JP4871846B2 - Film with transparent conductive film for touch panel and touch panel using the same - Google Patents

Description

  The present invention relates to a film with a transparent conductive film for a touch panel and a touch panel using the film, and particularly relates to a technique for improving light resistance and strength characteristics of the film.

In electronic devices such as personal digital assistants (PDAs), notebook personal computers, OA devices, medical devices, and car navigation systems, touch panels for combining these displays with input means are widely used.
A common touch panel is, for example, a resistive film type touch panel disclosed in Patent Document 1, and has a pair of transparent conductive films in which a transparent electrode such as ITO is formed as a transparent conductive film on one side of a transparent planar member. It has a configuration in which films are arranged to face each other at a predetermined interval. In use, the image display of the display is transmitted through a display surface such as an LCD (liquid crystal display).

  The transparent planar member in the touch panel is partially deformed by being pressed by an input means such as a finger or a stylus pen from the user, and input is achieved by contacting the other film. Therefore, in order to give the base film of the transparent planar member the necessary input resistance (keying durability), the good strength of the cyclic olefin resin such as polyethylene terephthalate (PET), polycarbonate (PC), or norbornene. A transparent film material is used.

Further, in the base film, the main surface on which the transparent electrode is formed has, for example, a hard coat (HC) layer, a first refraction layer, and a second refraction layer for the purpose of ensuring performance such as predetermined translucency and durability. A composite layer is formed by laminating layers and a transparent conductive film in the same order.
Japanese Patent Laid-Open No. 2003-197035 JP 2000-89914 A JP 2003-54951 A Japanese Patent No. 3510698 Japanese Patent Laid-Open No. 2005-42024

However, the conventional film with a transparent conductive film does not have excellent adhesion between the base film and the composite layer or between the layers in the composite layer, and there is a problem of peeling in some cases.
That is, each layer constituting the film with a transparent conductive film is composed mainly of an organic material or an inorganic material, but due to the compatibility between these materials, chemical characteristics, surface characteristics of the film, etc. In addition, uniform adhesion is difficult to obtain.

  In the resistive touch panel, the transparent conductive film is repeatedly deformed by pressing (keystroke) and restored by releasing the pressing force every time a user inputs. For this reason, due to variations in mechanical strength, chemical characteristics, and the like of each layer, separation may gradually occur between the layers. For example, there is a problem that the transparent conductive film and the second refractive layer are peeled off and the touch panel performance is deteriorated. This problem may also occur when a transparent conductive film is formed directly on the hard coat layer by a thin film method.

  Furthermore, when the key is repeatedly pressed by the user, fine cracks (so-called microcracks) may occur in the hard coat layer over time. The microcrack is inevitably generated due to the properties of the hard coat layer, and is not so problematic during normal use. However, when the adhesion between the hard coat layer and the base film is low, When the touch panel is attached to or detached from the display, the microcracks may be damaged by external stress due to external stress, or the hard coat layer may be peeled off from the base film.

Furthermore, if the touch panel is used for outdoor applications, navigation systems, PDAs, and the like, it is more susceptible to the effects of sunlight, ultraviolet irradiation, high temperature, and high humidity environments than indoor applications. In this case, each layer constituting the touch panel may be affected by the above-described influence, causing a chemical change and peeling between adjacent layers.
Moreover, in the manufacturing process of a touch panel, various processes using wet methods, such as a wet etching method, may be given with respect to the film with a transparent conductive film for touch panels. When performing such a process, for example, an alkaline liquid may adhere to the surface of any layer and cause a chemical change to cause separation between adjacent layers. For this reason, in order to exhibit the stable touch panel performance, it is also important to have predetermined chemical resistance.

In addition, the transparent conductive film generally has a property that the resistance value increases as the humidity or temperature increases. In this case, accurate input information (mainly input position information) cannot be obtained due to unnecessary changes in the resistance value, which may adversely affect the performance of the touch panel. For this reason, there is a need for a film with a transparent conductive film that can be driven satisfactorily even under high temperature and high humidity environments.
Thus, in the film with a transparent conductive film for touch panels, there is still some room for improvement.

The present invention has been made in view of the above problems. As a first object, the present invention can be manufactured at a relatively low cost, and can prevent peeling and exhibit stable touch panel performance over a long period of time. A film with a transparent conductive film for a touch panel and a touch panel using the film are provided.
Moreover, as a second object, in addition to the above effects, a film with a transparent conductive film for a touch panel that can be expected to maintain stable touch panel performance by exhibiting excellent wet heat durability under a high temperature and high humidity environment. I will provide a.

  In order to solve the above problems, the present invention provides a transparent base film in which a composite layer in which a hard coat layer, a first refractive layer, a second refractive layer, and a transparent conductive film are laminated in the same order is disposed on at least one surface of a transparent base film. A film with a conductive film, wherein the hard coat layer is added so that inorganic fine particles are dispersed or combined, and the first refractive layer includes a composite material containing an organic component and an inorganic component, and a particulate inorganic filler The concentration of the inorganic component is inclined and oriented from the first refractive layer side to the second refractive layer side, and the second refractive layer is made of a material containing silicon oxide. .

Here, the particulate inorganic filler can be composed mainly of at least one selected from the group consisting of TiO ₂ , SiO ₂ , Al ₂ O ₃ , and ZrO ₂ .
Moreover, when the film with a transparent conductive film is placed in a second state at a humidity of 90% and a temperature of 120 ° C. for 2 hours from the first state at a humidity of 60% and a temperature of 25 ° C., the film immediately before the previous placement is performed. The ratio of the resistance value of the transparent conductive film immediately after the above placement to the resistance value of the transparent conductive film can be set to 2 or less.

In order to achieve this condition, it is preferable to use one containing one or more compounds containing at least any one of Si, Ti, Al, and Zr as the inorganic component of the composite material. It is.
The hard coat layer contains at least one of inorganic atoms of Si, Ti, Al, and Zr. The total number of inorganic atoms (herein simply referred to as “the number of inorganic atoms”) and the number of carbon atoms. In the case where the ratio is represented by the number of inorganic atoms / number of carbon atoms, the surface of the hard coat layer facing the first refractive layer can be configured so that the ratio is adjusted to 1/750 or more and 1/2 or less. .

Furthermore, the surface of the hard coat layer facing the first refractive layer can be made smooth.
The inorganic fine particles of the hard coat layer may be made of any material of SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ O ₃ so as to have an average particle diameter of 1 nm to 200 nm.
Furthermore, in this invention, an uneven | corrugated process can also be given with respect to the surface of the said hard-coat layer which faces a said 1st refractive layer.

The inorganic fine particles of the hard coat layer may be made of any material of SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ O ₃ so as to have an average particle diameter of 0.5 μm or more and 5 μm or less. .
Here, at least one of the second refractive layer and the transparent conductive film may be formed by a thin film method.

