JP2015112811A - Tone correction film and transparent conductive film using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film that suppresses coloring of transmitted light, has a high total ray transmittance, and can suppress increase in a haze value when the film is subjected to a heat treatment.SOLUTION: The transparent conductive film includes a low-refractive tone correction layer laminated on a surface of a transparent base film comprising a polyester film having low crystallization of oligomer. The low-refractive tone correction layer comprises silica fine particles and an active energy ray-curable resin and has a refractive index of 1.33 to 1.53 to light at a wavelength of 400 nm and a film thickness of 10 to 55 nm. A high-refractive tone correction layer can be laminated between the transparent base film and the low-refractive tone correction layer, where the high-refractive tone correction layer comprises metal oxide fine particles and an active energy ray-curable resin and has a refractive index of 1.66 to 1.76 to light at a wavelength of 400 nm and a film thickness of 0.4 to 1.5 μm. A tin-doped indium oxide layer having a refractive index of 1.85 to 2.35 and a film thickness of 5 to 50 nm is laminated on the low-refractive tone correction layer.

Description

  The present invention relates to a color correction film for a touch panel and a transparent conductive film in which a transparent conductive layer is laminated on the color correction film.

  Currently, touch panels are widely used as devices that can input information by directly touching an image display unit. A touch panel is an input device that transmits light on a display screen such as a liquid crystal display device. As a typical form, a capacitive type that utilizes the change in current capacity that occurs between a transparent electrode and a finger. There is a touch panel.

  As a transparent conductive film for a touch panel, a transparent conductive film made of metal oxide such as indium oxide containing tin oxide (tin-doped indium oxide, ITO) or zinc oxide is laminated on a transparent base film. Commonly used. Such a transparent conductive film often has a yellow coloration at the same time that the total light transmittance is reduced due to a reduction in the transmittance in the short wavelength region of visible light derived from reflection and absorption in the transparent conductive layer. . For this reason, there is a problem that it is difficult to accurately express the color of the display device arranged under the touch panel.

  In order to solve this problem, Patent Document 1 proposes a transparent conductive film in which a transparent conductive layer is combined with a multilayer optical film. The transparent conductive film described in Patent Document 1 has a high refractive index layer (first color tone correction layer), a low refractive index layer (second color tone correction layer), and in order from the surface of the polyester film that is a transparent substrate film. In this configuration, tin-doped indium oxide layers are stacked. The high refractive index layer is formed of metal oxide fine particles and an ultraviolet curable binder, and has a refractive index of 1.63 to 1.86 and a film thickness of 40 to 90 nm at a light wavelength of 400 nm. The low refractive index layer has a refractive index of 1.33 to 1.53 and a film thickness of 10 to 50 nm at a light wavelength of 400 nm. The tin-doped indium oxide layer has a refractive index of 1.85 to 2.35 at a light wavelength of 400 nm and a film thickness of 5 to 50 nm. With such a configuration, an effect of reducing transmitted light coloring is realized.

JP 2011-98563 A

  However, in the transparent conductive film of Patent Document 1, since a general polyester film is used as a transparent substrate film, when laminating an ITO layer as a transparent conductive layer, by heat treatment when crystallizing ITO, It turned out that the oligomer derived from a polyester film precipitates on the surface of a transparent base film, a transparent conductive film whitens and the total light transmittance falls.

  Therefore, an object of the present invention is to provide a transparent conductive film having a high total light transmittance by suppressing coloring of transmitted light and suppressing whitening due to heat treatment, and a color tone correction film used as a base film thereof. It is to provide.

  As a means for that, the color tone correction film of the present invention has a low-refractive color tone correction layer laminated on one surface of the transparent substrate film. The low bend color tone correction layer includes silica fine particles and an active energy ray-curable resin, and has a refractive index of 1.33 to 1.53 and a film thickness of 10 to 55 nm with respect to light having a wavelength of 400 nm. In addition, the transparent substrate film is an oligomer low precipitation polyester film.

  As the transparent substrate film with a small amount of oligomer precipitation, specifically, a low oligomer polyester film having a cyclic trimer content of less than 1.0 wt% can be suitably used. The transparent substrate film is preferably covered with an oligomer sealing film that seals oligomer precipitation.

  In addition, a high bend color tone correction layer can be laminated between the transparent substrate film and the low bend color tone correction layer. In this case, the high-reflective color tone correcting layer includes metal oxide fine particles and an active energy ray-curable resin, and has a refractive index of 1.66 to 1.76 and a film thickness of 0.4 to 1 with respect to light having a wavelength of 400 nm. .5 μm.

  Further, according to the present invention, a tin-doped indium oxide layer having a refractive index of 1.85 to 2.35 and a film thickness of 5 to 50 nm with respect to light having a wavelength of 400 nm is formed on the low color tone correction layer of the color correction film. A transparent conductive film in which (ITO layer) is laminated can also be provided.

  In this specification, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.

  In the color tone correction film or transparent conductive film of the present invention, the coloring of transmitted light can be suppressed by appropriately setting the refractive index and film thickness of each layer laminated on the transparent substrate film.

  The refractive index has wavelength dispersion, and the refractive index tends to increase in the short wavelength region. In general, the refractive index adjustment of each layer often uses the value of sodium D-line (light with a wavelength of 589 nm), but includes metal oxide fine particles such as the high-reflective color tone correction layer and tin-doped indium oxide layer of the present invention. In the layer, the influence of the wavelength dispersion of the refractive index is increased. On the other hand, transmittance control at a wavelength of 400 nm is important for suppressing the yellowness of transmitted light. However, when the refractive index of each layer is adjusted with the refractive index of the wavelength 589 nm, the transmittance at the wavelength of 400 nm cannot be adjusted accurately, and thus the yellowness reduction effect cannot be sufficiently obtained. Therefore, by setting the refractive index of each layer with reference to light having a wavelength of 400 nm, the effect of suppressing transmitted light coloring can be maximized.

