JP2006044231A - Gas barrier film, substrate for display using the same and display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gas barrier film capable of winding, which is hardly elongated or deflected by heat or the like on its processing or usage, has a high dimensional stability and can form a stable barrier layer hardly changed by chmicals or the like on its processing or usage and is excellent in gas barrier property to water vapor, oxygen or the like, and to provide a substrate for a display using the same and the display. <P>SOLUTION: A substrate film 11 with a deflection temperature under load of at least 150°C, at least a gas barrier layer 13A and a smoothing layer 15A or the smoothing layer 15A and the gas barrier layer 13A are formed in the order on the substrate film 11, the substrate film 11 preferably comprises a polyethylene naphthalate, the gas barrier layer 13A comprises an inorganic oxide, an inorganic oxynitride, an inorganic oxycarbide or an inorganic oxynitride-carbide and the smoothing layer 15A is a material containing a cardopolymer, sol-gel or acrylic skeleton. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a gas barrier film, and more particularly, for example, a gas barrier film suitable for display substrates or display coating applications, capable of withstanding heat during processing and use, and excellent in gas barrier properties, and the same The present invention relates to a display substrate and a display using the above.

In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated.
Also, “EL” is “electroluminescence”, “LCD” is “liquid crystal display”, “PET” is “polyethylene terephthalate”, “PEN” is “polyethylene naphthalate” abbreviation, functional expression, common name, or industry term It is.
In the definition of film and sheet in JIS-K6900, a sheet is a thin and generally flat product whose thickness is small relative to the length and width. A film has a thickness compared to the length and width. A thin, flat product that is extremely small and has an arbitrarily limited maximum thickness, usually supplied in the form of a roll. Therefore, it can be said that a sheet with a particularly thin thickness is a film, but the boundary between the sheet and the film is not clear and is difficult to distinguish clearly. In this specification, both a thick sheet and a thin sheet are used. Is defined as “film”.

(Technical Background) Currently, various types of displays are used, and their practical application is being studied. Except for the cathode ray tube type, all of them are aimed at thinning, and moreover, 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 has conventionally constituted a display. Alternatively, for the purpose of extending the lifetime 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 a processing step of laminating various functional layers for causing the synthetic resin film to function as a display, or Heat resistance, moisture resistance, mechanical strength, etc. are required for heat, humidity and mechanical external forces such as processing steps for forming a gas barrier layer that imparts gas barrier properties.
However, general synthetic resin films have much lower heat resistance or moisture resistance than glass substrates, so heating in the metal thin film formation process by vapor deposition or the like, or heating after coating with a thermosetting resin paint Poor chemical resistance is unavoidable, such as deformation due to heating in a curing process or the like, or deformation caused by moisture absorption due to contact with an aqueous solution in a metal thin film etching process or resist developing process. The resulting display or gas barrier film also suffers from dimensional accuracy problems such as loss of flatness, delamination due to misalignment with laminated metal thin films, or misalignment with preset dimensions. . Furthermore, in an organic electronic device such as an LCD or EL display panel, and an organic transistor such as an organic transistor, when the formed element is exposed to water vapor or oxygen, the performance deteriorates, and the light is not emitted or the circuit is not driven. Such troubles also occur.
For this reason, gas barrier films used for display substrates, organic electronic device substrates, and displays are less prone to flatness and peeling due to heat generated during processing and use, tension during heating, and the like. In order to increase the dimensional stability, it is difficult to cause the heat resistance, the thermal expansion of 150 ° C. or more, the coefficient of linear expansion of 50 ppm or less, and particularly in the display such as LCD and EL display panel, the formed element is water vapor, oxygen, etc. There is a demand for ultra-high gas barrier properties so as not to degrade performance when touched.

  (Main application) The main application of the gas barrier film of the present invention is not particularly limited, as long as it is an application that requires heat resistance and gas barrier properties as well as the aforementioned display substrate. It can be used not only for packaging materials such as foods and pharmaceuticals but also for organic electronic devices such as touch panels, illumination film substrates, solar cell film substrates, circuit board film substrates, electronic paper, and organic transistors.

(Prior Art) Conventionally, a gas barrier laminated film is a gas barrier film consisting of two layers of a polymer resin substrate, an inorganic compound vapor-deposited layer, and a coating agent coating layer mainly composed of a water / alcohol mixed solution. (For example, refer to Patent Document 1).
The gas barrier laminate film comprises an inorganic compound vapor-deposited layer, one or more metal alkoxides or hydrolysates thereof, and an isocyanate compound having at least two isocyanate groups in the molecule, on the polymer resin substrate. It is known that the mixed solution is composed of two layers, preferably a coating layer of a coating agent containing tin chloride, melamine, melamine resin, and formaldehyde (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, all of 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 transmission rate is about 1 cc / m ² · day · atm, the water vapor transmission rate is about 0.1 g / m ² · day, and the oxygen transmission rate is about 0.3 cc / m ² · day · atm. There is a drawback that it is insufficient to prevent the deterioration of the light emitting layer of an organic EL device, etc., and further, the heat resistance at 150 ° C. or higher, chemical resistance, and low linear expansion are described and referred to. Not.

Japanese Patent Laid-Open No. 7-164591 JP 7-268115 A JP-A-11-222508

  Accordingly, the present invention has been made to solve such problems. Its purpose is to have a heat resistance of 150 ° C or higher, and it is difficult to stretch and bend due to heat during processing and use, so it has high dimensional stability and high chemical resistance, so it can be used during processing and use. Provides a gas barrier film with excellent gas barrier properties such as water vapor and oxygen, as well as a display substrate, a substrate for organic electronic devices, and a display. It is to be.

In order to solve the above-mentioned problems, a gas barrier film according to the invention of claim 1 includes a base film having a deflection temperature under load of 150 ° C. or more, and at least a gas barrier layer and a smoothing layer or a smoothing on the base film. The layer and the gas barrier layer are formed in this order.
The gas barrier film according to the invention of claim 2 is such that the substrate film is polyethylene naphthalate.
The gas barrier film according to the invention of claim 3 is such that the gas barrier layer is an inorganic oxide, an inorganic oxynitride, an inorganic oxycarbide or an inorganic oxynitride carbide.
The gas barrier film according to the invention of claim 4 is such that the smoothing layer contains a cardo polymer.
The gas barrier film according to the invention of claim 5 is such that the smoothing layer contains an acrylic skeleton.
The gas barrier film according to the invention of claim 6 is such that the smoothing layer has a silane coupling agent having an organic functional group and a hydrolyzable group, and a crosslink having an organic functional group that reacts with the organic functional group of the silane coupling agent. It is made to be the coating film of the coating composition comprised from the active compound at least as a raw material.
The gas barrier film according to the invention of claim 7 is the gas barrier film according to any one of claims 1 to 6, wherein at least one stress relaxation layer is formed on at least one side of the base film. That's what it did.
The gas barrier film according to the invention of claim 8 is such that a transparent conductive film is formed on the gas barrier layer or the smoothing layer surface of the gas barrier film of any one of claims 1 to 6.
A display substrate according to the invention of claim 9 is formed by using the gas barrier film according to any one of claims 1 to 7.
The display substrate according to the invention of claim 10 is such that a transparent conductive film is formed on the gas barrier layer or the smoothing layer surface of the gas barrier film according to any one of claims 1 to 7.
The display substrate according to the invention of claim 11 is such that an auxiliary electrode layer is formed on the transparent conductive layer surface of the display substrate of claim 10.
A display according to a twelfth aspect of the present invention is made by using the display substrate according to any one of the ninth to eleventh aspects.
An organic EL element according to the invention of claim 13 is formed by using the display substrate according to any one of claims 9 to 11.
According to a fourteenth aspect of the present invention, there is provided a liquid crystal display device using the display substrate according to any one of the ninth to eleventh aspects.
A color filter according to a fifteenth aspect of the present invention is formed using the display substrate according to the tenth aspect.
According to a sixteenth aspect of the present invention, there is provided a display comprising the color filter according to the fifteenth aspect.
An organic EL element according to a seventeenth aspect of the present invention is formed by using the color filter according to the fifteenth aspect.

