JP5114961B2 - Film with transparent conductive film and display substrate, display, liquid crystal display device and organic EL element comprising the film with transparent conductive film - Google Patents

Description

  The present invention relates to a film with a transparent conductive film. More specifically, the present invention relates to a film with a transparent conductive film having a high total light transmittance and a high degree of coloration, and a display substrate, a display, and a liquid crystal display device comprising the film with the transparent conductive film. In addition, the present invention relates to an organic EL element.

  Conventionally, displays of various display methods have been used, and practical application has been studied. Except for the cathode ray tube type, all of them are aimed at thinning, and more flexible ones have been demanded.

  Therefore, it has been studied to use a synthetic resin sheet or a synthetic resin film instead of a glass substrate that conventionally constitutes a display. For the purpose of extending the life of the display, a display substrate using a gas barrier film that blocks oxygen and water vapor from the outside world has been studied.

  In addition to mechanical strength, smoothness, gas barrier properties, etc., the synthetic resin film as a display substrate material is processed by laminating various layers to give display functions to the synthetic resin film, or a gas barrier layer is added. Heat resistance or moisture resistance is required in processing. However, since general synthetic resin films have much lower heat resistance or moisture resistance than glass substrates, heating in the process of forming a metal thin film by vapor deposition, etc., heat curing process after coating with a thermosetting resin paint, etc. Deformation due to heating in the film or deformation caused by moisture absorption due to contact with an aqueous solution in the metal thin film etching process or resist development process is unavoidable, and the flatness of the resulting display or gas barrier film is impaired, or the laminated metal There arises troubles such as peeling due to deviation from the thin film or deviation from a preset dimension. Further, in a display such as a liquid crystal display panel or an EL display panel, when a formed element is exposed to water vapor, performance deteriorates, and troubles such as no light emission occur.

  For this reason, in gas barrier films used for displays and display substrates, heat resistance of 150 ° C. or higher is required in order to increase dimensional stability so that elongation and deflection are less likely to occur due to heat generated during processing and use and tension during heating. In particular, in displays such as liquid crystal display panels and EL display panels, ultra-high gas barrier properties are required so that formed elements do not deteriorate in performance due to contact with water vapor or oxygen.

  Conventionally, a gas barrier film is formed by forming a gas barrier film composed of two layers of an inorganic compound vapor deposition layer and a coating layer of a coating agent mainly composed of a water / alcohol mixed solution on a polymer resin substrate. It is known (see, for example, Patent Document 1).

  In addition, the gas barrier laminate film is composed of two layers: a polymer resin substrate, an inorganic compound deposition layer, and a coating agent coating layer mainly composed of a mixed solution of a metal alkoxide or a hydrolyzate thereof and an isocyanate compound. Those are known (for example, see Patent Document 2).

  Furthermore, what forms a gas interruption | blocking layer on a transparent heat resistant base material using a sputtering method is known (for example, refer patent document 3).

However, the films described in Patent Documents 1 to 3 have water resistance and moisture resistance, have flexibility to withstand a certain degree of deformation, and exhibit gas barrier properties, but are described in the examples. Thus, the oxygen permeability is about 1 cc / m ² · day · atm, the water vapor permeability is about 0.1 g / m ² · day, and the oxygen permeability is about 0.3 cc / m ² · day · atm. There is a problem that it is insufficient to prevent the deterioration of the light emitting layer of the organic EL element and the like, and further, the heat resistance of 150 ° C. or more, the chemical resistance, and the low linear expansion are described and referred to. Not.
Japanese Patent Laid-Open No. 7-164591 JP 7-268115 A JP-A-11-222508

  When the surface flatness of the transparent conductive film is high, the chemical resistance, particularly acid resistance is not sufficient. On the other hand, when the surface flatness is low, the light emitting layer provided in contact with the transparent conductive film may be damaged. .

  The present invention has a film with a transparent conductive film capable of providing a display having good surface flatness and high emission luminance, a display substrate, a display, a liquid crystal display device and an organic EL comprising the film with the transparent conductive film It relates to an element.

Therefore, the film with a transparent conductive film according to the present invention comprises a transparent substrate and a transparent conductive film, and the transparent conductive film has 1 to 100 crystalline secondary particles having an average particle diameter of 0.1 to 1 μm on the surface. It is characterized by having pieces / μm ² .

Such a film with a transparent conductive film according to the present invention includes, as a preferred embodiment, the transparent conductive film having 150 to 10,000 particles / μm ³ of crystalline secondary particles having an average particle diameter of 0.1 to 1 μm. To do.

  Such a film with a transparent conductive film according to the present invention includes, as a preferred embodiment, the transparent conductive film having a half-width of 1.5 to 9.5 at the maximum peak angle of the crystal phase.

  In addition, a display substrate according to the present invention is characterized by comprising the above-mentioned film with a transparent conductive film.

  The display according to the present invention is characterized by comprising the above-mentioned display substrate.

  In addition, a liquid crystal display device according to the present invention is characterized by comprising the above-described display substrate.

  And the organic EL element by this invention consists of said display substrate, It is characterized by the above-mentioned.

The film with a transparent conductive film according to the present invention comprises a transparent substrate and a transparent conductive film, and the transparent conductive film has 1 to 100 crystalline secondary particles having an average particle diameter of 0.1 to 1 μm on the surface. since those having [mu] m ^2, has a good surface flatness, by the surface resistance of the transparent conductive film is low, the transparent conductive film-attached film that can provide a higher emission luminance display, and which It is possible to provide a display substrate, a display, a liquid crystal display device, and an organic EL element using the above.
And the film with a transparent conductive film by this invention is equipped with the outstanding acid resistance.

  Such a film with a transparent conductive film according to the present invention is particularly suitable as a film substrate for a display, but also for a touch panel, a film substrate for lighting, a film substrate for solar cells, a film substrate for circuit boards, electronic paper, etc. It is useful.

<Film with transparent conductive film>
The film with a transparent conductive film according to the present invention comprises a transparent substrate and a transparent conductive film, and the transparent conductive film has 1 to 100 particles / μm on the surface of crystalline secondary particles having a particle diameter of 0.1 to 1 μm. It is characterized by having ² .

  The film with a transparent conductive film comprising the transparent substrate and the transparent conductive film according to the present invention is limited to (i) a film with a transparent conductive film having one layer each of the transparent substrate and the transparent conductive film. For example, (b) a film with a transparent conductive film in which either one or both of a transparent base material and a transparent conductive film are formed, and (c) (a) or (b) above, a transparent group Examples include a film with a transparent conductive film in which one or two or more layers or materials other than the material and the transparent conductive film are formed. In addition, as a preferable specific example of layers or materials other than such a transparent base material and a transparent conductive film, a gas barrier layer, a smoothing layer (detailed postscript), etc. can be mentioned, for example.

  Moreover, in the film with a transparent conductive film according to the present invention, the transparent conductive film does not always need to be formed uniformly over substantially the entire surface of the transparent substrate. Therefore, the film with a transparent conductive film according to the present invention is, for example, a film in which a transparent conductive film is partially formed on a transparent substrate, for example, a film in which a transparent conductive film is formed in a pattern on a transparent substrate. Include.