  In addition, by using a polyester film having a low oligomer content as the transparent substrate film, the number of oligomers that can be precipitated in the heat treatment during the formation of the ITO layer is fundamentally reduced, and the oligomer derived from the polyester film is precipitated. Whitening can be suppressed, and high total light transmittance can be obtained. In addition, if the transparent base film is covered with an oligomer sealing film, oligomer precipitation itself can be suppressed, and thus whitening can be more reliably suppressed.

It is a schematic diagram explaining the definition of the curvature after heat processing.

≪Color tone correction film≫
[Embodiment 1]
In the color correction film of Embodiment 1, only the low bending color correction layer is laminated on one surface (front side) of the transparent base film. Below, the component of this color tone correction film is demonstrated in order.

<Transparent substrate film>
As the transparent substrate film, a film made of polyester such as polyethylene terephthalate (PET) is basically used, and in particular, a polyester film having a small amount of oligomer precipitation on the surface of the transparent substrate film is used. That is, a polyester film having as little content of the cyclic trimer as an oligomer as possible, specifically, the content of the cyclic trimer is at least less than 1.0 wt%, preferably less than 0.6 wt%, more preferably 0.8. A low oligomer polyester film of less than 3 wt% is used. When the content of the cyclic trimer exceeds 1.0 wt%, whitening due to the precipitation of the oligomer becomes remarkable during the formation of the ITO layer. For example, when a polyethylene terephthalate film is used as the transparent substrate film, the oligomer that can be precipitated is an ethylene terephthalate cyclic trimer.

  The polyester used as a raw material may be obtained by a melt polymerization reaction. However, if a raw material obtained by solid-phase polymerization of a polyester polyester after melt polymerization is used, the amount of oligomer contained in the raw material Can be reduced. The amount of oligomer contained in the polyester raw material is preferably 0.7 wt% or less, more preferably 0.5 wt% or less, and particularly preferably 0.2 wt% or less. If the amount of oligomer in the polyester raw material is small, the amount of oligomer contained in the polyester film of the present invention is also reduced. In addition, you may obtain a polyester film using two or more types of polyester raw materials.

  For example, in the case of a PET film, a liquid phase polycondensation step in which a dicarboxylic acid containing terephthalic acid and a diol containing ethylene glycol are subjected to liquid phase polycondensation, and a cyclic trimer is obtained from the polymer obtained in the liquid phase polycondensation step. In order to reduce, it can manufacture via the solid-phase polycondensation process heated to the temperature below a melting point in inert atmosphere. In addition, the esterification process which esterifies terephthalic acid and ethylene glycol can also be performed before a liquid phase polycondensation process.

  As the dicarboxylic acid, terephthalic acid is a main component (for example, the content of terephthalic acid is 90 mol% or more with respect to all dicarboxylic acids), and phthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4 Aromatic dicarboxylic acids such as dicarboxylic acids and diphenoxyethanedicarboxylic acids can be used together.

  As the diol, monoethylene glycol as a main component (for example, the content of monoethylene glycol with respect to all diols is 90 mol% or more), trimethylene glycol, propylene glycol, tetramethylene glycol, neopentyl glycol, hexanemethylene glycol, Aliphatic glycols such as dodecamethylene glycol can be used.

  In addition to aromatic dicarboxylic acids, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid can also be used as raw materials. In addition, aromatic diols such as alicyclic glycols such as cyclohexanedimethanol, bisphenol, hydroquinone, and 2,2-bis (4-β-hydroxyphenyl) propane can be used as raw materials. Furthermore, polyfunctional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol can be used as a raw material.

  In addition, it is preferable to contain about 1.0-5.0 mol% of diethylene glycol (DEG) in all the diol components. This is because within this range, the reduction rate of the cyclic trimer is increased in the solid phase polycondensation step. In order to suppress the formation of DEG, a basic compound such as a tertiary amine such as triethylamine, a quaternary ammonium salt such as tetraethylammonium hydroxide, or an alkali metal compound such as sodium carbonate may be added as an additive. It is valid. The amount of DEG produced can also be controlled by the ratio of dicarboxylic acid and diol in the esterification reaction step. The esterification reaction product (low-order condensate) of dicarboxylic acid and diol obtained in the esterification step is supplied to the liquid phase polycondensation step. The PET obtained in the liquid phase polycondensation reaction is usually cut into particles (chips) after water cooling. In addition, the content of the ethylene terephthalate cyclic trimer, which is an oligomer, can be reduced by passing through a solid phase polycondensation step of heating to a temperature below the melting point in an inert atmosphere.

  The liquid phase polycondensation reaction is preferably performed in the presence of a polycondensation catalyst and a stabilizer. Examples of the polycondensation catalyst include germanium compounds, antimony compounds, titanium compounds, and the like. Examples of the germanium compound include amorphous germanium dioxide and crystalline germanium dioxide. Examples of titanium compounds include tetraalkyl titanates such as tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate, and partial hydrolysates thereof. And titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, titanyl potassium oxalate, titanyl calcium oxalate, titanyl succinate strontium succinate, trimellitic acid titanium, titanium sulfate, titanium chloride and the like. Examples of the antimony compound include antimony trioxide, antimony acetate, antimony tartrate, antimony potassium tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenylantimony.

  Examples of the stabilizer include phosphate esters such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, trioctyl phosphate, triphenyl phosphate; triphenyl phosphite, trisdodecyl phosphite, trisnonyl phenyl phosphite, etc. Phosphites; acid phosphates such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, dioctyl phosphate, ethyl diethylphosphonoacetate, and phosphoric acid, polyphosphoric acid And phosphorus compounds.

  In the polyester film, particles may be blended mainly for the purpose of imparting easy slipperiness. The type of particles to be blended is not particularly limited as long as it is a particle capable of imparting slipperiness. Specific examples include silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, and magnesium phosphate. , Particles of kaolin, aluminum oxide, titanium oxide and the like. The method for adding particles to the polyester film is not particularly limited, and a conventionally known method can be adopted. For example, it can be added at any stage for producing the polyester film, but it can also be preferably added at the esterification stage or after the transesterification reaction in the polycondensation reaction step. Further, in the polyester film, in addition to the above-mentioned particles, conventionally known antioxidants, antistatic agents, thermal stabilizers, lubricants, dyes, pigments, ultraviolet absorbers, especially benzoxazinone-based ultraviolet rays, if necessary. An absorbent or the like can also be added.

