JP2013161404A - Conductive film and touch panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive film excellent in conductivity and heat resistance and a touch panel with excellent visibility including the conductive film.SOLUTION: The conductive film has a conductive layer containing a transparent conductive material and a cellulose ester compound other than cellulose acylate on a cellulose acylate film. The transparent conductive material is at least one kind of transparent conductive material selected from a conductive polymer, conductive metal or carbon nano-tube. The cellulose acylate film contains at least one of an ester compound, a sugar ester compound, a glycolate ester compound, a phthalate ester compound, a phosphate ester compound or a polyhydric alcohol ester compound expressed by the following general formula (X), and is different from the cellulose ester compound. The general formula (X): B-(G-A)-G-B.

Description

  The present invention relates to a conductive film and a touch panel.

  In recent years, image display devices such as liquid crystal display devices have attracted attention, and as one of their uses, application to portable electronic notebooks, portable multimedia devices, and the like is expected. As input devices such as these portable electronic notebooks and portable multimedia devices, those in which a touch panel is placed on a display element of an image display device are mainly used. As the touch panel, for example, a capacitance method or the like can be mentioned, and the conductive film of the capacitance method touch panel generally has a metal oxide of tin oxide or indium tin oxide as a main component on one surface of the base film. The conductive layer is composed of two conductive films patterned by a laser ablation method, chemical etching, or the like.

  Transparent conductive materials such as metal nanowires such as silver, which are excellent in transparency and low resistance, as a conductive layer that replaces tin oxide or indium tin oxide due to the yellowness problem caused by low transmittance in the short wavelength region in recent years There has been proposed a conductive layer containing (see Patent Document 1).

  On the other hand, a polyethylene terephthalate film (PET film) is usually used as the base film because it is excellent in processability and handleability.

  However, when a conductive film composed of a PET film is used for a touch panel or the like, a rainbow pattern (interference fringes) is likely to occur due to black display.

  For this reason, when a cellulose acylate film excellent in isotropy is used as a base film instead of PET film, not only the improvement of iridescent patterns (interference fringes) but also transparent conductive materials such as metal nanowires such as silver It was found that the adhesive layer was excellent in adhesion with the conductive layer.

  This is because the conductive layer has hydrophilicity by the cellulose ester compound contained as a dispersant in the composition of the transparent conductive material, and the layers containing the hydrophilic cellulose compound are laminated to each other, so that the adhesiveness is excellent. It is estimated to be.

  However, a conductive film having a conductive layer made of a transparent conductive material such as a metal nanowire such as silver on a cellulose acylate film may cause curling or increase in haze after a heat test assuming long-term use. It has been found that there are problems such as a decrease in total light transmittance. Since optical characteristics are deteriorated and the visibility is remarkably lowered when used in an image display device such as a touch panel, it has been desired to solve these problems.

Special table 2009-505358

  This invention is made | formed in view of the said problem and the situation, The solution subject is providing electroconductivity film with favorable electroconductivity and excellent heat resistance. Moreover, it is providing the touch panel excellent in visibility provided with the electroconductive film.

  As a result of examining the cause of the above-mentioned problem in order to solve the above problems, the present inventor can control the compatibility with the conductive layer by including a compound having a specific structure in the cellulose acylate film, and a heat resistance test. It has been found that subsequent increases in curling, haze and the like can be suppressed, and it is up to the present invention.

  That is, the said subject which concerns on this invention is solved by the following means.

  1. A conductive film having a conductive layer containing a transparent conductive material and a cellulose ester compound other than cellulose acylate on a cellulose acylate film, wherein the transparent conductive material is a conductive polymer, a conductive metal Or an ester compound represented by the following general formula (X), a sugar ester compound, a glycol, which is at least one transparent conductive material selected from carbon nanotubes, and wherein the cellulose acylate film is different from the cellulose ester compound A conductive film comprising at least one of an acid ester compound, a phthalic acid ester compound, a phosphoric acid ester compound or a polyhydric alcohol ester compound.

Formula (X) B- (GA) _n -GB
(In the formula, B represents a hydroxy group or a carboxylic acid residue. G represents an alkylene glycol residue having 2 to 12 carbon atoms, an arylene glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol having 4 to 12 carbon atoms. Represents a residue, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an arylene dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
2. 2. The conductive film according to item 1, wherein the transparent conductive material is a conductive metal.

  3. 3. The conductive film according to item 1 or 2, wherein the conductive metal is a metal nanowire.

  4). The said cellulose acylate film contains the ester compound or the said sugar ester compound represented by the said general formula (X), The electroconductive film as described in any one of said Claims 1-3 characterized by the above-mentioned. .

  5. The film thickness of the said cellulose acylate film is 5-34 micrometers, The electroconductive film as described in any one of said 1st-4 characterized by the above-mentioned.

  6). The conductive film according to any one of Items 1 to 5, which has a hard coat layer on a surface opposite to the conductive layer.

  7). 7. The conductive film according to item 6, wherein the hard coat layer contains an active energy ray-curable isocyanurate derivative.

  8). When the retardation value was measured at an optical wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55%, the in-plane retardation value Ro was in the range of 0 to 10 nm, and the conductive film was in the thickness direction. Retardation value Rt exists in the range of -10-10nm, The electroconductive film as described in any one of said 1st term | claim 7-7 characterized by the above-mentioned.

  9. The conductive film according to any one of Items 1 to 8, wherein the conductive film is a transparent conductive film.

  10. A conductive film comprising the conductive film according to any one of the first to ninth aspects.

  By the above means of the present invention, a conductive film having good conductivity and excellent heat resistance can be provided. Moreover, the touch panel excellent in visibility provided with the electroconductive film can be provided.

  The expression mechanism or action mechanism of the effect of the present invention is not clear, but is presumed as follows.

  It is presumed that the curl generated after the heat resistance test is generated due to a change in the balance of moisture caused by heat because the layers having hydrophilicity are laminated. In addition, it is estimated that the haze and the decrease in the total light transmittance that increase after the heat resistance test are due to the fact that the compatibility between the conductive layer and the cellulose acylate film is so high that reactions between the layers occur. For such a problem, by adding a compound having a specific structure to the cellulose acylate film, it is possible to control the compatibility with a conductive layer containing a transparent conductive material such as moisture control or silver nanowire, and after the heat test It is considered that curl and haze increase and total light transmittance decrease can be suppressed.

It is a schematic sectional drawing which shows an example of a touch panel. It is a schematic explanatory drawing which shows another example of a touch panel. It is a schematic plan view which shows the example of arrangement | positioning of the electroconductive layer in the touch panel shown in FIG. It is a schematic sectional drawing which shows another example of a touch panel. It is a schematic sectional drawing which shows another example of a touchscreen.

  The conductive film of the present invention is a conductive film having a conductive layer containing a transparent conductive material and a cellulose ester compound other than cellulose acylate on a cellulose acylate film, wherein the transparent conductive material is It is at least one transparent conductive material selected from a conductive polymer, a conductive metal, or a carbon nanotube, and the cellulose acylate film is represented by the following general formula (X), which is different from the cellulose ester compound. It contains at least one of an ester compound, a sugar ester compound, a glycolic acid ester compound, a phthalic acid ester compound, a phosphoric acid ester compound or a polyhydric alcohol ester compound. This feature is a technical feature common to the inventions according to claims 1 to 10.

  As an embodiment of the present invention, it is preferable that the transparent conductive material is a conductive metal from the viewpoint of the conductivity of the present invention.

  As an embodiment of the present invention, from the viewpoint of conductivity of the present invention, the conductive metal is preferably a metal nanowire.

  Moreover, it is preferable that the said cellulose acylate film contains the ester compound or the said sugar ester compound represented by the said general formula (X) from a viewpoint of dimensional stability and the effect expression of this invention.

  Moreover, it is preferable that the film thickness of the said cellulose acylate film is 5-34 micrometers from the expression effect of this invention being acquired suitably in a more severe heat test.

  Furthermore, it is preferable to have a hard coat layer on the surface opposite to the conductive layer. Thereby, the effect of curl suppression is increased.

  As an embodiment of the present invention, the hard coat layer contains an active energy ray-curable isocyanurate derivative because particularly excellent optical properties (haze and total light transmittance) and curling suppression effects can be obtained. Is preferred.

  Further, when the conductive film was measured for a retardation value at an optical wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55%, the in-plane retardation value Ro was in the range of 0 to 10 nm, and the thickness was It is preferable that the retardation value Rt in the direction is in the range of −10 to 10 nm because excellent visibility is obtained when used in a touch panel.

  As an embodiment of the present invention, since the visibility when used in a touch panel is excellent, the conductive film is preferably a transparent conductive film.

  The conductive film of the present invention can be suitably included in a touch panel.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

  First, the conductive layer containing the transparent conductive material according to the present invention will be described. In the present invention, the transparent conductive material is at least one transparent conductive material selected from a conductive polymer, a conductive metal, or a carbon nanotube.

  Here, transparent means that the total light transmittance is 50% or more. The total light transmittance is preferably 85% or more, more preferably 90% or more.

<Transparent conductive material>
[Conductive polymer]
The conductive polymer used in the present invention is preferably an organic polymer having a π-conjugated main chain, such as polypyrroles, polythiophenes, polyacetylenes, polyphenylenes, polyphenylene vinylenes, polyanilines, polyacene. , Polythiophene vinylenes, and copolymers thereof. Among these, a polymer selected from polypyrrole, polythiophene, poly (N-methylpyrrole), poly (3-methylthiophene), poly (3-methoxythiophene), poly (3,4-ethylenedioxythiophene), or A copolymer is preferably used. Polypyrrole, polythiophene, and poly (3,4-ethylenedioxythiophene) are particularly preferable.

  Furthermore, the conductive polymer of the present invention can contain a polyanion and other dopants. Examples of polyanions include polymeric carboxylates and polymeric sulfonic acids. Examples of the polymeric carboxylic acid include polyacrylic acid, polymethacrylic acid, and polymaleic acid. Examples of the polymeric sulfonic acid include restyrene sulfonic acid and polyvinyl sulfonic acid.

  These polymeric carboxylic acids and sulfonic acids may be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable low molecular compounds such as acrylates and styrene. Specific examples include polyvinyl sulfonic acid, polystyrene sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly-2-acrylamido-2-methylpropane sulfonic acid, polyisoprene sulfonic acid, polyvinyl carboxylic acid, Examples thereof include polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly-2-acrylamido-2-methylpropane carboxylic acid, polyisoprene carboxylic acid, and polyacrylic acid. These homopolymers may be sufficient and 2 or more types of copolymers may be sufficient. Among these polyanions, polyacrylsulfonic acid, polymethacrylsulfonic acid, polystyrenesulfonic acid, and all or part of which are metal salts are preferably used. In particular, polystyrene sulfonic acid is most preferable. The number average molecular weight of such a polyanion is suitably in the range of 1,000 to 2,000,000, and preferably in the range of 2,000 to 500,000.

  The ratio between the polyanion and the conductive polymer is preferably within the range of 0.5 to 10 g of the polyanion with respect to 1 g of the conductive polymer, from the viewpoint of coating film strength, conductivity and the like, and within the range of 1 to 5 g. More preferably, it is within. Other dopants may be donor or acceptor as long as the conductive polymer can be oxidized and reduced. Examples of the donor dopant include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, dimethyldiethylammonium, and the like. Examples of acceptor dopants include halogen compounds, Lewis acids, proton acids, organic cyano compounds, organometallic compounds, fullerenes, hydrogenated fullerenes, hydroxylated fullerenes, carboxylated fullerenes, and sulfonated oxides. Fullerenes can be used. Furthermore, it is preferable from the stability of the composition that a small amount of a polar organic solvent such as diethylene glycol, triethylene glycol, tetraethylene glycol, dimethylformamide, dimethyl sulfoxide or the like is added to the conductive polymer-containing composition.

  The addition amount of the polar organic solvent is 0.5% to 50%, preferably 1% to 10% with respect to the 1% aqueous solution of π-conjugated polymer from the viewpoint of film durability and transparency.

[Conductive metal]
Examples of the conductive metal include metal nanoparticles, metal nanowires, and metal oxides oxidized by a conductive polymer and incorporated as an oxide in the conductive polymer.

(Metal nanoparticles)
As the metal element constituting the metal nanoparticles, an element selected from gold, platinum, silver, copper, zinc, palladium, rhodium, iridium, ruthenium, nickel, aluminum, tin, lead, carbon, and titanium is preferable. Moreover, you may contain the compound containing these elements. In particular, gold, platinum, silver, copper, zinc, palladium, rhodium, iridium, and ruthenium are preferable.

  The metal nanoparticles are transparent. In the present application, the metal nanoparticles mean that the surface plasmon absorption disappears or the surface plasmon absorption is wavelength-shifted, that is, the absorption wavelength range (or absorption maximum wavelength) is outside the visible wavelength range (380 to 780 nm). This refers to a metal nanoparticle that shifts and has no surface plasmon absorption in the visible light wavelength region, and has a total light transmittance of 50% or more.

  There is no restriction | limiting in particular in the manufacturing method of a metal nanoparticle, For example, it can manufacture using well-known methods, such as a liquid phase method and a gaseous-phase method. Examples of the liquid phase method include a chemical liquid phase method such as a liquid phase reduction method, an alkoxide method, a reverse micelle method, a hot soap method, a hydrothermal reaction method, and a physical liquid phase method such as a spray drying method. Can be used. As the vapor phase method, for example, a general chemical vapor deposition method (CVD method), a physical vapor deposition method (PVD), or the like can be used.

  In general, the absorption spectrum of surface plasmon absorption of metal nanoparticles varies depending on the size and shape of the same element. For example, in gold nanoparticles, it is known that the absorption maximum wavelength near 530 nm moves to the longer wavelength side as the particle diameter increases. It is also known that rod-shaped gold nanorods have specific absorption from the visible to the near-infrared region due to the difference between the major axis and minor axis ratio (aspect ratio). There is no particular limitation on the method for eliminating the surface plasmon absorption of the metal nanoparticles or shifting the wavelength of the surface plasmon absorption, that is, shifting the absorption wavelength range (or absorption maximum wavelength) to outside the visible light wavelength range. Composite and composite of two or more metals can be preferably applied.

  Compounding with an organic compound includes a method of partially coating metal nanoparticles with a π-conjugated polymer and a method of partially modifying the surface of metal nanoparticles with a compound having a thiol group. The composite of two or more kinds of metals includes a method in which metal nanoparticles are partially or completely covered with different metals.

  Also, in order to uniformly disperse the metal nanoparticles in the conductive polymer, the metal complex may be used as a polymerization oxidant for the conductive polymer to generate the metal nanoparticles simultaneously with the polymerization of the conductive polymer. Good. As the metal complex used, chloroauric acid, chloroplatinic acid, palladium chloride, rhodium chloride, hexachloroiridium salt and the like are preferable. Particularly preferred are chloroauric acid and chloroplatinic acid. In order to perform the polymerization reaction of the conductive polymer quickly and sufficiently, another oxidation polymerization agent such as ammonium persulfate or iron chloride may be added in addition to the metal complex.