  The inventors of the present invention have made extensive studies, and with respect to a resin film substrate having a deflection temperature under load of 150 ° C. or more, particularly preferably a polyethylene naphthalate substrate, an inorganic thin film layer formed by a smoothing layer and a vacuum film formation method, In combination, heat resistance and ultra-high gas barrier properties can be achieved, and a polyethylene naphthalate base material and an inorganic thin film can be obtained by having a heat resistance of 150 ° C. or higher and a linear expansion coefficient of preferably 50 ppm / K or lower. Excellent adhesion to the layer, can be wound up, is not easily stretched or bent due to heat during processing or use, has high dimensional stability, and changes in quality due to chemicals during processing or use It was difficult to solve the problem by finding that it has good processability that can form a film stably.

According to the first aspect of the present invention, it has a heat resistance of 150 ° C. or higher, and is less prone to elongation and deflection due to heat during processing and use. Therefore, it has high dimensional stability and gas barrier properties such as water vapor and oxygen. An excellent gas barrier film is provided.
According to the present invention of claim 2, since it has a heat resistance of 150 ° C. or higher and a low coefficient of linear expansion, it is difficult to cause elongation or deflection due to heat during processing or use, and therefore has high dimensional stability, and Since the chemical resistance is high, it is possible to form a stable gas barrier film that is unlikely to be altered by chemicals during processing or use, so that a gas barrier film having excellent gas barrier properties such as water vapor and oxygen is provided.
According to the present invention of claims 3 to 6, a gas barrier film excellent in gas barrier properties such as water vapor and oxygen is provided.
According to the seventh aspect of the present invention, there is provided a gas barrier film that is free from warping and distortion and excellent in gas barrier properties such as water vapor and oxygen.
According to the eighth aspect of the present invention, there is provided a gas barrier film for a film substrate such as a touch panel, a solar cell, a circuit board, and electronic paper.
According to the present invention of claims 9 to 10, it has a heat resistance of 150 ° C. or higher and a low coefficient of linear expansion, and is less prone to elongation or deflection due to heat during processing or use, so dimensional stability is high. In addition, since the chemical resistance is high, it is possible to form a stable gas barrier film that is unlikely to be altered by chemicals during processing or use, and thus a display substrate having excellent gas barrier properties such as water vapor and oxygen is provided.
According to the present invention of claim 11, there is provided a display substrate that is more stable and has higher conductivity.
According to the twelfth aspect of the present invention, there is provided a display having high heat resistance, dimensional stability (low linear expansion) and chemical resistance and excellent gas barrier properties such as water vapor and oxygen.
According to the thirteenth aspect of the present invention, there is provided an organic EL device having high heat resistance, dimensional stability (low linear expansion) and chemical resistance, excellent gas barrier properties such as water vapor and oxygen, and a long life.
According to the present invention of claim 14, a liquid crystal display device having the effects of claims 9 to 11 is provided.
According to the present invention of claim 15, a color filter having the effect of claim 10 is provided.
According to the present invention of claim 16, a display having the effect of claim 15 is provided.
According to the present invention of claim 17, an organic EL element having the effect of claim 15 is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing one embodiment of the gas barrier film of the present invention.
FIG. 2 is a cross-sectional view showing one embodiment of the gas barrier film of the present invention.
FIG. 3 is a cross-sectional view showing one embodiment of the gas barrier film of the present invention.
FIG. 4 is a cross-sectional view showing one embodiment of the display substrate of the present invention.

As shown in FIG. 1A, the gas barrier film 10 of the present invention has a base film 11 and a gas barrier layer 13A and a smoothing layer 15A laminated on at least one side of the base film 11. It consists of base film 11 / gas barrier layer 13A / smoothing layer 15A, or, as shown in FIG. 1 (B), gas barrier layer 13A and smoothing layer 15A are laminated in this reverse order, The base film 11 / smoothing layer 15A / gas barrier layer 13A may be used. In short, the layers may be configured so that the gas barrier layer and the smoothing layer are adjacent to each other.
Further, as shown in FIG. 2A, a gas barrier layer is further provided on the surface of the smoothing layer to form a base film 11 / gas barrier layer 13A / smoothing layer 15A / gas barrier layer 13B, or FIG. ), A smoothing layer may be further provided on the surface of the gas barrier layer to form a base film 11 / smoothing layer 15A / gas barrier layer 13A / smoothing layer 15B. Furthermore, you may provide a gas barrier layer and / or a smoothing layer in this layer structure. In short, the gas barrier layer and the smoothing layer may have one set adjacent to each other, and the one set may be laminated by repeating a plurality of sets. By repeating in this way, the gas barrier property can be remarkably improved. it can.
Furthermore, in order to evenly relieve the film stress of each layer, it is preferable to have a symmetric or nearly symmetric layer structure, so that the stress relieving layer is disposed on at least one side of the base film so as to cancel out the film stress. It is preferable to form. That is, in the configuration example of the approximate symmetry layer shown in FIG. 3A, the stress relaxation layer 31 / the substrate film 11 / the gas barrier layer 13A / the smoothing layer 15A is used. Here, as the stress relaxation layer 31, the gas barrier layer 13C is preferably a stress relaxation layer, and both stress relaxation and gas barrier property improvement can be achieved. In the configuration example of the front / back symmetry layer shown in FIG. 3B, the layer configuration is the same as that of the stress relaxation layer 31 / base film 11 / gas barrier layer 13A / smoothing layer 15A, but the gas barrier layer 13C is used as the stress relaxation layer 31. / By making the smoothing layer 15C into two layers, stress relaxation and gas barrier property improvement can be achieved by making the front and back symmetrical. Even in the layer configuration of the base film 11 / stress relaxation layer 31 / gas barrier layer 13A / smoothing layer 15A in the configuration example of the asymmetric layer shown in FIG. 3C, the gas barrier layer 13C in which the stress state is changed as the stress relaxation layer 31 and the like What is necessary is just to have the stress relaxation layer 31 which has the stress relaxation function of 1 layer or multiple layers in the at least one side of the base film 11. FIG.
Furthermore, as shown in FIG. 4, it can be set as a display substrate by providing a transparent electrode layer, an auxiliary electrode layer or other layers as required, on the smoothing layer or gas barrier layer surface.
That is, one set of gas barrier layer / smoothing layer or smoothing layer / gas barrier layer is essential, and other layers may be provided or sandwiched between other layers.

  (Base film) The thermal properties required for the base film 11 are also defined by the maximum continuous use temperature, and the maximum continuous use temperature is 150 ° C or higher. Since the maximum continuous use temperature of each resin is equal to the deflection temperature under load of each resin, the deflection temperature under load as the base film 11 is 150 ° C. or higher, more preferably the linear expansion coefficient of the base film 11 is 50 ppm / K. It is the following resin film. When the deflection temperature under load is less than 150 ° C., the base film 11 is easily softened by heat generated when the gas barrier layer 13A is formed on the base film 11 and the external force applied to the base film 11 causes the base film 11 to be softened. Is easy to deform. In this sense, it is preferable that the deflection temperature under load is high, but it is 300 ° C. or lower in the range specifically exemplified below. When the deflection temperature under load exceeds 300 ° C., the flexibility of the base film itself is lowered and the flexibility is lost, so that continuous processing becomes difficult.

  Specific examples of the resin film of the base film 11 include thermoplastic resins such as polyamide, polyacetal, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, or syndiotactic polystyrene, which are thermosetting. Examples of preferred resins include polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, fluororesin, and polyether nitrile. In addition, as an example of a synthetic resin as a material constituting the base film 11, a polycarbonate, a modified polyphenylene ether, a polycyclohexene, or a polynorbornene-based resin, which is a thermoplastic resin in an amorphous resin, Polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, thermoplastic polyimide, and the like can be exemplified as more preferable resins. Especially, since a polycarbonate has low water absorption, the base film 11 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 the base film 11, 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 ( (Trade name: “ZEONOR”); 150 ° C. or norbornene resin (trade name: “ARTON” manufactured by JSR Corporation); 155 ° C.

  (Polyester) The polyester constituting the base film 11 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 11 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 thereof, 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, “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.

