than polyisobutylene, and can make a reaction point in polyisobutylene. By the said reaction point formation, the crosslinking reaction of polyisobutylene can be started.

As a photoinitiator, in addition to the said hydrogen extraction type photoinitiator, the cleavage type photoinitiator which the photoinitiator itself cleaves by irradiation of an active energy ray and generate | occur | produces a radical is also known. However, when a cleavage type photoinitiator is used for polyisobutylene, the main chain of polyisobutylene will be cut | disconnected by the photoinitiator which the radical generate | occur | produced, and it cannot crosslink. In contrast, polyisobutylene can be crosslinked as described above by using a hydrogen drawing type photopolymerization initiator.

Examples of the hydrogen drawing type photopolymerization initiator include acetophenone, benzophenone, o-benzoylbenzoate methyl-4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dimethylbenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butyl Benzophenone compounds such as peroxycarbonyl) benzophenone and 3,3'-dimethyl-4-methoxybenzophenone; Thioxanthone type compounds, such as 2-isopropyl thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, and 2, 4- dichloro thioxanthone; Aminobenzophenone compounds such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphor quinone and the like; Aromatic ketone compounds such as acetonaphtone and 1-hydroxycyclohexylphenyl ketone; And quinone aromatic compounds such as aromatic aldehydes such as terephthalaldehyde and methylanthraquinone. These can be used individually by 1 type or in mixture of 2 or more types. Among these, a benzophenone type compound is preferable from a reactive viewpoint, and benzophenone is more preferable.

It is preferable that it is 0.001-10 weight part with respect to 100 weight part of polyisobutylene, It is more preferable that it is 0.005-10 weight part, and, as for content of a hydrogen draw type | mold photoinitiator, it is more preferable that it is 0.01-10 weight part. By including a hydrogen drawing type photoinitiator in the said range, a crosslinking reaction can be advanced to the target density.

The rubber-based pressure-sensitive adhesive composition may further contain a polyfunctional radical polymerizable compound. The polyfunctional radically polymerizable compound can function as a crosslinking agent of polyisobutylene.

A polyfunctional radically polymerizable compound is a compound which has at least two radically polymerizable functional groups which have unsaturated double bonds, such as a (meth) acryloyl group or a vinyl group. As a specific example of a polyfunctional radically polymerizable compound, For example, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanedi Oldi (meth) acrylate, 1,10-decanedioldi (meth) acrylate, 2-ethyl-2-butylpropanedioldi (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol A ethylene oxide addition Water di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, dioxane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Esterates of (meth) acrylic acid and polyhydric alcohols such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and EO-modified diglycerin tetra (meth) acrylate, 9,9- Bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene etc. are mentioned. These can be used individually by 1 type or in mixture of 2 or more types. Among these, esterified products of (meth) acrylic acid and a polyhydric alcohol are preferred from the viewpoint of compatibility with polyisobutylene, and bifunctional (meth) acrylates having two (meth) acryloyl groups. , Trifunctional (meth) acrylate having three or more (meth) acryloyl groups is more preferable, and tricyclodecane dimethanol di (meth) acrylate and trimethylolpropane tri (meth) acrylate are particularly preferable.

It is preferable that content of a polyfunctional radically polymerizable compound is 20 weight part or less with respect to 100 weight part of polyisobutylene, It is more preferable that it is 15 weight part or less, It is more preferable that it is 10 weight part or less. In addition, the lower limit of content of a polyfunctional radically polymerizable compound is not specifically limited, For example, it is preferable that it is 0.1 weight part or more with respect to 100 weight part of said polyisobutylenes, It is more preferable that it is 0.5 weight part or more, 1 weight part It is more preferable that it is above. When content of a polyfunctional radically polymerizable compound exists in the said range, it is preferable from the viewpoint of the durability of the obtained rubber adhesive layer.

It is preferable that it is about 1000 or less, for example, and, as for the molecular weight of a polyfunctional radically polymerizable compound, it is more preferable that it is about 500 or less.