  The average particle diameter of the metal nanoparticles is preferably in the range of 2 to 100 nm, more preferably in the range of 3 to 80 nm, and particularly preferably in the range of 5 to 50 nm. If the particle size is 100 nm or less, the influence of light scattering can be reduced, and a smaller particle size is preferable because a decrease in light transmittance and haze deterioration can be suppressed. On the other hand, it is preferably larger than 2 nm from the viewpoint of stability, more preferably larger than 3 nm from the viewpoint of conductivity, and more preferably 5 nm or more. When two or more kinds of metal nanoparticles are used in combination, the average particle diameter of at least one kind of metal nanoparticles before combination and / or the average particle diameter of metal nanoparticles after combination is larger than 3 nm. It is preferably 5 nm or more.

  The volume fraction of metal nanoparticles in the conductive layer is preferably 10% or more and 90% or less, and more preferably 20% or more and 80% or less. If the volume fraction of the metal nanoparticles is 10% or more, the conductivity improvement effect by adding the metal nanoparticles can be significantly expressed, and the conductivity can be improved as the volume fraction increases. preferable. On the other hand, from the viewpoint of transparency, the volume fraction of metal nanoparticles is preferably 90% or less, and more preferably 80% or less.

(Metal nanowires)
As a metal element of the metal nanowire, an element having a bulk conductivity of 1 × 10 ⁶ S / m or more can be used. Specific examples include metal atoms such as Ag, Cu, Au, Al, Rh, Ir, Co, Zn, Ni, In, Fe, Pd, Pt, Sn, and Ti. Two or more kinds of metal nanowires can be used in combination, but from the viewpoint of conductivity, an element selected from Ag, Cu, Au, Al, and Co is preferably used. In particular, a metal nanowire made of Ag (hereinafter also referred to as silver) is preferable.

  The shape of the metal nanowire is not particularly limited and can be appropriately selected according to the purpose.For example, it can take any shape such as a columnar shape, a rectangular parallelepiped shape, a columnar shape with a polygonal cross section, The average long axis length of the metal nanowire is 1 μm or more, preferably 5 μm or more, and more preferably 10 μm or more. When the long axis length of the metal nanowire is less than 1 μm, when the conductive layer is produced, the number of metal-to-metal junctions is reduced, making it difficult to conduct, and as a result, the resistance may be increased. . The minor axis average length φ (nm) of the metal nanowire is preferably in the range of 5 to 200 nm. If the φ (nm) of the metal nanowire is less than 5 nm, sufficient heat resistance is not exhibited. If it exceeds 200 nm, haze due to metal scattering increases, and the conductive layer containing the metal nanowire Light transmittance and visibility may be reduced. The average length of each of the major axis and the minor axis of the metal nanowire can be determined by observing using a transmission electron microscope (TEM), for example.

  The content of each metal atom in the metal nanowire can be measured by, for example, ICP (High Frequency Inductively Coupled Plasma) after dissolving the sample with acid or the like.

(Method for producing metal nanowires)
There is no restriction | limiting in particular in the manufacturing method of metal nanowire, Well-known means, such as a liquid phase method and a gaseous-phase method, can be used. Silver nanowires are particularly preferable because Ag nanowires having a uniform shape can be synthesized in a large amount by a liquid phase method in which a silver salt such as silver nitrate is reduced in a polyol such as ethylene glycol or polyvinylpyrrolidone. Examples of the synthesis method include Xia. Y, et. al. , Chem. Mater. Journal Volume 14, 2002, p. 4736-4745 and Xia. Y, et. al. , Nanoletters, Vol. 3, 2003, p. 955-960.

  Moreover, the metal nanowire containing metals other than silver and silver can be manufactured by adding metal salts other than silver to a silver nanowire dispersion composition, and performing oxidation-reduction reaction. In the metal nanowire containing silver and a metal other than silver, the metal other than silver is preferably either gold or platinum, or both. The solvent of the silver nanowire dispersion liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include water, propanol, acetone, and ethylene glycol. These may be used alone or in combination of two or more.

  The dispersion after the oxidation-reduction reaction is further desalted. The desalting treatment can be performed by a method such as ultrafiltration, dialysis, gel filtration, decantation, and centrifugation after forming the metal nanowires.

(Conductive composition containing metal nanowires)
Although there is no restriction | limiting in particular as content of metals, such as silver, in a metal nanowire containing electrically conductive composition, It is preferable to contain in the range of 0.1-99 mass% in a composition, 0.3-95 More preferably within the range of mass%. When the content is less than 0.1% by mass, the load in the drying process is large during production, and when it exceeds 99% by mass, the particles tend to aggregate. From the viewpoint of transparency, it is preferable to contain metal nanowires having a major axis length of 10 μm or more in an amount of 0.01% by mass or more, more preferably 0.05% by mass or more.

  As a dispersion solvent in the metal nanowire-containing conductive composition, water is mainly used, and it is preferable to use an organic solvent miscible with water in a proportion of 50% by volume or less. As the organic solvent, for example, an alcohol compound having a boiling point of 50 to 250 ° C., more preferably 55 to 200 ° C., is preferably used. By using such an alcohol compound in combination, the drying load can be reduced when the conductive layer is formed by coating.

  The alcohol compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methanol, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 200, polyethylene glycol 300, glycerin, propylene glycol, diester Propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1-ethoxy-2-propanol, ethanolamine, diethanolamine, 2- (2-amino Ethoxy) ethanol, 2-dimethylaminoisopropanol and the like are mentioned, and ethanol and ethylene glycol are preferable. These may be used alone or in combination of two or more.

  The electrical conductivity of the metal nanowire-containing conductive composition is preferably 1 mS / cm or less, more preferably 0.1 mS / cm or less, and even more preferably 0.05 mS / cm or less. The viscosity at 20 ° C. is preferably in the range of 0.5 to 100 mPa · s, and more preferably in the range of 1 to 50 mPa · s. The conductive composition of the metal nanowire may contain various additives, for example, a surfactant, a polymerizable compound, an antioxidant, an antisulfurizing agent, a corrosion inhibitor, a viscosity modifier, an antiseptic, and the like as necessary. it can.

  There is no restriction | limiting in particular as a corrosion inhibitor, According to the objective, it can select suitably, An azole is suitable. Examples of azoles include benzotriazole, tolyltriazole, mercaptobenzothiazole, mercaptobenzotriazole, mercaptobenzotetrazole, (2-benzothiazolylthio) acetic acid, 3- (2-benzothiazolylthio) propionic acid, and these Examples thereof include at least one selected from alkali metal salts, ammonium salts, and amine salts. By containing a corrosion inhibitor, an excellent rust prevention effect can be exhibited. Next, the carbon nanotube will be described.

〔carbon nanotube〕
Carbon nanotubes are generally known, and are carbon-based fiber materials having a shape in which a graphite-like carbon atomic surface (graphene sheet) having a thickness of several atomic layers is wound into a cylindrical shape, and the number of peripheral walls thereof Are broadly divided into single-walled nanotubes (SWNT) and multi-walled nanotubes (MWNT), and are divided into chiral, helical, zigzag, and armchair types based on the difference in the structure of graphene sheets. ing. Any type of carbon nanotube can be used in the present invention as long as it is referred to as such a carbon nanotube. A mixture of these various carbon nanotubes may be used.

The carbon nanotubes are preferably single-walled nanotubes having a large aspect ratio, that is, thin and long. For example, carbon nanotubes having an aspect ratio of 10 ³ or more, preferably 10 ⁴ or more can be mentioned. The length of the carbon nanotube is usually 1 μm or more, preferably 50 μm or more, more preferably 500 μm or more, and the upper limit of the length is not particularly limited, but is, for example, about 10 mm. As the outer diameter, extremely minute carbon nanotubes on the order of nm are known. The carbon nanotubes are preferably surface-treated with an organic compound, and specifically, it is preferable to improve the dispersibility of each primary particle using a surfactant.

  The method for producing the carbon nanotube is not particularly limited. Specifically, catalytic hydrogen reduction of carbon dioxide, arc discharge method, laser evaporation method, CVD method, vapor phase growth method, HiPco method in which carbon monoxide is reacted with an iron catalyst at high temperature and high pressure to grow in the gas phase, etc. Is mentioned. Moreover, in order to remove residues such as by-products and catalytic metals, carbon nanotubes that have been further purified by various purification methods such as washing methods, centrifugal separation methods, filtration methods, oxidation methods, chromatographic methods, etc. Is more preferable because various functions are sufficiently exhibited.

  The conductive polymer, the conductive metal, and the carbon nanotube which are the transparent conductive materials according to the present invention may be used alone or in combination. Moreover, from the manifestation of the effect of the present invention, the transparent conductive material according to the present invention is preferably a conductive metal, more preferably a metal nanowire.

[Ionic liquid]
The transparent conductive material according to the present invention may contain an ionic liquid. Examples of the ionic liquid include 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1-ethylpyridinium, 1-butylpyridinium, 1-hexylpyridinium, Examples thereof include N, N, N-trimethyl-N-propylammonium, N-methyl-N-propylpiperidinium, N, N, N-trimethyl-N-propylphosphonium and the like.

[Other additives]
The conductive layer containing the transparent conductive material according to the present invention can optionally contain an additive as necessary. Specific examples include surfactants, organic solvents, ultraviolet absorbers, antioxidants, deterioration inhibitors, pH adjusters, polymerization inhibitors, surface modifiers, defoamers, plasticizers, and antibacterial agents. . These may be used individually by 1 type and may use 2 or more types together.

  Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  Next, specific examples of these surfactants are shown, but the present invention is not limited thereto. Examples of the anionic surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl carboxylic acid, alkyl naphthalene sulfonic acid, α-olefin sulfonic acid, dialkyl sulfosuccinic acid, α-sulfonated fatty acid, N-methyl-N-oleyl taurine, Petroleum sulfonic acid, alkyl sulfuric acid, sulfated oil and fat, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene styrenated phenyl ether sulfuric acid, alkyl phosphoric acid, polyoxyethylene alkyl ether phosphoric acid, polyoxyethylene alkyl phenyl ether phosphoric acid, naphthalene sulfone Acid formalin condensate, methyl naphthalene sulfonic acid formalin condensate, butyl naphthalene / naphthalene sulfonic acid formalin condensate, naphthol methylene sulfonic acid formalin condensate, Creoso Examples thereof include tart oil sulfonic acid formalin condensate, naphthalene sulfonic acid formaldehyde condensate, polystyrene sulfonic acid and salts thereof.

  Cationic surfactants include primary to tertiary fatty amines, quaternary ammonium, tetraalkylammonium, trialkylbenzylammonium alkylpyridinium, 2-alkyl-1-alkyl-1-hydroxyethylimidazolinium, N, N -Dialkylmorpholinium, polyethylene polyamine fatty acid amide, urea condensate of polyethylene polyamine fatty acid amide, quaternary ammonium of urea condensate of polyethylene polyamine fatty acid amide, and salts thereof.

  Examples of amphoteric surfactants include N, N-dimethyl-N-alkyl-N-carboxymethyl ammonium betaine, N, N, N-trialkyl-N-sulfoalkylene ammonium betaine, N, N-dialkyl-N, N-bispolyoxyethylene ammonium sulfate betaine, betaines such as 2-alkyl-1-carboxymethyl-1-hydroxyethylimidazolinium betaine, and aminocarboxylic acids such as N, N-dialkylaminoalkylenecarboxylate Can be mentioned.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polystyryl phenyl ether, polyoxyethylene-polyoxypropylene glycol, polyoxyethylene-polyoxypropylene alkyl ether, many Polyhydric alcohol fatty acid partial ester, polyoxyethylene polyhydric alcohol fatty acid partial ester, polyoxyethylene fatty acid ester, polyglycerin fatty acid ester, polyoxyethylenated castor oil, fatty acid diethanolamide, polyoxyethylene alkylamine, triethanolamine fatty acid partial ester And trialkylamine oxide. Moreover, you may use fluorine-type surfactants, such as fluoroalkyl carboxylic acid, perfluoroalkyl carboxylic acid, perfluoroalkyl benzenesulfonic acid, and perfluoroalkyl polyoxyethylene ethanol. Examples of commercially available products include Megafac F-477, F-410, and F-114 manufactured by DIC.

  As the content of the surfactant, it is not possible to uniformly define the molecular weight and ability of the surfactant used, but it is preferably in the range of 1 to 100% by mass, and in the range of 1 to 50% by mass. Is more preferable. As the type of solvent, a hydrophilic solvent or a hydrophobic solvent can be arbitrarily used, but an aqueous coating method having excellent environmental properties can be applied in handling and coating formation of a conductive composition containing a transparent conductive material. It is preferable to use a hydrophilic solvent.

  Hydrophilic solvents include water, methanol, ethanol, isopropyl alcohol, propyl alcohol, butanol and other alcohols; acetone, methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone and other ketones; ethylene glycol, ethylene glycol methyl ether, ethylene glycol Ethylene glycols such as mono-n-propyl ether; propylene glycols such as propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol butyl ether, propylene glycol propyl ether; ethers such as tetrahydrofuran; dimethylformamide, dimethylacetamide Amides such as N-methylpyrrolidone, N-ethylpyrrolidone, etc. Lorridones; esters such as methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, methyl propionate; dimethyl sulfoxide, γ-butyrolactone, methyl lactate, ethyl lactate, methyl β-methoxyisobutyrate, methyl α-hydroxyisobutyrate Hydroxy esters such as aniline, anilines such as N-methylaniline, and carbonates such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propylene carbonate, and butylene carbonate.

  Examples of the hydrophobic solvent include ketones having 5 to 10 carbon atoms such as 4-methylpentan-2-one, halogenated hydrocarbons such as chloroform and methylene chloride, aromatic hydrocarbons such as toluene, benzene and xylene, Aliphatic or alicyclic hydrocarbons such as hexane and cyclohexane are exemplified.

[Method of forming conductive layer]
As a method for forming a conductive layer by forming a transparent conductive material and a cellulose ester compound according to the present invention on a cellulose acylate film (hereinafter also referred to as a base film), high productivity and production cost are available. It is preferable to use a liquid phase film forming method such as a coating method or a printing method from the viewpoints of both reduction and environmental load reduction. As coating methods, roll coating method, bar coating method, dip coating method, spin coating method, casting method, die coating method, blade coating method, bar coating method, gravure coating method, curtain coating method, spray coating method, doctor coating method Etc. can be used. As the printing method, a letterpress (letter) printing method, a stencil (screen) printing method, a lithographic (offset) printing method, an intaglio (gravure) printing method, a spray printing method, an ink jet printing method, and the like can be used.

  After forming the conductive layer, a drying treatment can be appropriately performed. Although there is no restriction | limiting in particular as conditions of a drying process, It is preferable to process at the temperature of the range which does not damage a base film or an electroconductive layer.

<Conductive layer>
The conductive layer is formed of a conductive composition containing a transparent conductive material and a cellulose ester compound. For example, what formed the electroconductive composition by coating on a cellulose acylate film, and drying is mentioned.

  The conductive layer is preferably transparent. Transparent means that the total light transmittance is 50% or more. The total light transmittance is preferably 85% or more, more preferably 90% or more.

