JP2007084843A - Thin film deposition method and article manufactured by the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an article such as a liquid crystal panel or the like, constituted of a base body having a functional thin film on its outer surface and a space filled with a gas or a liquid therein, by which the article excellent in durability can be manufactured and which is excellent in productivity. <P>SOLUTION: A process for depositing the thin film is characterized in that the thin film is deposited at least one surface of the outer surface side of the base body having a space filled with the gas or the liquid therein by an atmospheric plasma treatment. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention provides various functionalities to an article having a high yield, high durability, and no performance deterioration with time, for example, a liquid crystal panel, a touch panel, or the like having a space in which gas or liquid is contained. The present invention relates to a method for forming a thin film and an article obtained thereby.

  Devices or articles such as liquid crystal panels, touch panels, FEDs, multi-layer glass and packaging bags have a structure in which gas or liquid is contained in an internal space formed by two substrates or sealing materials, etc. Other members (for example, a polarizing plate, an antireflection film, etc.) are combined with the two substrates to be configured.

  In these devices or articles, various functional thin films can be formed on the surface of the members constituting them by various thin film forming methods such as vapor deposition, sputtering, ion plating, plasma CVD, etc. It is well known to perform surface treatment.

  For example, in a liquid crystal panel, a conductive material thin film, an antireflection film or the like formed for antistatic is incorporated in a constituent member such as a polarizing plate, or a front substrate such as a liquid crystal panel or a touch panel has, for example, An antifouling film or the like that protects the surface of the member from fingerprints, oil stains due to contact, and the like is formed. Further, there is a surface treatment for imparting a function such as improvement of adhesion between members by performing a treatment such as hydrophilization or hydrophobization on the surface of these constituent members.

  For example, in Patent Document 1, in a projector liquid crystal display panel, a transparent conductive film is formed on the surface of a glass substrate in order to avoid the problem of dust adhering to the surface.

  Patent Document 2 describes an example in which a film provided with an antireflection layer and further an antifouling layer is used as a plastic film used as one of touch panel substrates.

  However, conventionally, when a thin film is applied to a device such as a touch panel or a liquid crystal panel for high functionality, the film is formed on glass or a resin base material which is a member constituting the device, and then the panel is assembled. The process is taken.

  Therefore, during the panel manufacturing process, the treated surfaces of these members are subject to chemical or mechanical damage due to processes such as cleaning and etching (using a solvent) and the substrate bonding process, and bonding. Due to the occurrence of stress, strain, etc. on the substrate in the process, for example, a device such as a touch panel or a liquid crystal panel is assembled using a resin substrate or a glass substrate on which a transparent conductive film or an antifouling film is previously formed. This is due to the above-mentioned problem, and it has been a problem to cause performance deterioration with time.

  It is only necessary that these processes can be performed on the assembled device or article.

  However, as an example of conventionally performing such a process on an assembled device or article, for example, in Patent Documents 3 to 7, etc., an example of using a corona discharge process or an atmospheric pressure plasma CVD process (atmospheric pressure plasma process) is used. Although known, an example of forming a thin film on the surface of an assembled device or article has not been known so far.

  This is because when a thin film is formed on the outer surface of the assembled device or article, if the conditions relating to the thin film formation must be performed under severe conditions such as under vacuum, the assembled device or article. This is thought to be due to factors such as influencing the characteristics and quality of the product and making the manufacturing process difficult and large.

The plasma CVD method, especially the atmospheric pressure plasma CVD process, can be applied when a large-scale vacuum facility is not used among the thin film forming methods, and when the quality is insufficient depending on the coating method, etc., which cannot be performed in a vacuum system. From the above, the present inventor used the plasma CVD method to manufacture the device, and formed a thin film on the constituent member, thereby assembling the device or the article without using the method. A method for directly forming a functional thin film on a device or article and imparting desired properties to the article or device was studied.
JP 2000-147470 A JP 2004-21550 A JP-A-6-63180 JP-A-6-285365 JP 2004-341542 A JP-A-8-320475 JP-A-9-179805

  Accordingly, an object of the present invention is to form a thin film on each constituent member in a device or article such as a liquid crystal panel, touch panel, FED (internal decompression), etc., which is composed of a substrate having a space in which gas or liquid is contained. In contrast to the conventional manufacturing method in which the device or article is manufactured by assembling the device after the functionality is provided, the device or article functions after the assembly of the device or article by atmospheric pressure plasma treatment on the outer surface side of the substrate. It is to provide a method for manufacturing a device or an article such as a liquid crystal panel or a touch panel that is superior in durability over time and has a higher productivity than conventional methods.

  The above object of the present invention is achieved by the following means.

  1. A thin film forming method comprising forming a thin film on at least one surface on the outer surface side of a substrate having a space containing a gas or a liquid therein by atmospheric pressure plasma treatment.

  2. The atmospheric pressure plasma treatment is characterized in that a thin film forming gas is introduced into a discharge space and excited to form an indirect excitation gas, and then the substrate is exposed to the indirect excitation gas to form a thin film on the substrate. 2. The method for forming a thin film as described in 1 above.

  3. The thin film is formed by forming the thin film on at least one surface on the outer surface side of the substrate having a space in which a gas or liquid is contained, by the thin film forming method according to any one of 1 to 3 above. Goods to do.

  4). 4. The article according to 3 above, wherein the substrate having a space in which gas or liquid is contained constitutes a resistive touch panel or a liquid crystal display device.

  According to the present invention, it is possible to provide a method for manufacturing a device or an article such as a liquid crystal panel or a touch panel that has excellent durability over time and good productivity.

  Hereinafter, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

  The present invention is a thin film forming method characterized in that a thin film is formed by atmospheric pressure plasma treatment on at least one surface on the outer surface side of a substrate having a space in which a gas or liquid is contained.

  The gas or liquid contained in the inside of the substrate means air, an inert gas such as a rare gas or nitrogen gas, a gas such as oxygen, or a vacuum (reduced pressure) filled in a space or void formed by the substrate. For example, a liquid crystal panel, a touch panel, or an FED (internal depressurization) may be used as the article having a constant pressure gas or liquid (including liquid crystal) in a state and including a base having a space in which gas or liquid is contained. ), Articles such as multi-layer glass, etc., which have a structure in which a gas or liquid is contained in an internal space formed between two substrates (substrates) (also by a sealing material). These basic structures are combined with other members (for example, polarizing plates, antireflection films, etc.). In addition, the enclosed space may include other articles such as a spacer.

  In the present invention, a thin film is formed by atmospheric pressure plasma discharge treatment (plasma CVD treatment) on at least one surface of the outer surface of the substrate of the device or article, and the surface of the device or article is antistatic. It is a thin film forming method for imparting various functions such as imparting functions such as antireflection, forming an antifouling layer, and imparting an antifouling function.

  Generally, in such a device or article, imparting these functions to the substrate is performed by forming functional thin films on the surface of the constituent members by various thin film forming methods, and assembling and assembling these members. To a typical device or article.

  As a method for forming a thin film, various methods such as an evaporation method (resistance heating method, electron beam method), a sputtering method, an ion plating method, a plasma CVD method and the like well known so far are used.

In the present invention, a thin film is formed on the outer surface of a substrate such as a device or an article having a space in which a gas or liquid is contained inside the assembled structure. As a thin film forming method, for example, under vacuum This is characterized by the use of atmospheric pressure plasma treatment that does not affect the characteristics and quality of the assembled device or article. The term “the substrate or liquid is encapsulated” means a state after the substrate is bonded and liquid crystal, gas, and other necessary articles are sealed inside.
It is difficult to form a thin film on the outer surface of a device or article consisting of a substrate having a space in which gas or liquid is contained, depending on the method using a vacuum facility or the coating method, etc. However, according to the present invention, it is understood that the performance of a device or an article having a space in which a gas or liquid is contained is not affected, but rather, the durability with respect to the function to be provided is improved. It was.

  According to the thin film forming method according to the present invention, for example, after forming a panel such as a liquid crystal panel or a touch panel, using an atmospheric pressure plasma treatment (AGP), a film is formed on a constituent member serving as a base, Compared to the assembly process, in the process of assembling the device from the components, the thin film formed on the surface of the component is less exposed to chemicals and is not exposed to slight scratches or stress such as bending. Improved durability of the article over time is provided. Further, productivity can be improved because processing for imparting final functionality can be performed in accordance with the yield of an article made of a substrate having a space containing gas or liquid inside the panel or the like.

  Hereinafter, the present invention will be described with some examples.

FIG. 1 is a schematic cross-sectional view of the configuration of a liquid crystal display element.
On both sides of a liquid crystal cell having a structure in which a liquid crystal compound is enclosed inside by two opposing substrates 20 (with a transparent conductive film and an alignment film) and a sealing material 21, polarizing plates 22 are orthogonal to the polarization axes, respectively. Thus, a set is arranged to constitute a liquid crystal panel. Each polarizing plate is configured to sandwich a polarizer between two polarizing plate protective films, and on the polarizing plate protective film surface on the viewing side of the polarizing plate serving as the outermost surface (viewing side). In addition, an antireflection layer, an antistatic layer, an antiglare layer, an antifouling layer, and the like are formed through a hard coat layer, and these thin films are improved in visibility by improving antireflection and antiglare properties in liquid crystal display elements. Functions such as improvement and prevention of dirt are given. In FIG. 1, an antireflection layer 23, an antistatic layer 24, and an antifouling layer 25 are formed.

