JP5933137B1 - Transparent conductive film lamination film and transparent conductive film - Google Patents

Abstract

A transparent conductive film laminating film 1 on which a patterned transparent conductive film is laminated, comprising a transparent plastic substrate 2 and a functional layer 3 laminated on at least one surface of the transparent plastic substrate 2, and having functionality When the layer 3 has a refractive index of 1.52 to 2.00 and a patterned transparent conductive film is laminated on the transparent conductive film laminating film 1, a portion where the transparent conductive film exists and a transparent conductive film exist. The transparent conductive film laminating film 1 in which the functional layer 3 contains a colorant so that b * of the L * a * b * color system in the portion not to be -2 to 2 respectively. According to the transparent conductive film laminating film 1, it is possible to make it difficult to visually recognize the pattern of the transparent conductive film even when the layer configuration is simplified.

Description

  The present invention relates to a transparent conductive film laminating film and a transparent conductive film produced using the film.

  A touch panel that can input information by directly touching the image display unit has an input device that transmits light disposed on various displays. Typical types include a resistive touch panel and a capacitance type touch panel. A touch panel is mentioned.

  In these touch panels, a transparent conductive film in which a transparent conductive film made of tin-doped indium oxide (ITO) or the like is laminated on a transparent plastic substrate may be used.

  In a capacitive touch panel, in order to detect the touch position of a finger, after the transparent conductive film is laminated, for example, two transparent conductive films patterned in a line shape are crossed with each other. And arranged in a grid pattern. In the capacitive touch panel thus obtained, there are a portion where the transparent conductive film is laminated and a portion where the transparent conductive film is not laminated, and the reflectance and color are different depending on the presence or absence of the transparent conductive film. There is a problem that the lattice-like pattern of the transparent conductive film formed by the transparent conductive film is recognized, and as a result, the visibility as a display is lowered.

  In order to make it difficult to see the lattice pattern, that is, the portion where the transparent conductive film is laminated, a hard coat layer is laminated on the transparent substrate film (transparent plastic substrate), and further, a high refractive index layer and a low refractive index. A transparent conductive film formed by sequentially laminating a layer and a transparent conductive film has been proposed (see Patent Document 1).

JP 2011-134482 A

  However, the formation of a plurality of hard coat layers, high refractive index layers, and low refractive index layers as described above is problematic in terms of the manufacturing process and has a problem of high production costs. Even if the hard coat layer is omitted, the high-refractive index layer and the low-refractive index layer have a film thickness (for example, several tens of nanometers) at which optical interference occurs, and are transparent using the optical interference. It is difficult to see the patterning of the conductive film, and with such a film thickness, it is difficult to develop hardness that can withstand actual use.

  The present invention has been made in view of the above situation, and even when the layer configuration is simplified, the transparent conductive film in which the pattern of the transparent conductive film is difficult to be visually recognized, and the transparent conductive film used for the production thereof are laminated. The object is to provide a film.

  In order to achieve the above object, first, the present invention provides a transparent conductive film laminating film in which patterned transparent conductive films are laminated, wherein the transparent plastic substrate and at least one surface of the transparent plastic substrate are provided. When the transparent conductive film patterned on the transparent conductive film laminating film is laminated, the functional layer has a refractive index of 1.52 to 2.00. The functional layer contains a colorant so that b * of the L * a * b * color system in the part where the transparent conductive film is present and the part where the transparent conductive film is not present are -2 to 2, respectively. A transparent conductive film laminating film is provided (Invention 1).

  According to the said invention (invention 1), while controlling the refractive index of a functional layer as mentioned above, a functional layer contains a coloring agent by a predetermined amount, The conventional high refractive index layer and low refractive index There is no need to form a layer, and the pattern of the transparent conductive film can be made difficult to visually recognize.

  In the said invention (invention 1), it is preferable that the said functional layer is directly laminated | stacked on the said transparent plastic base material, and the said transparent conductive film is laminated | stacked directly on the said functional layer (invention 2).

  In the said invention (invention 1 and 2), it is preferable that the thickness of the said functional layer is 0.05-10 micrometers (invention 3).

  In the said invention (invention 1-3), it is preferable that the said functional layer is a hard-coat layer (invention 4).

  2ndly this invention was equipped with the said transparent conductive film lamination | stacking film (invention 1-4) and the patterned transparent conductive film laminated | stacked on the said functional layer of the said transparent conductive film lamination | stacking film. A transparent conductive film is provided (Invention 5).