The rubber-based pressure-sensitive adhesive composition may include at least one tackifier selected from the group consisting of a tackifier including a terpene skeleton, a tackifier including a rosin skeleton, and a hydrogenated substance thereof. When the rubber-based pressure-sensitive adhesive composition contains a tackifier, a rubber-based pressure-sensitive adhesive layer having high adhesion to various adherends and high durability even under a high temperature environment can be formed.

As a tackifier containing a terpene skeleton, for example, terpene polymers such as α-pinene polymer, β-pinene polymer, dipentene polymer and the terpene polymer are modified (phenol modified, styrene modified, aromatic modified, hydrogenated modified, hydrocarbon modified, etc.). The modified terpene resin etc. can be mentioned. Examples of the modified terpene resin include terpene phenol resins, styrene modified terpene resins, aromatic modified terpene resins, hydrogenated terpene resins (hydrogenated terpene resins), and the like. Examples of the hydrogenated terpene resin herein include a hydride of a terpene polymer, a hydrogenated substance of another modified terpene resin, and a terpene phenol resin. Among these, the hydrogenated substance of terpene phenol resin is preferable from a viewpoint of the compatibility with respect to a rubber-based adhesive composition, or adhesive characteristics.

It is preferable that a tackifier contains a cyclohexanol skeleton from a viewpoint of adhesive characteristic. Compared to the phenol skeleton, the cyclohexanol skeleton may have a good balance of compatibility with the base polymer, in particular polyisobutylene. As a tackifier containing a cyclohexanol frame | skeleton, hydrogenated substances, such as a terpene phenol resin and rosin phenol resin, are preferable, for example, and completely hydrogenated additives, such as a terpene phenol resin and rosin phenol resin, are more preferable.

The amount of the tackifier added is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, further preferably 20 parts by weight or less based on 100 parts by weight of a base polymer such as polyisobutylene. Moreover, the addition amount of a tackifier is 0.1 weight part or more, Preferably it is 1 weight part or more, More preferably, it is 5 weight part or more. Adhesion characteristics can be improved by making the addition amount of a tackifier into the said range. When the amount of the tackifier is added in a large amount exceeding the above range, the cohesive force of the pressure-sensitive adhesive composition tends to decrease.

In the rubber-based pressure-sensitive adhesive composition, a diluent (for example, an organic solvent such as toluene, xylene, n-heptane, dimethyl ether, etc.), a softener, and a crosslinking agent (for example, a polyisocyanate, an epoxy compound, an alkyl ether melamine) within a range that does not impair the effects of the present invention. Compound, etc.), filler, anti-aging agent, ultraviolet absorber, etc., and arbitrary appropriate additives can be added. The kind, combination, addition amount, etc. of an additive can be suitably set according to the objective.

An adhesive layer is produced by apply | coating the said adhesive composition to arbitrary appropriate resin films, such as a separator, and performing drying (heat drying), irradiation of an active energy ray, etc. as needed. The coating method, drying conditions, active energy ray irradiation conditions, and the like can be selected as appropriate methods or conditions according to the composition of the rubber-based pressure-sensitive adhesive composition.

After an adhesive layer is formed on a separator, for example, it may be bonded to the film base material with a conductive layer, and may be directly formed on the film base material with a conductive layer. The pressure-sensitive adhesive layer can be protected by the separator until its exposed surface.

The thickness of the pressure-sensitive adhesive layer may be set to an appropriate value depending on the purpose and the like. It is preferable that the thickness is 250 micrometers or less, It is more preferable that it is 100 micrometers or less, It is further more preferable that it is 55 micrometers or less. Moreover, it is preferable that it is 1 micrometer or more from a viewpoint of durability, and, as for the thickness, it is more preferable that it is 5 micrometers or more.

The gel fraction of the pressure-sensitive adhesive layer is preferably 10% to 98%, more preferably 25% to 98%, still more preferably 45% to 90% from the viewpoint of compatibility between durability and adhesive force.