  Conventionally, in these liquid crystal display panels, these functional thin films formed on the viewing side surface are, for example, known thin film formation on a film substrate such as a cellulose ester, in which a polarizing plate serves as a protective film for a polarizing plate. After forming by a method, this can be used as a protective film for a polarizing plate, and after forming a polarizing plate with another polarizing plate protective film and a polarizer in between, this polarizing plate is combined with a liquid crystal cell It is formed on the surface of the liquid crystal panel viewing side. Usually, these functional thin films are formed on a film material by a coating method such as a sol-gel method, a vacuum deposition method, a sputtering method, a plasma CVD method, or the like.

  In the liquid crystal panel, therefore, a functional thin film is once formed on the cellulose ester film, which is a member constituting the polarizing plate, and the functional thin film is formed on the member (in this case). , A polarizing plate protective film) is used as one of the constituent materials, and the final antireflection performance and antistatic performance of the liquid crystal panel, antifouling resistance of the external surface on the viewing side, and the like are imparted.

  Accordingly, the liquid crystal panel shown in FIG. 1 has an alignment film and a transparent conductive film surface opposed to each other between two substrates (glass or resin film) with a transparent conductive film serving as an alignment film and electrodes, and is spaced by a sealing material. After the liquid crystal material is sealed in the space kept at, and a liquid crystal cell is formed, two polarizing plates with the polarization axes orthogonal to each other are arranged on the upper and lower surfaces of the liquid crystal cell. Here, for simplification, wiring electrodes, driving circuits, wirings and the like in each pixel of the liquid crystal panel are not shown.

  The polarizing plate has a structure in which both sides of the polarizer are sandwiched by the protective film for polarizing plate, and is on the outermost surface of the polarizing plate on the viewing side, that is, on the protective film surface for polarizing plate on the outermost surface side of the liquid crystal panel. Uses an antireflection layer, an antistatic layer, an antifouling film, or the like in which these functional layers are formed in advance.

  These liquid crystal panels are manufactured by patterning wiring electrodes on a substrate, forming a circuit such as a driving element, forming cells by making glass substrates face each other with a certain gap using a sealing material, and between the glass substrates. A step of encapsulating a liquid crystal material in the cell formed in the step, a step of sealing the liquid crystal material, a step of arranging a polarizing plate in the produced liquid crystal cell, etc. It is formed through a number of processes such as a process for forming functional thin films such as an antistatic layer, an antireflection layer, and an antifouling layer on the polarizing plate protective film, and a process for attaching to a polarizer.

  A base member as a constituent member on which a functional thin film is formed and a constituent member such as a polarizing plate are subjected to such various steps in the manufacturing process of the liquid crystal panel.

  Looking at the production process of the polarizing plate in more detail, an antireflection film (for example, a hard code layer / medium refractive index layer / high refractive index layer / low refractive index layer) is formed on the cellulose ester film once used as a protective film for the polarizing plate. This is combined with another resin film (for example, a cellulose acetate film having a thickness of about 50 μm), and a polarizing plate is formed by sandwiching a polarizer.

  In order to improve adhesion with a polarizer (typically, a polyvinyl alcohol film containing iodine having a thickness of about 20 μm can be oriented by uniaxial stretching), the surface of the cellulose ester film on the polarizer side is Alkaline treatment is performed for partial hydrolysis. Also, adhesion with the polarizer and adhesion using polyvinyl alcohol, cutting process of the produced polarizing plate, alignment with the separately produced liquid crystal cell when forming the liquid crystal panel, There is a need for a process that requires a fine adjustment of the possibility of contact with the drug, such as a process of aligning the polarization axis with the other polarizing plate on the opposite side and bonding them together.

  By these, for example, a structural member such as a protective film for a polarizing plate having an antireflection layer, an antifouling layer or the like formed on the surface thereof is used in a chemical action such as a solvent or a chemical or in a bonding process, such as a hot roll There are not a few cases such as heat generated by bending, mechanical action due to bending, misalignment, etc., and occurrence of minor scratches caused by other process equipment such as rolls that come into contact accidentally or inevitably. You will be exposed to the opportunity of failure.

  In the present invention, for example, in the above case, a liquid crystal panel is used except that a cellulose ester film having no antireflection layer or antifouling layer is used as a protective film for a polarizing plate, except that the polarizing plate is produced. After that, a thin film such as an antireflection layer, an antistatic layer or an antifouling layer is formed on the outer surface of the liquid crystal panel (the polarizing plate surface on the viewing side) by atmospheric pressure plasma treatment. When these thin films are formed on the constituent members, they are formed by various known methods as described above. In the present invention, the thin film is formed of a substrate having a space in which a gas or liquid is contained. In order to form the device or article on the outer surface after the formation of the device or article, the atmospheric pressure plasma treatment having the least influence on the article such as the formed liquid crystal panel is optimal. In this case, the durability of the panel may be improved. understood.

  Next, a liquid crystal panel for a liquid crystal projector will be described.

  First, the configuration of the liquid crystal projector will be briefly described.

  FIG. 2 is a schematic diagram showing the configuration of the liquid crystal projector. The liquid crystal projector includes a light source 11 and includes, for example, a metal halide lamp 12 that emits strong light source light and a spheroid reflector 13. In front of the light source 11, a heat ray cut filter 14, spectroscopes (half mirrors) 15a, 15b, 15c, dichroic mirrors 16a, 16b, liquid crystal display devices 17a, 17b, 17c, a cross prism 18, and a projection lens 19 are sequentially provided. Is arranged. Further, each of the liquid crystal display devices 17a, 17b, and 17c has a color filter function of any one of R (red), G (green), and B (blue) primary colors. 26, an incident side polarizing plate 22a, and an output side polarizing plate 22b. The liquid crystal panel 26 has a configuration in which liquid crystals are held in a gap between a pair of glass substrates.

  In the projector configured as described above, the strong light source light emitted from the metal halide lamp 12 passes through the heat ray cut filter 14 and removes unnecessary infrared rays. Further, the light is reflected and passed by the half mirrors 15a, 15b, and 15c and the dichroic mirrors 16a and 16b, and enters the liquid crystal panel 26 of each of the liquid crystal display devices 17a to 17c from the incident side polarizing plate 22a side. The light emitted from the liquid crystal panel 26 passes through the exit-side polarizing plate 22b and then enters the cross prism 18 to synthesize R, G, and B light, and is enlarged and projected by the projection lens 19, and is projected onto the front screen or the like. An image is projected. This structure is a three-panel type in which three liquid crystal panels 26 are incorporated corresponding to light sources of RGB three primary colors, but a single-plate type using one liquid crystal panel is also known.

  By the way, the thickness of the liquid crystal panel 26 is about 1 to 2 mm and is relatively thin. For this reason, a partial heating due to unevenness in the intensity distribution of the light source light and a cooling mechanism for reducing an increase in temperature due to radiant heat from the light source 11 are usually incorporated. An air cooling method is generally used in which air is blown directly onto the panel surface for cooling. In this method, dust inevitably hits the surface of the liquid crystal panel, and the dust is more likely to adhere to the surface of the liquid crystal panel 26 and other optical components due to static electricity, and an antistatic layer is formed on the surface.

  Next, FIG. 3 and FIG. 4 show schematic views of the front and cross section of the liquid crystal panel used here.

  4 is a cross-sectional view taken along line AA in FIG. 3 and 4, the liquid crystal panel 1 can be used as the liquid crystal panel 26 in the liquid crystal display devices 17a to 17c in the projector shown in FIG. 2, and as shown in FIG. It has a package structure in which the metal frame 3 is integrated.

  The liquid crystal cell 2 holds a liquid crystal compound in the gap between the pair of glass substrates 4 a and 4 b and has a light-transmissive display region 5. Each of the glass substrates 4a and 4b does not display on the side of the glass substrate in contact with the liquid crystal, but has a transparent conductive layer that constitutes a wiring electrode, circuit wiring, and the like. Control orientation. In this example, the glass substrate 4a is located on the light source light incident side, and the glass substrate 4b is located on the light source light emission side. Furthermore, a flexible connector 6 for external connection is attached to the back side of one glass substrate 4a. After the attachment, an electrode part (not shown) of the flexible connector and an electrode part (not shown) on the liquid crystal cell 2 side are provided. In order to prevent leakage, an insulating material 8 such as silicon rubber is applied. In addition, the surface of the glass substrate 4a (incident side of the light source light) and the surface of the glass substrate 4b (exit side of the light source light) cover the substantially entire surfaces of the glass substrates 4a and 4b and are transparent and conductive. Each of the membranes 7 is disposed. This transparent conductive film 7 is used as an antistatic layer, for example, by spin-coating a conductive polymer or the like, or depositing ITO (indium and tin oxide) used as a transparent electrode of the liquid crystal cell 2. Alternatively, it is provided by spin coating (sol-gel method) or the like and has a thickness of about 50 to 200 nm.

  The metal frame 3 is a conductive metal material, preferably having a high thermal conductivity, such as a material that can absorb heat accumulated in the liquid crystal cell 2 and function as an efficient heat exchange medium, such as copper. , Iron, or a metal such as aluminum or nickel. Of course, these composite materials may be used. As shown in FIGS. 3 and 4, the metal frame 3 is divided into two metal halves in the front and rear, the two halves in front and behind sandwich the periphery of the liquid crystal cell 2, and the liquid crystal cell 2 The display region 5 is surrounded by a transparent conductive film 7 so as to be in close contact with the surfaces of the glass substrates 4a and 4b so as to function as an outer frame, and between the transparent conductive film 7 and the metal frame 3 is electrically connected. In an electrically conductive state.