  In the manufacturing process of various devices using a conductive layer, heat resistance that can withstand the process of bonding (paneling) with a thermoplastic resin of 150 ° C. or higher and the solder reflow process of wiring portions of 220 ° C. or higher is generally required. . From the viewpoint of providing a highly reliable conductive layer for the manufacturing process, it preferably has heat resistance against heating at 240 ° C. for 30 minutes, and particularly preferably has heat resistance against heating for 60 minutes. The film thickness of the conductive layer is preferably in the range of 10 nm to 5 μm, more preferably in the range of 50 nm to 1 μm. The refractive index is preferably in the range of 1.3 to 2.3, and more preferably in the range of 1.35 to 1.8. The refractive index can be measured according to JIS K7142-2008.

  The conductive layer may be a single layer or a plurality of layers of two or more layers. Further, the surface resistivity of the conductive layer is preferably 1000Ω / □ or less, and more preferably 500Ω / □ or less. Further, when three conductive layers are provided, when the refractive index of the first conductive layer is n1, the refractive index of the second conductive layer is n2, and the refractive index of the third conductive layer is n3, n2 < Those satisfying the relationship of n3 ≦ n1 are preferable.

  When the refractive index n3 of the third conductive layer is 1.9 to 2.1, the refractive index n1 of the first conductive layer is 1.9 to 2.3, and further 2.0 to 2 .2 is preferred. The refractive index n2 of the second conductive layer is preferably 1.3 to 1.7, and more preferably 1.4 to 1.6.

  The thickness of the first conductive layer is preferably 10 to 200 nm, more preferably 15 to 60 nm. The thickness of the second conductive layer is preferably 10 nm or more, more preferably 10 to 300 nm, and particularly preferably 20 to 120 nm. The thickness of the third conductive layer is not particularly limited, but it is preferably 10 nm or more in order to obtain a continuous film having a good conductivity of 1000Ω / □ or less in surface resistance.

<Cellulose ester compound>
Next, the cellulose ester compound according to the present invention will be described. The effect expression of this invention is acquired by making a conductive layer contain a cellulose-ester compound in addition to a transparent conductive material. Examples of the cellulose ester compound include carboxymethylcellulose (CMC), 2-hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), methylcellulose (MC), and the like. These cellulose ester compounds are preferably added to the conductive composition within a range of 0.01 to 20 parts by mass from the viewpoint of the stability of the conductive composition and the manifestation of the effects of the present invention. It is preferable to add in the range of 0.01-10 mass parts in an ionic composition.

<Anchor layer>
An anchor layer may be provided between the conductive layer and the cellulose acylate film. One or two or more anchor layers can be provided. The anchor layer is formed of an inorganic material, an organic material, or a mixture of an inorganic material and an organic material. The formation of the anchor layer is effective for suppressing optical interference fringes (rainbow patterns) generated by the difference in refractive index between the base film and the conductive layer.

As the inorganic material for forming the anchor layer, for example, SiO ₂ , MgF ₂ , A1 ₂ O ₃ or the like is preferably used as an inorganic material. Examples of organic substances include organic substances such as acrylic resins, urethane resins, melamine resins, alkyd resins, and siloxane polymers. In particular, as the organic substance, it is desirable to use a thermosetting resin made of a mixture of a melamine resin, an alkyd resin, and an organosilane condensate.

  The anchor layer can be formed by using the above materials by a vacuum deposition method, a sputtering method, an ion plating method, a coating method, or the like.

  The thickness of the anchor layer is usually 100 nm or less, preferably in the range of 15 to 100 nm, more preferably in the range of 20 to 60 nm. You may use together.

  When the anchor layer has a two-layer structure, the first anchor layer preferably has a refractive index (n) in the range of 1.5 to 1.7, more preferably 1.5 to 1.65, and It is preferably within the range of 5 to 1.6. The thickness is preferably within the range of 100 to 220 nm, more preferably 120 to 215 nm, and even more preferably within the range of 130 to 210 nm. The second anchor layer preferably has a refractive index (n) in the range of 1.4 to 1.5, more preferably in the range of 1.41 to 1.49, more preferably in the range of 1.42 to 1.48. Is preferably within. The thickness (d) is preferably in the range of 20 to 80 nm, more preferably 20 to 70 nm, and even more preferably in the range of 20 to 60 nm.

  Next, the cellulose acylate film will be described.

<Cellulose acylate film>
The cellulose acylate film is different from the ester compound, and the ester compound, sugar ester compound, glycolic acid ester compound, phthalic acid ester compound, phosphoric acid ester compound or polyhydric alcohol ester compound represented by the general formula (X) It contains at least one of the above. First, the cellulose acylate resin constituting the cellulose acylate film will be described.

(Cellulose acylate resin)
The cellulose acylate resin constituting the cellulose acylate film according to the present invention (hereinafter also referred to as cellulose acylate) is preferably a lower fatty acid ester of cellulose. The lower fatty acid in the lower fatty acid ester of cellulose means a fatty acid having 6 or less carbon atoms. For example, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, etc. Also, mixed fatty acid esters such as cellulose acetate butyrate can be used.

  Among the cellulose acylate resins mentioned above, cellulose diacetate, cellulose triacetate and cellulose acetate propionate are preferably used as the lower fatty acid ester of cellulose. These cellulose acylates can be used alone or in combination.

  Cellulose diacetate is preferably used in an average acetylation degree (bound acetic acid amount) in the range of 51.0 to 56.0%. Examples of commercially available products include L20, L30, L40, and L50 manufactured by Daicel Corporation, and Ca398-3, Ca398-6, Ca398-10, Ca398-30, and Ca394-60S manufactured by Eastman Chemical Japan Co., Ltd. .

  Cellulose triacetate preferably has an average degree of acetylation (bound acetic acid amount) in the range of 54.0 to 62.5%, and more preferably has an average degree of acetylation of 58.0 to 62.5%. Cellulose triacetate within the range.

  The cellulose triacetate has a degree of acetyl group substitution in the range of 2.80 to 2.95, a number average molecular weight (Mn) of 125,000 or more and less than 155000, a weight average molecular weight (Mw) of 265,000 or more and less than 310,000, Mw / Mn is in the range of 1.9 to 2.1, cellulose triacetate A, acetyl group substitution degree is in the range of 2.75 to 2.90, number average molecular weight (Mn) is 155000 or more, less than 180,000, Mw is preferably 290000 or more and less than 360,000, and Mw / Mn preferably contains cellulose triacetate B in the range of 1.8 to 2.0.

  Cellulose acetate propionate has an acyl group having 2 to 4 carbon atoms as a substituent. When the substitution degree of acetyl group is X and the substitution degree of propionyl group or butyryl group is Y, the following formula (I ) And (II) are preferably satisfied at the same time.

Formula (I) 2.6 ≦ X + Y ≦ 3.0
Formula (II) 0 ≦ X ≦ 2.5
Among them, it is preferable that 1.9 ≦ X ≦ 2.5 and 0.1 ≦ Y ≦ 0.9. The number average molecular weight (Mn) and molecular weight distribution (Mw) of cellulose acylate can be measured using high performance liquid chromatography. The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G
(Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (GL Science Co., Ltd.)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 samples were used. The 13 samples are preferably used at approximately equal intervals.

(Thermoplastic acrylic resin)
The cellulose acylate film may be used in combination with a thermoplastic acrylic resin. When used in combination, the mass ratio of the thermoplastic acrylic resin to the cellulose acylate resin is preferably in the range of thermoplastic acrylic resin: cellulose acylate resin = 95: 5 to 50:50.

  Thermoplastic acrylic resins also include thermoplastic methacrylic resins. Although it does not restrict | limit especially as a thermoplastic acrylic resin, From within the range of 50-99 mass% of methyl methacrylate units, and within the range of 1-50 mass% of other monomer units copolymerizable with this. Is preferred. Other monomers that can be copolymerized include alkyl methacrylates having 2 to 18 carbon atoms, alkyl acrylates having 1 to 18 carbon atoms, acrylic acid, methacrylic acid, and the like. Unsaturated group-containing divalent carboxylic acids such as saturated acid, maleic acid, fumaric acid and itaconic acid, aromatic vinyl compounds such as styrene and α-methylstyrene, α, β-unsaturated nitriles such as acrylonitrile and methacrylonitrile, Maleic anhydride, maleimide, N-substituted maleimide, glutaric anhydride and the like may be mentioned, and these may be used alone or in combination of two or more.

  Among these, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl acrylate, 2-ethylhexyl acrylate, and the like are preferable from the viewpoint of thermal decomposition resistance and fluidity of the copolymer, and methyl acrylate and n -Butyl acrylate is particularly preferably used. Moreover, it is preferable that a weight average molecular weight (Mw) exists in the range of 80000-500000, More preferably, it exists in the range of 110000-500000.

  The weight average molecular weight of the acrylic resin can be measured by gel permeation chromatography. Commercially available acrylic resins include, for example, Delpet 60N, 80N (Asahi Kasei Chemicals Corporation), Dialnal BR52, BR80, BR83, BR85, BR88 (Mitsubishi Rayon Co., Ltd.), KT75 (Electrochemical Industry Co., Ltd.) )) And the like. Two or more acrylic resins can be used in combination.

  Subsequently, the compound which concerns on this invention contained in a cellulose acylate film is demonstrated. The compound according to the present invention is an ester compound represented by the general formula (X), which is different from the cellulose ester compound, in that the dimensional stability under environmental changes and the object effect of the present invention are exhibited well. The cellulose acylate film contains at least one of an ester compound, a glycolic acid ester compound, a phthalic acid ester compound, a phosphoric acid ester compound or a polyhydric alcohol ester compound. First, the ester compound represented by the general formula (X) will be described.

<Ester compound represented by general formula (X)>
Formula (X) B- (GA) _n -GB
(In the formula, B is a hydroxy group or carboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms, an arylene glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol residue having 4 to 12 carbon atoms. , A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an arylene dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.)
In general formula (X), B may be a terminal atom or functional group contained in G.

  In the general formula (X), the compound having a carboxylic acid residue is not particularly limited, and known aliphatic carboxylic acids, alicyclic carboxylic acids, aromatic carboxylic acids and the like can be used.

  Examples of the compound having an alkylene glycol residue having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,2 -Propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2 -Diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), 3-methyl-1, 5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3 There are hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, etc., and these glycols are one kind or two or more kinds Used as a mixture. In particular, an alkylene glycol having 2 to 12 carbon atoms is particularly preferable because of excellent compatibility with cellulose acetate.

  Examples of the compound having an arylene glycol residue having 6 to 12 carbon atoms include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol and the like, and these glycols can be used as one kind or a mixture of two or more kinds.

  Examples of the compound having an oxyalkylene glycol residue having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like. It can be used as a mixture of two or more.

  Examples of the compound having an alkylenedicarboxylic acid residue having 4 to 12 carbon atoms include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and the like. Each is used as one or a mixture of two or more.

  Examples of the compound having an arylenedicarboxylic acid residue having 6 to 12 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and the like.

  Although the specific example of a compound represented by general formula (X) below is shown, it is not limited to this.

<Sugar ester compound>
Next, the sugar ester compound will be described. The sugar ester compound is a compound obtained by esterifying all or part of the OH group of a sugar such as the following monosaccharide, disaccharide, trisaccharide or oligosaccharide. Examples of the sugar include glucose, galactose, mannose, fructose, xylose, arabinose, lactose, sucrose, nystose, 1F-fructosyl nystose, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, raffinose And kestose. In addition, gentiobiose, gentiotriose, gentiotetraose, xylotriose, galactosyl sucrose, and the like are also included.

  The sugar ester compound is different from the cellulose ester compound and the cellulose acylate resin.

  Among these compounds, compounds having a furanose structure and a pyranose structure are particularly preferable. Among these, sucrose, kestose, nystose, 1F-fructosyl nystose, stachyose and the like are preferable, and sucrose is more preferable. As oligosaccharides, maltooligosaccharides, isomaltooligosaccharides, fructooligosaccharides, galactooligosaccharides, and xylo-oligosaccharides can also be preferably used.

  The monocarboxylic acid used for esterifying the sugar is not particularly limited, and known aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid and the like can be used. The carboxylic acid to be used may be one kind or a mixture of two or more kinds.

  Preferred aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, 2-ethyl-hexanecarboxylic acid, undecylic acid, lauric acid , Saturated fatty acids such as tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid, melicic acid, and laccelic acid, Examples include unsaturated fatty acids such as undecylenic acid, oleic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid and octenoic acid.

  Examples of preferred alicyclic monocarboxylic acids include cyclopentane carboxylic acid, cyclohexane carboxylic acid, cyclooctane carboxylic acid, or derivatives thereof.

  Examples of preferred aromatic monocarboxylic acids include benzoic acid, aromatic monocarboxylic acids having an alkyl group or alkoxy group introduced into the benzene ring of benzoic acid, cinnamic acid, benzylic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, tetralin An aromatic monocarboxylic acid having two or more benzene rings such as carboxylic acid, or a derivative thereof can be mentioned, and more specifically, xylic acid, hemelic acid, mesitylene acid, planicylic acid, γ-isojurylic acid, Julylic acid, mesitic acid, α-isoduric acid, cumic acid, α-toluic acid, hydroatropic acid, atropic acid, hydrocinnamic acid, salicylic acid, o-, m, p-anisic acid, creosote acid, o-, m, p-homosalicylic acid, o-pyrocatechuic acid, β-resorcylic acid, vanillic acid, isovanillic acid, veratrum acid o- veratric acid, gallic acid, asarone acid, mandelic acid, homoanisic acid, homovanillic acid, homoveratric acid, o- homoveratric acid, Futaron acid, can be mentioned p- coumaric acid, especially benzoic acid.

  Among the ester compounds esterified, an acetyl compound into which an acetyl group has been introduced by esterification is preferable. Although the specific example of the sugar ester compound which can be used for this invention below is shown, it is not limited to these.

  The sugar ester compound is preferably a compound represented by the general formula (Y). Below, the compound shown by general formula (Y) is demonstrated.

(Wherein, R ₁ to R ₈ is a hydrogen atom, a substituted or unsubstituted alkylcarbonyl group having a carbon number of 2 to 22, or a substituted or unsubstituted arylcarbonyl group having a carbon number of 2 to 22, R ₁ ~ R ₈ may be the same or different.)
Although the compound shown with general formula (Y) below is shown more concretely (compound Y-1-Y-23), it is not limited to these.

  The substitution degree distribution can be adjusted to the desired substitution degree by adjusting the esterification reaction time or mixing compounds having different substitution degrees.

<Glycolic acid ester compound>
Next, a glycolic acid ester compound (hereinafter also referred to as a glycolate compound) will be described. The glycolate compound is not particularly limited, but alkylphthalylalkyl glycolates can be preferably used. Examples of alkyl phthalyl alkyl glycolates include methyl phthalyl methyl glycolate, ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate, octyl phthalyl octyl glycolate, methyl phthalyl ethyl Glycolate, ethyl phthalyl methyl glycolate, ethyl phthalyl propyl glycolate, methyl phthalyl butyl glycolate, ethyl phthalyl butyl glycolate, butyl phthalyl methyl glycolate, butyl phthalyl ethyl glycolate, propyl phthalyl butyl glycol Butyl phthalyl propyl glycolate, methyl phthalyl octyl glycolate, ethyl phthalyl octyl glycolate, octyl phthalyl methyl glycolate, octyl phthalate Ethyl glycolate and the like, preferably ethyl phthalyl ethyl glycolate, propyl phthalyl propyl glycolate, butyl phthalyl butyl glycolate.