  Furthermore, the present invention is a touch panel in which a pair of substrates with a transparent conductive film are arranged to face each other at a predetermined interval, and at least one of the substrates with a transparent conductive film is any one of the transparent conductive films for a touch panel according to the present invention. It is a film with attachment, It was set as the structure by which the said composite layer of the said film is arrange | positioned so as to oppose the other board | substrate with a transparent conductive film.

  According to the film with a transparent conductive film of the present invention having the above-described configuration, the hardness of the outermost surface portion is more than the hardness of the other first refractive layer portion due to the inorganic component concentrated on the outermost surface of the first refractive layer. Can also be high. As a result, the difference in stress between the outermost surface of the first refractive layer and the second refractive layer disposed in contact with the first refractive layer is suppressed, and as a result, in the film, the internal generated in the composite layer at the time of keystroke Stress can be reduced.

In addition, since the inorganic component in the first refractive layer and the inorganic component (silicon oxide) in the second refractive layer have the same homogenous characteristics, affinity is exerted, so that the usage environment with a relatively large amount of UV irradiation is used. Even so, an improvement in adhesion between the two layers and an effect of preventing peeling can be expected.
Furthermore, in the portion of the first refractive layer facing the base film, the affinity for the hard coat layer containing the ultraviolet curable resin material is ensured by the abundant organic components, so the hard coat layer and Good adhesion can be maintained even between the first refractive layers. Moreover, since such a 1st refractive layer can be produced with the material structure similar to the past, there also exists a merit which can be manufactured at the cost similar to the past.

  Furthermore, the particulate inorganic filler dispersed in the first refractive layer interacts with each other via the second refractive layer, improving the affinity between the transparent conductive film and the first refractive layer as a total performance, peeling, etc. It has been experimentally found that the occurrence of this problem is suppressed. Due to this effect, durability of the composite layer itself is improved, and good touch panel characteristics can be expected over a long period of time. Furthermore, when a transparent conductive film is formed by the thin film method by adding the particulate inorganic filler, it has been confirmed that it can be crystallized more rapidly in a relatively low temperature environment than conventional methods. The effect of suppressing deterioration of each resin material can also be expected.

  Further, when at least one of the second refractive layer and the transparent conductive film is formed by a thin film method, there is no need to use a wet method or the like in the film formation process. For this reason, even if an unnecessary alkaline liquid adheres to the surface of any one of the layers, generation of a chemical reaction by the liquid can be avoided, so that damage to the film with a transparent conductive film can be effectively prevented. In addition, this damage prevention effect can avoid the unstable resistance value of the transparent conductive film, and thus has an advantage of maintaining good conductive characteristics over time.

Therefore, since the film with a transparent conductive film of the present invention can effectively prevent peeling of each layer constituting the composite layer, even when this is applied to a touch panel, good keystroke durability / resistance Performance such as chemical properties can be expected.
In order to achieve the numerical range of the resistance value ratio of the transparent conductive film in the transition from the first state to the second state, Si, Ti, Al, Zr are included in the inorganic component of the composite material of the second refractive layer. By using one or more compounds containing at least one of these elements (inorganic atoms), the resistance value of the transparent conductive film can be prevented from increasing even under high temperature and high humidity environments, and user input position information Stable touch panel input characteristics can be achieved without mistakes. Such good wet heat durability exhibits a great advantage in use in a car navigation system, for example.

Embodiments and examples of the present invention will be described below, but the present invention is naturally not limited to these forms, and may be appropriately modified and implemented without departing from the technical scope of the present invention. be able to.
<Embodiment 1>
(Configuration of film with transparent conductive film)
FIG. 1 is a cross-sectional view showing a laminated structure of a film 1 with a transparent conductive film in the first embodiment.

The film 1 with a transparent conductive film is formed by disposing a composite layer 4 on one side of a transparent base film 40. The composite layer 4 is configured by laminating an HC (hard coat) layer 41, a middle refraction layer 42, a low refraction layer 43, and an ITO film 13 in this order from the base film 40 side.
The base film 40 is a transparent resin film excellent in keystroke durability. Examples of materials include PET, PC, “Arton” manufactured by JSR, “Zeonor” manufactured by Nippon Zeon.

The base film 40 may be provided with irregularities on at least the surface (upper surface in FIG. 1) facing the HC layer 41. As a result, the adhesion with the HC layer 41 is increased, and the pressing force from the direction perpendicular to the surface of the film 1 is dispersed at the time of input by the user, thereby providing keystroke durability and improving mechanical strength. Can do.
Although not shown in FIG. 1, an HC layer is provided on the lower surface side of the base film 40 in order to ensure the operability (writing property) of the user's finger or stylus pen as input means and the wear resistance of the surface. An HC layer similar to 41 may be provided.

The HC layer 41 is a transparent inorganic fine particle (here, silica) of at least one of SiO ₂ , TiO ₂ , ZrO ₂ , and Al ₂ O ₃ having a particle diameter of 1 nm to 200 nm in an ultraviolet curable resin having a thickness of 1 μm to 10 μm. (SiO ₂ ) particles 411) are dispersed or composited.
The HC layer 41 has a fine uneven region 412 mainly for the purpose of improving adhesion with the middle refractive layer 42 and ensuring antiglare (AG) characteristics. The uneven region 412 can be manufactured using relatively large inorganic fine particles of at least one of SiO ₂ , TiO ₂ , ZrO ₂ , and Al ₂ O _{3 having} a particle size of 0.5 μm or more and 5 μm or less. Further, it can be formed by a process such as embossing or etching, or spraying on the surface using the inorganic fine particles.

  In addition, the uneven | corrugated | grooved area | region 412 is not an essential component, but the upper surface of the HC layer 41 can be made into a smooth surface, and the transparency of a film can also be improved. Here, the HC layer 41 contains at least one inorganic atom of Si, Ti, Al, and Zr, and the number of inorganic atoms (the inorganic atoms described above) on the outermost surface facing the middle refractive layer 42. The atomic ratio represented by the number of carbon atoms / number of carbon atoms is set to 1/750 or more and 1/2 or less. This ratio is an important threshold for ensuring good adhesion to the middle refractive layer 42 made of an organic / inorganic composite material containing the titanium oxide sol 420 as an inorganic component.

The ratio of the number of inorganic atoms / number of carbon atoms in the HC layer 41 specifically refers to a value measured by X-ray photoelectron spectroscopy (referred to as ESCA or XPS).
The middle refraction layer 42 is a first refraction layer in the film 1 with a transparent conductive film, and on the outermost surface of the HC layer 41, a compound containing at least one of Si, Ti, Al, and Zr is 1 An organic / inorganic composite material containing an inorganic component (here, titanium oxide sol 420) containing two or more species is contained, and a particulate inorganic filler having a predetermined particle size is dispersed.

