JP2007168218A - Conductive laminate and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive laminate in which a high refractive index metal compound layer, a metal thin film layer, a high refractive transparent thin film layer, a low refractive index thin film layer and an antifouling layer are sequentially laminated on a substrate with a damp cloth. Conductive laminate in which high-refractive-index metal compound layer and metal thin film layer do not peel off even when rubbed under load for a long time, optical functional filter, optical display device and optical article having the conductive laminate Is to provide.
A conductive laminate having a conductive functional layer and an antifouling layer formed by laminating a metal thin film layer and a metal compound layer on at least a substrate, wherein the antifouling layer comprises a reactive functional group. A conductive laminate having a pure water falling angle of 50 ° or less.
[Selection] Figure 1

Description

  The present invention relates to a conductive laminate, and more particularly to a conductive antireflection laminate useful as an antireflection filter used on the front surface of an optical display device such as a flat panel display (FPD).

  In an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel (PDP), there is a problem that it becomes difficult to recognize an image due to reflection of external light on a display screen. In recent years, optical display devices have been increasingly taken not only indoors but also outdoors, and the reflection of external light on the display screen has become a more serious problem.

  In order to reduce reflection of external light, an antireflection laminate having a low reflectance over a wide range of wavelengths in the visible light region is provided on the front surface of the optical display device. Moreover, electromagnetic wave shielding performance can be imparted by imparting conductivity to the antireflection laminate. For example, an unnecessary electromagnetic wave generated from the inside of the PDP can be shielded by providing a conductive laminate having an electromagnetic wave shielding property on the front surface of the image display unit of the PDP.

  However, in a laminate in which transparent thin film layers and metal thin film layers typified by metal alloy oxide layers are alternately laminated, there is a problem that the adhesion between the transparent thin film layer and the metal thin film layer is not good. (See, for example, Patent Document 1), and is proved by, for example, a simple friction test consisting of wiping the coated surface with a wet cloth (see, for example, Patent Document 1). On the other hand, as a countermeasure, a metal such as titanium is formed as a primer layer between the metal alloy oxide layer and the metal layer, so that no visible change occurs even if it is rubbed hard for a long time with a wet cloth ( For example, see Patent Document 1).

  When a laminated body in which transparent thin film layers and metal thin film layers are alternately laminated is placed on the outermost surface of an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel (PDP), use a damp cloth or the like. Since wiping the surface is easily expected, the transparent thin film layer and the metal layer must not be peeled off even when wiping with a damp cloth or the like. However, the method of forming a metal primer layer between the transparent thin film layer and the metal layer has a problem that the transmittance of the laminate is lowered. A case where the laminate is an antireflection film is not preferable because high transmittance is required. In addition, since the number of layers generally increases by forming a primer layer, in terms of actually producing a laminate, the equipment cost of the film forming apparatus and the material cost of the primer layer are incurred, and the process This is also not preferable in that many problems such as complications occur. Further, in the scratch resistance, the points such as the denseness, hardness, and stress of the thin film itself in the laminate are important points, and in order to form a strong thin film in the scratch resistance, the film forming method is limited. There are also problems such as.

In some cases, a surface of the conductive laminate is provided with an antifouling layer made of a fluorine-containing silicon compound and having water repellency, oil repellency and low friction (for example, see Patent Document 2). However, the antifouling layer made of a fluorine-containing silicon compound has water and oil repellency effects, but when the test for wiping the coated surface with a damp cloth was performed for a long time, the effect was insufficient.
JP 2000-192227 A Japanese Patent Laid-Open No. 11-156987

  An object of the present invention is to wet a conductive laminate in which a high refractive index metal compound layer, a metal thin film layer, a high refractive transparent thin film layer, a low refractive index thin film layer, and an antifouling layer are sequentially laminated on a substrate. Conductive laminate in which the high refractive index metal compound layer and the metal thin film layer do not peel off even when rubbed with a load over a long period of time, an optical functional filter having the conductive laminate, and an optical display device And providing an optical article.

  The invention according to claim 1 is a conductive laminate having a conductive functional layer formed by laminating a metal thin film layer and a metal compound layer on at least a substrate, and the antifouling layer is a reaction layer. The conductive laminate is a layer obtained from an organic silicon compound bonded to a functional functional group, and has a pure water falling angle of 50 ° or less.

  The invention according to claim 2 is the conductive laminate according to claim 1, wherein the contact angle of pure water on the surface of the antifouling layer is 90 ° or more.

  The invention of claim 3 is characterized in that the organic silicon compound bonded to the reactive functional group of the antifouling layer has one or more silicon atoms bonded to the reactive functional group. The conductive laminate according to 1 or 2.

  The invention according to claim 4 is characterized in that the difference in pure water contact angle before the wiping test and after 100 times is within 5 °. It is a laminate.

  The invention according to claim 5 is characterized in that the conductive functional layer is a high refractive index metal compound layer / metal thin film layer / high refractive index metal compound layer. Is a conductive laminate.

  The invention according to claim 6 is the conductive laminate according to any one of claims 1 to 5, wherein the metal thin film layer is silver or an alloy containing silver.

  A seventh aspect of the present invention is the conductive laminate according to any one of the first to sixth aspects, wherein a low refractive index layer is provided between the conductive functional layer and the antifouling layer. .

  The invention according to claim 8 is a display characterized in that the conductive laminate according to any one of claims 1 to 7 is provided on the front surface of the display.

The conductive laminate of the present invention is rubbed with a wet cloth for a long time without increasing the number of layers in order to strengthen the adhesion between the high refractive index metal compound layer and the metal thin film layer. However, the transparent thin film layer and the metal thin film layer are not peeled off.
Moreover, the function which the electroconductive functional layer containing a metal layer has is maintained for a long period of time.

Hereinafter, the present invention will be described with reference to FIG.
FIG. 1 is a cross-sectional view showing an example of the conductive laminate of the present invention. The conductive laminate 1 includes a base material 2, a hard coat layer 3 provided on the base material 2, a primer layer 4 provided on the hard coat layer 3, and a conductive material provided on the primer layer 4. Functional layer 5, low refractive index transparent thin film layer 6 provided on conductive functional layer 5, antifouling layer 7 provided on low refractive index transparent thin film layer 6, and the other surface of substrate 2 And having an adhesive layer 8 provided on the substrate.

