JP2014065260A - Transparent laminated film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent laminated film which has a metal oxide thin film containing a reduced amount of carbon-containing components and having a large refractive index, and a method for producing the same.SOLUTION: The transparent laminated film includes a transparent polymer film and a thin film laminate which is disposed on at least one surface of the transparent polymer film and which is formed by laminating a plurality of thin films. The thin film laminate has a metal oxide thin film and a metal thin film. The metal oxide thin film is formed by irradiating a coating film formed by applying and drying a solution containing a metal alkoxide with microwave plasma.

Description

  The present invention relates to a transparent laminated film in which a plurality of thin films are laminated on a transparent polymer film, and a method for producing the same.

For example, optical functional films are used for transparent electrodes such as displays and touch panels, electromagnetic wave shields, heat shield films, and the like. As an optical functional film, a transparent laminated film in which metal oxide thin films and metal thin films are alternately laminated on a transparent polymer film is known. For example, in Patent Documents 1 to 3, a transparent laminated film in which a titanium dioxide (TiO ₂ ) thin film and an Ag—Cu alloy thin film or an Ag—Bi alloy thin film are alternately laminated on a polyethylene terephthalate (PET) film. Is disclosed.

International Publication No. 2010/0774050 JP 2008-105251 A JP 2011-133721 A JP 2000-327310 A

  For example, when a transparent laminated film is used as a heat-shielding film that is attached to a window glass, it not only reflects the near-infrared light component (heat rays) of solar energy, but also ensures lighting and viewability. It is necessary to transmit the visible light component. In the transparent laminated film, the metal oxide thin film functions as a high refractive index layer to ensure the transparency of visible light components.

  In the conventional metal oxide thin film, the refractive index is about 1.8, and it is difficult to increase it further. In addition, the refractive index fluctuates greatly due to a slight difference in film thickness, which makes it difficult to stabilize the quality.

  As described in Patent Documents 1 to 4, the formation of the metal oxide thin film utilizes hydrolysis and polycondensation reaction (sol-gel reaction) of metal alkoxide. Specifically, a solution containing a metal alkoxide is applied and dried, and then irradiated with ultraviolet rays to form a metal oxide thin film. Under the present circumstances, drying of a coating film is performed at the temperature of 120 degrees C or less in order to prevent the deformation | transformation and shrinkage | contraction of the transparent polymer film of a base material. Also in the irradiation of ultraviolet rays, the irradiation amount and the irradiation time are adjusted so that the temperature of the transparent polymer film is 120 ° C. or lower. However, it is difficult to fully complete the hydrolysis reaction under such conditions. For this reason, the —OR group (R is an alkyl group or the like) of the metal alkoxide tends to remain. In addition, when the metal alkoxide is chelated, the chelating agent (such as acetylacetone) is likely to remain bonded.

  In the transparent laminated films described in Patent Documents 1 to 3, an organic component (a component containing carbon) is intentionally left to impart flexibility to the metal oxide thin film. However, as a result of investigation by the present inventors, it has been found that the component containing residual carbon affects the refractive index of the metal oxide thin film. Moreover, when the component containing carbon moves to an adjacent thin film, the thin film may be cracked. For example, a barrier thin film may be interposed between the metal oxide thin film and the metal thin film, but the barrier thin film may be cracked, which may cause corrosion of the metal thin film.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the transparent laminated film which has a metal oxide thin film with few components containing carbon, and a large refractive index, and its manufacturing method.

  (1) In order to solve the above problems, a transparent laminated film of the present invention comprises a transparent polymer film, and a thin film laminate in which a plurality of thin films are laminated on at least one surface of the transparent polymer film. The thin film laminate includes a metal oxide thin film and a metal thin film, and the metal oxide thin film is applied with a solution containing a metal alkoxide and dried to a coating film formed by microwave plasma. It is characterized by being formed by irradiation.

  The metal oxide thin film which comprises the thin film laminated body of the transparent laminated film of this invention is formed by the sol gel reaction of a metal alkoxide. As described above, in the coating film formed by the sol-gel reaction, the -OR group remains or the chelating agent remains bonded. However, in the metal oxide thin film of the present invention, the formed coating film is irradiated with microwave plasma. The remaining —OR group is decomposed by irradiation with microwave plasma. In addition, the bound chelating agent is also cleaved and decomposed. In this way, the carbon-containing component remaining in the coating film is reduced. As a result, the refractive index of the metal oxide thin film can be increased, for example, by polycondensation of the metal alkoxide and increasing the density. When the refractive index of the metal oxide thin film is large, the visible light transmittance of the transparent laminated film is increased. Therefore, the transparent laminated film of the present invention is excellent in daylighting and viewability. Moreover, when a transparent laminated film is affixed on a window glass, the difference with the part which is not affixed is not conspicuous. Therefore, the transparent laminated film of the present invention is also excellent in design properties.

  Moreover, generation | occurrence | production of the crack of an adjacent thin film by the movement of the said component can be suppressed by reducing the carbon containing component which remains in a coating film. For example, when a barrier thin film is interposed between the metal oxide thin film and the metal thin film, cracking of the barrier thin film can be suppressed. Thereby, corrosion of a metal thin film can be suppressed. Therefore, the transparent laminated film of this invention is excellent in durability.

  In the case of microwave plasma, plasma with a relatively low potential and high density is generated. For this reason, even if it irradiates with microwave plasma, there is little possibility that the surface of the coating film becomes rough or the coating film is deformed. That is, the carbon-containing component can be reduced without roughening the surface of the coating film. On the other hand, for example, when irradiated with radio frequency (RF) plasma, charged particles in the plasma accelerated by a bias (applied potential) collide with the surface of the coating film, so that the surface of the coating film becomes rough. End up. Therefore, the smoothness of the coating film cannot be maintained. Moreover, since the plasma density is also small, the effect of reducing the carbon-containing component is small.

  The metal oxide thin film is formed by applying and drying a solution containing a metal alkoxide on the surface of a transparent polymer film of a base material or an adjacent metal thin film. Even if the surface of the base is uneven, the solution is applied so as to fill the unevenness. For this reason, the adhesiveness of the coating film (metal oxide thin film) with respect to a transparent polymer film or an adjacent thin film improves. In addition, a smooth metal oxide thin film can be formed without reflecting irregularities on the surface of the base.

  (2) Moreover, the manufacturing method of the transparent laminated film of this invention manufactures the transparent laminated film which laminates at least a metal oxide thin film and a metal thin film on at least one surface of a transparent polymer film, and forms a thin film laminated body. The method of forming the metal oxide thin film includes: a coating film forming process in which a solution containing a metal alkoxide is applied and dried to form a coating film; and the coating film is irradiated with microwave plasma to form a metal film. And a microwave plasma treatment step of forming an oxide thin film.