The particulate inorganic filler can be composed of at least one of TiO ₂ , SiO ₂ , Al ₂ O _{3, and} ZrO ₂ . The average particle diameter is not particularly limited, and can be, for example, about 10 nm to 70 nm. The layer thickness is set to 40 nm or more and 90 nm or less.
The refractive index of the middle refractive layer 41 is set to 1.6 to 1.9, which is higher than the refractive index of the low refractive layer 43 described later. The refractive index of a single titanium oxide is about 2.2 to 2.4, and decreases to a range of 1.6 to 1.9 by combining with an organic material. A preferable light transmission characteristic can be realized. Here, the inorganic in the composite material is a condensate (sol) of several to several dozens. For this reason, it can be distinguished in size from the particulate inorganic filler.

Here, in the middle refraction layer 42, as a characteristic part of the present invention, the concentration of the inorganic material is increased from the HC layer 41 side toward the low refraction layer 43 side along the thickness direction (so as to be inorganic rich). And the concentration of the organic material is decreased in the same order.
In this way, if the concentration distribution of the organic / inorganic component is tilted along the thickness direction of the middle refractive layer 42 and is symmetrically localized near both surfaces in the thickness direction of the layer 42, By the inorganic component concentrated on the outermost surface of the middle refractive layer 42, the hardness of the outermost surface portion can be made higher than the hardness of the other portions of the middle refractive layer 42. As a result, the difference in stress between the outermost surface of the middle refractive layer 42 and the low refractive layer 43 disposed in contact therewith is suppressed, and as a result, the generation of internal stress during keystroke is reduced. Further, when the inorganic component in the middle refractive layer 42 includes a Si component, the Si component and the Si component in the low refractive layer 43 have an affinity for each other. The adhesion between each other is not harmed.

  Further, in the middle refractive layer 42, by adding the particulate inorganic filler, the adhesion between the ITO film 13 and the low refractive layer 43 is improved, and an effect of suppressing the occurrence of problems such as peeling can be obtained. Although the details of the principle of the effect are unclear, the durability of the composite layer itself is improved by this effect, so that good touch panel characteristics can be expected to be maintained over a long period of time. Further, it has been confirmed that when the particulate inorganic filler is added, it can be easily crystallized at a relatively low temperature compared to the conventional case when the ITO film 13 is formed by a thin film method. Accordingly, when the annealing process is performed after the conductive film material is formed on the low refractive layer 43, the annealing process can be performed at a low temperature in a short time, so that the resin components such as the HC layer 41 and the base film 40 are kept under a high temperature condition. There is no exposure. Therefore, the ITO film 13 can be quickly crystallized, and the effect of suppressing the deterioration of each resin material due to heating is also exhibited, which is preferable.

From the above, when the film 1 is used for a touch panel, good keystroke durability can be imparted, and any peeling of the ITO film 13, the low refractive layer 43, and the middle refractive layer 42 is effective. Can be prevented.
On the other hand, the organic component concentrated on the lowermost surface of the middle refraction layer 42 can ensure the affinity with the HC layer 41 and maintain good adhesion. Therefore, even if a micro crack occurs in the HC layer 41, it is possible to effectively prevent the HC layer 41 from being broken and the middle refractive layer 42 from being peeled off from the HC layer.

In addition, when the Si component is contained in the middle refraction layer 42, good adhesion between the middle refraction layer 42 and the HC layer 41 is ensured by the affinity with the Si component contained in the HC layer 41. It is like that.
The low refraction layer 43 is a second refraction layer provided in the composite layer 5 and is formed by forming a SiO ₂ material by sputtering, and has a layer thickness of 15 nm or more and 35 nm or less. The refractive index of the low refractive layer 43 is set to 1.46, and the preferred range is 1.35 to 1.5.

  Here, the conventional low refractive layer 43 is generally formed by a sol-gel method using a solution in which material components are dispersed. The sol-gel method is one of the application methods, and is said to be efficient as a method for forming a film over a relatively large area, but there are some problems when used for manufacturing a film with a transparent conductive film for a touch panel. is there. According to the studies by the inventors, it has been found that a film formed by the sol-gel method may be dissolved again when an alkaline solution or the like used for etching is attached to the film surface. As described above, the film formed by the sol-gel method has a property that is not excellent in chemical resistance, and when the touch panel is used outdoors, the possibility that a liquid that is larger than neutrality adheres to the film surface is not low. In addition, it is relatively difficult to maintain thickness accuracy with the application method, and there is a problem in maintaining stable touch panel performance including appearance quality.

  On the other hand, in the present invention, the low refraction layer 43 is formed by using the sputtering method instead of the sol-gel method, thereby eliminating the risk of unnecessary solution components remaining in the low refraction layer 43 and the chemical resistance. The problem was fundamentally solved. Further, an unnecessary change in the resistance value of the transparent conductive film due to the solution is suppressed, and the optical characteristics can be controlled satisfactorily. Furthermore, compared to the coating method, the accuracy of film formation can be improved, and there is an advantage that appearance quality (color unevenness) can be suppressed when a laminated structure with other layers is formed.

  The ITO (Indium Tin Oxide) film 13 is an example of a transparent conductive film, and is a crystal formed by depositing In oxide by a thin film method (for example, a sputtering method, an electron beam method, a sulfur beam method, a vacuum deposition method, etc.). Transparent conductive film. Here, the surface resistance is 200 to 1 kΩ / sq. And a thin film having a thickness of 20 nm to 40 nm and a refractive index of about 2. Although not shown in FIG. 1, the ITO film 13 is actually formed with a predetermined electrode pattern having a stripe structure on the surface of the low refractive layer. Transparent conductive film materials include (antimony-added lead oxide, fluorine-added tin oxide, aluminum-added zinc oxide, potassium-added zinc oxide, silicon-added zinc oxide, zinc oxide-tin oxide system, indium oxide-tin oxide, tin oxide film) One or more selected from the above can be used.

Similarly to the low-refractive layer 43, the ITO film 13 is conventionally formed by a coating method using a paste in which a conductive material is dispersed in a binder. In the present invention, a transparent conductive film is formed by using a thin film method. It is devised to avoid the risk of solution components mixing into the membrane components.
In addition, “crystallinity” in the definition of the ITO film 13 refers to a film in which the [222] plane diffraction peak can be clearly confirmed in X-ray diffraction.

  Further, in Japanese Patent No. 3510698, a layer containing titanium oxide, zirconium oxide or the like is provided as a layer corresponding to the middle refractive layer 42 of the present application, and a layer formed by hydrolyzing an organosilicon compound thereon, a crystalline ITO film In this conventional technique, the concentration of the organic and inorganic components is not a gradient composition along the thickness direction of the layer, and a low refractive layer is formed by sputtering. This is different from the present invention in that it is not done. That is, in the present invention, by setting the organic / inorganic concentration to a gradient composition, the affinity with other layers positioned above and below the middle refraction layer 42 is increased, and the solvent component is not included in the low refraction layer. Since it imparts resistance, both techniques are clearly different in this respect as well.