  According to the transparent conductive film laminating film of the present invention, it is possible to make it difficult to visually recognize the pattern of the transparent conductive film even when the layer configuration is simplified. Moreover, the transparent conductive film which concerns on this invention is a thing in which the pattern of a transparent conductive film is hard to be visually recognized even when a layer structure is simple.

It is sectional drawing of the film for transparent conductive film lamination which concerns on one Embodiment of this invention. It is sectional drawing of the transparent conductive film which concerns on one Embodiment of this invention.

Hereinafter, embodiments of the present invention will be described.
[Transparent conductive film lamination film]
FIG. 1 is a cross-sectional view of a transparent conductive film laminating film according to an embodiment of the present invention. The transparent conductive film laminating film 1 according to this embodiment includes a transparent plastic substrate 2 and a functional layer 3 laminated on one side (the upper side in FIG. 1) of the transparent plastic substrate 2.

  In the transparent conductive film laminating film 1 according to this embodiment, the functional layer 3 is preferably laminated directly on the transparent plastic substrate 2, and the transparent conductive film is preferably laminated directly on the functional layer 3. Thereby, it is not necessary to form a conventional high refractive index layer or low refractive index layer, the layer configuration can be simplified, and the production cost of the transparent conductive film laminating film 1 is reduced by a simple manufacturing process. be able to. “Directly laminated on a transparent plastic substrate” means a plastic film body of a transparent plastic substrate or a layer provided integrally with the plastic film body (for example, a layer such as an easy-adhesion layer, which has a high refractive index. It means to be laminated without interposing a conventional layer such as a high refractive index layer and a low refractive index layer on the refractive index layer and the low refractive index layer).

<Functional layer>
The functional layer 3 of the transparent conductive film laminating film 1 according to this embodiment has a refractive index of 1.52 to 2.00, preferably 1.55 to 1.90, and particularly preferably 1.65. ~ 1.85. When the refractive index of the functional layer 3 is within such a range, the difference in refractive index from the transparent conductive film is reduced. Thereby, the reflected light intensity in the portion where the transparent conductive film exists and the reflected light intensity in the portion where the transparent conductive film does not exist become close, and the pattern of the transparent conductive film becomes difficult to be visually recognized. In addition, the refractive index in this specification shall be the value measured with the ellipsometer based on JISK7142: 2008.

  Moreover, the functional layer 3 of the transparent conductive film laminating film 1 according to the present embodiment is present when the patterned transparent conductive film is laminated on the transparent conductive film laminating film 1. The colorant is contained so that the b * of the L * a * b * color system of the part and the part where the transparent conductive film does not exist is -2 to 2, respectively. In general, since a transparent conductive film has a yellowish color, a difference in appearance based on the color is large between a portion where the transparent conductive film is present and a portion where the transparent conductive film is not present. However, when the functional layer 3 contains a colorant and b * is set to -2 to 2 as described above, the yellow color of the portion where the transparent conductive film is present is alleviated and the portion where the transparent conductive film is present is reduced. The difference in appearance based on the color and the color of the portion where the transparent conductive film does not exist is reduced. Thereby, combined with the effect of the refractive index, the pattern of the transparent conductive film is more difficult to be visually recognized.

  The b * is −2 to 2, as described above, preferably −1.9 to 1.9, particularly preferably −1.8 to 1.8, and more preferably −1.7 to 1.7. Note that the value of b * conforms to JIS Z8722.

  Any colorant can be used without particular limitation as long as it satisfies the above b * value and does not adversely affect the transparent conductive film. The colorant is preferably a blue colorant from the viewpoint of setting b * to a predetermined value. Further, the blue colorant may be a pigment or a dye, but it is preferable to use a pigment from the viewpoint of thermal stability when forming a transparent conductive film.

  Examples of blue pigments include bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, inorganic metal phthalocyanine blue (for example, copper phthalocyanine blue), phthalocyanine blue partially chlorinated, first sky blue, induslen blue BC, etc. 1 type can be used individually or in mixture of 2 or more types. Among these, cobalt blue or copper phthalocyanine blue is particularly preferable from the viewpoints of heat resistance and hardness.

  The functional layer 3 preferably contains 0.01 to 30% by mass of a colorant, particularly preferably 0.05 to 25% by mass, and more preferably 0.4 to 18% by mass. 5 to 18% by mass is most preferable. When the functional layer 3 contains a colorant within such a range, the above b * can easily stably enter the above-described range, and the film strength of the functional layer 3 can be secured.

  Here, the functional layer 3 is preferably a hard coat layer. Thereby, the transparent conductive film laminating film 1 according to the present embodiment does not require a separate hard coat layer.