  The film with a transparent conductive film according to the present invention preferably has a total light transmittance of 75% or more, particularly 80% or more. Here, the total light transmittance is determined by JIS K7361-1.

  1 and 2 show particularly preferred specific examples of the film with a transparent conductive film according to the present invention. The film with a transparent conductive film according to the present invention shown in FIG. 1 has a layer configuration of “transparent substrate 10 / transparent conductive film 11”, expressed from the bottom layer, and the present invention shown in FIG. The film with a transparent conductive film 1 is expressed from the bottom layer as “second gas barrier layer 13B / second smoothing layer 14B / second gas barrier layer 13B / transparent substrate 10 / first gas barrier layer 13A / first smoothing”. 14A / first gas barrier layer 13A / transparent conductive film 11 ”, and the display substrate according to the present invention shown in FIG. 3 includes“ gas barrier layer 13 / transparent substrate 10 / gas barrier layer ”. 13 / smoothing layer 14 / gas barrier layer 13 / transparent conductive layer 11 / auxiliary electrode layer 15 ”.

  The following is described about each layer of the film 1 with a transparent conductive film by this invention shown by FIG.

(1) Transparent conductive film The transparent conductive film 11 is a coating mainly composed of an inorganic oxide formed by coating a hydrolyzate such as a metal alkoxide or a transparent electroconductive particle and a hydrolyzate such as a metal alkoxide. It may be a layer or a film formed by a vacuum film forming method such as a resistance heating vapor deposition method, an induction heating vapor deposition method, an EB vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, or a plasma CVD method. possible. In particular, as the transparent conductive film, it is preferable to use an EB vapor deposition method, a sputtering method, or an ion plating method that has a low resistance value and is capable of surface treatment. The material of the transparent conductive film is appropriately selected from indium-tin oxide (ITO), indium-tin-zinc oxide (ITZO), ZnO ₂ system, CdO system, SnO ₂ system, etc. Among them, indium-tin oxide (ITO) is preferable in terms of excellent transparency and conductivity, and the tin content in the indium-tin oxide (ITO) is 5 to 15 mol%. Particularly preferred. The thickness of the indium-tin oxide (ITO) film is preferably 10 nm to 1000 nm, more preferably 60 nm to 450 nm, and still more preferably 100 to 200 nm. When the thickness is less than 10 nm, the conductivity when used as a transparent electrode layer becomes insufficient, and when it exceeds 1000 nm, the transparency and bending resistance are deteriorated, which is not preferable. The indium-tin oxide (ITO) film may be non-crystalline or crystalline, and may be non-crystalline-crystalline intermediate (mixed type). In order to form the film in the present application, the mixed type is more excellent.

The transparent conductive film in the present invention preferably has a crystalline secondary particle having an average particle diameter of 0.1 to 0.5 μm at a density of 1 to 100 particles / μm ² . The particle diameter of particularly preferable crystalline secondary particles is 0.1 to 0.3 μm, and the preferable density is 3 to 80 particles / μm ² , and surface irregularities (maximum height difference of the surface) are within this range. Is more preferably 1.5 to 35 / μm ² , and the surface roughness Ra is reduced within this range, whereby the transparent conductive film in an image display device such as an organic EL element is reduced. It is possible to impart a property in which a short circuit (short circuit) due to the protrusion hardly occurs. Here, the crystalline particles are specifically those whose crystallinity has been confirmed by measurement using an automatic X-ray diffractometer RINT 2000 manufactured by Rigaku Corporation, and the particle size thereof is Nanopics 1000 (product name: manufacturer) Is based on JIS B0601 by observation by Seiko Instruments Inc., and the density can be easily determined by considering the measurement range at the time of particle diameter measurement. In the ITO film, the (222) plane has a maximum peak, and the half width is preferably 1.5 to 9.5. Especially preferably, it is 2.0-8.3, More preferably, it is 2.5-6.0. The maximum peak of the crystal phase is calculated by RINT2000 / PC series (product name: manufacturer is Rigaku Corporation).

In addition, the transparent conductive film in this invention can obtain desired resistivity, and can be produced within the range of 0.5 * 10 < ^-4 > ^-10 < ³ > (omega | ohm) * cm.

  As a method for forming the preferable transparent conductive film, any method can be adopted as long as the crystalline secondary particles having the above particle diameter and density are formed. In the present invention, the transparent conductive film having the required thickness is not formed in one continuous process, but the transparent conductive film is formed in a plurality of times and formed each time. A method comprising accumulating the transparent conductive films thus formed, and a method of performing treatment with an oxidizing gas after the formation of the transparent conductive films is preferable.

  In the present invention, each time a transparent conductive film having a thickness of 0.3 to 10 nm is formed per time, any one of plasma treatment, ion bombardment treatment, glow discharge treatment, arc discharge treatment, and spraying treatment is performed in an oxidizing gas. It is particularly preferable that the transparent conductive film is formed by accumulating the transparent conductive films formed at each time.

  When the formation thickness of the transparent conductive film per time is less than 0.3 nm, the crystal growth is not sufficient, and it is not preferable in that the conductivity is lowered. This is because the surface roughness increases because crystal growth proceeds excessively. The thickness of forming the transparent conductive film per time is particularly preferably 0.5 to 10 nm. The thickness of forming the transparent conductive film per time may be the same or different at each time. The same effect can be obtained by adjusting the temperature of the substrate on which the transparent conductive film is formed.

  In the present invention, as an apparatus used for forming a transparent conductive film, an apparatus capable of alternately performing film formation and annealing time is preferable as long as it is a vacuum film forming method. Etc. are preferable.

(2) Transparent base material As the transparent base material 10 of the film 1 with a transparent conductive film according to the present invention, a synthetic resin film conventionally used as a material for a substrate for a display can be used. In the present invention, a synthetic resin film having a total light transmittance of 60 to 99%, preferably 80 to 95% is preferable. Although the thickness of a base material can be suitably determined according to the specific use etc. of a film with a transparent conductive film, Preferably it is 12-300 micrometers, Most preferably, it is 50-200 micrometers. Here, the transparency is determined by the total light transmittance. In the film 1 with a transparent conductive film according to the present invention, the surface of the transparent substrate 10 and the surface on which the first gas barrier layer 13A or the second gas barrier layer 13B is formed are improved in order to improve wettability and adhesion with the layer. In addition, a known resin layer called an easy adhesion layer, an adhesion promoting layer, a primer layer, an undercoat layer, an anchor coat layer, or the like may be formed.

  Specific examples of the resin film of the base film include a thermoplastic resin such as polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, or syndiotactic polystyrene, which is a thermosetting resin. Examples of preferable resins include polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, fluororesin, and polyether nitrile. Examples of the synthetic resin of the material constituting the base film include polycarbonate, modified polyphenylene ether, polycyclohexene, or polynorbornene-based resin that is a thermoplastic resin in an amorphous resin, and polysulfone in a thermosetting resin. , Polyethersulfone, polyarylate, polyamideimide, polyetherimide, or thermoplastic polyimide can be exemplified as more preferable resins. Especially, since a polycarbonate has low water absorption, the base film comprised using this has a low humidity expansion coefficient, and is especially preferable.