<About the film production method>
Here, the example of a manufacturing method of the film with a transparent conductive film of this invention is demonstrated.
The following procedure can be mentioned as an example of the whole manufacturing method of the film 1 with a transparent conductive film in this Embodiment 1. FIG.
1. Production of HC layer Ultraviolet curing including particles (here, silica particles 411) composed of any of SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ O ₃ having a particle diameter of 1 nm to 200 nm on the base film 40 A mold resin material is applied and dried to remove the solvent. Thereafter, photo-radical polymerization is performed by UV irradiation using a high-pressure mercury lamp or the like to form an HC layer 41 having a thickness of about 1 μm to 10 μm.

Here, the dispersion of the inorganic fine particles (silica particles 411) in the HC layer 41 so that the ratio of the number of inorganic atoms / the number of carbon atoms on the outermost surface of the HC layer 41 is 1/750 or more and 1/2 or less. Adjust the degree of complexation.
Here, when silica particles 411 having a particle size of 1 nm to 200 nm are used, white turbidity due to visible light scattering does not occur, and transparency is not lost. Further, if silica particles 411 having a particle size of 0.5 μm or more and 5 μm or less are used, the uneven region 412 can be imparted to the HC41 layer, and the effect of improving the adhesion with the middle refractive layer 42, AG characteristics, and the like can be obtained.

As a structural example of the HC layer 41 formed by combining inorganic fine particles, for example, a layer structure made of a radiation curable resin composition having a predetermined composition described in Patent Document 5 can be used. .
In this layer structure, (A) silica particles having a polymerizable unsaturated group are arranged on the surface layer, (B) a radical polymerizable compound having two or more functional groups, and (C) at least an inorganic acid salt and an organic acid salt. Any salt and (D) the organic polymer which has a structural unit derived from alkylene glycol are comprised.

  The “silica particles having a polymerizable unsaturated group on the surface layer” of (A) include, for example, silica particles (Aa), a polymerizable unsaturated group, and an organic compound represented by the structural formula shown below (hereinafter referred to as “organic compound”). (Ab) ”).

[In the above structural formula, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
The silica particles (Aa) are preferably powdery or solvent-dispersed sol. In the case of a solvent-dispersed sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. The number average particle diameter of the silica particles (Aa) is preferably in the range of 0.001 μm to 2 μm, more preferably in the range of 0.001 μm to 0.2 μm, and particularly preferably in the range of 0.001 μm to 0.1 μm. However, it should be noted that if the number average particle diameter exceeds 2 μm, the transparency of the HC layer tends to be lowered or the surface condition when coated becomes worse.

Various surfactants and amines may be added to improve the dispersibility of the silica particles (Aa). The shape of the silica particles (Aa) may be any of a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, but a spherical shape is preferable.
The specific surface area of the silica particles (Aa) (by BET method using nitrogen) is preferably an 10~1,000m ² / g, more preferably 100 to 500 m ² / g.

These silica particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, an organic solvent dispersion of fine oxide particles that is commercially available as a solvent dispersion sol of the above oxide can be used directly. In particular, in applications requiring excellent transparency in the HC layer, it is preferable to use a solvent-dispersed sol of oxide.
Next, the organic compound (Ab) is preferably a compound having a silanol group or a compound that generates a silanol group by hydrolysis.

  The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited. An acrylamide group can be mentioned as a suitable example. These polymerizable unsaturated groups are structural units that undergo addition polymerization with active radical species.

  In addition, the structure of the chemical formula 1 included in the organic compound (Ab) specifically includes [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (= S) -NH-]. An organic compound (Ab) may have these structures individually by 1 type or 2 types or more. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — A configuration having at least one of the NH— groups is preferred.

When the organic compound (Ab) has the structure of Chemical Formula 1, characteristics such as excellent mechanical strength, adhesion to the substrate, and heat resistance can be imparted to the HC layer.
The organic compound (Ab) is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). Is preferred). Examples of such a silanol group-forming compound include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. An alkoxy group or an aryloxy group is bonded to a silicon atom. Bonded compounds, that is, alkoxysilyl group-containing compounds or aryloxysilyl group-containing compounds are preferred. The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the silica particles (Aa) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

  Preferable specific examples of the organic compound (Ab) include, for example, compounds represented by the following structural formula (2).

In the above structural formula, R ¹ and R ² may be the same or different, but are a hydrogen atom or a C1-C8 alkyl group or aryl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, An octyl group, a phenyl group, a xylyl group, and the like. p is an integer of 1 to 3.
Examples of the group represented by [(R ¹ O) pR ² _3-p Si-] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. be able to. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.

R ³ is a divalent organic group having a C1 to C12 aliphatic or aromatic structure, and may include a chain, branched, or cyclic structure.
R ⁴ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
R ⁵ is a (q + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.

Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. Moreover, q is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
The synthesis of the organic compound (Ab) used in the layer structure can be obtained, for example, by the method described in JP-A-9-100111.

  The amount of the organic compound (Ab) in the surface layer of the silica particles (Aa) is preferably 0.01% by weight or more, more preferably 100% by weight, with the total of the silica particles (Aa) and the organic compound (Ab) being 100% by weight. 0.1% by weight or more, particularly preferably 1% by weight or more. If it is less than 0.01% by weight, the dispersibility of the reactive silica particles (A) in the composition is not sufficient, and the resulting cured film may not have sufficient transparency and scratch resistance.

Moreover, the compounding ratio of the silica particles (Aa) in the raw material during the production of the reactive silica particles (A) is preferably 5 to 99% by weight, and more preferably 10 to 98% by weight.
The blending (content) amount of component (A) in the layer structure is preferably 5 to 90% by weight, with the total of components (A), (B), (C) and (D) being 100% by weight, 10 to 80% by weight is more preferable. When the blending (content) amount of the component (A) is less than 5% by weight, a high hardness HC layer may not be obtained. On the other hand, when the blending (content) amount of the component (A) exceeds 90% by weight, the film formability may be insufficient.

2. Production of Medium Refraction Layer On the HC layer 41 produced above, an organic / inorganic composite material containing particulate inorganic filler and TiO ₂ as an inorganic component is applied, and the first refractive layer has a thickness of 40 nm to 90 nm. A refractive layer 42 (with a refractive index of 1.6 or more and 1.9 or less) is formed. Here, a coating material having a gradient composition is used as the organic / inorganic composite material.