  The manufacturing method of the transparent laminated film of this invention has a coating-film formation process and a microwave plasma processing process in the process of forming a metal oxide thin film. According to the production method of the present invention, the transparent laminated film of the present invention having a smooth metal oxide thin film having a large refractive index can be produced relatively easily.

It is a left-right direction sectional view of the microwave plasma processing apparatus of a first embodiment. It is a perspective view of the plasma production | generation part in the same microwave plasma processing apparatus. It is sectional drawing of the front-back direction of the microwave plasma processing apparatus of 2nd embodiment. It is a perspective view of the plasma production | generation part in the same microwave plasma processing apparatus. It is a graph which shows the composition ratio of the atom in a metal oxide thin film. It is a graph which shows the change of the refractive index with respect to the irradiation time of microwave plasma. ₂ is a SPM photograph of the surface of the TiO ₂ thin film of Example 1. 4 is a SPM photograph of the surface of a TiO ₂ thin film of Comparative Example 1. 4 is a SPM photograph of the surface of a TiO ₂ thin film of Comparative Example 2.

  Hereinafter, embodiments of the transparent laminated film and the production method thereof of the present invention will be described.

<Transparent laminated film>
The transparent laminated film of this invention is equipped with a transparent polymer film and a thin film laminated body.

[Transparent polymer film]
The material of the transparent polymer film is not particularly limited as long as it has transparency in the visible light region and can form a thin film on the surface. For example, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, polystyrene, polyimide, polyamide, polybutylene terephthalate, polyethylene naphthalate, polysulfone, polyethersulfone, polyetheretherketone, polyvinyl Examples include alcohol, polyvinyl chloride, polyvinylidene chloride, triacetyl cellulose, polyurethane, and cycloolefin polymer. Among these, polyethylene terephthalate, polycarbonate, polymethyl methacrylate, and cycloolefin polymer are preferable because they are excellent in transparency, durability, workability, and the like. The transparent polymer film may be a laminate of films of different materials.

  The transparent polymer film may have a surface treatment layer such as an easy adhesion layer on one side or both sides. When using the transparent polymer film in which the easily bonding layer is formed in the single side | surface, it is desirable to arrange | position a thin film laminated body in the surface in which the easily bonding layer is not formed. By doing so, the crack suppression effect when forming the metal oxide thin film is increased.

  The thickness of the transparent polymer film may be appropriately determined in consideration of the use of the transparent laminated film, the material of the transparent polymer film, optical characteristics, durability, and the like. The thickness of the transparent polymer film is preferably 25 μm or more, more preferably 50 μm or more, from the viewpoints that wrinkles are difficult to occur during processing and breakage is difficult. On the other hand, from the viewpoints of winding ease, economy, etc., it is 500 μm or less, more preferably 250 μm or less.

[Thin film laminate]
The thin film laminate is formed by laminating a plurality of thin films including a metal oxide thin film and a metal thin film. The thin film laminate may include two or more metal oxide thin films and metal thin films having the same or different chemical composition and film thickness. A thin film laminated body may be arrange | positioned only at either one side of a transparent polymer film, and may be arrange | positioned at both surfaces. As a basic structure of the thin film laminate, a structure in which metal oxide thin films and metal thin films are alternately laminated can be exemplified. Moreover, the thin film arrange | positioned in contact with a transparent polymer film among the thin films which comprise a thin film laminated body is good in it being a metal oxide thin film. In this case, excellent optical characteristics such as high visible light transmittance can be obtained.

(1) Metal oxide thin film A metal oxide thin film is formed by applying microwave plasma to a coating film formed by applying and drying a solution containing a metal alkoxide. The method for forming the metal oxide thin film will be described in detail in the method for producing the transparent laminated film of the present invention described later. For example, when a titanium alkoxide is used as the metal alkoxide, a high refractive index is easily realized. In the solution, the metal alkoxide is desirably chelated. Metal alkoxide reacts with water to hydrolyze and polycondensate (sol-gel reaction). The reaction rate of the sol-gel reaction of metal alkoxide is very high. Therefore, by chelating the metal alkoxide, rapid reaction with water can be suppressed, and solidification during coating and adhesion of solid components to the coating apparatus can be suppressed. Further, by slowing the reaction rate, defects such as cracks in the metal oxide thin film can be reduced.

  When chelating a metal alkoxide, the chelating agent bonded to the metal alkoxide tends to remain in the coating film. However, when the coating film is irradiated with microwave plasma, the chelating agent is cut and decomposed. In addition, the remaining —OR group is also decomposed. Therefore, in the metal oxide thin film, there are few components containing carbon. From the viewpoint of increasing the refractive index and suppressing the cracking of the adjacent thin film due to the movement of the carbon-containing component, for example, the carbon content in the metal oxide thin film is 100% of the total atoms constituting the metal oxide thin film. It is desirable to be 5% or less. It is more preferable that it is 1% or less. The carbon content can be determined from, for example, a spectrum obtained by analyzing a metal oxide thin film by X-ray photoelectron spectroscopy (XPS).

  The smaller the carbon content, the greater the refractive index of the metal oxide thin film. For example, the refractive index for light having a wavelength of 633 nm is desirably 1.90 or more. More preferably, it is 1.95 or more.

  Since the coating film is irradiated with microwave plasma, the surface of the coating film is less likely to be rough. For example, the arithmetic average roughness (Ra) of the surface of the metal oxide thin film is desirably 1.2 nm or less. It is more preferable that Ra is 1.0 nm or less. Further, the maximum height (Rmax) of the surface of the metal oxide thin film is desirably 10 nm or less. Rmax is more preferably 8 nm or less. The surface roughness of the metal oxide thin film may be measured according to JIS B0601: 2001.

  The thickness of the metal oxide thin film may be appropriately determined in consideration of low reflectivity, high transparency, heat ray reflectivity, color tone, and the like in the visible light region of the transparent laminated film. The thickness of the metal oxide thin film is preferably 16 nm or more, more preferably 18 nm or more, and still more preferably 20 nm or more from the viewpoints of low reflectivity in the visible light region, high transparency, and easy colouration. On the other hand, from the viewpoints of heat ray reflectivity and crack suppression, it is preferably 150 nm or less, more preferably 120 nm or less, and still more preferably 90 nm or less.