  The deflection temperature under load is defined in JIS K7191, which is a more practical index as a thermal property required for a base film, particularly a behavior with respect to an external force. As the deflection temperature under load of each resin, for example, polyethylene naphthalate resin (PEN); 155 ° C., polycarbonate resin; 160 ° C., polyarylate resin; 175 ° C., polyethersulfone resin; 210 ° C., cycloolefin polymer (Nippon Zeon ( 150 ° C. or norbornene resin (manufactured by JSR Corporation, trade name: “Arton”); 155 ° C.

  (Polyester) The polyester constituting the base film 10 layer is preferably a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. In addition, some general polyesters have a deflection temperature under load of 150 ° C. or less, but the polyester as the base film 10 layer mentioned here has a deflection temperature under load of 150 ° C. or more. Specific examples of the polyester include polyethylene terephthalate, polyethylene isophthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate, and the like. It may be a blend of these copolymers or a small proportion of other resins. Among these polyesters, polyethylene terephthalate and polyethylene-2,6-naphthalate are preferable because of a good balance between mechanical properties and optical properties. In particular, polyethylene-2,6-naphthalate is superior to polyethylene terephthalate in terms of mechanical strength, low thermal shrinkage, and a small amount of oligomer generated during heating. Because it is high, the surface of the polyethylene naphthalate resin film is stable and less damaged, for example, when the gas barrier property is formed after forming the pattern layer by etching using a resist, especially including an etching process. Therefore, it is preferable because a gas barrier film can be formed and excellent gas barrier properties can be imparted.

  The polyester may be a homopolymer or a copolymer obtained by copolymerizing the third component, but a homopolymer is preferred. When the polyester is polyethylene terephthalate, isophthalic acid copolymerized polyethylene terephthalate is optimal as the copolymer. The isophthalic acid copolymerized polyethylene terephthalate preferably contains 5 mol% or less of isophthalic acid. The polyester may be copolymerized in a range in which the copolymer component or copolymer alcohol component other than isophthalic acid does not impair the characteristics, for example, in a proportion of 3 mol% or less with respect to the total acid component or the total alcohol component. Examples of the copolymer acid component include aromatic dicarboxylic acids such as phthalic acid and 2,6-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and 1,10-decanedicarboxylic acid. Examples of the alcohol component include aliphatic diols such as 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, and alicyclic diols such as 1,4-cyclohexanedimethanol. it can. These can be used alone or in combination of two or more.

  When the polyester is polyethylene-2,6-naphthalenedicarboxylate, naphthalenedicarboxylic acid is used as the main dicarboxylic acid component, and ethylene glycol is used as the main glycol component. Examples of naphthalenedicarboxylic acid include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. Among these, 2,6-naphthalenedicarboxylic acid is preferable. Here, the “main” means at least 90 mol%, preferably at least 95 mol% of all repeating units in the constituent components of the polymer that is a component of the film of the present invention.

(3) Smoothing layer In the film 1 with a transparent conductive film according to the present invention, a first smoothing layer 14A and a second smoothing layer 14B (collectively smoothing layer 14) are formed on the surface of the gas barrier layer 13 as necessary. Can be provided). The smoothing layer 14 may be a sol-gel material, an ionizing radiation curable resin, a thermosetting resin, or a photoresist material as long as it is applied for the purpose of flattening the surface, but preferably has a gas barrier function. It has excellent coating performance. In order to improve the coating performance, an ionizing radiation curable resin is preferable, and a resin that undergoes a crosslinking polymerization reaction and changes to a three-dimensional polymer structure when irradiated with ultraviolet rays (UV) or electron beams (EB). That is, an ionizing radiation curable resin obtained by appropriately mixing a reactive prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule, or coating suitability. In consideration of the above, etc. using a liquid composition obtained by mixing a thermoplastic resin such as urethane, polyester, acrylic, butyral, vinyl or the like with the ionizing radiation curable resin as necessary. It can be formed by applying, drying, and curing by a known coating method such as a roll coating method, a Miya bar coating method, or a gravure coating method.

  Although the thickness of a smoothing layer can be suitably determined according to the specific use etc. of a film with a transparent conductive film, Preferably it is 0.05-10 micrometers, Most preferably, it is 0.1-5 micrometers.

Ionizing radiation curable resin As the above ionizing radiation curable resin, specifically, those having an acrylate functional group, that is, those having an acrylic skeleton and those having an epoxy skeleton are suitable, and the hardness of the coating film In view of heat resistance, solvent resistance, and scratch resistance, a structure having a high cross-linking density is preferred, and bifunctional or higher acrylate monomers such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di Examples include acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In the above, “(meth) acrylate” means both acrylate and methacrylate.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when it is cured by irradiating with ultraviolet rays, as a photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl Ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like, n-butylamine, triethylyl as photosensitizers Luamine, poly-n-butylphosphine and the like are preferably used alone or as a mixture. The addition amount of the photopolymerization initiator and the photosensitizer is generally about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin. In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, antifoaming agents, thickeners, etc. are added to the coating composition as necessary. can do.

As a coating amount, about 0.5-15 g / m < ² > is suitable as solid content. In addition, as an ultraviolet ray source used for hardening, the light source of an ultra high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, and a metal halide lamp lamp can be used. As a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm can be used, and as an electron beam source, a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, or a straight line Various electron beam accelerators such as a type, a dynamitron type, and a high frequency type can be used.

〔ここで、一般式（ａ）において、Ａ^１はアルキレン基を表し、Ｒ^４は水素原子、低級アルキル基、または下記一般式（ｂ）を表される基を表す。Ｒ^５は水素原子または低級アルキル基を表す。Ｒ^６は炭素数１〜４のアルキル基、アリール基または不飽和脂肪族残基を表す。分子中にＲ^６が複数存在する場合、それらは互いに同一であっても異なっていてもよい。Ｒ^７は水素原子、炭素数１〜４のアルキル基またはアシル基を表し、水素原子、炭素数１〜３のアルキル基またはアシル基であることが好ましい。分子中にＲ^７が複数存在する場合、それらは互いに同一であっても異なっていてもよい。ｗは０、１、２のいずれかであり、ｚは１〜３の整数であり、かつｗ＋ｚ＝３である。一般式（ｂ）において、Ａ^２は、直接結合またはアルキレン基を表し、Ｒ^８およびＲ^９は、それぞれ独立して、水素原子または低級アルキル基を表す。Ｒ^４、Ｒ^５、Ｒ^８およびＲ^９の少なくとも１つは水素電子である〕

Sol-Gel Method As a material for the smoothing layer in the present invention, for example, a sol-gel material using a sol-gel method capable of forming a coating film of the same material system is preferable in order to obtain good adhesion to the barrier layer. It is. The sol-gel method is composed of at least a silane coupling agent having an organic functional group and a hydrolyzable group and a crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent. It is a coating method and a coating film of a coating composition. Examples of the silane coupling agent having an organic functional group and a hydrolyzable group (hereinafter sometimes simply referred to as a silane coupling agent) include the following general formula (a) disclosed in JP-A-2001-207130. Preferred are aminoalkyl dialkoxysilanes or aminoalkyltrialkoxysilanes.