  The thus configured liquid crystal front panel 1 is attached with the metal frame 3 grounded to the projector. When attached in this manner, static electricity that is to be charged on the surface of the liquid crystal cell 2, that is, the transparent conductive film 7, flows from the transparent conductive film 7 to the metal frame 3, and is further discharged through the ground of the projector.

  Also in this case, the liquid crystal panel is manufactured on the glass substrate (also referred to as a substrate) constituting the pair of glass substrates 4a and 4b, first on the surface on the outer surface side of the substrate, and firstly the antistatic layer. A transparent conductive layer (for example, an ITO film) is opposed to each other when forming a liquid crystal cell on the opposite side, and a transparent conductive film and an alignment film serving as an electrode are formed on each surface containing a liquid crystal material therebetween. Paint. This order may of course be reversed. Although not shown in the drawing, a wiring electrode is formed by patterning on the transparent conductive film.

  The pair of glass substrates 4a and 4b as the constituent members thus manufactured are held at regular intervals by a sealing material (omitted) with the transparent electrode pattern and the surface having the alignment film facing each other. A liquid crystal compound (material) is sealed in a gap formed by the glass substrates 4a and 4b and the sealing material, and is sandwiched and fixed using the metal frame, and a space in which the liquid crystal material is enclosed between the substrates is formed. A liquid crystal panel is produced.

  In the conventional assembly of the liquid crystal panel shown in FIGS. 3 and 4, apart from the steps of forming and removing the resist material and etching in the patterning of the thin film material in the formation of wiring electrodes, drive elements and circuits in the liquid crystal panel However, when an antistatic layer is to be formed on the external surface of the liquid crystal panel, a conductive thin film is formed in advance on the external surface side of the glass substrate that is the base (constituent member) of the liquid crystal panel. The substrates must be opposed to each other with a constant gap, and a liquid crystal material must be injected and sealed to produce a liquid crystal cell. That is, it is necessary to form a functional layer in advance on the constituent members.

  These thin films formed on a glass substrate, which is a constituent member, are also used in the panel manufacturing process to align the glass substrates, adjust the gap, bond them together (crimping, heating, etc.), apply an adhesive, It will be exposed to many processes, such as sealing and fixing with a metal frame.

  In the present invention, the functional thin film formed on the outermost surface of these liquid crystal panels is formed after manufacturing the liquid crystal panel, that is, after the liquid crystal panel without forming the outermost antistatic layer is prepared, this outer surface is formed. An antistatic layer, for example, a transparent conductive thin film such as ITO is formed using atmospheric pressure plasma treatment.

  Further, as an example to which the thin film forming method of the present invention can be advantageously applied, a touch panel will be described with reference to FIG.

  FIG. 5 is a diagram for explaining the structure and manufacturing process of the touch panel. FIG. 5A is a view for explaining a manufacturing process of the lower substrate 32, and a plan view and a cross-sectional view along AA of the lower substrate 32, and FIG. 5B is a manufacturing process of the upper substrate 31. FIG. 4 is a plan view of the upper substrate 31 and a cross-sectional view along BB.

  In FIG. 5, 31 is an upper substrate, 32 is a lower substrate, and the lower substrate is made of a soda glass plate having a thickness of 1.1 mm. A transparent electrode (resistor) 34 is uniformly formed on the transparent electrode 34. A dot spacer 35 is formed on the surface. The upper substrate 31 is composed of, for example, a micro glass plate having a thickness of 0.2 mm, or a highly transparent resin film, for example, a norbornene-based transparent thermoplastic resin film (thickness of 25 to 250 μm) having an aliphatic cyclic structure. Similar to the lower substrate 32, a transparent electrode (resistor) 33 is formed.

  On the other hand, lead electrodes 38a and 38b connected to both ends for applying a potential to both ends of the transparent electrode 34 on the lower substrate are provided on the upper substrate 31 as well as the lower substrate 32. The routing electrodes 37a and 37b are formed simultaneously so as to apply a potential in a direction orthogonal to the electrodes (resistors).

  The transparent electrode is formed by sputtering, plasma CVD, or the like at about 50 to 4000 mm.

  The routing electrode is formed by, for example, a printing method (for example, screen printing) using silver paste or the like, and is formed by baking at 100 to 200 ° C. for about 1 hour after printing.

  The dot spacer has a role of keeping the upper and lower substrates in a fixed gap. For example, a square or circular shape having a size of about 30 to 40 μm and a thickness of about 3 to 12 μm of an acrylic resist having a thickness of about 4 to 4 are used. It is obtained by forming a pattern uniformly by a photolithography process at intervals of about 5 mm (or a photo-curing resin by printing).

  Further, the sealing agent 36 is printed on the peripheral portion of the lower substrate 32, and at this time, an opening 36 a of the sealing agent 36 is provided in a part of the peripheral portion of the lower substrate 32.

  The upper substrate 31 is arranged on the lower substrate 32 so that the transparent electrode 34 formed on the lower substrate 32 and the transparent electrode 33 formed on the upper substrate 31 face each other, By heating, the upper and lower substrates are adhered and bonded by the sealing agent 36.

  The structure of the touch panel is shown in a sectional view in FIG. 6A shows a place where the upper substrate and the lower substrate are overlapped and arranged, and FIG. 6B shows a state where the upper and lower substrates are bonded and cured to form a touch panel.

  A control circuit for detecting signals from the routing electrodes, monitoring the electrode voltage, switching the drive voltage, and the like for determining each coordinate is not shown, but the transparent electrodes on the upper and lower substrates by pressing from the upper substrate side (Resistive film) When the electrodes 33 and 34 are in contact, the transparent electrodes have their potential application directions orthogonal to each other. And by measuring the potential of the upper substrate from the transparent resistance film side of the lower substrate.

  Therefore, according to a conventional manufacturing method, a touch panel having an antifouling layer formed on the upper substrate surface is first a substrate having a thickness of about 150 to 250 μm, for example, glass, used as the upper substrate, for example, by sputtering or plasma CVD. An antifouling film is formed on the substrate or the resin film.

  The order may be either, but after forming, for example, an ITO film as a transparent electrode (resistive film) on the substrate, an antifouling layer is formed on the back surface, and lead-out electrodes 37a and 37b are formed on the transparent electrode. . As the antifouling layer, for example, a fluorine-containing organic compound (complex) described in Japanese Patent Application Laid-Open No. 2004-360039 or the like is used as a thin film forming gas. The antifouling layer formed by the atmospheric pressure plasma method is used, but is not limited thereto.

  At the same time, as shown in FIG. 5, a transparent electrode 34 is formed on a lower substrate 32 made of a soda glass plate having a thickness of 1.1 mm, and lead-out electrodes 38a and 38b connected to the transparent electrode 34 are similarly formed. To do. Further, after forming a dot spacer 35 on the transparent electrode 34, a sealing agent 36 is printed on the periphery of the lower substrate 32. At this time, an opening 36 a of the sealing agent 36 is provided in a part of the peripheral portion of the lower substrate 32.

The upper substrate 31 on which the antifouling layer 39 is formed is overlapped on the lower substrate 32, adhered with the sealing agent 36, and then the upper and lower substrates 31, 32 are overlapped and set, and then a curing jig or the like is used. Pressing and heating for a predetermined time, the sealing agent 36 is baked or cured and pasted so that the upper and lower substrates have a predetermined gap. For example, an epoxy resin or an acrylic resin adhesive may be used as the sealing material, and the sealing material may be held for about 5 minutes at a heating temperature of 90 ° C. and a pressing force of about 0.5 kg / cm ² . Then, the opening part 36a of a sealing agent is sealed and a touch panel is manufactured. FIG. 7 is a sectional view showing an example of a touch panel having an antifouling layer formed on the outer surface.

  The touch panel in the conventional form is realized by the above manufacturing process.

  The antifouling layer is formed on the substrate surface of the upper substrate on the touch side opposite to the transparent resistance film.

  Therefore, in the above manufacturing process, after forming the transparent resistance film, even when the antifouling layer is formed on the upper substrate surface, which is a constituent member serving as a base, printing of the lead electrode on the back surface, firing, etc. There is a high possibility that damage due to crimping and heating with a jig or film defects will occur in the step of bonding to the lower substrate.

  Therefore, in this case as well, the antifouling layer may be formed in this case by atmospheric pressure plasma treatment after the touch panel shown in FIG. 5 or 6 (the antifouling layer is not formed) is manufactured. Thereby, a touch panel having an antifouling layer on the outer surface of the upper substrate shown in FIG. 7 is obtained.

  Atmospheric pressure plasma treatment is a method capable of forming a thin film at atmospheric pressure or a pressure in the vicinity thereof, and a high-performance thin film can be obtained without requiring a very high temperature. Even after forming a panel or article having a space, the device or article is not exposed to harsh conditions, and the functional thin film has good durability without being deteriorated in performance or function (in this case) Can obtain an antifouling film). For example, a device or an article such as a touch panel or a liquid crystal panel can be easily formed into a thin film on its outer surface by transporting and introducing it into a plasma discharge treatment chamber under atmospheric pressure.

  Further, in order to be able to process completed articles such as panels and devices without being subjected to strong bending stress or the like, a plasma discharge processing apparatus having a flat frame shown in FIG. 8 or FIG. 9 is preferable.

  As described above, an example of the antifouling film is shown. However, the same applies to the case of forming an antireflection film or a conductive film for preventing electrification, and the film is formed on the surface of the constituent member before or during the assembly. There is a limit to how to do this.

  The thin film forming method according to the present invention can be applied to any device or article composed of a substrate having a space in which a gas or a liquid is contained, and is formed on the viewing side surface of a liquid crystal display device or a touch panel. For example, not only the antistatic layer, the antireflection layer, and the antifouling layer, but also other display devices such as FED (internal decompression), an antireflection film formed on the outermost surface of each device, It is useful as a means for forming an antifouling film, antistatic and other various functional films.