(2) Metal thin film As the metal, for example, silver, gold, platinum, copper, aluminum, chromium, titanium, zinc, tin, nickel, cobalt, niobium, tantalum, tungsten, zirconium, lead, palladium, indium, or these An alloy etc. can be illustrated. The metal may be contained not only in one kind but also in two or more kinds. Among these, silver or a silver alloy is desirable because it is excellent in visible light transmittance and heat ray reflectivity during lamination. In addition, a silver alloy containing silver as a main component and containing at least one of copper, bismuth, gold, palladium, platinum, and titanium is preferable because durability against an environment such as heat, light, and water vapor is improved. . In particular, because of its large silver diffusion suppression effect and cost advantage, it contains a silver alloy containing copper (Ag—Cu alloy), a silver alloy containing bismuth (Ag—Bi alloy), and silver containing titanium. An alloy (Ag—Ti alloy) is preferred.

  From the viewpoint of heat ray reflectivity, the thickness of the metal thin film is preferably 3 nm or more, more preferably 5 nm or more, and even more preferably 7 nm or more. On the other hand, from the viewpoints of visible light transmittance, economy, etc., it is 30 nm or less, more preferably 20 nm or less, and further preferably 15 nm or less.

(3) Barrier thin film In order to suppress the metal constituting the metal thin film from diffusing into the adjacent metal oxide thin film, a barrier thin film made of a metal oxide can be formed on at least one surface of the metal thin film. . When a barrier thin film is interposed between the metal oxide thin film and the metal thin film, the adhesion between them is also improved.

  Examples of metal oxides constituting the barrier thin film include titanium oxide, zinc oxide, indium oxide, tin oxide, indium and tin oxide, magnesium oxide, and aluminum oxide. Zirconium oxide, niobium oxide, cerium oxide and the like can be exemplified. These may be contained not only in one kind but also in two or more kinds. Further, the metal oxide may be a double oxide in which two or more metal oxides are combined.

The barrier thin film may be mainly composed of a metal oxide contained in the metal oxide thin film described above. In this case, the effect of suppressing the diffusion of the metal constituting the metal thin film is enhanced, and the adhesion with the metal oxide thin film is improved. For example, when the metal oxide thin film is a TiO ₂ thin film, the barrier thin film is preferably a titanium oxide thin film mainly composed of an oxide of titanium (Ti). When the barrier thin film is a titanium oxide thin film, the titanium oxide thin film may be a thin film formed as a titanium oxide from the beginning, or may be a thin film formed by post-oxidizing a metal titanium thin film, and is partially oxidized. It may be a thin film formed by post-oxidizing a titanium oxide thin film.

  The thickness of the barrier thin film may be smaller than the thickness of the metal oxide thin film described above. This is because the diffusion of the metal constituting the metal thin film occurs at the atomic level, so that it is not necessary to increase the thickness to a level necessary to ensure the refractive index. When the barrier thin film is formed thin, the film formation cost is reduced accordingly, and thus the manufacturing cost of the transparent laminated film itself can be reduced.

  From the viewpoint of ensuring barrier properties, the thickness of the barrier thin film is preferably 1 nm or more, more preferably 1.5 nm or more, and even more preferably 2 nm or more. On the other hand, from the viewpoint of economy and the like, it is preferably 15 nm or less, more preferably 10 nm or less, and further preferably 8 nm or less.

  When the barrier thin film is mainly composed of titanium oxide, the atomic molar ratio of titanium to oxygen (Ti / O ratio) in the titanium oxide is 1.0 / 4.0 or more from the viewpoint of barrier properties and the like. Preferably it is 1.0 / 3.8 or more, more preferably 1.0 / 3.5 or more, even more preferably 1.0 / 3.0 or more, and most preferably 1.0 / 2.8 or more. Good. On the other hand, from the viewpoint of visible light transmittance and the like, the Ti / O ratio is 1.0 / 0.5 or less, more preferably 1.0 / 0.7 or less, still more preferably 1.0 / 1.0 or less, Even more preferably 1.0 / 1.2 or less, and most preferably 1.0 / 1.5 or less.

  The Ti / O ratio can be calculated from the composition of the barrier thin film. As a composition analysis method for the barrier thin film, for example, energy dispersive X-ray fluorescence analysis (EDX) may be used. The composition analysis method is as follows. First, using an ultra-thin section method (microtome) or the like, a thin film laminate including a barrier thin film to be analyzed is cut in the thickness direction to produce a test piece having a thickness of 100 nm or less. Next, the position of the barrier thin film is confirmed from the cross section by a transmission electron microscope (TEM). Subsequently, an electron beam is emitted from the electron gun of the EDX apparatus, and the electron beam is incident near the central portion in the thickness direction of the barrier thin film to be analyzed. Electrons incident from the surface of the test specimen enter to a certain depth and generate various electron beams and X-rays. By detecting and analyzing the generated characteristic X-rays, the elements constituting the barrier thin film can be specified.

<Method for producing transparent laminated film>
In the method for producing a transparent laminated film of the present invention, a thin film laminate is formed by laminating at least a metal oxide thin film and a metal thin film on at least one surface of a transparent polymer film. About the formation method of a thin film laminated body, what is necessary is just to follow an already well-known method except the process of forming a metal oxide thin film. Therefore, here, the description will focus on the step of forming the metal oxide thin film. A method for forming a metal thin film will be described last. The step of forming the metal oxide thin film includes a coating film forming step and a microwave plasma processing step.

[Coating film forming process]
This step is a step of forming a coating film by applying and drying a solution containing a metal alkoxide. In this step, first, a solution in which a metal alkoxide is mixed in a predetermined solvent is prepared. The metal alkoxide is represented, for example, by the following general formula (a).
M (OR) _m ... (a)
[In formula (a), M is a metal atom. R is 1 or more types of a C1-C10 alkyl group, an aryl group, and an alkenyl group, and may be same or different. m is the valence of the metal atom M. In addition, a multimer having two or more repeating units [(MO) _n ; n is an integer of 2 or more] in one molecule may be used.

  Examples of the metal atom M include titanium, zirconium, and aluminum. Among these, titanium is preferable because it is easy to achieve a high refractive index. Specific examples include tetra n-butoxy titanium, tetra i-propoxy titanium, and tetrakis (2-ethylhexyloxy) titanium.

  Solvents include alcohols such as methanol, ethanol, propanol, butanol, heptanol and isopropyl alcohol, organic acid esters such as ethyl acetate, ketones such as acetonitrile, acetone and methyl ethyl ketone, cycloethers such as tetrahydrofuran and dioxane, formamide, Examples include acid amides such as N, N-dimethylformamide, hydrocarbons such as hexane, aromatics such as toluene, and the like. Any of these may be used alone or in admixture of two or more.