[In the general formula (a), A ¹ represents an alkylene group, and R ⁴ represents a hydrogen atom, a lower alkyl group, or a group represented by the following general formula (b). R ⁵ represents a hydrogen atom or a lower alkyl group. R ⁶ represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or an unsaturated aliphatic residue. When a plurality of R ⁶ are present in the molecule, they may be the same as or different from each other. R ⁷ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an acyl group, and is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group. When a plurality of R ⁷ are present in the molecule, they may be the same as or different from each other. w is 0, 1, or 2, z is an integer of 1 to 3, and w + z = 3. In the general formula (b), A ² represents a direct bond or an alkylene group, and R ⁸ and R ⁹ each independently represent a hydrogen atom or a lower alkyl group. At least one of R ⁴ , R ⁵ , R ⁸ and R ⁹ is a hydrogen electron.

  Specific examples of the aminoalkyl dialkoxysilane or aminoalkyltrialkoxysilane represented by the above formula (a) include N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl). ) Γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltriisopropoxysilane, N-β (aminoethyl) γ-aminopropyltributoxysilane, N-β (aminoethyl) γ-amino Propylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylmethyl Dibutoxysilane, N-β (aminoethyl) γ-aminopropylethyldimethyl Xisilane, N-β (aminoethyl) γ-aminopropylethyldiethoxysilane, N-β (aminoethyl) γ-aminopropylethyldiisopropoxysilane, N-β (aminoethyl) γ-aminopropylethyldibutoxysilane Γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane , Γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldiisopropoxysilane, γ Aminopropyl ethyl dibutoxy silane, .gamma.-aminopropyl triacetoxysilane, and the like, may be used alone or two or more thereof.

  The “crosslinkable compound having an organic functional group that reacts with the organic functional group of the silane coupling agent” (sometimes simply referred to as a crosslinkable compound) is a functional group that can react with an amino group. It has a glycidyl group, a carboxyl group, an isocyanate group, or an oxazoline group, and specific examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, nonaethylene Glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Diglycidyl ethers such as pentyl glycol diglycidyl ether, adipic acid diglycidyl ether, o-phthalic acid diglycidyl ether, glycerol diglycidyl ether; glycerol triglycidyl ether, diglycerol triglycidyl ether, triglycidyl tris (2-hydroxyethyl) ) Triglycidyl ethers such as isocyanurate and trimethylolpropane triglycidyl ether; tetraglycidyl ethers such as pentaerythritol tetraglycidyl ether; other polyglycidyl ethers or polymers having a glycidyl group as a functional group; tartaric acid and adipic acid Dicarboxylic acids such as; carboxyl-containing polymers such as polyacrylic acid; hexamethylene diisocyanate, xylylene diisocyanate Isocyanates such as carbonates; oxazoline-containing polymers; alicyclic epoxy compounds, etc., and one or more of these can be used, but in terms of reactivity, they have two or more glycidyl groups. Are preferably used.

  The amount of the crosslinkable compound used is preferably 0.1 to 300% (mass basis, the same applies hereinafter) with respect to the silane coupling agent, and more preferably 1 to 200%. When the crosslinkable compound is less than 0.1%, the flexibility of the coating film becomes insufficient, and when it exceeds 300%, the gas barrier property may be lowered. The silane coupling agent and the crosslinkable compound are stirred while heating as necessary to obtain a coating composition.

  By coating and drying the coating composition using the silane coupling agent and the crosslinkable compound as raw materials on the thin film layer, hydrolysis and condensation of the silane coupling agent and crosslinking with the crosslinkable compound proceed. Thus, a polysiloxane coating film having a crosslinked structure is obtained.

  The above composition may further contain a silane compound having a hydrolyzable group and not having an organic functional group such as an amino group. Specifically, tetramethoxysilane, tetraethoxysilane, tetraisopropoxy Silane, tetrabutoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldiisopropoxysilane, diethyldibutoxysilane, vinyltrimethoxy Silane, vinyltriethoxysilane, γ-glycidpropyltrimethoxysilane, γ-glycidpropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. 1 type, or 2 or more types of these can be used.

  When containing a silane compound having the above-mentioned hydrolyzable group and not having an organic functional group such as an amino group, co-hydrolysis of an organic functional group such as an amino group and a silane coupling agent having a hydrolyzable group Condensation and crosslinking with a crosslinkable compound proceed to obtain a polysiloxane coating film having a crosslinked structure.

  The coating composition further comprises a (co) hydrolysis of a silane coupling agent having an organic functional group such as an amino group and a hydrolyzing group and / or a hydrolyzing group and not having an organic functional group such as an amino group. A decomposition condensate may be contained. In addition to these, various inorganic and organic additives such as silane compounds, solvents, curing catalysts, wettability improvers, plasticizers, antifoaming agents, thickeners, etc. are added to the coating composition as necessary. can do.

Cardo polymer As a material for the smoothing layer, a cardo polymer is preferably contained. The cardo polymer is a polymer having the following cardo structure, which is synthesized from a monomer having a cardo structure and another polymerizable monomer, and can be applied to a cardo polyester polymer, a cardo acrylic polymer, a cardo epoxy polymer, etc. Is a cardo epoxy polymer. The smoothing layer should just contain the cardo polymer as a main component.

In addition, for the smoothing layer, additives such as plasticizers, fillers, antistatic agents, lubricants, antiblocking agents, antioxidants, UV absorbers, light stabilizers, and the like are modified as necessary. Resin for use may be added.

  The cardo polymer has a unique structure called a cardo structure in the main chain skeleton of the polymer, and the cardo structure has a large number of aromatic rings. Due to its steric hindrance, the fluorene skeleton part and the main chain The direction is twisted, so the central carbon atom part can change the bond angle relatively freely, so it is strong and strong, but it is not brittle even at low temperatures, and it has high hardness and scratch resistance. It is estimated that

  Moreover, since the layer containing a cardo polymer has a good leveling property, it fills and covers a defect, and the surface after drying becomes smoother. In addition, since it has good affinity and wettability with the inorganic compound (gas barrier layer 13A of the present invention), it fills, covers, and closes defects such as holes, recesses, and cracks. A super-smoothing function is exhibited by a synergistic effect of leveling properties, and smoothing, that is, Ra and Rmax on the surface can be significantly reduced.

  In this way, by increasing the surface smoothness, the gas permeation proceeds to adsorb gas to the material surface, dissolve in the material, diffuse in the material, and diffuse to the opposite surface, so that oxygen or water vapor, etc. By reducing the adsorption site (surface area), the adsorption on the surface of the first stage can be greatly reduced, so that the gas barrier property can be remarkably improved.