  The film thickness of the transparent substrate film is usually about 25 to 400 μm, preferably about 25 to 188 μm. In addition, when a transparent base film is formed with PET resin, the refractive index with respect to the light with a wavelength of 400 nm is 1.72.

<Oligomer sealing film>
Moreover, it is preferable to coat | cover a transparent base film with the oligomer sealing film (primer layer) which seals the cyclic trimer which precipitates as an oligomer. Thereby, precipitation of an oligomer can be suppressed more. The oligomer sealing film contains an organic compound containing a metal element and a binder polymer. The organic compound containing a metal element is not particularly limited, but it is preferable to use an organic compound having a metal element belonging to groups IVA and IIIB in the periodic table. An organic compound containing aluminum, titanium, or zirconium is preferable in terms of superiority.

Specific examples of the organic compound having an aluminum element include aluminum alcoholates such as (CH ₃ O) ₃ Al and (C ₂ H ₅ O) ₃ Al, aluminum salts such as stearic acid, octylic acid and benzoic acid, aluminum tris ( Acetylacetonate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-isopropoxide-monomethylacetoacetate, aluminum organic acid chelate, etc. Is exemplified. Among these, it is preferable to contain an aluminum chelate in the oligomer sealing film in that the oligomer precipitation preventing property is particularly good.

  Specific examples of the organic compound having a titanium element include, for example, titanium orthoesters such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate; titanium acetylacetonate, Examples thereof include titanium chelates such as titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolamate, and titanium ethylacetoacetate.

Specific examples of the organic compound having a zirconium element include zirconium acetate, zirconium normal propyrate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, zirconium bisacetylacetonate and the like. As the organic compound containing the metal element, only one type may be used, or two or more types may be appropriately mixed and used.

  The content of the organic compound containing a metal element contained in the oligomer sealing film may be 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight. If it is less than 10% by weight, the effect of preventing oligomer precipitation may be insufficient. On the other hand, when it exceeds 90% by weight, the amount increases unnecessarily, and the optical performance of the oligomer sealing film tends to deteriorate.

  Specific examples of the binder polymer include polyvinyl alcohol, polyacrylamide, polyalkylene glycol, polyalkyleneimine, methylcellulose, hydroxycellulose, starches, polyurethane, polyacrylate, chlorinated polymer (polyvinyl chloride, vinyl chloride vinyl acetate copolymer). Etc.). Among the above-mentioned binder polymers, it is preferable to contain polyvinyl alcohol in the coating layer because the oligomer precipitation preventing performance is further improved.

  The content of the binder polymer contained in the oligomer sealing film is not particularly limited, but is preferably in the range where the total content with the organic compound containing a metal element does not exceed 100% by weight, preferably 10-80. A range of about% by weight is preferable. If the content of the binder polymer is less than 10% by weight, the physical strength may be insufficient and may be easily damaged. On the other hand, if it exceeds 80% by weight, the effect of preventing oligomer precipitation may be insufficient. In addition, the degree of polymerization of the binder polymer is not particularly limited, but usually 100 or more, preferably 300 to 40,000 is suitably used for applications.

  Moreover, you may use a crosslinking agent together in the oligomer sealing film in the range which does not impair the main point of this invention. Specific examples thereof include methylolated or alkylolized urea, melamine, guanamine, acrylamide, polyamide, epoxy compound, aziridine compound, block polyisocyanate, silane coupling agent, titanium coupling agent, zirco. -An aluminate coupling agent etc. are mentioned. These crosslinking components may be previously bonded to the binder polymer.

  Further, inorganic particles may be contained for the purpose of improving the sticking property and slipperiness of the oligomer sealing film. Specific examples thereof include silica, alumina, kaolin, calcium carbonate, titanium oxide, barium salt and the like. Moreover, an antifoamer, a coating property improving agent, a thickener, an organic lubricant, organic polymer particles, an antioxidant, a UV absorber foaming agent, a dye, and the like may be contained as necessary.

  In the present invention, the thickness of the oligomer sealing film is not particularly limited as long as it can be formed as a film, but is preferably 5 nm to 1000 nm, more preferably 5 nm to 500 nm. When the oligomer sealing film is less than 5 nm, the oligomer sealing may be insufficient, and the amount of oligomer deposited from the surface after heat treatment may be whitened. On the other hand, when it coats exceeding 1000 nm, malfunctions, such as a slipperiness fall, may arise.

<Low bending tone correction layer>
The low-reflective color tone correction layer is a layer that corrects the color tone of the color tone correction film or the transparent conductive film (suppresses coloring of the transmitted color) by adjusting the refractive index and the film pressure within a predetermined range (details will be described later). is there. The low bend color tone correction layer is made of a cured product obtained by curing a coating solution for low bend color tone correction layer containing silica fine particles and an active energy ray-curable resin with active energy rays (for example, ultraviolet rays and electron beams).

  The active energy ray curable resin serves as a binder for the low-bending color tone correction layer. As the active energy ray curable resin, one or more kinds selected from a monofunctional monomer and a polyfunctional monomer of (meth) acrylate are used. Specifically, (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester and the like are preferable as the monofunctional monomer. Examples of the polyfunctional monomer include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like. In the present specification, “(meth) acrylate” means acrylate or methacrylate. The same applies to “(meth) acrylic acid” and “(meth) acryloyl group”. The active energy ray-curable resin preferably has a refractive index of 1.4 to 1.7 with respect to light having a wavelength of 400 nm. The content of the active energy ray-curable resin in the low bend color tone correction layer is about 5 to 80 wt%.

  The silica fine particles are blended in order to actively reduce the refractive index of the low bend color tone correction layer. As such silica fine particles, colloidal silica and hollow silica fine particles are preferable. The refractive indexes of colloidal silica and hollow silica fine particles with respect to light having a wavelength of 400 nm vary depending on the production method, but are preferably 1.25 to 1.55. It is preferable that 20 to 90 wt% of silica fine particles is contained in the low bend color tone correction layer. If the content of the silica fine particles is less than 20 wt%, the refractive index of the low-refractive-color tone correcting layer cannot be in a predetermined range (details will be described later). On the other hand, when the content of silica fine particles is more than 90 wt%, the coating film strength becomes weak.