As a method for forming a layer having a specific gradient composition, for example, a solution in which an organic polymer compound having a coupling silicon-containing group is dissolved in an appropriate solvent such as alcohol, ketone, ether, and titanium alkoxide are used. Is mixed with a reaction solution obtained by hydrolytic condensation reaction in a specific solvent. As a result, the coupling silicon-containing group in the organic polymer compound is hydrolyzed and selectively reacted with the hydrolysis condensate of titanium alkoxide to obtain a coating agent for forming an organic / inorganic composite gradient film. It is done.
Next, a particulate inorganic filler is added to the obtained coating agent for forming an organic / inorganic composite gradient film to obtain the coating agent of the present invention. As the particulate inorganic filler, those prepared by a liquid phase method such as an alkoxide method or other gas phase methods can be used. These are dispersed, for example, by surface treatment in the same type of solvent as the coating agent for forming the organic / inorganic composite gradient film, and at the same time, the stability in the liquid and in the coating process is also maintained. Thus, the coating agent of the present invention can be obtained by adding to the coating agent for forming the organic / inorganic composite gradient film. When this is applied on the HC layer 41, it exerts an adsorbing ability with respect to the resin component substrate of the coating agent of the present invention, and an inclined structure is formed. Thereafter, the intermediate refractive layer 42 as the gradient composition layer is formed by heat drying.

3. Production of Low Refractive Layer A SiO ₂ film having a thickness of 15 nm or more and 35 nm or less is formed on the obtained middle refractive layer 42 by a sputtering method using an Si material under oxygen gas introduction conditions. As a result, a second refractive layer (low refractive layer) is obtained.
4). Production of ITO Film On the obtained low refractive layer 43, an In oxide material was formed by a sputtering method, and the surface resistance was 200Ω / sq. 1 kΩ / sq. Thereafter, a transparent conductive thin film (ITO film 13) having a thickness of 20 nm to 40 nm is formed. The crystal structure of the ITO film 13 is, for example, a film in which the SnO ₂ composition of the In ₂ O ₃ —SnO ₂ ceramic target is lowered (for example, the SnO ₂ composition is contained in 3 to 10 wt%) during film formation by the sputtering method. It can be obtained by forming a film by heating the substrate at a temperature of about 150 ° C.

The film with a transparent conductive film is completed by the above procedure.
As an example of an actual manufacturing method based on the above manufacturing steps, first, a PET film having a thickness of 188 μm and a width of 300 mm (“Cosmo Shine A4300” manufactured by Toyobo Co., Ltd.) is prepared as a base film.
Next, as a material for the HC layer 41, inorganic fine particles are added to “Desolite Z7524” manufactured by JSR Corporation so that the final composition is 43 wt%, and this is appropriately diluted with an organic solvent. Then, a final thickness of about 6 μm is formed on the surface of the base film 40 by a roll coating method.

Subsequently, as the middle refractive layer 42, an inorganic / organic gradient material using titanium alkoxide is prepared by adjusting the coating material so that the ratio of the solid content in the solid content is 40 wt%, and is formed by a roll coating method.
Next, as the low refractive layer 43, SiO ₂ is formed by sputtering.
An ITO film is formed on the transparent conductive film by a sputtering method.

The film with a transparent electrode film of the example is produced as described above.
(Composite material of the present invention)
In the film with a transparent conductive film 1 of the first embodiment, the titanium oxide sol 420, which is a condensate of titanium alkoxide, is used as the base material of the middle refractive layer 42. However, the composite material used for the middle refractive layer of the present invention is the same. It is not limited to. For example, as a component of the gradient material, an inorganic component containing two components of Ti and Si compound (a condensate having a repeating unit of MO as a main skeleton, where M is Ti and Si, and these are regular Alternatively, those bonded at random) can be used.

In addition, it is suitable for the content rate of Si compound in the inorganic component contained in the middle refraction layer to be set to 50 wt% or more, for example, in the range where the refractive index is 1.6 or more and 1.9 or less.
According to the middle refractive layer using the inorganic component having such a configuration, in addition to the effect of preventing peeling between the layers in the first embodiment, an effect of improving excellent wet heat durability can be obtained.
That is, in the film 1 with a transparent conductive film in which the SiO ₂ layer and the transparent conductive film are sequentially formed on the middle refractive layer containing the organic component, the resistance value distribution of the transparent conductive film in the film width direction is stabilized. In addition, the resistance value is prevented from increasing due to an increase in at least one of environmental humidity and environmental temperature, and drastically increases heat resistance (resistance that can suppress the increase in resistance value in response to temperature or humidity changes). Can be raised. Therefore, it is possible to realize a touch panel with high operation reliability without erroneous input position information by the user over a wide temperature / humidity range.

The wet heat durability of such a film with a transparent conductive film is, for example, in a touch panel that is assumed to be used in an environment of high temperature and high humidity (120 ° C., 90% in the test described later) such as use in a car navigation system. Even in such a severe environment, stable touch panel performance can be expected.
<Embodiment 2>
FIG. 3 is an assembly diagram showing a configuration example of an inner type resistive touch panel 2 (hereinafter referred to as “touch panel 2”) according to the second embodiment of the present invention and an LCD combined therewith. . FIG. 4 is a cross-sectional view of the touch panel 2.

As shown in FIGS. 3 and 4, the touch panel 2 includes a polarizing plate 11, an upper planar member 5A, a resistive film 13, a spacer 16, a resistive film 14, a wiring substrate 30, and a lower planar member 5B in order from the top. It becomes. Below the lower planar member 5B, the LCD main body 20 and the polarizing plate 21 which are the panel configuration are laminated in the same order, and the entire LCD touch panel is configured.
The display attached to the touch panel 2 is not limited to the LCD, and other types of display sulfur such as CRT and PDP may be used.

The touch panel 2 employs a so-called “4 wire system” input detection method and has a configuration called “FF inner type” in which film materials are used for both the planar members 5A and 5B. Here, the application to an in-car car navigation system is assumed.
The polarizing plates 11 and 21 are each composed of, for example, a dye-based linear polarizing plate having a thickness of 200 μm. One of the polarizing plates 11 is laminated on the surface of the upper planar member 5A as a feature of the inner type touch panel. Thereby, the effect | action which suppresses the reflected light quantity resulting from the visible light which injects into the inside of a touch panel to about half or less compared with the case where the said polarizing plate is not provided is made | formed.

  20 directly laminated on the lower planar member 5B is an LCD main body. This is a known TFT type LCD substrate, and constitutes a unit in which a transparent layer, a color filter, a liquid crystal molecular layer, a TFT substrate, and a transparent layer (not shown) are laminated in the same order from top to bottom. The LCD body 20 may be other than the TFT type, and is not limited to the above laminated structure. The polarizing plate 21 is laminated under the LCD main body 20.

  The resistance films 13 and 14 are respectively ITO (Indium Tin Oxide), antimony-added tin oxide, and fluorine-added tin oxide having a known resistance value (surface resistance) on the opposing surfaces of the upper planar member 5A and the lower planar member 5B. Resistive film (transparent conductive film) such as aluminum-added zinc oxide, potassium-added zinc oxide, silicon-added zinc oxide, potassium-added zinc oxide, zinc oxide-tin oxide, indium oxide-tin oxide, or other metal materials ). By using these materials to form a film by a method such as CVD, vacuum deposition, sputtering, or sulfur beam, the resistance films 13 and 14 having a predetermined area are uniformly formed on the surfaces of the planar members 5A and 5B. . Then, by providing a rib spacer 18 having a height of about 50 μm composed of an adhesive material, an adhesive sheet, a double-sided tape having an adhesive material layer on both surfaces, the resistance films 13 and 14 are usually opposed to each other at a constant interval. Has been placed.