  The functional layer 3 is preferably composed of a cured product obtained by curing a composition containing a curable component such as an active energy ray curable component and a thermosetting component and a colorant, and in particular, active energy ray curable. It is preferable to be composed of a cured product obtained by curing a composition containing an ionic component and a colorant (hereinafter sometimes referred to as “composition C”) with active energy rays. Thereby, the functional layer 3 can be a hard coat layer.

  Here, active energy rays refer to those having energy quanta among electromagnetic waves or charged particle beams, and specific examples include ultraviolet rays and electron beams. Among active energy rays, ultraviolet rays that are easy to handle are particularly preferable.

  As the active energy ray-curable component, those capable of imparting a desired refractive index and hardness to the functional layer 3 may be appropriately selected. Specific examples of the active energy ray-curable component include polyfunctional (meth) acrylate monomers, (meth) acrylate prepolymers, and polymers having active energy ray curability. Of these, polyfunctional (meth) acrylate monomers and / or (meth) acrylate prepolymers are preferred. The polyfunctional (meth) acrylate monomer and the (meth) acrylate prepolymer may be used alone or in combination. In the present specification, (meth) acrylate means both acrylate and methacrylate. The same applies to other similar terms.

  Examples of the multifunctional (meth) acrylate monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and polyethylene glycol diene. (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate phosphoric acid, allylation Cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentae Thritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol Multifunctional (meth) such as hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, adamantane di (meth) acrylate, 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene An acrylate is mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.

  On the other hand, examples of the (meth) acrylate-based prepolymer include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, polyol acrylate-based prepolymers, and the like.

  Examples of the polyester acrylate-based prepolymer include esterification of a hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polyvalent carboxylic acid and a polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding alkylene oxide to carboxylic acid with (meth) acrylic acid.

  The epoxy acrylate prepolymer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. For example, a phenol novolac acrylate-based prepolymer is preferable.

  The urethane acrylate-based prepolymer can be obtained, for example, by esterifying, with (meth) acrylic acid, a polyurethane oligomer obtained by a reaction between polyether polyol or polyester polyol and polyisocyanate.

  The polyol acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  The above prepolymers may be used alone or in combination of two or more.

  Among the active energy ray-curable components, it is preferable to use a monomer or a prepolymer having an aromatic ring or a polycyclic aromatic skeleton, and in particular, to use a prepolymer having an aromatic ring or a polycyclic aromatic skeleton. Is preferred. Since these compounds have a high refractive index, the functional layer 3 obtained easily satisfies the above-described refractive index and has a preferable hardness.

  As the prepolymer having an aromatic ring, a prepolymer having two or more aromatic rings is preferable. For example, a phenol novolak acrylate prepolymer, a cresol novolak acrylate prepolymer, or the like is preferable.

  Examples of the prepolymer having a polycyclic aromatic skeleton include a fluorene skeleton, a naphthalene skeleton, an anthracene skeleton, a triphenylene skeleton, a tetraphen skeleton, a tetracene skeleton, a chrysene skeleton, a pyrene skeleton, a pentacene skeleton, a hexacene skeleton, a heptacene skeleton, and a coronene skeleton. And prepolymers having a ketrene skeleton and the like. Among these, prepolymers having a fluorene skeleton are preferred. Specifically, an acrylate prepolymer having a fluorene skeleton is preferable.

  It is preferable that the composition C further contains a photopolymerization initiator. By containing the photopolymerization initiator as described above, the active energy ray-curable component can be efficiently cured, and the polymerization curing time and the irradiation amount of the active energy ray can be reduced.

  Examples of such a photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-di Tylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylaminobenzoate, oligo [2-hydroxy-2-methyl-1 [4- (1-methylvinyl) phenyl] propanone], 2 4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. These may be used alone or in combination of two or more.

  The photopolymerization initiator is preferably used in an amount of 0.5 to 15 parts by mass, particularly 1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable component.

  The functional layer 3 (composition C) may contain a refractive index adjusting agent for adjusting the refractive index, for example, a metal oxide, if desired. Examples of the metal oxide include titanium oxide, zirconium oxide, tantalum oxide, zinc oxide, indium oxide, hafnium oxide, cerium oxide, tin oxide, niobium oxide, tin-doped indium oxide (ITO), and antimony-doped tin oxide (ATO). Etc. These metal oxides may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, it is preferable to use zirconium oxide from the viewpoint of refractive index and transparency.

  The metal oxide is preferably contained in the functional layer 3 in the form of fine particles. In this case, the average particle diameter of the metal oxide fine particles is preferably 1 to 150 nm, and particularly preferably 5 to 40 nm. In addition, let the average particle diameter of the metal oxide fine particle in this specification be the value measured by the measuring method using the zeta potential measuring method.