  When the metal alkoxide is chelated, a chelating agent can be used as a solvent. In this case, the solvent may be a chelating agent or a mixture of the chelating agent and other solvents. Examples of chelating agents include β-diketones such as acetylacetone, benzoylacetone, and dibenzoylmethane, β-ketoacid esters such as ethyl acetoacetate and ethyl benzoylacetate, triethanolamine, lactic acid, 2-ethylhexane-1,3diol, Examples thereof include 1,3 hexanediol.

  When a solution containing a metal alkoxide is applied to the surface of a substrate and dried under predetermined conditions, the solvent (chelating agent) is removed. Thereby, the hydrolysis reaction of the metal alkoxide proceeds. The method for applying the solution is not particularly limited. Examples include spin coating, roll coating, spray coating, and bar coating. The drying may be performed within a temperature range where the resin film does not deform. Drying may be performed, for example, in a temperature range of 80 ° C. to 120 ° C. for about 0.5 to 5 minutes. In order to promote the sol-gel reaction, after drying, irradiation with light energy such as ultraviolet rays, electron beams, X-rays, or the like may be performed. Since it is difficult to apply a heat load to the transparent polymer film, irradiation with light energy, particularly irradiation with ultraviolet rays is preferable. For irradiation with ultraviolet rays, a mercury lamp, a xenon lamp, a deuterium lamp, an excimer lamp, a metal halide lamp, or the like may be used.

[Microwave plasma treatment process]
This step is a step of forming a metal oxide thin film by irradiating the formed coating film with microwave plasma. Hereinafter, embodiments of the microwave plasma processing will be described.

(1) First Embodiment First, the configuration of the microwave plasma processing apparatus of this embodiment will be described. FIG. 1 shows a cross-sectional view in the left-right direction of the microwave plasma processing apparatus. FIG. 2 is a perspective view of a plasma generation unit in the microwave plasma processing apparatus. In FIG. 2, the chamber is omitted. As shown in FIG. 1, the microwave plasma processing apparatus 2 includes a chamber 8, a sample holding plate 21, a microwave transmission unit 50, and a plasma generation unit 30.

  The chamber 8 is made of aluminum and has a rectangular parallelepiped box shape. The chamber 8 includes a first gas supply hole 80, a second gas supply hole 81, an exhaust hole 82, a waveguide hole 83, and a stepped portion 84. The first gas supply hole 80 and the second gas supply hole 81 are respectively formed on the right wall and the left wall of the chamber 8 one by one. A downstream end of a first gas supply pipe (not shown) is connected to the first gas supply hole 80. A downstream end of a second gas supply pipe (not shown) is connected to the second gas supply hole 81. The exhaust hole 82 is formed in the lower wall of the chamber 8. A vacuum exhaust device (not shown) for exhausting the gas inside the chamber 8 is connected to the exhaust hole 82. The waveguide hole 83 is formed in the right wall of the chamber 8. The downstream end of the tube part 51 described later is inserted into the waveguide hole 83. The step portion 84 is formed between the waveguide hole 83 and the first gas supply hole 80. The step portion 84 goes around the inner surface of the side wall of the chamber 8. The stepped portion 84 has a stepped shape that protrudes inward from above to below.

  The sample holding plate 21 is made of stainless steel and has a rectangular plate shape. A pair of leg portions 210 are disposed on the lower surface of the sample holding plate 21 in the left-right direction. Each of the pair of leg portions 210 is made of stainless steel and has a cylindrical shape. The outer peripheral surfaces of the pair of leg portions 210 are covered with an insulating layer. The sample holding plate 21 is attached to the lower wall of the chamber 8 via a pair of legs 210.

  A sample 20 is disposed on the upper surface of the sample holding plate 21. The sample 20 has a rectangular sheet shape. The sample 20 includes a PET film 200 and a coating film 201. The coating film 201 is formed on the upper surface of the PET film 200.

  The microwave transmission unit 50 includes a tube unit 51, a microwave power source 52, a microwave oscillator 53, an isolator 54, a power monitor 55, and an EH matching unit 56. The microwave oscillator 53, the isolator 54, the power monitor 55, and the EH matching unit 56 are connected by the tube part 51. The tubular body 51 is connected to the right end of the waveguide 31 of the plasma generation unit 30 through the waveguide hole 83.

  As shown in FIGS. 1 and 2, the plasma generation unit 30 includes a waveguide 31, a slot antenna 32, and a dielectric part 33. The waveguide 31 extends in the left-right direction. The waveguide 31 is formed by the chamber 8 and the slot antenna 32.

  The slot antenna 32 is made of aluminum and has a rectangular plate shape. The slot antenna 32 is disposed so as to close the lower opening of the waveguide 31. That is, the slot antenna 32 forms the lower wall of the waveguide 31. The slot antenna 32 has six slots 320 having a long hole shape. The slot 320 has a long hole shape extending in the left-right direction. The slot 320 is disposed at a position where the electric field is strong.

  The dielectric portion 33 is made of quartz and has a rectangular parallelepiped shape. The dielectric portion 33 is disposed on the lower surface of the slot antenna 32. The dielectric portion 33 covers the slot 320 from below. The dielectric portion 33 is disposed in the step portion 84 of the chamber 8. The dielectric portion 33 is nonmagnetic and plays a role of keeping the inside of the chamber 8 in a vacuum.

  Next, a microwave plasma processing method will be described. In the processing method according to the present embodiment, first, an evacuation apparatus (not shown) is operated to discharge the gas inside the chamber 8 and make the inside of the chamber 8 in a reduced pressure state. Next, the first gas argon gas is supplied from the first gas supply pipe, and the second gas oxygen gas is supplied from the second gas supply pipe into the chamber 8. At this time, the flow rate of the supplied gas is adjusted so that the pressure in the chamber 8 becomes a desired pressure in the range of about 1 to 100 Pa. Subsequently, the microwave power source 52 is turned on. When the microwave power source 52 is turned on, the microwave oscillator 53 generates a microwave. The generated microwave propagates in the tubular body portion 51. Here, the isolator 54 suppresses the microwave reflected from the plasma generation unit 40 from returning to the microwave oscillator 53. The power monitor 55 monitors the output of the generated microwave and the output of the reflected microwave. The EH matching device 56 adjusts the amount of reflected microwaves.

  The microwaves that have passed through the tube part 51 propagate inside the waveguide 31. The microwave propagating through the waveguide 31 enters the slot 320 of the slot antenna 32. 1 passes through the slot 320 and enters the dielectric portion 33 as indicated by a hollow arrow Y1 in FIG. The microwave incident on the dielectric portion 33 propagates along the lower surface 330 of the dielectric portion 33 as indicated by a hollow arrow Y2 in FIG. At this time, the incident direction (arrow Y1) of the microwave that enters the dielectric portion 33 from the slot 320 is orthogonal to the lower surface 330 of the dielectric portion 33. For this reason, the microwave incident on the dielectric part 33 changes the traveling direction by 90 ° and propagates on the lower surface 330 of the dielectric part 33 (arrow Y2). Due to the strong electric field of the propagating microwave, the argon gas in the chamber 8 is ionized, and the microwave plasma P <b> 1 is generated below the dielectric portion 33. In this way, the surface of the coating film 201 of the sample 20 is irradiated with the microwave plasma P1.