  As an example of the film formation pattern of the resistance films 13 and 14, the resistance films 13 and 14 are formed in a rectangular shape on the opposing surfaces of the planar members 5A and 5B. The lead lines 131, 132, 141, and 142 are disposed along a pair of sides parallel to the y-axis or the x-axis of the formed resistance films 13 and 14, respectively, thereby forming xy orthogonal coordinates as a whole. To form. The lead wires 131, 132, 141, 142 are provided with electrode terminals 131a, 132a, 141a, 142a. Reference numeral 133 denotes a connection line for connecting the electrode terminal 132a and the lead wire 132.

  On the other hand, a flexible connector 30 is interposed between the resistance films 13 and 14 at a predetermined position. The flexible connector 30 includes a flexible substrate 301 made of a resin material such as PET or polyimide, and wirings 302 to 305 made of a material having good conductivity such as Au, Ag, Cu on the surface of the substrate. Become. Electrode terminals 302 a to 305 a are formed on the wirings 302 to 305.

The input detection principle (4-wire method) on the touch panel 2 in which the electrical wiring is made with the above configuration is as follows. First, a DC voltage of about 0 to 5 V is applied between the lead lines 131 and 132 along the y-axis during driving. When the input is made by the user, the position data in the y-axis direction is obtained using the lead lines 141 and 142 along the x-axis as voltage detection electrodes.
Next, voltage is applied between the lead lines 141 and 142 along the x-axis, and the lead lines 131 and 132 along the y-axis are used as voltage detection electrodes to acquire position data in the x-axis direction. Thereby, coordinate information of both xy is obtained. In the touch panel 2, such detection steps are alternately repeated to sequentially acquire input information from the user, and a function as a GUI (Graphical User Interface) is exhibited.

  The upper and lower planar members 5A and 5B are respectively composed of the planar members 5 (base film 40, HC layer 41, middle refractive layer 42, and low refractive layer 43 stacked in the same order as shown in FIG. A substrate with a transparent conductive film). At least the opposing surfaces of the upper and lower planar members 5A and 5B are subjected to fine unevenness treatment (non-glare treatment) using a method such as thermocompression bonding of a carrier having a desired surface roughness during film production. Thus, the occurrence of Newton rings in the planar members 5A and 5B arranged in close proximity to each other is effectively suppressed, and the visibility is improved. Note that the non-glare process may be appropriately performed as necessary.

  Further, on the surface of the lower planar member 5B facing the upper planar member 5A, hemispherical protrusion spacers 16 are arranged at regular intervals in a matrix along the xy direction. It is the structure which suppresses an unnecessary contact. The protrusion spacer 16 can be made of a photo-curing acrylic resin, and is set to have a height of 10 μm and a diameter of 10 μm to 50 μm, for example, in accordance with the facing distance between the upper and lower planar members 5A and 5B. . In this figure, the size of the protrusion spacer 16 is shown larger than the actual size for easy illustration. The protrusion spacer 16 may have a shape other than a hemispherical shape, such as a conical shape or a cylindrical shape.

  Here, the touch panel 2 according to the second embodiment is characterized in that the upper planar member 5A and the resistive film 13, and the lower planar member 5B and the resistive film 14 are respectively used for the touch panel with a transparent conductive film described in the first embodiment. It is in the point which used the film 1 with a transparent conductive film (1A, 1B in FIG. 4). In the film 1, as described in Embodiment 1, the adhesion between the layers 40 to 43 and 13 is improved as compared with the conventional configuration. In particular, the peeling durability of the resistive film 13 is improved by the particulate inorganic filler contained in the middle refractive layer 42 of the film 1. For this reason, the touch panel 2 prevents peeling of each layer in the film 1, and can exhibit excellent keystroke durability and chemical resistance.

As a result, stable quality can be maintained even in outdoor use where the amount of ultraviolet irradiation is relatively large or in an in-vehicle car navigation system that tends to be in a high temperature environment.
The configuration of the touch panel of the present invention is not limited to the configuration of FIGS. 3 and 4, and for example, the lower planar member 5 </ b> B may be a so-called FG type configured with a glass substrate.
Moreover, in the structure of the said FG type, instead of a glass substrate, the laminated body (F-FG type) which adheres the film material of the said planar member to the glass plate or the resin board with the adhesive material suitably. Or F-FP type) may be provided. Further, the number of laminated films and the glass substrate, the order of lamination, and the like can be appropriately changed and adjusted.

In addition, the touch panel having the above-described configuration can also be applied to an LCD having polarizing plates on both sides.
Furthermore, the present invention may employ any method as an input method for the touch panel itself, and may have a configuration of an input method (capacitance method) other than the resistance film method.
<Performance confirmation experiment>
In order to confirm the performance of the present invention, films with transparent conductive films of various samples (Examples 1 to 6 and Comparative Examples 1 and 2) having a laminated structure shown in Table 1 were prepared.

For the base film, Toyobo Co., Ltd. “Cosmo Shine (registered trademark) A4300” (PET film with a thickness of 188 μm and a width of 1100 mm), or “Zeonor (registered trademark)” (with a thickness of 100 μm, manufactured by Nippon Zeon Co., Ltd.) An optical film having a width of 1100 mm was used.
The HC layer was formed in the following manner.
(1) When forming a clear HC film using a paint obtained by appropriately diluting “Desolite (registered trademark) Z7524 (previously containing 38 wt% of inorganic fine particles having an average particle diameter of 10 nm) with an organic solvent” manufactured by JSR Corporation Then, a film having a thickness of about 6 μm was formed on the surface of the base film “ZEONOR (registered trademark)” which was previously subjected to corona treatment by a roll coating method.
(2) In the case of depositing AGHC (2-1) In the case of depositing AGHC on a PET film “Desolite Z7524 (already containing 38 wt% of inorganic fine particles having an average particle diameter of 10 nm) manufactured by JSR Corporation” Silica particles having a particle size of 1.2 μm and an average particle size of 2.0 μm were added, so that the final composition was 43 wt% (nano size 38 wt%, micro size 5 wt%), which was appropriately diluted with an organic solvent. The paint was formed to a thickness of about 6 μm on the surface of the base film “Cosmo Shine A4300” by roll coating.

(2-2) When AGHC is formed on an optical film “Desolite Z7524 (already containing 38 wt% of inorganic fine particles having an average particle diameter of 10 nm) manufactured by JSR Corporation has an average particle diameter of 1.2 μm and an average particle diameter. 2.0 μm silica particles were added so that the final composition was 39 wt% (nano size 38 wt%, micro size 1 wt%). A film having a thickness of about 2 μm was formed on the surface of the treated base film “ZEONOR”.