F. Image Display

The film laminate can be applied to an image display device. Therefore, this invention includes the image display apparatus using the said film laminated body. Representative examples of the image display device include a liquid crystal display device and an organic EL display device. The image display apparatus by embodiment of this invention is equipped with the said film laminated body at the visual recognition side, and a film laminated body is arrange | positioned so that a conductive layer may become between a polarizer and a display cell. By arranging the film laminate in this manner, the image display device can be an inner touch panel type input display device.

EXAMPLE

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples. In addition, the measuring method of each characteristic is as follows.

(1) thickness

About the conductive layer, the cross section was observed using the transmission electron microscope ("H-7650" by Hitachi, Ltd.), and the measurement was performed. The thickness of the other substrate was measured using a film thickness meter (Dig-Dial Gauge DG-205, manufactured by Peacock).

(2) phase difference value

The refractive indices nx, ny and nz of the resin film (retardation film) used by the Example and the comparative example were measured by the automatic birefringence measuring apparatus (The Prince Biological Instruments Co., Ltd. product, automatic birefringence meter KOBRA-WPR). The measurement wavelength of in-plane phase difference Re was 450 nm and 550 nm, the measurement wavelength of thickness direction phase difference Rth was 550 nm, and the measurement temperature was 23 degreeC.

(3) photoelastic coefficient

The resin film used by the Example and the comparative example was cut | disconnected in the size of 20 mm x 100 mm, and the sample was produced. This sample was measured with the light of wavelength 550nm with the ellipsometer (M-150 by Nippon spectroscopy company), and the photoelastic coefficient was obtained.

(4) reduced viscosity

The resin sample was dissolved in methylene chloride, and a resin solution with a concentration of 0.6 g / dL was precisely prepared. Performing measurements in the memory te Rika Kogyo produced by Ube temperature 20.0 ℃ ± 0.1 ℃ using a rod-shaped tube and the viscosity was measured the passage of the solvent, time t _0, and the transit time t of solution. T ₀ and t obtained by using the values obtained a relative viscosity η _rel using the following equation (i), also with a relative viscosity η _rel obtained were calculated the specific viscosity η _sp by the following formula (ii).

η _rel = t / t ₀ (i)

η _sp = (η-η ₀ ) / η ₀ = η _rel -1 (ii)

Then, by dividing the specific viscosity η _sp to a concentration c [g / dL] thus obtained, it was determined for a reduced viscosity η _sp / c.

(5) glass transition temperature

It measured using the differential scanning calorimeter DSC6220 made from SAI Nano Technology. About 10 mg of the resin sample was put into the aluminum pan of the same company, and it sealed, and it heated up from 30 degreeC to 220 degreeC at the temperature increase rate of 20 degree-C / min under 50 mL / min of nitrogen stream. After maintaining temperature for 3 minutes, it cooled to 20 degree-C / min to 30 degreeC. It hold | maintained at 30 degreeC for 3 minutes, and heated up again at 220 degreeC at the speed | rate of 20 degree-C / min. From the DSC data obtained at the second temperature increase, the extrapolated, which is the temperature of the intersection point between the straight line extending the base line on the low temperature side to the high temperature side and the slope of the curve of the step change portion of the glass transition is maximized. ) Glass transition start temperature was calculated | required and it was set as glass transition temperature.

(6) melt viscosity

The pellet-shaped resin sample was vacuum-dried at 90 degreeC for 5 hours or more. The dried pellets were measured with a capillary rheometer manufactured by Dongyang Sejong Co., Ltd. The measurement temperature was 240 degreeC, melt viscosity was measured between shear rates 9.12-1824sec _{- 1} , and the value of melt viscosity in 91.2sec- ₁ was used. As the orifice, a die diameter of 1 mm x 10 mmL was used.

(7) refractive index

In the unstretched film produced by the Example mentioned later and a comparative example, the rectangular test piece of 40 mm in length and 8 mm in width was cut out, and it was set as the measurement sample. The refractive index n _D was measured by the multi-wavelength Abbe refractometer DR-M4 / 1550 made by Atago Co., Ltd. using an interference filter of 589 nm (D line). The measurement was carried out at 20 ° C. using monobromonaphthalene as the interface solution.