(2) Second Embodiment The difference between the microwave plasma processing apparatus of the present embodiment and the microwave plasma processing apparatus of the first embodiment is the configuration of the plasma generation unit. Therefore, the difference will be mainly described here.

  First, the configuration of the microwave plasma processing apparatus of this embodiment will be described. FIG. 3 shows a cross-sectional view in the front-rear direction of the microwave plasma processing apparatus of the present embodiment. FIG. 4 is a perspective view of a plasma generation unit in the microwave plasma processing apparatus. In FIG. 3, the parts corresponding to those in FIG. As shown in FIG. 3, the microwave plasma processing apparatus 2 includes a chamber 8, a sample holding plate 21, and microwave plasma irradiation means 4.

  The sample holding plate 21 is made of stainless steel and has a rectangular plate shape. A pair of leg portions 210 are arranged on the front surface of the sample holding plate 21 in the left-right direction. Each of the pair of leg portions 210 is made of stainless steel and has a cylindrical shape. The outer peripheral surfaces of the pair of leg portions 210 are covered with an insulating layer. The sample holding plate 21 is attached to the front wall of the chamber 8 via a pair of legs 210.

  A sample 20 is disposed on the rear surface of the sample holding plate 21. The sample 20 has a rectangular sheet shape. The sample 20 includes a PET film 200 and a coating film 201. The coating film 201 is formed on the rear surface of the PET film 200.

  The microwave plasma irradiation unit 4 includes a plasma generation unit 40 and a microwave transmission unit 50. The microwave transmission unit 50 includes a tube unit 51, a microwave power source 52, a microwave oscillator 53, an isolator 54, a power monitor 55, and an EH matching unit 56. The microwave oscillator 53, the isolator 54, the power monitor 55, and the EH matching unit 56 are connected by the tube part 51. The tubular body 51 is connected to the rear side of the waveguide 41 of the plasma generation unit 40 through a waveguide hole formed in the rear wall of the chamber 8.

  As shown in FIGS. 3 and 4, the plasma generation unit 40 includes a waveguide 41, a slot antenna 42, a dielectric part 43, and a dielectric part fixing plate 44. The waveguide 41 is made of aluminum and has a rectangular parallelepiped box shape opening upward. The waveguide 41 extends in the left-right direction. The slot antenna 42 is made of aluminum and has a rectangular plate shape. The slot antenna 42 closes the opening of the waveguide 41 from above. That is, the slot antenna 42 forms the upper wall of the waveguide 41. Four slots 420 are formed in the slot antenna 42. The slot 420 has a long hole shape extending in the left-right direction. The slot 420 is disposed at a position where the electric field is strong.

  The dielectric portion 43 is made of quartz and has a rectangular parallelepiped shape. The dielectric part 43 is disposed on the front side of the upper surface of the slot antenna 42. The dielectric part 43 covers the slot 420 from above.

  The dielectric portion fixing plate 44 is made of stainless steel and has a flat plate shape. The dielectric portion fixing plate 44 is disposed on the rear side of the upper surface of the slot antenna 42. The dielectric part fixing plate 44 supports the dielectric part 43 from behind.

  Next, a microwave plasma processing method will be described. In the processing method of the present embodiment, as in the first embodiment, first, the inside of the chamber 8 is depressurized, and then the argon gas of the first gas is supplied from the first gas supply pipe and the second gas supply pipe is supplied with the first gas. Two oxygen gases are supplied into the chamber 8 respectively. Subsequently, the microwave power source 52 is turned on to generate a microwave from the microwave oscillator 53. The generated microwave propagates in the tubular body portion 51. The microwaves that have passed through the tube part 51 propagate inside the waveguide 41. The microwave propagating inside the waveguide 41 enters the slot 420 of the slot antenna 42. Then, as indicated by a hollow arrow Y 1 in FIG. 4, the light passes through the slot 420 and enters the dielectric part 43. The microwave that has entered the dielectric portion 43 propagates mainly along the front surface 430 of the dielectric portion 43, as indicated by a hollow arrow Y2 in FIG. Due to the strong electric field of the microwave, the argon gas in the chamber 8 is ionized, and the microwave plasma P <b> 2 is generated in front of the dielectric portion 43. In this way, the surface of the coating film 201 of the sample 20 is irradiated with the microwave plasma P2.

(3) Others For example, in the microwave plasma processing apparatus of the above embodiment, the material and shape of the chamber and the sample holding plate are not particularly limited. The material of the slot antenna, the number of slots, the shape, the arrangement, etc. are not particularly limited. For example, the slots may be arranged in three or more rows in addition to one row and two rows. The number of slots may be odd or even. Further, the slots may be arranged in a zigzag shape by changing the arrangement angle of the slots. The material and shape of the dielectric part are not particularly limited. As a material of the dielectric portion, a material having a low dielectric constant and hardly absorbing microwaves is desirable. For example, aluminum oxide (alumina) other than quartz is suitable. The frequency of the microwave is not particularly limited. It may be 8.35 GHz, 1.98 GHz, 915 MHz, or the like.

In the above embodiment, the microwave plasma treatment was performed in two kinds of mixed gas atmospheres. However, the microwave plasma treatment may be performed in one kind of gas atmosphere. As gas species to be used, in addition to argon (Ar) and oxygen (O ₂ ), helium (He), neon (Ne), krypton (Kr), xenon (Xe) and other rare gases, nitrogen (N ₂ ), such as hydrogen _{(H 2)} can be mentioned.

  The microwave plasma treatment is desirably performed under a pressure of 100 Pa or less because it is easy to maintain a stable plasma. Moreover, it is desirable to carry out under the pressure of 0.01 Pa or more from the reason that plasma can be easily generated. In addition, when the microwave is incident along the generated microwave plasma as in the plasma generation unit of the second embodiment, the microwave easily propagates to the microwave plasma. For this reason, the energy of the generated microwave plasma is increased. Therefore, stable plasma can be generated even under a low pressure of 1 Pa or less.

  The effect of reducing the carbon-containing component varies depending on the density of the generated microwave plasma and the irradiation time of the microwave plasma. For example, the longer the microwave plasma irradiation time, the more carbon-containing components can be removed. For example, the reduction rate of the carbon content before and after the microwave plasma irradiation is desirably 30% or more. In this case, the microwave plasma irradiation time may be about 1 to 5 minutes.