Here, the first refractive layers of Examples 1 to 6 and Comparative Example 2 use a gradient material composed of an organic component and an inorganic component containing two components of TiO ₂ or TiO ₂ and SiO ₂ in a ratio of 40:60. Furthermore, a coating material was obtained by adjusting an inorganic filler composed of TiO ₂ or TiO ₂ and SiO ₂ so that the ratio in the solid content was 40 wt% with respect to the gradient material. Then, on the surface of any HC layer prepared in the above (2-1) or (2-2), the prepared coating material was formed to have a thickness of about 70 nm or about 75 nm based on the roll coating method. The first refractive layer of Comparative Example 1 was formed using a sol-gel material so as to have a thickness of about 70 nm.

The second refractive layer (low refractive layer) of Examples 1 to 6 and Comparative Example 2 was obtained by forming a SiO ₂ film having a thickness of 26 nm or 30 nm by sputtering in an oxygen gas atmosphere using a Si target material. It was. The second refractive layer of Comparative Example 1 was obtained by forming a 26 nm thick SiO ₂ film by hydrolysis of organosilicon.
As a transparent conductive film, an ITO film having a thickness of about 30 nm was obtained by a sputtering method using a target material of In ₂ O ₃ —SnO ₂ (95 wt% / 5 wt%).

Next, in order to investigate the performance of the film with a transparent conductive film when the composition of the gradient material of the first refractive layer (medium refractive layer) was changed, the following performance measurement experiment was performed. Each evaluation item and its specific measurement method are as follows.
(1) The ratio of the number of inorganic atoms / number of carbon atoms on the surface of the HC layer was measured by X-ray photoelectron spectroscopy (referred to as ESCA or XPS) after the formation of the HC layer.

(2) The total light transmittance was measured based on JIS K7361-1.
(3) The haze value was measured based on JIS K7136.
(4) Spectral transmittance and peak wavelength are measured using a spectrophotometer, light is incident from the film formation surface, the transmittance of light having a wavelength of 400 nm to 800 nm is measured, and the peak wavelength and the spectral transmittance of the peak wavelength are measured. And asked.

(5) The resistance value was measured using a resistivity measuring device (Loresta).
(6) In the sliding durability test, cotton impregnated with ethanol was attached to a 2 cm ² flat indenter, and sliding was performed 300 times in a reciprocating manner by applying a constant load (400 g / cm ² ).
The presence or absence of peeling of the transparent conductive film was determined by measuring the surface resistance value of the sliding portion and changing the resistance value. With respect to the material with the occurrence of peeling of 300 times or less, sliding was performed every 10 times, and the number of sliding times when peeling was evaluated.

(7) Measurement of wet heat durability The wet heat endurance test for the film with a transparent conductive film was performed in a high temperature / high humidity environment (temperature 120 ° C., humidity 90%) from the first state at room temperature 25 ° C. and humidity 60%. In 2 hours). Each surface resistance value before the transition and immediately after the end of the transition was measured, and the resistance value after the processing was divided by the resistance value before the processing to obtain the resistance change ratio.

In this evaluation, the smaller the resistance change ratio, the better the wet heat durability when this transparent conductive film-attached film is assembled on a touch panel. However, this evaluation condition is considerably severe set in the test, and even if the numerical value is high, it cannot be used at all for the touch panel.
8) Measurement of resistance value distribution Films were formed based on a roll-to-roll method using a wide film (1100 mm width) and slit into small rolls of 370 mm, 360 mm, and 370 mm. Thereafter, nine surface resistance values were measured in the TD direction with a small roll. Then, the degree of resistance value distribution was evaluated by dividing the standard deviation of the measured surface resistance values at 9 points by the average value at 9 points. The higher the resistance value distribution, the greater the variation in resistance value in the measurement region.

(9) The reflected color and appearance of each sample were evaluated by visual observation.
Table 2 shows the experimental results of each sample.

(Consideration of results)
As shown in the results of the experiment shown in Table 2, in Comparative Examples 1 and 2, the sliding durability both stopped at 10 times or less. On the other hand, in Examples 1-6, even if it slid 300 times or more, peeling did not occur, and sliding durability much superior to Comparative Examples 1 and 2 was confirmed. From this experiment, it was found that the present invention can exhibit the sliding durability required as a touch panel very well as compared with the conventional configuration.

The reason why such a result was obtained is that the transparent conductive film and the second refractive layer (low refractive layer) in the samples of Examples 1 to 6 and Comparative Examples 1 and 2 have the same configuration. It seems that the difference in composition in the monorefringent layer (medium refractive layer) influenced. That is, in the first refractive layers of Examples 1 to 6, TiO ₂ fine particles or SiO ₂ fine particles in addition to them are added as the particulate inorganic filler. There is no filler. Therefore, it is considered that the presence of the inorganic filler component imparts some characteristics to the first refractive layer, and the adhesion between the transparent conductive film and the second refractive layer is drastically improved. In addition, the detailed principle is unknown from the experiment, and its elucidation is a future subject.

  Furthermore, about the external appearance of each sample, although Examples 1-6 and the comparative example 2 were favorable, in the comparative example 1, the coating nonuniformity was seen. In addition, the reflected colors were white or yellow of colors similar to those in Examples 1 to 6 and Comparative Example 2. These colors were in line with market demands, and ideal reflection colors were good. However, in Comparative Example 1 only, the reflected light was shifted to the long wavelength (red) side. For this reason, when Comparative Example 1 was used for the touch panel, it was found that there is a possibility that the image display performance may be adversely affected. Such a result shows that the first refractive layer was formed by sputtering in Examples 1 to 6 and Comparative Example 2, but only Comparative Example 1 was formed using a sol-gel material for the first refractive layer, and the second refractive layer Is formed by organosilicon hydrolysis, and it is understood that such a difference in manufacturing method appears in the appearance performance.

  Next, looking at the total light transmittance, practically good performance was confirmed in any of the samples of Examples 1 to 6 and Comparative Examples 1 and 2. Moreover, in the result of the spectral transmission wavelength performed about Examples 1-6, and the peak wavelength, all the transmission wavelengths are settled between 522 nm-553 nm, and the transmittance | permeability is also a high numerical value of 88.3% or more. confirmed. Therefore, any of Examples 1 to 6 can be evaluated as having excellent optical characteristics.

In addition, the haze value in the samples of Examples 1 to 6 was 13.7% at the maximum, and it was found that all of the examples had good surface characteristics that suppressed irregular reflection of external light.
Next, considering wet heat durability, Examples 3 to 5 have a smaller maximum change value than Examples 1, 2, and 6. Further, the distribution of resistance values in Examples 3 to 5 converges smaller than the distribution of resistance values in Examples 1, 2, and 6. From these results, it is considered that Examples 3 to 5 have excellent wet heat durability, and can exhibit stable operation reliability even in a harsh environment. In addition, since the wet heat durability test conducted this time is set to considerably severe conditions, even in Examples 1, 2, and 6, there is no problem in operation under normal outdoor use environment. It exhibits reliability.