(Base material)
Examples of the substrate 2 include a transparent inorganic compound molded product or an organic compound molded product. Transparency in the present invention means that light having a wavelength in the visible light region may be transmitted. The shape of the molded product is not particularly limited as long as the surface is smooth, and examples thereof include a plate shape and a roll shape. The substrate 2 may be a transparent inorganic compound molded product or an organic compound molded product laminate.

Examples of the inorganic compound molded product having transparency include soda lime glass, borosilicate glass, quartz glass, Pyrex (registered trademark) glass, alkali-free glass, lead glass, and the like.
An example of the organic compound molding having transparency is plastic. Examples of the plastic include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinyl acetal, polyurethane, polyethyl methacrylate, polycarbonate, polystyrene, polyethylene sulfide, polyether sulfone, polyolefin, polyarylate, polyether ether. Examples thereof include ketones, polyethylene terephthalate, polyethylene naphthalate, and triacetyl cellulose.

  The thickness of the base material 2 is appropriately selected according to the intended use, and is usually 25 to 300 μm. The organic compound molded product may contain known additives such as ultraviolet absorbers, plasticizers, lubricants, colorants, antioxidants, flame retardants and the like.

(Hard coat layer)
In the present invention, the hard coat layer 3 may be provided. The hard coat layer 3 is a layer that protects the surface of the base material 2 or each layer formed on the base material 2 from mechanical trauma such as scratches caused by pencils and the like, and scratches caused by steel wool. The material for forming the hard coat layer 3 may be any material having transparency, appropriate hardness and mechanical strength, and examples thereof include resin materials such as acrylic resins, organic silicon resins, and polysiloxanes.

  Acrylic resins include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol (meth) acrylate, ethylene glycol di (meth) acrylate, and triethylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (meth) acryloyloxypropionate, trimethylol Ethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (2-h Roxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2.1] heptane, poly 1,2-butadiene di (meth) acrylate 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecane ethylene glycol di (meth) acrylate, 10-decanediol (meth) acrylate, 3,8-bis (meth) acryloyl Oxymethyltricyclo [5.2.10] decane, hydrogenated bisphenol A di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxydiethoxyphenyl) propane, 1,4-bis ((meta ) Acryloyloxymethyl E) Cyclohexane, hydroxypivalate ester neopentyl glycol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, epoxy-modified bisphenol A di (meth) acrylate, and the like.

  Examples of the organic silicon resin include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapentaethoxysilane, tetrapentaisoproxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, Examples include butoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethylethoxysilane, dimethylmethoxysilane, dimethylpropoxysilane, dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane, and hexyltrimethoxysilane.

  The hard coat layer 3 is formed by depositing these resin materials on the substrate 2 and curing them by heat curing, ultraviolet curing, or ionizing radiation curing. The thickness of the hard coat layer 3 is 0.5 μm or more, preferably 3 to 20 μm, more preferably 3 to 6 μm in terms of physical film thickness.

  Transparent hard particles having an average particle diameter of 0.01 to 3 μm may be dispersed in the hard coat layer 3 and subjected to a process called antiglare. The fine particles in the hard coat layer 3 have fine irregularities on the surface, improving the light diffusibility and further reducing the reflection of light.

  The hard coat layer 3 is preferably subjected to a surface treatment. By performing the surface treatment, the adhesion with an adjacent layer can be improved. Examples of the surface treatment of the hard coat layer 3 include corona treatment, vapor deposition, electron beam treatment, high frequency discharge plasma treatment, sputtering treatment, ion beam treatment, atmospheric pressure glow discharge plasma treatment, and alkali treatment. Method, acid treatment method and the like.

(Primer layer)
Further, the primer layer 4 may be provided between the hard coat layer 3 and the conductive functional layer 5.
The primer layer 4 is a layer that improves the adhesion between the hard coat layer 3 and the conductive functional layer 5. Examples of the material of the primer layer 4 include metals such as silicon, nickel, chromium, tin, gold, silver, platinum, zinc, titanium, tungsten, zirconium, and palladium; alloys composed of two or more of these metals; Products, fluorides, sulfides, nitrides and the like. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as adhesion is improved.

The thickness of the primer layer 4 should just be a grade which does not impair the transparency of the base material 2, Preferably it is 0.1-10 nm by a physical film thickness.
The primer layer 4 can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a chemical vapor deposition (CVD) method, or a wet coating method.

(Conductive functional layer)
The conductive functional layer 5 imparts electromagnetic wave shielding properties to the conductive laminate. Moreover, antireflection properties can be imparted by optical design. Furthermore, it can also have infrared cut property. Moreover, when providing the below-mentioned low-refractive-index layer, the antireflective property can be provided by optically designing the low-refractive-index layer together.

The conductive functional layer 5 is formed by alternately laminating metal compound layers and metal thin film layers, and the lowermost layer and the uppermost layer are metal compound layers. The metal compound layer is preferably a high refractive index metal compound layer having a refractive index in the range of 1.9 to 2.5.
In FIG. 1, the conductive functional layer 5 includes a high refractive index metal compound layer 11, a metal thin film layer 12, and a high refractive index metal compound layer 13 in this order from the substrate 2 side.

  The high refractive index metal compound layers 11 and 13 are layers having a refractive index of light having a wavelength of 550 nm of 1.7 or more and an extinction coefficient of light having a wavelength of 550 nm of 0.5 or less.

  Examples of materials for the high refractive index metal compound layers 11 and 13 include indium, tin, titanium, silicon, zinc, zirconium, niobium, magnesium, bismuth, cerium, chromium, tantalum, aluminum, germanium, gallium, antimony, neodymium, lanthanum, Metals such as thorium and hafnium; oxides, fluorides, sulfides, and nitrides of these metals; oxides, fluorides, sulfides, and mixtures of nitrides. The chemical composition of oxides, fluorides, sulfides, and nitrides may not match the stoichiometric composition as long as the chemical composition maintains transparency.