  The blending ratio of the refractive index adjusting agent (metal oxide) in the functional layer 3 is appropriately set so that the refractive index of the functional layer 3 is in the above-described range. Specifically, it is preferably 50 to 1000 parts by mass, particularly preferably 80 to 800 parts by mass, and 100 to 500 parts by mass with respect to 100 parts by mass of the active energy ray-curable component. Further preferred.

  The functional layer 3 (composition C) can contain various desired additives as long as the effects of the present invention are not hindered. Examples of various additives include a dispersant, a crosslinking agent, a curing agent, and an antioxidant.

  The thickness of the functional layer 3 is preferably 0.05 to 10 μm, particularly preferably 0.1 to 7 μm, and more preferably 0.2 to 5 μm. When the thickness of the functional layer 3 is in the above range, it is possible to make it difficult to visually recognize the pattern of the transparent conductive film while keeping the concentration of the colorant low. Furthermore, the thickness of the functional layer 3 is 0.4 to 3 μm from the viewpoint of suppressing the volatile components from the functional layer 3 under vacuum conditions to a lower level while imparting hard coat properties. Most preferred.

  The pencil hardness measured according to JIS K5600-5-4 of the functional layer 3 is preferably HB or more, particularly preferably F or more, and further preferably H or more. The transparent conductive film laminating film 1 that satisfies the requirements of the functional layer 3 has a high surface hardness and excellent scratch resistance.

<Transparent plastic substrate>
There is no restriction | limiting in particular as the transparent plastic base material 2 used in this embodiment, The thing which has transparency from the well-known plastic film as a conventional optical base material can be selected suitably, and can be used. Examples of such plastic films include polyester films such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate (PEN), polyethylene films, polypropylene films, cellophane, diacetyl cellulose films, triacetyl cellulose films, and acetyl cellulose. Butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ether ketone film, polyether sulfone Film, polyetherimide film, polyimide film, Fluororesin film, a polyamide film, an acrylic resin film, norbornene resin film, a plastic film such as a cycloolefin resin film or a laminated film of them, and the like.

  Among these, a polyester film, a polycarbonate film, a polyimide film, a norbornene resin film, a cycloolefin resin film, and the like are preferable because they have strength suitable for a touch panel and the like. Among these, from the viewpoint of transparency and thickness accuracy, a polyester film is particularly preferable, and among them, polyethylene terephthalate (PET) excellent in adhesion to the thermoplastic resin in the functional layer 3 is more preferable.

  The transparent plastic substrate 2 has an easy-adhesion layer on at least one surface from the viewpoint of improving the adhesion with the functional layer 3 (the easy-adhesion layer is laminated on at least one surface of the plastic film body). It is also preferable that it is a transparent plastic substrate). The easy-adhesion layer is not particularly limited, but preferred is a layer formed by blending a predetermined amount of organic or inorganic fine particles with a thermoplastic resin such as an acrylic resin, a urethane resin, or an ester resin. Furthermore, the thickness of the easy-adhesion layer is preferably about several nm to 1 μm, and preferably about 10 nm to 300 nm, from the viewpoint of sufficient adhesion without affecting the optical properties of the functional layer 3. Is particularly preferred. In addition, an easily bonding layer may exist in the functional layer 3 side of the transparent plastic base material 2, may exist in the opposite side, and may exist in both sides.

  There is no restriction | limiting in particular in the thickness of the transparent plastic base material 2, Although it selects suitably according to a use, Usually, 15-300 micrometers, Preferably it is the range of 30-250 micrometers. Moreover, this transparent plastic base material 2 can be surface-treated by the oxidation method, the uneven | corrugated method, etc. on one side or both surfaces as needed for the purpose of improving the adhesiveness with the layer provided in the surface. As the oxidation method, for example, corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, etc. are used, and as the unevenness method, for example, sand blast method, solvent treatment method, etc. are used. It is done. These surface treatment methods are appropriately selected according to the type of the transparent plastic substrate 2, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

<Physical Properties of Transparent Conductive Film Laminating Film>
The total light transmittance (value measured according to JIS K7361) of the transparent conductive film laminating film 1 according to the present embodiment is preferably 80% or more, particularly preferably 83% or more, and further It is preferably 85% or more. Moreover, it is preferable that the haze value (value measured according to JISK7136) of the film 1 for transparent conductive film lamination which concerns on this embodiment is 3.0% or less, and it is especially 2.0% or less. More preferably, it is 1.0% or less. By satisfy | filling said physical property, the film 1 for transparent conductive film lamination has high transparency, and will become a suitable thing as an optical use.