  (Copolymer) When the polyester is a copolymer, a compound having two ester-forming functional groups in the molecule can be used as the copolymer component constituting the copolymer. Examples of such a compound include oxalic acid, adipic acid, Phthalic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, phenylindanedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, tetralindicarboxylic acid, Dicarboxylic acids such as decalin dicarboxylic acid and diphenyl ether dicarboxylic acid, oxycarboxylic acids such as p-oxybenzoic acid and p-oxyethoxybenzoic acid, or propylene glycol, trimethylene glycol, tetramethylene glycol, hexamethyle Glycol, cyclohexane methylene glycol, neopentyl glycol, ethylene oxide adduct of bisphenol sulfone, ethylene oxide adduct of bisphenol A, diethylene glycol, can be preferably used dihydric alcohols such as polyethylene oxide glycol. These compounds may be used alone or in combination of two or more. Of these, the acid component is preferably isophthalic acid, terephthalic acid, 4,4′-diphenyldicarboxylic acid, 2,7-naphthalenedicarboxylic acid, p-oxybenzoic acid, and the glycol component is trimethylene glycol. , An ethylene oxide adduct of hexamethylene glycol neopentyl glycol and bisphenol sulfone.

  The polyethylene-2,6-naphthalenedicarboxylate may be one in which a terminal hydroxyl group and / or a carboxyl group is partially or entirely blocked with a monofunctional compound such as benzoic acid or methoxypolyalkylene glycol. Further, it may be copolymerized with a very small amount of, for example, a trifunctional or higher functional ester-forming compound such as glycerin and pentaerythritol within a range in which a substantially linear polymer is obtained.

Polyester is a conventionally known method, for example, a method of directly obtaining a low-polymerization degree polyester by reaction of dicarboxylic acid and glycol, a lower alkyl ester of dicarboxylic acid and glycol are conventionally known transesterification catalysts, such as sodium, potassium, It can be obtained by a method of performing a polymerization reaction in the presence of a polymerization catalyst after reacting using one or more of compounds containing magnesium, calcium, zinc, strontium, titanium, zirconium, manganese and cobalt. Examples of the polymerization catalyst include antimony compounds such as antimony trioxide and antimony pentoxide, germanium compounds represented by germanium dioxide, tetraethyl titanate, tetrapropyl titanate, tetraphenyl titanate or a partial hydrolyzate thereof, and titanyl ammonium oxalate. , Titanium compounds such as potassium titanyl oxalate and titanium trisacetylacetonate can be used.
When polymerization is performed via a transesterification reaction, a phosphorus compound such as trimethyl phosphate, triethyl phosphate, tri-n-butyl phosphate, or normal phosphoric acid is usually added for the purpose of deactivating the transesterification catalyst before the polymerization reaction. However, the content in the polyethylene-2,6-naphthalene dicarboxylate as the phosphorus element is preferably 20 to 100 ppm by weight from the viewpoint of the thermal stability of the polyester. The polyester may be converted into chips after melt polymerization, and further subjected to solid phase polymerization under heating under reduced pressure or in an inert gas stream such as nitrogen.

  The polyester is preferably a polyester having an ethylene terephthalate unit or an ethylene-2,6-carboxylate unit of 90 mol% or more, preferably 95% or more, more preferably 97% or more. The intrinsic viscosity of the polyester is preferably 0.40 dl / g or more, and more preferably 0.40 to 0.90 dl / g. If the intrinsic viscosity is less than 0.40 dl / g, process cutting may occur frequently. On the other hand, if it is higher than 0.9 dl / g, melt extrusion is difficult because of high melt viscosity, and the polymerization time is long and uneconomical. The polyester may contain a colorant, an antistatic agent, an antioxidant, an organic lubricant, a catalyst, and the like as necessary.

  The polyester film (with a coating layer) improves wettability with the layer (resulting in smoothing of the forming layer) and adhesion when forming another layer on at least one side of the base material layer film made of polyester. Therefore, a coating layer may be provided. The coating layer is also called an adhesion promoting layer, a primer layer, an undercoat layer, an anchor coat layer or the like depending on the purpose. This coating layer contains a polymer binder and fine particles, and the polymer binder and the fine particles have substantially the same refractive index. Having substantially the same refractive index means that the refractive index difference between them is 0.04 or less. More preferably, it is 0.02 or less, More preferably, it is 0.01 or less, Most preferably, it is 0.005 or less. When the difference in refractive index exceeds 0.04, light is greatly scattered due to the difference in refractive index at the boundary between the polymer binder and the fine particles, the haze of the coating layer is increased, and the transparency is deteriorated.

  (Binder) The polymer binder is preferably a polyester resin and a mixture of an acrylic resin having an oxazoline group and a polyalkylene oxide chain from the viewpoint of imparting good adhesiveness. The polymer binder is preferably soluble or dispersible in water, but water-soluble one containing some organic solvent can also be preferably used. As the polyester resin constituting the polymer binder, a polyester obtained from the following polybasic acid component and diol component can be used. That is, as the polyvalent base component, for example, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, Examples include pyromellitic acid, dimer acid, and 5-sodium sulfoisophthalic acid. As the polyester resin constituting the polymer binder, it is preferable to use a copolymerized polyester using two or more kinds of dicarboxylic acid components. The polyester resin may contain an unsaturated polybasic acid component such as maleic acid or itaconic acid, or a hydroxycarboxylic acid component such as p-hydroxybenzoic acid, if it is in a slight amount. Examples of the diol component of the polyester resin include ethylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylene glycol, dimethylolpropane, and the like ( Examples thereof include ethylene oxide) glycol and poly (tetramethylene oxide) glycol.

  The glass transition point of the polyester resin of the polymer binder is preferably 40 to 100 ° C, more preferably 60 to 80 ° C. Within this range, excellent adhesion and excellent scratch resistance can be obtained. On the other hand, if the deflection temperature under load is less than 40 ° C., blocking tends to occur between the films, and if it exceeds 100 ° C., the coating film becomes hard and brittle, and the scratch resistance is deteriorated. The polymer binder of the coating layer usually has a refractive index in the range of 1.50 to 1.60.

  As an acrylic resin having an oxazoline group and a polyalkylene oxide chain that may be used as a component of a polymer binder, for example, an acrylic resin comprising a monomer having an oxazoline group as shown below and a monomer having a polyalkylene oxide chain is used. Resin can be used. Examples of the monomer having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2 -Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline can be exemplified. One or a mixture of two or more of these can be used. Among these, 2-isopropenyl-2-oxazoline is preferred because it is easily available industrially. By using an acrylic resin having an oxazoline group, the cohesive force of the coating layer is improved, and the adhesiveness to the hard coat, the adhesive layer and the like is further strengthened. Further, it is possible to impart scratch resistance to the metal roll in the film forming process or in the hard coat processing process.

  Examples of the monomer having a polyalkylene oxide chain include those obtained by adding polyalkylene oxide to the ester part of acrylic acid or methacrylic acid. Examples of the polyalkylene oxide chain include polymethylene oxide, polyethylene oxide, polypropylene oxide, and polybutylene oxide. The repeating unit of the polyalkylene oxide chain is preferably 3 to 100. By using an acrylic resin having a polyalkylene oxide chain, the compatibility of the polyester resin of the polymer binder of the coating layer and the acrylic resin is better than that of an acrylic resin not containing a polyalkylene oxide chain, and the transparency of the coating layer is improved. Can be improved. If the repeating unit of the polyalkylene oxide chain is less than 3, the compatibility between the polyester resin and the acrylic resin is poor and the transparency of the coating layer is poor. If it exceeds 100, the moisture and heat resistance of the coating layer is lowered, and the humidity and temperature are high. Therefore, the adhesion with a hard coat is deteriorated, which is not preferable.