<Phthalic acid ester compound>
Examples of the phthalic acid ester compound include diethyl phthalate, dimethoxyethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, dioctyl phthalate, dicyclohexyl phthalate, and dicyclohexyl terephthalate.

<Phosphate ester compound>
Examples of the phosphate ester compound include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, and the like.

<Polyhydric alcohol ester compound>
The polyhydric alcohol ester compound is a plasticizer comprising an ester of a divalent or higher aliphatic polyhydric alcohol and a monocarboxylic acid, and preferably has an aromatic ring or a cycloalkyl ring in the molecule. Preferably it is a 2-20 valent aliphatic polyhydric alcohol ester compound. Specific examples are shown below, but are not limited thereto.

  Among these compounds, the compound represented by the general formula (X) or the sugar ester compound is preferable from the viewpoint that the objective effect of the present invention is better exhibited after a more severe heat resistance test.

  The ester compound, sugar ester compound, glycolic acid ester compound, phthalic acid ester compound, phosphoric acid ester compound or polyhydric alcohol ester compound represented by the general formula (X) may be used alone or in combination of two or more. Moreover, it is preferable to contain 1-30 mass% of addition amounts in a base film, It is more preferable to make 5-25 mass% contain, It is especially preferable to make 5-20 mass% contain.

  Moreover, it is preferable that the base film which concerns on this invention contains an acrylic plasticizer from the point which is easy to control a cellulose acylate film to the retardation value mentioned later.

  The acrylic plasticizer is preferably contained in an amount of 1 to 50% by mass, more preferably 5 to 35% by mass, and particularly preferably 5 to 25% by mass with respect to cellulose acetate.

  The acrylic plasticizer is preferably an acrylic polymer, and the acrylic polymer is preferably a homopolymer or copolymer of acrylic acid or alkyl methacrylate.

  Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, t-), pentyl acrylate ( n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), nonyl acrylate (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2-hydroxypropyl), acrylic Acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl), acrylic acid 2-ethoxyethyl), etc., or the acrylic acid ester may include those obtained by changing the methacrylic acid ester.

  The acrylic polymer is a homopolymer or copolymer of the above-mentioned monomers, but the acrylic acid methyl ester monomer unit preferably has 30% by mass or more, and the methacrylic acid methyl ester monomer unit has 40% by mass or more. preferable. In particular, a homopolymer of methyl acrylate or methyl methacrylate is preferred.

  In addition, when making the base film which concerns on this invention contain the said acrylic plasticizer, it is preferable to make the usage-amount contain 1-50 mass% with respect to a cellulose acylate, and make it contain 5-35 mass%. Is more preferable, and 5 to 25% by mass is particularly preferable.

(UV absorber)
The base film according to the present invention may contain an ultraviolet absorber. Since the ultraviolet absorber absorbs ultraviolet rays of 400 nm or less, durability can be improved. In particular, the ultraviolet absorber preferably has a transmittance of 10% or less at a wavelength of 370 nm, more preferably 5% or less, and still more preferably 2% or less. Specific examples of the ultraviolet absorber are not particularly limited. For example, oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, triazine compounds, nickel complex salts, inorganic powders. Examples include the body.

  More specifically, for example, 5-chloro-2- (3,5-di-sec-butyl-2-hydroxylphenyl) -2H-benzotriazole, (2-2H-benzotriazol-2-yl) -6 -(Linear and side chain dodecyl) -4-methylphenol, 2-hydroxy-4-benzyloxybenzophenone, 2,4-benzyloxybenzophenone, etc. can be used. Commercially available products may be used. For example, TINUVIN such as TINUVIN 109, TINUVIN 171, TINUVIN 234, TINUVIN 326, TINUVIN 327, and TINUVIN 328 manufactured by BASF Japan Ltd. can be preferably used.

  Preferred ultraviolet absorbers are benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and triazine ultraviolet absorbers, and particularly preferred are benzotriazole ultraviolet absorbers and benzophenone ultraviolet absorbers.

  In addition, a discotic compound such as a compound having a 1,3,5 triazine ring is also preferably used as the ultraviolet absorber. As the UV absorber, a polymer UV absorber can be preferably used, and a polymer type UV absorber is particularly preferably used.

  As a benzotriazole ultraviolet absorber, TINUVIN 109 (octyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole-2-) manufactured by BASF Japan Ltd., which is a commercial product, is available. Yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate), TINUVIN 928 (2 -(2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol) and the like can be used. As the triazine-based ultraviolet absorber, TINUVIN 400 (2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -manufactured by BASF Japan Ltd., which is a commercial product, is available. Reaction product of 5-hydroxyphenyl and oxirane), TINUVIN 460 (2,4-bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5 Triazine), TINUVIN 405 (2- (2,4-dihydroxyphenyl) -4,6-bis- (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidic acid ester Reaction products) and the like.

  The ultraviolet absorber is added by dissolving the ultraviolet absorber in an alcohol such as methanol, ethanol, butanol or the like, an organic solvent such as methylene chloride, methyl acetate, acetone, dioxolane, or a mixed solvent thereof, and then becomes a base film. It may be added to the resin solution (dope) or directly during the dope composition. For an inorganic powder that does not dissolve in an organic solvent, a dissolver or a sand mill is used in the organic solvent and cellulose acetate to disperse and then added to the dope.

  The usage-amount of a ultraviolet absorber has the preferable inside of the range of 0.5-10 mass% with respect to a base film, and the inside of the range of 0.6-4 mass% is still more preferable.

(Antioxidant)
The base film according to the present invention may further contain an antioxidant (deterioration inhibitor). The antioxidant has a role of delaying or preventing the cellulose acetate film from being decomposed by a residual solvent amount of halogen in the cellulose acetate film, phosphoric acid of a phosphoric acid plasticizer, or the like.

  As the antioxidant, hindered phenol compounds are preferably used. For example, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl). -4-hydroxyphenyl) propionate], triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 5-triazine, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- 3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate Etc.

  The addition amount of these compounds is preferably 1 to 10,000 ppm, more preferably in the range of 10 to 1000 ppm by mass ratio with respect to the cellulose acetate film.

(Fine particles)
The base film according to the present embodiment has, for example, acrylic particles, silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, and hydrated silicic acid in order to improve handling properties. It is preferable to contain matting agents such as inorganic fine particles such as calcium, aluminum silicate, magnesium silicate, and calcium phosphate, and a crosslinked polymer. The acrylic particles are not particularly limited, but are preferably multi-layered acrylic granular composites. Among these, silicon dioxide is preferable in that the haze of the cellulose acylate film can be reduced.

  The primary average particle diameter of the fine particles is preferably 20 nm or less, more preferably in the range of 5 to 16 nm, and particularly preferably in the range of 5 to 12 nm.

(Disadvantage)
The substrate film according to the present invention preferably has a defect of 5 μm or more in diameter of 1/10 cm square or less. More preferably, it is 0.5 piece / 10 cm square or less, more preferably 0.1 piece / 10 cm square or less. Here, the diameter of the defect indicates the diameter when the defect is circular, and when the defect is not circular, the range of the defect is determined by observing with a microscope by the following method, and the maximum diameter (diameter of circumscribed circle) is determined.

  The range of the defect is the size of the shadow when the defect is observed with the transmitted light of the differential interference microscope when the defect is a bubble or a foreign object. When the defect is a change in surface shape, such as transfer of a roll flaw or an abrasion, the size can be confirmed by observing the defect with reflected light of a differential interference microscope.

  When the number of defects is greater than 1/10 cm square, for example, when the film is tensioned during processing in a later process, the film may break with the defects as a starting point, and productivity may decrease. Moreover, when the diameter of a defect becomes 5 micrometers or more, it can confirm visually by polarizing plate observation etc., and when used as an optical member, a bright spot may arise.

  Moreover, even when it cannot confirm visually, when a hard-coat layer is formed, a coating film cannot be formed uniformly and it may become a fault (coating omission). Here, the defect is a void in the film (foaming defect) generated due to the rapid evaporation of the solvent in the drying process of the solution casting, a foreign matter in the film forming stock solution, or a foreign matter mixed in the film forming. This refers to foreign matter (foreign matter defect) in the film. In addition, the base film preferably has a breaking elongation of at least one direction of 10% or more, more preferably 20% or more, in the measurement based on JIS-K7127-1999. The upper limit of the elongation at break is not particularly limited, but is practically about 250%. In order to increase the elongation at break, it is effective to suppress defects in the film caused by foreign matter and foaming.

(optical properties)
The base film preferably has a total light transmittance of 90% or more, more preferably 93% or more. Moreover, as a realistic upper limit, it is about 99%. The haze value is preferably 2% or less, more preferably 1.5% or less. The total light transmittance and haze value can be measured according to JIS K7361 and JIS K7136.

  Further, the haze of the conductive film according to the present invention is preferably 6% or less, more preferably 3.5% or less, and particularly preferably 2.5% from the viewpoint of visibility when used in an image display device such as a touch panel. It is as follows. The total light transmittance is preferably 85% or more.

  The retardation of the base film is preferably in the range where the in-plane retardation value Ro is 0 to 5 nm and the retardation value Rt in the thickness direction is -10 to 10 nm at a wavelength of 590 nm. Further, Rt is more preferably within a range of −5 to 5 nm.

  Ro and Rt are values defined by the following formulas (I) and (II).

Formula _{(I) Ro = (n x} -ny) × d
Formula (II) Rt = {(n x + n y) / 2-n z} × d
(Wherein, n _x is a refractive index in a slow axis direction in the substrate film surface, n _y is the refractive index in the direction perpendicular to the slow axis in the base film surface, the thickness of the n _z is a substrate film (The refractive index in the direction, d represents the thickness (nm) of the substrate film, respectively.)
The retardation can be determined at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH (relative humidity) using, for example, KOBRA-21ADH (manufactured by Oji Scientific Instruments). It is preferable to use a base film controlled to the above-mentioned retardation from the viewpoint of excellent visibility when used in an image display device such as a touch panel. Retardation can be adjusted by the kind and addition amount of a plasticizer mentioned above, the film thickness of a base film, stretching conditions, and the like.

  The refractive index of the base film is preferably in the range of 1.45 to 1.55. The refractive index can be measured according to JIS K7142-2008.

(Formation of base film)
Next, although the example of the film forming method of a base film is demonstrated, it is not limited to this. As a method for forming the base film, a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, or a hot press method can be used.

(Organic solvent)
An organic solvent useful for forming a resin solution (dope composition) in the case of producing a base film by a solution casting film forming method can be used as long as it dissolves cellulose acylate resin and other additives at the same time. Can be used without limitation. For example, as the chlorinated organic solvent, methylene chloride, as the non-chlorinated organic solvent, methyl acetate, ethyl acetate, amyl acetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-trifluoroethanol, 2,2,3,3-hexafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro- 2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, etc. Can, methylene chloride, methyl acetate, ethyl acetate, may be used preferably acetone. The solvent is preferably a dope composition in which a cellulose acylate resin and other additives are dissolved within a total range of 15 to 45% by mass.

(Solution casting film forming method)
In the solution casting film forming method, a step of preparing a dope by dissolving a resin and an additive in a solvent, a step of casting the dope on a belt-shaped or drum-shaped metal support, and drying the cast dope as a web It is performed by the step of performing, the step of peeling from the metal support, the step of stretching or maintaining the width, the step of further drying, and the step of winding up the finished cellulose acylate film.

  As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used.

  The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferred because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. A preferable support temperature is appropriately determined within a range of 0 to 100 ° C, and more preferably within a range of 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing warm air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short.

  When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. .

  In particular, it is preferable to perform drying efficiently by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In order for the base film to obtain good flatness, the residual solvent amount when peeling the web from the metal support is preferably within the range of 10 to 150% by mass, more preferably 20 to 40% by mass. Or in the range of 60-130 mass%, Most preferably, it exists in the range of 20-30 mass% or 70-120 mass%. The amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  Further, in the drying process of the base film, the web is peeled off from the metal support and dried, and the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less, particularly preferably. It is in the range of 0 to 0.01% by mass.

  In the film drying step, generally, a roll drying method (a method in which webs are alternately passed through a plurality of rolls arranged above and below) and a method in which the web is dried while being conveyed by a tenter method are employed. In the stretching step, the film can be sequentially or simultaneously stretched in the longitudinal direction (MD direction) and the width direction (TD direction) of the film. The draw ratios in the biaxial directions perpendicular to each other are preferably finally in the range of 1.0 to 2.0 times in the MD direction and 1.05 to 2.0 times in the TD direction, respectively. It is preferable to carry out within 1.0 to 1.5 times and 1.05 to 2.0 times in the TD direction. For example, a method in which peripheral speed differences are applied to a plurality of rolls and a roll peripheral speed difference is used to stretch in the MD direction, both ends of the web are fixed with clips and pins, and the distance between the clips and pins is increased in the traveling direction. And a method of stretching in the MD direction, a method of stretching in the transverse direction and stretching in the TD direction, a method of stretching the MD direction and the TD direction at the same time, and stretching in both directions.

  These width maintenance or width direction stretching in the film forming process is preferably performed by a tenter, and may be a pin tenter or a clip tenter.

  The film transport tension in the film forming process such as a tenter depends on the temperature, but is preferably in the range of 120 to 200 N / m, and more preferably in the range of 140 to 200 N / m. The most preferable range is 140 to 160 N / m.

  The temperature during stretching is (Tg-30) to (Tg + 100) ° C., more preferably (Tg-20) to (Tg + 80) ° C., more preferably (Tg-5), where the glass transition temperature of the base film is Tg. It is in the range of ~ (Tg + 20) ° C.

  The Tg of the base film can be controlled by the material type constituting the film and the ratio of the constituting materials. The Tg at the time of drying the base film is preferably 110 ° C. or higher, more preferably 120 ° C. or higher. Especially preferably, it is 150 degreeC or more. The glass transition temperature is preferably 190 ° C. or lower, more preferably 170 ° C. or lower. The Tg of the cellulose acylate film can be determined by the method described in JIS K7121. The stretching temperature is preferably 150 ° C. or more and the stretching ratio is 1.15 times or more because the surface is appropriately roughened. Roughening the surface of the base film is preferable because it improves slipperiness and improves surface processability.

[Melt casting method]
The base film may be formed by a melt casting film forming method. In the melt casting film forming method, a composition containing other additives such as cellulose acylate resin and plasticizer is heated and melted to a temperature exhibiting fluidity, and then a melt containing fluid cellulose acylate is obtained. It means casting.

  In the melt casting film forming method, the melt extrusion method is preferable from the viewpoint of mechanical strength and surface accuracy. A plurality of raw materials used for melt extrusion are usually preferably kneaded and pelletized in advance.

  Pelletization may be performed by a known method. For example, dry cellulose acylate, plasticizer, and other additives are fed to an extruder using a feeder and kneaded using a single or twin screw extruder, and then formed into a strand from a die. Can be extruded, water-cooled or air-cooled, and then cut.

  The additives may be mixed before being supplied to the extruder, or may be supplied by individual feeders.

  A small amount of additives such as particles and antioxidants are preferably mixed in advance in order to mix uniformly.