  Indium oxide and tin oxide mixture (ITO), indium oxide and cerium oxide mixture (ICO), indium oxide and zinc oxide mixture, zinc oxide and aluminum oxide mixture, zinc oxide and gallium oxide A mixture of tin oxide and antimony oxide, a mixture containing antimony and indium in tin oxide, a mixture containing zirconium in silicon, and the like. Among these, ITO and ICO have a refractive index in visible light of 2.0 or more and an extinction coefficient close to zero, so that transparency in the visible light region is excellent and light absorption by the material is small. Therefore, it is preferable. In addition, ITO and ICO have high free electron density, that is, low specific resistance, so that sputtering film formation by a DC power supply is possible. The use of a direct current power source increases the film formation rate and consequently contributes to high productivity.

  The plurality of high refractive index metal compound layers are not necessarily made of the same material, and are appropriately selected according to the purpose. The high refractive index metal compound layers 11 and 13 can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method.

The metal thin film layer 12 preferably has a refractive index of light having a wavelength of 550 nm of 1.0 or less and an extinction coefficient of 10.0 or less.
Examples of the material of the metal thin film layer 12 include metals such as gold, silver, copper, platinum, aluminum, and palladium; and alloys containing two or more of these metals. Of these. Silver, an alloy containing silver, and a mixture containing silver are preferable. Silver has a small refractive index of light with a wavelength of 550 nm as 0.055, while its extinction coefficient is as large as 3.32. Since the ratio of the extinction coefficient to the refractive index is larger than that of other metals, the metallicity is high, that is, the electrical conductivity is high.

  Silver thin films are easily corroded by oxygen, sulfur, halogen, alkali, and the like, resulting in aggregation, migration, and the like. On the other hand, it is known that the chemical stability of silver improves when silver contains other metal elements. Examples of metal elements contained in silver include gold, copper, platinum, tin, aluminum, nickel, magnesium, titanium, bismuth, zirconium, neodymium, palladium, zinc, indium, germanium, iridium, osmium, ruthenium, rhenium, and rhodium. Etc. Two or more of these metal elements may be contained in silver. In the case where these metal elements are contained in silver, the content thereof may be a level that contributes to corrosion resistance without deteriorating the optical performance of the metal thin film layer 12 or the conductive laminate 1. The atomic percent is about 20 atomic percent.

The metal thin film layer 12 preferably has a physical film thickness of 5 to 15 nm.
The metal thin film layer 12 can be formed by a conventionally known method such as a vapor deposition method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method. When the sputtering method is used, film formation is possible with a direct current power source, and a high film formation rate is obtained, so that productivity is excellent.

The conductive functional layer is not limited to the conductive functional layer 5 having the three-layer structure in the illustrated example, and the metal compound layer and the metal thin film layer are alternately provided, and the uppermost layer and the lowermost layer are the metal compound layer. If it is, it has a five-layer structure in which three metal compound layers and two metal thin film layers are alternately provided, or seven or more layers in which four or more layers are laminated and three or more layers are laminated. It may be.
By increasing the number of metal compound layers, the conductive laminate can have a wide wavelength range in the visible light region where the reflectance is low.
However, when a low refractive index layer described later is provided, the conductive laminate has a sufficiently wide wavelength range in the visible light region where the reflectance is lowered by the low refractive index transparent thin film layer. From the viewpoint of thinning, a three-layer structure of metal compound layer / metal thin film layer / metal compound layer is preferable.

(Low refractive index layer)
A low refractive index layer 6 may be provided between the conductive functional layer and the antifouling layer. By providing the low refractive index layer 6, the reflectance can be lowered and the wavelength range in the visible light region where the reflectance can be lowered can be widened.
The low refractive index layer 6 is a layer in which the refractive index of light having a wavelength of 550 nm is less than 1.7 and the extinction coefficient of light having a wavelength of 550 nm is 0.5 or less. By providing the low-refractive-index transparent thin film layer 6 so as to be in contact with the high-refractive-index metal compound layer 13 of the conductive functional layer 5, the conductive laminate 1 has a wavelength range in the visible light region where the reflectance is low. Wide enough.

Examples of the material for the low refractive index layer 6 include silicon oxide, titanium nitride, magnesium fluoride, barium fluoride, calcium fluoride, cerium fluoride, hafnium fluoride, lanthanum fluoride, sodium fluoride, aluminum fluoride, fluorine fluoride. Lead fluoride, strontium fluoride, ytterbium fluoride and the like can be mentioned.
The thickness of the low refractive index layer 6 is preferably 15 to 70 nm in terms of physical film thickness.
The low refractive index layer 6 can be formed by a method such as an evaporation method, a sputtering method, an ion plating method, an ion beam assist method, a CVD method, or a wet coating method.

(Anti-fouling layer)
The antifouling layer 7 needs to have a pure water falling angle of 50 ° or less.
When the scratch test is performed, the lower the falling angle of the thin film surface, the more the water existing between the cloth and the thin film surface is pushed out by the reciprocating cloth even if there is no inclination. Although it is not unambiguous from the following formula (2), basically, the lower the falling angle, the smaller the interaction energy E, and water is always pushed out from the surface of the thin film, so that the water hardly acts on the thin film. On the other hand, the higher the falling angle, the easier the interaction energy E becomes, and the water existing between the cloth and the surface of the thin film is not pushed out by the reciprocating cloth, and the water easily acts on the thin film.
Generally, in order to improve antifouling properties, the contact angle is increased, but even if only the contact angle is increased, the falling angle is not necessarily lowered. When the tumbling angle is 50 ° or less, the high refractive index metal compound layer and the metal thin film layer are not peeled off even if a load is rubbed with a wet cloth for a long time.