(4) Gas Barrier Layer In the film 1 with a transparent conductive film according to the present invention, gas barrier layers 13A and 13B (collectively referred to as the gas barrier layer 13) can be provided on the curable resin layer surface as necessary. The material of the gas barrier layer 13 is not particularly limited as long as it has gas barrier properties. For example, metals such as aluminum, nickel, chromium, iron, cobalt, zinc, gold, silver, copper; silicon, germanium, carbon Semiconductors such as silicon oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, zinc oxide, cerium oxide, hafnium oxide, barium oxide, etc .; silicon nitride, aluminum nitride Nitrides such as boron nitride and magnesium nitride; carbides such as silicon carbide, sulfides and the like can be applied. Further, an oxynitride, an oxycarbide layer further containing carbon, an inorganic nitride carbide layer, an inorganic oxynitride carbide, or the like, which is a composite of two or more selected from them, can also be applied.

  Preferred are inorganic oxides (MOx) such as aluminum oxide, silicon oxide, magnesium oxide, calcium oxide, zirconium oxide, and titanium oxide, inorganic nitride (MNy), inorganic carbide (MCz), inorganic oxide carbide (MOxCz), Inorganic nitride carbide (MNyCz), inorganic oxynitride (MOxNy), inorganic oxynitride carbide (MOxNyCz) [wherein M represents a metal atom, x represents an oxygen atom, y represents the number of nitrogen atoms, z Indicates the number of carbon atoms]. Preferred M is a metal element such as Si, Al, or Ti.

  Moreover, the thing which added or substituted the metal, the semiconductor, etc. to them, those mixtures, etc. can be used.

  In addition, about composition of the gas barrier layer 13, surface analyzers, such as a photoelectron spectrophotometer, an X-ray photoelectron spectrometer (Xray Photoelectron Spectroscopy, XPS), a secondary ion mass spectrometer (Secondary Ion Mass Spectroscopy, SIMS), are used, for example. By performing elemental analysis of the silicon oxide film using a method of analyzing by ion etching in the depth direction, the above-described composition ratio and physical properties can be confirmed.

Gas Barrier Layer Manufacturing Method The gas barrier layer 13 manufacturing method is not particularly limited, but preferably a vacuum deposition method, a sputtering method, an ion plating method, a Cat-CVD method, a plasma CVD method, an atmospheric pressure plasma CVD method, or the like. Formed by applying. Selection may be made in consideration of the type of film forming material, easiness of film forming, process efficiency, and the like.

  For example, the vapor deposition method uses resistance heating, high-frequency induction heating, beam heating such as electron beam or ion beam, etc., to heat and evaporate the material in the crucible and attach it to a flexible substrate (plastic film, etc.) This is a method for obtaining a thin film. At this time, the heating temperature and the heating method differ depending on the material, purpose, etc., and a reactive vapor deposition method that causes an oxidation reaction or the like can also be used.

  The plasma CVD method is a type of chemical vapor deposition method, in which raw materials are vaporized and supplied during plasma discharge, and the gases in the system are mutually activated by collision and become radicals, which are not effective only by thermal excitation. The reaction at the low temperature possible is possible. The substrate is heated from behind by a heater, and a film is formed by a reaction during discharge between the electrodes. It is classified into HF (several tens to hundreds of kHz), RF (13.56 MHz), and microwave (2.45 GHz) depending on the frequency used for generating plasma. In the case of using a microwave, the method is roughly classified into a method in which a reaction gas is excited and a film is formed in an after glow, and an ECR plasma CVD in which a microwave is introduced into a magnetic field (875 Gauss) that satisfies the ECR condition. When classified by the plasma generation method, it is classified into a capacitive coupling method (parallel plate type) and an inductive coupling method (coil method).

  The ion plating method is a combined technique of vacuum vapor deposition and plasma. In principle, a gas plasma is used to make part of the evaporated particles ion or excited particles and activate them to form a thin film. Therefore, reactive ion plating that combines the vaporized particles using the reactive gas plasma to synthesize the compound film is extremely effective. Since the operation is in plasma, the first condition is to obtain a stable plasma. In many cases, low-temperature plasma using weakly ionized plasma in a low gas pressure region is used. The means for generating a discharge is roughly classified into a direct current excitation type and a high frequency excitation type. In addition, a hollow cathode or an ion beam may be used for the evaporation mechanism.

<Display substrate>
The display substrate according to the present invention comprises the film with a transparent conductive film according to the present invention.

  In such a display substrate according to the present invention, as shown in FIG. 3, the transparent electrode layer 11 and, if necessary, an auxiliary electrode layer or a necessary layer are provided on the surface of the curable resin layer, the gas barrier layer 13 or the smoothing layer 14. Depending on the above, those provided with other layers are included.

<Display>
A display according to the present invention comprises the display substrate according to the present invention.

  When the film with a transparent conductive film of the present invention is used as a substrate for a display, the layers necessary for each display method can be laminated on either the front or back of the film with a transparent conductive film. Since these layers may be laminated between the base film and the gas barrier layer, the film with a transparent conductive film of the present invention has a display function between the base film and the thin film layer. Including a layer for the purpose.

  The display may be any display using the above-described display substrate. Depth of a plasma display panel (PDP), a liquid crystal display (LCD), an organic or inorganic electroluminescence display (ELD), a field emission display (FED), etc. Therefore, it can be suitably applied to a thin type with a small amount.

<Liquid crystal display device>
A liquid crystal display device according to the present invention comprises the display substrate according to the present invention. In general, a liquid crystal display (LCD) is a glass substrate in which a transparent electrode is placed inside, and liquid crystal is sandwiched between layers with an alignment layer, etc., and the periphery is sealed. With a color filter for colorization. The film with a transparent conductive film of the present invention can be applied to the outside of the glass substrate of such a liquid crystal display, or the film with a transparent conductive film of the present invention can be used instead of the glass substrate. In particular, if both of the two glass substrates are replaced with the film with a transparent conductive film of the present invention, the entire display can be made flexible.

  Some types of liquid crystals have optical anisotropy and some epoxy resins cannot be used, but can be applied without using a polarizing plate or by changing the position of the liquid crystal layer. Or a polymer-dispersed liquid crystal.

Plastic liquid crystal is used for displays used in mobile devices such as personal digital assistants, communication devices (for example, mobile phones), notebook computers, amusement devices (for example, small computer game machines), and is lightweight, thin, durable, and has a high display. Capability can be enhanced such as capacity and good visibility, and low power consumption corresponding to miniaturization of battery capacity can be supported. For example, it is about 1/3 of the weight of a conventional glass substrate, is about 1/2 thin, and is about 10 times more durable than glass. It is also possible to obtain good visibility.

  The polymer-dispersed liquid crystal is aligned by applying an electric field to small particles of liquid crystal dispersed in the polymer, and is used as an optical shutter. Unlike TN (Twisted Nematic) type liquid crystal, it uses a scattering-non-scattering state, so there is no need for a polarizing plate in principle, it is bright as much as the polarizing plate is unnecessary, the image display operation speed is fast, and the liquid crystal injection process is unnecessary. There are advantages such as easy gap control and no rubbing, and it can also be applied to a projection type.

<Organic EL device>
The organic EL device according to the present invention comprises the above-mentioned display substrate.