  The extruder is preferably processed at a temperature as low as possible so that it can be pelletized so that the shearing force is suppressed and the resin does not deteriorate (molecular weight reduction, coloring, gel formation, etc.). For example, in the case of a twin screw extruder, it is preferable to rotate in the same direction using a deep groove type screw. From the uniformity of kneading, the meshing type is preferable.

  A film is formed using the pellets obtained as described above. Of course, the raw material powder can be directly fed to the extruder by a feeder without being pelletized to form a film as it is.

  Using a single or twin screw extruder, the pellets are melted at a temperature of about 200 to 300 ° C., filtered through a leaf disk type filter or the like to remove foreign matter, and then formed into a film from a T die. The cellulose acylate film is formed by niping the film with a cooling roll and an elastic touch roll and solidifying the film on the cooling roll.

  When introducing into the extruder from the supply hopper, it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  The extrusion flow rate is preferably adjusted stably by introducing a gear pump or the like. Further, a stainless fiber sintered filter is preferably used as a filter used for removing foreign substances. The stainless steel fiber sintered filter is a united stainless steel fiber body that is intricately intertwined and compressed, and the contact points are sintered and integrated. The density of the fiber is changed depending on the thickness of the fiber and the amount of compression, and the filtration accuracy is improved. Can be adjusted.

  Additives such as plasticizers and particles may be mixed with the resin in advance, or may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer.

  The temperature of the cellulose acylate film on the touch roll side when the cellulose acylate film is nipped between the cooling roll and the elastic touch roll is preferably not less than Tg (Tg + 110 ° C.) of the film. A well-known roll can be used for the roll which has the elastic body surface used for such a purpose.

  The elastic touch roll is also called a pinching rotator. As the elastic touch roll, a commercially available one can be used.

  When peeling the base film from the cooling roll, it is preferable to control the tension to prevent deformation of the film.

  Moreover, it is preferable to stretch | stretch the base film obtained as mentioned above by the said stretching operation after passing the process which contact | connects a cooling roll.

  As a stretching method, a known roll stretching machine, a tenter or the like can be preferably used. The stretching temperature is preferably carried out in the temperature range of Tg to (Tg + 60) ° C. of the resin that usually constitutes the film.

  Prior to winding, the ends may be slit and cut to the width of the product, and knurling (embossing) may be applied to both ends to prevent sticking or scratching during winding. The knurling method can be performed by heating or pressurizing using a metal ring having an uneven pattern on the side surface. In addition, since the cellulose acylate film is deformed and cannot be used as a product, the clip holding portions at both ends of the film are usually cut out and reused.

(Physical properties of cellulose acylate film)
The film thickness of the cellulose acylate film is generally within the range of 5 to 200 μm, and preferably 10 to 60 μm. More preferably, it exists in the range of 5-34 micrometers. When the film thickness of the cellulose acylate film is in the range of 5 to 34 μm, it is suitably exhibited from the manifestation of the effects of the present invention in a more severe heat resistance test.

  The width of the cellulose acylate film is preferably within the range of 1 to 4 m. If it exceeds 4 m, conveyance becomes difficult.

  The length of the cellulose acylate film is preferably in the range of 1000 to 10000 m, more preferably in the range of 1000 to 8000 m. By setting it as the range of the said length, it is excellent in the productivity and handling property of a base film. Moreover, arithmetic mean roughness Ra of a base film becomes like this. Preferably it is 2-10 nm, More preferably, it exists in the range of 2-5 nm. The arithmetic average roughness Ra can be measured according to JIS B0601: 1994.

(Hard coat layer)
The film thickness of the base film of the conductive film according to the present invention is a thin film, and after a more severe heat resistance test, it is particularly preferable from the viewpoint of curling suppression to have a hard coat layer on the surface opposite to the conductive layer. . The hard coat layer may be provided on the conductive layer or between the base film.

  The hard coat layer preferably contains an actinic radiation curable resin from the viewpoint of excellent mechanical film strength (abrasion resistance, pencil hardness). That is, it is a layer mainly composed of a resin that is cured through a crosslinking reaction by irradiation with active rays (also called active energy rays) such as ultraviolet rays and electron beams. As the actinic radiation curable resin, a component containing a monomer having an ethylenically unsaturated double bond is preferably used, and an actinic radiation curable resin layer is formed by curing by irradiation with actinic radiation such as ultraviolet rays or electron beams. The Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin curable by ultraviolet irradiation is particularly excellent in mechanical film strength (abrasion resistance, pencil hardness). It is preferable from the point. Examples of the ultraviolet curable resin include an ultraviolet curable acrylate resin, an ultraviolet curable urethane acrylate resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable resin. A curable epoxy resin or the like is preferably used, and an ultraviolet curable acrylate resin is particularly preferable.

  As the ultraviolet curable acrylate resin, a polyfunctional acrylate is preferable. The polyfunctional acrylate is preferably selected from the group consisting of pentaerythritol polyfunctional acrylate, dipentaerythritol polyfunctional acrylate, pentaerythritol polyfunctional methacrylate, and dipentaerythritol polyfunctional methacrylate. Here, the polyfunctional acrylate is a compound having two or more acryloyloxy groups or methacryloyloxy groups in the molecule.

  Examples of the polyfunctional acrylate monomer include ethylene glycol diacrylate, diethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and tetramethylolmethane triacrylate. , Tetramethylolmethane tetraacrylate, pentaglycerol triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tri / tetraacrylate, ditrimethylolpropane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, pentaerythritol tetraacrylate, glycerol triacrylate relay , Dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tris (acryloyloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol di Methacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethane tetramethacrylate, pentaglycerol trimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pen Pentaerythritol tetramethacrylate, glycerol trimethacrylate, dipentaerythritol trimethacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, etc. isocyanurate derivatives of the active energy ray-curable are preferably exemplified.

  From the object effect of the present invention, the hard coat layer preferably contains an active energy ray-curable isocyanurate derivative.

  The active energy ray-curable isocyanurate derivative is not particularly limited as long as it is a compound having a structure in which one or more ethylenically unsaturated groups are bonded to an isocyanuric acid skeleton. A compound having three or more ethylenically unsaturated groups and one or more isocyanurate rings in the same molecule shown is preferable from the viewpoint of the object effect of the present invention. The kind of ethylenically unsaturated group is an acryloyl group, a methacryloyl group, a styryl group, and a vinyl ether group, more preferably a methacryloyl group or an acryloyl group, and particularly preferably an acryloyl group.

In the formula, L ² is a divalent linking group, preferably a substituted or unsubstituted alkyleneoxy group or polyalkyleneoxy group having 7 or less carbon atoms in which a carbon atom is bonded to the isocyanurate ring, Particularly preferred are alkyleneoxy groups, which may be the same or different. R ² represents a hydrogen atom or a methyl group, and may be the same or different. Although the specific compound shown by General formula (1) is shown below, it is not restricted to these.

  Examples of the other compounds include isocyanuric acid diacrylate compounds, and isocyanuric acid ethoxy-modified diacrylates represented by the following general formula (2) are preferable.

  Other examples include ε-caprolactone-modified active energy ray-curable isocyanurate derivatives, specifically, compounds represented by the following general formula (3).

One of R _{1 to} R _{3 in} the chemical structural formula is attached with a functional group represented by the following a, b and c, and at least one of R _{1 to} R ₃ is a functional group of b.

a: -H, or _{- (CH 2) n -OH (} n = 1~10, preferably n = 2 to 6)
b: — (CH ₂ ) _n —O— (COC ₅ H ₁₀ ) _m —COCH═CH ₂ (n = 1 to 10, preferably n = 2 to 6, m = 2 to 8)
c: — (CH ₂ ) _n —O—R (R is a (meth) acryloyl group, n = 1 to 10, preferably n = 2 to 6)
Although the specific compound shown by General formula (3) is shown below, it is not restricted to these.

  As a commercial item of an isocyanuric acid triacrylate compound, Shin-Nakamura Chemical Co., Ltd. A-9300 etc. are mentioned, for example. As a commercial item of an isocyanuric acid diacrylate compound, Toagosei Co., Ltd. Aronix M-215 etc. are mentioned, for example. Examples of the mixture of the isocyanuric acid triacrylate compound and the isocyanuric acid diacrylate compound include Aronix M-315 and Aronix M-313 manufactured by Toagosei Co., Ltd. As the ε-caprolactone-modified active energy ray-curable isocyanurate derivative, A-9300-1CL manufactured by Shin-Nakamura Chemical Co., Ltd., which is ε-caprolactone-modified tris- (acryloxyethyl) isocyanurate, manufactured by Toagosei Co., Ltd. Examples include, but are not limited to, Aronix M-327.

  As these commercial products, Adekaoptomer N series, Sun Rad H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (manufactured by Sanyo Chemical Industries, Ltd.) , Aronix M-6100, M-8030, M-8060, Aronix M-215, Aronix M-315, Aronix M-313, Aronix M-327 (manufactured by Toagosei Co., Ltd.), NK-ester A-TMM-3L , NK-ester AD-TMP, NK-ester ATM-35E, NK ester A-DOG, NK ester A-IBD-2E, A-9300, A-9300-1CL (Shin Nakamura Chemical Co., Ltd.), PE- 3A (Kyoeisha Chemical) etc. are mentioned. You may mix the said active ray curable resin individually or in mixture of 2 or more types. The viscosity at 25 ° C. of the actinic radiation curable resin is preferably 20 mPa · s or more and 2000 mPa · s or less. By using such a low-viscosity resin, a protrusion shape described later can be easily obtained. Specifically, within the viscosity range of the resin, sufficient fluidity of the resin composition (composition comprising an active ray curable resin and an additive other than a solvent) can be easily obtained in the drying step, and a protrusion shape can be obtained. It is easy to be done.

  The viscosity of the actinic radiation curable resin can be measured using a B-type viscometer under the condition of 25 ° C. with the resin stirred and mixed with a disper. A monofunctional acrylate may also be used.

  Monofunctional acrylates include isobornyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isostearyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxyethyl acrylate, lauryl acrylate, isooctyl acrylate, tetrahydrofurfuryl acrylate, behenyl Examples include acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and cyclohexyl acrylate. Such monofunctional acrylates can be obtained from Nippon Kasei Kogyo Co., Ltd., Shin-Nakamura Chemical Co., Ltd., Osaka Organic Chemical Co., Ltd., etc.

  When using a monofunctional acrylate, it is preferable to contain in the range of polyfunctional acrylate: monofunctional acrylate = 80: 20-99: 2 by the mass ratio of polyfunctional acrylate and monofunctional acrylate.

(Photopolymerization initiator)
The hard coat layer preferably contains a photopolymerization initiator to accelerate the curing of the actinic radiation curable resin. The amount of the photopolymerization initiator is preferably contained in a mass ratio in the range of photopolymerization initiator: active ray curable resin = 20: 100 to 0.01: 100. Specific examples of the photopolymerization initiator include alkylphenone series, acetophenone, benzophenone, hydroxybenzophenone, Michler ketone, α-amyloxime ester, thioxanthone and the like, and derivatives thereof. In particular, it is not limited to these.

  A commercial item may be used for such a photoinitiator, for example, Irgacure 184, Irgacure 907, Irgacure 651, etc. by BASF Japan Ltd. are mentioned as a preferable illustration.

(Conductive agent)
The hard coat layer may contain a conductive agent in order to impart antistatic properties. Preferred conductive agents include metal oxide particles or π-conjugated conductive polymers. An ionic liquid is also preferably used as the conductive compound.

(Additive)
From the viewpoint of coatability, the hard coat layer contains additives such as silicone surfactants, fluorine surfactants, anionic surfactants, and fluorine-siloxane graft compounds, fluorine compounds, and acrylic copolymers. Also good. Moreover, you may contain the compound whose HLB value is 3-18. The HLB value is Hydrophile-Lipophile-Balance, hydrophilic-lipophilic-balance, and is a value indicating the hydrophilicity or lipophilicity of a compound. The smaller the HLB value, the higher the lipophilicity, and the higher the value, the higher the hydrophilicity. The HLB value can be obtained by the following calculation formula.

HLB = 7 + 11.7Log (Mw / Mo)
In the formula, Mw represents the molecular weight of the hydrophilic group, Mo represents the molecular weight of the lipophilic group, and Mw + Mo = M (molecular weight of the compound). Alternatively, according to the Griffin method, HLB value = 20 × total formula weight of hydrophilic part / molecular weight (J. Soc. Cosmetic Chem., 5 (1954), 294) and the like. Specific examples of the compound having an HLB value of 3 to 18 are listed below, but the present invention is not limited thereto. Figures in parentheses indicate HLB values.

  Made by Kao Corporation: Emulgen 102KG (6.3), Emulgen 103 (8.1), Emulgen 104P (9.6), Emulgen 105 (9.7), Emulgen 106 (10.5), Emulgen 108 (12. 1), Emulgen 109P (13.6), Emulgen 120 (15.3), Emulgen 123P (16.9), Emulgen 147 (16.3), Emulgen 210P (10.7), Emulgen 220 (14.2) , Emulgen 306P (9.4), Emulgen 320P (13.9), Emulgen 404 (8.8), Emulgen 408 (10.0), Emulgen 409PV (12.0), Emulgen 420 (13.6), Emulgen 430 (16.2), Emulgen 705 (10.5), Emulgen 707 (12.1), Emulgen 7 9 (13.3), Emulgen 1108 (13.5), Emulgen 1118S-70 (16.4), Emulgen 1135S-70 (17.9), Emulgen 2020G-HA (13.0), Emulgen 2025G (15. 7), Emulgen LS-106 (12.5), Emulgen LS-110 (13.4), Emulgen LS-114 (14.0), manufactured by Nissin Chemical Industry Co., Ltd .: Surfynol 104E (4), Surfynol 104H (4), Surfinol 104A (4), Surfinol 104BC (4), Surfinol 104DPM (4), Surfinol 104PA (4), Surfinol 104PG-50 (4), Surfinol 104S (4), Surfi Knoll 420 (4), Surfynol 440 (8), Surfynol 46 (13), Surfinol 485 (17), Surfinol SE (6), manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-4272 (7), X-22-6266 (8), KF-351 (12), KF-352 (7), KF-353 (10), KF-354L (16), KF-355A (12), KF-615A (10), KF-945 (4), KF-618 (11), KF -6011 (12), KF-6015 (4), KF-6004 (5). Examples of the silicone surfactant include polyether-modified silicone, and the KF series manufactured by Shin-Etsu Chemical Co., Ltd. can be used. Examples of the acrylic copolymer include commercially available compounds such as BYK-350 and BYK-352 manufactured by BYK Japan. Examples of the fluorosurfactant include Megafac RS series manufactured by DIC Corporation, Megafac F-444 Megafac F-556, and the like. The fluorine-siloxane graft compound refers to a compound of a copolymer obtained by grafting polysiloxane and / or organopolysiloxane containing siloxane and / or organosiloxane alone on at least a fluorine-based resin. Such a fluorine-siloxane graft compound can be prepared by a method as described in Examples described later. Or as a commercial item, Fuji Chemical Industries Ltd. ZX-022H, ZX-007C, ZX-049, ZX-047-D etc. can be mentioned. Moreover, as a fluorine-type compound, Daikin Industries Ltd. OPTOOL DSX, OPTOOL DAC, etc. can be mentioned.