The mechanical equilibrium when the water droplet slides down the inclined surface is represented by the following formula (1).
mg sin α = 2πrE (1)
m: droplet mass g: acceleration of gravity α: falling angle r: radius of water droplet contact surface E: interaction energy between solid and liquid

In Eq. (1), E has a value specific to the material and does not depend on the size of the droplet. Therefore, when V is the volume, m = ρV (ρ: droplet density) Shown in (2).
sin α = (2πE / ρg) (r / V) (2)

  Since 2πE / ρg is constant if the liquid of the surface material is constant, a straight line can be obtained by plotting sin α on the vertical axis and r / V on the horizontal axis. At this time, 2πE / ρg represents the gradient of the straight line. This indicates that the more the gradient is steeper, the more difficult the droplets are to slip, and the more gentle the droplet is, the easier it is to slip.

  In addition, although the falling angle is low, if the contact angle is low, it may not show a high level of water and oil repellency against external dirt such as fingerprints and magic, and the wiping property of fingerprints is good. When high antifouling properties are required, for example, the contact angle of pure water on the antifouling layer 7 surface is preferably 90 ° or more from the viewpoint of waterproofing and antifouling properties.

The antifouling layer 7 is made of a layer obtained from an organosilicon compound bonded to a reactive functional group. Here, the reactive functional group in the present invention means a group capable of reacting with and bonding to the metal compound layer of the conductive functional layer 5 or the material of the low refractive index layer 6.
In addition, the organosilicon compound bonded to the reactive functional group preferably has one or more silicon atoms bonded to the reactive functional group.

Although it is difficult to analyze whether or not the reactive functional group of the antifouling layer and the metal compound layer of the conductive functional layer 5 or the material of the low refractive index layer 6 are bonded, the wiping test was performed 100 times. If there is no difference in pure water contact angle between after and before the wiping test, the antifouling layer is firmly bonded to the metal compound layer of the conductive functional layer 5 or the material of the low refractive index layer 6 as the lower layer. It is estimated that Specifically, the difference is within 5 °, preferably within 2 °.
The wiping test is reciprocated at a load of 200 g using a scratch tester “AB-301 Gakushin type friction fastness tester” manufactured by Tester Sangyo Co., Ltd. “AB-301 Gakushin type friction fastness tester”... JISL-0849 is used as a reference standard.

  Specifically, the reactive functional group of the organosilicon compound having a siloxane bond as the main chain is reacted with the material of the low refractive index transparent thin film layer 6, and the siloxane bond having two or more silicon atoms is the main chain. In the case of an organosilicon compound, it is a layer formed by reacting reactive functional groups.

  Examples of the reactive functional group include a hydrolyzable group and a halogen atom. Hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, and butoxy groups; alkoxyalkoxy groups such as methoxymethoxy, methoxyethoxy, and ethoxyethoxy groups; alkenyloxy groups such as allyloxy and isopropenoxy groups An acyloxy group such as an acetoxy group, a propionyloxy group, a butylcarbonyloxy group or a benzoyloxy group; a ketoxime group such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a cyclopentanoxime group or a cyclohexanoxime group; Amino groups such as N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N, N-diethylamino group, N-cyclohexylamino group; N -Methylacetamide , N- ethyl acetamide group, an amido group such as N- methylbenzamide group; N, N- dimethylamino group, N, an amino group, such as N- diethylamino group and the like. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Of these, a methoxy group, an ethoxy group, and an isopropenoxy group are preferable.

  Examples of the organosilicon compound having a siloxane bond having at least one silicon atom bonded to a reactive functional group as the main chain include a compound represented by the following formula (1).

  In formula (1), R1 is the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms, and alkyl such as methyl group, ethyl group, prohyl group, butyl group, hexyl group, octyl group, decyl group, etc. Group, cycloalkyl group such as cyclohexyl group, vinyl group, allyl group, propenyl group, butenyl group, alkenyl group such as hexenyl group, aryl group such as phenyl group, tolyl group, aralkyl group such as benzyl group phenylethyl group, etc. In particular, a methyl group, an ethyl group, a phenyl group, and a phenylethyl group are preferable, R2, X1, and X2 represent a reactive functional group, R3 is a monovalent hydrocarbon group of hydrocarbons 1 to 10, Although the same thing as illustrated by R1 can be mentioned, this may be substituted for a part or all of the hydrogen atoms bonded to the carbon atom with a fluorine atom. Examples of such a substituent include a trifluoropropyl group, k is an integer of 0 to 100, m is an integer of 0 to 100, n is an integer of 0 to 5, and R4 and R5 are alkylene groups. R6 and R7 each represent a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms, and examples of the monovalent hydrocarbon group for R6 and R7 include a methyl group, an ethyl group, Alkyl groups such as propyl, butyl, pentyl, hexyl, heptyl and octyl; cycloalkyl such as cyclopentyl and cyclohexyl; aryl groups such as phenyl, tolyl and xylyl; benzyl and phenethyl An aralkyl group such as a group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; and p and q each represent an integer of 1 to 3.

  The antifouling layer 7 can be formed by a wet process such as a microgravure method, a screen coating method, or a dip coating method in addition to a vacuum dry process such as an evaporation method, a sputtering method, a CVD method, or a plasma polymerization method. The physical film thickness of the antifouling layer 7 is about 1 to 30 nm, preferably about 3 to 15 nm.

(Adhesive layer)
Moreover, you may provide the adhesion layer 8 in the opposite side to the side in which the electroconductive functional layer of the base material 2 is provided.
The adhesive layer 8 only needs to transmit light having a wavelength in the visible light region and have adhesiveness.
From the viewpoint of optical performance, the pressure-sensitive adhesive layer 8 preferably has a refractive index of light having a wavelength of 500 to 600 nm of 1.45 to 1.7 and an extinction coefficient of approximately 0.
Examples of the material of the pressure-sensitive adhesive layer 8 include acrylic adhesives, silicon adhesives, urethane adhesives, polyvinyl butyral adhesives (PVA), ethylene-vinyl acetate adhesives (EVA), polyvinyl ether, and saturated amorphous polyesters. And melamine resin.