  The coating solution for the low bend color tone correction layer also contains a photopolymerization initiator. The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the coating solution for the low-bending color tone correction layer with active energy rays such as ultraviolet rays (UV). The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The photopolymerization initiator is preferably contained in an amount of 1 to 10 wt% in the coating solution for the low bend color tone correction layer. If the content of the photopolymerization initiator in the coating solution for the low bend color correction layer is less than 1 wt%, the curing of the active energy ray-curable resin is insufficient, and if it exceeds 10 wt%, the amount is undesirably increased.

  The low bend color tone correction layer is formed by blending silica fine particles and an active energy ray-curable resin so that the refractive index with respect to light having a wavelength of 400 nm is 1.33 to 1.53, respectively. When the refractive index of the low bend color tone correcting layer is less than 1.33, the ratio of particles in the coating film increases, and the haze value increases, so the total light transmittance decreases. In addition, when the refractive index of the low-refractive-color-tone correction layer is larger than 1.53, the b * value of the transmitted color in the L * a * b color system defined in JIS Z 8729 becomes large, and the transparent The transmitted color yellow of the conductive film is clearly recognized. Further, the film thickness after drying and curing of the low bend color tone correction layer needs to be 10 to 55 nm. When the film thickness of the low-refractive-color tone correcting layer is outside this range, the value of b * increases, and the yellowish coloring of the transparent color of the transparent conductive film is clearly recognized.

[Embodiment 2]
In the color tone correction film of the present invention, a high refractive index correction layer having a higher refractive index than these can be laminated between the transparent substrate film and the low refractive index correction layer.

<High bending color correction layer>
The high-refractive color tone correction layer is a layer that corrects the color tone of the color-tone correction film or the transparent conductive film (suppresses the coloring of the transmitted color) by the relative relationship with the refractive index of the low-refractive color tone correction layer. Moreover, the surface hardness of a transparent conductive film can also be improved. The high-reflective color tone correction layer cures a coating solution for a high-refractive color tone correction layer containing metal oxide fine particles, an active energy ray-curable resin, and a photopolymerization initiator with active energy rays (for example, ultraviolet rays and electron beams). Made of cured product.

  The active energy ray-curable resin serves as a binder for the high-bending color tone correction layer. As the active energy ray curable resin, the same type as the active energy ray curable resin used in the low bending color tone correction layer can be used. The active energy ray-curable resin preferably has a refractive index of 1.4 to 1.7 with respect to light having a wavelength of 400 nm.

  The active energy ray-curable resin is contained in an amount of 10 to 50 wt% (10 to 50 parts by weight in 100 parts by weight of the coating solution for the high bend color tone correction layer excluding the solvent) in the high bend color tone correction layer. When the content of the active energy ray-curable resin is less than 10 wt%, the relative amount of the active energy ray-curable resin with respect to the coating film is small and the coating film becomes brittle. On the other hand, if the content of the active energy ray-curable resin exceeds 50 wt%, the refractive index of the high-refractive-color tone correcting layer is out of the predetermined range, which is not preferable.

  The metal oxide fine particles are blended in order to adjust the refractive index of the highly bent color tone correction layer. As such metal oxide fine particles, titanium oxide and zirconium oxide are preferable. The refractive index of titanium oxide or zirconium oxide with respect to light having a wavelength of 400 nm varies depending on the production method, but is 1.9 to 3.0.

  The metal oxide fine particles are contained in an amount of 45 to 85 wt% in the high-refractive color tone correction layer (45 to 85 parts by weight in 100 parts by weight of the coating solution for the high-refractive color tone correction layer excluding the solvent). If the content of the metal oxide fine particles is less than 45 wt%, the refractive index of the high-refractive-color tone correcting layer is out of the predetermined range, which is not preferable. On the other hand, when the content of the metal oxide fine particles exceeds 85 wt%, the relative amount of the metal oxide fine particles with respect to the coating film increases, and the coating film becomes brittle.

  The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the coating solution for a high color tone correction layer with active energy rays such as ultraviolet rays (UV). The photopolymerization initiator may be the same type as the photopolymerization initiator used in the low bend color tone correction layer coating solution. The photopolymerization initiator is contained in an amount of 1 to 10 parts by weight in 100 parts by weight of the coating solution for the high bending color tone correction layer excluding the solvent. When the content of the photopolymerization initiator is less than 1 part by weight, the active energy ray curable resin is not sufficiently cured. On the other hand, if the content of the photopolymerization initiator exceeds 10 parts by weight, the photopolymerization initiator is unnecessarily increased, which is not preferable.

  The total sum of the metal oxide fine particles, the active energy ray-curable resin, and the photopolymerization initiator in the high bend color tone correction layer is 99 to 100 wt%. When the total of these is 99 wt%, a fluorine-based or silicon-based leveling agent can be added as less than 1 wt% as another additive in order to improve the uniformity of the coated surface.

  The solvent for the coating liquid for the high color tone correction layer is not particularly limited as long as it is a known one that has been conventionally used for the coating liquid for forming each layer in this type of color tone correction film. An ester solvent can be selected in a timely manner.

  The high bend color tone correction layer includes the metal oxide fine particles and the active energy ray-curable resin in the above ranges, respectively, so that the refractive index with respect to light having a wavelength of 400 nm is 1.66 to 1.76. When the refractive index of the high refractive color tone correcting layer is outside this range, the b * value of the transmitted color in the L * a * b color system defined in JIS Z 8729 becomes large, and the transparent conductive film transmits light. The yellowish color is clearly recognized. Further, the film thickness after drying and curing of the high bending color tone correction layer needs to be 0.4 to 1.5 μm. Even if the film thickness of the high color correction layer is less than 0.4 μm, the b * value of the transmitted color in the L * a * b color system increases, and the transparent yellow color of the transparent conductive film becomes clear. Be recognized. On the other hand, when the film thickness of the highly bent color tone correction layer is larger than 1.5 μm, the warp after the heat treatment becomes large.