  These components are preferably added in the range of 0.005 parts by mass or more and 5 parts by mass or less with respect to the solid component in the hard coat composition.

(UV absorber)
A hard-coat layer may further contain the ultraviolet absorber demonstrated with the base film mentioned above. As a structure of the film in the case of containing the ultraviolet absorber, when it is constituted by two or more layers, it is preferable that the hard coat layer in contact with the cellulose acylate film contains the ultraviolet absorber.

  The content of the ultraviolet absorber is preferably in the range of mass ratio and ultraviolet absorber: hard coat layer constituting resin = 0.01: 100 to 10: 100. When two or more layers are provided, the thickness of the hard coat layer in contact with the cellulose film is preferably in the range of 0.05 to 2 μm. Two or more layers may be formed as a simultaneous multilayer. The simultaneous multi-layer is to form a hard coat layer by applying two or more hard coat layers on a base material without going through a drying step. In order to laminate the second hard coat layer on the first hard coat layer without a drying process, the layers are stacked one after another by an extrusion coater or simultaneously by a slot die having a plurality of slits. Can be done.

(solvent)
The hard coat layer is prepared by diluting the components forming the hard coat layer with a solvent that swells or partially dissolves the cellulose acylate film, and forms the hard coat layer composition on the cellulose acylate film by the following method. It is preferable to provide a hard coat layer by coating, drying and curing. As the solvent, ketone (methyl ethyl ketone, acetone, etc.) and / or acetate ester (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohol (ethanol, methanol), propylene glycol monomethyl ether, cyclohexanone, methyl isobutyl ketone, etc. are preferable. The coating amount of the hard coat layer is suitably in the range of 0.1 to 40 μm, preferably in the range of 0.5 to 30 μm, as the wet film thickness. Further, the dry film thickness is in the range of 0.01 to 20 μm, preferably 0.5 to 10 μm. As a method for applying the hard coat layer, known methods such as a gravure coater, a dip coater, a reverse coater, a wire bar coater, a die coater, and an ink jet method can be used.

(Hard coat layer forming method)
After applying the hard coat layer composition, it may be dried and cured (irradiated with active rays (also referred to as UV curing treatment)), and if necessary, may be subjected to heat treatment after UV curing. The heat treatment temperature after UV curing is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 120 ° C. or higher. By performing the heat treatment after UV curing at such a high temperature, a hard coat layer having excellent film strength can be obtained.

  Drying is preferably performed by a high-temperature treatment in which the temperature in the decreasing rate drying section is 90 ° C. or higher. More preferably, the temperature in the decreasing rate drying section is 90 ° C. or higher and 125 ° C. or lower. By setting the temperature of the rate-decreasing drying section to a high temperature treatment, convection occurs in the coating resin during the formation of the hard coat layer, and as a result, irregular surface roughness tends to appear on the hard coat layer surface, which will be described later. It is easy to control the arithmetic average roughness Ra.

  In general, it is known that the drying process changes from a constant state to a gradually decreasing state when drying starts. The decreasing section is called the decreasing rate drying section. In the constant rate drying section, the amount of heat flowing in is all consumed for solvent evaporation on the coating film surface, and when the solvent on the coating film surface decreases, the evaporation surface moves from the surface to the inside and enters the decreasing rate drying section. Thereafter, the temperature of the coating film surface rises and approaches the hot air temperature, so that the temperature of the actinic radiation curable resin composition rises, the resin viscosity decreases, and the fluidity increases.

  As a light source for UV curing treatment, any light source that generates ultraviolet rays can be used without limitation. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used.

Irradiation conditions vary depending on each lamp, but the irradiation amount of active rays is usually within a range of 50 to 1000 mJ / cm ² , preferably 50 to 300 mJ / cm ² . In the UV curing treatment, oxygen removal (for example, replacement with an inert gas such as nitrogen purge) can be performed to prevent reaction inhibition by oxygen. The cured state of the surface can be controlled by adjusting the removal amount of the oxygen concentration. This makes it possible to control the presence state of the additive on the hard coat layer surface, and as a result, it is easy to control θΔ within the above range. When irradiating actinic radiation, it is preferably performed while applying tension in the film transport direction, and more preferably while applying tension in the width direction. The tension to be applied is preferably within a range of 30 to 300 N / m. The method for applying the tension is not particularly limited, and the tension may be applied in the conveying direction on the back roll, or the tension may be applied in the width direction or biaxial direction by a tenter. Thereby, a film having further excellent flatness can be obtained.

(Surface shape)
The arithmetic average roughness Ra (JIS B0601: 1994) of the hard coat layer is preferably in the range of 2 to 100 nm, particularly preferably in the range of 5 to 80 nm.

  The height of the protrusion shape for obtaining the arithmetic average roughness Ra is preferably in the range of 2 nm to 4 μm. The width of the protrusion shape is in the range of 50 nm to 300 μm, preferably 50 nm to 100 μm. The 10-point average roughness Rz of the hard coat layer is 10 times or less of the center line average roughness Ra, and the average mountain valley distance Sm is preferably within the range of 5 to 150 μm, more preferably within the range of 20 to 100 μm, It is preferable that the standard deviation of the height of the convex portion from within a range of 0.5 μm or less, the standard deviation of the average mountain-valley distance Sm with respect to the center line is 20 μm or less, and the surface having an inclination angle of 0 to 5 degrees is 10% or more. The above-mentioned arithmetic average roughness Ra, Sm, Rz is a value measured with an optical interference type surface roughness meter (manufactured by ZYGO, NewView) according to JIS B0601: 1994.

(hardness)
The conductive film having the hard coat layer of the present invention has a pencil hardness, which is an index of hardness, of HB or more, more preferably H or more. If it is more than HB, it is hard to be damaged in the polarizing plate forming step. The pencil hardness is determined by adjusting the humidity of the produced optical film at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more, and then using a test pencil specified by JIS S 6006 under a load of 500 g. Or it is the value which measured the functional layer according to the pencil hardness evaluation method which JISK5400 prescribes | regulates.

<Other layers>
In the conductive film of the present invention, an antireflection layer can be provided on the conductive layer or the hard coat layer.

<Antireflection layer>
The antireflection layer is preferably laminated in consideration of the refractive index, the film thickness, the number of layers, the layer order, and the like so that the reflectance is reduced by optical interference. The antireflection layer is composed of a low refractive index layer having a lower refractive index than the protective film as the support, or a combination of a high refractive index layer and a low refractive index layer having a higher refractive index than the protective film as the support. Preferably it is.

  Particularly preferably, it is an antireflection layer composed of three or more refractive index layers, and three layers having different refractive indexes from the support side are divided into medium refractive index layers (high refractive index layers having a higher refractive index than the support). Are preferably laminated in the order of a layer having a lower refractive index) / a high refractive index layer / a low refractive index layer. Alternatively, an antireflection layer having a layer structure of four or more layers in which two or more high refractive index layers and two or more low refractive index layers are alternately laminated is also preferably used.

(Low refractive index layer)
The low refractive index layer preferably contains silica-based fine particles, and the refractive index is preferably in the range of 1.30 to 1.45 when measured at 23 ° C. and a wavelength of 550 nm.

  The film thickness of the low refractive index layer is preferably in the range of 5 nm to 0.5 μm, more preferably 10 nm to 0.3 μm, and most preferably in the range of 30 nm to 0.2 μm.

  The composition for forming a low refractive index layer preferably contains at least one kind of particles having an outer shell layer and porous or hollow inside as silica-based fine particles. In particular, the particles having the outer shell layer and having a porous or hollow inside are preferably hollow silica-based fine particles.

  The composition for forming a low refractive index layer may contain an organosilicon compound represented by the following general formula (OSi-1) or a hydrolyzate thereof, or a polycondensate thereof.

General formula (OSi-1): Si (OR) ₄
In the organic silicon compound represented by the general formula, R represents an alkyl group having 1 to 4 carbon atoms. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane and the like are preferably used.

  In addition, a silane coupling agent, a curing agent, a surfactant and the like may be added as necessary. Further, it may contain a compound having a thermosetting property and / or a photocuring property mainly containing a fluorine-containing compound containing a fluorine atom in a range of 35 to 80% by mass and containing a crosslinkable or polymerizable functional group. . Specifically, a fluorine-containing polymer or a fluorine-containing sol-gel compound is used. As the fluorine-containing polymer, for example, a hydrofluorinated monomer in addition to a hydrolyzate or dehydration condensate of a perfluoroalkyl group-containing silane compound [eg (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane] Examples thereof include fluorine-containing copolymers having units and cross-linking reactive units as constituent units. In addition, you may add a solvent, a silane coupling agent, a hardening | curing agent, surfactant, etc. as needed.

(High refractive index layer)
The refractive index of the high refractive index layer is preferably adjusted to a refractive index in the range of 1.4 to 2.2 by measuring at 23 ° C. and a wavelength of 550 nm. The thickness of the high refractive index layer is preferably in the range of 5 nm to 1 μm, more preferably 10 nm to 0.2 μm, and most preferably in the range of 30 nm to 0.1 μm. The means for adjusting the refractive index can be achieved by adding metal oxide fine particles and the like. Metal oxide The metal oxide fine particles used preferably have a refractive index in the range of 1.80 to 2.60, more preferably in the range of 1.85 to 2.50.

  The kind of metal oxide fine particles is not particularly limited, and Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S A metal oxide having at least one element selected from can be used.

<Image display device>
A touch panel using the conductive film of the present invention will be described. Examples of the touch panel include a surface capacitive touch panel, a projection capacitive touch panel, and a resistive touch panel.

  An example of a surface capacitive touch panel will be described with reference to FIG. In FIG. 1, the touch panel 10 includes a conductive layer 12 on a base film 11, and is electrically connected to an external detection circuit (not shown) on the conductive layer 12 at the end of the base film 11. The electrode terminal 18 is formed. Reference numeral 13 denotes a conductive layer serving as a shield electrode, reference numerals 14 and 17 denote protective films, reference numeral 15 denotes an intermediate protective film, and reference numeral 16 denotes an antiglare film.

  Surface-type capacitive touch panel In FIG. 1, when an arbitrary point on the conductive layer 12 is touched with a finger or the like, the resistance value between the electrode terminal 18 and the ground point of the conductive layer 12 is reached at the touched point. Change occurs. The surface capacitive touch panel is a system in which the change of the resistance value is detected by the external detection circuit, and the coordinates of the touched point are specified.

  Another example of the surface capacitive touch panel will be described with reference to FIG. In FIG. 2, the touch panel 20 includes a conductive layer 22 on the base film 21, a conductive layer 23 on the base film 25, an insulating layer 24 that insulates the conductive layer 22 from the conductive layer 23, fingers, and the like. And an insulating cover layer (not shown) that generates a capacitance between the contact object 27 and the conductive layer 22 or the conductive layer 23, and detects the position of the contact object such as a finger. Depending on the configuration, the conductive layers 22 and 23 may be integrated, and the insulating layer 24 may be an air layer.

  Further, when a surface-type capacitive touch panel is touched with a finger or the like on an insulating cover layer (not shown), the capacitance value between the finger and the conductive layer 22 or the conductive layer 23 changes. This is a method in which the change in the capacitance value is detected by an external detection circuit, and the coordinates of the touched point are specified.

  Specifically, as shown in FIG. 3, a plurality of conductive layers 22 configured by a conductive pattern of the conductive layer 22 of the touch panel 20 and the conductive layer 23 and capable of detecting positions in the X-axis direction, A plurality of conductive layers 23 in the Y-axis direction are arranged so as to be connectable to external terminals, and a plurality of electrical layers 22 and conductive layers 23 are in contact with a contact target such as a fingertip, so that contact information is large. Point input is performed, and coordinate positions in the X-axis direction and the Y-axis direction are specified.

  Next, an example of a resistive touch panel, which is another example of the touch panel, will be described with reference to FIG. In FIG. 4, the touch panel 30 can come into contact with the conductive layer 32 via the base film 31 provided with the conductive layer 32, the spacers 36 provided on the conductive layer 32, and the air layer 34. And a base film 35 of the conductive layer 33. When the resistance film type touch panel is touched with a finger or the like from the base film 35 side, the base film 35 is pressed, the pressed conductive layer 32 and the conductive layer 33 come into contact, and the potential change at this position is observed. By detecting with an external detection circuit (not shown), the coordinates of the touched point are specified.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, although the display of "part" or "%" is used in an Example, unless otherwise indicated, "part by mass" or "mass%" is represented.

Example 1
(Preparation of cellulose acylate film 1)
-Adjustment of silicon dioxide dispersion Aerosil R812 (manufactured by Nippon Aerosil Co., Ltd.) (average primary particle diameter 7 nm)
10 parts by mass Ethanol 90 parts by mass The above was stirred and mixed with a dissolver for 30 minutes, and then dispersed with Manton Gorin. 88 parts by mass of methylene chloride was added to the silicon dioxide dispersion while stirring, and the mixture was stirred and mixed for 30 minutes with a dissolver to prepare a silicon dioxide dispersion dilution. It filtered with the fine particle dispersion | distribution dilution liquid filter (Advantech Toyo Co., Ltd .: Polypropylene wind cartridge filter TCW-PPS-1N).
-Preparation of dope composition 1 (cellulose acylate resin)
Cellulose triacetate A (cellulose triacetate synthesized from linter cotton, acetyl group substitution degree 2.88, Mn = 14000) 90 parts by mass (additive)
Exemplified Compound X-1 5 parts by mass Exemplified Compound X-12 4 parts by mass (UV absorber)
TINUVIN 928 (manufactured by BASF Japan Ltd.) 3 parts by mass (fine particles)
Silicon dioxide dispersion dilution 4 parts by mass (solvent)
Methylene chloride 432 parts by mass Ethanol 38 parts by mass The above was put into a sealed container, heated and stirred, and dissolved completely. Azumi filter paper No. Azumi filter paper No. 24 was used to prepare a dope (dope composition 1).

  Next, the belt casting apparatus was used to uniformly cast on a stainless steel band support. With the stainless steel band support, the solvent was evaporated until the residual solvent amount reached 100%, and the stainless steel band support was peeled off. The cellulose acylate film web was evaporated at 35 ° C., slit to 1.15 m width, and stretched 1.15 times in the TD direction (film width direction) with a tenter at a drying temperature of 150 ° C. Dried. Then, it was dried for 15 minutes while being transported in a drying device at 120 ° C. with a number of rolls, slitted to a width of 1.3 m, knurled with a width of 10 mm and a height of 5 μm at both ends of the film, and wound around a core. The cellulose acylate film 1 was obtained. The cellulose acylate film 1 had a thickness of 30 μm and a winding length of 5000 m.

  In addition, the draw ratio of MD direction computed from the rotational speed of a stainless steel band support body and the driving speed of a tenter was 1.01 times.

(Production of cellulose acylate films 2 to 7)
Cellulose acylate films 2 to 7 were produced in the same manner as in the production of cellulose acylate film 1 except that the additives were changed as described in the column of cellulose acylate film in Table 1.