  The (acrylic) acrylic resin can be copolymerized with the monomers exemplified below as other copolymerization components. That is, alkyl acrylate, alkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, cyclohexyl, etc.); Hydroxy-containing monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate and allyl glycidyl ether; acrylic acid and methacrylic acid Carboxy groups such as itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.) Monomers having salts thereof: acrylamide, methacrylamide, N-alkyl acrylamide, N-alkyl methacrylamide, N, N-dialkyl acrylamide, N, N-dialkyl methacrylate (alkyl groups include methyl, ethyl, n-propyl Group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), N-alkoxyacrylamide, N-alkoxymethacrylamide, N, N-dialkoxyacrylamide, N, N -Dialkoxymethacrylamide (alkoxy groups include methoxy, ethoxy, butoxy, isobutoxy, etc.), acryloylmorpholine, N-methylolacrylamide, N-methylolmethacrylamide, N-phenylacrylic Monomers having an amide group such as N-phenylmethacrylamide; monomers of acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl isocyanate, allyl isocyanate, styrene, α-methyl styrene, vinyl methyl ether, vinyl ethyl ether Vinyl trialkoxysilane, alkylmaleic acid monoester, alkyl fumaric acid monoester, alkylitaconic acid monoester, acrylonitrile, methacrylonitrile, vinylidene chloride, ethylene, propylene, vinyl chloride, vinyl acetate and butadiene.

  The content ratio of the polyester resin forming the coating layer is preferably 5 to 95% by weight, and particularly preferably 50 to 90% by weight. The content ratio of the acrylic resin having an oxazoline group and a polyalkylene oxide chain forming the coating layer in the coating layer is preferably 50 to 90% by weight, and particularly preferably 10 to 50% by weight. When the polyester resin exceeds 95% by weight, or the acrylic resin having an oxazoline group and a polyalkylene oxide chain is less than 5% by weight, the cohesive force of the coating layer is lowered, and the adhesion to the hard coat or the pressure-sensitive adhesive is insufficient. This is not preferable. If the acrylic resin exceeds 90% by weight, the adhesion to the polyester film is lowered, and the adhesion to the hard coat or the pressure-sensitive adhesive may be insufficient, which is not preferable.

(Fine particles) As the fine particles constituting the coating layer, it is preferable to use composite inorganic particles of silica and titania. The composite inorganic particles of silica and titania can be arbitrarily adjusted in refractive index, and the refractive index can be easily adjusted. Since the refractive index of the polymer binder is in the range of 1.50 to 1.60, the refractive index of the polymer binder and the fine particles can be easily matched. The refractive index of the fine particles is also preferably in the range of 1.50 to 1.60, similar to the polymer binder. The average particle diameter of the fine particles is preferably in the range of 40 to 120 nm. If the average particle diameter is smaller than 40 nm, sufficient lubricity and scratch resistance may not be obtained. This is not preferable because the total light transmittance is lowered.
The content of the fine particles is preferably in the range of 0.1 to 10% by weight of the coating layer. If it is less than 0.1% by weight, sufficient lubricity and scratch resistance cannot be obtained, and if it exceeds 10% by weight, the cohesive strength of the coating film is lowered and the adhesiveness is deteriorated. This is not preferable because the rate decreases.

  (Aliphatic wax) It is preferable to contain an aliphatic wax in the coating layer because the film surface can be lubricated, and the content is preferably 0.5 to 30% by weight, more preferably 1 to 10% by weight. %. If the content is less than 0.5% by weight, the slipperiness of the film surface may not be obtained, which is not preferable. If it exceeds 30% by weight, adhesion to a polyester film substrate and easy adhesion to a hard coat or a pressure-sensitive adhesive may be insufficient, which is not preferable. Specific examples of the aliphatic wax include plant waxes such as carnauba wax, candelilla wax, rice wax, wood wax, jojoba oil, palm wax, rosin-modified wax, olicuric wax, sugar cane wax, esparto wax, and bark wax. , Animal waxes such as beeswax, lanolin, whale wax, ibota wax, shellac wax, mineral waxes such as montan wax, ozokerite, ceresin wax, petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam, and fishertro push wax And synthetic hydrocarbon waxes such as polyethylene wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax. Among these, carnauba wax, paraffin wax, and polyethylene wax are particularly preferable because they are easy to adhere to hard coats and pressure-sensitive adhesives and have good lubricity. These are preferably used as water dispersions because they can reduce the environmental burden and are easy to handle.

  (Additive) The coating layer may contain other fine particles to the extent that it does not affect the transparency in order to further improve the lubricity and scratch resistance. Examples of the other fine particles include calcium carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, silicon oxide, sodium silicate, aluminum hydroxide, iron oxide, zirconium oxide, barium sulfate, titanium oxide, tin oxide, and trioxide. Examples thereof include inorganic fine particles such as antimony, carbon black, and molybdenum disulfide, and organic fine particles such as acrylic crosslinked polymer, styrene crosslinked polymer, silicone resin, fluororesin, benzoguanamine resin, phenol resin, and nylon resin. Among these, for the water-insoluble solid substance, it is preferable to select fine particles whose specific gravity does not exceed 3 in order to avoid sedimentation in the aqueous dispersion.

  (Film forming method) The oriented polyester film is obtained by, for example, melt-extruding the above polyester into a film shape, and cooling and solidifying it with a casting drum to form an unstretched film. A desired film can be obtained by stretching biaxially at a magnification of 2.0 to 5.0 and heat-setting at a temperature of (Tm-100) to (Tm-5) ° C. for 1 to 100 seconds. Stretching can be performed by a generally used method such as a method using a roll or a method using a stenter. The stretching may be performed simultaneously in the longitudinal direction and the transverse direction, or may be sequentially performed in the longitudinal direction and the transverse direction. In the case of sequential stretching, the coating layer is formed by applying an aqueous coating liquid to a uniaxially oriented film stretched in one direction, stretching in the other direction as it is, and heat fixing. As a coating method, a roll coating method, a gravure coating method, a roll brush method, a spray method, an air knife coating method, an impregnation method, a curtain coating method, or the like can be used alone or in combination. Here, Tg represents the glass transition temperature of the polymer, and Tm represents the melting point of the polymer.

  Furthermore, when performing a relaxation | loosening process, it is effective to perform heat processing in the temperature of (X-80) -X degreeC of a film. Here, X represents the heat setting temperature. The method of relaxation treatment is a method in which both ends of the film are cut off in the middle of the heat setting zone and the take-off speed is reduced with respect to the supply speed of the film until the film is wound on the roll after heat setting. A method of heating with an IR heater between rolls, a method of transporting a film on a heated transport roll and reducing the speed of the transport roll after the heated transport roll, while transporting the film on a nozzle that blows hot air after heat fixing, A method of reducing the take-off speed over the supply speed, or a method of reducing the speed of the transport roll by transporting the film onto a heating transport roll after winding with a film forming machine, or heating in a heating oven or IR heater There is a method to reduce the roll speed after the heating zone from the roll speed before the heating zone while transporting the zone. Of may be used a method, it is preferable to perform relaxation by the deceleration rate of the take-off side of the speed from 0.1 to 10% with respect to the speed of the supply side.

(Pattern layer) The base film 11 may be provided with other layers such as a pattern layer. As the pattern layer, a single or plural kinds of color filter layers formed by forming a resin film disposed on the base film 11 into a desired pattern, or a laminate of such a color filter layer and a color conversion layer. Such as the body. The color filter layer is preferably formed in a pattern of one or more types to form a pixel. For example, a black matrix layer may be formed between a red color filter layer, a green color filter layer, a blue color filter layer, and each color filter layer (pixel). Since the pattern is usually formed by a photolithography method using a chemical such as an etchant, chemical resistance is important. If the chemical resistance is low, the surface of the base film is damaged such as alteration, and the gas barrier layer to be formed next cannot be formed densely and with good adhesion, so that high gas barrier properties cannot be exhibited.
However, by using a resin having a deflection temperature under load of 150 ° C. or more and a linear expansion coefficient of preferably 50 ppm / K or less, preferably polyethylene naphthalate (PEN), the heat resistance and chemical resistance are excellent, so the layer is dense. Since a film can be formed with good adhesion, a high gas barrier property can be exhibited.

  (Gas barrier layer) The material of the gas barrier layer 13A 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; Semiconductors such as germanium and carbon; inorganic oxides such as silicon oxide, aluminum oxide, magnesium oxide, indium oxide, calcium oxide, zirconium oxide, titanium oxide, boron oxide, zinc oxide, cerium oxide, hafnium oxide, and barium oxide; silicon nitride Nitride such as aluminum nitride, boron nitride and magnesium nitride; carbide such as silicon carbide, sulfide 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), and inorganic oxynitride carbide (MOxNyCz), and preferred M is a metal element such as Si, Al, or Ti. Moreover, it is the thing which added or substituted the metal, the semiconductor, etc. to them, or those mixtures.