Synthesis Example of Monomer

Synthesis Example 1 Synthesis of Bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl] methane (BPFM)

It synthesize | combined by the method of Unexamined-Japanese-Patent No. 2015-25111.

Synthesis Example 2 Synthesis of 6,6'-Dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiinane (SBI)

It synthesize | combined by the method of Unexamined-Japanese-Patent No. 2014-114281.

[Synthesis example of polycarbonate resin, and characteristic evaluation]

The symbol of the compound used by the following example and the comparative example is as follows.

BPFM: bis [9- (2-phenoxycarbonylethyl) fluorene-9-yl] methane

BCF: 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (manufactured by Osaka Chemical Co., Ltd.)

BHEPF: 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Chemical Co., Ltd.)

ISB: isosorbide (Rocket Flureza, trade name: POLYSORB)

SBI: 6,6'-dihydroxy-3,3,3 ', 3'-tetramethyl-1,1'-spirobiindane

SPG: Spiroglycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

PEG: polyethylene glycol number average molecular weight: 1000 (manufactured by Sanyo Chemical Co., Ltd.)

DPC: diphenyl carbonate (manufactured by Mitsubishi Chemical Corporation)

Example 1

1-1. Production of Film Base with Conductive Layer

SBI 6.04 parts (0.020 mol), ISB 59.58 parts (0.408 mol), BPFM 34.96 parts (0.055 mol), DPC 79.39 parts (0.371 mol), and calcium acetate monohydrate 7.53 x 10 ^-4 parts by weight as catalyst (4.27 × 10 ⁻⁶ mol) was added to a reaction vessel, and the reaction apparatus was purged with nitrogen under reduced pressure. The raw material was dissolved while stirring for 10 minutes at 150 degreeC under nitrogen atmosphere. It heated up over 220 minutes to 220 degreeC as a reaction 1st step, and was made to react at normal pressure for 60 minutes. The pressure was then decompressed over 90 minutes from atmospheric pressure to 13.3 kPa, held at 13.3 kPa for 30 minutes, and the resulting phenol was taken out of the reaction system. Subsequently, the pressure was reduced over 15 minutes to 0.10 kPa or less, heating up the fruit temperature to 245 degreeC over 15 minutes as a 2nd step of reaction, and the phenol which generate | occur | produced was taken out of the reaction system. After reaching | attaining predetermined | prescribed stirring torque, it pressured back to normal pressure with nitrogen, stopped reaction, the produced polyester carbonate resin was extruded in water, the strand was cut | disconnected, and the pellet was obtained. The reduced viscosity of the obtained resin was 0.375 dL / g, the glass transition temperature was 165 ° C, the melt viscosity was 5070 Pa · s, the refractive index was 1.5454, and the photoelastic coefficient was 14 × 10 ^-12 m ² / N.

Resin pellets vacuum-dried at 100 ° C. for 5 hours or more were subjected to a T die (width 200 mm, set temperature: 250 ° C.) using a single screw extruder manufactured by Isuzu Chemical Co., Ltd. (screw diameter 25 mm, cylinder set temperature: 255 ° C.). ). The extruded film was rolled into a winding machine while cooling with a chill roll (set temperature: 155 ° C), and a film having a thickness of 100 μm was prepared for the unstretched film. The 120 mm x 150 mm rectangular test piece was cut out with the polycarbonate resin film obtained as mentioned above with a safety razor, and it extended | stretched 161 degreeC in the longitudinal direction with a drawing speed of 5 mm / sec by a batch type biaxial drawing apparatus (Brukner). Uniaxial stretching of 1 × 1.25 times was performed.

The resin film (thickness 89 micrometers) obtained as mentioned above was used as a film base material. Re (550) of the obtained resin film was 130 nm, Rth (550) was 130 nm, and showed refractive index characteristics of nx> ny = nz. In addition, Re (450) / Re (550) of the obtained resin film was 0.86. The slow axis direction of the resin film was 0 degrees with respect to the longitudinal direction. Furthermore, the obtained resin film was 85 degreeC and 85% R.H. The amount of deformation when exposed to the environment was 0.35% contraction in the slow axis direction and 0.16% expansion in the fast axis direction.