  Next, a method for forming a metal thin film and a barrier thin film will be described. Examples of the method for forming a metal thin film include chemical vapor deposition, physical vapor deposition (PVD) such as vacuum deposition, sputtering, ion plating, MBE, and laser ablation, thermal CVD, and plasma CVD. A vapor phase method such as a vapor deposition method (CVD) can be exemplified. Of these methods, sputtering methods such as a DC magnetron sputtering method and an RF magnetron sputtering method are preferable from the viewpoints of obtaining a dense film quality and relatively easy film thickness control. In addition, the metal thin film may be oxidized within the range which does not impair the function of a metal thin film by receiving the post-oxidation etc. which are mentioned later.

  In addition, as a method for forming the barrier thin film, a vapor phase method, in particular, a sputtering method such as a DC magnetron sputtering method or an RF magnetron sputtering method can be preferably used as in the case of the metal thin film. The barrier thin film may be formed as a metal oxide thin film from the beginning by using a vapor phase method, or a metal thin film or a partially oxidized metal oxide thin film is formed in advance, and then the barrier thin film is formed. It can also be formed by oxidation. The partially oxidized metal oxide thin film means a metal oxide thin film that has room for further oxidation.

  When forming a metal oxide thin film from the beginning, for example, a gas containing oxygen as a reactive gas is mixed with an inert gas such as argon or neon as a sputtering gas, and the thin film is formed while reacting the metal and oxygen. What is necessary is just to form (reactive sputtering method). When the titanium oxide thin film having the Ti / O ratio described above is formed by using the reactive sputtering method, the oxygen concentration in the atmosphere (the volume ratio of the gas containing oxygen to the inert gas) is the film thickness range described above. In consideration of the above, an optimal ratio may be selected.

  On the other hand, when a metal thin film or a partially oxidized metal oxide thin film is formed in advance and oxidized later, after forming the thin film laminate on the transparent polymer film, the metal in the thin film laminate A thin film or a partially oxidized metal oxide thin film may be post-oxidized. Examples of the post-oxidation method include heat treatment, pressure treatment, chemical treatment, and natural oxidation. Heat treatment is desirable from the standpoint that post-oxidation can be performed relatively easily and reliably. As the heat treatment, a transparent polymer film on which a thin film laminate is formed is placed in a heating atmosphere such as a heating furnace, a method of immersing in warm water, a method of microwave heating, a metal thin film or a partially oxidized metal Examples thereof include a method of electrically heating an oxide thin film. In order to perform post-oxidation while suppressing thermal deformation and fusion of the transparent polymer film, the heating temperature is 30 ° C to 60 ° C, preferably 32 ° C to 57 ° C, more preferably 35 ° C to 55 ° C. Good. When placed in a heated atmosphere, the heating time is 5 days or longer, preferably 10 days or longer, more preferably 15 days or longer.

  Next, the present invention will be described more specifically with reference to examples.

<Comparison of carbon-containing component and refractive index>
A metal oxide thin film was formed on a glass substrate, and the extent to which the carbon-containing component remaining in the coating film was reduced by irradiation with microwave plasma was examined. Moreover, the change of the refractive index accompanying the change of a carbon containing component was investigated.

[Example 1]
First, a metal alkoxide solution obtained by dissolving tetra n-butoxytitanium in a mixed solvent composed of acetylacetone, butanol, and isopropyl alcohol was applied to the surface of a glass substrate with a spin coater. Acetylacetone is a solvent and a chelating agent for tetra-n-butoxytitanium. Next, the coated glass substrate was placed in a drying oven and dried at 110 ° C. for 2 minutes. Thereafter, the mercury film was irradiated with ultraviolet rays for 15 seconds using a mercury lamp (coating film forming step). Subsequently, the coating film was irradiated with microwave plasma using the microwave plasma processing apparatus of the first embodiment (microwave plasma processing step). The reference numerals of members in the following microwave plasma processing correspond to those in FIG. First, the glass substrate on which the coating film was formed was placed on the upper surface of the sample holding plate 21 with the coating film facing up. Then, the gas inside the chamber 8 was discharged from the exhaust hole 82, and the internal pressure of the chamber 8 was set to 1 × 10 ⁻² Pa. Next, argon gas and oxygen gas were supplied into the chamber 8, and the internal pressure of the chamber 8 was set to 6 Pa. Subsequently, the microwave power source 52 was turned on, and the microwave plasma P1 was generated by the oscillated microwave having an output of 1.0 kW. In this state, the surface of the coating film was irradiated with microwave plasma P1 for 5 minutes. In this way, a TiO ₂ thin film was formed. The thickness of the TiO ₂ thin film was 26 nm. Formed was a TiO ₂ thin film was a TiO ₂ thin film of Example 1.

[Example 2]
A TiO ₂ thin film was formed in the same manner as in Example 1 except that the microwave plasma irradiation time was 1 minute. Formed was a TiO ₂ thin film was a TiO ₂ thin film of Example 2.

[Comparative Example 1]
A TiO ₂ thin film was formed in the same manner as in Example 1 except that the coating film was not irradiated with microwave plasma. Formed was a TiO ₂ thin film was a TiO ₂ thin film of Comparative Example 1.

[Measurement of carbon-containing components and refractive index]
The TiO ₂ thin films of Examples 1 and 2 and Comparative Example 1 were analyzed with an X-ray photoelectron spectrometer (XPS analyzer), and the composition ratio of atoms in the thin film was determined. FIG. 5 shows the composition ratio of atoms in each TiO ₂ thin film.

As shown in FIG. 5, the TiO ₂ thin film of Comparative Example 1, that is, the content ratio of carbon that was 7% when not irradiated with microwave plasma was 4% when irradiated with microwave plasma for 1 minute. Was reduced to 1% when irradiated for 5 minutes. From the above, it was confirmed that the carbon-containing component of the metal oxide thin film can be reduced only by irradiating with microwave plasma for about 1 to 5 minutes.

Further, the refractive indexes of the TiO ₂ thin films of Examples 1 and 2 and Comparative Example 1 were measured using an ellipsometer. FIG. 6 shows the refractive index of each TiO ₂ thin film. As shown in FIG. 6, the refractive index of the TiO ₂ thin film of Comparative Example 1 that was not irradiated with microwave plasma was 1.77. In contrast, in the TiO ₂ thin film of Example 2 irradiated with microwave plasma for 1 minute, the refractive index was 1.90, and in the TiO ₂ thin film of Example 1 irradiated with microwave plasma for 5 minutes, The refractive index was 1.99. That is, the refractive index increased as the carbon content decreased. From the above, it was confirmed that the refractive index of the metal oxide thin film can be increased only by irradiating with microwave plasma for about 1 to 5 minutes.