<Method for forming each layer>
In the color tone correction film of Embodiment 1, the low flexion color tone correction layer can be formed by applying a coating solution for the low flexion color tone correction layer on the transparent substrate film and then curing by applying active energy rays. In the color tone correction film of Embodiment 2, after applying the coating solution for the high color tone correction layer on the transparent substrate film and forming the high color tone correction layer by irradiating active energy rays, on the high color tone correction layer. The coating solution for the low bend color tone correction layer is applied, and the active energy ray is irradiated again to cure and form the low bend color tone correction layer. There are no particular restrictions on the application method of the coating solution for the high color tone correction layer and the coating solution for the low color tone correction layer. For example, the roll coating method, spin coating method, dip coating method, spray coating method, bar coating method, knife coating method. Any known method such as a die coating method, an ink jet method, or a gravure coating method may be employed. The type of active energy ray is not particularly limited, but it is preferable to use ultraviolet rays from the viewpoint of convenience and the like. In addition, in order to improve the adhesiveness of the highly bent color tone correction layer, it is possible to perform a pretreatment such as a corona discharge treatment on the surface of the transparent substrate film in advance.

≪Transparent conductive film≫
Each of the transparent conductive films has a tin-doped indium oxide layer on the low-bending color tone correction layer of the color tone correction film of the first embodiment or the second embodiment. The color of transmitted light of the transparent conductive film can be evaluated by b * of the Lab color system defined in JIS Z 8729, and preferably −1 ≦ b * ≦ 1. In the case of b *> 1, the transparent conductive film appears to be colored yellow, which is not preferable. On the other hand, when b * <− 1, the transparent conductive film appears to be colored blue, which is not preferable.

  The total light transmittance of the transparent conductive film is preferably 88% or more. If the total light transmittance is less than 88%, the visibility deteriorates, which is not preferable. Further, the haze value is less than 1%. A haze value of 1% or more is not preferable because it becomes white and visibility deteriorates.

<Tin-doped indium oxide layer>
The tin-doped indium oxide layer (ITO layer) is a transparent conductive layer, and has a refractive index of 1.85 to 2.35 and a film thickness of 5 to 50 nm with respect to light having a wavelength of 400 nm. If the refractive index is out of this range, the optical interference with the high-refractive color tone correction layer and the low-refractive color tone correction layer will not work properly, so the transparent conductive film will be colored and the total light transmittance will also decrease. To do. When the thickness of the ITO layer is less than 5 nm, it is difficult to form the ITO layer to a uniform thickness, and a stable resistance cannot be obtained, which is not preferable. In addition, when the thickness of the ITO layer is greater than 50 nm, the absorption of light by the ITO layer itself is strong, and the effect of reducing the coloring of the transmitted color is diminished, and the total light transmittance tends to be small.

<Formation of tin-doped indium oxide layer>
The method for forming the tin-doped indium oxide layer is not particularly limited, and for example, a vapor deposition method, a sputtering method, an ion plating method, and a CVD method can be employed. Among these, the vapor deposition method and the sputtering method are particularly preferable from the viewpoint of controlling the layer thickness. In addition, after forming a tin dope indium oxide layer, it anneals within the range of 100 to 200 degreeC, and crystallizes. Specifically, when crystallization is performed at a high temperature, the refractive index of the tin-doped indium oxide layer tends to decrease. Accordingly, the refractive index of the tin-doped indium oxide layer can be adjusted by controlling the annealing temperature and time.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the scope of these examples. Moreover, the refractive index, the transmitted color, the total light transmittance, the film thickness, and the haze value in each example were measured by the methods shown below.

<Refractive index (high refractive color correction layer, low refractive color correction layer)>
(1) A coating solution for each layer is formed on a PET film (trade name “A4100”, manufactured by Toyobo Co., Ltd.) having a refractive index of 1.72 with respect to light having a wavelength of 400 nm by a dip coater (produced by Sugiyama Motochemical Co., Ltd.). Each of the films was applied by adjusting the thickness of the layer so that the film thickness after drying and curing was about 100 to 500 nm.
(2) After drying, it was cured by irradiating with 400 mJ ultraviolet rays using a 120 W high-pressure mercury lamp in a nitrogen atmosphere by an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.). The back surface of the cured PET film was roughened with sandpaper, and the reflection spectrum was measured with a reflection spectral film thickness meter (“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.).
(3) From the reflectance read from the reflection spectrum, the constant of the wavelength dispersion formula (Formula 1) of n-Cauchy shown below was determined, and the refractive index at a wavelength of 400 nm was determined.
N (λ) = a / λ ⁴ + b / λ ² + c (Formula 1)
(N: refractive index, λ: wavelength, a, b, c: chromatic dispersion constant)

<Refractive index (ITO layer)>
(1) Sputtering was performed on a PET film (trade name “A4100” manufactured by Toyobo Co., Ltd.) having a refractive index with respect to light having a wavelength of 400 nm using an ITO target of indium: tin = 10: 1. A tin-doped indium oxide layer (ITO layer) as a transparent conductive layer having a thickness of 20 nm was formed, and annealed under the conditions of the following examples and comparative examples to produce a transparent conductive film.
(2) The reflection spectrum was measured with a reflection spectral film thickness meter (“FE-3000”, manufactured by Otsuka Electronics Co., Ltd.) after roughening the back surface of the transparent conductive film with sandpaper and painting with a black paint.
(3) From the reflectance read from the reflection spectrum, the refractive index at a wavelength of 400 nm of light was obtained using the above (Formula 1).
In addition, the refractive index of each layer described in each table (described later) is a refractive index obtained from the sample for refractive index measurement.

<Transparent color>
Using a color difference meter (“SQ-2000”, manufactured by Nippon Denshoku Industries Co., Ltd.), the transmitted color and b * of the transparent conductive film were measured. This b * is a value in the L * a * b * color system defined in JIS Z 8729.

<Total light transmittance / haze value>
The total light transmittance (%) and haze value of the transparent conductive film were measured with a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.).