  Such a display composed of organic EL elements has a transparent electrode disposed on the inside of two substrates, and (a) an injection function, (b) a transport function, and (c) light emission between them, for example. An organic EL element layer composed of a composite layer or the like in which layers having various functions are stacked is sandwiched and the periphery is sealed. In the case of constituting an EL display, for example, the thin display substrate of the present invention (including the patterned transparent conductive layer and auxiliary electrode layer) / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode. / The layer structure which consists of a sealing layer can be mentioned. The layer structure is not particularly limited, and specifically, anode / light emitting layer / cathode, anode / hole injection layer / light emitting layer / cathode, anode / light emitting layer / electron injection layer / cathode, anode / Many layer structures such as hole injection layer / light emitting layer / electron injection layer / cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode can be handled. It is not limited to this configuration, and may be accompanied by a color filter for colorization or other means (layers). As in the liquid crystal display, the film with the transparent conductive film of the present invention can be applied to the outside of the glass substrate, or the film with the transparent conductive film of the present invention can be used instead of the glass substrate, If both glass substrates are replaced with the film with a transparent conductive film of the present invention, the entire display can be made flexible. In particular, organic EL elements are chemically unstable due to the use of fluorescent light emission, and are extremely vulnerable to moisture. Therefore, a high water vapor barrier property after a product is desired. In order to ensure the water vapor barrier property of the laminated structure, the base film of the gas barrier film is preferably one having a deflection temperature under load of 150 ° C. or higher, preferably 160 ° C. or higher.

<Solar cell>
The film with a transparent conductive film according to the present invention is also suitable for application to a solar cell that requires moisture resistance such as an organic solar cell or a dye-sensitized solar cell or that requires content protection.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.
The materials and forming methods of the respective layers used in the examples and comparative examples are collectively described.

(1) Substrate:
“Polyethylene naphthalate” (Teonex Q65 (100 μm) manufactured by Teijin Ltd.) was used as the base material of the example.

(2) Smoothing layer:
As a sol-gel layer used as a smoothing layer, a coating agent mainly composed of aminoalkyltrialkoxysilane is applied by a spin coating method, and is heated on a hot plate at 120 ° C. for 2 minutes and then in an oven at 160 ° C. It is dried for 1 hour to form a sol-gel layer (planarization layer) having a thickness of 1.2 μm.

As a UV curable resin layer used as a smoothing layer, the following UV curable resin composition is applied, dried at 120 ° C. for 2 minutes, and then UV-cured by UV irradiation using a high-pressure mercury lamp. A curable resin layer having a thickness of 0.8 μm was formed.
-Pentaerythritol triacrylate: 50 parts by Nippon Kayaku Co., Ltd.-Photopolymerization initiator (Irgacure 184; manufactured by Ciba Geigy) 2 parts-Solvent (toluene) 50 parts

  As a smoothing layer which is a thermosetting resin, V-259-EH (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) is applied by a spin coating method, dried at 120 ° C. for 2 minutes, and further heated at 160 ° C. for 60 minutes. It dried and formed the smoothing layer with a film thickness of 1 micrometer.

(3) Gas barrier layer:
The formation method of the gas barrier layer 13 of an Example and a comparative example is as follows.
SiOx (x = 1.5 to 2.0) is placed in the film forming chamber of the ion plating apparatus, silicon dioxide is used as a vapor deposition material, and the film thickness of silicon oxide is 100 nm under the following film forming conditions. A gas barrier layer was provided so that

<Film formation conditions>
Film forming pressure: 1.7 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Oxygen gas flow rate: 10 sccm
・ Applied power: 11.0kW
SiON was placed in a film forming chamber of a magnetron sputtering apparatus, silicon nitride was used as a target, and a gas barrier layer was provided so that the film thickness of silicon oxynitride was 100 nm under the following film forming conditions.

<Film formation conditions>
Film forming pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Oxygen gas flow rate: 5 sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.2 kW
SiOC is placed in the film formation chamber of the plasma CVD apparatus, hexamethyldisiloxane (HMDSO) is used as a source gas, and a gas barrier layer is formed so that the silicon oxide carbide film thickness becomes 100 nm under the following film formation conditions. Was provided.

<Film formation conditions>
・ Film pressure: 10Pa
Argon gas flow rate: 10 sccm
・ Oxygen gas flow rate: 30 sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.8kW