  The thickness of the gas barrier layer 13A is not particularly limited as long as it is a thickness useful as a gas leakage preventing property (gas barrier property), but is preferably 30 to 10000 mm, more preferably 70 to 8000 mm, and more preferably 100 to 5000 mm. is there. If the total light transmittance is 70% or more, the color need not be particularly colorless. If it is less than 30 mm, the gas barrier property as a display substrate is not sufficient, and if it exceeds 10,000 mm, its own stress increases and flexibility is impaired.

  (Production method of gas barrier layer) The production method of the gas barrier layer 13A is not particularly limited, but preferably a vacuum deposition method, a sputtering method, an ion plating method, a HotWire-CVD method, a thermal CVD method or a plasma CVD method is used. 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. Sputtering is a method in which a discharge gas (such as argon) is introduced into a vacuum chamber and a high frequency voltage or a direct current voltage is applied between the target and a flexible substrate (such as a plastic film) to turn the discharge gas into plasma. This is a method of obtaining a thin film by causing a target material to fly by making it collide with a target and to adhere to the substrate. Further, a reactive sputtering method in which a reaction gas such as oxygen is introduced to cause an oxidation reaction may be used. The same applies to the CVD method.

  (Lamination) The gas leakage prevention function of the gas barrier film 10 of the present invention is mainly composed of a flexible base material and an inorganic thin film. Further, a plastic film is applied to the inorganic thin film via a conventionally known adhesive. A laminated layer may be used. Examples of the adhesive used include natural rubber-based, synthetic rubber-based, polyester-based, polyurethane-based, acrylic-based, silicone-based adhesives, and the like, and preferably polyurethane, polyester, polyisocyanate, Or it is the adhesive agent which consists of these mixtures. The film thickness of the adhesive is preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm. Moreover, as a plastic film to laminate | stack, the thing similar to the base film 11 mentioned above etc. are mentioned, The film thickness of the said plastic film is 5-500 micrometers, Preferably it is 8-300 micrometers.

  (Smoothing layer) The smoothing layer may be a sol-gel material, a 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, a radiation curable resin is preferable, and a resin that undergoes a crosslinking polymerization reaction and changes to a three-dimensional polymer structure by irradiation with ultraviolet rays (UV) or electron beams (EB), That is, an ionizing radiation curable resin in which a reactive prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or epoxy group in the molecule is appropriately mixed, or coating suitability, etc. In consideration of the above, the ionizing radiation curable resin is rolled using a liquid composition obtained by mixing a urethane-based, polyester-based, acrylic-based, butyral-based, or vinyl-based thermoplastic resin as necessary. Apply, dry, and harden by well-known coating methods such as coating method, Miyabar coating method, gravure coating method, dip coating method, die coating method, slide coating method, and three-reverse method. It can be formed by. 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.

  As the ionizing radiation curable resin, specifically, those having an acrylate-based functional group, that is, those having an acrylic skeleton are appropriate, and the hardness, heat resistance, solvent resistance, and scratch resistance of the coating film are appropriate. In view of the above, it is preferable that the structure has a high crosslink density, and bifunctional or higher acrylate monomers such as ethylene glycol di (meth) acrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri (meth) acrylate, penta Examples include erythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. In the above, acrylate and / or methacrylate are described as (meth) acrylate. 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, etc., and n-butylamine, triethylyl as photosensitizers Luamine, poly-n-butylphosphine and the like can be 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.

  (Sol-gel method) As a material for the smoothing layer in the present invention, a sol-gel material using a sol-gel method capable of forming a coating film of the same material system is also suitable for obtaining adhesion to the barrier layer. The sol-gel method is a coating composition comprising 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 the coating method and coating film of an object. 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, for example, the following general formula (a) disclosed in JP-A-2001-207130. Is an aminoalkyl dialkoxysilane or aminoalkyltrialkoxysilane.

（但し、Ａ¹はアルキレン基を表す。Ｒ⁴は水素原子、低級アルキル基、または、下記一般式（ｂ）で表される。）

(Wherein, A ¹ represents an alkylene group .R ⁴ is a hydrogen atom, a lower alkyl group, or represented by the following general formula (b).)

（ただし、Ａ²は直接結合またはアルキレン基を表し、Ｒ⁸、Ｒ⁹は水素原子または低級アルキル基を表す）で表される基を表す。Ｒ⁵は水素原子または低級アルキル基を表す。Ｒ⁶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Ｒ⁶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。Ｒ⁷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Ｒ⁷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。ただし、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｒ⁹のうちの少なくとも一つが水素原子である。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。）

(Wherein A ² represents a direct bond or an alkylene group, and R ⁸ and R ⁹ represent a hydrogen atom or a lower alkyl group). 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. However, at least one of R ⁴ , R ⁵ , R ⁸ and R ⁹ is a hydrogen atom. w is 0, 1, or 2, z is an integer of 1 to 3, and w + z = 3. )

  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 glycidyl group that is a functional group capable of reacting with an amino group. Having a carboxyl group, an isocyanate group, or an oxazoline group, specific examples include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, and nonaethylene glycol diester. Glycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neope Diglycidyl ethers such as til 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: 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 4, 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.

  (Cardopolymer) 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 the affinity and wettability are good with the inorganic compound such as the 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 surface of the material, dissolve in the material, diffuse in the material, and dissipate to the opposite surface. 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.

(Multiple Layer Configuration) As described above, the layer configuration is as follows: base film 11 / gas barrier layer 13A / smoothing layer 15A / gas barrier layer 13B / other layers, base film 11 / smoothing layer 15A / gas barrier layer 13A. / Smoothing layer 15B / Other layers, etc.
Among the layer configurations, at least one set of gas barrier layer / smoothing layer or smoothing layer / gas barrier layer is included, and the material of the gas barrier layer and the smoothing layer may be any of those described above. Materials other than the one set of gas barrier layer and smoothing layer may have the above or similar functions, and of course, all may be the above.

  (Stress Relaxation Layer) As the stress relaxation layer 31, the (approximate symmetry) stress relaxation layer 31 (gas barrier layer 13C) shown in FIG. 3A and the (front and back symmetry) stress relaxation layer 31 (gas barrier shown in FIG. 3B) are used. Layer 13C / smoothing layer 15C), and (asymmetric) stress relaxation layer 31 (gas barrier layer 13C) shown in FIG. 3C, at least one surface of the base film 11 is at least 1 What is necessary is just to have the stress relaxation layer 31 of the layer. In order to alleviate the film stress evenly, it is preferable that the layer structure be symmetrical or close to symmetrical. The stress relaxation layer 31 is a material that has a reverse stress to the gas barrier layer 13C and preferably has no optical anisotropy. For example, the same material as the gas barrier layer 13A and the smoothing layer 15A described above, or a similar material thereof. Examples thereof include those having a function, for example, an ultraviolet curable resin which is a hard coat resin.

  When manufacturing the gas barrier film 10 of the present invention, that is, to form a plurality of layers such as the gas barrier layer 13, the smoothing layer 15 and, if necessary, the stress relaxation layer 31 on the base film 11, all It can be processed (referred to as winding) in a continuous web form (referred to by those skilled in the art as winding). Examples of the winding machine for the gas barrier film 10 include a winding-type sputtering apparatus, a CVD apparatus, and an ion plating apparatus as exemplified in Japanese Patent Application Laid-Open No. 2003-149407. In addition, regarding the coating of the smoothing layer and the stress relaxation layer, for example, a normal winding gravure coating method, a comma coating method, a dip coating method, and a die coating method as exemplified in JP-A-2002-18339 It is possible to use a slide coating method, a three-reverse method, a two-reverse method, and the like. Further, in the pre-processing and the post-processing, the same winding type processing is possible, such as a web-shaped heating device as exemplified in JP-A-5-52474 and JP-A-5-64740. Can be used. Furthermore, the gas barrier film 10 of the present invention is used to form a transparent electrode layer, an auxiliary electrode layer, if necessary, an organic EL functional layer described later, a color filter, etc. A machine can be used. The winding process is easy to set up, is a continuous operation, has high production efficiency, has little material loss, has a good yield, and can be manufactured at low cost.