As these various functional thin films, for example, there is an antireflection layer,
As the antireflection film, MgF ₂ , LiF ₂ , ThF 4, SiO, SiO ₂ , ZrO ₂ , CeO ₂ , Al ₂ O ₃ , Ta ₂ O ₅ , TiO ₂ and other fluorides and oxides are vacuum-deposited. And an optical member with an antireflection film by laminating on a roll film such as a polyester film with a hard coat or a triacetyl cellulose film by a dry coat such as a sputtering method or a wet coat such as a dip coat or a spin coat. is there.

  The antireflective layer is typically composed of three layers having different refractive indexes from the substrate side. The middle refractive index layer (having a refractive index higher than that of the support or hard coat layer and having a refractive index higher than that of the high refractive index layer). (Lower layer) / High refractive index layer / Low refractive index layer.

  The refractive index of the low refractive index layer is a layer having a refractive index of 1.20 to 1.55, preferably 1.30 to 1.55, and is composed of inorganic fine particles having a constant refractive index such as silicon oxide and an organic polymer. A porous layer or a layer made of a fluorine-containing polymer can be used. The thickness of the low refractive index layer is preferably 50 to 400 nm, more preferably 50 to 200 nm, and still more preferably 60 to 150 nm.

  The refractive index of the high refractive index layer and the medium refractive index layer, for example, the high refractive index layer is 1.55 to 2.30, preferably 1.57 to 2.20. The refractive index of the medium refractive index layer is The refractive index of the transparent support is adjusted to be an intermediate value between the refractive index of the high refractive index layer and the refractive index of the high refractive index layer. The thickness of the high refractive index layer and the medium refractive index layer is 5 nm to 1 μm.

  The high refractive index layer and the medium refractive index layer are formed using an inorganic compound having a high refractive index such as titanium oxide.

  In addition, as the antifouling film, for example, a water-repellent surface formed by a sol-gel method from an alkoxysilane compound having a perfluoropolyether group, an alkoxysilane having a fluoroalkyl, or the like (for example, described in JP-A-2004-21550), In addition, there are an alkoxysilane containing a fluorine-containing alkyl group described in JP-A-2004-360039 or the like, or a thin film having a water-repellent surface obtained by atmospheric pressure plasma treatment using another metal compound.

  Moreover, as a transparent conductive film used for antistatic, a film made of a conductive polymer, a metal oxide layer such as ITO used as a transparent electrode, a layer containing these particles, or an ionic compound (polymer) And a layer having a film thickness of several nm to several tens of nm formed by various methods such as coating, sputtering, and plasma CVD.

  As described above, in order to form a functional thin film such as the antireflection layer, antistatic layer, or antifouling layer on the substrate, as described above, various methods such as coating, sputtering, and plasma CVD are used. In the present invention, atmospheric pressure plasma treatment is used as a means for forming these functional thin films on the surface of these devices and articles after they are formed.

  Next, atmospheric pressure plasma discharge treatment will be described.

  In the atmospheric pressure plasma discharge treatment, a thin film forming gas or a treatment gas is introduced into a discharge space composed of a first electrode and a second electrode facing each other under an atmospheric pressure or a pressure near atmospheric pressure, and an electric field is applied. The thin film forming gas or the processing gas is excited to expose the substrate to the excited thin film forming gas (indirect excitation gas), thereby forming a thin film on the substrate or performing surface modification. .

  For example, as the thin film forming gas, a rare gas is contained as a discharge gas, and an organometallic compound such as alkoxysilane is contained as a raw material gas, which is introduced into a discharge space composed of a first electrode and a second electrode. By applying a high frequency potential between the first electrode and the second electrode, the thin film forming gas is excited, and the substrate is exposed to the excited thin film forming gas, so that a thin film corresponding to the thin film forming material is deposited on the substrate. It is formed.

  Under atmospheric pressure or pressure near atmospheric pressure is a pressure of 20 kPa to 200 kPa, and a more preferable pressure between electrodes to which a voltage is applied is 70 kPa to 140 kPa. Under these pressures, a thin film having various properties can be formed on the base film by changing the thin film forming gas to be introduced and the reactive gas in various ways.

  Hereinafter, the apparatus used for the plasma discharge processing according to the present invention will be specifically described with reference to the drawings.

  FIG. 8 is a schematic view showing an example of an atmospheric pressure plasma discharge treatment apparatus according to the present invention.

  FIG. 8 is a sectional view showing an example of the entire plasma discharge processing apparatus. 120 is a plasma discharge treatment apparatus, 101 is a plasma discharge treatment vessel, and a substrate (substrate) to be treated conveyed from the previous process is transferred to a treatment chamber 102 where plasma treatment is continuously performed under atmospheric pressure or a pressure in the vicinity thereof. Plasma treatment is performed between the pair of counter electrodes 103 and 104. The processing chamber 102 is constituted by a partitioned processing chamber having an inlet 102A and an outlet 102B of the base material (substrate) F. The processing chamber will be described below. A spare chamber 110 is provided adjacent to the processing chamber 102 on the inlet side of the substrate, and a spare chamber 111 is provided adjacent to the spare chamber 110. A spare chamber 112 is also provided on the outlet side adjacent to the processing chamber 102. In the case of providing a preliminary chamber, two may be provided on the inlet side of the base material F and one on the outlet side. However, the present invention is not limited to this. Alternatively, two may be provided on the inlet side and not provided on the outlet side, or two or more may be provided on the inlet side and two or more may be provided on the outlet side. In any embodiment, the internal pressure in the processing chamber 102 needs to be higher than the internal pressure of the preliminary chamber adjacent to the processing chamber 102, and is preferably 0.25 Pa or more. Thus, by providing a pressure difference between the processing chamber 102 and the preliminary chamber, it is possible to prevent external air from being mixed in, to effectively use the reaction gas, and to further improve the processing effect. When two or more spare chambers are provided adjacent to the processing chamber 102 on the inlet side and two or more spare chambers are provided on the outlet side, the differential pressure between the spare chamber 110 and the adjacent spare chamber 111 is close to the processing chamber 2. The internal pressure of the auxiliary chamber 110 on the side is preferably set high, and is preferably set high by 0.25 Pa or more. In this way, by providing a pressure difference between the plurality of preliminary chambers, it is possible to more effectively prevent external air from being mixed in, to enable more effective use of the reaction gas, and to further improve the treatment effect. The preliminary chamber 110 or 111 preferably has at least one component of the processing gas from the viewpoint of efficient use of the reaction gas and improvement of the processing effect. Further, in order to provide a plurality of preliminary chambers and provide a pressure difference, it is preferable to provide the decompression means 115. Examples of the pressure reducing means include a suction fan or a vacuum pump. It is necessary that the processing chamber 102, the spare chamber 110, and the spare chamber 111 are partitioned from each other. As the partitioning means, here, at least one pair of nip rolls 107 on the inlet side, and on the outlet side. At least a pair of nip rolls 108 is provided. The nip roll 107 or 108 has a function of closing or partitioning while being in contact with the substrate F. However, since the rooms cannot be partitioned completely, a means for providing a pressure difference functions effectively. Further, as the partitioning means, a predetermined gap with respect to the base material F may be maintained and non-contacting means may be used. For example, in the case of a device or article on which a base material or a substrate to be processed is configured, Although not shown, an air curtain system or the like is adopted. In the case where a spare chamber is not provided, a partition may be provided between the processing chamber and the outside.

  The pair of counter electrodes 103 and 104 is composed of a metal base material and a dielectric (the distinction is not shown), and by combining the metal base material to coat the dielectric material having an inorganic property, Further, it may be constituted by a combination in which a ceramic material is sprayed on a metal base material and then a dielectric material sealed with a substance having an inorganic property is coated. As the metal base material, metals such as silver, platinum, stainless steel, aluminum, and iron can be used, but stainless steel is preferable because it is easy to process. Dielectric lining materials include silicate glass, borate glass, phosphate glass, germanate glass, tellurite glass, aluminate glass, vanadate glass, etc. Of these, borate glass is preferable because it is easy to process. As the ceramic used for the thermal spraying of the dielectric, alumina is preferable, and a sealing material such as silicon oxide is preferable. Moreover, what makes an alkoxylane type | system | group sealing material mineralize by sol-gel reaction is used preferably.

  A high frequency power source 105 is connected to one electrode 103 of the pair of counter electrodes 103 and 104, and the other electrode 104 is grounded by a ground 106 so that an electric field can be applied between the pair of counter electrodes 103 and 104. Has been.

  The high frequency electric field has a sine waveform, but it is also possible to apply a pulsed electric field. The meaning of this pulsing is that the plasma gas temperature can be changed by changing the ON / OFF duty ratio. Thereby, it may be possible to change the shape of the surface irregularities. For example, the pulse waveforms shown in FIGS. 1A to 1D of JP-A-10-130851 may be used.

  The processing chamber 102 is composed of a space between the counter electrodes 103 and 104, and the base material F is conveyed in contact with the electrode 104 through the discharge portion. A reaction gas supply port I (supply means) and a discharge port O (discharge means) for discharging the treated exhaust gas are provided in the processing chamber 102, and the reaction gas (thin film forming gas) is provided from the reaction gas supply port. Or a processing gas), a high-frequency potential is applied between the opposing electrodes by a high-frequency power source 105 to generate a plasma discharge in a discharge portion between the electrodes, and the surface of the substrate conveyed on the electrode 4 A thin film is formed. The treated exhaust gas is discharged from the discharge port.