<Manufacture of transparent conductive film lamination film>
The transparent conductive film laminating film 1 according to this embodiment can be preferably produced by the following method. In this method, as an example, the above-described composition C (a composition containing an active energy ray-curable component and a colorant) is used.

  Specifically, first, a coating layer of the composition C is formed on one main surface of the transparent plastic substrate 2. At this time, the coating agent containing the composition C may be directly applied to one main surface of the transparent plastic substrate 2 to form a coating layer, or the coating agent containing the composition C may be applied to the cover sheet. After forming the coating layer, the coating layer with the cover sheet may be bonded to one main surface of the transparent plastic substrate 2.

  As the cover sheet, those exemplified above as the plastic film can be used. In addition, a release sheet in which one side or both sides of the plastic film is release-treated with a release agent can also be used.

  The coating layer is formed by preparing a coating agent containing the composition C and optionally a solvent, and applying the coating agent to the transparent plastic substrate 2 or the cover sheet, followed by drying. The coating agent may be applied by a conventional method, for example, a bar coating method, a knife coating method, a Mayer bar method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method. Drying can be performed, for example, by heating at 40 to 150 ° C. for about 30 seconds to 5 minutes.

  Next, the functional layer 3 is formed by irradiating the coating layer with active energy rays such as ultraviolet rays and electron beams to cure the composition C. At this time, in order to improve the efficiency of curing, it is preferable to irradiate active energy rays in a state where the coating layer is shielded from oxygen. In order to shield the coating layer from oxygen, if a cover sheet is attached to the coating layer, the cover sheet is left as it is. If the cover layer is not attached to the coating layer, a new sheet is used. It is preferable that the cover sheet is laminated on the coating layer, or the transparent plastic substrate 2 and the laminate of the coating layer are placed in an atmosphere having a low oxygen concentration, preferably in a nitrogen atmosphere.

UV irradiation, high-pressure mercury lamp, a fusion H lamp, can be carried out by a xenon lamp or the like, the dose of ultraviolet ray is illuminance 50~1000mW / cm ^2, about the amount of light 50~1000mJ / cm ² is preferred. On the other hand, the electron beam irradiation can be performed by an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad.

  The transparent conductive film laminating film 1 described above is suitably used as a production material for a transparent conductive film described later.

[Transparent conductive film]
FIG. 2 is a cross-sectional view of a transparent conductive film according to an embodiment of the present invention. The transparent conductive film 10 according to this embodiment is obtained by laminating a patterned transparent conductive film 4 on the functional layer 3 of the transparent conductive film laminating film 1 described above. In the transparent conductive film 10, the presence of the functional layer 3 makes it difficult for the pattern of the transparent conductive film 4 to be visually recognized.

<Transparent conductive film>
As a material of the transparent conductive film 4 in the transparent conductive film 10 according to the present embodiment, any material having both transparency and conductivity can be used without particular limitation. For example, tin-doped indium oxide (ITO), iridium oxide ( IrO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), fluorine-doped tin oxide (FTO), indium oxide-zinc oxide (IZO), zinc oxide (ZnO), gallium-doped zinc oxide (GZO) And transparent conductive metal oxides such as aluminum-doped zinc oxide (AZO), molybdenum oxide (MoO ₃ ), and titanium oxide (TiO ₂ ). These metal oxide thin films become transparent conductive films having both transparency and conductivity by employing appropriate film forming conditions.

  The film thickness of the transparent conductive film 4 is preferably 4 to 800 nm, more preferably 5 to 500 nm, and particularly preferably 10 to 100 nm. When the film thickness of the transparent conductive film 4 is within such a range, the film becomes a continuous thin film and stable conductivity is obtained, and there is no possibility that the transparency is lowered.

<Physical properties of transparent conductive film>
In the transparent conductive film 10, the absolute value of the difference (reflectance difference) between the reflectance (%) in the portion where the transparent conductive film 4 is present and the reflectance (%) in the portion where the transparent conductive film 4 is not present, It is preferably 10.0 points (difference in reflectance%) or less at a wavelength of 380 to 780 nm, particularly preferably 9.5 points or less, and further preferably 9.0 points or less. Thereby, the pattern of the transparent conductive film 4 becomes difficult to be visually recognized. The reflectance difference can be achieved by the presence of the functional layer 3 described above.

<Manufacture of transparent conductive film>
The transparent conductive film 10 which concerns on this embodiment can be manufactured by the method shown below, for example. First, after manufacturing the transparent conductive film laminating film 1 as described above, a known method such as a vacuum deposition method, a sputtering method, a CVD method, an ion plating method, a spray method, or a sol-gel method is formed on the functional layer 3. The method is appropriately selected according to the type of material and the required film thickness, and the transparent conductive film 4 is formed.