  When performing the winding process, not only the base film 11 used in the present invention but also the gas barrier layer 13 and the smoothing layer 15 are extremely flat and smooth, and are formed by a vacuum method such as CVD. Since the film immediately after the film is highly active, wrinkles are generated when it is wound up, and air is embraced to form convex portions (called a pyramid phenomenon by those skilled in the art), causing tarmi and distortion, and the surface of the substrate. Alternatively, there is a high risk that the coating solution on the back side will transfer to the opposite side (referred to as a blocking phenomenon by those skilled in the art). For this reason, it is preferable to perform a knurling process on the end part and a clean paper sandwiching process as a winding handling method even in the formation process of the base material and each layer, particularly when the layers are formed on both sides. It is effective.

  Moreover, the gas barrier film 10 of the present invention may be subjected to various treatments such as pretreatment, posttreatment, or annealing treatment. The annealing treatment may be maintained at a temperature of 100 to 230 ° C. for 10 to 180 minutes. The dangling bonds may be recombined, or the resin component of the smooth layer and the stress relaxation layer may be absorbed into the gas barrier layer. The permeability and / or oxygen permeability can be reduced.

  As pretreatment, it is preferable to perform heat treatment or vacuum deaeration treatment before forming the gas barrier layer. For example, it may be maintained at a temperature of 100 to 230 ° C. for 10 to 180 minutes, or at a temperature of 15 to 200 ° C. for 0.1 to 1000 hPa for 10 to 180 minutes. This is to prevent the coating residual liquid (solvent) contained in the smooth layer or the stress relaxation layer from volatilizing and forming impurities into the film when the gas barrier layer is formed, and to develop a desired function. is there. Similarly, for the purpose of removing impurities, it is preferable to provide a cleaning step before forming the gas barrier layer, the smoothing layer, the stress relaxation layer, and the anchor layer. Examples of the cleaning method include ultrasonic cleaning, alkali cleaning, neutral detergent cleaning, plasma cleaning, and UV cleaning.

  As the post-treatment, in the aging treatment after forming the layer, for example, in the formation of the smoothing layer, in the case of using the sol-gel method in which the coating solution is slowly soaked, the temperature ranges from 25 to 100 ° C. Storage for 14 days can reduce water vapor transmission rate and / or oxygen transmission rate.

  (Display Substrate) Furthermore, as shown in FIG. 4, a transparent electrode layer, or an auxiliary electrode layer or other layer as necessary, is provided on the smoothing layer or gas barrier layer surface to form a display substrate. Can do. That is, one set of gas barrier layer / smoothing layer or smoothing layer / gas barrier layer is essential, and other layers may be provided or sandwiched between other layers.

  (Solar cell) It 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 whose contents need to be protected.

  (Display) When the gas barrier film 10 of the present invention is used as the substrate 20 of the display, a layer necessary for each display method can be laminated on either the front or back of the gas barrier film 10, depending on circumstances. Since these layers may be laminated between the base film and the gas barrier layer, the gas barrier film 10 of the present invention has a display function between the base film and the thin film layer. Including a layer for interposing.

There are various types of displays to which the gas barrier film 10 of the present invention is applied. Typical examples include liquid crystal displays and organic EL elements.
(LCD) In general, a liquid crystal display is one in which a transparent electrode is arranged on the inside of two glass substrates, liquid crystal is sandwiched between alignment layers and the like, and the periphery is sealed. Yes, with color filters for colorization. The gas barrier film of the present invention can be applied to the outside of the glass substrate of such a liquid crystal display, or the gas barrier film 10 of the present invention can be used in place of the glass substrate. In particular, if both of the two glass substrates are replaced with the gas barrier film 10 of the present invention, the entire display can be made flexible.

  Some types of liquid crystals have optical anisotropy and some cannot use PEN, but can be applied without using a polarizing plate or by changing the position of the liquid crystal layer. Is a polymer-dispersed liquid crystal. Plastic liquid crystal is used for displays used in mobile devices such as personal digital assistants, communication devices (cell phones, etc.), notebook personal computers (PCs), and amusements (handy game machines), and is lightweight (about 1/3 of glass) and thin ( About 1/2) glass, durability (about 10 times that of glass), high display capacity, display without parallax (no double image even in reflection mode), etc. It can cope with low power consumption. 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 liquid crystal, since it uses a scattering-non-scattering state, in principle, no polarizing plate is required, the polarizing plate is unnecessary and it is brighter, the image display operation speed is faster, the liquid crystal injection process is unnecessary, and the cell gap control is easy. There is an advantage that rubbing is unnecessary, and it can be applied to a projection type.

  (Organic EL) The organic EL display also has a transparent electrode on the inside of two substrates, and, for example, (a) an injection function, (b) a transport function, and (c) a light emission function. The organic EL element layer which consists of a composite layer etc. which laminated | stacked the layer which has each function of these is pinched | interposed and the circumference | surroundings are sealed. The basic configuration is substrate / gas barrier layer / smoothing layer / transparent conductive layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode, but is not limited to this configuration. In some cases, a color filter for colorization or other means (layers) may be used. As in the liquid crystal display, the gas barrier film 10 of the present invention can be applied to the outside of the glass substrate, or the gas barrier film 10 of the present invention can be used instead of the glass substrate. If all the glass substrates are replaced with the gas barrier film 10 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, it is preferable that the substrate film of the gas barrier film has a very small humidity expansion coefficient and / or temperature expansion coefficient in addition to a deflection temperature under load of 150 ° C. or higher. . A polyethylene naphthalate (PEN) film as a preferable base film 11 of the present invention has a deflection temperature under load of 155 ° C., a thermal expansion coefficient of 8 ppm, and a humidity expansion coefficient of 0.5 ppm, which is also high in dimensional stability. preferable.

  (Color filter) The color filter is obtained by forming a color conversion layer in a pattern on a display substrate. As the pattern layer, a single or a plurality of types of color filter layers formed by forming a resin film disposed on a base film into a desired pattern, or a laminate of such a color filter layer and a color conversion layer. Etc. The color filter layer is preferably formed in a pattern of one or more types to form a pixel. For example, a black matrix layer may be formed between a red color filter layer, a green color filter layer, a blue color filter layer, and each color filter layer (pixel). Since the pattern is usually formed by a photolithography method using a chemical such as an etchant, chemical resistance is important. If the chemical resistance is low, the surface of the base film is damaged such as alteration, and the gas barrier layer to be formed next cannot be formed densely and with good adhesion, so that high gas barrier properties cannot be exhibited. However, since it is a resin having a deflection temperature under load of 150 ° C. or more and a linear expansion property of preferably 50 ppm / K or less, and preferably using polyethylene naphthalate (PEN), the gas barrier layer has excellent heat resistance and chemical resistance. Is dense and can form a film with good adhesion, so that a high gas barrier property can be exhibited.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this.

  As the base film of the example, a Teonex film Q65 (manufactured by Teijin Ltd., polyethylene naphthalate: film product name) having a thickness of 100 μm and a deflection temperature under load of 155 ° C. was used.