On the surface of the said resin film (retardation film), the transparent conductive layer (25 nm in thickness) which consists of an indium-tin composite oxide is formed by sputtering, and the film with a conductive layer which has a laminated structure of a resin film (retardation film) / conductive layer is carried out. The substrate was produced. The specific sequence is as follows: a sintered body of 10 wt% tin oxide and 90 wt% indium oxide in a vacuum atmosphere (0.40 Pa) in which Ar and O ₂ (flow ratio is Ar: O ₂ = 99.9: 0.1) were introduced. Is used as a target, the film temperature is 130 ° C., and the horizontal magnetic field is 100 mT. The RF superimposed DC magnetron sputtering method (discharge voltage 150 V, RF frequency 13.56 MHz, ratio of RF power to DC power (RF power / DC power) ) Was used 0.8). The obtained transparent conductive layer was heated in 150 degreeC warm air oven, and the crystal conversion process was performed.

1-2. Fabrication of Polarizer

A long roll of a polyvinyl alcohol (PVA) resin film (manufactured by Kuraray, product name 'PE3000') having a thickness of 30 µm was uniaxially stretched in the longitudinal direction to be 5.9 times in the longitudinal direction by a roll stretching machine, and at the same time, swelling, dyeing, The polarizer with a thickness of 12 micrometers was produced by performing crosslinking and a washing process, and finally performing a drying process.

Specifically, the swelling treatment was stretched 2.2 times while treating with pure water at 20 ° C. Subsequently, the dyeing treatment was elongated 1.4 times while treating in an aqueous solution at 30 ° C. in which the weight ratio of iodine and potassium iodide in which the iodine concentration was adjusted was 45.0% so that a single transmittance of the polarizer obtained was 45.0%. In addition, the crosslinking process employ | adopted the 2nd step crosslinking process, and the 1st step crosslinking process extended | stretched 1.2 times, processing in the aqueous solution which melt | dissolved boric acid and potassium iodide at 40 degreeC. The boric acid content of the crosslinking treatment aqueous solution of the 1st step was 5.0 weight%, and potassium iodide content was 3.0 weight%. The crosslinking treatment of the second stage was stretched 1.6 times while treating in an aqueous solution in which boric acid and potassium iodide were dissolved at 65 ° C. The boric acid content of the crosslinking treatment aqueous solution of the 2nd step was 4.3 weight%, and potassium iodide content was 5.0 weight%. In addition, the washing | cleaning process was processed by the potassium iodide aqueous solution of 20 degreeC. The potassium iodide content of the aqueous solution of the washing process was 2.6 weight%. Finally, the drying process was dried for 5 minutes at 70 degreeC, and the polarizer was obtained.

The TAC film was bonded together on the one side of the said polarizer through the polyvinyl alcohol-type adhesive agent, and the polarizing plate which has a structure of a protective film / polarizer was obtained.

1-3. Fabrication of Low Moisture Permeable Substrate

Al, SiO _{2 using a} commercially available COP film (manufactured by Nippon Xeon Co., Ltd., trade name "Zeonia", thickness of 40 µm) as a support substrate And a first oxide layer (thickness 30 nm) on the substrate by a DC magnetron sputtering method using a sputtering target containing ZnO. Next, using the Si target, a second oxide layer (50 nm) was formed on the first oxide layer of the laminate of the substrate / first oxide layer. In this manner, a low-moisture-permeable substrate having a structure of a supporting substrate / first oxide layer (AZO) / second oxide layer (SiO ₂ ) was produced. The water vapor transmission rate of the obtained low moisture-permeable base material was 0.01 g / (m <2> * day). In addition, the water vapor transmission rate was measured by the following measuring methods.

<Measurement of the moisture permeability of the low moisture permeability base material>

The low-moisture-permeable base material was cut out in circular shape of 10 cm (phi), and it was set as the measurement sample. About this measurement sample, the moisture permeability in 40 degreeC and 92% R.H. was measured by the test method according to JISK7129B using the vapor permeation tester "PREMATRAN-W3 / 33" by MOCON.