<Warpage after heat treatment>
A transparent conductive film cut to a length of 50 mm and a width of 100 mm is left in a thermostatic bath at 150 ° C. for 1 hour to perform heat treatment. After that, as shown in FIG. 1, the transparent conductive film is placed on the flat surface with the ITO layer facing upward, and the amount of warping at the four corners (1), (2), (3) and (4) is measured. Measure the average value (warp average value). The average value of warpage was determined to be less than 10 mm, and the average value of warpage was determined to be 10 mm or more.

[Preparation of composition for oligomer sealing film (E-1)]
The following raw materials were mixed to prepare an oligomer sealing film composition (E-1).
Organic compound containing titanium element: Titanium lactate TC-310 (manufactured by Matsumoto Pharmaceutical Co., Ltd.) 50% by weight
-PVA-based resin: 25% by weight of polyvinyl alcohol having a saponification degree = 88 mol% and a polymerization degree = 500
Crosslinking agent: 20% by weight of gamma-glycidoxypropyltrimethoxysilane
-Particle: 5% by weight of silica sol having an average particle diameter of 65 nm

[Preparation of oligomer sealing film composition (E-2)]
The following raw materials were mixed to prepare an oligomer sealing film composition (E-2).
・ High refractive index fine particle dispersion [trade name: titanium oxide slurry (solid content 20% dispersion) manufactured by CIK Nanotech Co., Ltd.] 0.9% by weight
・ Polyester resin aqueous dispersion 20.7% by weight
・ Water 78.4% by weight

(Preparation of highly bent color tone correction layer)
The following raw materials were used as the coating solution for the high bending color tone correction layer, and the respective raw materials were mixed in the composition described in Table 1 to prepare coating solutions C-1 to C-5 for the high bending color correction layer. The refractive index of the high bend color tone correction layer formed using the obtained coating liquids C-1 to C-5 for the high bend color tone correction layer was measured. The results are also shown in Table 1.

  As the metal oxide fine particles, zirconium oxide fine particle dispersion (ZRMEK 25% -F47, manufactured by CI Kasei Co., Ltd.) or titanium oxide fine particle dispersion (RTTMIK15WT% -N24, manufactured by CI Chemical Co., Ltd.) was used. Further, as an active energy ray curable resin, hexafunctional urethane acrylate (purple light UV-7600B manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used. The metal oxide fine particles and the active energy ray curable resin, the photopolymerization initiator, and the solvent were mixed at a weight ratio of 95: 5: 100. IRGACURE184 (I-184) manufactured by Ciba Specialty Chemicals Co., Ltd. was used as a photopolymerization initiator. Further, methyl isobutyl ketone was used as a solvent.

[Preparation of coating solution for low bending color tone correction layer]
The following raw materials were used as the coating solution for the low bending color tone correction layer, and the respective raw materials were mixed in the composition described in Table 2 below to prepare coating solutions L-1 to L-5 for the low bending color correction layer. The refractive index of the low bend color tone correction layer formed using the obtained coating solutions L-1 to L-5 for the low bend color tone correction layer was measured. The results are shown in Table 2.

  As silica fine particles, “PL-1” manufactured by Fuso Chemical Industry Co., Ltd. or acrylic modified hollow silica fine particles “Thruria NAU” manufactured by JGC Catalysts & Chemicals Co., Ltd. were used. Further, a zirconium oxide fine particle dispersion (ZRMEK 25% -F47, manufactured by CI Kasei Co., Ltd.) was used as the metal oxide fine particles. Further, dipentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) was used as the active energy ray curable resin. IRGACURE907 (I-907) manufactured by Ciba Specialty Chemicals Co., Ltd. was used as a photopolymerization initiator. Isopropyl alcohol was used as a solvent. The fine particle component (silica fine particles or metal oxide fine particles), the active energy ray-curable resin, the photopolymerization initiator, and the solvent were mixed at a weight ratio of 95: 5: 4000.

[Formation of transparent substrate film (low oligomer polyester film (PET-OL1))]
Starting from 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate and 0.008 parts by weight of antimony trioxide are added to 100 parts by weight of dimethyl terephthalate. The ester exchange reaction was performed by heating and raising the temperature. Next, 0.026 parts by weight of trimethyl phosphate is added to the transesterification reaction product with respect to 100 parts by weight of dimethyl terephthalate, and then transferred to a polycondensation reaction layer. Subsequently, the reaction system was gradually depressurized while being heated and heated, and polymerization was performed at 290 ° C. under a reduced pressure of 1 mmHg to obtain a polyester having an intrinsic viscosity of 0.54. The obtained polyester was heat-treated at 225 ° C. for 30 hours under a reduced pressure of 1 mmHg to carry out solid phase polymerization to obtain a polyester C having an intrinsic viscosity of 1.1.

  The polyester C is fed to an extruder, melted at 285 ° C., extruded onto a casting drum cooled to 40 ° C., and then led to a tenter having a linear motor driven simultaneous biaxial stretching machine. Was preheated and heated with hot air, and simultaneously biaxially stretched at 95 ° C. in the longitudinal direction 3.5 times and in the transverse direction 4.3 times. Thereafter, the composition for the oligomer sealing film (E-2) was uniformly applied to both surfaces with a roll coater, heat-fixed in a hot air atmosphere at 240 ° C. for 3 seconds in the same tenter, and longitudinally at the same temperature. After performing a 3% relaxation treatment in each of the lateral directions, the film was rolled up to obtain a laminated low oligomer polyester film (PET-OL1) having a thickness of 100 μm and coated with an oligomer sealing film. The film thickness of the oligomer sealing film was 80 nm on both sides.