The formation method of the gas barrier layer of an Example and a comparative example is as follows.
SiOxNy (x = 0.7, y = 0.7) is placed in the film forming chamber of the magnetron sputtering apparatus, silicon nitride is used as the target, and the film thickness of silicon oxynitride is as follows. A gas barrier layer was provided so as to be 100 nm.
<Film formation conditions>
・ Film formation pressure: 2.5 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Nitrogen gas flow rate: 20sccm
・ RF power frequency: 13.56 MHz
・ Applied power: 1.2 kW
SiOx (x = 1.7) is placed in the film forming chamber of the ion plating apparatus, silicon dioxide is used as a target, and a gas barrier is formed so that the film thickness of silicon oxide becomes 100 nm under the following film forming conditions. A layer was provided.
<Film formation conditions>
Film forming pressure: 2.7 × 10 ⁻¹ Pa
Argon gas flow rate: 30sccm
・ Oxygen gas flow rate: 10 sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 2.0kW
SiOx (x = 1.5) is disposed in a film forming chamber of a pressure gradient ion plating apparatus with a feedback electrode, silicon dioxide is used as a film forming material, and a silicon oxide film is formed under the following film forming conditions. A gas barrier layer was provided so as to have a thickness of 100 nm.
<Film formation conditions>
Film deposition pressure: 8.0 × 10 ⁻² Pa
・ Argon gas flow rate for plasma gas: 12 sccm
-Input current: 8.5A
-Input voltage: 85V
-Input power: 7.2 kW
SiOxCz (x = 1.0, z = 1.0) is placed in the film formation chamber of the plasma CVD apparatus, HMDSO is used as the source gas, and the film thickness of silicon oxide carbide is as follows. A gas barrier layer was provided so as to be 100 nm.
<Film formation conditions>
-Film formation pressure: 6.6 Pa
Argon gas flow rate: 10 sccm
・ Oxygen gas flow rate: 30sccm
・ RF power supply frequency: 13.56 MHz
・ Applied power: 1.8kW
In addition, the composition analysis of said gas barrier layer was measured using the photoelectron spectroscopy analyzer (the product made by VG Scientific, model number ESCA-LAB220i-XL).

Moreover, the formation method of the smoothing layer of an Example and a comparative example is as follows.
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 dried on a hot plate at 120 ° C. for 2 minutes and then in a dryer at 160 ° C. for 1 hour. Then, a sol-gel layer (flattening layer) having a thickness of 1 μm is formed.
As the photoresist layer used as the smoothing layer, a resist solution (CFPR CL-016S) manufactured by Tokyo Ohka Co., Ltd., which is a photoresist material, is spin-coated and baked at 120 ° C. for 30 minutes to form a uniform resist film (smooth) Formation layer).
As a UV curable resin layer used as a smoothing layer, a UV curable acrylate to which a photopolymerization initiator is added (Nihon Kayaku Co., Ltd., 50 parts pentaerythritol triacrylate, Irgacure 184 (Ciba Geigy Corporation photopolymerization initiator) 2 parts ) And dried on a hot plate at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays (UV) using a high-pressure mercury lamp and UV-cured to form a smoothing layer having a thickness of 2 μm.
As the cardo polymer layer used as the smoothing layer, a coating agent V-259-EH (trade name, manufactured by Nippon Steel Chemical Co., Ltd.) mainly composed of cardo polymer is applied by a spin coating method and dried at 120 ° C. for 2 minutes. Further, it is dried with hot air at 160 ° C. for 60 minutes to form a smoothing layer having a film thickness of 1.0 μm.

  (Example 1) Each of the following layers was formed on the above base film under the above conditions, and the base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (sol-gel agent) of Example 1 A gas barrier film was obtained.

  (Example 2) Each of the following layers was formed under the above conditions, and a gas barrier film composed of a base film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (photoresist layer) was formed. Obtained.

  Example 3 The following layers were formed under the above conditions to obtain a gas barrier film consisting of a base film (PEN) / gas barrier layer (SiOxCz) / smoothing layer (UV curable resin).

  Example 4 The following layers were formed under the above conditions to obtain a gas barrier film comprising a base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (cardo polymer).

  (Example 5) Each of the following layers was formed under the above conditions to obtain a gas barrier film composed of a base film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer). It was.

  Example 6 The following layers were formed under the above conditions to obtain a gas barrier film consisting of a base film (PEN) / gas barrier layer (SiOxCz) / smoothing layer (cardo polymer).

  (Example 7) Each of the following layers is formed under the above conditions to obtain a gas barrier film composed of a base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (cardo polymer) / gas barrier layer (SiOxNy). It was.

  (Example 8) Each of the following layers was formed under the above conditions, and from base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.5) A gas barrier film was obtained.

  Example 9 The following layers are formed under the above conditions to obtain a gas barrier film comprising a base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (cardo polymer) / gas barrier layer (SiOxCz). It was.

  (Example 10) Each of the following layers was formed under the above conditions, and from base film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOxNy) A gas barrier film was obtained.

  (Example 11) Each of the following layers was formed under the above conditions, and from base film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOx) A gas barrier film was obtained.

  (Example 12) Each of the following layers was formed under the above conditions, and from base film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz) A gas barrier film was obtained.

  (Example 13) The following layers were formed under the above conditions to obtain a gas barrier film consisting of a base film (PEN) / gas barrier layer (SiOxCz) / smoothing layer (cardopolymer) / gas barrier layer (SiOxNy). It was.

  (Example 14) Each of the following layers was formed under the above conditions, and from base film (PEN) / gas barrier layer (SiOxCz) / smoothing layer (cardo polymer) / gas barrier layer (SiOx; x = 1.7) A gas barrier film was obtained.

  (Example 15) The following layers were formed under the above conditions to obtain a gas barrier film consisting of a base film (PEN) / gas barrier layer (SiOxCz) / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz). It was.

  (Example 16) Each of the following layers was formed under the above conditions, and a smoothing layer (cardo polymer) / gas barrier layer (SiOxNy) / base film (PEN) / gas barrier layer (SiOxNy) / smoothing layer (cardo polymer) A gas barrier film consisting of

  (Example 17) Each of the following layers was formed under the above conditions, and a smoothing layer (cardo polymer) / gas barrier layer (SiOx; x = 1.7) / base film (PEN) / gas barrier layer (SiOx; x) = 1.7) / A gas barrier film comprising a smoothing layer (cardo polymer) was obtained.

  (Example 18) Each of the following layers was formed under the above conditions to form a gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) / gas barrier layer (SiOxNy) / substrate film (PEN) / gas barrier layer (SiOxNy) / A gas barrier film comprising a smoothing layer (cardo polymer) / gas barrier layer (SiOxNy) was obtained.

  (Example 19) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOxNy) / base film (PEN) / A gas barrier film consisting of gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.7) was obtained.

  (Example 20) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOxCz) / smoothing layer (cardopolymer) / gas barrier layer (SiOxNy) / substrate film (PEN) / gas barrier layer (SiOxNy) / A gas barrier film composed of a smoothing layer (cardo polymer) / gas barrier layer (SiOxCz) was obtained.

  (Example 21) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.7) base film (PEN) / gas barrier A gas barrier film consisting of layer (SiOx; x = 1.7) / smoothing layer (cardo polymer) / gas barrier layer (SiOxNy) was obtained.

  (Example 22) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.7) / group A gas barrier film consisting of a material film (PEN) / gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardo polymer) / gas barrier layer (SiOx; x = 1.7) was obtained.

  (Example 23) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOxCz / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz / base film (PEN) / gas barrier layer (SiOx; x = 1)) .7) A gas barrier film consisting of: smoothing layer (cardo polymer) / gas barrier layer (SiOxCz) was obtained.

  (Example 24) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz) / base film (PEN) / gas barrier layer (SiOxCz) / A gas barrier film comprising a smoothing layer (cardo polymer) / gas barrier layer (SiOxNy) was obtained.

  (Example 25) Each of the following layers was formed under the above conditions, and a gas barrier layer (SiOx; x = 1.7) / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz) / base film (PEN) / A gas barrier film consisting of gas barrier layer (SiOxCz) / smoothing layer (cardo polymer) / gas barrier layer (SiOx; x = 1.7) was obtained.

  (Example 26) Each of the following layers was formed under the above conditions to form a gas barrier layer (SiOxCz) / smoothing layer (cardopolymer) / gas barrier layer (SiOxCz) / substrate film (PEN) / gas barrier layer (SiOxCz) / A gas barrier film composed of a smoothing layer (cardo polymer) / gas barrier layer (SiOxCz) was obtained.

  (Example 27) Each of the following layers was formed on the above base film under the above conditions, and the base film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (sol-gel agent) A gas barrier film comprising:

  (Example 28) Each of the following layers was formed under the above conditions, and a gas barrier film comprising a base film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (photoresist layer) was formed. Obtained.

  (Example 29) Each of the following layers was formed under the above conditions, and a gas barrier film consisting of a base film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (UV curable resin) was formed. Obtained.