[Preparation of conductive composition]
(Preparation of dispersant (1))
Synthesis of Monomer A 45 parts by mass of 2-thiobarbituric acid and 14 parts by mass of sodium hydroxide were dissolved in 200 parts by mass of dimethyl sulfoxide and heated to 25 ° C. To this was added dropwise 57.5 parts by mass of chloromethylstyrene, and the mixture was further heated and stirred at 55 ° C. for 5 hours. After heating and stirring, 150 parts by mass of methanol and 150 parts by mass of distilled water were added to the reaction solution and stirred for 1 hour. Subsequently, this solution was poured into 2 parts by mass of distilled water while stirring, and the obtained precipitate was filtered and washed to obtain 80 parts by mass of monomer A.
Synthesis of polymerizable oligomer A 500 parts by mass of JEFFAMINE M-2005 (manufactured by Huntsman) and 0.06 parts by mass of hydroquinone monomethyl ether were dissolved in 500 parts by mass of 1-methyl-2-pyrrolidone and cooled to 10 ° C. To this, 38 parts by mass of Karenz MOI (manufactured by Showa Denko KK) and 38 parts by mass of 1-methyl-2-pyrrolidone were added dropwise. 1100 mass parts of 1-methyl- 2-pyrrolidone solutions of 50 mass% polymerizable oligomer A were obtained by stirring at 25 degreeC after completion | finish of dripping for 1 hour.
-Preparation of additive (1) The following monomer solution was introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer, heated while flowing nitrogen into the flask, heated to 80 ° C, and stirred for 30 minutes.

  Then, the following initiator solution was added, and it heat-stirred at 80 degreeC for 2 hours. After the heating and stirring, the following initiator solution was further added, followed by heating and stirring at 80 ° C. for 2 hours. After stirring for the last 2 hours, 7.3 parts by mass of 1-methyl-2-pyrrolidone was added, and 25% by mass of 1-methyl-2-methylated graft polymer (dispersant (1)) represented by the following structural formula: A pyrrolidone solution was obtained.

Monomer solution / monomer A 2.0 mass parts / polymerizable oligomer A (50 mass% 1-methyl-2-pyrrolidone solution)
32.0 parts by mass, methacrylic acid 2.0 parts by mass, n-dodecyl mercaptan 0.2 parts by mass, 1-methyl-2-pyrrolidone 30.7 parts by mass initiator solution, 2,2'-azobis (isobutyric acid) Dimethyl (V-601 manufactured by Wako Pure Chemical Industries, Ltd.)
0.2 parts by mass 1-methyl-2-pyrrolidone 3.0 parts by mass (Preparation of water-insoluble polymer (1))
8.6 parts by mass of 1-methoxy-2-propanol was added in advance to the reaction vessel, the temperature was raised to 90 ° C., and cyclohexyl methacrylate, methyl methacrylate, methacrylic acid and glycidyl methacrylate as monomers (addition mass ratio was 46 mol%: 2 mol in order) %: 19 mol%: 34 mol%) was added and stirred. Subsequently, a mixed solution consisting of 1 part by mass of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 8.6 parts by mass of 1-methoxy-2-propanol was reacted at 90 ° C. in a nitrogen gas atmosphere. It was dripped in over 2 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.

  Next, 0.03 parts by mass of hydroquinone monomethyl ether and 0.08 parts by mass of tetraethylammonium bromide were added to the acrylic resin solution, and the mixture was further reacted for 4 hours. A solution of a water-insoluble polymer (1) having a group (weight average molecular weight (Mw); 30,000, 1-methoxy-2-propanol 45% solution) was obtained. In addition, as a measuring method of a weight average molecular weight, it measured using gel permeation chromatography (GPC).

(Preparation of conductive composition 1)
-Preparation of additive solution A A silver nitrate solution was prepared by dissolving 0.55 g of silver nitrate powder in 50 ml of pure water. Next, 1N ammonia water was added to the silver nitrate solution until it became transparent, and pure water was added so that the total amount became 100 ml to prepare an additive solution A.
-Preparation of additive solution B 0.55 g of glucose powder was dissolved in 140 ml of pure water to prepare additive solution G.
-Preparation of Additive Solution C Additive Solution C was prepared by dissolving 0.55 g of HTAB (hexadecyl-trimethylammonium bromide) in 28 ml of pure water.
-Preparation of hydroxypropylmethylcellulose (HPMC) solution 95 ml of pure water was added to 0.55 g of hydroxypropylmethylcellulose (HPMC), and the mixture was dissolved by stirring at 85 ° C while heating. An HPMC solution was prepared.

  Subsequently, 21 ml of additive solution A was placed in a three-necked flask. While stirring at room temperature, 41 ml of pure water, 21 ml of additive liquid C and 17 ml of solution B were added in this order, and the mixture was heated at 90 ° C. for 5 hours with stirring at 200 rpm. The obtained silver nanowire dispersion was cooled, 0.05 g of propylene glycol monomethyl ether was added with stirring to 1 g of silver in the silver nanowire dispersion, and water was removed by centrifugation. After removing water, 8 parts by mass of this silver nanowire dispersion, 8 parts by mass of HPMC solution, and Megafac F-477 (fluorine surfactant, manufactured by DIC Corporation) were added and stirred, A conductive composition 1 containing silver nanowires was prepared.

(Preparation of conductive compositions 2 to 4)
In the preparation of the conductive composition 1, the silver nanowire-containing conductive composition was similarly prepared except that the cellulose ester compound hydroxypropylmethylcellulose (HPMC) was changed as described in the column of the conductive layer in Table 1. 2 to 4 were produced.

(Preparation of conductive composition 5)
A silver nitrate aqueous solution was added to an aqueous solution containing ferrous sulfate and sodium citrate to reduce silver ions, thereby preparing a colloidal dispersion of silver nanoparticles having an average particle diameter of 10 nm.

  A colloidal dispersion of palladium nanoparticles having an average particle diameter of 2.4 nm was prepared by adding an aqueous palladium acetate solution to an aqueous solution containing ferrous sulfate and sodium citrate to reduce palladium ions. The colloidal dispersion of silver nanoparticles and the colloidal dispersion of palladium nanoparticles are mixed and stirred at a molar ratio of 1: 3 to form a composite by a self-organization reaction, and a silver-palladium (Pd) composite nanoparticle colloid dispersion. Got. 8 parts by mass of the HPMC solution prepared with the conductive composition 1 and 8 parts by mass of the silver-Pd composite nanoparticle colloidal dispersion and 0.25 of Megafac F-477 (fluorine surfactant, manufactured by DIC Corporation) Part by mass was added and stirred.

  The silver-Pd composite nanoparticle colloidal dispersion was subjected to water washing treatment and concentration treatment (concentration 30 parts by mass) using an ultrafiltration membrane, and then a conductive polymer (PEDOT / PSS: poly (3,4-ethylene). Dioxythiophene) / poly (styrene sulfonate)) 1.3 parts by mass dispersion (BaytronPH500: manufactured by HC Starck) and dimethyl sulfoxide (DMSO: manufactured by Wako Pure Chemical Industries) with respect to PEDOT / PSS What was added so that it might become 5 mass parts was added, and it fully stirred and mixed until each component became uniform, and the electrically conductive composition 5 was obtained.

(Preparation of conductive composition 6)
Chloroauric acid (HAuCl ₄ .4H ₂ O) and aqueous iron sulfate solution in a 1: 2.5 aqueous solution of 3,4-ethylenedioxythiophene monomer and polystyrene sulfonic acid so that the Au content is 1.0 mass% In addition to polymerization of polyethylenedioxythiophene and formation of gold nanoparticles, a conductive polymer solution containing gold nanoparticles was obtained. Next, the product in this solution was taken out, purified with distilled water, and then dispersed again in distilled water. 8 parts by mass of a metal nanoparticle-containing conductive polymer solution dispersed with distilled water, 8 parts by mass of an HPMC solution prepared with the conductive composition 1, and Megafac F-477 (fluorine surfactant, manufactured by DIC Corporation) ) Was added and stirred to obtain a conductive composition 6.

(Preparation of conductive composition 7)
Conductive polymer (PEDOT / PSS: poly (3,4-ethylenedioxythiophene) / poly (styrene sulfonate)) 1.3 parts by mass Dispersion (BaytronPH500: manufactured by HC Starck) 8 parts by mass 8 parts by mass of the HPMC solution prepared with the conductive composition 1 and 0.25 parts by mass of Megafac F-477 (fluorine surfactant, manufactured by DIC Corporation) were added and stirred, and the conductive polymer-containing polymer was added. A conductive composition 7 was obtained.

(Preparation of conductive composition 8)
13 parts by mass of high-purity single-walled carbon nanotubes (manufactured by Carbon Nanotechnology Inc .; hereinafter referred to as “SWNT”) were added to 87 parts by mass of a 20% aqueous solution of sodium dodecylbenzenesulfonate with stirring at 100 rpm. Subsequently, sonication was performed for 1 hour. Next, using acrylamide gel, the pH of the electrophoresis buffer was adjusted to 8, and gel electrophoresis was performed under the conditions of an electrophoresis temperature of 20 ° C. and an applied voltage of 200 V to fractionate carbon nanotubes. Subsequently, a voltage was applied in a direction perpendicular to the migration direction, and only the carbon nanotubes having a fiber length of about 1 μm or more were recovered from the gel to prepare a 10 mass% carbon nanotube dispersion. Next, 50 parts by mass of 40% aqueous solution of EMIBF ₄ obtained by adding 1-ethyl-3-methylimidazolium: BF ₄ (hereinafter “EMIBF ₄ ”) as an ionic liquid to a 20% aqueous solution of sodium dodecylbenzenesulfonate was added. 10 parts by mass of ethylene glycol was added with stirring to prepare a polymer solution. To 100 parts by mass of this polymer solution, 100 parts by mass of the carbon nanotube dispersion was added with stirring, and then stirred for 1 hour. To 8 parts by mass of the obtained carbon nanotube-containing conductive composition, 8 parts by mass of the HPMC solution prepared with the conductive composition 1 and MegaFac F-477 (fluorine surfactant, manufactured by DIC Corporation) were added. 0.25 part by mass was added and stirred to obtain a conductive composition 8 containing a conductive polymer.

[Preparation of Conductive Film 1]
The content ratio (conductive composition 1 / water-insoluble polymer / additive) of the conductive composition 1, the adjusted water-insoluble polymer (1) and the additive (1) is 100/100/5. Stir and mix. This coating composition 1 was coated on the B side (casting belt surface) of the cellulose acylate film 1 by die coating so that the average thickness after drying was 0.5 μm, and dried at a drying temperature of 150 ° C. for 10 minutes. The conductive layer 1 was provided. Moreover, after drying, it wound up and produced the conductive film 1.

[Preparation of Conductive Films 2-14]
Transparent conductive films 2 to 14 were prepared in the same manner except that the conductive composition 1 and the cellulose acylate film 1 were changed as shown in Table 1 in the production of the transparent conductive film 1.

  In addition, about the cellulose ester compound of the electroconductive layer of Table 1, hydroxypropyl methylcellulose was shown as HPMC, carboxymethylcellulose was shown as CMC, and 2-hydroxyethylcellulose was shown as HEC.

  Further, ethyl phthalyl ethyl glycolate, which is a glycolic acid ester compound contained in a cellulose acylate film, is indicated as EPEG, dibutyl phthalate, which is a phthalic acid ester compound, is DBP, and triphenyl phosphate, which is a phosphoric acid ester compound, is indicated as TPP. . Moreover, the compound A (above-mentioned exemplary compound B-9) and compound B (above-mentioned exemplary compound B-6) which are polyhydric alcohol ester compounds are as follows. Comparative compound triethyl acetyl citrate was shown as comparative compound A, and butyl oleate was shown as comparative compound B.

《評価》
上記作製した導電性フィルム１〜１４について耐熱試験を実施後、以下の内容について評価した。得られた結果を表１に示した。
・耐熱試験
上記作製した導電性フィルム１〜１４を、各３０ｃｍ×３０ｃｍサイズで切り出し、切り出した各サンプルを１１０℃の高温サーモに５００時間投入した。

<Evaluation>
After the heat resistance test was conducted on the produced conductive films 1 to 14, the following contents were evaluated. The obtained results are shown in Table 1.
-Heat resistance test The produced conductive films 1 to 14 were cut out in a size of 30 cm x 30 cm, and the cut out samples were put in a high-temperature thermostat at 110 ° C for 500 hours.

a. Haze / total light transmittance The conductive films 1 to 14 after the heat resistance test were conditioned for 4 hours in an atmosphere of 23 ° C. and 55% RH, and the haze and total light transmittance were determined according to JIS K7361 and JIS K7136 ( NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) and the obtained results are shown in Table 1. The lower the haze value is, the better the clearness is, and those exceeding 6% are not preferable because the visibility when used in an image display device deteriorates. Further, the total light transmittance is preferably as high as possible, and specifically 85% or more is preferable.

b. Curl The conductive films 1 to 14 after the heat resistance test are placed on the side of the conductive layer with respect to the base film in an atmosphere of 23 ° C. and 55% RH, and after standing for 5 minutes, the four corners of the conductive films 1 to 14 are lifted ( H) was measured using a stainless ruler (JIS class 1), and evaluated based on the following criteria from the measurement result of the average value (n = 4).

[Evaluation criteria]
A: The film float is 1 mm or less. B: The film float exceeds 1 mm, 5 mm or less. Δ: The film float exceeds 5 mm, 10 mm or less. Levels with practical problems Levels exceeding 10 mm are levels at which problems occur in subsequent processes such as bonding when a conductive film is incorporated into a touch panel.

c. Adhesion evaluation Conductive films 1 to 14 after the heat resistance test were conditioned for 4 hours in an atmosphere of 23 ° C. and 55% RH, and then cut in 11 mm vertically and horizontally at intervals of 1 mm by a method according to JISK5400. 100 grids were prepared, cellophane tape was applied and peeled off at an angle of 90 degrees, and the number of grids remaining without peeling was counted. Evaluation was made according to the following criteria.

[Evaluation criteria]
(Double-circle): It did not peel at all.

◯: The peeled area ratio was less than 5%. Δ: The peeled area ratio was less than 10%. X: The peeled area ratio was 10% or more. Table 1 shows the results of practical problems.

d. Surface resistance The surface resistance (Ω / □) of the conductive films 1 to 14 is determined according to JIS K 7194: 1994 (resistivity test method by conductive probe four-probe method), Loresta-GP MCP-T610 (Mitsubishi Measured by using Chemical Co., Ltd. Subsequently, the surface resistance (Ω / □) of the conductive films 1 to 14 after the heat test was measured using Loresta-GP MCP-T610 and evaluated according to the following criteria.

[Evaluation criteria]
R1 (Resistivity after aging) / R0 (Resistivity before aging) × 100 = Resistivity change (%)
◎: Resistivity change is less than 80% ○: Resistivity change is less than 120%, 80% or more △: Resistivity change is less than 150%, 120% or more ×: Resistivity change is 150% or more A level.