[Formation of transparent substrate film (low oligomer polyester film (PET-OL2))]
[Polyester A adjustment]
100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol are used as starting materials, 0.01 part by weight of tetrabutoxy titanate as a catalyst is added to the reactor, the reaction start temperature is set to 150 ° C., and the methanol is gradually distilled off. The reaction temperature was raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. This reaction mixture was transferred to a polycondensation tank, and an ethylene glycol slurry of silica particles having an average particle size of 2.5 μm was added so that the content of the particles with respect to polyester was 0.06% by weight, and a polycondensation reaction was performed for 4 hours. went. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.55 due to a change in stirring power of the reaction vessel, and the polymer was discharged under nitrogen pressure to obtain a polyester having an intrinsic viscosity of 0.55. The obtained polyester was heat-treated at 220 ° C. for 30 hours under a reduced pressure of 1 mmHg to carry out solid phase polymerization to obtain polyester A having an intrinsic viscosity of 0.67.

[Polyester B adjustment]
Starting from 100 parts by weight of dimethyl terephthalate and 60 parts by weight of ethylene glycol, 0.09 parts by weight of magnesium acetate tetrahydrate as a catalyst is added to the reactor, the reaction start temperature is 150 ° C., and methanol is distilled off. At the same time, the reaction temperature was gradually raised to 230 ° C. after 3 hours. After 4 hours, the transesterification reaction was substantially terminated. This reaction mixture was transferred to a polycondensation tank, 0.02 part of orthophosphoric acid was added, and then 0.02 part of germanium dioxide was added to carry out a polycondensation reaction for 4 hours. That is, the temperature was gradually raised from 230 ° C. to 280 ° C. On the other hand, the pressure was gradually reduced from normal pressure, and finally 0.3 mmHg. After the start of the reaction, the reaction was stopped at a time corresponding to an intrinsic viscosity of 0.63 due to a change in stirring power in the reaction tank, and the polymer was discharged under nitrogen pressure to obtain polyester B having an intrinsic viscosity of 0.63.

  The mixed raw materials in which the polyesters A and B are mixed at a ratio of 95% by weight and 5% by weight are supplied to an extruder, melted at 285 ° C., then extruded onto a casting drum cooled to 40 ° C., and cooled and solidified. Thus, a non-oriented sheet was obtained. Next, it is led to a tenter having a linear motor driven simultaneous biaxial stretching machine, preheated and heated with hot air at 95 ° C, and simultaneously at 95 ° C, 3.5 times in the vertical direction and 4.3 times in the horizontal direction. Biaxial stretching was performed. Then, the composition for oligomer sealing film (E-1) is applied uniformly on one side and the composition for oligomer sealing film (E-2) is applied on the other side with a roll coater, and hot air at 240 ° C. in the same tenter. Thickness covered with an oligomer sealing film by performing heat setting in an atmosphere for 3 seconds, performing 3% relaxation treatment in the longitudinal and transverse directions at the same temperature, and then winding the film into a roll. A 100 μm laminated low oligomer polyester film (PET-OL2) was obtained. The film thickness of the oligomer sealing film was 80 nm on both sides.

(Example 1-1)
Apply a coating solution (L-1) for low-reflective color tone correction layer on one surface of the low oligomer polyester film (PET-OL1) with a bar coater, and cure it by irradiating 400 mJ ultraviolet rays with a 120 W high-pressure mercury lamp. Thus, a low-refractive color tone correction layer was formed to produce a color tone correction film (see Table 3 below).

(Example 1-2 to Example 1-5)
A color correction film was produced in the same manner as in Example 1-1 except that the low bend color correction layer was made of the material and film thickness described in Table 3 below.

(Example 1-6)
A color correction film was prepared in the same manner as in Example 1-1 except that the transparent base film was an oligomer-encapsulated polyester film (PET-OL2).

(Example 2-1)
One side of the low oligomer polyester film (PET-OL1) is coated with a coating solution (C-1) for a high color tone correction layer with a bar coater, and cured by irradiating with 400 mJ ultraviolet rays with a 120 W high pressure mercury lamp. Thus, a hard coat layer was formed. Subsequently, a low bending color tone correction layer coating liquid (L-1) is applied onto the high bending color tone correction layer with a bar coater, and cured by irradiating with 400 mJ ultraviolet rays with a 120 W high pressure mercury lamp. A color correction layer was formed to produce a color correction film (see Table 4 below).

(Example 2-2 to Example 2-9)
A color correction film was produced in the same manner as in Example 2-1, except that the high bend color correction layer and the low bend color correction layer were made of the materials and film thicknesses shown in Table 4 below.

(Example 2-10)
A color tone correction film was produced in the same manner as in Example 2-1, except that the base material was an oligomer-encapsulated polyester film (PET-OL2).

(Example 3-1)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low bend color correction layer of the color correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ) And an annealing treatment at 150 ° C. for 30 minutes to produce a transparent conductive film. About the obtained transparent conductive film, the transmitted color b *, the total light transmittance, the haze value, and the warp after heat treatment were measured by the above methods. The results are shown in Table 5 below.

(Example 3-2 to Example 3-6)
A transparent conductive film was produced in the same manner as in Example 3-1, except that the color tone correction film described in Table 5 was used.

(Example 3-7)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low bend color correction layer of the color correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 30 nm) And annealed at 150 ° C. for 100 minutes to produce a transparent conductive film.

(Example 3-8)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low bend color correction layer of the color correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ), And subjected to an annealing treatment at 120 ° C. for 60 minutes to produce a transparent conductive film.

(Example 4-1)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ) And an annealing treatment at 150 ° C. for 30 minutes to produce a transparent conductive film. About the obtained transparent conductive film, the transmitted color b *, the total light transmittance, the haze value, and the warp after heat treatment were measured by the above methods. The results are shown in Table 6 below.

(Example 4-2 to Example 4-10)
A transparent conductive film was produced in the same manner as in Example 4-1, except that the color tone correction film described in Table 6 was used.

(Example 4-11)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color tone correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 30 nm) And annealed at 150 ° C. for 100 minutes to produce a transparent conductive film.

(Example 4-12)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ), And subjected to an annealing treatment at 120 ° C. for 60 minutes to produce a transparent conductive film.

(Comparative Example 1-1 to Comparative Example 1-3)
A color correction film was produced in the same manner as in Example 1-1 except that the low bend color correction layer was made of the materials and film thicknesses shown in Table 7 below.