<Comparison of surface roughness>
The surface roughness of the TiO ₂ thin film of Example 2 and Comparative Example 1 was measured. The TiO ₂ thin film of Example 2 is irradiated with microwave plasma for 1 minute, and the TiO ₂ thin film of Comparative Example 1 is not irradiated with microwave plasma. The surface of each TiO ₂ thin film of Example 2 and Comparative Example 1 was observed with a scanning probe microscope (SPM). 7 shows an SPM photograph of the surface of the TiO ₂ thin film of Example 2. Figure 8 shows the SPM photograph of the surface of the TiO ₂ thin film of Comparative Example 1.

7 and 8, it can be seen that the TiO ₂ thin film of Example 2 has a smooth surface despite being irradiated with microwave plasma. When the surface roughness was measured, the TiO ₂ thin film of Example 2 was Ra = 0.6 nm and Rmax = 5.4 nm. In the TiO ₂ thin film of Comparative Example 1, Ra = 0.6 nm and Rmax = 4.3 nm. There is no significant difference in the surface roughness between the two. Thus, it was confirmed that the smoothness of the TiO ₂ thin film can be maintained even when irradiated with microwave plasma.

On the other hand, in the same manner as in Example 1, a metal alkoxide solution was applied to the surface of a glass substrate, dried, and a TiO ₂ thin film formed by irradiating ultraviolet rays was irradiated with RF plasma for 1 minute. The TiO ₂ thin film irradiated with RF plasma for 1 minute is referred to as the TiO ₂ thin film of Comparative Example 2. Then, the surface of the TiO ₂ thin film of Comparative Example 2 was observed with SPM. Figure 9 shows the SPM photograph of the surface of the TiO ₂ thin film of Comparative Example 2. As shown in FIG. 9, large irregularities were observed on the surface of the TiO ₂ thin film of Comparative Example 2. When the surface roughness of the TiO ₂ thin film of Comparative Example 2 was measured, Ra = 1.3 nm and Rmax = 17.6 nm. Accordingly, it can be seen that when the RF plasma is irradiated, the surface of the TiO ₂ thin film becomes rough and the unevenness increases. Further, the refractive index of the TiO ₂ thin film of Comparative Example 2 was measured using an ellipsometer, the refractive index was 1.86. When the RF plasma was irradiated, the effect of increasing the refractive index was smaller than when the microwave plasma was irradiated for the same time (Example 2).

In the TiO ₂ thin film of Comparative Example 2, the surface roughness was increased. Therefore, the power was reduced so as not to roughen the surface as much as possible, and the same TiO ₂ thin film as above was irradiated with Rf plasma for 1 minute or 5 minutes. TiO ₂ thin TiO ₂ film comparing Examples 3-1 were irradiated with RF plasma 1 minute, 5 minutes irradiated TiO ₂ thin TiO ₂ film Comparative Example 3-2, and referred. Then, the measured surface roughness of the TiO ₂ thin film of Comparative Example 3-1 and 3-2, the surface roughness of the TiO ₂ thin film of Comparative Example 3-1, Ra = 0.6nm, Rmax = 5.6nm The surface roughness of the TiO ₂ thin film of Comparative Example 3-2 was Ra = 0.7 nm and Rmax = 7.8 nm. In this case, the refractive index of the TiO ₂ thin film of Comparative Example 3-1 and 3-2, was measured with an ellipsometer, for any film, the refractive index was 1.78. In this way, if conditions such as power are adjusted, it is possible to irradiate the Rf plasma without roughening the surface. However, in such a case, it can be seen that the refractive index of the metal oxide thin film hardly changes.

<Comparison of optical properties>
Three types of transparent laminated films comprising a transparent polymer film and a three-layered thin film laminate were produced, and the optical properties of each were measured. In any transparent laminated film, the thin film laminate is a thin film (second layer) formed by post-oxidizing a TiO ₂ thin film (first layer) | [metal Ti thin film / Ag—Cu alloy thin film / metal Ti thin film]. │consists of TiO ₂ thin film (third layer). A thin film (titanium oxide thin film) formed by post-oxidizing a metal Ti thin film is included in the barrier thin film. The barrier thin film is included in the Ag-Cu alloy thin film as a thin film accompanying the Ag-Cu alloy thin film (metal thin film), and the number of laminated layers is counted. In the three types of transparent laminated films, only the TiO ₂ thin film (metal oxide thin film) is different. That is, three types of transparent laminated films were manufactured using the TiO ₂ thin film of each of Example 1, Example 2, and Comparative Example 1. In the transparent laminated film, only the film thickness differs between the first TiO ₂ thin film and the third TiO ₂ thin film. The transparent laminated film using the TiO ₂ thin film of Example 1 is referred to as the transparent laminated film of Example 1. Thus, corresponding to the number of TiO ₂ thin films used were numbered transparent laminated film produced. The transparent laminated films of Examples 1 and 2 are included in the transparent laminated film of the present invention.

As the transparent polymer film, a 50 μm thick PET film (manufactured by Toyobo Co., Ltd., “Cosmo Shine (registered trademark) A4100”) having an easy-adhesion layer formed on one side thereof was used. First, a TiO ₂ thin film was formed as a first layer on the surface of the PET film opposite to the easily adhesive layer surface. The method of forming the TiO ₂ thin film is as described in [Example 1], [Example 2], and [Comparative Example 1].

Next, a thin film constituting the second layer was formed on the first layer. That is, first, a lower metal Ti thin film was formed on the first TiO ₂ thin film by sputtering. Subsequently, an Ag—Cu alloy thin film was formed on the lower metal Ti thin film by sputtering. Finally, the upper metal Ti thin film was formed on the Ag—Cu alloy thin film by sputtering. For sputtering, a DC magnetron sputtering apparatus was used. The film formation conditions of the upper and lower metal Ti thin films are as follows: Ti target, vacuum ultimate pressure: 6.7 × 10 ⁻⁴ Pa, inert gas: Ar, gas pressure: 3.3 × 10 ⁻¹ Pa, input power : 1.5 kW, film formation time: 1.1 seconds. The film formation conditions of the Ag—Cu alloy thin film are as follows: Ag—Cu alloy target (Cu content: 4 atomic%), vacuum ultimate pressure: 6.7 × 10 ⁻⁴ Pa, inert gas: Ar, gas pressure: 3.3 × 10 ⁻¹ Pa, input power: 1.5 kW, and film formation time: 1.1 seconds.