  The distance between the opposing electrodes is the distance between the dielectric surfaces, and is preferably 0.1 to 20 mm, particularly preferably 0.5 to 5 mm from the viewpoint of performing uniform discharge.

  In addition, temperature control medium (water or silicon oil) circulates to control the electrode surface temperature during plasma discharge treatment and to keep the surface temperature of the substrate or substrate and the article to be treated at a predetermined value. It has a structure that can be done. For example, the metallic base material structure of the electrode is a metallic pipe that serves as a jacket so that the temperature during discharge can be adjusted.

In the atmospheric pressure plasma discharge processing apparatus of the present invention, the high-frequency voltage applied between the opposing electrodes is a high-frequency voltage exceeding 100 kHz and power (output density) of 1 W / cm ² or more is supplied, and the processing gas Is excited to generate plasma.

  In the present invention, the upper limit of the frequency of the high-frequency voltage applied between the electrodes is preferably 150 MHz or less, and more preferably 15 MHz or less. Moreover, as a lower limit of the frequency of a high frequency voltage, Preferably it is 200 kHz or more, More preferably, it is 800 kHz or more.

Further, the upper limit value of the power supplied between the electrodes is preferably 50 W / cm ² or less, more preferably 20 W / cm ² or less. The lower limit is preferably 1.2 W / cm ² or more. The discharge area (cm ² ) refers to an area in a range where discharge occurs in the electrode.

  The value of the voltage applied to the application electrode from the high frequency power supply is appropriately determined. For example, the voltage is about 10 V to 10 kV / cm, and the power supply frequency is adjusted to over 100 kHz and 150 MHz or less as described above.

  As for the power supply method, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.

  In the present invention, it is necessary to employ an electrode capable of maintaining a uniform glow discharge state by applying such a voltage in a plasma discharge processing apparatus.

  In the present invention, the power source for applying a voltage to the applied electrode is not particularly limited, but a high frequency power source (3 kHz) manufactured by Shinko Electric, a high frequency power source manufactured by Shinko Electric (5 kHz), a high frequency power source manufactured by Shinko Electric (10 kHz), and Kasuga. Electric high frequency power supply (15 kHz), Shinko Electric high frequency power supply (50 kHz), HEIDEN Laboratory impulse high frequency power supply (100 kHz in continuous mode), Pearl Industrial high frequency power supply (200 kHz), Pearl Industrial high frequency power supply (800 kHz), Pearl Industrial A high-frequency power source (2 MHz) manufactured by Pearl Industries, a high-frequency power source manufactured by Pearl Industries (13.56 MHz), a high-frequency power source manufactured by Pearl Industries (27 MHz), a high-frequency power source manufactured by Pearl Industries (150 MHz), or the like can be used. Preferably, it is a high frequency power source of more than 100 kHz to 150 MHz, preferably a high frequency power source of 200 kHz to 150 MHz, particularly preferably 800 kHz to 15 MHz.

  Using these apparatuses, as a thin film forming gas composed of a discharge gas, a reactive gas, etc., for example, as a discharge gas, a rare gas such as helium or argon is used, and a raw material gas for the thin film is contained as a reactive gas in this plasma. By performing the discharge treatment, various functional thin films can also be produced, for example, by preparing a laminated film having a plurality of structures such as an antistatic layer, an antireflection layer, an antifouling layer, and a gas barrier film. Moreover, it can carry out by setting plasma discharge conditions for every process.

  It is also possible to install several of these apparatuses in succession to form different thin films. For example, after the formation of the antireflection layer, the formation of the antifouling layer can also be carried out continuously.

  Next, another example of the plasma discharge processing apparatus used in the present invention is shown in FIG. In this atmospheric pressure plasma discharge apparatus, the structure, in particular, the application of an electric field and the structure of the discharge part are different from those in FIG.

  The atmospheric pressure plasma discharge device shown in FIG. 9 applies two or more electric fields having different frequencies to the discharge space, and applies an electric field obtained by superimposing a first high-frequency electric field and a second high-frequency electric field.

The frequency ω2 of the second high-frequency electric field is higher than the frequency ω1 of the first high-frequency electric field, the strength V1 of the first high-frequency electric field, the strength V2 of the second high-frequency electric field, and the discharge start The relationship with the electric field strength IV is
V1 ≧ IV> V2
Or V1> IV ≧ V2 is satisfied,
The power density of the second high frequency electric field is 1 W / cm ² or more.

  By taking such a discharge condition, for example, a discharge gas having a high discharge start electric field strength such as nitrogen gas can start discharge, maintain a high density and stable plasma state, and form a high-performance thin film. I can do it.

  When the discharge gas is nitrogen gas by the above measurement, the discharge start electric field strength IV (1/2 Vp-p) is about 3.7 kV / mm. Therefore, in the above relationship, the first applied electric field strength is By applying V1 ≧ 3.7 kV / mm, the nitrogen gas can be excited to be in a plasma state.

  Here, the frequency of the first power source is preferably 200 kHz or less. The electric field waveform may be a continuous wave or a pulse wave. The lower limit is preferably about 1 kHz.

  On the other hand, the frequency of the second power source is preferably 800 kHz or more. The higher the frequency of the second power source, the higher the plasma density, and a dense and high-quality thin film can be obtained. The upper limit is preferably about 200 MHz.

  The application of a high frequency electric field from such two power sources is necessary to start the discharge of a discharge gas having a high discharge start electric field strength by the first high frequency electric field, and the high frequency of the second high frequency electric field. In addition, it is possible to increase the plasma density by a high power density and form a dense and high-quality thin film.

  In addition to applying two or more electric fields having different frequencies to the discharge space, the device shown in FIG. 9 causes plasma discharge between the counter electrodes similar to the device shown in FIG. The gas introduced into is excited into a plasma state, but the excited or plasma state gas is blown out to the outside of the counter electrode, and the substrate in the vicinity of the counter electrode (either standing or transported) It is an example of a jet-type apparatus in which a functional thin film is formed on a substrate by exposing it to (good).

  The plasma discharge treatment apparatus 200 has a counter electrode composed of a first electrode 211 and a second electrode 212, and a first frequency from the first power source 221 is provided between the counter electrodes between the first electrode 211 and the first electrode 211. A high frequency voltage V1 of ω1 is applied, and a high frequency voltage V2 of the second frequency ω2 from the second power source 222 is applied from the second electrode 212. The first power source 221 only needs to be capable of applying a higher frequency voltage (V 1> V 2) than the second power source 222, and the first frequency ω 1 of the first power source 221 is the second frequency of the second power source 222. It is only necessary to have an ability smaller than the frequency ω2.

  A first filter 223 is installed between the first electrode 211 and the first power source 221 such that a current from the first power source 221 flows toward the first electrode 211, and a current from the first power source 221 is provided. Is designed so that the current from the second power source 222 can easily pass.

  Further, a second filter 224 is installed between the second electrode 212 and the second power source 222 so that the current from the second power source 222 flows toward the second electrode 212. It is designed to make it difficult to pass the current and pass the current from the first power source 221 easily.

  A gas G is introduced from a gas supply means (not shown here) between the counter electrodes (discharge space) 213 between the first electrode 211 and the second electrode 212, and a high-frequency voltage is applied from the first electrode 211 and the second electrode 212. This is applied to generate a discharge, and while the gas G is in a plasma state, the gas G is blown out in the form of a jet to the lower side (the lower side of the paper) to form a processing space formed by the lower surface of the counter electrode and the base material. A functional thin film is formed in the vicinity of the processing position 214 on the substrate that is filled and transported at an angle. During the formation of the functional thin film, the carrier medium and electrodes of the substrate are heated or cooled by a medium supplied via piping from an electrode temperature adjusting means (not shown here). Depending on the temperature of the base material during the plasma discharge treatment, the physical properties and composition of the functional body to be obtained may change, and it is desirable to appropriately control this. As the temperature control medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desirable to uniformly adjust the temperature inside the electrode so that the temperature unevenness of the substrate in the width direction or the conveyance direction does not occur as much as possible.

  FIG. 9 shows a measuring instrument used for measuring the above-described high-frequency voltage (applied voltage) and discharge start voltage. 225 and 226 are high-frequency probes, and 227 and 228 are oscilloscopes.

  In addition to the voltage applying means having the two power sources, these plasma discharge treatment apparatuses 200 also have a gas supply means and an electrode temperature adjusting means, which are not shown in FIG.

  In addition, since a plurality of jet-type atmospheric pressure plasma discharge treatment devices can be connected in series and discharged in the same plasma state at the same time, the gas can be processed many times and processed at high speed. In addition, if each apparatus jets gas in different plasma states, it is possible to continuously form stacked functional bodies having different layers.

  The electrodes used for these are preferably those obtained by thermally spraying ceramics as a dielectric material on a conductive metallic base material and sealing with an inorganic compound sealing material. The ceramic dielectric may be covered by about 1 mm with a single wall. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is particularly preferable because it is easily processed. The dielectric layer may be a lining-processed dielectric provided with an inorganic material by lining.

  The conductive metallic base material is also a metal such as titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, etc., a composite material of iron and ceramics or a composite material of aluminum and ceramics, etc. Titanium metal or titanium alloy is particularly preferred.

  When the dielectric is provided on one of the electrodes, the distance between the opposing electrodes is the distance between the dielectric surfaces, and is preferably 0.1 to 20 mm, particularly preferably 0.5 to 2 mm from the viewpoint of performing uniform discharge. is there.