  The transparent conductive film 4 formed as described above forms a resist mask having a predetermined pattern by a photolithography method, and performs an etching process by a known method, for example, patterning into a stripe pattern or the like. Thereby, the transparent conductive film 10 which has the patterned transparent conductive film 4 is obtained. The line width and spacing of the patterned transparent conductive film are not particularly limited, but are preferably 0.01 to 100 mm, and particularly preferably 0.1 to 50 mm.

  As described above, the transparent conductive film 10 according to the present embodiment does not have a high refractive index layer or a low refractive index layer, and the pattern of the transparent conductive film 4 is hardly visible even when the layer configuration is simplified.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  For example, another layer may be laminated on the surface opposite to the functional layer 3 side in the transparent conductive film laminating film 1.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples etc.

[Preparation Example 1] (Preparation of functional layer coating agent F1)
20 parts by mass of phenol novolac acrylic prepolymer (trade name “Hitaroid 7663” manufactured by Hitachi Chemical Co., Ltd.) as an active energy ray-curable component (solid content converted value; the same applies hereinafter) and fine zirconium oxide particles as a refractive index adjuster 80 parts by mass (trade name “ZRMIBK15WT% -F85” manufactured by CIK Nanotech Co., Ltd., average particle size 20 nm) and cobalt blue as a blue colorant (trade name “CBDMIBK15WT% -R13” manufactured by CIK Nanotech Co., Ltd.) 7.5 Mass parts and 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by BASF Corporation) as a photopolymerization initiator are mixed uniformly using methyl ethyl ketone as a diluting solvent to obtain a solid content. A functional layer coating agent F1 having a concentration of 7.5% was prepared.

[Preparation Example 2] (Preparation of functional layer coating agent F2)
Fluorene skeleton-introduced acrylic prepolymer (made by Taisei Fine Chemical Co., Ltd., trade name “Acryt 8DK-3000”) as an active energy ray-curable component, and cobalt blue (produced by CIK Nanotech Co., Ltd., trade name) as a blue colorant 15 parts by mass of “CBDMIBK15WT% -R13”) and 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by BASF Corporation) as a photopolymerization initiator are used as a dilution solvent. Were mixed uniformly to prepare a functional layer coating agent F2 having a solid content of 7.5%.

[Preparation Example 3] (Preparation of functional layer coating agent F3)
100 parts by mass of dipentaerythritol hexaacrylate as an active energy ray-curable component and 300 parts by mass of zirconium oxide fine particles (trade name “ZRMIBK15WT% -F85”, average particle diameter 20 nm, manufactured by CIK Nanotech Co., Ltd.) as a refractive index adjusting agent And 2 parts by mass of copper phthalocyanine blue (manufactured by Nihongo Bix, trade name “NSP-CZ9664Blue”) as a blue colorant, and 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, trade name “ 6 parts by mass of Irgacure 184 ") were uniformly mixed using methyl ethyl ketone as a diluent solvent to prepare a functional layer coating agent F3 having a solid content concentration of 7.5%.

[Preparation Example 4] (Preparation of functional layer coating agent F4)
100 parts by mass of fluorine-containing acrylic prepolymer (trade name “OPSTA TU1001”; photopolymerization initiator-containing product manufactured by JSR Corporation) as an active energy ray-curable component is uniformly mixed with methyl ethyl ketone as a diluting solvent, and solid A functional layer coating agent F4 having a partial concentration of 7.5% was prepared.

[Preparation Example 5] (Preparation of functional layer coating agent F5)
Fluorine-containing acrylic prepolymer as an active energy ray-curable component (manufactured by JSR, trade name “OPSTAR TU1001”; photopolymerization initiator-containing product) 100 parts by mass and cobalt blue as a blue colorant (manufactured by CIK Nanotech) , Trade name “CBDMIBK15WT% -R13”) and 15 parts by mass were uniformly mixed using methyl ethyl ketone as a diluent solvent to prepare a functional layer coating agent F5 having a solid content concentration of 7.5%.

[Preparation Example 6] (Preparation of functional layer coating agent F6)
100 parts by mass of dipentaerythritol hexaacrylate as an active energy ray-curable component, 15 parts by mass of cobalt blue (manufactured by CIK Nanotech Co., Ltd., trade name “CBDMIBK15WT% -R13”) as a blue colorant, and a photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone (BASF, trade name “Irgacure 184”) 5 parts by mass uniformly using methyl ethyl ketone as a diluent solvent, a functional layer having a solid content concentration of 7.5% Coating agent F6 was prepared.