The conductive laminate of the present invention includes CRT filters, liquid crystal display filters, plasma display panel filters, electroluminescence (EL) display filters, field emission display (FED) filters, rear projection television filters, and the like. It can be used as an optical filter.
In the plasma display panel filter, in addition to the conductive laminate of the present invention, as other layers, an anti-glare layer that ensures anti-glare properties, an anti-Newton ring layer that suppresses the occurrence of Newton rings, a color correction layer, an infrared cut A layer, an ultraviolet cut layer, a gas barrier layer, an antistatic layer, an electromagnetic wave shielding layer, or the like may be provided.

  The conductive laminate of the present invention can be used by being provided on the front surface of an optical display device such as a CRT, a liquid crystal display device, or a plasma display panel.

  In addition, the conductive laminate of the present invention can be used as an optical article such as a light source reflector used in a liquid crystal display device.

Examples of the present invention will be specifically described below.
<Example 1>
An ionizing radiation curable acrylic resin is formed by wet coating on the base material 2, a triacetyl cellulose film having a thickness of 80 μm (refractive index of light having a wavelength of 550 nm of 1.51) (hereinafter referred to as TAC film). Then, a hard coat layer 3 having a physical film thickness of 5 μm was formed.

A primer layer 4, a conductive functional layer 5, and a low refractive index transparent thin film layer 6 are formed on the hard coat layer-deposited TAC film by a roll-to-roll vacuum film forming apparatus shown in FIG.
An outline of the vacuum film forming apparatus shown in FIG. 2 will be described. An outline of the vacuum film forming apparatus shown in FIG. 2 will be described. First, sputtering cathodes 1 to 5 (SC1, SC2, SC3, SC4, SC5) can be switched between a dual magnetron sputtering method (hereinafter referred to as DMS method) and a pulse magnetron sputtering method (hereinafter referred to as PMS method). In Example 1, since the DMS method is used, DMS cathodes are arranged, and partitions are provided so that different film formation pressures can be set for each cathode. By using this film forming apparatus, the TAC raw fabric is set on the unwinding roller a, and the TAC film is conveyed in the direction of the winding roller b, whereby the primer layer 4 in the conductive laminate 1 exemplified in the present invention. The conductive functional layer 5 and the low-refractive-index transparent thin film layer 6 can all be laminated in only one outward path.
In both DMS and PMS methods, positive and negative voltages are applied alternately at the two cathodes, so bombardment to the substrate side due to high-energy particles during film formation is large. Compared with normal DC magnetron sputtering and RF magnetron sputtering. Thus, a film having a large ion assist effect, a dense film having a high film hardness and a high film stress is formed.

Using the film forming apparatus shown in FIG. 2, while transporting the TAC film, SiO _x is deposited on the hard coat layer 3 by the DMS method on the SC 1 on which the Si target is arranged, and a primer layer having a physical film thickness of 3 nm. 4 was formed. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 30 sccm, respectively, and the film formation pressure was 0.3 Pa.

Subsequently, the conductive functional layer 5 including the high refractive index metal compound layer 11, the metal thin film layer 12, and the high refractive index metal compound layer 13 was formed as follows.
Using the film forming apparatus shown in FIG. 2, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is deposited on the primer layer 4 by SC2 while transporting the TAC film. Thus, a high refractive index metal compound layer 11 having a physical thickness of 27 nm (a refractive index of light having a wavelength of 550 nm of 2.2 and an extinction coefficient of 0.001) was formed. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 3 sccm, respectively, and the film formation pressure was 0.3 Pa.

  Next, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, at SC3, 1.5 atomic% of gold and 0.5 atomic% of copper in silver are deposited on the high refractive index metal compound layer 11. The metal thin film layer 12 having a physical film thickness of 9 nm (with a refractive index of 0.09 for light having a wavelength of 550 nm and an extinction coefficient of 3.51) was formed by depositing an alloy containing. At this time, Ar was used as the sputtering gas, the flow rate was 200 sccm, and the film formation pressure was 0.3 Pa.

Further, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is added to the metal thin film layer 12 by SC4 in SC4. A high refractive index metal compound layer 13 having a physical film thickness of 20 nm (a refractive index of light having a wavelength of 550 nm of 2.2 and an extinction coefficient of 0.001) was formed by the method. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 3 sccm, respectively, and the film formation pressure was 0.3 Pa.

Next, using the apparatus shown in FIG. 2, while transporting the TAC film, in SC5, SiO ₂ is deposited on the high refractive index metal compound layer 13 by the DMS method, and a low refractive index transparent with a physical film thickness of 40 nm is obtained. A thin film layer 6 (refractive index of light of wavelength 550 nm 1.46, extinction coefficient 0) was formed. At this time, Si targets are respectively arranged on the two pairs of cathodes shown in the sputter cathode 5 in FIG. 2, and sine waves are alternately applied to the cathodes on which the two pairs of Si targets are arranged. The frequency was 40 kHz. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 100 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

  Furthermore, the organic silicon compound represented by the following formula (2) is vacuum-resisted by resistance heating on the low refractive index transparent thin film layer 6 using a vacuum film forming apparatus different from the vacuum film forming apparatus shown in FIG. An antifouling layer 7 having a physical film thickness of 6 nm was formed by vapor deposition. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Example 2>

A primer layer 4, a conductive functional layer 5, and a low refractive index transparent thin film layer 6 are formed on the hard coat layer-deposited TAC film by a roll-to-roll vacuum film forming apparatus shown in FIG.
Sputter cathodes 1 to 5 (SC1, SC2, SC3, SC4, and SC5) in FIG. 2 are each provided with a PMS cathode, and a partition is provided so that a different deposition pressure can be set for each cathode. It is.

Using the film forming apparatus shown in FIG. 2, while transporting the TAC film, SiO _x was deposited on the hard coat layer 3 by the PMS method at SC1 to form a primer layer 4 having a physical film thickness of 3 nm. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 30 sccm, respectively, and the film formation pressure was 0.3 Pa.

Subsequently, the conductive functional layer 5 including the high refractive index metal compound layer 11, the metal thin film layer 12, and the high refractive index transparent thin film layer 13 was formed as follows.
Using the film forming apparatus shown in FIG. 2, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is deposited on the primer layer 4 by SC2 while transporting the TAC film by the PMS method. Thus, a high refractive index metal compound layer 11 having a physical thickness of 27 nm (a refractive index of light having a wavelength of 550 nm of 2.2 and an extinction coefficient of 0.001) was formed. At this time, the _{O 2} using Ar, as a reactive gas as the sputtering gas, the flow rate is respectively 200 sccm, 3 sccm, the film formation pressure was subjected to film formation as 0.3 Pa.