<Example 1>
An ITO film having a thickness of 0.5 nm was formed on the base material using a magnetron sputtering method under the conditions of power 2.0 kW, Ar gas 500 sccm, and target ITO. By repeating these two steps 300 times, an ITO film of 150 nm could be obtained. As a result of measuring the ITO film as the uppermost layer, the particle diameter of the crystalline secondary particles: 0.3 μm and the crystalline secondary particles: 5 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 4.15. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 2>
An ITO film having a thickness of 15 nm was formed on the substrate by resistance heating vacuum deposition. The vapor deposition material is ITO particles, and the heating temperature is 1500 ° C. Next, plasma treatment was performed for 15 seconds with a DC power supply under conditions of power 1 kW, Ar 200 sccm, and oxygen 500 sccm. By repeating these two steps 10 times, an ITO film of 150 nm could be obtained. As a result of measuring the ITO film as the uppermost layer, the particle diameter of the crystalline secondary particles: 0.8 μm and the crystalline secondary particles: 15 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 6.50. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 3>
An ITO film having a thickness of 150 nm was formed on the base material by an ion plating method using an electric power of 7.0 kW, an Ar gas of 50 sccm, an ITO particle as an evaporation material, and a substrate temperature of 100 ° C. As a result of measuring the ITO film as the uppermost layer, the particle diameter of the crystalline secondary particles: 0.5 μm and the crystalline secondary particles: 30 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 1.50. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 4>
A gas barrier film with a transparent conductive film, in which each layer is formed from the bottom layer under the above conditions with a base film / gas barrier layer (SiON) layer structure, and an ITO layer is formed on the top layer in the same manner as in Example 1. Got. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.3 μm and the crystalline secondary particles: 5 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 3.38. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 5>
A gas barrier film with a transparent conductive film, in which each layer is formed from the bottom layer under the above conditions with a base film / gas barrier layer (SiOC) layer structure, and an ITO layer is formed on the top layer in the same manner as in Example 2. Got. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.8 μm and the crystalline secondary particles: 15 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 2.50. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 6>
A gas barrier film with a transparent conductive film, in which each layer is formed from the bottom layer under the above conditions with a base film / gas barrier layer (SiOx) layer structure, and an ITO layer is formed on the top layer in the same manner as in Example 3. Got. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.5 μm and the crystalline secondary particles: 30 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 5.42. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 7>
Each layer is formed under the above conditions from the bottom layer to the base film / gas barrier layer (SiON) / smoothing layer (thermosetting resin layer), and the ITO layer is the top layer in the same manner as in Example 1. A gas barrier film with a transparent conductive film formed on was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.3 μm and the crystalline secondary particles: 5 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 3.86. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 8>
Each layer is formed under the above conditions from the bottom layer to the base film / gas barrier layer (SiOx) / smoothing layer (UV curable resin layer), and the ITO layer is made the top layer in the same manner as in Example 2. A gas barrier film with a transparent conductive film formed was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.8 μm and the crystalline secondary particles: 15 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 5.27. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 9>
Each layer is formed under the above conditions from the bottom layer to the base film / gas barrier layer (SiOx) / smoothing layer (sol-gel layer), and the ITO layer is formed on the top layer in the same manner as in Example 3. A gas barrier film with a transparent conductive film was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.5 μm and the crystalline secondary particles: 30 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 2.64. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 10>
Each layer is formed from the bottom layer under the above conditions, with the gas barrier layer (SiON) / base film / gas barrier layer (SiON) / smoothing layer (thermosetting resin layer) / gas barrier layer (SiON) formed under the above conditions. A gas barrier film with a transparent conductive film obtained by forming an ITO layer as the uppermost layer by the same method as in Example 1 was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.3 μm and the crystalline secondary particles: 5 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 6.24. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 11>
Each layer is formed from the bottom layer under the above conditions, with the gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (thermosetting resin layer) / gas barrier layer (SiOx) formed and implemented. A gas barrier film with a transparent conductive film obtained by forming an ITO layer as the uppermost layer by the same method as in Example 2 was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.8 μm and the crystalline secondary particles: 15 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 5.87. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 12>
Each layer was formed from the bottom layer under the above conditions with the gas barrier layer (SiOC) / base film / gas barrier layer (SiOC) / smoothing layer (sol-gel layer) / gas barrier layer (SiOC), and Example 1 A gas barrier film with a transparent conductive film obtained by forming an ITO layer as the uppermost layer by the same method was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.5 μm and the crystalline secondary particles: 30 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 4.84. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 13>
Layer structure of gas barrier layer (SiOC) / smoothing layer (sol-gel layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (sol-gel layer) / gas barrier layer (SiOC) from the lowest layer Each layer was formed under the above conditions, and a gas barrier film with a transparent conductive film was obtained by forming an ITO layer as the uppermost layer in the same manner as in Example 1. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.3 μm and the crystalline secondary particles: 5 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 5.31. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 14>
Gas barrier layer (SiON) / smoothing layer (UV curable resin layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (UV curable resin layer) / gas barrier layer (SiON) Each layer was formed under the above-mentioned conditions, and a gas barrier film with a transparent conductive film was obtained by forming an ITO layer as the uppermost layer by the same method as in Example 2. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.8 μm and the crystalline secondary particles: 15 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 3.49. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 15>
Gas barrier layer (SiON) / smoothing layer (thermosetting resin layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (thermosetting resin layer) / gas barrier layer (from the bottom layer) A layer structure of (SiON) was formed under the above conditions, and a gas barrier film with a transparent conductive film formed by forming an ITO layer as the uppermost layer by the same method as in Example 3 was obtained. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 0.5 μm and the crystalline secondary particles: 30 particles / μm ² were obtained. The full width at half maximum at the maximum peak of the crystal phase was 4.45. Furthermore, when the ITO layer was patterned with an etching solution in order to form a 15 μm line using a photolithographic method, the residue of ITO particles could not be confirmed with an optical microscope, and good patterning was possible.

<Example 16>
A resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on the indium tin oxide of the gas barrier film with a transparent conductive film of Example 14, and then patterned by a photolithographic method. A transparent electrode layer having a stripe pattern with a width of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm is formed at a position corresponding to the color fluorescence conversion layer, and a gas barrier layer (SiON) / smoothing layer (UV curing) Resin layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (UV curable resin layer) / gas barrier layer (SiON) / transparent electrode layer (ITO) A substrate was obtained.

As a result of evaluating the characteristics of the obtained display substrate, the water vapor transmission rate is 0.01 g / m ² · day or less and the oxygen transmission rate is 0.01 cc / m ² · day · atm or less. And there was no significant growth or deflection.

<Example 17>
A display substrate was obtained in the same manner as in Example 16 except that the gas barrier film of Example 15 was used.

As a result of evaluating the characteristics of the obtained display substrate, the water vapor transmission rate is 0.01 g / m ² · day or less and the oxygen transmission rate is 0.01 cc / m ² · day · atm or less. And there was no significant growth or deflection.

<Example 18>
A liquid crystal display was manufactured using the display substrate of Example 8 with a well-known technique and configuration, and the LCD display was continuously driven for 100 hours.

<Example 19>
(1) A sheet (30 cm × 21 cm) polycarbonate (PC) film having a deflection temperature under load of 160 ° C. and a thickness of 200 μm was used as the substrate 11.

(2) Formation of blue color filter layer A blue filter material (Color Mosaic CB-7001: trade name, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied onto the polycarbonate (PC) film using a spin coating method. The coating film was patterned by a photolithographic method to form a blue color filter layer having a stripe pattern with a line width of 0.1 mm, a pitch (period) of 0.33 mm, and a film thickness of 6 μm.

(3) Formation of green conversion layer Coumarin 6 (0.7 parts by mass) as a fluorescent dye was dissolved in 120 parts by mass of propylene glycol monoethyl acetate (PEGMA) as a solvent. 100 parts by mass of “V259PA / P5” (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) as a photopolymerizable resin was added to the obtained solution and dissolved to obtain a coating solution.

  On the transparent support substrate on which the blue color filter layer obtained in the above step is formed, the coating solution prepared as described above is applied using a spin coating method, patterned by a photolithographic method, and line width A green color conversion layer having a stripe pattern of 0.1 mm, a pitch (period) of 0.33 mm, and a film thickness of 10 μm was formed.

(4) Formation of red conversion layer As fluorescent dyes, coumarin 6 (0.6 parts by mass), rhodamine 6G (0.3 parts by mass), and basic violet 11 (0.3 parts by mass) were used as propylene glycol mono-monomers. It was dissolved in 120 parts by mass of ethyl acetate (PEGMA). 100 parts by mass of a photopolymerizable resin “V259PA / P5” (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) was added to the solution and dissolved to obtain a coating solution.

  On the transparent support substrate on which the blue color filter layer and the green color conversion layer are formed, the coating solution prepared as described above is applied using a spin coating method, and patterned by a photolithographic method, with a line width of 0.1 mm, A red color conversion layer having a stripe pattern with a pitch (period) of 0.33 mm and a film thickness of 10 μm was formed.

  The line-shaped patterns of the red color conversion layer, the green color conversion layer, and the blue color filter layer formed as described above are arranged in parallel with the gap width between them being 0.01 mm to form each color conversion layer.

(5) Formation of gas barrier layer and smoothing layer Each layer is sequentially formed on both surfaces of the base material including the color conversion layer formed in the above-described step in the same manner as in Example 15 to obtain a gas barrier layer (SiON) / smoothing layer. (Thermosetting resin layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (thermosetting resin layer) / gas barrier layer (SiON) were obtained.

(6) Formation of transparent electrode layer A transparent electrode (indium tin oxide) was formed on the entire surface of the gas barrier layer (SiON) by sputtering. After applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) on this indium tin oxide, patterning is carried out by a photolithographic method, and at a position corresponding to the fluorescence conversion layer of each color. A transparent electrode layer having a stripe pattern with a width of 0.094 mm, a gap of 0.016 mm, and a film thickness of 100 nm was formed.