Next, a TiO ₂ thin film was formed on the _second layer in the same manner as in the first layer except that the film thickness was different. The transparent laminated film thus obtained was heat-treated at 40 ° C. for 300 hours in a heating furnace, and the second layer of the thin film laminate [metal Ti thin film / Ag—Cu alloy thin film / metal Ti thin film] Was post-oxidized. Table 1 shows the configurations of the transparent laminated films of Examples 1 and 2 and Comparative Example 1.

  In Table 1, the Ti / O ratio in the barrier thin film (titanium oxide thin film) was determined as follows. First, the transparent laminated film was cut out with a microtome (“ULTROM V2088” manufactured by LKB Co., Ltd.) to prepare a test piece having a thickness of 100 nm including a barrier thin film. Next, the cross section of the test piece was confirmed using a field emission electron microscope (HRTEM) (manufactured by JEOL Ltd., “JEM2001F”). Then, an electron beam was emitted from an electron gun of an EDX apparatus (resolution of 133 eV or less) (manufactured by JEOL Ltd., “JED-2300T”), and the electron beam was made incident near the center of the thickness of the barrier thin film. The constituent element analysis of the barrier thin film was performed by detecting and analyzing the generated characteristic X-rays. Moreover, the film thickness of each thin film was measured from cross-sectional observation of the test piece with a field emission electron microscope (same as above).

The content of the subelement (Cu) in the Ag-Cu alloy thin film was determined as follows. First, an Ag—Cu alloy thin film was formed on a glass substrate under the same film forming conditions to prepare a test piece. Next, the produced test piece was immersed in a 6% HNO ₃ solution, and elution was performed by ultrasonic waves for 20 minutes. Thereafter, using the obtained sample solution, the Cu content was measured by the concentration method of ICP analysis.

  The optical properties of the three types of transparent laminated films produced were measured. The measurement method for each item is as follows. As a measurement sample, a 25 μm thick acrylic adhesive sheet (manufactured by Nitto Denko Corporation, “CS9621”) is attached to the outermost surface of the thin film laminate of the transparent laminated film, and the adhesive layer of this adhesive sheet is What was affixed on the single side | surface of the float glass of thickness 3mm was used. Moreover, the measurement light at the time of measuring optical characteristics was incident from the float glass surface side.

[Visible light transmittance and visible light reflectance]
Based on JIS A5759, the transmission spectrum of wavelength 300-1000nm was measured using the spectrophotometer (the Shimadzu Corporation make, "UV3100"), and the visible light transmittance | permeability and the visible light reflectance were calculated.

[Solar radiation transmittance]
In accordance with JIS A5759, using a spectrophotometer (same as above), a transmission spectrum with a wavelength of 300 to 2500 nm was measured, and the solar transmittance was calculated.

[Shielding coefficient]
In accordance with JIS A5759, after measuring the prescribed parameters, the shielding coefficient was calculated.

Table 2 summarizes the measurement results of the optical characteristics.

  As shown in Table 2, in the transparent laminated films of Examples 1 and 2 having a metal oxide thin film having a refractive index of 1.90 or more, the visible light transmittance is higher than that of the transparent laminated film of Comparative Example 1. It became high. That is, the higher the refractive index of the metal oxide thin film, the higher the visible light transmittance. Moreover, in the transparent laminated film of Examples 1, 2, the visible light reflectance fell compared with the transparent laminated film of the comparative example 1. There was no change in solar transmittance and shielding coefficient. As mentioned above, it was confirmed that the transparent laminated film of this invention is excellent in daylighting property, viewability, and designability.

  The transparent laminated film of the present invention is suitable for heat shielding films, display display electrodes such as liquid crystal displays and plasma displays, touch panel electrodes, light control sheet electrodes, electromagnetic wave shields and the like. Especially, when it uses as a thermal-insulation film used by affixing on a window glass, the effect by this invention is fully exhibited.

2: Microwave plasma processing apparatus, 20: Sample, 21: Sample holding plate, 200: PET film, 201: Coating film, 210: Leg, 30: Plasma generator, 31: Waveguide, 32: Slot antenna, 33: Dielectric part, 320: Slot, 330: Lower surface, 4: Microwave plasma irradiation means, 40: Plasma generation part, 41: Waveguide, 42: Slot antenna, 43: Dielectric part, 44: Dielectric part Fixed plate, 420: slot, 430: front surface, 50: microwave transmission section, 51: tube section, 52: microwave power source, 53: microwave oscillator, 54: isolator, 55: power monitor, 56: matching unit, 8: chamber, 80: first gas supply hole, 81: second gas supply hole, 82: exhaust hole, 83: waveguide hole, 84: stepped portion, P1, P2: microwave plasma.

Claims (11)

A transparent polymer film, and a thin film laminate formed by laminating a plurality of thin films disposed on at least one surface of the transparent polymer film,
The thin film laminate includes a metal oxide thin film and a metal thin film,
The metal oxide thin film is formed by irradiating microwave plasma to a coating film formed by applying and drying a solution containing a metal alkoxide.   2. The transparent laminated film according to claim 1, wherein a content ratio of carbon in the metal oxide thin film is 5% or less with respect to 100% of all atoms constituting the metal oxide thin film.   The transparent laminated film of Claim 1 or Claim 2 whose arithmetic mean roughness (Ra) of the surface of the said metal oxide thin film is 1.2 nm or less.   The transparent laminated film according to claim 1, wherein the metal alkoxide is chelated in the solution.   The transparent laminated film according to any one of claims 1 to 4, wherein the metal alkoxide includes titanium alkoxide.   The transparent laminated film according to any one of claims 1 to 5, wherein a refractive index of the metal oxide thin film is 1.90 or more.   The said thin film laminated body is a transparent laminated film in any one of Claim 1 thru | or 6 which has the barrier thin film which is formed in at least one surface of the said metal thin film, and consists of a metal oxide.   The transparent laminated film according to any one of claims 1 to 7, which is used as a heat shielding film. A method for producing a transparent laminated film comprising forming a thin film laminate by laminating at least a metal oxide thin film and a metal thin film on at least one surface of a transparent polymer film,
The step of forming the metal oxide thin film includes a coating film forming step in which a solution containing a metal alkoxide is applied and dried to form a coating film, and the coating film is irradiated with microwave plasma to form a metal oxide thin film. A method for producing a transparent laminated film, comprising: a microwave plasma treatment step.   The method for producing a transparent laminated film according to claim 9, wherein the solution contains a chelating agent for chelating the metal alkoxide.   The method for producing a transparent laminated film according to claim 9 or 10, wherein the microwave plasma irradiation is performed under a pressure of 0.01 Pa or more and 100 Pa or less.