  Next, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, at SC3, 1.5 atomic% of gold and 0.5 atomic% of copper in silver are deposited on the high refractive index metal compound layer 11. A metal thin film layer 12 having a physical film thickness of 9 nm (with a refractive index of 0.09 for light having a wavelength of 550 nm and an extinction coefficient of 3.51) was formed by depositing an alloy containing. At this time, Ar was used as the sputtering gas, the flow rate was 200 sccm, and the film formation pressure was 0.3 Pa.

Further, using the film forming apparatus shown in FIG. 2, while transporting the TAC film, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is formed on the metal thin film layer 12 by SC4 at SC4. A high refractive index metal compound layer 13 having a physical film thickness of 20 nm (a refractive index of light having a wavelength of 550 nm of 2.2 and an extinction coefficient of 0.001) was formed by the method. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 3 sccm, respectively, and the film formation pressure was 0.3 Pa.

Next, using the apparatus shown in FIG. 2, while transporting the TAC film, in SC5, SiO ₂ is deposited on the high refractive index metal compound layer 13 by the PMS method, and a low refractive index transparent having a physical film thickness of 40 nm is obtained. A thin film layer 6 (refractive index of light of wavelength 550 nm 1.46, extinction coefficient 0) was formed. At this time, Si targets are respectively disposed on the two pairs of cathodes shown in the sputter cathode 5 in FIG. 2, and DC pulse waves are alternately applied to the cathodes on which the two pairs of Si targets are disposed. However, the frequency was 40 kHz. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 100 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

  Further, a vacuum by resistance heating is applied to the organosilicon compound represented by the above formula (2) on the low refractive index transparent thin film layer 6 by using a vacuum film forming apparatus different from the vacuum film forming apparatus shown in FIG. An antifouling layer 7 having a physical film thickness of 6 nm was formed by vapor deposition. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Example 3>
The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 are formed on the hard coat layer-deposited TAC film by a roll-to-roll vacuum film forming apparatus shown in FIG.
An outline of the vacuum film forming apparatus shown in FIG. 2 will be described. An outline of the vacuum film forming apparatus shown in FIG. 2 will be described. First, an RF magnetron sputter cathode is used for the sputter cathodes 1 and 7 (SC1, SC7), a DC magnetron sputter cathode is used for the sputter cathodes 2, 3, 4 (SC2, SC3, SC4), and a sputter cathode. A DMS cathode is arranged at 5 and a PMS cathode is arranged at the sputter cathode 6 (SC6), and a partition is provided so that the film formation pressure can be set at each cathode. By using this film forming apparatus, the TAC raw fabric is set on the unwinding roller a, and the TAC film is conveyed in the direction of the winding roller b, whereby the primer layer 4 in the conductive laminate 1 exemplified in the present invention. The conductive functional layer 5 and the low-refractive-index transparent thin film layer 6 can all be laminated in only one outward path.

Using the film forming apparatus shown in FIG. 3, while conveying the TAC film, formed at SC1, on the hard coat layer 3, a SiO _x deposited by RF magnetron sputtering method, a primer layer 4 of a physical thickness 3nm did. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 30 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

Subsequently, the conductive functional layer 5 including the high refractive index metal compound layer 11, the metal thin film layer 12, and the high refractive index metal compound layer 13 was formed as follows.
Using the film forming apparatus shown in FIG. 3, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium is applied on the primer layer 4 by DC magnetron sputtering on the primer layer 4 while conveying the TAC film. A high refractive index metal compound layer 11 having a physical film thickness of 27 nm (refractive index of light having a wavelength of 550 nm, 2.2, extinction coefficient of 0.001) was formed by the method. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 3 sccm, respectively, and the film formation pressure was 0.3 Pa.

  Next, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, at SC3, 1.5 atomic% of gold and 0.5 atomic% of copper in silver are formed on the high refractive index metal compound layer 11. Was deposited by a DC magnetron sputtering method to form a metal thin film layer 12 having a physical film thickness of 9 nm (refractive index of light having a wavelength of 550 nm of 0.09, extinction coefficient of 3.51). At this time, Ar was used as the sputtering gas, the flow rate was 200 sccm, and the film formation pressure was 0.3 Pa.

Further, using the film forming apparatus shown in FIG. 3, while transporting the TAC film, a transparent conductive oxide material (ICO) containing 10 atomic% of cerium in indium on the metal thin film layer 12 is converted into DC by SC4. A high refractive index metal compound layer 13 having a physical film thickness of 20 nm (refractive index of light having a wavelength of 550 nm, 2.2, extinction coefficient of 0.001) was formed by magnetron sputtering. At this time, Ar was used as the sputtering gas, O ₂ was used as the reactive gas, the flow rates were 200 sccm and 3 sccm, respectively, and the film formation pressure was 0.3 Pa.

Next, using the apparatus shown in FIG. 3, while transporting the TAC film, in SC5, SiO ₂ is deposited on the high refractive index metal compound layer 13 and the low refractive index transparent thin film layer 6 having a physical thickness of 40 nm is deposited. (Refractive index 1.46 of light with a wavelength of 550 nm, extinction coefficient 0) was formed. Si targets are respectively arranged on the two pairs of cathodes shown in the sputter cathode 5 in FIG. 3, and sine waves are alternately applied to the cathodes on which the two pairs of Si targets are arranged. Was 40 kHz. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 100 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