As two high-frequency power sources installed in such an atmospheric pressure plasma discharge processing apparatus, as a first power source (high-frequency power source),
Applied power symbol Manufacturer Frequency Product name A1 Shinko Electric 3kHz SPG3-4500
A2 Shinko Electric 5kHz SPG5-4500
A3 Kasuga Electric 15kHz AGI-023
A4 Shinko Electric 50kHz SPG50-4500
A5 HEIDEN Research Laboratories 100kHz * PHF-6k
A6 Pearl Industry 200kHz CF-2000-200k
A7 Pearl Industry 400kHz CF-2000-400k
And the like, and any of them can be used.

In addition, as the second power source (high frequency power source)
Applied power supply symbol Manufacturer Frequency Product name B1 Pearl Industry 800kHz CF-2000-800k
B2 Pearl Industry 2MHz CF-2000-2M
B3 Pearl Industry 13.56MHz CF-5000-13M
B4 Pearl Industry 27MHz CF-2000-27M
B5 Pearl Industry 150MHz CF-2000-150M
And the like, and any of them can be preferably used.

  Of the above power supplies, * indicates a HEIDEN Laboratory impulse high-frequency power supply (100 kHz in continuous mode). Other than that, it is a high-frequency power source that can apply only a continuous sine wave.

  In the present invention, it is preferable to employ an electrode capable of maintaining a uniform and stable discharge state by applying such an electric field in an atmospheric pressure plasma discharge treatment apparatus.

In the present invention, the electric power applied between the electrodes facing each other supplies power (power density) of 1 W / cm ² or more to the second electrode (second high-frequency electric field) to excite the discharge gas to generate plasma. The energy is applied to the thin film forming gas to form a thin film. The upper limit value of the power supplied to the second electrode is preferably 50 W / cm ² , more preferably 20 W / cm ² . The lower limit is preferably 1.2 W / cm ² . The discharge area (cm ² ) refers to the area in which discharge occurs between the electrodes.

Further, by supplying power (output density) of 1 W / cm ² or more to the first electrode (first high frequency electric field), the output density is improved while maintaining the uniformity of the second high frequency electric field. I can do it. Thereby, a further uniform high-density plasma can be generated, and a further improvement in film forming speed and an improvement in film quality can be achieved. Preferably it is 5 W / cm ² or more. The upper limit value of the power supplied to the first electrode is preferably 50 W / cm ² .

  The waveform of the high frequency electric field is not particularly limited. There are a continuous sine wave continuous oscillation mode called a continuous mode, an intermittent oscillation mode called ON / OFF intermittently called a pulse mode, and either of them may be adopted, but at least the second electrode side (second The high-frequency electric field is preferably a continuous sine wave because a denser and better quality film can be obtained.

  Next, the mixed gas supplied to the discharge space in the plasma discharge process will be described.

  The supplied mixed gas contains a discharge gas and a thin film forming gas. The discharge gas and the thin film forming gas may be mixed and supplied, or may be supplied separately.

  The discharge gas is a gas that can cause a glow discharge that can form a functional body, and itself functions as a medium for transferring energy. Examples of the discharge gas include nitrogen, rare gas, air, hydrogen gas, oxygen, and the like. These may be used alone as a discharge gas or may be mixed. In the present invention, nitrogen gas and / or Group 18 atom of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, etc. are used as such discharge gas. Among these, nitrogen, helium, and argon are preferably used.

  The amount of discharge gas is preferably 90 to 99.9% by volume with respect to the total amount of gas supplied to the discharge space.

  The thin film forming gas is a raw material that receives energy from the discharge gas, is excited and becomes active, and chemically deposits on the substrate to form a functional thin film.

  In the present invention, various functional thin films can be formed by selecting these thin film forming gases.

  The mixed gas forming the functional thin film used in the present invention will be described. The mixed gas to be used is basically a mixed gas of a discharge gas and a thin film forming gas. Further, an additive gas may be added. The mixed gas preferably contains 90 to 99.9% by volume of discharge gas.

  Various gases such as hydrogen gas, oxygen gas, ozone, carbon dioxide, water (water vapor), ammonia, and nitrogen oxide may be used simultaneously as the additive gas for promoting the reaction for forming the functional thin film. The content is 0.01-5 volume% with respect to mixed gas.

  In the present invention, as a thin film forming gas used for forming a functional thin film, metals such as an organometallic compound, a metal halide, a metal hydride compound, etc. can be used, such as Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc. be able to.

  A typical example of a functional thin film that can be formed using atmospheric pressure plasma treatment and a thin film forming gas used for production are shown below, but are not limited thereto. The film thickness of the functional thin film formed using the thin film forming gas by the plasma CVD method is preferably in the range of 0.1 to 1000 nm.

When a conductive thin film used for, for example, an antistatic layer or an electrode film is formed by the plasma CVD method according to the present invention, the surface specific resistance is 1 × 10 ¹² Ω / cm ² , preferably 1 × 10. What is necessary is just to form an oxide, nitride, carbide or the like of a metal of ¹¹ Ω / cm ² or less, and as a thin film forming gas, typically, for example, tris (2,4-pentanedionate) indium, By using an organometallic compound such as dibutyldiacetoxytin, a conductive thin film such as ITO, In ₂ O ₃ , or SnO ₂ can be obtained. Further, IZO and the like can be obtained by using a metal compound such as a β-diketone complex of zinc and a β-ketocarboxylic acid ester complex.

  In addition, if it is simply a conductive thin film, it is formed by using a corresponding metal organic compound as a thin film forming gas (raw material gas) using a single metal element or a thin film of a plurality of different metal element composites or alloys.

The protective film, also used for the insulating film or the like, a dielectric thin film, for example, SiO _2, SiO, to obtain a thin film such as Si ₃ N _4, as the organometallic compound, tetraethoxysilane (TEOS), tetrabutoxytitanate It can be obtained by selecting an alkoxysilane such as silane or isopropoxysilane, an organic silazane, or the like. Further, a titanium oxide thin film can be obtained from titanium tetraisopropoxide or the like.

Further, in order to obtain an antireflection film, for example, an organic silane compound such as tetraethoxysilane (TEOS) is used, and it is also used for a low refractive index layer and a medium refractive index layer (SiO ₂ ). (TiO ₂ ) used for the layer and the high refractive index layer can be obtained using an organometallic titanium compound such as titanium tetraisopropoxide.

  Examples of the antifouling layer include fluorine-containing organic compounds (complexes) described in JP-A-2004-360039, for example, silane having an organic group having a fluorine atom, silazane, etc., and organic having a fluorine atom. An organometallic compound such as Ti or Sn having a group can be used as a thin film forming gas.

Similarly, by selecting the raw metal compound, the following thin films can be formed on the outermost surface after forming the device or article having a space containing gas or liquid inside by atmospheric pressure plasma treatment. It is.
Reflective film Ag, Al, Au, Cu
Selective absorption membrane ZrC-Zr
Selective permeable membrane In ₂ O ₃ , SnO ₂
Abrasion resistant film Cr, Ta, Pt, TiC, TiN
Corrosion resistant film Al, Zn, Cd, Ta, Ti, Cr
Heat resistant film W, Ta, Ti
Lubricating film MoS ₂
Decorative film Cr, Al, Ag, Au, TiC, Cu

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1:
Touch panel production (antifouling layer film on touch panel)
A touch panel was produced by the following method.

  As shown in FIG. 5, a transparent resistance film 34 was formed on a lower substrate 32 made of a soda glass plate having a thickness of 1.1 mm, and routing electrodes 38 a and 38 b connected to the transparent resistance film 34 were formed. The transparent resistance film 34 was formed by sputtering an ITO film having a thickness of 200 mm as follows.

<Production of ITO film>
That is, a cleaned glass substrate is introduced into a vacuum chamber, and DC magnetron sputtering (condition: substrate) using an ITO target (indium: tin = 95: 5 (molar ratio)) with a SnO ₂ content of 10 mass%. An ITO thin film having a thickness of 200 mm was formed at a support temperature of 250 ° C. and an oxygen pressure of 1 × 10 ⁻³ Pa).

  Subsequently, the glass substrate on which the ITO film was formed was etched by a wet method to form electrode patterns, that is, conductive and non-conductive regions. Specifically, after masking portions other than the non-conductive region with a resist, the ITO film in the non-conductive region portion (exposed portion) was removed by immersion in a 25% hydrochloric acid aqueous solution. Thereafter, the resist was removed by immersion in a 1.5% sodium hydroxide nest solution, followed by washing with water and drying.

  The lead-out electrode was formed by printing a silver paste film with a thickness of 5 μm and firing at 130 ° C. for 60 minutes.

  Further, a dot spacer 35 was formed on the transparent electrode 34. After the ITO film was formed, the dot spacers were formed into a pattern on the ITO film by a photolithography process using an acrylic resist uniformly in a circular shape with a size of 30 μm and a thickness of 6 μm and an interval of 5 mm.

  Further, after forming the dot spacers 35, as shown in FIG. 1, the sealing material 36 was printed on the periphery of the lower substrate 32 with a width of 1.5 mm by the screen printing method. An epoxy resin adhesive was used. The sealing material includes a spacer member so that the upper and lower substrates can be held at a required interval.

  On the other hand, as shown in FIG. 2, a transparent electrode 33 and lead-out electrodes 37a and 37b were formed in the same manner on the upper substrate 31 made of a transparent film made of a polyethersulfone resin having a thickness of 125 μm, similarly to the lower substrate 32.

  Next, as shown in FIG. 6A, the upper substrate 31 is overlaid with the lower substrate 32 on which the sealing agent 36 is printed facing down. At this time, the transparent electrode 34 formed on the lower substrate 32 and the transparent electrode 33 formed on the upper substrate 31 are disposed so as to face each other.