表１の結果から判るように、導電性高分子、導電性金属、カーボンナノワイヤのうちの少なくとも一種の透明導電性材料を含有する導電性層と一般式（Ｘ）で表されるエステル化合物、糖エステル化合物（Ｙ−１、Ｙ−１２）、グリコール酸エステル化合物、フタル酸エステル化合物、リン酸エステル化合物、多価アルコールエステル化合物（化合物Ａ、化合物Ｂ）のうちの少なくとも一種の化合物を含有するセルロースアシレートフィルムから構成される本発明の導電性フィルムは、耐熱試験後の光学特性（ヘイズ・全光線透過率）、カール、密着性及び抵抗値に優れていることがわかる。本発明の中でも透明導電性材料が導電性金属、更には導電性金属の中でも銀ナノワイヤで構成される導電性層を有する本発明の導電性フィルムは、特に光学特性（ヘイズ・全光線透過率）、カール、密着性及び抵抗値に優れていることがわかる。

As can be seen from the results in Table 1, a conductive layer containing at least one transparent conductive material among conductive polymers, conductive metals, and carbon nanowires, and ester compounds and sugars represented by the general formula (X) Cellulose containing at least one compound of ester compounds (Y-1, Y-12), glycolic acid ester compounds, phthalic acid ester compounds, phosphoric acid ester compounds, polyhydric alcohol ester compounds (compound A, compound B) It turns out that the electroconductive film of this invention comprised from an acylate film is excellent in the optical characteristic (haze and total light transmittance) after a heat test, curl, adhesiveness, and resistance value. In the present invention, the conductive film of the present invention having a conductive layer comprising a conductive metal as a transparent conductive material and silver nanowires among the conductive metals is particularly optical characteristics (haze / total light transmittance). It can be seen that the curl, adhesion and resistance are excellent.

Example 2
The conductive film 1 produced in Example 1 and the conductive films 7 to 9 were evaluated in the same manner as in Example 1 after performing a durability test in the same manner except that the conditions of the heat resistance test were changed as follows. The obtained results are shown in Table 2.
Heat resistance test Each conductive film was cut out in a size of 30 cm x 30 cm, and each cut out sample was put in a high-temperature thermostat at 120 ° C for 750 hours.

表２の結果から判るように、より過酷な耐熱試験では、セルロースアシレートフィルムが一般式（Ｘ）で表されるエステル化合物又は糖エステル化合物（Ｙ−１、Ｙ−１２）を含有すことで、本発明の発現効果が好適に得られる事から、好ましいことがわかる。

As can be seen from the results in Table 2, in a more severe heat resistance test, the cellulose acylate film contains an ester compound or a sugar ester compound (Y-1, Y-12) represented by the general formula (X). From the fact that the expression effect of the present invention is suitably obtained, it can be seen that it is preferable.

Example 3
About the electroconductive film 1 and the electroconductive film 2 produced in Example 1, the hard coat layer is formed on the surface opposite to the surface on which the electroconductive layer is provided by the following method. 15-18 were produced. Subsequently, the conductive film 1 and the conductive films 15 to 18 were evaluated in the same manner as in Example 1 after performing a durability test in the same manner except that the conditions of the heat test were changed to the following. The obtained results are shown in Table 3.
Heat resistance test Each conductive film was cut out in a size of 30 cm × 30 cm, and each cut out sample was put into a high temperature thermostat at 150 ° C. for 1000 hours.

表３の結果から判るように、より過酷な耐熱試験では、セルロースアシレートフィルムが一般式（Ｘ）で表されるエステル化合物又は糖エステル化合物（Ｙ−１、Ｙ−１２）を含有すことで、より良好に本発明の目的効果を発揮することがわかる。

As can be seen from the results in Table 3, in a more severe heat resistance test, the cellulose acylate film contains an ester compound or a sugar ester compound (Y-1, Y-12) represented by the general formula (X). It can be seen that the object and effects of the present invention are exhibited more satisfactorily.

[Production of Conductive Films 15 and 16]
Extruded with the following hard coat layer composition 1 filtered through a polypropylene filter having a pore diameter of 0.4 μm on each of the surfaces of the conductive film 1 and the conductive film 2 that are opposite to the conductive layer forming surface. After coating with a coater, drying at 80 ° C., and then purging with nitrogen so that the atmosphere has an oxygen concentration of 1.0% by volume or less, the irradiation part is irradiated with an illuminance of 100 mW / cm ² using an ultraviolet lamp. The coating layer was cured by setting the amount to 0.2 J / cm ² , and the hard coat layer 1 having a dry film thickness of 2 μm was formed and wound to prepare conductive films 15 and 16.

<< Hard Coat Layer Composition 1 >>
(Actinic radiation curable resin)
Pentaerythritol tri / tetraacrylate (NK ester A-TMM-3L, manufactured by Shin-Nakamura Chemical Co., Ltd.) 100 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive)
KF-354L (polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.)
2 parts by mass (solvent)
Propylene glycol monomethyl ether 20 parts by mass Methyl acetate 30 parts by mass Methyl ethyl ketone 70 parts by mass [Preparation of conductive films 17 and 18]
What filtered the following hard-coat layer composition 2 with the filter made from a polypropylene with the hole diameter of 0.4 micrometer on each of the surface on the opposite side to the conductive layer formation surface of the produced said conductive film 1 and the conductive film 2, After applying with an extrusion coater, drying at 80 ° C., and purging with nitrogen so that the oxygen concentration is 1.0 volume% or less, the illuminance of the irradiated part is 100 mW / cm ² using an ultraviolet lamp, The coating layer was cured with an irradiation amount of 0.2 J / cm ² , the hard coat layer 2 having a dry film thickness of 2 μm was formed and wound up, and conductive films 17 and 18 were produced.

<< Hard Coat Layer Composition 2 >>
(Actinic radiation curable resin)
Tris (2-acryloyloxyethyl) isocyanurate (mixture of isocyanuric acid ethoxy-modified diacrylate (Aronix M-315, manufactured by Toagosei Co., Ltd.))
100 parts by mass (photopolymerization initiator)
Irgacure 184 (manufactured by BASF Japan) 6 parts by mass (additive)
KF-354L (polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.)
2 parts by mass (solvent)
Propylene glycol monomethyl ether 20 parts by weight Methyl acetate 30 parts by weight Methyl ethyl ketone 70 parts by weight Pentaerythritol tri / tetraacrylate is PETA, and a mixture of tris (2-acryloyloxyethyl) isocyanurate and isocyanuric acid ethoxy-modified diacrylate is listed in the table. It was shown in 3.

  As can be seen from the results in Table 3, the conductive layer of the conductive film of the present invention has a hard coat layer on the opposite side, so that excellent optical properties (haze / total) even after a very severe heat test. It can be seen that it is preferable from the viewpoint of obtaining the effect of suppressing light transmittance and curling. Furthermore, the hard coat layer contains an active energy ray-curable isocyanurate derivative as an actinic ray curable resin, from the viewpoint of obtaining particularly excellent optical properties (haze / total light transmittance) and curling suppression effects. It turns out that it is more preferable. In addition, about the conductive films 15-18 which had the hard-coat layer before a heat test, the hardness was confirmed by the pencil hardness test. Using the test pencil specified by JIS-S6006, according to the pencil hardness evaluation method specified by JIS-K5400, the surface of the hard coat layer is scratched 5 times with a pencil of each hardness using a weight of 500 g, up to one scratch. As a result of measuring the hardness, all were H or more.

Example 4
In the preparation of the dope composition 1 of the cellulose acylate film 1 of Example 1, the same procedure was performed except that 8 parts by mass of the acrylic polymer synthesized below was added instead of 4 parts by mass of the additive X-12. Dope composition 2 was prepared. Next, in the production of the cellulose acylate film 1, cellulose acylate films 8 to 11 were produced in the same manner except that the stretching conditions in the TD direction by the tenter were changed as described in Table 4.

(Synthesis of acrylic polymer)
Methyl acrylate 10 parts by weight 2-hydroxyethyl acrylate 1 part by weight Azobisisobutyronitrile (AIBN) 1 part by weight Toluene 30 parts by weight Four-necked flask (input, thermometer, reflux condenser, nitrogen introduction) And the temperature is gradually raised to 80 ° C., and polymerization is performed for 5 hours while stirring. After the polymerization, the polymer solution is poured into a large amount of methanol to precipitate, and further washed with methanol. Purification and drying gave an acrylic polymer having a weight average molecular weight of 5,000 (measured by GPC).

  Next, the conductive films 19-23 were produced similarly except having provided the electroconductive layer composition 1 of Example 1 on both surfaces to the produced cellulose acylate films 8-11.

  Subsequently, these conductive films 19 to 23 were evaluated in the same manner as in Example 1 after performing a heat resistance test in the same manner as in Example 1.

  Next, the in-plane retardation value Ro and the thickness direction retardation value Rt of the cellulose acylate film 1 and 8 to 11 were measured by the following methods.

Using a measurement automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments), three-dimensional refractive index measurement is performed at a wavelength of 590 nm in an environment of 23 ° C. and 55% RH. each direction of the refractive indices n _x a, n _y, seek n _z, were determined Ro and Rt of the cellulose acylate film from the following equation.

_{Ro = (n x -n y)} × d
Rt = a _{((n x + n y)} / 2-n z) × d.

(Wherein, n _x is a refractive index in a slow axis direction in the substrate film surface, n _y is the refractive index in the direction perpendicular to the slow axis in the base film surface, the thickness of the n _z is a substrate film (The refractive index in the direction, d represents the thickness (nm) of the substrate film, respectively.)
These obtained results are shown in Table 4.

  Next, an inner touch panel was produced using each of the produced conductive films 19 to 23 (FIG. 5). A dot spacer was previously formed on the conductive layer film (1A) of one of the two conductive films, and then the two conductive layer films were opposed to produce an inner touch panel. The obtained inner touch panel is assembled under the upper surface side polarizing plate of the liquid crystal display device having the configuration of the upper surface side polarizing plate / liquid crystal cell / lower surface side polarizing plate to produce a liquid crystal display device, and the inner touch panel is mounted in the dark room. The black display screen was observed by changing the front direction and the visual field direction, and the visibility was evaluated according to the following criteria. The results obtained are shown in Table 4.

  For the production of touch panels, "latest touch panel technology" (issued July 6, 2009, Techno Times), supervised by Yuji Mitani, "Touch Panel Technology and Development", CMC Publishing (2004, 12), FPD International The method described in the 2009 Forum T-11 Lecture Textbook, Cypress Semiconductor Corporation Application Note AN2292 was referred to.

  In Table 4, the acrylic polymer in the cellulose acylate film was indicated as AP.

本発明に係る導電性フィルムをタッチパネルに用いることで、本発明の発現効果に優れ、かつ優れた視認性が得られるため好ましいことが判る。中でも、面内リターデーション値Ｒｏを０〜５ｎｍ、厚さ方向のリターデーション値Ｒｔを−１０〜１０ｎｍの範囲に調整したセルロースアシレートフィルムを用いた本発明に係る導電性フィルムをタッチパネルに用いることで、特に優れた視認性が得られるため、好ましいことが判る。 <Evaluation>
Visibility evaluation ○: No change in color of touch panel Δ: Some change in color of touch panel is observed ×: Large change in color of touch panel

It can be seen that the use of the conductive film according to the present invention for a touch panel is preferable because the expression effect of the present invention is excellent and excellent visibility is obtained. In particular, the conductive film according to the present invention using the cellulose acylate film in which the in-plane retardation value Ro is adjusted to 0 to 5 nm and the retardation value Rt in the thickness direction is adjusted to the range of -10 to 10 nm is used for the touch panel. Thus, it can be seen that it is preferable because particularly excellent visibility is obtained.

Example 5
In the production of the conductive film 1 of Example 1, conductive films 24 to 27 were produced in the same manner except that the film thickness of the cellulose acylate film 1 was changed as described in Table 5. Subsequently, the conductive film 1 and the conductive films 24 to 27 were evaluated in the same manner as in Example 1 after performing a durability test in the same manner except that the conditions of the heat resistance test were changed as follows. The obtained results are shown in Table 5.
-Heat resistance test Each conductive film was cut out in a size of 30 cm x 30 cm, and each cut out sample was put in a high temperature thermostat at 110 ° C for 750 hours.

表５の結果から判るように、より過酷な耐熱試験では、セルロースアシレートフィルムの膜厚が５〜３４μｍの範囲内において、本発明の発現効果が好適に得られる事から、好ましい範囲であることがわかる。

As can be seen from the results in Table 5, in the more severe heat resistance test, the expression effect of the present invention is suitably obtained within the range of the film thickness of the cellulose acylate film of 5 to 34 μm. I understand.

DESCRIPTION OF SYMBOLS 10 Touch panel 11 Base film 12 Conductive layer 13 Conductive layer 14 Protective film 15 Intermediate protective film 16 Anti-glare film 17 Protective film 18 Electrode terminal 20 Touch panel 21 Base film 22 Conductive layer 23 Conductive layer 24 Insulating layer 26 Drive Circuit 27 Target object 30 such as finger Touch panel 31 Base film 32 Conductive layer 33 Conductive layer 34 Air layer 35 Base film 36 Spacer A Inner touch panel 1A Conductive layer 1B Conductive layer 1C Cellulose acylate film 1E Liquid crystal cell 1F1 Upper surface side polarizing plate 1F2 Lower surface side polarizing plate 1G Reflector DS Dot spacer

Claims (10)

A conductive film having a conductive layer containing a transparent conductive material and a cellulose ester compound other than cellulose acylate on a cellulose acylate film, wherein the transparent conductive material is a conductive polymer, a conductive metal Or an ester compound represented by the following general formula (X), a sugar ester compound, a glycol, which is at least one transparent conductive material selected from carbon nanotubes, and wherein the cellulose acylate film is different from the cellulose ester compound A conductive film comprising at least one of an acid ester compound, a phthalic acid ester compound, a phosphoric acid ester compound or a polyhydric alcohol ester compound.
Formula (X) B- (GA) _n -GB
(In the formula, B represents a hydroxy group or a carboxylic acid residue. G represents an alkylene glycol residue having 2 to 12 carbon atoms, an arylene glycol residue having 6 to 12 carbon atoms, or an oxyalkylene glycol having 4 to 12 carbon atoms. Represents a residue, A represents an alkylene dicarboxylic acid residue having 4 to 12 carbon atoms or an arylene dicarboxylic acid residue having 6 to 12 carbon atoms, and n represents an integer of 1 or more.) The conductive film according to claim 1, wherein the transparent conductive material is a conductive metal.   The conductive film according to claim 1, wherein the conductive metal is a metal nanowire.   The said cellulose acylate film contains the ester compound or the said sugar ester compound represented by the said general formula (X), The electroconductive film as described in any one of Claims 1-3 characterized by the above-mentioned.   The film thickness of the said cellulose acylate film is 5-34 micrometers, The electroconductive film as described in any one of Claims 1-4 characterized by the above-mentioned.   The conductive film according to claim 1, further comprising a hard coat layer on a surface opposite to the conductive layer.   The conductive film according to claim 6, wherein the hard coat layer contains an active energy ray-curable isocyanurate derivative.   When the retardation value was measured at an optical wavelength of 590 nm under an environment of a temperature of 23 ° C. and a relative humidity of 55%, the in-plane retardation value Ro was in the range of 0 to 10 nm, and the conductive film was in the thickness direction. Retardation value Rt exists in the range of -10-10 nm, The electroconductive film as described in any one of Claims 1-7 characterized by the above-mentioned.   The conductive film according to claim 1, wherein the conductive film is a transparent conductive film.   A touch panel comprising the conductive film according to claim 1.

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