  Further, a vacuum by resistance heating is applied to the organosilicon compound represented by the above formula (2) on the low refractive index transparent thin film layer 6 by using a vacuum film forming apparatus different from the vacuum film forming apparatus shown in FIG. An antifouling layer 7 having a physical film thickness of 6 nm was formed by vapor deposition. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Example 4>
The primer layer 4, the high-refractive-index metal compound layer 11, the metal thin film layer 12, and the high-refractive-index metal compound layer 13 are formed by the same means as in Example 3. In SC6, the high-refractive-index metal compound layer is formed. 13 _was deposited using PMS method to form a low-refractive-index transparent thin film layer 6 having a physical film thickness of 40 nm (a refractive index of 1.46 for light having a wavelength of 550 nm and an extinction coefficient of 0). In each of the two pairs of cathodes shown in the sputter cathode 5 in FIG. 2, Si targets are arranged, and a DC pulse wave voltage is applied alternately to the cathode on which the two pairs of Si targets are arranged. The frequency was 40 kHz. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 100 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

  Further, an organic silicon compound represented by the above formula (2) is deposited on the low-refractive-index transparent thin film layer 6 by a vacuum evaporation method using resistance heating in the same manner as in Example 1 to provide an antifouling film having a physical film thickness of 6 nm. Layer 7 was formed. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Example 5>
The primer layer 4, the high-refractive-index metal compound layer 11, the metal thin film layer 12, and the high-refractive-index metal compound layer 13 are formed by the same means as in Example 3. At SC7, the high-refractive-index metal compound layer is formed. SiO ₂ was deposited on the substrate 13 by RF magnetron sputtering to form a low-refractive-index transparent thin film layer 6 having a physical film thickness of 40 nm (a refractive index of 1.46 for light having a wavelength of 550 nm and an extinction coefficient of 0). .
The frequency of RF magnetron sputtering was 13.56 MHz. Further, the sputtering gas was Ar, the reactive gas was O ₂ , the flow rates were 200 sccm for Ar and 100 sccm for O ₂ , respectively, and the film formation pressure was 0.3 Pa.

  Further, an organic silicon compound represented by the above formula (2) is deposited on the low-refractive-index transparent thin film layer 6 by a vacuum evaporation method using resistance heating in the same manner as in Example 1 to provide an antifouling film having a physical film thickness of 6 nm. Layer 7 was formed. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Example 6>
After the primer layer 4, the high refractive index metal compound layer 11, the metal thin film layer 12, and the high refractive index metal compound layer 13 are formed by the same means as in Example 3, the roll-to- Using a roll-to-roll type vacuum film forming apparatus different from the roll type vacuum film forming apparatus, SiO ₂ is deposited on the high refractive index metal compound layer 13 by using an electron beam vapor deposition method to obtain a physical film thickness. A 40 nm low-refractive-index transparent thin film layer 6 (a refractive index of 1.46 light having a wavelength of 550 nm and an extinction coefficient of 0) was formed.

  Further, an organic silicon compound represented by the above formula (2) is deposited on the low-refractive-index transparent thin film layer 6 by a vacuum evaporation method using resistance heating in the same manner as in Example 1 to provide an antifouling film having a physical film thickness of 6 nm. Layer 7 was formed. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative Example 1>
The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed in exactly the same manner as in Example 1, and the antifouling layer 7 had a siloxane bond represented by the following formula (3) as the main chain. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative example 2>
The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed in the same manner as in Example 2, and the siloxane bond represented by the above formula (3) was used as the main chain for the antifouling layer 7. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative Example 3>
The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed in the same manner as in Example 3, and the antifouling layer 7 had a siloxane bond represented by the above formula (3) as the main chain. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative example 4>
In the same manner as in Example 4, the primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed, and the antifouling layer 7 had the siloxane bond represented by the above formula (3) as the main chain. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative Example 5>
In the same manner as in Example 5, the primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed, and the antifouling layer 7 had a siloxane bond represented by the above formula (3) as the main chain. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Comparative Example 6>
In the same manner as in Example 6, the primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 were formed, and the antifouling layer 7 had a siloxane bond represented by the above formula (3) as the main chain. A fluorine-containing silicon compound not deposited was deposited by resistance heating vacuum deposition to form an antifouling layer 7 having a physical thickness of 6 nm. Furthermore, the adhesive layer 8 was formed on the other surface of the TAC film by applying an acrylic adhesive to obtain the conductive laminate 1.

<Evaluation>
The following evaluation was performed about the electroconductive laminated body 1 obtained in Examples 1-6 and Comparative Examples 1-6. The results are shown in Tables 1-4.
(1) Wet cloth scratch test-1:
A clean waste (GUARDNER CO., Ltd. CLEANROOM WIPER) in which pure water was sufficiently impregnated into the samples formed in Examples 1 to 6 and Comparative Examples 1 to 6 was used as a scratch tester (TESTER SANGYO CO., Ltd.). Affixed to a scientific vibration-type friction fastness tester AB-301), a load of 500 gf is applied, and a 100, 200, 300, 400, 500 reciprocal scratch test is performed on each sample, and the sample wears. The state is observed with an optical microscope. At this time, whether or not the wear is a result of delamination at the interface between the high refractive index thin film layer 11 / metal thin film layer 12 and the interface between the metal thin film layer 12 / high refractive index thin film layer 13 is determined by using a lens reflection measuring device. It measured with (OLYMPUS company make USPM-RU), and confirmed from the obtained spectral curve (Table 1).

(2) Wet cloth abrasion test-2:
For samples formed according to Examples 1 to 6 and Comparative Examples 1 to 6, a chemical dust cloth (Sassa, manufactured by Dainippon Insect Chrysanthemum Co., Ltd.) containing a mineral oil and a nonionic surfactant was used as a scratch tester (TESTER SANGYO). CO., Ltd. Gakushin-type friction fastness tester AB-301), 500 gf load is applied, and 100, 200, 300, 400, 500 reciprocal scratch tests are performed on each sample. The wear state of the sample is observed with an optical microscope. At this time, whether or not the wear is a result of delamination at the interface between the high refractive index thin film layer 11 / metal thin film layer 12 and the interface between the metal thin film layer 12 / high refractive index thin film layer 13 is determined by using a lens reflection measuring device. A spot size of 12.5 μm was measured by (USPM-RU manufactured by OLYMPUS) and confirmed from the obtained spectral curve (Table 2).