Next, the stacked upper and lower substrates 31 and 32 were set on a jig for adhesion and curing, and held at a heating temperature of 90 ° C. and a pressure of 0.5 kg / cm ² for 5 minutes, and the sealing material was cured and dried. Furthermore, once the pressure is released, and then again held at 150 ° C. with a pressure of 0.2 to 0.25 kg / cm ² for 60 minutes, gradually cooled, and adjusted and cured so that the distance between the upper and lower substrates is about 10 μm. It was. Then, the opening 36a of the sealing agent shown in FIG. 5 was sealed. The touch panel was manufactured by the above manufacturing process.

  Next, this touch panel was transferred to an atmospheric pressure plasma CVD apparatus, and an antifouling layer was formed on the outer surface of the upper substrate.

(Touch panel 2)
An antifouling layer was formed on the upper substrate side of the touch panel produced above using an apparatus according to the vacuum vapor deposition apparatus described in JP-A No. 11-71665 (shown in FIG. 10).

  In the vacuum vapor deposition apparatus described in JP-A-11-71665, the web transport of the vapor deposition source is carried out using a plain weave impregnated with the vapor deposition source, but this is used not in the web but in a normal vapor deposition boat.

  That is, a solution KP801M (manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by diluting fluoroalkylsilazane with metaxylene hexafluoride to 3% by mass is impregnated into a plain fabric of alumina fiber and dried to produce an alumina fiber-impregnated carrier. Used as a deposition source for a deposition boat.

  In the vacuum deposition apparatus, the touch panel was set such that the deposition surface was the upper substrate side surface of the touch panel.

A predetermined amount of the vapor deposition source obtained by the impregnation was put in a vapor deposition boat, and the vacuum chamber was evacuated to 10 ⁻⁴ Torr or less. Incidentally, the sealing of the touch panel was not performed completely at this time, so that the pressure difference between the inside and outside of the panel did not occur. Thereafter, the vapor deposition boat was heated to 360 ° C. to evaporate, and vapor deposition was performed until the film thickness reached 30 nm. Then, after cooling slowly and releasing pressure reduction gradually, it sealed enough. This produced the touch panel 2 in which the antifouling layer was formed on the surface of the touch panel substrate.

(Touch panel 3)
The prepared touch panel is placed on a gantry so that the upper substrate side is on the top, and a coating solution obtained by diluting the following compound 1 with isopropyl alcohol on the outer surface so that the average dry film thickness is 30 nm. The film was coated with a wire bar so that the wet film thickness was 15 μm, dried, and then heat treated at 90 ° C. for 5 hours, and an antifouling layer was formed on the outer surface of the upper substrate by a coating method.

Compound 1: CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃
The touch panel in which the antifouling layer was produced by the coating method as described above was designated as touch panel 3.

(Touch panel 4)
By using the plasma discharge processing apparatus shown in FIG. 8, an antifouling layer was laminated on the outer surface of the touch panel produced above on the upper substrate side using the following mixed gas for forming an antifouling layer so as to have a thickness of 30 nm. The high frequency power source used here applied a discharge power of 0.5 W / cm ² at a high frequency power source of 50 kHz manufactured by Shinko Electric. The composition of the mixed gas is as follows.

<Mixed gas>
Noble gas (argon) 98.7% by volume
Thin film forming gas (perfluorooctylethyltriethoxysilane, manufactured by Toray Dow Corning Silicone Co., Ltd., AY43-158E) 1.3% by volume
The produced touch panel was designated as touch panel 4.

(Touch panel 5)
An antifouling film was formed on the outer surface on the upper substrate side of the produced touch panel using an atmospheric pressure plasma discharge treatment apparatus shown in FIG.

<Production of electrode>
The electrode is a titanium alloy with a length of 50 mm, a width of 600 mm, and a height of 50 mm, and a wall thickness of 10 mm (hollow jacket). Further, alumina ceramic is sprayed on the surface constituting the discharge space of the electrode until it reaches 1 mm. After coating, a coating solution in which an alkoxysilane monomer was dissolved in an organic solvent was applied to the alumina ceramic coating, dried, and then heated at 150 ° C. to perform a sealing treatment to form a dielectric. The film thickness of the dielectric was 1 mm, and the portion of the electrode not covered with the dielectric was connected to a high frequency power supply or grounded by ground. The gap between the gas discharge port and the base material was 10 mm.

The electrode gap was set to 1 mm so as to face each other in parallel, and the A2 and B3 were installed as the first power source and the second power source, respectively. The frequency of the first power source is 5 kHz, the high frequency voltage is 12 kV / mm, the frequency of the second power source is 13.56 MHz, the high frequency voltage is 0.8 kV / mm, the power (output density) of the first electrode is 1 W / cm ² , Atmospheric pressure plasma treatment was performed at a power of 2 electrodes of 10 W / cm ² .

  The following was used as the mixed gas. Similarly to the touch panel 4, the touch panel 5 was manufactured by setting the film thickness of the antifouling layer to 30 nm.

<Mixed gas>
Noble gas (argon) 98.7% by volume
Thin film forming gas (perfluorooctylethyltriethoxysilane, manufactured by Toray Dow Corning Silicone Co., Ltd., AY43-158E) 1.3% by volume
(Touch panel 1)
Using a vacuum vapor deposition apparatus described in JP-A-11-71665 (shown in FIG. 10), a transparent film made of a polyethersulfone resin having a thickness of 125 μm as an upper substrate (width 500 mm, thickness 100 μm, length 500 m) Roll) was continuously processed to form an antifouling layer on one side.

  That is, a solution (KP801M (manufactured by Shin-Etsu Chemical Co., Ltd.)) in which the fluoroalkylsilazane is diluted to 3% by mass with meta-xylene hexafluoride is impregnated into a plain fabric of alumina fibers having a width of 300 mm, a thickness of 2 mm, and a length of 5 m. It was made to dry and it was set as the ribbon-like impregnation support | carrier as a vapor deposition source (22).

A vapor deposition source (42) as a ribbon-like impregnated carrier produced by impregnating alumina fiber with KP801M (manufactured by Shin-Etsu Chemical Co., Ltd.) and a polyethersulfone film as a substrate to be treated (49) are wound up and vacuum-deposited. The vacuum chamber (40) was evacuated to 10 ⁻⁴ Torr or lower. Thereafter, the ribbon-like impregnated carrier was evaporated by contacting with a heat roller as a heating source (43) preliminarily heated to 360 ° C. while being fed at 5 cm / min using an evaporation source feeding mechanism (45). The traveling speed of the film-like substrate (49) at this time was 5 m / min.

  As in the production of the touch panels 2 to 5, except that a polyethersulfone film having an antifouling layer formed in this manner is used as the upper substrate, as shown in FIGS. The lead electrodes 37a and 37b are sequentially formed, and the lower substrate similar to the above in which the transparent resistance film 34, the lead electrodes 38a and 38b, the dot spacer 35, and the sealing material 36 are sequentially formed, and the touch panel 2 are manufactured. The touch panel 1 was manufactured by bonding and curing under the same conditions as those of the touch panel on which the antifouling layer used in the above was not formed, and adjusting and sealing the substrate interval.

  About each obtained touch panel, the contact angle with respect to the water of the upper substrate surface was measured, and durability was evaluated.

(Measurement of contact angle)
About each produced touch panel sample 1-5, the contact angle with respect to the water of the antifouling film surface is measured in 23 degreeC and 55% environment using Kyowa Interface Science company contact angle meter CA-W immediately after preparation. did. In addition, the measurement was performed at 10 locations at random and the average value was obtained.

  Next, the following forced wear treatment was performed to evaluate the durability.

<Forced wear treatment>
Each optical film surface (antifouling layer coated surface side) is rubbed 10 times with a wear test group HEIDEN-14DR using a commercially available gauze under a load of 40 kPa and a moving speed of 10 mm / min (wear treatment). Then, under the same conditions, the contact angle of the antifouling film surface with water was also measured. The measurement was performed at 10 random locations as described above, and the average value was obtained.

  The above results are shown in Table 1.

  According to Table 1, the initial contact angle with respect to water immediately after the production is not greatly changed by any method, but the contact angle after the forced wear treatment is large on the panel surface after the panel production. The antifouling film formed by the atmospheric pressure plasma method shows no change and high durability.

Example 2
(Production of liquid crystal panel 1)
The liquid crystal panel shown in FIGS. 3 and 4 was produced.

  In the figure, an ITO film was prepared by the following method so that the thickness of each glass substrate to be the glass substrates 4a and 4b of the liquid crystal cell 2 was 100 nm. A glass substrate having a thickness of 0.7 mm was used.

To 2.22 g of 2-methoxymethanol, 0.4 g of monoethanolamine, 3.8 g of indium acetate, and 0.16 g of Sn (OC ₄ H ₉ ) ₄ were added, and the mixture was stirred and mixed for 10 minutes. The substrate was coated with a wire bar. After coating, it was heated at 120 ° C. for 8 hours using an electric furnace to form a tin-doped indium oxide film (80 nm) on the glass substrate.

  Further, an ITO thin film (100 nm) was formed as a transparent electrode on the other surface by the same method. After the ITO film is formed, the ITO film to be a transparent electrode is patterned by a photolithography method using a resist to form a wiring electrode in each pixel, and a wiring with a flexible connector is formed thereon. An alignment film was formed. Next, the two glass substrates 4a and 4b are fixed by using a sealing material so that the alignment films face each other at a fixed interval, and a liquid crystal material mixed with polystyrene beads as a spacer agent is enclosed. Then, the liquid crystal cell was formed by fixing with a sealing material. As the sealing material, an ultraviolet curable epoxy resin was used.