1-4. Production of acrylic pressure sensitive adhesive layer

In a detachable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube, 99 parts by weight of butyl acrylate (BA), 1 part by weight of 4-hydroxybutyl acrylate (4HBA) as a monomer component, and a polymerization initiator 0.2 parts by weight of azobisisobutyronitrile and ethyl acetate were added as a polymerization solvent so that the solid content was 20%, followed by nitrogen gas flow and stirring for about 1 hour while stirring. Thereafter, the flask was heated to 60 ° C. and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. 0.8 parts by weight of trimethylolpropanetolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) as a isocyanate-based crosslinking agent to the acrylic polymer solution (solid content 100 parts by weight), and a silane coupling agent (trade name: KBM-403 0.1 weight part of Shin-Etsu Chemical Co., Ltd. product was added, and the acrylic adhesive composition was prepared.

The obtained acrylic adhesive composition (solution) was apply | coated to the peeling process surface of the 38-micrometer-thick polyester film (brand name: diamond foil MRF, Mitsubishi Resin Co., Ltd. product) which peeled one side with silicone, and forms an application layer, It dried at 120 degreeC for 3 minutes. A 38-micrometer-thick polyester film (brand name: Diafoil MRF, Mitsubishi Resin Co., Ltd.) which peeled the said single side | surface with the silicone was bonded together on the said coating layer surface so that a peeling process surface and a coating layer surface may contact | connect, and a separator The adhesive sheet which consists of / acrylic-type adhesive layer (thickness 50micrometer) / separator was obtained. The water vapor transmission rate of the obtained acrylic adhesive layer was 1000 g / (m <2> * day) or more. The measuring method of water vapor transmission rate is as follows.

<Measurement of the moisture permeability of the adhesive layer>

One peeling liner of the obtained adhesive sheet (thickness of an adhesive layer: 50 micrometers) was peeled off, and it bonded to the triacetyl cellulose film (TAC film, thickness: 25 micrometers, Konica Minolta Co., Ltd. product) on the exposed adhesive surface. Thereafter, the other release liner was peeled off to obtain a sample for measurement. Next, using this measurement sample, the water vapor transmission rate (water vapor transmission rate) was measured by the water vapor transmission test method (Cup method, according to JIS Z 0208) under the following conditions.

Measuring temperature: 40 ℃

Relative Humidity: 92%

Measurement time: 24 hours

A constant temperature and humidity bath was used for the measurement.

1-5. Production of film laminate

The said acrylic adhesive layer was transferred to the polarizer surface of the said polarizing plate, and the said film base material with an electrically conductive layer was bonded together through this acrylic adhesive layer. At this time, it arrange | positioned so that the slow axis of a resin film (retardation film) and the absorption axis of a polarizer may make an angle of 45 degree | times, and the absorption axis of a polarizer might be parallel to a longitudinal direction. Moreover, it bonded together so that a polarizer surface and a resin film surface may face.

Next, the said acrylic adhesive layer was transferred to the conductive layer surface of the obtained laminated body, and the said low moisture permeable base material was bonded together through the said acrylic adhesive layer. At this time, it bonded together so that a support base material surface and a conductive layer surface may face. Thus, the film laminated body which has a structure of [protective film / polarizer / acrylic adhesive layer / resin film (phase difference film) / conductive layer / acrylic adhesive layer / low moisture-permeable base material] was obtained.

Comparative Example 1

A protective film / polarizer / acrylic adhesive layer was prepared in the same manner as in Example 1 except that a commercially available cycloolefin-based resin film (Nipon Xeon Co., Ltd., product name 'Zenooa', thickness 40 μm) was used as it was. / Resin film (retardation film) / conductive layer / acrylic pressure-sensitive adhesive layer / COP base material]. As a result of measuring the water vapor transmission rate similarly to Example 1, the water vapor transmission rate of this cycloolefin resin film was 10 g / (m <2> * day).