(3) Thin film strength test:
Using the thin film strength evaluation apparatus described in Japanese Patent No. 3562070, the Young's modulus (GPa) of the thin film portion of the samples prepared in Examples 1 to 6 and Comparative Examples 1 to 6 is measured (Table 3).

(4) Pure water falling angle and pure water contact angle measurement test:
The pure water falling angle and pure water contact angle of the samples formed in Examples 1 to 6 and Comparative Examples 1 to 6 were measured using an automatic contact angle meter (CA-V type manufactured by Kyowa Interface Chemical Co., Ltd.). .

(5) Wiping test:
The sample of Example 1 was reciprocated 100 times at a load of 200 g using a scratch tester “AB-301 Gakushin type friction fastness tester” manufactured by Tester Sangyo Co., Ltd. Table 5 shows pure water contact angles before the wiping test and when the test was performed 10, 30, 50, and 100 times.

  (1) As for the samples of Comparative Examples 1 to 6 in the evaluation of (2), the location where wear occurred was measured with a lens reflection measuring machine (USPM-RU manufactured by OLYMPUS). Under the conditions shown in Table 2 as “many scratches” and “film peeling”, delamination occurred at the interface between the high refractive index thin film layer 11 / metal thin film layer 12 and the interface between the metal thin film layer 12 / high refractive index thin film layer 13 I was able to confirm. In particular, delamination at the interface between the high refractive index thin film layer 11 and the metal thin film layer 12 occurred completely under the condition indicated as “film peeling”. From the spectral curve, the hard coat layer 3 to the primer layer 4 to Only the high refractive index thin film layer 11 was confirmed.

  On the other hand, in the samples of Examples 1 to 6 in the evaluation of (1) and (2), the film itself is not damaged, and the interface between the high refractive index thin film layer 11 / metal thin film layer 12 and the metal thin film layer 12 / high refraction. It was confirmed that no delamination occurred at the interface of the thin film layer 13.

  Moreover, it can confirm from the measurement result of evaluation (3) from the Young's modulus measurement result of the thin film in the electroconductive laminated body 1 of each Example. Regarding Examples 1 to 6, the low refractive index transparent thin film layer 6 was formed by RF magnetron sputtering method or electron beam evaporation method. 6 is lower than the Young's modulus of the thin films of Example 3 and Example 4 formed by the DMS method and the PMS method. The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 are all formed by the DMS method and the PMS. It can be confirmed that the Young's modulus of Examples 1 and 2 formed by the method is the highest. However, in each of the examples (2) and (3) in the moisture-resistant scratch test, no scratch was found in each example, and peeling at the interface between the metal layer 12 and the high refractive index metal compound layers 12 and 13 was observed. There wasn't.

  On the other hand, it can confirm from the measurement result of evaluation (3) from the Young's modulus measurement result of the thin film in the electroconductive laminated body 1 of each comparative example. As in the case of the examples, the Young's modulus of the thin films of Comparative Example 5 and Comparative Example 6 in which the low refractive index transparent thin film layer 6 was formed by the RF magnetron sputtering method or the electron beam evaporation method was low refractive index transparent thin film layer. 6 is lower than the Young's modulus of the thin films of Comparative Example 3 and Comparative Example 4 formed by the DMS method and the PMS method. The primer layer 4, the conductive functional layer 5, and the low refractive index transparent thin film layer 6 are all formed by the DMS method and the PMS. It can be confirmed that the Young's modulus of Comparative Examples 1 and 2 formed by the method is the highest. Moreover, although only the antifouling layer 7 is different from the example, the primer layer 4, the conductive functional layer 5, and the low refractive index thin film layer 6 are the same, and thus the obtained Young's modulus is also the same. It is almost equivalent. However, in the wet cloth scratch test of evaluations (2) and (3), peeling at the interface between the metal layer 12 and the high refractive index metal compound layers 12 and 13 was observed depending on the scratch conditions. This is an organic silicon compound having a siloxane bond of the above formula (2) as the main chain in terms of wet cloth scratch resistance in the antifouling layer 7 of the above formula (2) and the antifouling layer 7 of the above formula (3). Was clearly superior.

  Moreover, according to the measurement result of evaluation (5), the sample of Example 1 had almost the same pure water contact angle before the wiping test and after wiping 100 times. This is presumed that, since the reactive functional group of the antifouling layer was chemically bonded to the low refractive index layer, the pure water contact angle value was hardly changed even after 100 wiping tests.

It is a schematic sectional drawing which shows an example of the electroconductive laminated body of this invention. It is the schematic which shows an example of the apparatus used for film-forming of the electroconductive laminated body of this invention. It is the schematic which shows an example of the apparatus used for film-forming of the electroconductive laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Conductive laminated body 2 Base material 3 Hard coat layer 4 Primer layer 5 Conductive functional layer 6 Low refractive index layer 7 Antifouling layer 8 Adhesive layer 11 High refractive index metal compound layer 12 Metal thin film layer 13 High refractive index metal compound layer

Claims (8)

  A conductive laminate having a conductive functional layer formed by laminating a metal thin film layer and a metal compound layer at least on a base material, and an antifouling layer, wherein the antifouling layer is bonded to a reactive functional group. A conductive laminate having a layer obtained from an organic silicon compound and having a pure water falling angle of 50 ° or less.   The conductive laminate according to claim 1, wherein the contact angle of pure water on the surface of the antifouling layer is 90 ° or more.   3. The conductive material according to claim 1, wherein the organosilicon compound bonded to the reactive functional group of the antifouling layer has one or more silicon atoms bonded to the reactive functional group. Laminate.   The conductive laminate according to any one of claims 1 to 3, wherein the difference in pure water contact angle before the wiping test and after 100 times is within 5 °.   The conductive laminate according to claim 1, wherein the conductive functional layer is a high refractive index metal compound layer / metal thin film layer / high refractive index metal compound layer.   The conductive laminate according to claim 1, wherein the metal thin film layer is silver or an alloy containing silver.   The conductive laminate according to claim 1, wherein a low refractive index layer is provided between the conductive functional layer and the antifouling layer.   A display comprising the conductive laminate according to claim 1 provided on a front surface of the display.