[Preparation Example 7] (Preparation of functional layer coating agent F7)
20 parts by mass of fluorene skeleton-introduced acrylic prepolymer (made by Taisei Fine Chemical Co., Ltd., trade name “Acryt 8DK-3000”) as an active energy ray-curable component, and fine zirconium oxide particles (produced by CIK Nanotech Co., Ltd.) Diluting 80 parts by mass of a trade name “ZRMIBK15WT% -F85”, average particle diameter 20 nm) and 1 part by mass of 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184” manufactured by BASF) as a photopolymerization initiator Using methyl ethyl ketone as a solvent, the mixture was uniformly mixed to prepare a functional layer coating agent F7 having a solid concentration of 7.5%.

[Examples 1 to 3, Comparative Examples 1 to 5]
(1) Manufacture of transparent conductive film lamination film Ease of polyethylene terephthalate (PET) film (trade name “Cosmo Shine A4100”, thickness 50 μm, manufactured by Toyobo Co., Ltd.) having an easy-adhesion layer on one side as a transparent plastic substrate On the surface opposite to the adhesive layer, functional layer coating agents (F1 to F7) shown in Table 1 were applied with a Mayer bar. This was dried in an oven at 70 ° C. for 1 minute to form a coating layer. By irradiating this coating layer with ultraviolet rays under the following conditions, a functional layer having a thickness shown in Table 1 was formed to obtain a transparent conductive film laminating film.
<Ultraviolet irradiation conditions>
UV irradiation device: GS Yuasa Corporation, Nitrogen purge type small conveyor UV irradiation device CSN2-40
Light source: High-pressure mercury lamp Lamp power: 1.4 kW
Conveyor speed: 1.2 m / min Illuminance: 100 mW / cm ²
Light intensity: 240 mJ / cm ²

(2) Production of transparent conductive film Sputtering was performed on the functional layer of the transparent conductive film laminating film obtained above using an ITO target (10% by mass of tin oxide) to form a transparent conductive film having a thickness of 30 nm. The transparent conductive film was obtained.

[Test Example 1] (Measurement of refractive index)
(1) Refractive index of functional layer The easy-adhesion layer (surface opposite to the functional layer) of the transparent plastic substrate in the transparent conductive film laminated film produced in the examples and comparative examples is scraped off with a sandpaper, The surface was painted black with an oil-based pen (Zebra, trade name “Mackey Black”). For the surface on the functional layer side, a spectroscopic ellipsometer (manufactured by JA WOOLLAM, trade name “M-2000”) is used, and the refractive index at 589 nm of the functional layer is based on JIS K7142: 2008. Measured. At this time, the film thickness of the functional layer was also measured. The results are shown in Table 1.

(2) Refractive index of transparent conductive film Sputtering was carried out on the surface opposite to the easy-adhesion layer of the transparent plastic substrate used in the examples and comparative examples in the same manner as in the examples and comparative examples. A transparent conductive film was formed. Thereafter, as in the case of measuring the refractive index of the functional layer, the easy-adhesion layer was removed and its surface was painted black. Then, a spectroscopic ellipsometer (manufactured by JA WOOLLAM, product name “M-2000”) is used for the surface on the transparent conductive film side, and the refractive index at 589 nm of the transparent conductive film conforms to JIS K7142: 2008. Measured. As a result, the refractive index of the transparent conductive film was 1.95.

[Test Example 2] (Measurement of optical performance)
About the transparent conductive film lamination films obtained in Examples and Comparative Examples, using a haze meter (product name “NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.), the total light transmittance (%) was determined according to JIS K7361. While measuring, haze value (%) was measured according to JIS K7136. The results are shown in Table 1.

[Test Example 3] (Measurement of reflectance)
On the transparent conductive film of the transparent conductive film obtained in the Examples and Comparative Examples, a plurality of polyimide adhesive tapes (5 cm wide) were attached so as to be arranged in parallel at intervals of 5 cm.

  The obtained laminate was immersed in hydrochloric acid adjusted to 1 mol / l for 2 minutes, and the transparent conductive film portion to which the polyimide adhesive tape was not applied was etched. Subsequently, the laminate was sufficiently washed with ion-exchanged water, dried at 120 ° C. for 10 minutes, and then the polyimide adhesive tape was peeled off from the transparent conductive film. Thereby, the transparent conductive film by which the transparent conductive film was patterned was obtained so that the transparent conductive film part of width 5cm and the transparent conductive film non-existence part of width 5cm were repeated alternately.