  (Example 30) Each of the following layers was formed under the above conditions to obtain a gas barrier film comprising a base film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (cardopolymer). It was.

  (Example 31) Each of the following layers was formed under the above conditions to form a base film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.5) was obtained.

  (Example 32) Each of the following layers was formed under the above conditions, and gas barrier layer (SiOx; x = 1.5) / smoothing layer (cardopolymer) / gas barrier layer (SiOx; x = 1.5) / group A gas barrier film consisting of a material film (PEN) / gas barrier layer (SiOx; x = 1.5) / smoothing layer (cardo polymer) / gas barrier layer (SiOx; x = 1.5) was obtained.

(Example 33) A transparent electrode (indium zinc oxide) was entirely formed on the gas barrier layer (SiOzNy) surface of the gas barrier film of Example 7 by sputtering. On this indium zinc oxide, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), patterning is performed 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 is formed, and a base film (PEN) / gas barrier layer (SiOzNy) / smoothing layer (cardopolymer) / gas barrier A display substrate of Example 33 consisting of layer (SiOzNy) / transparent electrode layer (ITO) 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 34 A display substrate was formed in the same manner as in Example 33 on the gas barrier layer (SiOx; x = 1.5) surface of the gas barrier film produced in Example 32. 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 35)
(1) Formation of Blue Color Filter Layer As the transparent support substrate 11, a sheet-shaped (30 cm × 21 cm) polyethylene naphthalate (PEN) film having a deflection temperature under load of 155 ° C. and a thickness of 200 μm was used.
On the polyethylene naphthalate (PEN) film, a blue filter material (Color Mosaic CB-7001: trade name, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied 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.
(2) 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 by a spin coating method, patterned by a photolithographic method, and a line width of 0. A green conversion layer having a stripe pattern of 1 mm, a pitch (period) of 0.33 mm, and a film thickness of 10 μm was formed.
(3) 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. The red conversion layer, the green conversion layer, and the blue color filter layer correspond to the pattern layer 13.
(4) Formation of gas barrier layer and smoothing layer A gas barrier layer / smoothing layer / gas barrier layer were sequentially formed in the same manner as in Example 7 on the surface of the color conversion layer formed in the above step.
(5) Formation of transparent electrode layer A transparent electrode (indium zinc oxide) was formed on the entire surface of the smoothing layer by sputtering. On this indium zinc oxide, after applying a resist agent “OFRP-800” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), patterning is performed 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 is formed, and a base film (PEN) / pattern layer / gas barrier layer (SiOxNy) / smoothing layer (cardopolymer) ) / Gas barrier layer (SiOxNy) / transparent electrode layer (ITO) to obtain a color conversion filter substrate.
(6) Formation of organic EL related layer A color conversion filter substrate on which a transparent electrode layer is formed is mounted in a resistance heating vapor deposition apparatus, and a hole injection layer, a hole transport layer, an organic light emitting layer, and an electron injection layer are evacuated. The entire film was formed sequentially without breaking. 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 (α-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 the glove box (both oxygen and moisture concentrations were 10 ppm or less),
Organic EL color of Example 35 consisting of a base film / pattern layer / gas barrier layer / smoothing layer / transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode layer structure Got a display.
The organic EL color display was continuously driven for 100 hours, but could be displayed satisfactorily without problems.

(Example 36) Formation of the gas barrier layer and the smoothing layer in Example 35 was produced in the same manner as in Example 32, and the others were carried out in the same manner as in Example 35 to obtain an organic EL color display.
The organic EL color display was continuously driven for 500 hours, but was able to be displayed well with no dark spots.

  (Comparative Example 1) In the same manner as in Example 4, except that a base film is a polyethylene terephthalate (PET) resin film (manufactured by Toyobo Co., Ltd.) having a deflection temperature under load of 120 ° C. and a thickness of 200 μm. A gas barrier film was prepared.

(Evaluation) Evaluation is performed by the following measurement method, and the gas barrier film state and the layer structure of transparent electrode layer / hole injection layer / hole transport layer / organic light emitting layer / electron injection layer / cathode are provided on the gas barrier film. The water vapor transmission rate and oxygen transmission rate in the state of the organic EL element were measured, and the results are shown in Table 1.
The water vapor transmission rate was measured using a water vapor transmission rate measuring device (manufactured by MOCON, PERMATRAN-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, 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. When the detection limit is less than 0.01 cc / m ² · day · atm, it is expressed as 0.01 cc / m ² · day · atm or less.

(Evaluation results) The water vapor permeability of the gas barrier films of Examples 1 to 3 is 0.01 g / m ² · day or less, and the oxygen permeability is 0.02 cc / m ² · day · atm. It had gas barrier properties, and there was no significant elongation or deflection.
The gas barrier films of Examples 4 to 6 each have a water vapor transmission rate of 0.01 g / m ² · day or less and an oxygen transmission rate of 0.02 cc / m ² · day · atm. And there was no significant growth or deflection.
The gas barrier films of Examples 7 to 32 have a water vapor permeability of 0.01 g / m ² · day or less, an oxygen permeability of 0.01 cc / m ² · day · atm or less, and a sufficient gas barrier property, and There was no significant growth or deflection.
Further, when the gas barrier films of Examples 1 to 6 and 8 to 32 were formed into organic EL elements in the same manner as in Example 35 and the water vapor transmission rate and the oxygen transmission rate were measured, as shown in Table 1, the deterioration was observed. And sufficient gas barrier properties and no significant elongation or deflection.
As a result of evaluating the characteristics of the gas barrier film of Comparative Example 1, the water vapor permeability was 0.01 g / m ² · day or less and the oxygen permeability was 0.02 cc / m ² · day · atm. Although it was equivalent to 4-6, the transparent electrode layer and the organic EL element group were coated on the gas barrier film in the same manner as in Example 35, and the characteristics of the gas barrier film after drying at 180 ° C. for 6 hours. As a result, the oxygen transmission rate is 1.0 cc / m ² · day · atm and the water vapor transmission rate is 1.0 g / m ² · day. there were.

It is sectional drawing which shows one Example of the gas barrier film of this invention. It is sectional drawing which shows one Example of the gas barrier film of this invention. It is sectional drawing which shows one Example of the gas barrier film of this invention. It is sectional drawing which shows one Example of the board | substrate for displays of this invention.

Explanation of symbols

10: Gas barrier film 11: Base film 13A, 13B, 13C: Gas barrier layer 15A, 15B, 15C: Smoothing layer 20: Display substrate 21: Transparent electrode layer 23: Auxiliary electrode layer

Claims (17)

A base film having a deflection temperature under load of 150 ° C. or more, and a gas barrier comprising at least a gas barrier layer and a smoothing layer, or a smoothing layer and a gas barrier layer formed in this order on the base film. Sex film. 2. The gas barrier film according to claim 1, wherein the base film is polyethylene naphthalate. The gas barrier film according to claim 1, wherein the gas barrier layer is an inorganic oxide, an inorganic oxynitride, an inorganic oxycarbide, or an inorganic oxynitride carbide. The gas barrier film according to claim 1, wherein the smoothing layer contains a cardo polymer. The gas barrier film according to claim 1, wherein the smoothing layer contains an acrylic skeleton. The smoothing layer is composed of 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 as a raw material. The gas barrier film according to claim 1, wherein the gas barrier film is a coating film of a product. The gas barrier film according to claim 1, wherein at least one stress relaxation layer is formed on at least one side of the base film. A gas barrier film, wherein a transparent conductive film is formed on a gas barrier layer or a smoothing layer surface of the gas barrier film according to claim 1. A display substrate comprising the gas barrier film according to claim 1. A display substrate, wherein a transparent conductive film is formed on a gas barrier layer or a smoothing layer surface of the gas barrier film according to claim 1. An auxiliary electrode layer is formed on the transparent conductive layer surface of the display substrate according to claim 10. A display comprising the display substrate according to claim 9. An organic electroluminescence device comprising the display substrate according to claim 9. A liquid crystal display device comprising the display substrate according to claim 9. A color filter comprising the display substrate according to claim 10. A display comprising the color filter according to claim 15. An organic EL device comprising the color filter according to claim 15.

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