(Comparative Example 1-4)
As a transparent substrate film, a color tone correction film (S′1) was used in the same manner as in Example 1-1, except that a PET film “A4100” manufactured by Toyobo Co., Ltd. was used instead of the low oligomer polyester film (PET-OL1). -4) was produced.

(Comparative Example 2-1 to Comparative Example 2-7)
A color tone correction film was produced in the same manner as in Example 2-1, except that the high bend color tone correction layer and the low bend color tone correction layer were made of the materials and film thicknesses shown in Table 8 below.

(Comparative Example 2-8)
A color correction film was prepared in the same manner as in Example 2-1, except that a PET film “A4100” manufactured by Toyobo Co., Ltd. was used instead of the low oligomer polyester film (PET-OL1) as the transparent substrate film.

(Comparative Example 3-1 to Comparative Example 3-4)
A transparent conductive film was produced in the same manner as in Example 3-1, except that the color tone correction film described in Table 9 was used. About the obtained transparent conductive film, the transmitted color b *, the total light transmittance, the haze value, and the warp after heat treatment were measured by the above methods. The results are shown in Table 9 below.

(Comparative Example 3-5)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low bend color correction layer of the color correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 30 nm) And annealed at 150 ° C. for 130 minutes to produce a transparent conductive film.

(Comparative Example 3-6)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low bend color correction layer of the color correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ) And an annealing treatment at 100 ° C. for 60 minutes to produce a transparent conductive film.

(Comparative Example 3-7)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color tone correction film of Example 1-1, a tin-doped indium oxide layer (ITO layer having a thickness of 70 nm) ) And an annealing treatment at 150 ° C. for 30 minutes to produce a transparent conductive film.

(Comparative Example 4-1 to Comparative Example 4-8)
A transparent conductive film was produced in the same manner as in Example 4-1, except that the color tone correction film described in Table 10 was used. About the obtained transparent conductive film, the transmitted color b *, the total light transmittance, the haze value, and the warp after heat treatment were measured by the above methods. The results are shown in Table 10 below.

(Comparative Example 4-9)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color tone correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 30 nm) And annealed at 150 ° C. for 130 minutes to produce a transparent conductive film.

(Comparative Example 4-10)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 20 nm) ) And an annealing treatment at 100 ° C. for 60 minutes to produce a transparent conductive film.

(Comparative Example 4-11)
By performing sputtering using an ITO target of indium: tin = 10: 1 on the low color tone correction layer of the color tone correction film of Example 2-1, a tin-doped indium oxide layer (ITO layer having a thickness of 70 nm) ) And an annealing treatment at 150 ° C. for 30 minutes to produce a transparent conductive film.

(Results and Discussion)
From the results of Table 5, in Examples 3-1 to 3-8, since the relative balance between the refractive index and the film thickness of the low-reflective color tone correction layer and the tin-doped indium oxide layer is suitable, the value of the transmitted color b * is The transparent conductive film was small, sufficiently suppressed in coloration, achieved excellent total light transmittance, and small in warpage after heat treatment.

  From the results of Table 6, also in Examples 4-1 to 4-12, the relative balance between the refractive index and the film thickness of the high-refractive color tone correction layer, the low-refractive color tone correction layer, and the tin-doped indium oxide layer is preferable. The value of the transmitted color b * is small, coloring is sufficiently suppressed, an excellent total light transmittance is realized, and a transparent conductive film with small warpage after heat treatment can be obtained. By providing, hardness could be raised rather than Examples 3-1 to 3-8.

  Furthermore, in Examples 3-1 to 3-8 and Examples 4-1 to 4-12, since an oligomer low precipitation polyester film is used as a transparent substrate, whitening is suppressed and haze is reduced. done.

  On the other hand, from the results of Table 9, Comparative Examples 3-1 to 3-3 and Comparative Examples 3-5 to 3-7 are any of the refractive index and film thickness of the low bend color correction layer, the tin-doped indium oxide layer. Since the relative balance was poor, the value of the transmitted color b * was large and the transparent conductive film was colored, or the total light transmittance was low. Since Comparative Example 3-4 did not use the oligomer low precipitation polyester film, the result was high haze.

Further, from the results of Table 10, Comparative Examples 4-1 to 4-4, Comparative Examples 4-6 to 4-7, and Comparative Examples 4-9 to 4-11 show a high-refractive color tone correction layer and a low-refractive color tone correction layer. , Because the refractive index of the tin-doped indium oxide layer and the relative balance of either film thickness are poor, the value of the transmitted color b * is large, the transparent conductive film is colored, or the total light transmittance is low, or A high haze value was obtained. In Comparative Example 4-5, since the film thickness of the highly bent color tone correction layer was too large, the warp after the heat treatment was large. Since Comparative Example 4-8 did not use the oligomer low precipitation polyester film, it resulted in a high haze.

Claims (5)

A color correction film in which a low-reflective color correction layer is laminated on one surface of the transparent substrate film,
The low bend color tone correction layer includes silica fine particles and an active energy ray-curable resin, and has a refractive index of 1.33 to 1.53 and a film thickness of 10 to 55 nm with respect to light having a wavelength of 400 nm.
The color correction film, wherein the transparent substrate film is an oligomer low precipitation polyester film.   The color correction film according to claim 1, wherein the transparent base film is a low oligomer polyester film having a cyclic trimer content of less than 1.0 wt%.   The color correction film of Claim 1 or Claim 2 with which the said transparent base film is coat | covered with the oligomer sealing film which seals precipitation of an oligomer. A high color tone correction layer is laminated between the transparent base film and the low color tone correction layer,
The high bend color tone correction layer includes metal oxide fine particles and an active energy ray-curable resin, and has a refractive index of 1.66 to 1.76 and a film thickness of 0.4 to 1.5 μm with respect to light having a wavelength of 400 nm. The color correction film according to any one of claims 1 to 3. A tin-doped indium oxide layer is laminated on the low-flection color tone correction layer of the color tone correction film according to any one of claims 1 to 4.
The tin-doped indium oxide layer is a transparent conductive film having a refractive index of 1.85 to 2.35 and a film thickness of 5 to 50 nm with respect to light having a wavelength of 400 nm.

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