  From the above, it has been confirmed that Examples 1 to 6 have higher performance than Comparative Examples 1 and 2 for the anti-peeling performance in a normal use environment. Moreover, about wet heat durability in the severe use environment, it became clear that Example 3-5 was equipped with the very outstanding performance among Examples 1-6. Thus, it can be said that Example 3-5 has a favorable balance characteristic in all the evaluation items if it sees comprehensively.

Therefore, the superiority of the present invention was confirmed by the experiment.
In addition, the refractive index of the 1st refractive layer in Examples 1-6 has converged in the range of 1.65 to 1.75. As a result of the study by the inventors of the present application, the optimum range of the refractive index of the first refractive layer (medium refractive layer) is considered to be a range of 1.65 to 1.75, but a wider range (for example, 1.6 to 1.6). Even in 1.9), certain effects of the present invention can be obtained.

As for the particulate inorganic filler, TiO ₂ or SiO ₂ is used, but if it is SiO ₂ alone, the refractive index is too low. For this reason, it is necessary to take a form of either using 100% TiO ₂ or combining SiO ₂ and TiO ₂ . Moreover, as a material of the inorganic filler, any general transparent inorganic material can be used as long as the durability of the film with a transparent electrode film is improved. However, in order to achieve both durability and optical properties for the film with a transparent electrode film, it is necessary to use at least one of TiO ₂ and SiO ₂ as described above.

<Other matters>
In the touch panel 2 of the second embodiment, the configuration example in which the film of the first embodiment is applied to both of the two films 1A and 1B has been described. However, the present invention is not limited to this, and Even if only one of them is applied, an effect corresponding to this can be expected.
In the present invention, the low refractive layer (second refractive layer) is basically produced by a thin film method such as a sputtering method, but is not limited thereto, and other materials such as an ion beam method and a vapor deposition method are used. A thin film method or a thick film method such as a hydrolysis method may be used. However, when using the thick film method, it is necessary to pay attention so that a certain degree of adhesion with respect to the transparent conductive film on the low refractive layer can be obtained by the interaction with the particulate inorganic filler.

  That is, in the present invention, it is necessary to adjust the particulate inorganic filler and the transparent conductive film contained in the middle refractive layer so that they can interact with each other via the low refractive layer. It is thought that it is necessary to consider in advance.

  The film with a transparent conductive film for a touch panel of the present invention is a car that is expected to be used in outdoor use with a relatively large amount of ultraviolet irradiation or use under high temperature conditions in addition to a touch panel applied to a display of a general personal computer. It can be used for a display of a navigation system (a liquid crystal display integrated touch panel device).

It is a figure which shows the structure of the film with a transparent conductive film which concerns on Embodiment 1. FIG. It is an expanded sectional view of a film with a transparent conductive film. 5 is a configuration diagram of an LCD with a touch panel according to Embodiment 2. FIG. It is sectional drawing which shows another structural example of a touch panel and LCD.

Explanation of symbols

1, 1A, 1B Film with transparent conductive film 2 Touch panel 4 Composite layer 5, 5A, 5B Planar member
13, 14 Resistance film (transparent electrode film or electrode layer)
40 Base film 41 Hard coat (HC) layer 42 Middle refractive layer (first refractive layer)
43 Low refractive layer (second refractive layer)
131, 132, 141, 142 Lead line 133 Connection line 131a, 132a, 141a, 142a Electrode terminal 302, 303, 304, 305 Lead line 302a-305a Electrode terminal 301 Flexible substrate 411 Inorganic (silica) particles 412 Uneven region 420 Titanium oxide sol (Inorganic component)

Claims (11)

A film with a transparent conductive film in which a composite layer in which a hard coat layer, a first refractive layer, a second refractive layer, and a transparent conductive film are laminated in the same order is disposed on at least one surface of the transparent base film,
The hard coat layer is added so that inorganic fine particles are dispersed or combined,
The first refractive layer includes a composite material including an organic component and an inorganic component, and a particulate inorganic filler, and the concentration of the inorganic component is from the first refractive layer side toward the second refractive layer side. Tilt-oriented,
Said 2nd refractive layer is comprised with the material containing a silicon oxide. The film with a transparent conductive film for touchscreens characterized by the above-mentioned. _{2. The} transparent conductive film for a touch panel according to claim 1, wherein the particulate inorganic filler is mainly composed of at least one selected from the group consisting of TiO ₂ , SiO ₂ , Al ₂ O ₃ , and ZrO _2. Attached film. In the case of being placed in the second state at a humidity of 90% and a temperature of 120 ° C. for 2 hours from the first state at a humidity of 60% and a temperature of 25 ° C.,
The ratio of the resistance value of the transparent conductive film immediately after the end of the previous placement to the resistance value of the transparent conductive film immediately before the placement is within a range of 2 or less. Film with transparent conductive film for touch panels. The said composite material contains 1 type, or 2 or more types of the compound containing the inorganic atom of at least any one of Si, Ti, Al, and Zr as said inorganic component. Film with transparent conductive film for touch panels. The hard coat layer contains at least one inorganic atom of Si, Ti, Al, Zr,
In the case where the ratio of the number of inorganic atoms to the number of carbon atoms is represented by the number of inorganic atoms / the number of carbon atoms,
The film with a transparent conductive film for a touch panel according to claim 1, wherein the ratio is adjusted to 1/750 or more and 1/2 or less on a surface of the hard coat layer facing the first refractive layer. The film with a transparent conductive film for a touch panel according to claim 1, wherein the surface of the hard coat layer facing the first refractive layer is a smooth surface. The inorganic fine particles of the hard coat layer have an average particle diameter of 1 nm or more and 200 nm or less, and are composed of any one of SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ O _3. 6. The film with a transparent conductive film for a touch panel according to 6. The film with a transparent conductive film for a touch panel according to any one of claims 1 to 7, wherein a surface of the hard coat layer facing the first refractive layer is subjected to uneven treatment. The inorganic fine particles of the hard coat layer have an average particle size of 0.5 μm or more and 5 μm or less, and are composed of any one of SiO ₂ , ZrO ₂ , TiO ₂ , and Al ₂ O _3. The film with a transparent conductive film for touchscreens of Claim 8. The film with a transparent conductive film for a touch panel according to claim 1, wherein at least one of the second refractive layer and the transparent conductive film is formed by a thin film method. A touch panel in which a pair of substrates with a transparent conductive film are arranged to face each other at a constant interval,
At least one of the substrates with a transparent conductive film is a film with a transparent conductive film for a touch panel according to any one of claims 1 to 10,
The touch panel, wherein the composite layer of the film is disposed so as to face the other substrate with a transparent conductive film.

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