  About the part (pattern part) in which the transparent conductive film exists in the patterned transparent conductive film and the part (non-pattern part) in which the transparent conductive film does not exist, the reflectance (%) at wavelengths of 380 nm, 550 nm, and 780 nm, It was measured with a spectrophotometer (manufactured by Shimadzu Corporation, product name “UV-3600”). Based on the result, the reflectance difference (point) was calculated by subtracting the reflectance (%) of the portion where the transparent conductive film was not present from the reflectance (%) of the portion where the transparent conductive film was present. The results are shown in Table 1.

[Test Example 4] (Measurement of b *)
About the patterned transparent conductive film obtained in the same manner as in Test Example 3, the portion where the transparent conductive film exists (pattern portion) and the portion where the transparent conductive film does not exist (non-pattern portion) according to JIS Z8722, L * a * b * colorimetry by transmission measurement method using simultaneous measurement type spectroscopic color difference meter (Nippon Denshoku Industries Co., Ltd., SQ-2000) as a measuring device and C light source 2 ° field of view (C / 2) as a light source. The b * of the system was measured. The results are shown in Table 1.

[Test Example 5] (Pattern non-visibility evaluation)
On the transparent conductive film of the transparent conductive film obtained in the examples and comparative examples, a plurality of polyimide adhesive tapes (width 1 cm) were attached so as to be arranged in parallel at intervals of 1 cm.

  The obtained laminate was immersed in hydrochloric acid adjusted to 1 mol / l for 2 minutes, and the transparent conductive film portion to which the polyimide adhesive tape was not applied was etched. Subsequently, the laminate was sufficiently washed with ion-exchanged water, dried at 120 ° C. for 10 minutes, and then the polyimide adhesive tape was peeled off from the transparent conductive film. Thereby, the transparent conductive film by which the transparent conductive film was patterned was obtained so that the transparent conductive film part with a width of 1 cm and the transparent conductive film absence part with a width of 1 cm were alternately repeated.

Thereafter, the patterned transparent conductive film was placed on a white paper and placed at a position 1 m from the white fluorescent lamp (27 W; 3 wavelengths) so that the transparent conductive film was on the white fluorescent lamp side. In that state, whether or not the pattern of the transparent conductive film was visible was visually observed, and pattern invisibility was evaluated according to the following criteria. The results are shown in Table 1.
= Pattern non-visibility evaluation =
3: The pattern of the transparent conductive film was difficult to see.
2: There was a difference in color or reflection intensity depending on the presence or absence of the transparent conductive film, and the pattern of the transparent conductive film was visible.
1: There was a difference in color and reflection intensity depending on the presence or absence of the transparent conductive film, and the pattern of the transparent conductive film was visible.

[Test Example 6] (Evaluation of pencil hardness)
About the functional layer of the film for transparent conductive film lamination obtained by the Example and the comparative example, pencil hardness was evaluated based on JISK5600. The results are shown in Table 1.

  As is clear from Table 1, the transparent conductive film produced in the example is a transparent conductive film even if the transparent conductive film laminating film has a simple structure in which a functional layer is laminated on a transparent plastic substrate. This pattern was difficult to visually recognize and had a high surface hardness.

  INDUSTRIAL APPLICABILITY The present invention is extremely useful for producing a transparent conductive film in which a transparent conductive film pattern is hardly visible at low cost.

DESCRIPTION OF SYMBOLS 1 ... Film for transparent conductive film lamination 2 ... Transparent plastic base material 3 ... Functional layer 10 ... Transparent conductive film 4 ... Transparent conductive film

Claims (4)

A transparent conductive film laminating film in which patterned transparent conductive films are laminated,
A transparent plastic substrate,
A functional layer laminated on at least one side of the transparent plastic substrate,
The functional layer has a refractive index of 1.52 to 2.00,
When a transparent conductive film patterned on the transparent conductive film laminating film is laminated, the L * a * b * color system b in the portion where the transparent conductive film exists and the portion where the transparent conductive film does not exist The functional layer contains a colorant so that * is -2 to 2, respectively .
The functional layer is directly laminated on the transparent plastic substrate,
The transparent conductive film laminating film, wherein the transparent conductive film is directly laminated on the functional layer . The film for laminating a transparent conductive film according to claim 1 , wherein the functional layer has a thickness of 0.05 to 10 μm. The functional layer is a transparent conductive film laminated film according to claim 1 or 2, characterized in that a hard coat layer. The transparent conductive film laminating film according to any one of claims 1 to 3 ,
A transparent conductive film comprising: a patterned transparent conductive film laminated on the functional layer of the transparent conductive film laminating film.

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