(7) Formation of organic EL related layer On the transparent electrode layer surface, a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer are sequentially formed on the entire surface without breaking the vacuum in a resistance heating vapor deposition apparatus. did. During film formation, the internal pressure of the vacuum chamber was reduced to 1 × 10 ⁻⁴ Pa. As the hole injection layer, copper phthalocyanine (CuPc) was laminated so as to have a film thickness of 100 nm. As the hole transport layer, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (—NPD) was stacked so as to have a film thickness of 20 nm. As the organic light emitting layer, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (DPVBi) was laminated so as to have a film thickness of 30 nm. As the electron injection layer, aluminum chelate (tris (8-hydroxyquinoline) aluminum complex, Alq) was laminated so as to have a film thickness of 20 nm.

  Next, using a mask that can obtain a pattern with a width of 0.30 mm and an interval of 0.03 mm perpendicular to the stripe pattern of the anode (transparent electrode layer) without breaking the vacuum, a 200 nm thick Mg / Ag (mass) A cathode composed of 10/1 ratio layers was formed. The organic EL light-emitting device thus obtained was sealed with a sealing glass and a UV curable adhesive in a dry nitrogen atmosphere in a glove box (both oxygen and moisture concentrations were 10 ppm or less), and a gas barrier layer (SiON) / smooth Layer (thermosetting resin layer) / gas barrier layer (SiOx) / base film / gas barrier layer (SiOx) / smoothing layer (thermosetting resin layer) / gas barrier layer (SiON) / transparent electrode layer / hole injection An organic EL color display having a layer structure of layer / hole transport layer / organic light emitting layer / electron injection layer / cathode was obtained.

  The organic EL color display was continuously driven for 100 hours, but could be displayed satisfactorily without problems.

<Comparative Example 1>
In Example 1, a film with a transparent conductive film was obtained in which one thin film formation was 0.1 nm and the number of repetitions was 1500. As a result of measuring the uppermost ITO film, the presence of crystalline secondary particles could not be recognized.

<Comparative example 2>
In Example 3, the ITO layer is formed as the uppermost layer under the same conditions except that the substrate temperature is set to −10 ° C. As a result of measuring the ITO film, the particle diameter of the crystalline secondary particles: 5.0 μm and the crystalline secondary particles: 3 particles / μm ² were obtained.

Evaluation Evaluation is performed by measuring the water vapor transmission rate and the oxygen transmission rate in the particle diameter, gas barrier film state, and organic EL element state by the following measurement method, and the results are shown in Table 1 and the specification.

  The particle diameter was determined visually with Nanopics 1000 manufactured by Seiko Instruments Inc. in a measuring range of 4 μm.

The water vapor transmission rate was measured using a water vapor transmission rate measurement device (manufactured by MOCON, USA, PERMAT RAN-W 3/31: trade name) under the conditions of a measurement temperature of 37.8 ° C. and a humidity of 100% Rh. The detection limit is 0.01 g / m ² · day, and when it is less than the detection limit, it is expressed as 0.01 g / m ² / day or less.

The oxygen permeability was measured using an oxygen gas permeability measuring device (manufactured by MOCON, USA, OX-TRAN 2/20: trade name) under the conditions of a measurement temperature of 23 ° C. and a humidity of 90% Rh. The detection limit is 0.01 cc / m ² · day · atm, and when it is less than the detection limit, it is expressed as 0.01 cc / m ² / day or less. Moreover, when it is more than the detection limit maximum, it represents by (-).

(Summary of evaluation results)
The water vapor permeability of the gas barrier films of Examples 4 to 9 is 0.03 to 0.48 g / m ² · day, and the oxygen permeability is 0.03 to 0.56 cc / m ² · day · atm. 10 to 15 has a water vapor transmission rate of 0.01 g / m ² · day or less, an oxygen transmission rate of 0.01 cc / m ² · day · atm or less, sufficient gas barrier properties, and significant elongation and deflection. There wasn't.

  The results of evaluating the characteristics of the gas barrier films of Comparative Examples 1 and 2 were not at a level that could be used as a display substrate because Comparative Example 1 had a high surface resistance value and Comparative Example 2 had a large surface roughness.

Sectional drawing of the especially preferable specific example of the film with a transparent conductive film by this invention Sectional drawing of the especially preferable specific example of the film with a transparent conductive film by this invention Sectional view of a particularly preferred embodiment of a display substrate according to the present invention.

Claims (7)

The transparent conductive film comprises a transparent base material and a transparent conductive film made of indium-tin oxide. The transparent conductive film has (ii) 5 crystalline secondary particles having an average particle diameter of 0.3 μm on the surface / μm ² , (B) 30 / μm ² crystalline secondary particles having an average particle size of 0.5 μm on the surface , or (c) 15 crystalline / μm ² crystalline secondary particles having an average particle size of 0.8 μm on the surface. The film with a transparent conductive film characterized by having a surface resistance value of 19 to 45 Ω / □ .
(Here, the crystalline secondary particles are those whose crystallinity has been confirmed by measurement using Rigaku's automatic X-ray diffractometer RINT 2000, and the particle size is Nanopics 1000 manufactured by Seiko Instruments Inc. It was determined in accordance with JIS B0601 The film with a transparent conductive film according to claim 1 , wherein in the transparent conductive film, a half width at a maximum peak angle (222 plane) of the crystal phase is 1.5 to 9.5.
(Here, the maximum peak of the crystal phase is that obtained by RINT 2000 / PC series manufactured by Rigaku Corporation.) A display substrate comprising the film with a transparent conductive film according to claim 1 . A display comprising the display substrate according to claim 3 . A liquid crystal display device comprising the display substrate according to claim 3 . An organic EL device comprising the display substrate according to claim 3 . The transparent conductive film comprises a transparent base material and a transparent conductive film made of indium-tin oxide, and the transparent conductive film has (ii) 5 crystalline secondary particles having an average particle diameter of 0.3 μm on the surface / μm ^2. (B) Crystalline secondary particles with an average particle size of 0.5 μm on the surface are 30 particles / μm ² , or (C) Crystalline secondary particles with an average particle size of 0.8 μm on the surface is 15 particles / μm ² And a method for producing a film with a transparent conductive film having a surface resistance value of 19 to 45Ω / □ ,
Plasma treatment, ion bombardment treatment, glow discharge treatment in an oxidizing gas every time a transparent conductive film of 0.3 to 10 nm is formed on the transparent substrate on the transparent substrate. A method for producing a film with a transparent conductive film, wherein the step of performing either an arc discharge process or a spraying process is performed a plurality of times and the transparent conductive thin films formed at each time are accumulated.
(Here, the crystalline secondary particles are those whose crystallinity has been confirmed by measurement using Rigaku's automatic X-ray diffractometer RINT 2000, and the particle size is Nanopics 1000 manufactured by Seiko Instruments Inc. It was determined in accordance with JIS B0601

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