Comparative Example 2

[Protection] was carried out in the same manner as in Example 1, except that a commercially available polyimide-based resin film (trade name "TORMED", "thickness 25 µm") was used as it was instead of the low-moisture-permeable substrate. Film / polarizer / acrylic adhesive layer / resin film (retardation film) / conductive layer / acrylic adhesive layer / polyimide substrate]. The water vapor transmission rate of the polyimide resin film was 100 g / (m 2 · day) as a result of measuring the water vapor transmission rate in the same manner as in Example 1 except that MOCON's 'PERMTRAN' was used.

The film laminate obtained in the said Example and the comparative example was used for the durability test. The results are shown in Table 1.

<Durability test>

The film laminated body obtained by the Example and the comparative example was cut out in the rectangle of a predetermined | prescribed magnitude | size, and a cover glass (Matsunami Glass Co., Ltd. make, brand name ") is provided on the polarizing plate via the acrylic adhesive layer (acrylic adhesive layer produced in Example 1). Microslide glass' thickness 1.3 mu m) was laminated to obtain a test piece. The test piece was put in 85 degreeC and 85% R.H. Environment, it was taken out after 240 hours, and the presence or absence of the crack generation in the conductive layer was confirmed using the laser microscope ("VK-X200" by Keyence).

TABLE 1

As is apparent from Table 1, it is understood that no crack is generated in the film laminate of the examples, and it has excellent durability. On the other hand, it turns out that a crack has generate | occur | produced in the film laminated body of a comparative example and there exists a problem in durability.

[Industry availability]

The film laminated body of this invention is used suitably for a touchscreen type input display apparatus.

10: Film base material with conductive layer
11: film substrate
12: conductive layer
13: resin film
14: functional layer
20: low moisture permeability base material
21: support substrate
22: inorganic thin film
30: adhesive layer
40: polarizer
100: film laminate

Claims (10)

As a film laminated body for touch panels provided with the film base material with an electrically conductive layer, and the low moisture permeable base material laminated | stacked on one side of the said film base material with an electrically conductive layer,
The said film base material with a conductive layer has a film base material containing a resin film, and the conductive layer directly provided in at least one surface of the said film base material,
The water vapor transmission rate of the said low moisture-permeable base material at 40 degreeC and 92% RH is 1.0 g / (m <^2> * day) or less,
Film laminated body for touch panels. The method of claim 1,
The low-moisture-permeable base material includes a support base material and an inorganic thin film provided on one side of the support base material,
Film laminated body for touch panels. The method of claim 2,
The inorganic thin film contains at least one inorganic compound selected from the group consisting of oxides, nitrides, hydrides and composite compounds thereof,
Film laminated body for touch panels. The method according to any one of claims 1 to 3,
The film substrate shrinks in at least one direction under an 85 ° C., 85% RH environment,
Film laminated body for touch panels. The method according to any one of claims 1 to 4,
In-plane phase difference Re (550) of the said resin film is 100 nm-180 nm,
Film laminated body for touch panels. The method according to any one of claims 1 to 5,
The film base material further includes a functional layer provided on at least one side of the resin film,
The conductive layer is directly provided on the functional layer of the film base material,
Film laminated body for touch panels. The method according to any one of claims 1 to 6,
Further comprising a polarizing plate,
Film laminated body for touch panels. The method of claim 7, wherein
The said polarizing plate, the said film base material with a conductive layer, and the said low moisture-permeable base material are laminated | stacked in this order from the visual recognition side through an adhesive layer,
Film laminated body for touch panels. The method of claim 8,
Moisture permeability in 40 degreeC, 92% RH of any one or both of the contact bonding layer interposed between the said polarizing plate and the said film base material with a conductive layer, and the contact bonding layer interposed between the said film layer with a conductive layer and the said low moisture-permeable base material. Is less than or equal to 100 g / (m ² · day),
Film laminated body for touch panels. The method according to any one of claims 7 to 9,
The polarizing plate contains a polarizer and a retardation film,
Film laminated body for touch panels.

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