  Next, as shown in FIG. 4, the front and rear metal frames (made of copper) and the ITO film were sandwiched and fixed so that the ITO film was in close contact, and a liquid crystal panel was produced. The ITO film formed on the outer surface of the liquid crystal cell thus formed conducts with the metal frame and forms an antistatic layer. This was designated as a liquid crystal panel 1.

(LCD panel 2)
Next, a glass substrate similar to the liquid crystal panel 1 is used, but an ITO film serving as a transparent electrode of the liquid crystal cell is formed, but a glass substrate not forming an ITO film serving as an antistatic layer on the opposite surface is used. A liquid crystal panel was prepared in the same manner as described above. As a result, a liquid crystal panel in which an ITO film serving as an antistatic layer was not formed on either the light source light emitting side or the incident side was obtained.

  An antistatic layer was formed on both surfaces of the liquid crystal panel using the produced non-antistatic liquid crystal panel using the following film forming method.

  An ITO film was formed on the outer surface of the liquid crystal panel having no ITO film on the produced outer surface by the following method using a wire bar.

<ITO film forming method>
To 22.2 g of 2-methoxymethanol, 0.4 g of monoethanolamine, 3.8 g of indium acetate and 0.16 g of Sn (OC ₄ H ₉ ) ₄ were added and mixed with stirring for 10 minutes. Using the obtained liquid, it apply | coated using the wire bar on the glass substrate surface of both surfaces of a liquid crystal panel. After the application, it was heated at 120 ° C. for 8 hours using an electric furnace to form a tin-doped indium oxide film on the glass substrate.

  As a result, a panel 2 was obtained in which an ITO film (80 nm) was formed as an antistatic layer on the outer surface of either the light emitting side or the light incident side of the liquid crystal panel.

(Liquid crystal panel 3)
An ITO film was formed on the outer surface and both surfaces of the liquid crystal panel on which the ITO film was not formed on the outer surface used to produce the panel 2 by using atmospheric pressure plasma treatment.

  As the plasma discharge apparatus, an apparatus having a parallel plate type electrode as shown in FIG. 8 was used. The liquid crystal panel was placed between the electrodes, and a mixed gas was introduced to form a thin film. Until the ITO film having a thickness of 80 nm was formed on both surfaces of the liquid crystal panel, the medium for transporting was moved back and forth, and processing was performed by appropriately changing the processing surface, whereby the liquid crystal panel 3 was produced.

  In the plasma discharge device shown in FIG. 8, as a ground electrode, a 200 mm × 200 mm × 2 mm stainless steel plate is coated with a high-density, high adhesion alumina sprayed film, and then tetramethoxysilane is coated. A solution diluted with ethyl acetate is applied, dried, cured by ultraviolet irradiation and sealed, and the surface of the dielectric thus coated is polished, smoothed, and processed to have an Rmax of 5 μm. It was. As the application electrode, an electrode obtained by coating a dielectric with a dielectric on a hollow square pure titanium pipe under the same conditions as the ground electrode was used. A plurality of application electrodes were prepared and provided to face the ground electrode to form a discharge space.

Moreover, as a power source used for plasma generation, a high frequency power source JRF-10000 manufactured by JEOL Ltd. was used, and 5 W / cm ² of power was supplied at a frequency of 13.56 MHz.

  A mixed gas having the following composition was passed between the electrodes to form a plasma state, and the glass substrate was subjected to atmospheric pressure plasma treatment to form a tin-doped indium oxide film on the glass substrate.

(Mixed gas composition)
Discharge gas: Helium 98.5% by volume
Thin film forming gas 1: Oxygen 0.25% by volume
Thin film forming gas 2: 1.2% by volume of indium acetylacetonate
Thin film forming gas 3: 0.05% by volume of dibutyltin diacetate
(Liquid crystal panel 4)
An anti-static layer made of an ITO film was formed on the outer surface of a liquid crystal panel having no ITO film on the surface used for producing the panel 2 by the jet type plasma discharge treatment apparatus shown in FIG.

  As shown in FIG. 9, the plasma discharge processing apparatus has a gap between the processing space 214 between the bottom surfaces (upper and lower sides of the paper) of the counter electrodes (211 and 212) and the base material on the movable frame (omitted). It was set to 1.5 mm.

  A first power source 221 was connected to the first electrode 211, and a first filter 223 was installed therebetween. The first filter 223 is made difficult to pass the current from the first power supply 221 and the current from the second power supply 222 is made easy to pass. The second electrode 212 is connected to the second power supply 222, A second filter 224 was installed. The second filter 224 is provided with a filter that makes it difficult for the current from the second power supply to pass therethrough and facilitates the passage of the current from the first power supply 221. Each power source and each filter were grounded to earth.

The electrode gap between the first electrode 211 and the second electrode 212 is set to be 1 mm in parallel, and the frequency of the first power source is 5 kHz, the high frequency voltage is 12 kV / mm, and the frequency of the second power source is the first power source and the second power source, respectively. Is 13.56 MHz, the high frequency voltage is 0.8 kV / mm, the power (output density) of the first electrode is 7 W / cm ² , the power of the second electrode is 7 W / cm ² , and the following mixed gas G is supplied to the discharge space Then, the discharge is performed, the thin film forming gas is excited in the discharge space 213 and blown out in the form of a jet, the surface of the liquid crystal panel is exposed to the plasma mixed gas G °, and the movable platform is reciprocated until the film thickness reaches 80 nm. An ITO film was formed on the surface of the liquid crystal panel. It was formed on both sides of the panel in the same manner as the liquid crystal panel 3. The discharge start voltage of the mixed discharge gas of nitrogen and oxygen was 3.8 kV / mm.

<Mixed gas>
Thin film forming gas 1: tris (2,4-pentanedionate) indium
0.115% by volume
Thin film forming gas 2: Dibutyldiacetoxytin 0.0045% by volume
Additive gas (reducing gas): Hydrogen gas 0.23 vol%
Nitrogen gas 95.1% by volume
Oxygen gas 4.5% by volume
Thus, the liquid crystal panels 1-4 by which the transparent conductive film (ITO film | membrane) was formed in the surface side were each produced.

(Forced deterioration processing)
About each produced liquid crystal panel, after measuring the surface specific resistance (ohm / cm < ² >) of a display surface, each liquid crystal panel was left to stand in the environment of 60 degree | times and 95% RH for 2 weeks, respectively (forced deterioration process). Thereafter, the surface specific resistance was measured again. Table 2 shows the results. The measurement of the surface specific resistance was as follows.

<Surface specific resistance>
It measured using the terraohm meter model VE-30 by Kawaguchi Electric Co., Ltd. The electrodes used for the measurement were measured by placing two electrodes (the part in contact with the sample is 1 cm × 5 cm) in parallel with an interval of 1 cm, contacting the liquid crystal panel sample measurement surface with the electrodes, and measuring the measured values. The value multiplied by 5 was defined as the surface resistivity Ω / cm ² .

  The above results are shown in Table 2.

  As described above, it can be seen that the transparent conductive film formed using the atmospheric pressure plasma CVD process after the panel formation according to the method of the present invention is less deteriorated as an anti-static layer.

It is sectional drawing which shows the outline of a structure of a liquid crystal display element. It is the schematic which shows the structure of a liquid crystal projector. It is the schematic of the front of a liquid crystal panel. It is the schematic of a liquid crystal panel cross section. It is a figure for demonstrating the structure of a touchscreen. It is sectional drawing which shows the structure of a touchscreen. It is sectional drawing which shows an example of the touchscreen in which the pollution protection layer was formed. It is the schematic which shows an example of an atmospheric pressure plasma discharge processing apparatus. It is the schematic which shows another example of a plasma discharge processing apparatus. It is the schematic of the vacuum evaporation system used in the Example.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Liquid crystal panel 2 Liquid crystal cell 3 Metal frame 4a, 4b Glass substrate 5 Display area 7 Transparent electrically conductive film 17a, 19b, 17c Liquid crystal display device 20 Base | substrate 22, 22a, 22b Polarizing plate 26 Liquid crystal panel 31 Upper substrate 32 Lower substrate 33, 34 Transparent electrode 35 Dot spacer 37a, 37b, 38a, 38b Lead electrode 36 Sealing material 40 Vacuum tank 42 Deposition source 43 Heat source 44 Deposition roll 45 Deposition source feed mechanism 46 Unwinding mechanism 48 Winding mechanism 49 Substrate 101 Plasma discharge Processing vessel 102 Processing chamber 102A Inlet 102B Outlet 103, 104 Electrode 105 High frequency power source 106 Ground 115 Depressurizing means 211 First electrode 212 Second electrode 221 First power source 222 Second power source 120, 200 Plasma discharge processing apparatus

Claims (4)

A thin film forming method comprising forming a thin film on at least one surface on the outer surface side of a substrate having a space containing a gas or a liquid therein by atmospheric pressure plasma treatment. The atmospheric pressure plasma treatment is characterized in that a thin film forming gas is introduced into a discharge space and excited to form an indirect excitation gas, and then the substrate is exposed to the indirect excitation gas to form a thin film on the substrate. The thin film forming method according to claim 1. It was manufactured by forming a thin film on at least one surface on the outer surface side of a substrate having a space containing a gas or a liquid inside by the thin film forming method according to any one of claims 1 to 3. Goods to be. The article according to claim 3, wherein the substrate having a space in which a gas or liquid is contained constitutes a resistive touch panel or a liquid crystal display device.

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